JP6705191B2 - Aminated petroleum resin and method for producing the same - Google Patents
Aminated petroleum resin and method for producing the same Download PDFInfo
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Description
本発明は、新規なアミノ化石油樹脂及びその製造方法に関するものであり、さらに詳しくはタイヤ、印刷インキ、塗料、接着剤向け原料として好適な新規なアミノ化石油樹脂及びその製造方法を提供するものである。 The present invention relates to a novel aminated petroleum resin and a method for producing the same, and more specifically to a novel aminated petroleum resin suitable as a raw material for tires, printing inks, paints, and adhesives, and a method for producing the same. Is.
親油性の石油樹脂とシリカなどの無機フィラーとの複合化は、無機フィラーが親水性であるため無機フィラーの凝集が起こり一般的に難しい。そこで石油樹脂に対して極性のある官能基による変性を行い親水性を高めることにより無機フィラーとの親和性を改良することが行われる。石油樹脂の変性としては一般的にフェノール変性石油樹脂とマレイン酸変性石油樹脂が知られている。フェノール変性石油樹脂はＣ９留分とフェノール類をフリーデルクラフツ触媒の存在下で共重合して製造され、エポキシ樹脂とタルク、チタン白などの無機フィラーとをブレンドして船舶の防食塗料として使用されている（例えば特許文献1，２参照。）。一方、マレイン酸変性石油樹脂は石油樹脂と無水マレイン酸とを２００℃前後で反応させる方法で製造され、流動性の向上効果により酸化チタンやガラズビーズなどの無機物フィラーを配合してトラフィックペイント用途などで用いられている（例えば特許文献３参照。）。 It is generally difficult to combine a lipophilic petroleum resin and an inorganic filler such as silica because the inorganic filler is hydrophilic and aggregation of the inorganic filler occurs. Therefore, the affinity with the inorganic filler is improved by modifying the petroleum resin with a polar functional group to increase the hydrophilicity. Phenol-modified petroleum resin and maleic acid-modified petroleum resin are generally known as the modified petroleum resin. Phenol-modified petroleum resin is produced by copolymerizing C9 fraction and phenols in the presence of Friedel-Crafts catalyst. It is used as an anticorrosive paint for ships by blending epoxy resin with inorganic filler such as talc and titanium white. (See, for example, Patent Documents 1 and 2). On the other hand, maleic acid-modified petroleum resin is produced by a method of reacting petroleum resin and maleic anhydride at around 200° C., and is mixed with an inorganic filler such as titanium oxide or glass beads due to the effect of improving fluidity to be used for traffic paint applications. It is used (for example, refer to Patent Document 3).
近年、タイヤに対する要求性能として、低燃費性能が挙げられ、燃費性能を向上するためにタイヤを構成するゴム組成物の発熱の抑制により、タイヤにした時の転がり抵抗を小さくすることが行われている。ゴム組成物の発熱を抑制する方法として、シリカを配合することが広く知られている（例えば非特許文献１参照。）。 In recent years, as a performance required for a tire, low fuel consumption performance has been mentioned, and in order to improve the fuel consumption performance, by suppressing heat generation of a rubber composition constituting the tire, rolling resistance when the tire is made small is performed. There is. Blending silica is widely known as a method for suppressing heat generation of a rubber composition (see, for example, Non-Patent Document 1).
シリカ配合タイヤでは、シリカの凝集を抑えて高分散させることが転がり抵抗、耐摩耗性及び加工性の改善に繋がる。シリカ表面のシラノール基は弱酸性を示し、石油樹脂に塩基性が付与できればシラノール基と分子レベルで反応してシリカ表面が親油性になり、ゴムとブレンドした際にシリカの分散性が向上すると考えた。しかし、従来の変性石油樹脂はカルボン酸基やフェノール性水酸基といった酸性の官能基による変性に限られ、塩基性の官能基による変性は全く知られていない。 In the silica-blended tire, suppressing the agglomeration of silica to achieve high dispersion leads to improvements in rolling resistance, wear resistance and workability. The silanol group on the silica surface is weakly acidic, and if basicity can be imparted to the petroleum resin, it will react with the silanol group at the molecular level to make the surface of the silica lipophilic and improve the dispersibility of silica when blended with rubber. It was However, the conventional modified petroleum resin is limited to modification with an acidic functional group such as a carboxylic acid group or a phenolic hydroxyl group, and modification with a basic functional group is not known at all.
そこで、本発明は、一般的な石油樹脂に対して、アミノ基を含有した置換基を付与した新規なアミノ化石油樹脂及びその製造方法を提供することを目的とする。 Then, this invention aims at providing the novel aminated petroleum resin which added the substituent containing an amino group with respect to general petroleum resin, and its manufacturing method.
本発明者らは、前記課題を解決すべく鋭意研究を進めた結果、前記課題を解決しうる可能性のあるものとしてアミノ基を含有する新規なアミノ化石油樹脂、その製造方法を見出し、本発明を完成させるに至った。 As a result of intensive research to solve the above problems, the present inventors have found a novel aminated petroleum resin containing an amino group as a possibility of solving the above problems, a method for producing the same, and The invention was completed.
即ち、本発明は、下記一般式（１）で表されるアミノ基及び／又はその塩を含む置換基を有する石油樹脂であることを特徴とするアミノ化石油樹脂及びその製造方法に関するものである。
（Ｒ１）２Ｎ−Ｒ２− （１）
（ここで、Ｒ１はそれぞれ独立して水素又は炭素数１〜５の炭化水素基、Ｒ２は炭素数１〜５の炭化水素基を示す。）
以下に、本発明を詳細に説明する。
That is, the present invention relates to an aminated petroleum resin characterized by being a petroleum resin having a substituent containing an amino group represented by the following general formula (1) and/or a salt thereof, and a method for producing the same. ..
(R1) 2 N-R2- (1)
(Here, R1 each independently represents hydrogen or a hydrocarbon group having 1 to 5 carbon atoms, and R2 represents a hydrocarbon group having 1 to 5 carbon atoms.)
The present invention will be described in detail below.
本発明のアミノ化石油樹脂は、上記一般式（１）で表されるアミノ基及び／又はその塩を含む置換基により変性された石油樹脂であり、上記一般式（１）で表されるアミノ基及び／又はその塩を含む置換基を有することにより、例えばシリカと配合した際には、シリカ表面の弱塩基性のシラノール基との反応性を示すことが可能となるものである。そして、本発明でいうアミノ化、アミノ基とは、アミノと称されるものは無論のこと、アミノに類すると認知されているアミン塩、アンモニウム塩等のアミノ基より誘導される置換基をも含むものである。 The aminated petroleum resin of the present invention is a petroleum resin modified by a substituent containing an amino group represented by the above general formula (1) and/or a salt thereof, and is represented by the above general formula (1). By having a substituent containing a group and/or a salt thereof, it becomes possible to exhibit reactivity with a weakly basic silanol group on the surface of silica when blended with silica, for example. The term “amino group” as used in the present invention means that what is referred to as “amino” is, of course, a substituent derived from an amino group such as an amine salt or an ammonium salt that is recognized as similar to amino. It includes.
ここで、上記一般式（１）で表されるアミノ基のＲ１は、それぞれ独立して水素又は炭素数１〜５の炭化水素基、Ｒ２は炭素数１〜５の炭化水素基を示す。一般式（１）で表されるアミノ基としては、例えば２−アミノエチル基、２−ジエチルアミノエチル基、２−ジメチルアミノエチル基、２−ジイソプロピルアミノエチル基、及びそれらの塩酸塩、硝酸塩、硫酸塩などが挙げられ、中でも２−アミノエチル基、２−ジエチルアミノエチル基、２−ジメチルアミノエチル基、２−アミノエチル基の塩酸塩、２−ジエチルアミノエチル基の塩酸塩、２−ジメチルアミノエチル基の塩酸塩であることが好ましい。 Here, R1 of the amino group represented by the above general formula (1) independently represents hydrogen or a hydrocarbon group having 1 to 5 carbon atoms, and R2 represents a hydrocarbon group having 1 to 5 carbon atoms. Examples of the amino group represented by the general formula (1) include 2-aminoethyl group, 2-diethylaminoethyl group, 2-dimethylaminoethyl group, 2-diisopropylaminoethyl group, and their hydrochlorides, nitrates, and sulfuric acids. Examples thereof include salts. Among them, 2-aminoethyl group, 2-diethylaminoethyl group, 2-dimethylaminoethyl group, 2-aminoethyl group hydrochloride, 2-diethylaminoethyl group hydrochloride, 2-dimethylaminoethyl group. The hydrochloride salt of
さらに、該アミノ基を含む置換基としては、その置換基の一部に該アミノ基を有するものであってもよく、例えば、下記一般式（２）で表されるアミノ基を有するメルカプト基を挙げることができる。
（Ｒ３）２Ｎ−Ｒ４−Ｓ− （２）
（ここで、Ｒ３はそれぞれ独立して水素又は炭素数１〜５の炭化水素基、Ｒ４は炭素数１〜５の炭化水素基を示す。）
そして、Ｒ３はそれぞれ独立して水素又は炭素数１〜５の炭化水素基、Ｒ４は炭素数１〜５の炭化水素基を示すものであり、上記一般式（２）で表されるアミノ基を有するメルカプト基としては、例えば２−アミノエチルメルカプト基、２−ジエチルアミノエチルメルカプト基、２−ジメチルアミノエチルメルカプト基、２−ジイソプロピルアミノエチルメルカプト基及びそれらの塩酸塩、硝酸塩、硫酸塩などが挙げられ、中でも２−アミノエチルメルカプト基、２−ジエチルアミノエチルメルカプト基、２−ジメチルアミノエチルメルカプト基、２−アミノエチルメルカプト基の塩酸塩、２−ジエチルアミノエチルメルカプト基の塩酸塩、２−ジメチルアミノエチルメルカプト基の塩酸塩であることが好ましい。
Further, the substituent containing the amino group may have the amino group as a part of the substituent, and for example, a mercapto group having the amino group represented by the following general formula (2) may be used. Can be mentioned.
(R3) 2 N-R4-S- (2)
(Here, R3 each independently represents hydrogen or a hydrocarbon group having 1 to 5 carbon atoms, and R4 represents a hydrocarbon group having 1 to 5 carbon atoms.)
R3 is independently hydrogen or a hydrocarbon group having 1 to 5 carbon atoms, R4 is a hydrocarbon group having 1 to 5 carbon atoms, and is an amino group represented by the general formula (2). Examples of the mercapto group having include 2-aminoethylmercapto group, 2-diethylaminoethylmercapto group, 2-dimethylaminoethylmercapto group, 2-diisopropylaminoethylmercapto group and their hydrochlorides, nitrates, sulfates and the like. Among them, 2-aminoethylmercapto group, 2-diethylaminoethylmercapto group, 2-dimethylaminoethylmercapto group, 2-aminoethylmercapto group hydrochloride, 2-diethylaminoethylmercapto group hydrochloride, 2-dimethylaminoethylmercapto It is preferably the hydrochloride salt of the group.
本発明のアミノ化石油樹脂を構成する石油樹脂としては、一般的に石油樹脂として知られている範疇に属するものであれば特に限定はなく、例えば脂肪族系石油樹脂、芳香族系石油樹脂、脂肪族／芳香族共重合系石油樹脂、ＤＣＰＤ樹脂を挙げることができる。 The petroleum resin constituting the aminated petroleum resin of the present invention is not particularly limited as long as it belongs to the category generally known as petroleum resin, for example, aliphatic petroleum resin, aromatic petroleum resin, Examples thereof include aliphatic/aromatic copolymer petroleum resin and DCPD resin.
脂肪族共重合系石油樹脂とは、その原料として石油類の熱分解により得られる分解油のうち沸点範囲が１５〜７０℃の範囲にあるＣ５留分、例えばメチルブテン、ペンテン、イソプレン、ピペリレン、シクロペンテン、シクロペンタジエンなどを、単独重合又は共重合して得られた樹脂である。 The aliphatic copolymer petroleum resin is a C5 fraction having a boiling point in the range of 15 to 70° C., such as methylbutene, pentene, isoprene, piperylene, and cyclopentene, of cracked oil obtained by thermal decomposition of petroleum as a raw material. Is a resin obtained by homopolymerization or copolymerization of cyclopentadiene and the like.
芳香族系石油樹脂とは、その原料油として石油類の熱分解により得られる分解油のうち沸点範囲が１４０〜２８０℃の範囲にあるＣ９留分、例えばスチレン、そのアルキル誘導体であるα−メチルスチレンやβ−メチルスチレン、ビニルトルエン、インデン及びそのアルキル誘導体、ジシクロペンタジエン及びその誘導体などを、単独重合又は共重合して得られた樹脂である。 Aromatic petroleum resin is a C9 fraction having a boiling point in the range of 140 to 280° C. among cracked oils obtained by thermal decomposition of petroleum as a raw material oil, for example, styrene and α-methyl which is an alkyl derivative thereof. It is a resin obtained by homopolymerizing or copolymerizing styrene, β-methylstyrene, vinyltoluene, indene and its alkyl derivatives, dicyclopentadiene and its derivatives, and the like.
脂肪族／芳香族共重合系石油樹脂とは、その原料として前述のＣ５留分とＣ９留分とを共重合して得られた樹脂である。 The aliphatic/aromatic copolymer petroleum resin is a resin obtained by copolymerizing the above-mentioned C5 fraction and C9 fraction as a raw material thereof.
また、ＤＣＰＤ樹脂とは、シクロペンタジエン、メチルシクロペンタジエン、これらの２〜５量体などを、単独重合、共重合して得られた樹脂である。 Further, the DCPD resin is a resin obtained by homopolymerization or copolymerization of cyclopentadiene, methylcyclopentadiene, and dimers to pentamers thereof.
本発明のアミノ化石油樹脂を構成する石油樹脂の軟化点、分子量は特に制限はなく、液状又は固体状であってもよく、その際にアミノ化石油樹脂を構成する石油樹脂は液状又は固体状であってもよい。 The petroleum resin constituting the aminated petroleum resin of the present invention is not particularly limited in softening point and molecular weight, and may be liquid or solid, and the petroleum resin constituting the aminated petroleum resin may be liquid or solid. May be
本発明のアミノ化石油樹脂の製造方法としては、該アミノ化石油樹脂を製造することが可能である限りにおいて如何なる方法を用いてもよく、その中でも特に効率よく本発明のアミノ化石油樹脂を製造することが可能となることから、例えば下記一般式（３）で表されるメルカプタンにより石油樹脂を変性する方法により製造することができる。
（Ｒ５）２Ｎ−Ｒ６−Ｓ−Ｈ （３）
（ここで、Ｒ５はそれぞれ独立して水素又は炭素数１〜５の炭化水素基、Ｒ６は炭素数１〜５の炭化水素基を示す。）
その際のメルカプタンの具体的例示としては、２−アミノエタンチオール、２−ジエチルアミノエタンチオール、２−ジメチルアミノエタンチオール、２−ジイソプロピルアミノエタンチオール、及びそれらの塩酸塩、硝酸塩、硫酸塩などが挙げられ、特に２−アミノエタンチオール、２−ジエチルアミノエタンチオール、２−ジメチルアミノエタンチオール、２−アミノエタンチオール塩酸塩、２−ジエチルアミノエタンチオール塩酸塩、２−ジメチルアミノエタンチオール塩酸塩が好ましい。また、これらは単独または混合して使用することもできる。
As the method for producing the aminated petroleum resin of the present invention, any method may be used as long as it can produce the aminated petroleum resin, and among them, the aminated petroleum resin of the present invention can be produced particularly efficiently. Therefore, it can be produced by, for example, a method of modifying a petroleum resin with a mercaptan represented by the following general formula (3).
(R5) 2 N-R6-SH (3)
(Here, R5 each independently represents hydrogen or a hydrocarbon group having 1 to 5 carbon atoms, and R6 represents a hydrocarbon group having 1 to 5 carbon atoms.)
Specific examples of the mercaptan in that case include 2-aminoethanethiol, 2-diethylaminoethanethiol, 2-dimethylaminoethanethiol, 2-diisopropylaminoethanethiol, and their hydrochlorides, nitrates, sulfates and the like. Of these, 2-aminoethanethiol, 2-diethylaminoethanethiol, 2-dimethylaminoethanethiol, 2-aminoethanethiol hydrochloride, 2-diethylaminoethanethiol hydrochloride and 2-dimethylaminoethanethiol hydrochloride are particularly preferable. Moreover, these can also be used individually or in mixture.
本発明のアミノ化石油樹脂を製造する際には、効率よく製造することが可能となることから石油樹脂１００重量部に対して、メルカプタン０．１〜２５重量部の割合で用いることが好ましく、特に０．１〜２０重量部であることが好ましい。その際の反応は特に制限はなく、中でもラジカル開始剤の存在下、反応温度２０〜２５０℃で反応時間０．１〜５０時間の範囲で行うことが好ましい。また、ＴＨＦ、クロロホルム、トルエン、キシレンなどの石油樹脂とメルカプタンを溶解する不活性な溶剤の存在下で実施しても構わない。そして、未反応物として残存するメルカプタンは、加熱下で不活性ガスを吹き込み除去することが出来る。また、アミン変性後にテトラヒドロフランなどに溶解させた後、アルコールに滴下して再沈精製することで未反応のメルカプタンをアルコールに溶解除去することもできる。さらに、溶媒を用いる場合は反応後に溶媒を除去するための蒸留設備を設置していてもよい。 When producing the aminated petroleum resin of the present invention, it is preferable to use it in a ratio of 0.1 to 25 parts by weight of mercaptan with respect to 100 parts by weight of the petroleum resin because it can be efficiently produced. It is particularly preferably 0.1 to 20 parts by weight. The reaction at that time is not particularly limited, and it is particularly preferable to carry out the reaction in the presence of a radical initiator at a reaction temperature of 20 to 250° C. for a reaction time of 0.1 to 50 hours. Further, it may be carried out in the presence of an inert solvent which dissolves a petroleum resin such as THF, chloroform, toluene and xylene and mercaptan. The mercaptan remaining as an unreacted substance can be removed by blowing an inert gas under heating. Further, it is also possible to dissolve and remove unreacted mercaptan by dissolving it in tetrahydrofuran or the like after the amine modification and then dropping it in alcohol for reprecipitation purification. Further, when a solvent is used, a distillation facility for removing the solvent after the reaction may be installed.
本反応で用いられるラジカル開始剤は公知のラジカル開始剤を用いてもよく、例えば、過酸化物系（パーオキサイド）開始剤、アゾ系開始剤等を選択することができる。ラジカル開始剤の使用量に特に制限はなく、一般的には石油樹脂１００重量部に対して０．１〜３重量部の範囲で用いられる。 As the radical initiator used in this reaction, a known radical initiator may be used, and for example, a peroxide (peroxide) initiator, an azo initiator or the like can be selected. The amount of the radical initiator used is not particularly limited, and is generally used in the range of 0.1 to 3 parts by weight with respect to 100 parts by weight of the petroleum resin.
さらに、本発明のアミノ化石油樹脂は、本発明の目的を逸脱しない限りにおいて、通常樹脂組成物に配合される添加剤として、例えばフェノール系抗酸化剤、リン系抗酸化剤、硫黄系抗酸化剤、ラクトン系抗酸化剤、ヒンダードアミン光安定剤（ＨＡＬＳ）、紫外線吸収剤、顔料などを配合しても良い。 Further, the aminated petroleum resin of the present invention is, as long as it does not deviate from the object of the present invention, as an additive usually added to a resin composition, for example, a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant. Agents, lactone-based antioxidants, hindered amine light stabilizers (HALS), ultraviolet absorbers, pigments and the like may be added.
本発明により、新規なアミノ化石油樹脂を提供することが出来る。本アミノ化石油樹脂は、タイヤ、接着剤や印刷インキ、塗料などの用途で幅広く用いることができる。アミノ化石油樹脂を用いてシリカ配合タイヤを製造にした場合、転がり抵抗性、耐摩耗性、加工性の改良が期待できる。 According to the present invention, a novel aminated petroleum resin can be provided. The aminated petroleum resin can be widely used in applications such as tires, adhesives, printing inks and paints. When a silica-blended tire is produced using an aminated petroleum resin, improvement in rolling resistance, wear resistance, and workability can be expected.
以下に、実施例および比較例により本発明をさらに詳細に説明するが、本発明はこれら実施例に限定されるものではない。なお、実施例、比較例において用いた原料、分析、試験法は下記の通りである。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. The raw materials, analysis, and test methods used in Examples and Comparative Examples are as follows.
１．原料
（１）石油樹脂
脂肪族／芳香族共重合系石油樹脂Ａ（東ソー株式会社製、（商品名）ペトロタック７０）。
脂肪族／芳香族共重合系石油樹脂Ｂ（東ソー株式会社製、（商品名）ペトロタック９０）。
芳香族系石油樹脂Ｃ（東ソー株式会社製、（商品名）ペトコールＬＸ）。
1. Raw materials (1) Petroleum resin Aliphatic/aromatic copolymer petroleum resin A (manufactured by Tosoh Corporation, (trade name) PetroTac 70).
Aliphatic/Aromatic Copolymer Petroleum Resin B (Tosoh Corporation, (trade name) PetroTac 90).
Aromatic petroleum resin C (Tosoh Corporation, (trade name) Petcole LX).
（２）メルカプタン
メルカプタンａ：２−アミノエタンチオール（東京化成工業株式会社製）。
メルカプタンｂ：２−ジエチルアミノエタンチオール塩酸塩（東京化成工業株式会社製）。
(2) Mercaptan Mercaptan a: 2-aminoethanethiol (manufactured by Tokyo Chemical Industry Co., Ltd.).
Mercaptan b: 2-diethylaminoethanethiol hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.).
（３）ラジカル開始剤
ジ（３，５，５−トリメチルヘキサノイル）パーオキサイド（（商品名）パーロイル３５５、日油株式会社製）。
(3) Radical initiator di(3,5,5-trimethylhexanoyl) peroxide ((trade name) perloyl 355, manufactured by NOF CORPORATION).
２．分析方法
（１）軟化点
ＪＩＳ Ｋ−２２０７に従って測定。
2. Analysis method (1) Softening point Measured according to JIS K-2207.
（２）硫黄含有量
酸素フラスコ燃焼−イオンクロマトグラフィーにより測定。
(2) Sulfur content Measured by oxygen flask combustion-ion chromatography.
（３）重量平均分子量
ポリスチレンを標準物質としてゲル浸透クロマトグラフィーにより測定した。
(3) Weight average molecular weight It was measured by gel permeation chromatography using polystyrene as a standard substance.
３．タイヤ性能評価
（１）評価サンプル調整
バンバリーミキサー（容量１．７リットル）にて、溶液重合スチレン−ブタジエン共重合体ゴム（Ｓ−ＳＢＲ）（（株）ＪＳＲ製、（商品名）ＳＬ５５２）８０重量部とポリイソプレンゴム（ＩＲ）（（株）ＪＳＲ製、（商品名）ＩＲ２２００）２０重量部（合計ジエン系ゴム成分１００重量部）を３０秒間素練り後、ステアリン酸（新日本理化製）を２重量部、シリカ（東ソー・シリカ製、（商品名）Ｎｉｐｓｉｌ ＡＱ）を４５重量部、シランカップリング剤（信越シリコーン製、（商品名）ＫＢＥ４６）を３．６重量部、及び実施例１〜３で得られたアミノ化石油樹脂、比較例１〜３の未変性石油樹脂を投入し、全練り時間５分後取り出した。取り出し時のコンパウンド温度を１４０〜１５０℃となるようにラム圧や回転数で調整した。得られたコンパウンドを室温にて冷却した後、更に老化防止剤（大内新興製、（商品名）８１０ＮＡ）を１重量部、亜鉛華（井上石灰工業製）を３重量部、加硫促進剤１（大内新興製、（商品名）ノクセラーＣＺ）を１．２重量部、加硫促進剤２（大内新興製、（商品名）ノクセラーＤ）を１．５重量部、加硫剤として硫黄（鶴見化学工業製）１．５重量部を添加して約１分間混練り（取り出し時の温度を１１０℃以下とする）後、８インチロールを用いてシーティングして未加硫物の物性（ムーニー粘度）を測定した。更に蒸気加熱プレスを用い、加硫温度１５０℃、加硫時間３０分で加硫し加硫物特性（耐摩耗性、転がり抵抗性）を測定した。
3. Tire Performance Evaluation (1) Evaluation Sample Adjustment Using a Banbury mixer (capacity 1.7 liters), solution-polymerized styrene-butadiene copolymer rubber (S-SBR) (manufactured by JSR, (trade name) SL552) 80 weight Parts and polyisoprene rubber (IR) (manufactured by JSR, (trade name) IR2200) 20 parts by weight (total diene rubber component 100 parts by weight) for 30 seconds, and then stearic acid (manufactured by Shin Nippon Rika) 2 parts by weight, 45 parts by weight of silica (manufactured by Tosoh Silica, (trade name) Nipsil AQ), 3.6 parts by weight of silane coupling agent (manufactured by Shin-Etsu Silicone, (trade name) KBE46), and Examples 1 to 1 The aminated petroleum resin obtained in No. 3 and the unmodified petroleum resins of Comparative Examples 1 to 3 were added and taken out after a total kneading time of 5 minutes. The compound temperature at the time of taking out was adjusted by the ram pressure and the rotation speed so as to be 140 to 150°C. After cooling the obtained compound at room temperature, 1 part by weight of an antioxidant (manufactured by Ouchi Shinko Co., Ltd., (trade name) 810NA), 3 parts by weight of zinc flower (manufactured by Inoue Lime Industry), and a vulcanization accelerator 1.2 parts by weight of 1 (Ouchi Shinko, (brand name) Noxcellar CZ), 1.5 parts by weight of vulcanization accelerator 2 (Ouchi Shinko, (trade name) Noxceller D), as a vulcanizing agent After adding 1.5 parts by weight of sulfur (manufactured by Tsurumi Chemical Industry Co., Ltd.) and kneading for about 1 minute (the temperature at the time of taking out should be 110° C. or lower), sheeting with an 8-inch roll was performed and the physical properties of the unvulcanized product were measured. (Moonie viscosity) was measured. Further, using a steam heating press, vulcanization was carried out at a vulcanization temperature of 150° C. for a vulcanization time of 30 minutes, and vulcanizate properties (wear resistance, rolling resistance) were measured.
（２）物性評価方法
（ａ）ムーニー粘度
ムーニー粘度計（島津製作所製 （商品名）ＳＭＶ−２００型）を用い１２５℃、Ｌ型ロータにて測定した。石油樹脂が無添加の値を１００として指数表示した。
(2) Physical Property Evaluation Method (a) Mooney Viscosity It was measured with a L-type rotor at 125° C. using a Mooney viscometer (manufactured by Shimadzu Corporation (trade name) SMV-200 type). The value when no petroleum resin was added was set as 100 and indicated as an index.
（ｂ）耐摩耗性
ＪＩＳ Ｋ−６３０１の試験法に準じて測定した。摩耗試験はアルロン型摩耗試験機で測定した。傾角１５°、分銅６ポンド、試験回数１０００ｒｐｍでの摩耗減容を測定した。石油樹脂が無添加の値を１００として指数表示した。この値が小さい程、耐摩耗性が良好であることを示す。
(B) Abrasion resistance It was measured according to the test method of JIS K-6301. The abrasion test was performed using an Arlon type abrasion tester. The wear volume was measured at a tilt angle of 15°, a weight of 6 pounds, and a test frequency of 1000 rpm. The value when no petroleum resin was added was set as 100 and indicated as an index. The smaller this value is, the better the abrasion resistance is.
（ｃ）転がり抵抗性
粘弾性測定装置（レオメトリックス社製）を使用し、温度５０℃、歪み５％、周波数１５Ｈｚでｔａｎδを測定し、６０℃の値を転がり抵抗性とし、石油樹脂が無添加の値を１００として指数表示した。この値が小さい程、低発熱性が良好であることを示す。
(C) Using a rolling resistance viscoelasticity measuring device (manufactured by Rheometrics Inc.), tan δ was measured at a temperature of 50° C., a strain of 5% and a frequency of 15 Hz. The value of addition was set to 100 and displayed as an index. The smaller this value, the better the low heat buildup.
実施例１
脂肪族／芳香族共重合系石油樹脂Ａ（軟化点６８℃、重量平均分子量（Ｍｗ）１４６０）５００ｇとクロロホルム５００ｇを攪拌機の付いたガラス製フラスコに入れて、６０℃で加熱溶融させた。そこにメルカプタンｂ：２−ジエチルアミノエタンチオール塩酸塩（東京化成工業株式会社製）を６７．９ｇ加えた後、開始剤（商品名）パ−ロイル３５５（日油株式会社製）５ｇを滴下し、６３℃、８時間反応させた。その後、窒素気流化２２０℃、１５分で溶媒、未反応メルカプタンｂを除去し、アミノ化石油樹脂を得た。
Example 1
Aliphatic/aromatic copolymer petroleum resin A (softening point 68° C., weight average molecular weight (Mw) 1460) 500 g and chloroform 500 g were put into a glass flask equipped with a stirrer and heated and melted at 60° C. After 67.9 g of mercaptan b:2-diethylaminoethanethiol hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added thereto, 5 g of an initiator (trade name) Parloyl 355 (manufactured by NOF CORPORATION) was added dropwise. The reaction was carried out at 63°C for 8 hours. Then, the solvent and unreacted mercaptan b were removed at 220° C. for 15 minutes under a nitrogen stream to obtain an aminated petroleum resin.
このアミノ化石油樹脂の軟化点、硫黄含有量及び分子量を表１に示す。一方、アミノ化石油樹脂のプロトンＮＭＲのチャートは図１の通りで、それぞれのピークの帰属から２−ジエチルアミノエタンチオール塩酸塩で変性されたアミノ化石油樹脂であることが確認できた。 Table 1 shows the softening point, sulfur content and molecular weight of this aminated petroleum resin. On the other hand, the proton NMR chart of the aminated petroleum resin is as shown in FIG. 1, and it was confirmed from the assignment of the respective peaks that it was an aminated petroleum resin modified with 2-diethylaminoethanethiol hydrochloride.
また、表１にアミノ化石油樹脂のタイヤ性能評価の結果を示す。 Table 1 shows the results of tire performance evaluation of aminated petroleum resin.
実施例２，３
石油樹脂の種類、メルカプタンの使用量、種類を表１のように変更した以外は、実施例１と同様にしてアミノ化石油樹脂を調製した。
Examples 2 and 3
An aminated petroleum resin was prepared in the same manner as in Example 1 except that the type of petroleum resin, the amount of mercaptan used, and the type were changed as shown in Table 1.
それぞれのアミノ化石油樹脂の軟化点、硫黄含有量、分子量を表１に示す。 Table 1 shows the softening point, sulfur content, and molecular weight of each aminated petroleum resin.
また、表１に各種アミノ化石油樹脂のタイヤ性能評価の結果を示す。 Table 1 shows the results of tire performance evaluation of various aminated petroleum resins.
アミノ化石油樹脂１の代わりに、それぞれ脂肪族／芳香族共重合系石油樹脂Ａ、脂肪族／芳香族共重合系石油樹脂Ｂ、芳香族系石油樹脂Ｃを用いた以外は、実施例１と同様の方法により評価した結果を表２に示す。
Instead of the aminated petroleum resin 1, an aliphatic/aromatic copolymerization petroleum resin A, an aliphatic/aromatic copolymerization petroleum resin B, and an aromatic petroleum resin C were used, respectively. The results evaluated by the same method are shown in Table 2.
本発明は新規なアミノ化石油樹脂およびその製造方法を提供するものであり、該アミノ化石油樹脂は、タイヤ、接着剤や印刷インキ、塗料などの用途で幅広く用いることが期待できる。 The present invention provides a novel aminated petroleum resin and a method for producing the same, and the aminated petroleum resin can be expected to be widely used in applications such as tires, adhesives, printing inks and paints.
Claims (4)
（Ｒ１）２Ｎ−Ｒ２− （１）
（ここで、Ｒ１はそれぞれ独立して水素又は炭素数１〜５の炭化水素基、Ｒ２は炭素数１〜５の炭化水素基を示す。）
（Ｒ３）２Ｎ−Ｒ４−Ｓ− （２）
（ここで、Ｒ３はそれぞれ独立して水素又は炭素数１〜５の炭化水素基、Ｒ４は炭素数１〜５の炭化水素基を示す。） Der petroleum resin having a substituent containing an amino group and / or its salt represented by the following general formula (1) is, substituents containing amino groups and / or salts thereof represented by the following general formula (1) Is an amino group-containing mercapto group represented by the following general formula (2) and/or a salt thereof, an aminated petroleum resin.
(R1) 2 N-R2- (1)
(Here, R1 each independently represents hydrogen or a hydrocarbon group having 1 to 5 carbon atoms, and R2 represents a hydrocarbon group having 1 to 5 carbon atoms.)
(R3) 2 N-R4-S- (2)
(Here, R3 each independently represents hydrogen or a hydrocarbon group having 1 to 5 carbon atoms, and R4 represents a hydrocarbon group having 1 to 5 carbon atoms.)
（Ｒ５）(R5) ２Two Ｎ−Ｒ６−Ｓ−Ｈ （３）N-R6-S-H (3)
（ここで、Ｒ５はそれぞれ独立して水素又は炭素数１〜５の炭化水素基、Ｒ６は炭素数１〜５の炭化水素基を示す。）(Here, R5 each independently represents hydrogen or a hydrocarbon group having 1 to 5 carbon atoms, and R6 represents a hydrocarbon group having 1 to 5 carbon atoms.)
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