JP3312388B2 - Hydroxyl group-containing hydrogenated petroleum resin and production method thereof - Google Patents

Hydroxyl group-containing hydrogenated petroleum resin and production method thereof

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Publication number
JP3312388B2
JP3312388B2 JP16833992A JP16833992A JP3312388B2 JP 3312388 B2 JP3312388 B2 JP 3312388B2 JP 16833992 A JP16833992 A JP 16833992A JP 16833992 A JP16833992 A JP 16833992A JP 3312388 B2 JP3312388 B2 JP 3312388B2
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JP
Japan
Prior art keywords
petroleum resin
catalyst
hydroxyl group
hydrogenation
hydrogenated
Prior art date
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Expired - Fee Related
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JP16833992A
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Japanese (ja)
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JPH05331241A (en
Inventor
計治 御手洗
浩二 田中
英治 岡成
康一 川島
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Tosoh Corp
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Tosoh Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【産業上の利用分野】本発明は新規な水添石油樹脂及び
その製造方法に関する。更に詳しくは、構成成分及びそ
の物性値が限定された高品質の水添石油樹脂及びＣ9 留
分をフェノール類存在下重合して、更に該重合物を触媒
存在下、加圧下で水素下する高品質水添石油樹脂を製造
する方法に関する。The present invention relates to a novel hydrogenated petroleum resin and a method for producing the same. More specifically, a high-quality hydrogenated petroleum resin and its C9 fraction, whose constituent components and their physical property values are limited, are polymerized in the presence of phenols, and the polymer is subjected to hydrogenation under pressure in the presence of a catalyst. The present invention relates to a method for producing a quality hydrogenated petroleum resin.

【０００２】[0002]

【従来の技術】石油樹脂は、石油ナフサを熱分解又は触
媒を用いた接触分解により得られるＣ4 −Ｃ6 の脂肪族
オレフィンのスペント留分や、オレフィン性不飽和結合
を有するＣ8 以上の芳香族炭化水素のスペント留分に含
まれる一種以上の重合性物質をフリーデルクラフツ型触
媒や熱により、単独重合又は共重合して得られたＣ5
系，Ｃ9 系及びＣ5 −Ｃ9 系共重合石油樹脂，そしてそ
の他、テルペン樹脂，天然ロジン等がある。2. Description of the Related Art Petroleum resins can be used as a spent fraction of a C4-C6 aliphatic olefin obtained by pyrolysis or catalytic cracking of petroleum naphtha, or a C8 or higher aromatic carbon having an olefinically unsaturated bond. C5 obtained by homopolymerizing or copolymerizing one or more polymerizable substances contained in a hydrogen spent fraction with a Friedel-Crafts type catalyst or heat.
, C9 and C5 -C9 copolymerized petroleum resins, and others, such as terpene resins and natural rosin.

【０００３】これら石油樹脂は、粘着性，接着性，他の
樹脂との相溶性を有していることから、各種プラスチッ
クス，ゴム，油性物質に混溶され，塗料，印刷インキ，
接着剤，粘着剤，トラフィックペイント等の用途に用い
られる。[0003] Since these petroleum resins have tackiness, adhesiveness, and compatibility with other resins, they are mixed with various plastics, rubber, and oily substances, and are used as paints, printing inks, and the like.
Used for adhesives, adhesives, traffic paints, etc.

【０００４】しかしながら、石油樹脂は、一般に黄〜薄
茶色に着色している上に、独特の臭気を有し、又熱安定
性は低く、耐候性も低いといった課題を有する。[0004] However, petroleum resins are generally colored yellow to light brown, have a peculiar odor, have low thermal stability and low weather resistance.

【０００５】この課題解決法として、石油樹脂を触媒の
存在下で水素添加する方法があり、この方法で得られる
樹脂が水添石油樹脂である。この水添石油樹脂は、通常
無色透明〜白色であり，臭気がなく，熱安定性，耐候性
にも優れた性質を有し、且つ接着性，粘着性も高い。更
に、各種プラスチックス，例えばゴム，ポリオレフィ
ン，及びエチレン−酢酸ビニル共重合体などにも優れた
相溶性を有する。したがって、食品分野，サニタリ−分
野等の外，ホットメルト接着剤，印刷用途，各種プラス
チックス改質剤等の高品質が要求される分野に広く用い
られる。As a solution to this problem, there is a method of hydrogenating a petroleum resin in the presence of a catalyst, and the resin obtained by this method is a hydrogenated petroleum resin. This hydrogenated petroleum resin is generally colorless and transparent to white, has no odor, has excellent heat stability and weather resistance, and has high adhesiveness and tackiness. Furthermore, it has excellent compatibility with various plastics such as rubber, polyolefin, and ethylene-vinyl acetate copolymer. Therefore, it is widely used in fields requiring high quality, such as hot melt adhesives, printing applications, and various plastics modifiers, in addition to the food field, sanitary field, and the like.

【０００６】ところで、水添石油樹脂類は各種用途に用
いられているものの、その物性は様々であり、グレード
毎に使い分けられている。例えば、Ｃ5 系水添石油樹脂
は、原料が豊富で、その製造条件は比較的温和であり、
その為大量にしかも安価に造られているが、熱安定性，
粘着性に難がある。又、Ｃ9 系水添石油樹脂は、熱安定
性，粘着性はＣ5 系水添石油樹脂と比べて優れているも
のの、満足できるものではない。Although hydrogenated petroleum resins are used for various purposes, their physical properties are various, and they are used for each grade. For example, C5 hydrogenated petroleum resin is rich in raw materials, its production conditions are relatively mild,
Therefore, it is manufactured in large quantities and at low cost,
Poor tackiness. C9-based hydrogenated petroleum resin is superior in heat stability and adhesiveness to C5-based hydrogenated petroleum resin, but is not satisfactory.

【０００７】一方、天然物由来のロジン，テルペン系の
水添樹脂は、熱安定性，接着性，粘着性に優れており、
中でも重要な特性である接着性は格段に優れている。し
たがって、高品質が要求される分野に使用されている。
しかしながら、天然物由来であることから、高価であ
り、又資源的にも問題がある。更には、物性的に優れて
いるものの満足できる域には達していない。On the other hand, rosin and terpene-based hydrogenated resins derived from natural products are excellent in heat stability, adhesiveness and tackiness.
Among them, the adhesive property, which is an important property, is remarkably excellent. Therefore, it is used in fields where high quality is required.
However, since it is derived from natural products, it is expensive and has problems in resources. Furthermore, although it is excellent in physical properties, it does not reach a satisfactory range.

【０００８】又、特開昭５７−１６０１５号公報には、
石油類の熱分解留分で沸点が１４０〜２８０℃の留分１
００重量部にフェノール類０．１〜３．０重量部加え、
フリーデルクラフツ型触媒で重合し、該重合物を中和処
理、活性白土処理して、水素化することが提案されてい
る。該方法によって製造された水添石油樹脂は、熱安定
性，耐候性，色相，そして接着性，粘着性が改良されて
いるものの満足できるものではなく、前述の天然物由来
のロジン系，テルペン系の水添樹脂に比し劣る。Japanese Patent Application Laid-Open No. 57-16015 discloses that
Fraction 1 having a boiling point of 140 to 280 ° C, which is a pyrolysis fraction of petroleum
0.1 to 3.0 parts by weight of phenols are added to 00 parts by weight,
It has been proposed to polymerize with a Friedel-Crafts type catalyst, neutralize the polymer, treat with activated clay, and hydrogenate it. The hydrogenated petroleum resin produced by this method has improved thermal stability, weather resistance, hue, and adhesion and tackiness, but is not satisfactory. Is inferior to the hydrogenated resin.

【０００９】又、特開平１−２１０４０９号公報には、
ナフサを熱分解して得られる炭素数５の留分を、水酸基
を有する重合開始剤を用いて重合した液状石油樹脂、該
樹脂を水素化してなる液状石油樹脂を提案している。水
素化して得られる液状樹脂の物性は向上するものの、熱
安定性，接着性，粘着性いずれも満足できるものではな
い。[0009] Japanese Patent Application Laid-Open No. 1-210409 discloses that
A liquid petroleum resin obtained by polymerizing a C5 fraction obtained by thermally decomposing naphtha using a polymerization initiator having a hydroxyl group, and a liquid petroleum resin obtained by hydrogenating the resin have been proposed. Although the properties of the liquid resin obtained by hydrogenation are improved, none of the thermal stability, adhesiveness and tackiness are satisfactory.

【００１０】[0010]

【発明が解決しようとする課題】この様に、石油樹脂の
中で水添石油樹脂の物性は優れ、特に天然ロジン，テル
ペン系水添樹脂の物性は優れている。しかしながら、こ
れらは、要求される特性面，資源面，価格面から一長一
短あり、幅広い用途面から全てを満足できるものはな
い。本発明は、かかる該課題を解消し、安定した高品質
の水添石油樹脂を提供することにある。As described above, among the petroleum resins, the properties of the hydrogenated petroleum resin are excellent, and in particular, the properties of the natural rosin and terpene-based hydrogenated resins are excellent. However, these have advantages and disadvantages in terms of required characteristics, resources, and price, and none of them can satisfy all in a wide range of applications. An object of the present invention is to solve the above problem and to provide a stable and high-quality hydrogenated petroleum resin.

【００１１】[0011]

【課題を解決するための手段】本発明者らは、安定した
高品質の水添石油樹脂で、且つ資源の面で懸念がない水
添石油樹脂について鋭意検討した。その結果、構成成分
及び物性値が限定された水添石油樹脂を見い出し、該水
添石油樹脂は要求される性能を満足できること、加えて
原料面から資源の懸念がなく、大量に提供できることを
知見し、本発明を完成するに至った。Means for Solving the Problems The present inventors have intensively studied a hydrogenated petroleum resin which is a stable and high-quality hydrogenated petroleum resin and has no concern about resources. As a result, they found a hydrogenated petroleum resin with limited constituent components and physical properties, and found that the hydrogenated petroleum resin can satisfy the required performance, and that it can be provided in large quantities without concern about resources in terms of raw materials. Thus, the present invention has been completed.

【００１２】即ち、本発明は、常圧での沸点が１４０〜
２８０℃であるＣ９留分をフェノール類存在下、フリー
デルクラフツ型触媒を用いて重合し、該重合生成物であ
る石油樹脂を水素化触媒存在下、加圧下で水素添加して
なる、水酸基含量が０．２〜２ｍｅｑ．／ｇ，環水添率
が９０％以上，色相がＡＰＨＡで１００以下，臭素価が
１以下であり、且つＣ９系石油留分とフェノール類が主
構成成分であることを特徴とする水酸基含有水添石油樹
脂、及びその製造方法を提供するものである。以下、本
発明を詳細に説明する。That is, the present invention has a boiling point at normal pressure of 140 to
Free C9 fraction at 280 ° C in the presence of phenols
Polymerization is performed using a Del-Crafts type catalyst, and the polymerization product
Hydrogenated petroleum resin under pressure in the presence of a hydrogenation catalyst
Has a hydroxyl group content of 0.2 to 2 meq. / G, a ring hydrogenation rate of 90% or more, a hue of 100 or less in APHA, a bromine value of 1 or less, and a C9-based petroleum fraction and phenols as main constituent components It is intended to provide a petroleum resin and a method for producing the same. Hereinafter, the present invention will be described in detail.

【００１３】本発明の水酸基含有水添石油樹脂の骨子と
なるところは、水酸基含量が０．２〜２ｍｅｑ．／ｇで
あり、且つＣ9 系石油留分とフェノール類が主構成成分
であることである。The essential part of the hydroxyl group-containing hydrogenated petroleum resin of the present invention is that the hydroxyl group content is 0.2 to 2 meq. / G, and a C9-based petroleum fraction and phenols are main constituents.

【００１４】本発明者らは、石油樹脂の最大の特徴であ
る接着性，粘着性について詳細に検討した。その結果、
水酸基含量，水酸基付与物質，そして樹脂主構成物質の
３つが極めて重要であり、これらが厳密に制限されて始
めて目標とする天然物由来のロジン系，テルペン系水添
樹脂の接着性，粘着性を達成できることを把んだ。即
ち、水酸基含量が０．２〜２ｍｅｑ．／ｇであること。
０．２ｍｅｑ．／ｇよりも少ないと接着性，粘着性は、
急激に低下する。又、２ｍｅｑ．／ｇよりも多いと接着
性，粘着性の向上は殆どないばかりか、石油樹脂の熱安
定性，耐候性等の特性が低下する。０．２〜２ｍｅｑ．
／ｇの間で、接着性，粘着性は高く、熱安定性、耐候性
も高い。The present inventors have studied in detail the adhesiveness and tackiness, which are the most characteristic features of petroleum resins. as a result,
Hydroxy group content, hydroxyl group-imparting substance, and resin main constituent substances are extremely important, and the adhesion and tackiness of the target natural rosin-based and terpene-based hydrogenated resins cannot be improved until they are strictly restricted. I understood what I could achieve. That is, when the hydroxyl group content is 0.2 to 2 meq. / G.
0.2 meq. / G is less than the adhesiveness and tackiness.
It drops sharply. Also, 2meq. When the amount is more than / g, not only the adhesion and tackiness are hardly improved, but also the properties of the petroleum resin such as heat stability and weather resistance are reduced. 0.2 to 2 meq.
/ G, the adhesiveness and tackiness are high, and the thermal stability and weather resistance are also high.

【００１５】従来、水酸基付与物質としてアルコール
類，重合開始剤としての過酸化水素等が提案されている
が、これらの水酸基付与物質では本発明の目的は達成さ
れない。水酸基付与物質がフェノール類であって始めて
本発明の目的を達成できる。又、樹脂主構成物質はＣ9
系石油留分から成ること。主構成物質がＣ5 系石油留分
では、接着性，粘着性が満足できるものではなく、更に
熱安定性，耐候性等も満足できるものとはならない。主
構成物質がＣ9 系石油留分であって始めて本発明の目的
が達成できる。ここで、水酸基含量は、赤外吸光光度法
（ＩＲ法）核磁気共鳴スペクトル法（ＮＭＲ）等によっ
て解析、測定することができる。Conventionally, alcohols and hydroxyl peroxide as a polymerization initiator have been proposed as hydroxyl group-imparting substances, but the objects of the present invention cannot be achieved with these hydroxyl group-imparting substances. The object of the present invention can be achieved only when the hydroxyl group-providing substance is a phenol. The main component of the resin is C9
Consist of petroleum-based fractions. When the main constituent substance is a C5 petroleum fraction, the adhesiveness and tackiness are not satisfactory, and the thermal stability, weather resistance and the like are not satisfactory. The object of the present invention can be achieved only when the main constituent is a C9 petroleum fraction. Here, the hydroxyl group content can be analyzed and measured by infrared absorption spectroscopy (IR method), nuclear magnetic resonance spectroscopy (NMR) or the like.

【００１６】又、本発明では、主構成成分として、フェ
ノール類、Ｃ9 系石油留分以外の物質を若干含んでいて
も性能を落とさない範囲であれば構わない。具体的に
は、Ｃ5 系石油留分，ロジン系，テルペン系等が挙げら
れる。その範囲は、加える物質により異なるが、通常５
０重量％以内である。又、水添石油樹脂として環水添率
が９０％以上，色相がＡＰＨＡで１００以下，臭素価が
１以下であることも必須の要件である。これらは、熱安
定性，耐候性，色相，臭い，そして前述した接着性，粘
着性とも関係する。即ち、環水添率が９０％未満では、
熱，光等に対して不安定な環二重結合を多く有すること
になり、熱安定性，耐候性が急激に低下する。又、着色
や臭いも生ずる。従って、長期保存には不向きであり、
又使用中に劣化して本来の性能を発揮できなくなる。
又、色，臭いの面から衛生関係には使用できなくなり、
用途が限定されることになる。この環水添率は、紫外吸
光光度法（ＵＶ）で測定することができる。又、色相が
ＡＰＨＡで１００を越える場合、商品価値を落とすだけ
でなく、着色物質（微量の為同定は難）が原因と推察さ
れる樹脂の熱安定性，耐候性の低下が見られる。この色
相は、ＪＩＳーＫ０１０１に基ずいて測定できる。又、
臭素価が１を越える場合、鎖状二重結合を多く有するこ
とになり、熱安定性，耐候性が急激に低下する。従っ
て、ホットメルト分野等においては、加熱溶融時に劣化
して、特性が低下したり、長期使用時、貯蔵時に変質，
劣化したりする。又、商品として重要な着色，臭いも生
じることになる。更に、衛生関係には使用できなくな
り、用途が限定されることにもなる。この臭素価は、Ｊ
ＩＳ−Ｋ２５４３に基ずいて測定できる。Further, in the present invention, even if a small amount of a substance other than phenols and a C9-based petroleum fraction is contained as a main constituent component, it is sufficient that the performance is not deteriorated. Specific examples include a C5 petroleum fraction, a rosin type, and a terpene type. The range varies depending on the substance to be added.
It is within 0% by weight. It is also an essential requirement that the hydrogenated petroleum resin has a ring hydrogenation rate of 90% or more, a hue of 100 or less in APHA, and a bromine value of 1 or less. These are related to heat stability, weather resistance, hue, odor, and the above-mentioned adhesiveness and tackiness. That is, when the ring hydrogenation rate is less than 90%,
It has many ring double bonds that are unstable to heat, light, etc., and the thermal stability and weather resistance are rapidly reduced. In addition, coloring and odor also occur. Therefore, it is not suitable for long-term storage,
In addition, it deteriorates during use and cannot exhibit its original performance.
In addition, it can no longer be used for hygiene because of its color and smell.
Applications will be limited. This ring hydrogenation rate can be measured by ultraviolet absorption spectroscopy (UV). Further, when the hue exceeds 100 in APHA, not only does the commercial value decrease, but also the thermal stability and weather resistance of the resin, which are presumed to be due to the coloring substance (the identification is difficult due to the small amount), are observed. This hue can be measured based on JIS-K0101. or,
If the bromine number exceeds 1, the chain will have many chain double bonds, and the thermal stability and weather resistance will rapidly decrease. Therefore, in the field of hot melt, etc., it deteriorates when heated and melted, and its properties are deteriorated.
Or deteriorate. In addition, coloring and odor which are important as commodities are generated. Furthermore, it cannot be used for hygiene-related purposes, and its use is limited. This bromine number is J
It can be measured based on IS-K2543.

【００１７】他に、分子量，分子量分布等多くの物性に
ついて詳細に検討したが、水添石油樹脂の重要な具備す
べき特性、特に現在最良といわれている天然物由来のロ
ジン系，テルペン系水添樹脂の特性を越えるには、前述
の構成要件で必要且つ十分であるとの結論を得た。In addition, many physical properties such as molecular weight and molecular weight distribution were examined in detail, but important properties to be provided for hydrogenated petroleum resins, particularly rosin and terpene based waters derived from natural products which are now considered to be the best. It was concluded that the above-mentioned constitutional requirements were necessary and sufficient to exceed the properties of the additive resin.

【００１８】本発明で示す水添石油樹脂は、従来にない
構成要件と特性を有する高品質水添石油樹脂である。
又、その構成成分から、天然物由来でなく、大量に、低
廉に存在する石油化学品を原料とすることができ、有用
性の高いものである。The hydrogenated petroleum resin shown in the present invention is a high-quality hydrogenated petroleum resin having unprecedented constitutional requirements and characteristics.
In addition, petrochemicals that are not derived from natural products but are present in large quantities and at low cost can be used as raw materials, and are highly useful.

【００１９】本発明の水酸基含有水添石油樹脂は、石油
類の熱分解又は触媒を用いた接触分解により得られる分
解油留分のうち、常圧での沸点が１４０〜２８０℃であ
るＣ9 留分をフェノール類存在下、フリーデルクラフツ
型触媒を用いて重合し、該重合生成物である石油樹脂を
水素化触媒存在下、加圧下で水素添加して製造すること
ができる。The hydroxyl group-containing hydrogenated petroleum resin of the present invention comprises a C9 fraction having a boiling point at normal pressure of 140 to 280 ° C. among cracked oil fractions obtained by pyrolysis of petroleum or catalytic cracking using a catalyst. The polymer is polymerized in the presence of a phenol using a Friedel-Crafts type catalyst, and the polymerization product, a petroleum resin, is hydrogenated under pressure in the presence of a hydrogenation catalyst.

【００２０】熱分解又は触媒を用いた接触分解により得
られる分解油留分のうち、常圧での沸点が１４０〜２８
０℃であるＣ9 留分とは、スチレン，αーメチルスチレ
ン，βーメチルスチレン，ビニルトルエン，インデン，
アルキルインデン，ジシクロペンタジエン，エチルベン
ゼン，トリメチルベンゼン、ナフタリン等が主として含
まれ、これらは重合性を有し、通常混合物として得られ
る。Among cracked oil fractions obtained by thermal cracking or catalytic cracking using a catalyst, the boiling point at normal pressure is 140-28.
The C9 fraction at 0 ° C refers to styrene, α-methylstyrene, β-methylstyrene, vinyltoluene, indene,
It mainly contains alkylindene, dicyclopentadiene, ethylbenzene, trimethylbenzene, naphthalene, etc., which have polymerizability and are usually obtained as a mixture.

【００２１】又、フェノール類としては、フェノールあ
るいはクレゾール，キシレノール，P ーｔｅｒｔ−ブチ
ルフェノール，ｐーオクチルフェノール，ノニルーフェ
ノールなどのアルキル置換フェノール類等の分子中にフ
ェノール性水酸基を有する、通常炭素数６〜２０のフェ
ノール類が使用できる。これらは、単独で用いても、併
用しても良い。これらの内、特に好ましくはフェノール
であり、接着性，粘着性の高い水添石油を得ることがで
きる。重合反応時に存在させるフェノール類の量は、水
添石油樹脂の水酸基含量が０．２〜２ｍｅｑ．／ｇとな
る量であるが、，通常原料油１００重量部に対して４〜
３０重量部、好ましくは５〜２０重量部である。フェノ
ール化合物量が少なく、水酸基含量が０．２ｍｅｑ．／
ｇ未満の場合は該水添石油樹脂と種々のポリマーとの相
溶性が低下し、接着性は急激に低下する。又、水酸基含
量が２ｍｅｑ．／ｇを越えると接着性を改善できないば
かりか、熱安定性，耐候性等の物性が低下する。なお、
本発明のフェノール化合物の添加量には、フリーデルク
ラフツ型触媒の一部として添加されるフェノール等の添
加量は含まれない。ここで原料油とは、前述のＣ9 留分
であるが、水添石油樹脂の特性を落とさない範囲であれ
ば、Ｃ5 石油留分，ロジン系，テルペン系樹脂を加えて
も良い。この原料油とフェノール類をフリーデルクラフ
ツ型触媒を用いて重合する。Examples of the phenols include phenol and alkyl-substituted phenols such as cresol, xylenol, p-tert-butylphenol, p-octylphenol and nonyl-phenol, which have a phenolic hydroxyl group in the molecule and usually have 6 carbon atoms. Up to 20 phenols can be used. These may be used alone or in combination. Of these, phenol is particularly preferable, and hydrogenated petroleum having high adhesiveness and tackiness can be obtained. The amount of phenols present during the polymerization reaction is such that the content of hydroxyl groups in the hydrogenated petroleum resin is 0.2 to 2 meq. / G, usually 4 to 100 parts by weight of the base oil.
It is 30 parts by weight, preferably 5 to 20 parts by weight. The amount of the phenol compound is small, and the hydroxyl group content is 0.2 meq. /
If the amount is less than g, the compatibility between the hydrogenated petroleum resin and various polymers decreases, and the adhesiveness sharply decreases. When the hydroxyl group content is 2 meq. If it exceeds / g, not only the adhesiveness cannot be improved, but also the physical properties such as heat stability and weather resistance decrease. In addition,
The amount of the phenolic compound of the present invention does not include the amount of phenol added as a part of the Friedel-Crafts type catalyst. Here, the raw material oil is the aforementioned C9 fraction, but a C5 petroleum fraction, a rosin-based resin, and a terpene-based resin may be added as long as the properties of the hydrogenated petroleum resin are not deteriorated. The feedstock oil and phenols are polymerized using a Friedel-Crafts type catalyst.

【００２２】フリーデルクラフツ型触媒としては、三ふ
っ化ホウ素，塩化アルミニウム等が挙げられるが、三ふ
っ化ホウ素のエチルエーテル，フェノール，ブチルエー
テル，ブチルアルコール，メチルアルコール等を使用し
た錯体触媒が好ましい。重合条件としては、フェノール
化合物の存在下、原料油に対して０．０５〜５ｗｔ％の
フリーデルクラフツ型触媒を用い、重合温度０〜６０℃
である。Examples of the Friedel-Crafts type catalyst include boron trifluoride, aluminum chloride and the like, and a complex catalyst using boron trifluoride in ethyl ether, phenol, butyl ether, butyl alcohol, methyl alcohol or the like is preferable. As the polymerization conditions, a Friedel-Crafts type catalyst of 0.05 to 5% by weight based on the feed oil in the presence of a phenol compound was used, and the polymerization temperature was 0 to 60 ° C.
It is.

【００２３】次に、重合して得られた石油樹脂をフリー
デルクラフツ型触媒，未重合物を常法に従って分離除去
する。そして、該石油樹脂を水素化触媒存在下、加圧下
で水素添加する。Next, the petroleum resin obtained by the polymerization is separated and removed by a Friedel-Crafts type catalyst and an unpolymerized product according to a conventional method. Then, the petroleum resin is hydrogenated under pressure in the presence of a hydrogenation catalyst.

【００２４】水素化触媒としては、水素化能を有する触
媒であればいずれも使用でき、特に限定されない。例え
ば、第８族金属、即ちニッケル，パラジウム，白金，コ
バルト，ロジウム，ルテニウム等の金属を単独あるいは
第１ａ，２ａ，１ｂ，４ａの金属あるいは酸化物の中か
らの１種あるいは２種以上の組合わせより成るものが利
用でき、これらをアルミナ，シリカ，珪藻土，活性炭，
チタニア等の担体に担持したものが用いられる。特に好
ましくはニッケル金属を主成分とし、助触媒成分として
Ｍｇ，Ｃａ，Ｂａ，Ｓｒのアルカリ土類金属より選ばれ
た１種以上の酸化物，水酸化物，炭酸塩を珪藻土担体に
担持した水素化触媒である（特願平３−１５６０５３
号）。該触媒は、熱によるニッケル粒子のシンタリング
を抑制し、又、通常石油樹脂に含有されるイオウ化合物
による触媒被毒を抑制する。その結果、触媒寿命は向上
し繰り返し使用ができ、経済性は著しく向上する。又、
アルカリ土類金属の代わりにＣｕ金属を助触媒としても
同様の効果を発現するので好ましい。水素化触媒の使用
量は、特に限定されない。それは触媒の比表面積，金属
量及びその分散度，助触媒の種類と含量，水添率，石油
樹脂の種類，そのイオウ化合物含量，水添条件等が大き
く異なるからである。しかしながら、通常石油樹脂１０
０重量部に対して０．１〜３０重量部であり、適宜決定
する。又、触媒の形状についても制限はなく、粉末，ペ
レットいずれも使用できる。As the hydrogenation catalyst, any catalyst can be used as long as it has a hydrogenation ability, and it is not particularly limited. For example, a Group 8 metal, ie, a metal such as nickel, palladium, platinum, cobalt, rhodium, ruthenium or the like, alone or in combination of one or more of the metals or oxides of 1a, 2a, 1b, 4a Combinations can be used. These are alumina, silica, diatomaceous earth, activated carbon,
What is carried on a carrier such as titania is used. Particularly preferably, hydrogen containing nickel metal as a main component and at least one oxide, hydroxide or carbonate selected from alkaline earth metals of Mg, Ca, Ba and Sr as a promoter component supported on a diatomaceous earth carrier. (Japanese Patent Application No. 3-156053)
issue). The catalyst suppresses sintering of nickel particles due to heat and also suppresses catalyst poisoning by sulfur compounds usually contained in petroleum resins. As a result, the service life of the catalyst is improved, the catalyst can be used repeatedly, and the economic efficiency is significantly improved. or,
It is preferable to use a Cu metal as a co-catalyst instead of an alkaline earth metal since the same effect is exhibited. The amount of the hydrogenation catalyst used is not particularly limited. This is because the specific surface area of the catalyst, the amount of metal and its dispersity, the type and content of the cocatalyst, the degree of hydrogenation, the type of petroleum resin, the content of the sulfur compound, the hydrogenation conditions, and the like are greatly different. However, usually petroleum resin 10
It is 0.1 to 30 parts by weight with respect to 0 parts by weight, and is appropriately determined. There is no limitation on the shape of the catalyst, and both powder and pellets can be used.

【００２５】水素化反応条件としては、石油樹脂の種
類，イオウ化合物含有量，水素化触媒の種類，量あるい
は目的とする水添石油樹脂の性状に応じて決めるべきで
あるが、一般的には反応温度１５０〜３２０℃，反応圧
力３０〜３００Ｋｇ／ｃｍ2 ，反応時間１〜１０時間で
ある。The conditions for the hydrogenation reaction should be determined according to the type of petroleum resin, the content of the sulfur compound, the type and amount of the hydrogenation catalyst, or the properties of the desired hydrogenated petroleum resin. The reaction temperature is 150 to 320 ° C., the reaction pressure is 30 to 300 Kg / cm 2 , and the reaction time is 1 to 10 hours.

【００２６】本発明は、無溶剤下での水素化も可能であ
るが、溶剤存在下の方がより温和な条件で、より高品質
の水添石油樹脂が得られ、効果的、効率的である。この
溶剤として炭化水素，エーテル類，アルコール類，エス
テル類，ケトン類，アミド類等が使用可能であるが、溶
剤の安定性，価格，水素添加速度，水添石油樹脂の品質
等を考慮すると炭化水素類がより好ましい。更に好まし
い溶剤としては、常圧での沸点が１４０〜２８０℃の飽
和炭化水素，飽和環状炭化水素，芳香族炭化水素より選
ばれた１種以上の溶剤である。According to the present invention, hydrogenation in the absence of a solvent is also possible, but a higher quality hydrogenated petroleum resin can be obtained under milder conditions in the presence of a solvent, which is effective and efficient. is there. As the solvent, hydrocarbons, ethers, alcohols, esters, ketones, amides, etc. can be used. However, considering the stability of the solvent, the price, the hydrogenation rate, the quality of the hydrogenated petroleum resin, etc. Hydrogens are more preferred. More preferred solvents are one or more solvents selected from saturated hydrocarbons, saturated cyclic hydrocarbons, and aromatic hydrocarbons having a boiling point at normal pressure of 140 to 280 ° C.

【００２７】具体的溶剤としては、飽和鎖状炭化水素と
して、ｎ−ノナン，２−メチル−ノナン，３−メチル−
ノナン，４−メチル−ノナン，ｎ−デカン，イソ−デカ
ン，２−メチルデカン、３−メチルデカン，４−メチル
デカン，ｎ−ウンデカン，２−メチルウンデカン，３−
メチルウンデカン，４−メチルウンデカン，ｎ−ドデカ
ン，イソ−ドデカン，２−メチルドデカン，３−メチル
ドデカン，４−メチルドデカン，５−メチルドデカン，
２，３−ジメチルドデカン，２，３，４−トリメチルド
デカン，２，３，４，５−テトラメチルドデカン，ｎ−
トリデカン，メチルトリデカン，ジメチルトリデカン，
トリメチルトリデカン，ｎ−テトラデカン，メチルテト
ラデカン，ジメチルテトラデカン，トリメチルテトラデ
カン，ペンタデカン，アルキルペンタデカン，ヘキサデ
カン，アルキルヘキサデカン，ヘプタデカン，アルキル
ヘプタデカン，オクタデカン，アルキオクタデカン，ア
ルキルオクタデカン，ノナデカン，アルキルノナデカ
ン，エイコサン，アルキルエイコサン等を挙げることが
できる。飽和環状炭化水素として、トリメチルシクロヘ
キサン，テトラメチルシクロヘキサン，メチルエチルシ
クロヘキサン，ビシクロヘキサン，メチルビシクロヘキ
サン，ジメチルビシクロヘキサン，エチルビシクロヘキ
サン，メチルエチルビシクロヘキサン，ジエチルビシク
ロヘキサン等を挙げることができる。芳香族炭化水素と
して，ジエチルベンゼン，トリメチルベンゼン，テトラ
メチルベンゼン，メチルエチルベンゼン，イソプロピル
ベンゼン，Ｐ−シメン，アミルベンゼン，ナフタリン，
アルキルナフタリン，シクロヘキシルベンゼン，アルキ
ルシクロヘキシルベンゼン，フルオレン，アルキルフル
オレン等を挙げることができる。これらは、１種あるい
は２種以上の混合物でも良い。As a specific solvent, n-nonane, 2-methyl-nonane, 3-methyl-
Nonane, 4-methyl-nonane, n-decane, iso-decane, 2-methyldecane, 3-methyldecane, 4-methyldecane, n-undecane, 2-methylundecane, 3-
Methylundecane, 4-methylundecane, n-dodecane, iso-dodecane, 2-methyldodecane, 3-methyldodecane, 4-methyldodecane, 5-methyldodecane,
2,3-dimethyldodecane, 2,3,4-trimethyldodecane, 2,3,4,5-tetramethyldodecane, n-
Tridecane, methyltridecane, dimethyltridecane,
Trimethyltridecane, n-tetradecane, methyltetradecane, dimethyltetradecane, trimethyltetradecane, pentadecane, alkylpentadecane, hexadecane, alkylhexadecane, heptadecane, alkylheptadecane, octadecane, alkyloctadecane, alkyloctadecane, nonadecane, alkylnonadecane, eicosan, alkyl Eicosan and the like can be mentioned. Examples of the saturated cyclic hydrocarbon include trimethylcyclohexane, tetramethylcyclohexane, methylethylcyclohexane, bicyclohexane, methylbicyclohexane, dimethylbicyclohexane, ethylbicyclohexane, methylethylbicyclohexane, and diethylbicyclohexane. As aromatic hydrocarbons, diethylbenzene, trimethylbenzene, tetramethylbenzene, methylethylbenzene, isopropylbenzene, P-cymene, amylbenzene, naphthalene,
Examples thereof include alkylnaphthalene, cyclohexylbenzene, alkylcyclohexylbenzene, fluorene, and alkylfluorene. These may be one kind or a mixture of two or more kinds.

【００２８】常圧での沸点が１４０℃未満の溶剤は水素
添加時の圧力が増し、高圧操作が必要となり、設備が複
雑で高価なものとなる。又、常圧での沸点が２８０℃を
越える溶剤は、圧力的には良いが、第一の目的である水
素添加速度が小さくなり、効率が低下する。又、製品で
ある水添石油樹脂との分離も難しくなる。溶剤の好まし
い添加量は、石油樹脂１００重量部に対して１０〜１５
０重量部であり、更に好ましくは、２０〜１００重量部
である。水素化反応終了後，通常は濾過による触媒分
離、そして通常蒸留により溶剤を分離することにより，
目的とする水素化石油樹脂を得ることができる。触媒分
離時、同一溶剤で触媒を洗浄してもよい。又、回収溶剤
は再使用が容易である。A solvent having a boiling point of less than 140 ° C. at normal pressure increases the pressure during hydrogenation, requires high-pressure operation, and requires complicated and expensive equipment. A solvent having a boiling point of more than 280 ° C. at normal pressure is good in pressure, but the first purpose, namely, the hydrogenation rate is reduced, and the efficiency is reduced. Further, it is difficult to separate the product from the hydrogenated petroleum resin. A preferable addition amount of the solvent is 10 to 15 with respect to 100 parts by weight of the petroleum resin.
0 parts by weight, more preferably 20 to 100 parts by weight. After completion of the hydrogenation reaction, the catalyst is separated, usually by filtration, and the solvent is separated, usually by distillation.
The desired hydrogenated petroleum resin can be obtained. At the time of catalyst separation, the catalyst may be washed with the same solvent. The recovered solvent is easy to reuse.

【００２９】水素化反応の形式は，特に限定されず通常
の方法で行われる。例えば，回分式の懸濁床方式，流通
式の固定床方式，流通式の懸濁気泡塔方式等いずれも実
施できる。The type of the hydrogenation reaction is not particularly limited, and is carried out by a usual method. For example, any of a batch suspension type bed system, a flow type fixed bed type, and a flow type suspension bubble column method can be used.

【００３０】本発明で得られる水添石油樹脂は、粘着
性，接着性が極めて優れ、無色透明で無臭であり，且つ
耐熱性，耐候性に優れ、粘着剤，接着剤として，又ゴ
ム，塗料，プラスチック類，インキ等の添加剤として有
用，且つ有効にできる価値の高いものである。The hydrogenated petroleum resin obtained by the present invention has extremely excellent tackiness and adhesiveness, is colorless and transparent, is odorless, and has excellent heat resistance and weather resistance. It is useful and effective as an additive for plastics, inks and the like.

【００３１】[0031]

【実施例】以下、実施例及び比較例を挙げて本発明を具
体的に説明するが、本発明はこれらに限定するものでは
ない。The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

【００３２】実施例１ 石油類の熱分解により得られた分解油留分のうち、常圧
での沸点が１４０〜２２０℃の留分１００重量部にフェ
ノール６重量部を添加して、三弗化ホウ素フェノール
０．５ｗｔ％加えて３０℃で３時間重合した後、苛性ソ
ーダ水溶液で触媒を除去し、次いで水洗して蒸留により
未反応油 及び低重合物を除去して軟化点１２２℃の石
油樹脂（Ａ）を得た。電磁撹拌機及び加熱器を備えた内
容積３００ｍｌのステンレス製耐圧容器に、樹脂（Ａ）
７０ｇ，水素化触媒としてＮｉ／珪藻土触媒〔Ｎｉ（５
０ｗｔ％含有〕３．５ｇ，溶剤として市販パラフィン系
炭化水素（出光社製，ｂｐ：１６０〜２００℃）２１ｇ
を仕込み、窒素ガス，次に水素ガスで置換後、水素加圧
した。次に、撹拌，加熱し、温度２５０℃，圧力１００
Ｋｇ／ｃｍ2 ・Ｇで４時間保持した。その後、放冷し，
反応生成物より触媒と溶剤を分離し、水添石油樹脂を得
た。水添石油樹脂を分析したところ、水添率９５．４
％，臭素価１以下，色相ＡＰＨＡ２０以下，無色透明，
無臭，軟化点１２４℃，水酸基含量は０．３ｍｅｑ./ｇ
であった。このようにして得られた水酸基含有水添石油
樹脂（Ａ−１）を４０重量部，エチレン−酢酸ビニル共
重合体（東ソー株式会社製：ウルトラセン７２０，酢酸
ビニル含有２８％ＭＩ １５０）４０重量部，マイクロ
クリスタリンワックス（日本精蝋株式会社製：Ｈｉ−Ｍ
ｉｃ１０８０，融点１８３゜Ｆ）２０重量部を１８０℃
で溶融し、ホットメルト組成物を調製し、評価した結果
を表１に示した。EXAMPLE 1 6 parts by weight of phenol was added to 100 parts by weight of a fraction having a boiling point of 140 to 220 ° C. at normal pressure in the cracked oil fraction obtained by pyrolysis of petroleum, After adding 0.5 wt% of boron phenol and polymerizing at 30 ° C. for 3 hours, the catalyst is removed with an aqueous solution of caustic soda, followed by washing with water to remove unreacted oil and low-polymerized substances, and a petroleum resin having a softening point of 122 ° C. (A) was obtained. A resin (A) is placed in a 300 ml stainless steel pressure vessel equipped with an electromagnetic stirrer and heater.
70 g, Ni / diatomaceous earth catalyst [Ni (5
3.5 g, 21 g of a commercially available paraffinic hydrocarbon as a solvent (manufactured by Idemitsu Co., bp: 160 to 200 ° C.)
And then replaced with nitrogen gas and then hydrogen gas, and then pressurized with hydrogen. Next, stirring and heating were performed at a temperature of 250 ° C. and a pressure of 100.
It was kept at Kg / cm 2 · G for 4 hours. Then let it cool down,
The catalyst and the solvent were separated from the reaction product to obtain a hydrogenated petroleum resin. When the hydrogenated petroleum resin was analyzed, the hydrogenation rate was 95.4.
%, Bromine number 1 or less, hue APHA 20 or less, colorless and transparent,
Odorless, softening point 124 ° C, hydroxyl content 0.3 meq./g
Met. 40 parts by weight of the thus obtained hydroxyl group-containing hydrogenated petroleum resin (A-1), 40 parts by weight of an ethylene-vinyl acetate copolymer (manufactured by Tosoh Corporation: Ultracene 720, vinyl acetate-containing 28% MI 150) , Microcrystalline Wax (manufactured by Nippon Seiwa Co., Ltd .: Hi-M)
ic 1080, melting point 183 ° F.)
, And a hot melt composition was prepared and evaluated. The results are shown in Table 1.

【００３３】実施例２ フェノールを７重量部添加して重合した以外は全て実施
例１と同様に行い、軟化点が１２０℃の樹脂（Ｂ）を得
た。この樹脂（Ｂ）を水素化触媒としてＮｉ（４７ｗｔ
％）−Ｍｇ（ｗｔ％）−珪藻土（５０ｗｔ％）触媒３．
５ｇを添加して水素化した以外は実施例１と同様に行い
水添石油樹脂（Ｂ−１）を得た。得られた水添石油樹脂
の水添率は９４．６％，臭素価１以下，色相２０以下，
無色透明，無臭，軟化点１２３℃，水酸基含量０．４ｍ
ｅｑ．／ｇであった。この水酸基含有水添石油樹脂（Ｂ
−１）を使用して実施例１と同様にホットメルト組成物
を調製し、評価した結果を表１にに示した。Example 2 A resin (B) having a softening point of 120 ° C. was obtained in the same manner as in Example 1 except that polymerization was carried out by adding 7 parts by weight of phenol. Using this resin (B) as a hydrogenation catalyst, Ni (47 wt.
%)-Mg (wt%)-diatomaceous earth (50 wt%) catalyst3.
Hydrogenated petroleum resin (B-1) was obtained in the same manner as in Example 1 except that 5 g was added and hydrogenated. The hydrogenated petroleum resin obtained had a hydrogenation rate of 94.6%, a bromine number of 1 or less, a hue of 20 or less,
Colorless and transparent, odorless, softening point 123 ° C, hydroxyl content 0.4m
eq. / G. This hydroxyl group-containing hydrogenated petroleum resin (B
Using -1), a hot melt composition was prepared in the same manner as in Example 1, and the evaluation results are shown in Table 1.

【００３４】比較例１ 石油類の熱分解により得られた分解油留分のうち、常圧
での沸点が１４０〜２２０℃の留分１００重量部に、三
弗化ホウ素フェノール０．５ｗｔ％加えて４０℃で重合
した以外は全て実施例１と同様に処理し、樹脂（Ｃ）を
得た。この樹脂（Ｃ）を実施例１と全く同一条件で水素
化処理し、水添石油樹脂（Ｃ−１）を得た。得られた水
添石油樹脂（Ｃ−１）の水添率は、９８．２％，色相２
０以下，無色透明，無臭，軟化点１２３℃，水酸基含量
０．１ｍｅｑ．／ｇ以下であった。次いで、実施例１と
同様にホットメルト組成物を調製し、評価した結果を表
１に示した。Comparative Example 1 Of the cracked oil fraction obtained by pyrolysis of petroleum, 0.5 wt% of boron trifluoride phenol was added to 100 parts by weight of a fraction having a boiling point of 140 to 220 ° C. under normal pressure. All processes were carried out in the same manner as in Example 1 except that the polymerization was carried out at 40 ° C. to obtain a resin (C). This resin (C) was hydrogenated under the same conditions as in Example 1 to obtain a hydrogenated petroleum resin (C-1). The hydrogenation rate of the obtained hydrogenated petroleum resin (C-1) was 98.2% and the hue was 2
0, colorless and transparent, odorless, softening point 123 ° C, hydroxyl content 0.1 meq. / G or less. Next, a hot melt composition was prepared in the same manner as in Example 1, and the evaluation results are shown in Table 1.

【００３５】比較例２ 市販Ｃ9 系水添石油樹脂（荒川化学株式会社製，アルコ
ンＰ−１２５，軟化点１２２℃，水添率約９８％）を使
用し、実施例１と同様にホットメルト組成物を調製し、
評価した結果を表１に示した。Comparative Example 2 Using a commercially available C9 hydrogenated petroleum resin (Alcon P-125, manufactured by Arakawa Chemical Co., Ltd., softening point 122 ° C., hydrogenation ratio about 98%), the hot melt composition was the same as in Example 1. Prepare things,
The evaluation results are shown in Table 1.

【００３６】比較例３ 市販テルペン樹脂（安原油脂株式会社製，クリアロンＰ
−１２５，軟化点１２５℃）を使用し、実施例１と同様
にホットメルト組成物を調製し、評価した結果を表１に
示した。Comparative Example 3 Commercial terpene resin (Clearon P, manufactured by Yasuhara Yushi Co., Ltd.)
(−125, softening point 125 ° C.), a hot melt composition was prepared in the same manner as in Example 1, and the evaluation results are shown in Table 1.

【００３７】[0037]

【表１】 [Table 1]

【００３８】[0038]

【発明の効果】本発明によれば、高品質の新規な水添石
油樹脂、具体的には接着性，粘着性に極めて優れ、且つ
耐熱性，耐候性に優れた無色，無臭の水添石油樹脂及び
その製造方法を提供することができる。又、この水添石
油樹脂は資源的にも豊富で、大量に安価に提供可能であ
る。更に、その製造方法として、溶媒を添加して水素添
加する方法は、より温和な条件で効率よく該水添石油樹
脂を提供できる。According to the present invention, a novel high-quality hydrogenated petroleum resin, specifically, a colorless, odorless hydrogenated petroleum oil which is extremely excellent in adhesiveness and tackiness, and excellent in heat resistance and weather resistance A resin and a method for producing the resin can be provided. The hydrogenated petroleum resin is abundant in resources and can be provided in large quantities at low cost. Further, as a method for producing the hydrogenated petroleum resin, a method in which a solvent is added and hydrogenation is performed can be provided efficiently under milder conditions.

フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C08F 240/00 Continuation of front page (58) Field surveyed (Int.Cl. 7 , DB name) C08F 240/00

Claims (3)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】常圧での沸点が１４０〜２８０℃であるＣ
９留分をフェノール類存在下、フリーデルクラフツ型触
媒を用いて重合し、該重合生成物である石油樹脂を水素
化触媒存在下、加圧下で水素添加してなる、水酸基含量
が０．２〜２ｍｅｑ．／ｇ，環水添率が９０％以上，色
相がＡＰＨＡで１００以下，臭素価が１以下であり、且
つＣ９系石油留分とフェノール類が主構成成分であるこ
とを特徴とする水酸基含有水添石油樹脂。 1. C having a boiling point of 140 to 280 ° C. at normal pressure
9 fractions in the presence of phenols, Friedel Crafts type
Polymerization using a solvent, the petroleum resin as the polymerization product is hydrogenated
Hydrogenation under pressure in the presence of a catalyst for the formation of a catalyst having a hydroxyl group content of 0.2 to 2 meq. / G, a ring hydrogenation rate of 90% or more, a hue of 100 or less in APHA, a bromine value of 1 or less, and a C9-based petroleum fraction and phenols as main constituent components Petroleum resin. 【請求項２】石油類の熱分解又は触媒を用いた接触分解
により得られる分解油留分のうち、常圧での沸点が１４
０〜２８０℃であるＣ９留分をフェノール類存在下、フ
リーデルクラフツ型触媒を用いて重合し、該重合生成物
である石油樹脂を水素化触媒存在下、加圧下で水素添加
することを特徴とする、水酸基含量が０．２〜２ｍｅ
ｑ．／ｇ，環水添率が９０％以上，色相がＡＰＨＡで１
００以下，臭素価が１以下であり、且つＣ９系石油留分
とフェノール類が主構成成分である水酸基含有水添石油
樹脂の製造方法。2. The cracked oil fraction obtained by thermal cracking of petroleum or catalytic cracking using a catalyst has a boiling point of 14 at normal pressure.
A C9 fraction at 0 to 280 ° C. is polymerized in the presence of phenols using a Friedel-Crafts type catalyst, and the polymerization product, a petroleum resin, is hydrogenated under pressure in the presence of a hydrogenation catalyst. Having a hydroxyl group content of 0.2 to 2 me
q. / G, ring hydrogenation rate is 90% or more, hue is 1 in APHA
A method for producing a hydroxyl group-containing hydrogenated petroleum resin having a bromine number of 1 or less and a C9-based petroleum fraction and phenols as main components. 【請求項３】石油樹脂の水素化を、石油樹脂１００重量
部に対し、常圧での沸点が１４０〜２８０℃の飽和鎖状
炭化水素，飽和環状炭化水素，芳香族炭化水素より選ば
れた１種以上の溶剤１０重量部以上を混合して行う、請
求項２に記載の製造方法。3. Hydrogenation of a petroleum resin is selected from saturated chain hydrocarbons, saturated cyclic hydrocarbons and aromatic hydrocarbons having a boiling point at normal pressure of 140 to 280 ° C. per 100 parts by weight of petroleum resin. 3. The production method according to claim 2, wherein at least 10 parts by weight of one or more solvents are mixed.
JP16833992A 1992-06-04 1992-06-04 Hydroxyl group-containing hydrogenated petroleum resin and production method thereof Expired - Fee Related JP3312388B2 (en)

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JP3312388B2 true JP3312388B2 (en) 2002-08-05

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4734686B2 (en) * 1999-11-18 2011-07-27 荒川化学工業株式会社 Tackifier for polyurethane adhesive, binder for polyurethane adhesive, and polyurethane adhesive composition
JP4956869B2 (en) * 2001-05-28 2012-06-20 荒川化学工業株式会社 Binder for printing ink and printing ink, coating agent and coating composition containing the binder for printing ink
JP4581437B2 (en) * 2003-06-06 2010-11-17 東ソー株式会社 Aromatic petroleum resin for hot melt adhesive, aromatic petroleum resin composition for hot melt adhesive, and hot melt adhesive composition

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