JP2684494B2 - Method for producing partially hydrogenated petroleum resin - Google Patents
Method for producing partially hydrogenated petroleum resinInfo
- Publication number
- JP2684494B2 JP2684494B2 JP23764692A JP23764692A JP2684494B2 JP 2684494 B2 JP2684494 B2 JP 2684494B2 JP 23764692 A JP23764692 A JP 23764692A JP 23764692 A JP23764692 A JP 23764692A JP 2684494 B2 JP2684494 B2 JP 2684494B2
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- polymerization
- petroleum resin
- solvent
- hydrogenated petroleum
- molecular weight
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、粘着付与物性に優れた
部分水添石油樹脂を製造する方法に関するものであっ
て、本発明の方法により得られた部分水添石油樹脂はホ
ットメルト型接着剤や粘着テープの粘着付与剤などとし
て有効に利用することができる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a partially hydrogenated petroleum resin having excellent tackifying properties, wherein the partially hydrogenated petroleum resin obtained by the method of the present invention is a hot melt adhesive. It can be effectively used as an agent or a tackifier for adhesive tapes.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】従来よ
り、水添石油樹脂は、ホットメルト型接着剤や粘着テー
プの粘着付与剤として主に用いられており、その出発原
料により、種々の製造方法が知られている。例えば、シ
クロペンタジエン系化合物とビニル芳香族系化合物とを
出発原料とする水添石油樹脂は、通常、シクロペンタジ
エン系化合物とビニル芳香族系化合物とを溶媒中で重合
し、得られる重合体混合物から低分子量重合体と溶媒を
分離し、残余の重合体を、所望の水素化率に水添して製
造されている。この方法においては、分離された低分子
量重合体と重合溶媒とは、低分子量重合体が出発原料と
して利用できるために、低分子量重合体を重合溶媒から
分離することなく、重合反応系にリサイクルされて利用
されている。ところが、このようにして得られた水添石
油樹脂は、粘着付与物性が必ずしも充分でなく、その改
善が求められていた。BACKGROUND OF THE INVENTION Hydrogenated petroleum resins have hitherto been mainly used as hot-melt adhesives and tackifiers for pressure-sensitive adhesive tapes. The method is known. For example, a hydrogenated petroleum resin starting from a cyclopentadiene compound and a vinyl aromatic compound is usually a polymer mixture obtained by polymerizing a cyclopentadiene compound and a vinyl aromatic compound in a solvent. It is produced by separating the low molecular weight polymer and the solvent and hydrogenating the remaining polymer to a desired hydrogenation rate. In this method, the separated low molecular weight polymer and polymerization solvent are recycled to the polymerization reaction system without separating the low molecular weight polymer from the polymerization solvent because the low molecular weight polymer can be used as a starting material. Is used. However, the hydrogenated petroleum resin thus obtained does not always have sufficient tackifying properties, and its improvement has been demanded.
【０００３】本発明者は、粘着付与物性に優れた水添石
油樹脂を製造する方法、すなわち粘着付与剤として用い
たときに優れた粘着物性を与えうる水添石油樹脂を製造
する方法について鋭意研究を重ねた結果、水添石油樹脂
のうち部分水添石油樹脂については、重合時に副生する
低分子量重合体を、重合反応の出発原料として利用しな
い方が、粘着付与物性が向上することを見出し、この知
見に基づいて本発明を完成するに到った。The present inventor has earnestly studied a method for producing a hydrogenated petroleum resin having excellent tackifying properties, that is, a method for producing a hydrogenated petroleum resin capable of giving excellent tackifying properties when used as a tackifier. As a result, it was found that for partially hydrogenated petroleum resins among hydrogenated petroleum resins, tackifying physical properties are improved when the low molecular weight polymer produced as a by-product during the polymerization is not used as a starting material for the polymerization reaction. The present invention has been completed based on this finding.
【０００４】[0004]
【課題を解決するための手段】すなわち本発明は、シク
ロペンタジエン系化合物とビニル芳香族系化合物とを溶
媒中で重合反応し、得られた重合体混合物から低分子量
重合体及び前記溶媒を分離，回収した後、残余の重合体
を、核水添率０〜８０％に部分水素化して部分水添石油
樹脂を製造するとともに、前記低分子量重合体を含まな
い前記回収溶媒を、前記重合反応における溶媒として再
使用することを特徴とする部分水添石油樹脂の製造方法
を提供するものである。Means for Solving the Problems That is, according to the present invention, a cyclopentadiene compound and a vinyl aromatic compound are polymerized in a solvent, and a low molecular weight polymer and the solvent are separated from the obtained polymer mixture, After recovery, the residual polymer is partially hydrogenated to a nuclear hydrogenation rate of 0 to 80% to produce a partially hydrogenated petroleum resin, and the recovered solvent containing no low molecular weight polymer is used in the polymerization reaction. It is intended to provide a method for producing a partially hydrogenated petroleum resin, which is characterized by being reused as a solvent.
【０００５】本発明の方法で得られる部分水添石油樹脂
は、石油樹脂を構成するビニル芳香族炭化水素単位にお
ける芳香族核が完全には水添されていない水添石油樹脂
であり、スチレン─ブタジエンブロック共重合体やエチ
レン─酢酸ビニル共重合体などに粘着付与剤として配合
されてホットメルト型接着剤として用いられているもの
である。なお、核水添率がほぼ１００％である水添石油
樹脂は、完全水添樹脂と呼ばれ、粘着付与物性を始め種
々の性状が異なるものであって、本発明の部分水添石油
樹脂とは明確に区別される水添石油樹脂である。The partially hydrogenated petroleum resin obtained by the method of the present invention is a hydrogenated petroleum resin in which the aromatic nucleus in the vinyl aromatic hydrocarbon unit constituting the petroleum resin is not completely hydrogenated. It is used as a hot-melt adhesive by blending it as a tackifier with a butadiene block copolymer or an ethylene-vinyl acetate copolymer. The hydrogenated petroleum resin having a nuclear hydrogenation rate of almost 100% is called a completely hydrogenated resin, and has various properties such as tackifying physical properties, and is different from the partially hydrogenated petroleum resin of the present invention. Is a clearly distinguished hydrogenated petroleum resin.
【０００６】本発明の方法では、まずシクロペンタジエ
ン系化合物とビニル芳香族系化合物とを溶媒中で重合す
る。ここで、シクロペンタジエン系化合物としては、シ
クロペンタジエン，メチルシクロペンタジエン，エチル
シクロペンタジエンの他、これらの二量体や共二量体等
が挙げられる。また、ビニル芳香族系化合物としては、
例えばスチレン，αーメチルスチレン，ビニルトルエン
などが挙げられる。このような出発原料の使用割合は、
シクロペンタジエン系化合物：ビニル芳香族系化合物＝
３０：７０〜９０：１０（重量比）、好ましくは４０：
６０〜６０：４０（重量比）である。In the method of the present invention, first, a cyclopentadiene compound and a vinyl aromatic compound are polymerized in a solvent. Examples of the cyclopentadiene compound include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, and dimers and codimers thereof. Further, as the vinyl aromatic compound,
Examples thereof include styrene, α-methylstyrene, vinyltoluene and the like. The proportion of such starting materials used is
Cyclopentadiene compound: vinyl aromatic compound =
30:70 to 90:10 (weight ratio), preferably 40:
It is 60-60: 40 (weight ratio).
【０００７】本発明の方法において使用可能な重合溶媒
としては、芳香族系溶媒，ナフテン系溶媒，脂肪族炭化
水素系溶媒等が挙げられる。特に芳香族系溶媒を用いた
場合には、比較的分子量分布の狭い重合体が得られるの
で、本発明の方法における重合溶媒として好適である。
芳香族系溶媒としては、例えばキシレン，トルエン，ベ
ンゼンなどが挙げられる。また、ナフテン系溶媒として
は、例えばシクロヘキサン，エチルシクロヘキサン，ジ
メチルシクロヘキサン等が挙げられる。さらに、脂肪族
炭化水素系溶媒としては、例えばｎ−オクタン，イソオ
クタン，ケロシン等が挙げられる。本発明の方法におけ
る重合溶媒の使用量は、シクロペンタジエン系化合物１
００重量部に対して、通常、３０〜４００重量部、好ま
しくは６０〜２４０重量部である。重合溶媒の使用量が
少なくなると、重合体の軟化点を所定の範囲内に制御す
ることが難しくなり、分子量分布も広くなるため、最終
的に得られる部分水添石油樹脂の粘着付与剤としての性
能が低下するので好ましくない。また、重合溶媒の使用
量が多くなると、重合反応が進行しなくなり、重合度が
上がらなくなるので好ましくない。Examples of the polymerization solvent usable in the method of the present invention include aromatic solvents, naphthene solvents and aliphatic hydrocarbon solvents. Particularly, when an aromatic solvent is used, a polymer having a relatively narrow molecular weight distribution can be obtained, and thus it is suitable as a polymerization solvent in the method of the present invention.
Examples of the aromatic solvent include xylene, toluene, benzene and the like. Examples of the naphthene-based solvent include cyclohexane, ethylcyclohexane, dimethylcyclohexane and the like. Furthermore, examples of the aliphatic hydrocarbon solvent include n-octane, isooctane, kerosene and the like. The amount of the polymerization solvent used in the method of the present invention is cyclopentadiene compound 1
It is usually 30 to 400 parts by weight, preferably 60 to 240 parts by weight, relative to 00 parts by weight. When the amount of the polymerization solvent used is reduced, it becomes difficult to control the softening point of the polymer within a predetermined range, and the molecular weight distribution is widened, so that the finally obtained partially hydrogenated petroleum resin is used as a tackifier. It is not preferable because the performance is lowered. Further, when the amount of the polymerization solvent used is large, the polymerization reaction does not proceed and the degree of polymerization cannot be increased, which is not preferable.
【０００８】本発明の方法では、上記のように、まずシ
クロペンタジエン系化合物とビニル芳香族系化合物とを
溶媒中で重合するが、重合は２段以上の多段重合法によ
って行なうのが好ましい。各段階の重合は、連続重合法
でも回分重合法でもいずれの方法でも採用することがで
きるが、回分法による２段重合方法で行なうのが通常で
ある。In the method of the present invention, the cyclopentadiene compound and the vinyl aromatic compound are first polymerized in a solvent as described above, but the polymerization is preferably carried out by a multi-stage polymerization method of two or more stages. The polymerization at each stage can be carried out by either a continuous polymerization method or a batch polymerization method, but it is usually carried out by a two-stage polymerization method by a batch method.
【０００９】以下、回分法による２段重合法で行なう場
合の好ましい重合条件について説明する。まず第１段重
合条件について述べる。重合温度は１８０〜２８０℃で
ある。重合温度が１８０℃よりも低いと、重合速度が低
下し、生産効率が良くない。一方、２８０℃よりも重合
温度が高くなると、得られる樹脂の色相に悪影響が生ず
るので好ましくない。重合時間は０．５〜４時間であ
る。０．５時間よりも重合時間が短いと、分子量分布が
広くなり、粘着付与物性が低下するので好ましくない。
また、重合を長時間行なっても、それに見合う粘着付与
物性の向上は見られない。反応圧力は、重合温度，重合
槽内の原料組成，反応混合物組成により、変動するが、
通常、１０〜１５kg/cm2G である。出発原料の使用割合
は、前記したように、シクロペンタジエン系化合物：ビ
ニル芳香族系化合物＝３０：７０〜９０：１０（重量
比）の範囲である。Hereinafter, preferable polymerization conditions for carrying out the two-step polymerization method by the batch method will be described. First, the first stage polymerization conditions will be described. The polymerization temperature is 180 to 280 ° C. If the polymerization temperature is lower than 180 ° C., the polymerization rate will decrease, resulting in poor production efficiency. On the other hand, when the polymerization temperature is higher than 280 ° C., the hue of the obtained resin is adversely affected, which is not preferable. The polymerization time is 0.5 to 4 hours. When the polymerization time is shorter than 0.5 hours, the molecular weight distribution becomes broad and the tackifying properties are deteriorated, which is not preferable.
In addition, even if the polymerization is carried out for a long time, no improvement in the physical properties of tackifier commensurate with it is observed. The reaction pressure varies depending on the polymerization temperature, the raw material composition in the polymerization tank and the composition of the reaction mixture,
Usually, it is 10 to 15 kg / cm 2 G. As described above, the use ratio of the starting material is in the range of cyclopentadiene compound: vinyl aromatic compound = 30: 70 to 90:10 (weight ratio).
【００１０】次に、第２段重合条件について述べる。重
合温度は２４０〜２８０℃であり、第１段重合温度より
も６０℃程度高い温度の範囲で通常行なわれる。２４０
℃よりも重合温度が低くなると、重合に時間がかかり好
ましくない。一方、２８０℃よりも重合温度が高くなる
と、得られる樹脂の色相に悪影響が生ずる。重合時間
は、目的とする部分水添石油樹脂の軟化点，分子量など
の物性に応じて調整され、通常、０．５〜６時間であ
る。なお、反応圧力は第１段重合条件と同様である。Next, the second stage polymerization conditions will be described. The polymerization temperature is 240 to 280 ° C., and it is usually carried out in the range of a temperature about 60 ° C. higher than the first stage polymerization temperature. 240
If the polymerization temperature is lower than 0 ° C, the polymerization takes time, which is not preferable. On the other hand, when the polymerization temperature is higher than 280 ° C, the hue of the obtained resin is adversely affected. The polymerization time is adjusted depending on the physical properties such as the softening point and the molecular weight of the target partially hydrogenated petroleum resin, and is usually 0.5 to 6 hours. The reaction pressure is the same as the first-stage polymerization conditions.
【００１１】このようにして重合反応が終了した後、得
られた重合体混合物から低分子量重合体と溶媒（重合溶
媒）を分離，回収する。この方法として種々の方法があ
る。重合が回分重合法である場合には、重合槽を減圧し
て、重合溶媒，低分子量重合体を順次分離するのが普通
である。この際、重合溶媒が先に分離してくるので、ま
ず、この重合溶媒を貯槽に回収した後、さらに減圧し、
重合溶媒の回収槽とは別の分離回収槽に低分子量重合体
を回収すれば、低分子量重合体を含まない重合溶媒を容
易に回収することができる。また、重合溶媒と低分子量
重合体を、減圧により同じ貯槽に分離回収してから、低
分子量重合体と重合溶媒との分離を行なってもよい。重
合溶媒から低分子量重合体を分離する際の減圧は、３０
mmHg以下で行なうのが普通である。After the polymerization reaction is completed in this way, the low molecular weight polymer and the solvent (polymerization solvent) are separated and recovered from the obtained polymer mixture. There are various methods as this method. When the polymerization is a batch polymerization method, the polymerization tank is usually depressurized to sequentially separate the polymerization solvent and the low molecular weight polymer. At this time, since the polymerization solvent is separated first, first, after collecting this polymerization solvent in the storage tank, further reducing the pressure,
If the low molecular weight polymer is recovered in a separate recovery tank separate from the polymerization solvent recovery tank, the polymerization solvent containing no low molecular weight polymer can be easily recovered. Alternatively, the low molecular weight polymer and the low molecular weight polymer may be separated and collected in the same storage tank under reduced pressure, and then the low molecular weight polymer and the low molecular weight polymer may be separated. The reduced pressure when separating the low molecular weight polymer from the polymerization solvent is 30
It is usually done at mmHg or less.
【００１２】例えば芳香族系溶媒としてキシレンを用い
た場合には、反応終了後、常圧まで脱圧する過程で、低
分子量重合体を含まないキシレンが重合槽から分離，回
収され、さらに１０mmHg程度まで減圧することによっ
て、キシレンをわずかに含む低分子量重合体が分離，回
収される。減圧を行なう際に、バルブを切替え、回収槽
を切り替えて、低分子量重合体を含まないキシレンを容
易に回収することができる。For example, when xylene is used as the aromatic solvent, xylene containing no low molecular weight polymer is separated and recovered from the polymerization tank in the process of depressurizing to normal pressure after completion of the reaction, and further up to about 10 mmHg. By reducing the pressure, the low molecular weight polymer containing a small amount of xylene is separated and collected. When reducing the pressure, the valve can be switched and the recovery tank can be switched to easily recover the xylene containing no low molecular weight polymer.
【００１３】本発明において低分子量重合体とは、シク
ロペンタジエン, メチルシクロペンタジエン, エチルシ
クロペンタジエンなどのシクロペンタジエン単位が３〜
４個のホモ重合体（例えば、ジシクロペンタジエンとシ
クロペンタジエンとが重合すれば、シクロペンタジエン
単位が３個の重合体となる。）や、シクロペンタジエン
単位とビニル芳香族単位が３〜４個の共重合体を主成分
とする重合体を意味する。In the present invention, the low molecular weight polymer means that cyclopentadiene units such as cyclopentadiene, methylcyclopentadiene and ethylcyclopentadiene have 3 to 3 units.
4 homopolymers (for example, if dicyclopentadiene and cyclopentadiene are polymerized, a polymer having 3 cyclopentadiene units), or 3 to 4 cyclopentadiene units and 3 to 4 vinyl aromatic units. It means a polymer whose main component is a copolymer.
【００１４】本発明の方法では、このようにして低分子
量重合体と溶媒を分離した後の残余の重合体に水添を行
なう。水添の方法は種々あるが、連続２段水素化法で行
なうのが好ましい。この連続２段水素化法では、第１段
の水添工程で、重合体を構成するシクロペンタジエン系
化合物単位の水素化を主として行ない、第２段の水添工
程では、重合体のビニル芳香族化合物単位の芳香族核を
主に水素化する。In the method of the present invention, hydrogenation is carried out on the residual polymer after separating the low molecular weight polymer and the solvent in this way. There are various hydrogenation methods, but it is preferable to carry out the continuous two-stage hydrogenation method. In this continuous two-stage hydrogenation method, hydrogenation of cyclopentadiene-based compound units constituting the polymer is mainly carried out in the first-stage hydrogenation step, and in the second-stage hydrogenation step, the vinyl aromatic compound of the polymer is used. The aromatic nucleus of the compound unit is mainly hydrogenated.
【００１５】本発明の方法で目的とする石油樹脂は、完
全に水添したものでなく、核水添率が０〜８０％、好ま
しくは４０〜８０％となるように部分水添したものであ
る。核水添率が大きくなるにつれて、得られる石油樹脂
を粘着剤として用いたときのタックの向上効果は少なく
なり、核水添率が８０％を超えた場合には粘着付与物性
が向上せず、１００％の完全水添石油樹脂に至っては、
本発明の目的とするような効果は認められない。なお、
核水添率は、水添前の石油樹脂と部分水添石油樹脂との
７００cm-1における赤外線吸収スペクトルを測定して、
次の数式（Ｉ）により算出したものである。The petroleum resin which is the object of the method of the present invention is not completely hydrogenated but partially hydrogenated so that the nuclear hydrogenation rate is 0 to 80%, preferably 40 to 80%. is there. As the nuclear hydrogenation rate increases, the effect of improving tack when using the obtained petroleum resin as an adhesive decreases, and when the nuclear hydrogenation rate exceeds 80%, the tackifying physical properties do not improve, For 100% fully hydrogenated petroleum resin,
The effect intended by the present invention is not recognized. In addition,
The nuclear hydrogenation rate is obtained by measuring the infrared absorption spectrum of the petroleum resin before hydrogenation and the partially hydrogenated petroleum resin at 700 cm −1 .
It is calculated by the following mathematical formula (I).
【００１６】[0016]
【数１】 (Equation 1)
【００１７】水添は、溶媒としてシクロヘキサン，エチ
ルシクロヘキサン，ジメチルシクロヘキサンなどの脂環
式炭化水素を用い、或いは溶媒を用いずに行なうことが
できる。Hydrogenation can be carried out using alicyclic hydrocarbons such as cyclohexane, ethylcyclohexane and dimethylcyclohexane as a solvent, or without using a solvent.
【００１８】以下、連続２段水素化法による水添につい
て説明する。まず第１段水添工程について述べる。水添
温度は、通常、１００〜２５０℃である。温度が低すぎ
ると水添が充分に行なわれず、一方、温度が高すぎると
石油樹脂の分解が生ずるので、いずれも好ましくない。
また、水添時間は、液空間速度（ＷＨＳＶ）が０．０１
〜１ｈｒ-1となるように選択され、水添圧力は、通常、
２０〜５０kg/cm2G である。また、水添触媒としては、
通常、パラジウム系触媒が用いられる。The hydrogenation by the continuous two-stage hydrogenation method will be described below. First, the first stage hydrogenation step will be described. The hydrogenation temperature is usually 100 to 250 ° C. If the temperature is too low, hydrogenation will not be carried out sufficiently, while if the temperature is too high, the petroleum resin will be decomposed, so that neither is preferable.
Further, the hydrogenation time is 0.01 hour at a liquid hourly space velocity (WHSV).
The hydrogenation pressure is usually selected to be ˜1 hr −1 .
It is 20 to 50 kg / cm 2 G. Further, as the hydrogenation catalyst,
Usually, a palladium-based catalyst is used.
【００１９】次に第２段水添工程について述べると、水
添温度，水添時間及び水添圧力は、第１段水添工程と同
様であるが、水添触媒としてはニッケル系触媒，パラジ
ウム系触媒，ロジウム触媒，ルテニウム系触媒などが用
いられる。なお、水素使用量は、第１段水添工程と第２
段水添工程とを合計して、未水添石油樹脂を完全に水添
するのに必要な理論量のおよそ１．２５モル倍程度とす
るのが好ましい。Next, the second stage hydrogenation process will be described. The hydrogenation temperature, hydrogenation time and hydrogenation pressure are the same as those in the first stage hydrogenation process, but the hydrogenation catalysts are nickel-based catalysts, palladium-based catalysts and rhodium. A catalyst or ruthenium-based catalyst is used. The amount of hydrogen used is the same as in the first hydrogenation step and the second step.
It is preferable that the total amount of the step hydrogenation step is about 1.25 mol times the theoretical amount necessary for completely hydrogenating the unhydrogenated petroleum resin.
【００２０】一方、本発明の方法においては、低分子量
重合体を含まない重合溶媒を、重合反応における溶媒と
して再利用する。すなわち、上記のようにして得られた
低分子量重合体を含まない重合溶媒を、重合反応におけ
る溶媒として用い、シクロペンタジエン系化合物とビニ
ル芳香族系化合物とをこの溶媒中で重合反応し、得られ
た重合体混合物から低分子量重合体及び前記溶媒を分
離，回収した後の残余の重合体を、核水添率０〜８０％
に部分水素化して部分水添石油樹脂を製造する。前記し
たように、重合が回分重合法である場合には、重合槽を
減圧して、重合溶媒，低分子量重合体を順次分離するな
どして、低分子量重合体を含まない重合溶媒を回収し、
これを重合反応における溶媒として再利用する。ここで
低分子量重合体を重合溶媒から分離することなく、低分
子量重合体を含む重合溶媒を重合反応における溶媒とし
て再利用したのでは、粘着付与物性に優れた部分水添石
油樹脂を得ることはできない。On the other hand, in the method of the present invention, the polymerization solvent containing no low molecular weight polymer is reused as the solvent in the polymerization reaction. That is, a polymerization solvent containing no low molecular weight polymer obtained as described above was used as a solvent in the polymerization reaction, and a cyclopentadiene compound and a vinyl aromatic compound were subjected to a polymerization reaction in this solvent to obtain a product. The residual hydrogenated polymer after separating and recovering the low molecular weight polymer and the solvent from the polymer mixture was subjected to a nuclear hydrogenation rate of 0 to 80%.
Partially hydrogenated to produce a partially hydrogenated petroleum resin. As described above, when the polymerization is a batch polymerization method, the polymerization tank is depressurized, the polymerization solvent and the low molecular weight polymer are sequentially separated, and the polymerization solvent containing no low molecular weight polymer is recovered. ,
This is reused as a solvent in the polymerization reaction. Here, without separating the low molecular weight polymer from the polymerization solvent, by reusing the polymerization solvent containing the low molecular weight polymer as the solvent in the polymerization reaction, it is possible to obtain a partially hydrogenated petroleum resin having excellent tackifying physical properties. Can not.
【００２１】このようにして目的とする部分水添石油樹
脂を製造することができる。得られる部分水添石油樹脂
は、軟化点が７０〜１６０℃程度のものである。このよ
うな部分水添石油樹脂は、スチレン─ブタジエンブロッ
ク共重合体やエチレン─酢酸ビニル共重合体などのよう
なベースポリマーに、プロセスオイルのような可塑剤等
と共に配合されて、ホットメルト型接着剤として利用さ
れる。In this way, the desired partially hydrogenated petroleum resin can be produced. The partially hydrogenated petroleum resin obtained has a softening point of about 70 to 160 ° C. Such partially hydrogenated petroleum resin is blended with a base polymer such as a styrene-butadiene block copolymer or an ethylene-vinyl acetate copolymer together with a plasticizer such as process oil to obtain a hot melt adhesive. Used as an agent.
【００２２】[0022]
【実施例】次に本発明を実施例により詳しく説明する。 実施例１ （１）シクロペンタジエン系化合物とビニル芳香族系化
合物との重合 １リットルのオートクレーブに、ジシクロペンタジエン
１６０ｇ、スチレン１６０ｇ、キシレン３８４ｇをそれ
ぞれ供給した。重合溶媒には、キシレンを使用した。２
時間かけて２４０℃まで昇温を行ない、この温度に２時
間維持し、重合反応を行なった。さらに、３０分かけて
２６０℃まで昇温し、その温度に２．５時間維持し、重
合反応を終了した。その後、得られた重合体混合物を、
常圧まで２時間かけて徐々に脱圧し、キシレンを回収し
た。オートクレーブ内の温度は２００℃まで下がった。
次いで２０mmHgまで１．５時間かけて減圧し、2 時間維
持した。低分子量重合体４．８ｇを、先のキシレンとは
別の容器に回収した。オートクレーブ中に残った石油樹
脂は冷却して、樹脂１００重量部に対して、３００重量
部のエチルシクロヘキサンに溶解し、水添用原料とし
た。EXAMPLES The present invention will now be described in more detail with reference to examples. Example 1 (1) Polymerization of cyclopentadiene compound and vinyl aromatic compound To a 1 liter autoclave, 160 g of dicyclopentadiene, 160 g of styrene and 384 g of xylene were supplied. Xylene was used as the polymerization solvent. 2
The temperature was raised to 240 ° C. over a period of time, and this temperature was maintained for 2 hours to carry out a polymerization reaction. Furthermore, the temperature was raised to 260 ° C. over 30 minutes, and the temperature was maintained for 2.5 hours to complete the polymerization reaction. Then, the obtained polymer mixture,
The pressure was gradually released to normal pressure over 2 hours, and xylene was recovered. The temperature inside the autoclave dropped to 200 ° C.
Then, the pressure was reduced to 20 mmHg over 1.5 hours and maintained for 2 hours. 4.8 g of the low molecular weight polymer was recovered in a container separate from the above xylene. The petroleum resin remaining in the autoclave was cooled, dissolved in 300 parts by weight of ethylcyclohexane with respect to 100 parts by weight of the resin, and used as a raw material for hydrogenation.
【００２３】（２）部分水添石油樹脂の製造 上記（１）で得られた石油樹脂に、２段連続水添を行な
った。パラジウム０．５重量％のアルミナ担持パラジウ
ム触媒を充填した反応槽に、前記水添原料と、水添原料
中の石油樹脂１００重量部に対して０．０３５重量部の
割合の水素とを、液空間速度（ＷＨＳＶ）０．２５ｈｒ
-1，１８０℃で流して１段目の水添を行なった。次い
で、１段反応槽上部から流出する反応生成物を２段反応
槽下部に供給し、２段目の水添反応を行なった。触媒と
してはニッケル系触媒を用い、温度１３０℃，液空間速
度（ＷＨＳＶ）０．５５ｈｒ-1とし、第１段目と同量の
水素を用いて、第２段の水添反応を行なった。得られた
石油樹脂は、軟化点が１００℃、核水添率が６０％、臭
素価が５．５の部分水添石油樹脂であった。なお、臭素
価の測定は、ＪＩＳ−Ｋ−２６０５に準じて電気的滴定
法により行なった。この際には触媒として、塩化第２水
銀を試料に添加して測定を行なった。(2) Production of partially hydrogenated petroleum resin The petroleum resin obtained in (1) above was subjected to two-stage continuous hydrogenation. In a reaction tank filled with an alumina-supported palladium catalyst containing 0.5% by weight of palladium, the hydrogenated raw material and 0.035 part by weight of hydrogen based on 100 parts by weight of the petroleum resin in the hydrogenated raw material were mixed. Space velocity (WHSV) 0.25hr
-1 was subjected to first-stage hydrogenation flowing at 180 ° C.. Next, the reaction product flowing out from the upper part of the first-step reaction tank was supplied to the lower part of the second-step reaction tank to carry out the second-stage hydrogenation reaction. A nickel-based catalyst was used as the catalyst, the temperature was 130 ° C., the liquid hourly space velocity (WHSV) was 0.55 hr −1, and the second stage hydrogenation reaction was carried out using the same amount of hydrogen as in the first stage. The obtained petroleum resin was a partially hydrogenated petroleum resin having a softening point of 100 ° C., a nuclear hydrogenation rate of 60% and a bromine number of 5.5. The bromine number was measured by an electric titration method according to JIS-K-2605. At this time, mercuric chloride was added as a catalyst to the sample for measurement.
【００２４】（３）溶媒の再使用 溶媒として、上記（１）で回収されたキシレン（低分子
量重合体を含まないものである。）を用いたこと以外は
上記（１）と同様にして重合し、次いで得られた石油樹
脂を用いたこと以外は上記（２）と同様にして部分水添
石油樹脂を製造した。得られた部分水添石油樹脂は、上
記（２）で得られたものと同様のものであった。(3) Reuse of solvent Polymerization was carried out in the same manner as in (1) above except that xylene (which does not contain a low molecular weight polymer) recovered in (1) above was used as a solvent. Then, a partially hydrogenated petroleum resin was produced in the same manner as in (2) above, except that the obtained petroleum resin was used. The partially hydrogenated petroleum resin obtained was similar to that obtained in (2) above.
【００２５】（４）粘着剤の調製 スチレン−ブタジエンブロック共重合体（シェルジャパ
ン（株）製、カリフレックスＴＲ−ＫＸ６５）２５重量
部、上記（３）で得られた部分水添石油樹脂６０重量部
及びパラフィン系プロセスオイル（出光興産（株）製Ｐ
Ｓ−３２）１５重量部を、１４０℃で４０分間混練して
粘着剤を調製した。(4) Preparation of adhesive 25 parts by weight of styrene-butadiene block copolymer (Califlex TR-KX65 manufactured by Shell Japan Co., Ltd.), 60 parts by weight of partially hydrogenated petroleum resin obtained in the above (3) Parts and paraffinic process oil (P by Idemitsu Kosan Co., Ltd.)
15 parts by weight of S-32) was kneaded at 140 ° C. for 40 minutes to prepare an adhesive.
【００２６】（５）粘着テープの調製及び粘着物性の測
定 上記（４）で得られた粘着剤１００重量部をトルエン６
０重量部に溶解したものを、ポリエチレンテレフタレー
トフィルム上に塗布し、１００℃で１．５分間加熱し
て、厚さ４０〜５０μｍの粘着層を有する粘着テープを
調製した。この粘着テープを、ポリエチレン板と貼り合
わせ、ＪＩＳ−Ｚ−０２３７に準じて、１８０度引きは
がし法により粘着力を測定した。また、タックは、幅２
５ｍｍ、ループ長１０ｃｍのループタックで測定した。
引張試験はオリエンテック（株）製の引張試験機を用い
た。これら粘着物性の測定結果を第１表に示す。(5) Preparation of pressure-sensitive adhesive tape and measurement of pressure-sensitive adhesive properties 100 parts by weight of the pressure-sensitive adhesive obtained in (4) above was added to toluene 6
What was melt | dissolved in 0 weight part was apply | coated on the polyethylene terephthalate film, and it heated at 100 degreeC for 1.5 minutes, and prepared the adhesive tape which has a 40-50 micrometer-thick adhesive layer. This adhesive tape was attached to a polyethylene plate, and the adhesive strength was measured by a 180-degree peeling method according to JIS-Z-0237. Also, the tack has a width of 2
It was measured with a loop tack of 5 mm and a loop length of 10 cm.
For the tensile test, a tensile tester manufactured by Orientec Co., Ltd. was used. Table 1 shows the measurement results of these adhesive properties.
【００２７】比較例１ （１）シクロペンタジエン系化合物とビニル芳香族系化
合物との重合 実施例１（１）において、実施例１（１）で得られた重
合体混合物から、キシレンと低分子量重合体とを分離す
ることなく両者の混合物として一緒に回収したこと以外
は、実施例１（１）と同様にして行ない、石油樹脂を得
た。 （２）溶媒の再使用 上記（１）で回収されたキシレンと低分子量重合体との
混合物を溶媒として用いたこと以外は、上記（１）と同
様にして重合し、石油樹脂を得た。得られた石油樹脂を
冷却し、石油樹脂１００重量部に対して、エチルシクロ
ヘキサン３００重量部に溶解し、水添原料としたこと以
外は、実施例１（２）と同様にして、２段連続水添を行
ない、部分水添石油樹脂を製造した。得られた部分水添
石油樹脂の軟化点，核水添率，臭素価は、いずれも実施
例１（２）で得られたものと同様のものであった。 （３）粘着剤の調製及び（４）粘着テープの調製及び粘
着物性の測定 上記（２）で得られた部分水添石油樹脂を用いたこと以
外は、実施例１（４）と（５）と同様にして、粘着剤及
び粘着テープを調製し、粘着物性を測定した。その結果
を第１表に示す。Comparative Example 1 (1) Polymerization of Cyclopentadiene Compound and Vinyl Aromatic Compound In Example 1 (1), xylene and low molecular weight polymer were obtained from the polymer mixture obtained in Example 1 (1). A petroleum resin was obtained in the same manner as in Example 1 (1), except that the combined product was collected together as a mixture without separation. (2) Reuse of solvent A petroleum resin was obtained by polymerization in the same manner as in (1) above, except that the mixture of xylene and the low molecular weight polymer recovered in (1) above was used as a solvent. The obtained petroleum resin was cooled and dissolved in 300 parts by weight of ethylcyclohexane with respect to 100 parts by weight of the petroleum resin to prepare a hydrogenated raw material, and in the same manner as in Example 1 (2), two consecutive stages. Hydrogenation was carried out to produce a partially hydrogenated petroleum resin. The softening point, nuclear hydrogenation rate, and bromine number of the obtained partially hydrogenated petroleum resin were all the same as those obtained in Example 1 (2). (3) Preparation of pressure-sensitive adhesive and (4) Preparation of pressure-sensitive adhesive tape and measurement of pressure-sensitive adhesive properties Example 1 (4) and (5) except that the partially hydrogenated petroleum resin obtained in (2) above was used. In the same manner as above, an adhesive and an adhesive tape were prepared, and the adhesive physical properties were measured. Table 1 shows the results.
【００２８】実施例２ 重合溶媒としてキシレンを９６ｇ用いた他は、実施例１
と同様にして部分水添石油樹脂を製造し、得られた部分
水添石油樹脂について、実施例１と同様にして粘着特性
を測定した。その結果を第１表に示す。Example 2 Example 1 was repeated except that 96 g of xylene was used as a polymerization solvent.
A partially hydrogenated petroleum resin was produced in the same manner as in 1. and the adhesive properties of the obtained partially hydrogenated petroleum resin were measured in the same manner as in Example 1. Table 1 shows the results.
【００２９】比較例２ 重合溶媒としてキシレンを９６ｇ用いた他は、比較例１
と同様にして部分水添石油樹脂を製造し、得られた部分
水添石油樹脂について、比較例１と同様にして粘着特性
を測定した。その結果を第１表に示す。Comparative Example 2 Comparative Example 1 except that 96 g of xylene was used as a polymerization solvent.
A partially hydrogenated petroleum resin was produced in the same manner as in 1. and the adhesive properties of the obtained partially hydrogenated petroleum resin were measured in the same manner as in Comparative Example 1. Table 1 shows the results.
【００３０】 [0030]
【００３１】[0031]
【発明の効果】本発明の方法によれば、反応で副生する
低分子量重合体を、リサイクルすることなく、溶媒だけ
をリサイクルすることにより、粘着付与物性に優れた部
分水添石油樹脂を効率よく得ることができる。本発明の
方法により得られた部分水添石油樹脂は、ホットメルト
型接着剤や粘着テープの粘着付与剤などとして有効に利
用することができる。According to the method of the present invention, the partially hydrogenated petroleum resin having excellent tackifying properties can be efficiently produced by recycling only the solvent without recycling the low molecular weight polymer by-produced in the reaction. You can get well. The partially hydrogenated petroleum resin obtained by the method of the present invention can be effectively used as a hot-melt adhesive or a tackifier for pressure-sensitive adhesive tapes.
Claims (1)
香族系化合物とを溶媒中で重合反応し、得られた重合体
混合物から低分子量重合体及び前記溶媒を分離，回収し
た後、残余の重合体を、核水添率０〜８０％に部分水素
化して部分水添石油樹脂を製造するとともに、前記低分
子量重合体を含まない前記回収溶媒を、前記重合反応に
おける溶媒として再使用することを特徴とする部分水添
石油樹脂の製造方法。1. A cyclopentadiene compound and a vinyl aromatic compound are subjected to a polymerization reaction in a solvent, and a low molecular weight polymer and the solvent are separated and recovered from the obtained polymer mixture. And partially hydrogenating to a nuclear hydrogenation rate of 0 to 80% to produce a partially hydrogenated petroleum resin, and reuse the recovered solvent containing no low molecular weight polymer as a solvent in the polymerization reaction. Method for producing partially hydrogenated petroleum resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23764692A JP2684494B2 (en) | 1992-08-14 | 1992-08-14 | Method for producing partially hydrogenated petroleum resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23764692A JP2684494B2 (en) | 1992-08-14 | 1992-08-14 | Method for producing partially hydrogenated petroleum resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0656920A JPH0656920A (en) | 1994-03-01 |
| JP2684494B2 true JP2684494B2 (en) | 1997-12-03 |
Family
ID=17018411
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23764692A Expired - Lifetime JP2684494B2 (en) | 1992-08-14 | 1992-08-14 | Method for producing partially hydrogenated petroleum resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2684494B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1574526A4 (en) * | 2002-12-20 | 2007-06-06 | Idemitsu Kosan Co | Process for the production of hydrogenated petroleum resin |
| JP5651393B2 (en) * | 2010-07-08 | 2015-01-14 | 出光興産株式会社 | Production method of petroleum resin |
| WO2015147027A1 (en) | 2014-03-26 | 2015-10-01 | 丸善石油化学株式会社 | Method for producing hydrogenated petroleum resin |
| JP6987846B2 (en) * | 2017-03-16 | 2022-01-05 | 丸善石油化学株式会社 | Manufacturing method of hydrogenated petroleum resin |
| KR102313148B1 (en) * | 2017-06-30 | 2021-10-15 | 코오롱인더스트리 주식회사 | Partial hydrogenated petroleum resin, preparation method thereof, and the use of the same |
| KR102343368B1 (en) * | 2017-06-30 | 2021-12-24 | 코오롱인더스트리 주식회사 | Curable petroleum resin, preparation method thereof, and the use comprising of the same |
-
1992
- 1992-08-14 JP JP23764692A patent/JP2684494B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0656920A (en) | 1994-03-01 |
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