JP2005336345A - Method for producing new petroleum resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a new petroleum resin having high compatibility with EVA and high solubility in vegetable oils for ink and an aroma-free solvent, etc. <P>SOLUTION: The petroleum resin is produced by reacting a 4-5C chain diene with a 5-6C cyclic diene in the presence of an acid catalyst to form a multimer, mixing 5-50 pts. wt. of the multimer, 95-50 pts. wt. of an 8-10C vinyl aromatic hydrocarbon and an organic solvent and polymerizing at -30 to +150°C in the presence of a Friedel-Crafts catalyst. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel method for producing a petroleum resin. More specifically, the present invention relates to a novel method for producing a petroleum resin having excellent performance in hot melt adhesive applications and ink applications.

  A hydrocarbon resin obtained by polymerizing with a Friedel-Crafts-type catalyst using various fractions obtained in the cracking or refining of petroleum hydrocarbons as a raw material oil is generally called a petroleum resin. Since this petroleum resin is excellent in adhesiveness, tackiness, water resistance, chemical resistance and electrical insulation, it is widely used in various industrial fields such as adhesives, pressure-sensitive adhesives, printing inks, and asphalts.

  Among these, as the pressure-sensitive adhesive, it is blended with an ethylene-vinyl acetate copolymer (hereinafter referred to as “EVA”), wax, etc., and used as a hot melt adhesive.

  As raw materials for hot melt adhesives, (1) pyrolysis oil fractions containing vinyltoluene and indene obtained by pyrolysis of petroleum hydrocarbons, (2) turpentine oil and (3) phenolic compounds in specific proportions It has been proposed to use an aromatic petroleum resin that has been mixed and copolymerized using a Friedel-Crafts catalyst (see, for example, Patent Documents 1 to 3). However, these petroleum resins have a problem that they are not sufficiently compatible with EVA. Moreover, in order to fully exhibit the compatibility, it is necessary to use a large amount of expensive turpentine oil or phenol, which causes an economic problem.

  Moreover, in order to use petroleum resin as a raw material for printing ink, it is necessary to dissolve petroleum resin in an ink solvent. In recent years, due to environmental problems, the solvent for ink has been converted to vegetable oils and aromatic-free solvents that do not contain aromatic solvents. At that time, the petroleum resin consisting only of aromatic hydrocarbons has a problem of poor solubility. Therefore, petroleum cracking composed of C9 vinyl aromatic hydrocarbons and low-softening point aliphatic petroleum resins obtained by polymerizing petroleum cracking fractions composed of C5 olefins and diolefins using Friedel Crafts type catalysts. A petroleum resin composition comprising a copolymer resin obtained by polymerizing a fraction of 50 to 95% by weight and a dicyclopentadiene fraction of 5 to 50% by weight using a Friedel-Crafts type catalyst has been proposed (for example, patents). Reference 4). However, although this resin composition has increased solubility in the ink solvent, it has a problem that the thermal stability is lowered because the resin contains a large amount of dicyclopentadiene fraction. Furthermore, a method of modifying an aromatic petroleum resin with an unsaturated carboxylic acid, an aliphatic polybasic acid, or an alcohol has been proposed (see, for example, Patent Documents 5 to 6). However, this method requires a further reaction of the petroleum resin after polymerization, and there is a problem that the process becomes complicated.

JP 2001-59078 A (second page)

JP 2002-69408 A (page 2) JP-A-9-316294 (2nd page) Japanese Patent No. 3464504 (first page) Japanese Examined Patent Publication No. 47-47994 (2nd page) JP 2001-31718 A (2nd page)

  The present invention has been made in view of the above problems, and its purpose is to produce a novel petroleum resin that is highly compatible with EVA and has high solubility in vegetable oils and aroma-free solvents for ink. It is to provide a method.

  As a result of intensive studies to solve the above problems, the present inventors have found a novel method for producing a petroleum resin made of a specific raw material, and have completed the present invention.

  That is, the present invention provides a polymer having 5 to 50 parts by weight obtained by reacting a chain diene having 4 to 5 carbon atoms and a cyclic diene having 5 to 6 carbon atoms in the presence of an acid catalyst, and 8 to 10 carbon atoms. The present invention relates to a method for producing a petroleum resin characterized by polymerizing 95 to 50 parts by weight of a vinyl aromatic hydrocarbon.

  The chain diene having 4 to 5 carbon atoms used in the present invention is not particularly limited. Examples thereof include chain dienes such as butadiene, isoprene, trans-1,3-pentadiene, cis-1,3-pentadiene, and mixtures thereof. Moreover, a C5-C6 cyclic diene is not specifically limited. Examples thereof include cyclic dienes such as cyclopentadiene and methylcyclopentadiene, and mixtures thereof. Furthermore, among the pyrolysis oils obtained by pyrolysis of petroleum fractions, chain dienes and / or cyclic dienes contained in fractions having a boiling point in the range of 110 ° C. or less may be used. When such a fraction is used, it is used in a mixed state with other hydrocarbon compounds contained in the fraction without isolating the chain diene and / or cyclic diene from the fraction. May be.

  The multimer of the present invention is a compound obtained by reacting a chain diene having 4 to 5 carbon atoms and a cyclic diene having 5 to 6 carbon atoms in the presence of an acid catalyst, and its structure is particularly limited. It is not a thing. For example, di- to 10-mer oligomers and mixtures thereof can be mentioned.

  In the present invention, the acid catalyst for producing a multimer by reacting a chain diene having 4 to 5 carbon atoms and a cyclic diene having 5 to 6 carbon atoms in the presence of an acid catalyst is not particularly limited. . For example, Friedel-Crafts type catalysts such as aluminum trichloride, aluminum tribromide, boron trifluoride or their ethyl ether complexes, phenol complexes, butyl ether complexes, butyl alcohol complexes, methyl alcohol complexes; protons such as sulfuric acid and hydrochloric acid Examples thereof include solid acids such as acids, silica, and alumina; or acidic ion exchange resins. Of these, Friedel-Crafts type catalysts are preferred because of high resin yield and easy post-treatment such as catalyst removal, more preferably boron trifluoride and its complexes, particularly preferably boron trifluoride- It is a phenol complex. These catalysts can be used not only alone but also in a mixture of two or more.

  The amount of the acid catalyst used is not particularly limited, and is preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight, particularly preferably based on the diene, because the amount can be efficiently increased. Is 0.1 to 2% by weight.

  Furthermore, the reaction temperature for reacting the chain diene having 4 to 5 carbon atoms and the cyclic diene having 5 to 6 carbon atoms is not particularly limited, and is preferably −30 to 150 ° C. because the multimerization can be efficiently performed. More preferably, it is 0-100 degreeC. The reaction pressure is also not particularly limited, and is usually preferably 0.1 to 1 MPa in absolute pressure, more preferably 0.1 to 0.5 MPa. Moreover, the reaction atmosphere at the time of mass increase is not particularly limited. For example, it is preferably performed in an inert gas atmosphere such as nitrogen or argon, and more preferably in a nitrogen atmosphere. The reaction time depends on the temperature and diene concentration and cannot be determined in general, but is usually 0.01 to 10 hours. The reaction can be carried out by either a continuous flow method or a batch method.

  In the reaction for producing a multimer by reacting a chain diene having 4 to 5 carbon atoms and a cyclic diene having 5 to 6 carbon atoms in the presence of an acid catalyst, an organic solvent is used as necessary. The organic solvent to be used is not particularly limited. For example, pentane, cyclopentane, hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane and other aliphatic hydrocarbons, benzene, toluene, xylene, ethylbenzene, propylbenzene, trimethylbenzene, cumene, butylbenzene , Aromatic hydrocarbons such as dibutylbenzene, ethers such as 1,4-dioxane, tetrahydrofuran, furfural, butyl glycidyl ether, ketones such as acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, ethyl cellosolve, butyl cellosolve, etc. Esters, kerosene and the like. These organic solvents can be used alone or in combination of two or more. Moreover, as a linear diene having 4 to 5 carbon atoms and / or a cyclic diene having 5 to 6 carbon atoms, among the pyrolysis oils obtained by pyrolysis of petroleum fractions, the fraction having a boiling point in the range of 110 ° C. or less. When the contained diene is used, it may be used as it is without fractionating the entrained saturated and unsaturated hydrocarbons.

  The method for producing a petroleum resin according to the present invention comprises a polymer having 5 to 50 parts by weight of a multimer formed by reacting a chain diene having 4 to 5 carbon atoms and a cyclic diene having 5 to 6 carbon atoms in the presence of an acid catalyst. It is characterized by polymerizing 95 to 50 parts by weight of 8 to 10 vinyl aromatic hydrocarbons.

  The vinyl aromatic hydrocarbon having 8 to 10 carbon atoms used in the present invention is not particularly limited. Examples include styrene, α-methylstyrene, β-methylstyrene, vinyl toluene, indene, methylindene, and mixtures thereof. Furthermore, you may use the vinyl aromatic hydrocarbon contained in the fraction whose boiling point is the range of 140-280 degreeC among the pyrolysis oil obtained by thermal decomposition of a petroleum fraction. However, in the case where this fraction contains dicyclopentadiene such as dicyclopentadiene and dicyclopentadiene having a methyl group, these dicyclopentadienes are added to the distillate in order to avoid a decrease in the thermal stability of the resin. It is desirable to remove in advance from the minutes. The method for removing dicyclopentadiene is not particularly limited. For example, a method of decomposing dicyclopentadiene into cyclopentadiene by controlling the pyrolysis fraction at a temperature of 180 to 230 ° C., and then removing cyclopentadiene by distillation can be mentioned. The amount of dicyclopentadiene contained in the vinyl aromatic hydrocarbon having 8 to 10 carbon atoms is preferably 5% by weight or less, more preferably 3% by weight in the pyrolysis fraction in order to avoid a decrease in thermal stability. % Or less.

  Polymerization of a polymer obtained by reacting a chain diene having 4 to 5 carbon atoms and a cyclic diene having 5 to 6 carbon atoms in the presence of an acid catalyst with a vinyl aromatic hydrocarbon having 8 to 10 carbon atoms, A polymer of 5 to 50 parts by weight, 95 to 50 parts by weight of a vinyl aromatic hydrocarbon having 8 to 10 carbon atoms and an organic solvent are mixed and polymerized in the presence of a Friedel-Crafts catalyst. Such a polymerization method is not limited to yield. For example, a chain diene having 4 to 5 carbon atoms and a cyclic diene having 5 to 6 carbon atoms are reacted in the presence of an acid catalyst to form a multimer, and then unreacted unreacted dienes and the like are removed. The polymer is mixed in an amount of 5 to 50 parts by weight, 95 to 50 parts by weight of a vinyl aromatic hydrocarbon having 8 to 10 carbon atoms and an organic solvent, and polymerized in the presence of a Friedel-Crafts catalyst. Examples of the deactivation treatment include a method for removing the polymerization catalyst from the polymerization solution and a method for distilling off the organic solvent.

  In the production method of the present invention, the polymerization catalyst used for the polymerization of the multimer and the vinyl aromatic hydrocarbon is not particularly limited. For example, Friedel-Crafts type catalysts such as aluminum trichloride, aluminum tribromide, boron trifluoride or their ethyl ether complexes, phenol complexes, butyl ether complexes, butyl alcohol complexes, methyl alcohol complexes, minerals such as sulfuric acid, hydrochloric acid, etc. Examples thereof include solid acids such as acids, silica, alumina, silica alumina, and zeolite, heteropoly acids such as phosphotungstic acid and silicotungstic acid, and acidic ion exchange resins. Of these, Friedel-Crafts type catalysts are preferred because of high resin yield and excellent post-treatment after completion of the reaction such as removal of the polymerization catalyst, more preferably boron trifluoride and its complexes, particularly preferably three. Boron fluoride-phenol complex. These polymerization catalysts can be used alone or in combination of two or more.

  The amount of the polymerization catalyst used in the polymerization is not particularly limited, and is preferably 0.01 to 10% by weight, more preferably, based on the mixture of the multimer and the vinyl aromatic hydrocarbon, because the polymerization can be efficiently performed. 0.05 to 5% by weight, particularly preferably 0.1 to 2% by weight.

  In the polymerization reaction, the organic solvent used is not particularly limited. For example, pentane, cyclopentane, hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane and other aliphatic hydrocarbons, benzene, toluene, xylene, ethylbenzene, propylbenzene, trimethylbenzene, cumene, butylbenzene , Aromatic hydrocarbons such as dibutylbenzene, ethers such as 1,4-dioxane, tetrahydrofuran, furfural, butyl glycidyl ether, ketones such as acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, ethyl cellosolve, butyl cellosolve, etc. Esters, kerosene and the like. These organic solvents can be used alone or in combination of two or more. Further, a pyrolysis oil obtained by pyrolysis of petroleum fraction, that is, a hydrocarbon having no polymerizable unsaturated bond entrained by a vinyl aromatic hydrocarbon having 8 to 10 carbon atoms as a raw material of the present invention. You may use as it is, without fractionating.

  The polymerization temperature is not particularly limited. For example, -30-150 degreeC is preferable, More preferably, it is -20-100 degreeC. The pressure is not particularly limited, and is usually preferably 0.1 to 1 MPa in absolute pressure, more preferably 0.1 to 0.5 MPa. Moreover, the reaction atmosphere at the time of superposition | polymerization is not restrict | limited in particular, For example, it is preferable to carry out in inert gas atmosphere, such as nitrogen and argon, More preferably, it is nitrogen atmosphere.

  In the production method of the present invention, after completion of the polymerization reaction, the polymerization catalyst is deactivated, and then the polymerization catalyst is removed from the polymerization solution. The compound used for the deactivation treatment of the polymerization catalyst is not particularly limited as long as it is a compound having an effect of deactivating the polymerization catalyst. Examples thereof include alcohols such as methanol, ethanol and propanol, alkaline aqueous solutions such as sodium hydroxide and potassium hydroxide, amines such as ethylamine and diethylamine, aqueous ammonia, and water. Of these, alkaline aqueous solutions are preferred because they do not generate corrosive gases such as halogen, and sodium hydroxide aqueous solutions are more preferred. These compounds can be used not only alone but also in a mixture of two or more.

  The removal of the polymerization catalyst from the polymerization solution of the present invention is not particularly limited, and can be performed by an ordinary oil-water separation method, for example, decantation.

  Furthermore, in this invention, the petroleum resin manufactured by this invention can be obtained by removing the organic solvent from the polymerization solution from which the polymerization catalyst has been removed. There is no restriction | limiting in particular in the method of removing an organic solvent from a polymerization solution, For example, the method of distilling an organic solvent is mentioned. Moreover, in order to improve the handleability of the polymerization solution at the time of distillation, it is also possible to distill by adding an organic solvent prior to distillation of the organic solvent. The organic solvent added here is not particularly limited. For example, pentane, cyclopentane, hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, benzene, toluene, xylene, ethylbenzene, propylbenzene, trimethylbenzene. , Cumene, butylbenzene, dibutylbenzene, 1,4-dioxane, tetrahydrofuran, furfural, butyl glycidyl ether, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, ethyl cellosolve, butyl cellosolve, kerosene And various hydrocarbon solvents and various lubricating oils. These organic solvents can be used alone or as a mixture of two or more. Of these, tetrahydrofuran, hexane, and xylene are preferred because the amount of heat and time required for distillation can be reduced.

  The amount of the organic solvent to be added is not particularly limited, but it is preferable to add 1 to 200 parts by weight with respect to 100 parts by weight of the obtained petroleum resin from the viewpoint that the dissolved matter is likely to be uniform and the time required for distillation is shortened.

  Although the temperature during distillation cannot be generally stated depending on the type of organic solvent, for example, in the case of atmospheric distillation, 150 to 350 ° C. is preferable because the solvent is less likely to remain and the resin is less susceptible to thermal degradation. Preferably it is 200-300 degreeC. In the case of vacuum distillation, the distillation temperature can be lowered according to the type of solvent and the degree of vacuum.

  Although the distillation time depends on the type and amount of the obtained petroleum resin, the type and amount of the organic solvent, for example, 0.05 to 10 hours is preferable in order to suppress residual solvent and resin thermal degradation. Preferably it is 0.5 to 5 hours.

  The petroleum resin obtained by the production method of the present invention preferably has a polystyrene-equivalent number average molecular weight of 400 to 1200 because it is compatible with EVA and has excellent solubility in vegetable oils for inks and aroma-free solvents. Furthermore, it is preferable that it is 600-900. The number average molecular weight here is measured, for example, by dissolving the petroleum resin of the present invention in tetrahydrofuran and adjusting the polymer solution concentration to 50 g / l, and then injecting this solution into gel permeation chromatography at room temperature. can do.

  In addition, the petroleum resin obtained by the production method of the present invention has high compatibility with EVA and high solubility in vegetable oil for inks and aroma-free solvents. (A) According to JIS K-2207 The measured softening point is preferably 90 to 140 ° C, more preferably 95 to 135 ° C. Further, (b) the cloud point is preferably 190 ° C. or lower, more preferably 185 ° C. or lower. Furthermore, (c) hexane tolerance is preferably 20 ml or more, more preferably 25 ml or more. The cloud point here is measured according to the JIS K-2269 petroleum product cloud point test method, and is an index of compatibility with EVA. It becomes resin. Further, hexane tolerance is a titration amount in which n-hexane is dropped into a solution prepared by dissolving petroleum resin in soybean white squeezed oil to a concentration of 50% by weight to start clouding. Hexane tolerance is an indicator of the solubility of petroleum resin in soybean white-drawn oil. The higher the hexane tolerance, the better the petroleum resin is in solubility in an aroma-free solvent for ink.

  The petroleum resin obtained by the above production method is excellent in compatibility with EVA, and further has a performance excellent in solubility in vegetable oil for ink and aroma-free solvent.

  According to such a method for producing a petroleum resin, a novel petroleum resin having high compatibility with EVA and high solubility in vegetable oil for ink or aroma-free solvent can be obtained.

  In addition, the petroleum resin according to the present invention is a suitable raw material for hot melt adhesives and a suitable raw material for printing ink that does not contain an aromatic solvent.

  The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to these examples.

1. Raw material As a linear diene having 4 to 5 carbon atoms and a cyclic diene having 5 to 6 carbon atoms, a fraction having a boiling point in the range of 20 to 110 ° C. (hereinafter, Fraction A) was used. The composition of fraction A is shown in Table 1.

炭素数８〜１０のビニル芳香族炭化水素として、石油留分の熱分解により得られる沸点が１４０〜２８０℃の範囲の熱分解留分を２２０℃で反応させてジシクロペンタジエンをシクロペンタジエンに分解し、次いで１００℃で蒸留することによりジシクロペンタジエンの一部を除去した表２に示す組成の留分（以下、留分Ｂという）を使用した。

As a vinyl aromatic hydrocarbon having 8 to 10 carbon atoms, dicyclopentadiene is decomposed into cyclopentadiene by reacting at 220 ° C. a pyrolysis fraction having a boiling point of 140 to 280 ° C. obtained by pyrolysis of petroleum fraction. Then, a fraction having the composition shown in Table 2 (hereinafter referred to as fraction B) from which a part of dicyclopentadiene was removed by distillation at 100 ° C. was used.

２．分析方法
（１）数平均分子量測定
高速ＧＰＣ装置（東ソー（株）製、商品名Ｈ８０２０ＧＰＣ）を用い、下記条件で測定した。即ち、多量体及び石油樹脂をテトラヒドロフランに溶解し、樹脂の溶液濃度を５０ｇ／ｌに調製後、このポリマー溶液を、カラムとしてＴＳＫｇｅｌ２０００Ｈ（商品名）２本、ＴＳＫｇｅｌ３０００Ｈ（商品名）１本、及びＴＳＫｇｅｌ４０００Ｈ（商品名）１本が備わった上記ＧＰＣ装置に注入し、標準試料としてポリスチレンを用い、ポリスチレン換算値として数平均分子量を測定した。

2. Analysis method (1) Number average molecular weight measurement Using a high-speed GPC device (trade name H8020GPC, manufactured by Tosoh Corporation), measurement was performed under the following conditions. That is, a polymer and a petroleum resin are dissolved in tetrahydrofuran, and the solution concentration of the resin is adjusted to 50 g / l. (Product name) The product was injected into the GPC apparatus provided with one, and polystyrene was used as a standard sample, and the number average molecular weight was measured as a polystyrene conversion value.

(2) Softening point measurement It measured by the ring and ball method according to JIS K-2207 (1991).

(3) Cloud point measurement The petroleum resin 20g, EVA 20g, and wax 10g were mixed and dissolved, and measured according to the JIS K-2269 petroleum product cloud point test method. It shows that the compatibility of petroleum resin and EVA is so high that a cloud point is low.

(4) Hexane tolerance measurement Petroleum resin was dissolved in soybean white squeezed oil to prepare a 50 wt% solution. This solution was titrated with n-hexane to obtain a titration amount for starting cloudiness, which was defined as hexane tolerance, and was used as an index of solubility of petroleum resin in soybean white oil. The higher the hexane tolerance, the higher the solubility in white soybean oil.

Example 1
400 g of fraction A and 4 g of boron trifluoride-phenol complex were placed in a 1 l autoclave, sealed, and reacted at 80 ° C. for 30 minutes. After completion of the reaction, the autoclave was cooled, and unreacted components were removed by distillation to obtain 70 g of an oily product. As a result of analyzing the oily product with a high-speed GPC apparatus, the number average molecular weight of the obtained multimer was 570.

  440 g of fraction B and 60 g of the above multimer mixture were placed in a three-necked flask and stirred at 60 ° C. 3.75 g of boron trifluoride-phenol complex was added dropwise over 1 hour with stirring, and stirring was continued for another hour. After completion of the reaction, 250 g of a 1 wt% aqueous sodium hydroxide solution and 250 g of xylene were added to deactivate the polymerization catalyst, and then the aqueous layer was separated to remove the polymerization catalyst. The oil layer was heated at 220 ° C. for 30 minutes, and unreacted components were distilled to obtain 268.0 g of resin. As shown in Table 3, the evaluation of the obtained resin was a number average molecular weight of 830, a softening point of 108 ° C., a cloud point of 187 ° C., and a hexane tolerance of 33 ml.

Comparative Example 1
500 g of fraction B was placed in a three-necked flask and stirred at 60 ° C. 3.75 g of boron trifluoride-phenol complex was added dropwise over 1 hour with stirring, and stirring was continued for another hour. The operation after polymerization was in accordance with Example 1. 272.7 g of a resin having a number average molecular weight of 880 and a softening point of 127 ° C. was obtained. The cloud point of this resin was already cloudy at 220 ° C., and its compatibility with EVA was poor. Moreover, the hexane tolerance was 14 ml, and the solubility in a solvent was inferior.

Claims (11)

5 to 50 parts by weight of a multimer obtained by reacting a chain diene having 4 to 5 carbon atoms and a cyclic diene having 5 to 6 carbon atoms in the presence of an acid catalyst, and vinyl aromatic hydrocarbon 95 having 8 to 10 carbon atoms A method for producing a petroleum resin, comprising polymerizing ˜50 parts by weight. The acid catalyst for producing a multimer by reacting a chain diene having 4 to 5 carbon atoms and a cyclic diene having 5 to 6 carbon atoms in the presence of an acid catalyst is a Friedel-Crafts type catalyst. The method for producing a petroleum resin according to claim 1. The method for producing a petroleum resin according to claim 1 or 2, wherein a reaction temperature for producing a multimer is -30 to 150 ° C. 5 to 50 parts by weight of a multimer obtained by reacting a chain diene having 4 to 5 carbon atoms and a cyclic diene having 5 to 6 carbon atoms in the presence of an acid catalyst, and a vinyl aromatic hydrocarbon 95 having 8 to 10 carbon atoms A method for producing a petroleum resin, comprising mixing 50 parts by weight and an organic solvent and polymerizing in the presence of a Friedel-Crafts catalyst. 5. The petroleum resin according to claim 1, wherein the chain diene having 4 to 5 carbon atoms is butadiene, isoprene, trans-1,3-pentadiene and / or cis-1,3-pentadiene. Production method. The method for producing a petroleum resin according to claim 1, wherein the cyclic diene having 5 to 6 carbon atoms is cyclopentadiene and / or methylcyclopentadiene. Among pyrolysis oils obtained by pyrolysis of petroleum fractions, the boiling point is contained in the fraction having a boiling point of 110 ° C. or less as a chain diene having 4 to 5 carbon atoms and / or a cyclic diene having 5 to 6 carbon atoms. Diene is used, The manufacturing method of the petroleum resin of Claims 1-4 characterized by the above-mentioned. 8. The petroleum according to claim 1, wherein the vinyl aromatic hydrocarbon having 8 to 10 carbon atoms is styrene, α-methylstyrene, β-methylstyrene, vinyltoluene, indene and / or methylindene. Manufacturing method of resin. The petroleum aromatic hydrocarbon according to any one of claims 1 to 7, wherein a vinyl aromatic hydrocarbon contained in a fraction having a boiling point in a range of 140 to 280 ° C is used among pyrolysis oil obtained by pyrolysis of a petroleum fraction. Manufacturing method of resin. 10. The dicyclopentadiene fraction contained in a fraction having a boiling point in the range of 140 to 280 ° C. among pyrolysis oils obtained by pyrolysis of petroleum fractions is 5% by weight or less. The manufacturing method of the petroleum resin as described. The method for producing a petroleum resin according to claim 1, wherein the petroleum resin satisfies the following (a) to (c).
(A) Softening point measured according to JIS K-2207 is 90 to 140 ° C.
(B) Cloud point is 190 ° C or less (c) Hexane tolerance is 20ml or more