JP2011127006A - Aromatic-alicyclic copolymerized petroleum resin composition and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aromatic-alicyclic copolymerized petroleum resin composition having excellent long-time storage stability for 1 month or longer, especially the aromatic-alicyclic copolymerized petroleum resin composition free from formation of a gelatinous substance during storage and causing little variation of physical properties of the resin with time, and a method for producing the resin composition. <P>SOLUTION: There are provided the aromatic-alicyclic copolymerized petroleum resin composition containing 0.05-2 pts.wt. of a hindered amine compound based on 100 pts.wt. of an aromatic-alicyclic copolymerized petroleum resin having an olefinic double bond hydrogen areal ratio of ≤13% in proton NMR spectrum, and a method for producing the petroleum resin composition. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an aromatic-alicyclic copolymer petroleum resin composition excellent in storage stability in which no gel is generated even during polymerization or long-term storage for 1 month or more, and a method for producing the same.

  A method for producing a petroleum resin by polymerizing in the presence of a Friedel-Crafts catalyst using an unsaturated hydrocarbon-containing fraction obtained in the cracking and refining of petroleum as a raw material is well known. There are two types of hydrocarbon-containing fractions: a C5 fraction having a boiling range of 20 to 110 ° C. and a C9 fraction having a boiling range of 140 to 280 ° C. An aliphatic petroleum resin obtained from the C5 fraction, C9 fraction And an aliphatic / aromatic copolymer petroleum resin obtained by copolymerizing a C5 fraction and a C9 fraction. An alicyclic petroleum resin obtained by thermally polymerizing dicyclopentadiene is also known.

  Dicyclopentadiene such as dicyclopentadiene, methyldicyclopentadiene, dimethyldicyclopentadiene, etc., which is the raw material for this alicyclic petroleum resin, has an unsaturated bond in the resin when polymerized in the presence of Friedel-Crafts type catalyst. In a large amount, the hue of the resin deteriorates and gel formation occurs, resulting in a problem of deterioration in quality. For this reason, aliphatic petroleum resins, aromatic petroleum resins and aliphatic aromatic copolymer petroleum resins are generally produced from fractions obtained by removing dicyclopentadiene by distillation or the like.

  On the other hand, a method for producing a petroleum resin by polymerizing in the presence of a Friedel-Crafts catalyst using dicyclopentadiene as a raw material has been studied. A method has been proposed in which a cationically polymerizable aromatic hydrocarbon-containing fraction (C9 fraction) and dicyclopentadiene are polymerized in the presence of a Friedel-Crafts-type catalyst (see, for example, Patent Document 1). However, Patent Document 1 does not describe the addition of a hindered amine compound and the storage stability at which no gel is generated even after long-term storage of the resulting petroleum resin for 1 month or longer. Furthermore, the petroleum resin obtained in Patent Document 1 was poor in practicality because a gel was generated during storage in our study. In addition, a method of producing a petroleum resin using boron trifluoride (gas) as a Friedel-Crafts type catalyst and methanol as a cocatalyst is known (for example, see Patent Document 2). However, Patent Document 2 does not describe storage stability in which no gel is generated even when the obtained petroleum resin is stored for a long period of one month or longer. Further, boron trifluoride (gas) used in Patent Document 2 reacts with various inorganic compounds and organic compounds to easily form complex compounds, and generates intense white smoke in the air and is also a poison. Special attention is required.

  On the other hand, a method for improving the thermal stability and weather resistance by blending a hindered amine compound with petroleum resin has already been proposed (see, for example, Patent Document 3). However, this is only an effect on aliphatic petroleum resins, aromatic petroleum resins, and aliphatic aromatic copolymer petroleum resins, and alicyclic petroleum resins using dicyclopentadiene as a raw material are not described at all.

  Further, a phenol-modified aromatic petroleum resin composition to which a hindered amine compound is added (for example, see Patent Document 4) and an aliphatic-aromatic copolymer petroleum resin (for example, see Patent Document 5) have already been proposed. However, an aromatic-alicyclic petroleum resin composed of a C9 fraction and dicyclopentadiene has not been reported.

  A hydrocarbon resin to which a hindered amine compound is added has been proposed (see, for example, Patent Documents 6 to 8). However, no aromatic-alicyclic petroleum resin composed of a C9 fraction and dicyclopentadiene has been reported as a hydrocarbon resin. Further, there is no description or suggestion that the effect is excellent in storage stability in which gel does not occur even after long-term storage for 1 month or longer.

Japanese Patent Publication No.55-023286 (first page) JP 56-106912 A (first page) Japanese Patent Publication No. 3-35335 (first page) JP 2005-187735 A (first page) Japanese Patent Laying-Open No. 2006-028285 (first page) JP 2001-152115 A JP 2003-213073 A JP 2006-274191 A

  An object of the present invention is to provide an aromatic-alicyclic copolymerized petroleum resin composition that is excellent in storage stability and is advantageous in terms of cost, with no gel formation even during polymerization and long-term storage for one month or longer, and a method for producing the same Is intended to provide.

  As a result of intensive studies to solve the above problems, the present inventors have found that a hindered amine compound is added to an aromatic-alicyclic copolymer petroleum resin having an olefinic double bond hydrogen area ratio of a specific value or less. By containing a specific amount, an aromatic-alicyclic copolymer petroleum that is excellent in storage stability in which no gel-like substance is produced during storage and the change in physical properties is small, and no gel is generated even after long-term storage for 1 month or longer. The present inventors have found a resin composition and have completed the present invention.

  That is, the present invention is a proton NMR spectrum, and hindered amine compound 0.05-2 weight with respect to 100 weight part of aromatic-alicyclic copolymer petroleum resin whose olefinic double bond hydrogen area ratio is 13% or less. It is related with the aromatic-alicyclic copolymerization petroleum resin composition characterized by containing a part, and its manufacturing method.

  The aromatic-alicyclic copolymer petroleum resin in the present invention has a spectrum observed when proton NMR is measured, and the olefinic double bond hydrogen area ratio observed at 4.5 to 6.0 ppm is 13%. It is the following, Preferably it is 4 to 13%. When the area ratio of the olefinic double bond hydrogen exceeds 13%, the aromatic-alicyclic copolymer petroleum resin already generates a gel substance immediately after production.

  The raw material oil for obtaining the aromatic-alicyclic copolymer petroleum resin in the present invention is not particularly limited, and is obtained by pyrolysis of petroleum, C9 fraction having a boiling range of 140 to 280 ° C., and dicyclopentadiene. It is preferable to use a mixture of these as a raw material oil.

  The component constituting the C9 fraction is not particularly limited. For example, styrene, an alkyl derivative thereof such as α-methylstyrene, β-methylstyrene, vinyltoluene, indene, and an alkyl derivative thereof having 8 to 10 carbon atoms. Vinyl aromatic hydrocarbons; cyclic unsaturated hydrocarbons represented by dicyclopentadiene and derivatives thereof; other olefins having 10 or more carbon atoms, saturated aromatics having 9 or more carbon atoms, and the like.

  Examples of the dicyclopentadiene include dicyclopentadiene derivatives such as dicyclopentadiene, methyldicyclopentadiene, and dimethyldicyclopentadiene.

  In the present invention, when a mixture composed of C9 fraction and dicyclopentadiene is used as a raw material oil for aromatic-alicyclic copolymer petroleum resin, the mixing ratio of C9 fraction and dicyclopentadiene depends on the aromatic Since the aromatic-alicyclic copolymer petroleum resin composition has an excellent softening point and hue, it is preferably 10 to 90% by weight of C9 fraction, 90 to 10% by weight of dicyclopentadiene, and more preferably C9 fraction. It is 10 to 80% by weight and 90 to 20% by weight of dicyclopentadiene.

  The method for producing the aromatic-alicyclic copolymer petroleum resin in the present invention is not particularly limited, and can be produced, for example, by adding a catalyst to a mixture of C9 fraction and dicyclopentadiene and heating to polymerize. As the catalyst used for the polymerization, a Friedel-Crafts type catalyst can be generally used, and examples thereof include aluminum trichloride, aluminum tribromide, boron trifluoride or a phenol complex thereof, butanol complex and the like. Among them, a phenol complex of boron trifluoride and a butanol complex of boron trifluoride are preferable. The polymerization temperature is preferably from 0 to 100 ° C, particularly preferably from 0 to 80 ° C. The amount of the catalyst and the polymerization time are, for example, 0.1 to 2.0 parts by weight of the catalyst with respect to 100 parts by weight of the mixture (raw material oil) composed of the C9 fraction and dicyclopentadiene for 0.1 to 10 hours. A range is preferred. The reaction pressure is preferably atmospheric pressure to 1 MPa.

  The aromatic-alicyclic copolymer petroleum resin in the present invention preferably has a weight average molecular weight (Mw) of 500 to 5,000 from the viewpoint of processability.

  The hindered amine compound used in the present invention is not particularly limited as long as it is a compound belonging to the category referred to as a hindered amine compound. Among them, an aromatic having excellent storage stability in which no gel is generated even during long-term storage of 1 month or more. -Since an alicyclic copolymer petroleum resin composition is obtained, it is preferable that it is a compound which has a 2,2,6,6-tetraalkyl-4-piperidyl group shown to the following general formula.

ここで、一般式中のＲ１〜Ｒ４は互いに同一であっても相違していても良く炭素数１〜４のアルキル基であり、Ｒ５は水素又は置換基を持っていても良い炭素数１〜８のアルキル基もしくはアルコキシ基である。Ｒ１〜Ｒ４における炭素数１〜４のアルキル基としては、例えばメチル基、エチル基、プロピル基、ブチル基等が挙げられ、その中でもメチル基が好ましい。Ｒ５の置換基を持っていても良い炭素数１〜８のアルキル基としては、例えばメチル基、オクチル基等が挙げられ、置換基を持っていても良い炭素数１〜８のアルコキシ基としては、例えばメトキシ基、オクトキシ基等が挙げられる。これらの中でもＲ５としては、水素、メチル基、オクチル基等が好ましく、特に好ましくは水素、メチル基である。

Here, R1 to R4 in the general formula may be the same or different from each other and may be an alkyl group having 1 to 4 carbon atoms, and R5 may be hydrogen or a substituent having 1 to 1 carbon atoms. 8 is an alkyl group or an alkoxy group. As a C1-C4 alkyl group in R1-R4, a methyl group, an ethyl group, a propyl group, a butyl group etc. are mentioned, for example, Among these, a methyl group is preferable. As a C1-C8 alkyl group which may have a substituent of R5, a methyl group, an octyl group etc. are mentioned, for example, As a C1-C8 alkoxy group which may have a substituent, Examples thereof include a methoxy group and an octoxy group. Among these, as R5, hydrogen, a methyl group, an octyl group, etc. are preferable, Especially preferably, they are hydrogen and a methyl group.

  Examples of the compound having a 2,2,6,6-tetraalkyl-4-piperidyl group represented by a specific general formula include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, Tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) amino -1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4 -Piperidy ) Imino}] and the like, among which bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, Tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) amino -1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4 -Piperidyl) imino}] and the like.

  A compound having a 2,2,6,6-tetraalkyl-4-piperidyl group represented by the general formula is known to have a molecular weight of 400 to 4,000, and Ciba Japan is used as a hindered amine light stabilizer (HALS). These are commercially available from Co., Ltd. and ADEKA Co., Ltd., and these commercial products can also be used in the present invention.

  The aromatic-alicyclic copolymer petroleum resin composition of the present invention is 0.05-2 parts by weight of a hindered amine compound, preferably 0.1 parts per 100 parts by weight of the aromatic-alicyclic copolymer petroleum resin. -1.0 weight part is contained. When the content of the hindered amine compound is less than 0.05 parts by weight, the long-term storage stability of the obtained aromatic-alicyclic copolymer petroleum resin composition for 1 month or more is inferior.

  In the method for producing an aromatic-alicyclic copolymer petroleum resin composition of the present invention, 0.05-2 parts by weight of a hindered amine compound is blended with 100 parts by weight of an aromatic-alicyclic copolymer petroleum resin. Any method can be used if it is possible. Usually, an aromatic-alicyclic copolymer petroleum resin is easily oxidized to form a peroxide even at room temperature, and when the aromatic-alicyclic copolymer petroleum resin stored for a long period of one month or longer is heated and melted, The formed peroxide is decomposed, and it becomes easy to generate a gel-like substance, and to change the physical properties of the resin such as softening point and hue over time. Therefore, in order to obtain an aromatic-alicyclic copolymer petroleum resin composition that is more excellent in long-term storage stability for 1 month or more, a solvent coexisting after completion of the polymerization reaction of the aromatic-alicyclic copolymer petroleum resin, A method of blending a melted hindered amine compound with an aromatic-alicyclic copolymer petroleum resin in a molten state immediately after distilling off the low molecular weight compound is preferred. Furthermore, since the oxidation of molten aromatic-alicyclic copolymer petroleum resin, particularly oxidation by oxygen, can be prevented, the oxygen concentration in the blender at the time of blending is preferably 1000 ppm or less, more preferably 100 ppm or less, Especially preferably, it is 10 ppm or less.

  The aromatic-alicyclic copolymer petroleum resin composition in the present invention preferably has a softening point of 80 to 160 ° C., particularly preferably 90 to 150 ° C., and a hue of 13 or less, particularly preferably 12 or less.

  In addition, the aromatic-alicyclic copolymer petroleum resin composition of the present invention, as long as it does not deviate from the object of the present invention, usually includes, for example, phenolic antioxidants, phosphorus, and the like as additives added to the resin composition. -Based antioxidants, sulfur-based antioxidants, lactone-based antioxidants, ultraviolet absorbers, pigments, calcium carbonate, glass beads, and the like may be blended.

  As described above, the aromatic-alicyclic copolymer petroleum resin composition of the present invention is excellent in long-term storage stability of 1 month or more, particularly without formation of a gel-like substance during storage, Since the change is small, it can be suitably used for applications such as hot melt adhesives, pressure sensitive adhesives, pressure-sensitive adhesive tapes, floor adhesives, tires, printing inks, and asphalt.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention does not receive a restriction | limiting at all by these Examples. In addition, the analysis of the raw material oil used in the Example and the comparative example, polymerization preparation amount and CPD content rate, an additive, and the obtained composition and a test method are as follows.

1. Raw material (1) C9 fraction, composition of dicyclopentadiene: Table 1, Table 2
(2) Additive:
Hindered amine compound: Adekastab light stabilizer LA-77 (manufactured by ADEKA Corporation, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate), Adekastab light stabilizer LA-52 (manufactured by ADEKA Corporation) , Tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate), CHIMASSORB 944FDL (Ciba Japan Co., Ltd., poly [{6- ( 1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene { (2,2,6,6-tetramethyl-4-piperidyl) imino}])
Phenol antioxidant: IRGANOX1010 (Ciba Japan Co., Ltd.)
(3) Type of raw material oil and polymerization charge, CPD content, type and amount of additive: Table 3

２．分析方法
（１）原料油の各成分の含有量：ＪＩＳ Ｋ−０１１４（２０００年）に準拠してガスクロマトグラフ法を用いて分析した。
（２）重量平均分子量（Ｍｗ）：ポリスチレンを標準物質とし、ＪＩＳ Ｋ−０１２４（１９９４年）に準拠してゲル浸透クロマトグラフィーにより測定した。
（３）オレフィン性二重結合水素面積比率：芳香族−脂環族共重合石油樹脂をクロロホルム−ｄ（和光純薬工業（株）製）に溶解させ、ＮＭＲ（核磁気共鳴スペクトル）測定装置（型番ＧＳＸ２７０、日本電子（株）製）により測定した。得られたスペクトルについて下記の計算式に基づき面積比率を求めた。

2. Analysis method (1) Content of each component of feedstock: Analysis was performed using a gas chromatograph method in accordance with JIS K-0114 (2000).
(2) Weight average molecular weight (Mw): Measured by gel permeation chromatography according to JIS K-0124 (1994) using polystyrene as a standard substance.
(3) Olefinic double bond hydrogen area ratio: Aromatic-alicyclic copolymer petroleum resin is dissolved in chloroform-d (manufactured by Wako Pure Chemical Industries, Ltd.) and NMR (nuclear magnetic resonance spectrum) measuring device ( Model No. GSX270, manufactured by JEOL Ltd.). About the obtained spectrum, the area ratio was calculated | required based on the following formula.

Olefinic double bond hydrogen area ratio (%) = (olefinic double bond hydrogen peak area) / (total of all peak areas) × 100
Olefinic double bond hydrogen peak: 4.5-6.0 ppm
(4) Softening point: Measured by a method based on JIS K-2531 (1960) (ring and ball method).
(5) Hue: Measured according to ASTM D-1544-63T as a 50 wt% toluene solution.

3. Storage stability test method (1) Measurement of change with time 10 g of aromatic-alicyclic copolymer petroleum resin composition is put in an aging tester at 50 ° C., and samples are sampled at the initial stage and every two weeks thereafter, insoluble in toluene. Judgment of gel-like substance formation by a substance (gel-form substance formation time-dependent change), and changes over time in the physical properties of the softening point, hue, and molecular weight (physical-characteristic change over time) were measured.
(2) Determination of gel-like substance generation After 5 g of sample is dissolved in 5 g of toluene, it is transferred to a flat petri dish, and if an unmelted material can be visually confirmed on the petri dish, it is regarded as generation of a gel-like substance. .

Example 1
A glass autoclave having an internal volume of 2 liters was charged with 150 g of a C9 fraction having the composition A shown in Table 1 obtained by decomposition of naphtha as a raw oil and 350 g of a dicyclopentadiene (DCPD) fraction having the composition shown in Table 2. (C9 fraction / dicyclopentadiene = 30/70 (% by weight)). Next, after cooling to 40 ° C. in a nitrogen atmosphere, boron trifluoride butanol complex (Stella Chemifa Co., Ltd., boron trifluoride butanol) was used as a Friedel-Crafts type catalyst from a mixture of C9 fraction and dicyclopentadiene. 1.0 part by weight was added to 100 parts by weight of the raw material oil to be polymerized for 2 hours. Thereafter, the catalyst was removed with an aqueous caustic soda solution, and the unreacted oil in the oil phase was distilled to obtain an aromatic-alicyclic copolymer petroleum resin. As a result of measuring proton NMR of the copolymerized petroleum resin, the olefinic double bond hydrogen area ratio was 8%.

  Furthermore, 0.2 parts by weight of a hindered amine compound (manufactured by ADEKA, trade name Adeka Stab Light Stabilizer LA-77) was added at 100 ° C. to 100 parts by weight of the copolymer petroleum resin under a nitrogen stream having an oxygen concentration of 2 ppm. The mixture was blended under a stirring speed of 300 rpm to obtain an aromatic-alicyclic copolymer petroleum resin composition.

  Table 4 shows the measurement results of the storage stability (softening point, hue, weight average molecular weight (Mw), gel-like substance) of the obtained aromatic-alicyclic copolymer petroleum resin composition. The copolymerized petroleum resin composition did not produce a gel-like substance over time and had good long-term storage stability of 1 month or more.

Examples 2-5
An aromatic-alicyclic copolymer petroleum resin composition was obtained in the same manner as in Example 1 except that the amount of hindered amine compound added was as shown in Table 3.

  Table 4 shows the measurement results of the storage stability (softening point, hue, weight average molecular weight (Mw), gel-like substance) of the obtained aromatic-alicyclic copolymer petroleum resin composition. The copolymerized petroleum resin composition did not produce a gel-like substance over time and had good long-term storage stability of 1 month or more.

Examples 6, 7, and 8
Table 3 shows the polymerization temperature, the C9 fraction, and the amount of dicyclopentadiene charged with 1.0 part by weight of boron trifluoride phenol complex (Stella Chemifa Co., Ltd.) as a Friedel-Crafts catalyst. An aromatic-alicyclic copolymerized petroleum resin composition was obtained in the same manner as in Example 1 except for the above.

  Table 4 shows the measurement results of the storage stability (softening point, hue, weight average molecular weight (Mw), gel-like substance) of the obtained aromatic-alicyclic copolymer petroleum resin composition. The copolymerized petroleum resin composition did not produce a gel-like substance over time and had good long-term storage stability of 1 month or more.

Example 9
Change the hindered amine compound to tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate (Adekastab light stabilizer LA-52 (manufactured by ADEKA). Then, the charged amount was as shown in Table 3, and an aromatic-alicyclic copolymer petroleum resin composition was obtained in the same manner as in Example 1.

  Table 4 shows the measurement results of the storage stability (softening point, hue, weight average molecular weight (Mw), gel-like substance) of the obtained aromatic-alicyclic copolymer petroleum resin composition. The copolymerized petroleum resin composition did not produce a gel-like substance over time and had good long-term storage stability of 1 month or more.

Example 10
The hindered amine compound is converted into poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl- 4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] (CibaSSORB 944FDL, manufactured by Ciba Japan Co., Ltd.), and the amount charged is as shown in Table 3 In the same manner as in Example 1, an aromatic-alicyclic copolymer petroleum resin composition was obtained.

  Table 4 shows the measurement results of the storage stability (softening point, hue, weight average molecular weight (Mw), gel-like substance) of the obtained aromatic-alicyclic copolymer petroleum resin composition. The copolymerized petroleum resin composition did not produce a gel-like substance over time and had good long-term storage stability of 1 month or more.

比較例１
実施例１で得た芳香族−脂環族共重合石油樹脂にヒンダードアミン化合物を添加しないで、芳香族−脂環族共重合石油樹脂の貯蔵安定性を測定した。測定結果（軟化点、色相、重量平均分子量（Ｍｗ）、ゲル状物質）を表５に示した。該共重合石油樹脂は、ヒンダードアミン化合物を用いなかったことから初期にはゲルが発生しなかったが２週間後にはゲルが発生し、１ケ月以上の長期貯蔵安定性が不良であった。

Comparative Example 1
The storage stability of the aromatic-alicyclic copolymer petroleum resin was measured without adding a hindered amine compound to the aromatic-alicyclic copolymer petroleum resin obtained in Example 1. The measurement results (softening point, hue, weight average molecular weight (Mw), gel substance) are shown in Table 5. The copolymerized petroleum resin did not use a hindered amine compound, so that no gel was generated at the beginning. However, the gel was generated after 2 weeks, and the long-term storage stability for one month or more was poor.

Comparative Example 2
Aromatic-alicyclic ring in the same manner as described in Example 1 except that 0.2 part by weight of a phenolic antioxidant (Ciba Japan Co., Ltd., IRGANOX 1010) was blended instead of the hindered amine compound as an additive. A group-copolymerized petroleum resin composition was obtained.

  The storage stability measurement results (softening point, hue, weight average molecular weight (Mw), gel-like substance) of the obtained aromatic-alicyclic copolymer petroleum resin composition are shown in Table 5. The copolymer petroleum resin composition did not use a hindered amine compound but only a phenolic antioxidant, so that no gel was generated at the beginning, but a gel was generated after 4 weeks and stored for a long period of 1 month or longer. Stability was poor.

Comparative Example 3
A petroleum resin composition was obtained in the same manner as in Example 6 except that the composition and amount of the C9 fraction used as the raw material oil were as shown in Table 3. The olefinic double bond hydrogen area ratio of the petroleum resin was 15%.

  Table 5 shows the measurement results (softening point, hue, weight average molecular weight (Mw), gel substance) of the obtained petroleum resin composition. Since the copolymerized petroleum resin did not use a C9 fraction as a raw material, the formation of a gel-like substance was confirmed immediately after production, and the long-term storage stability for one month or more was poor.

Claims (3)

  The proton NMR spectrum contains 0.05 to 2 parts by weight of a hindered amine compound with respect to 100 parts by weight of an aromatic-alicyclic copolymer petroleum resin having an olefinic double bond hydrogen area ratio of 13% or less. A characteristic aromatic-alicyclic copolymer petroleum resin composition.   A mixture of an aromatic-alicyclic copolymer petroleum resin comprising 10 to 90% by weight of a C9 fraction having a boiling point range of 20 to 110 ° C. and 90 to 10% by weight of dicyclopentadiene obtained by thermal decomposition of petroleum. The aromatic-alicyclic copolymer petroleum resin composition according to claim 1, wherein the composition is used as a raw material.   The method for producing an aromatic-alicyclic copolymer petroleum resin composition according to claim 1 or 2, wherein the oxygen concentration in the blender when blending the hindered amine compound is 1000 ppm or less.