JP2006028285A - Aliphatic-aromatic copolymerized petroleum resin composition with good storage stability and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an aliphatic-aromatic copolymerized petroleum resin composition with good storage stability, particularly forming no gel-like matter during storage and slight in the change in resin physical properties with time, and to provide a method for producing the composition. <P>SOLUTION: The aliphatic-aromatic copolymerized petroleum resin composition is obtained by the following process: Using as feedstock oil a mixture of a fraction 20-110°C in boiling point and a fraction 140-280°C in boiling point in petroleum pyrolysis, an aliphatic-aromatic copolymerized petroleum resin ≤11% in the olefinic double bond hydrogen area ratio of its proton NMR spectrum is obtained and then compounded with a hindered amine compound in a compounding vessel with a specific oxygen concentration. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an aliphatic-aromatic copolymer petroleum resin composition having excellent storage stability and a method for producing the same.

  A method of producing a petroleum resin by polymerizing in the presence of a Friedel-Crafts catalyst using a hydrocarbon-containing fraction obtained during cracking and refining of petroleum as a raw material oil is well known. As such hydrocarbon-containing fractions, there are two types of C5 fraction having a boiling range of 20 to 110 ° C. and C9 fraction having a boiling range of 140 to 280 ° C. The petroleum resin obtained from these fractions depends on the raw material oil used. , An aliphatic petroleum resin obtained from the C5 fraction, an aromatic petroleum resin obtained from the C9 fraction, and an aliphatic-aromatic copolymer petroleum resin obtained by copolymerizing the C5 fraction and the C9 fraction. The

  In this C5 fraction, conjugated cyclic diolefins such as cyclopentadiene and methylcyclopentadiene are present, and these deteriorate the hue of the resin and promote the formation of gel. The deterioration of quality such as generation of gel-like substances and changes in resin properties with time has become a problem. Therefore, in general, an aliphatic-aromatic copolymer petroleum resin is produced using a fraction obtained by dimerizing, distilling, or the like removing a conjugated cyclic diolefin that adversely affects the physical properties of these petroleum resins (for example, Non-Patent Document 1). Further, as a method for removing conjugated cyclic diolefin, α-unsaturated carboxylic acid, α, β-unsaturated carboxylic acid represented by maleic anhydride, maleic acid ester, etc., utilizing the high reactivity of cyclopentadiene Alternatively, a method of adding a derivative thereof to cyclopentadiene and removing it by a chemical reaction is also known (for example, see Patent Document 1). However, the above-described method for producing a petroleum resin by removing the conjugated cyclic diolefin is not economically preferable because the yield and productivity of the obtained petroleum resin are reduced corresponding to the amount of conjugated cyclic diolefin removed. Further, the removal of the conjugated cyclic diolefin is not preferable from the viewpoint of the performance of the obtained petroleum resin because the softening point of the petroleum resin is lowered and the blocking tends to occur.

  Therefore, a method for producing a petroleum resin by polymerizing a conjugated cyclic diolefin such as cyclopentadiene or methylcyclopentadiene in the raw material oil is being studied. Since the cause of gelation and aging of petroleum resins is the oxidation of chemical structural sites such as conjugated double bonds and tertiary carbon present in the resin, many studies have been made on the addition of antioxidants. In addition, an effect has been found with a phenol-based antioxidant having a radical scavenging action and a phosphorus-based or sulfur-based antioxidant having a peroxide decomposing action (see, for example, Non-Patent Document 2). However, it is not always economical because a large amount of addition is necessary to exert the desired effect of the antioxidant, and when a plurality of antioxidants are added, a pre-blend is required.

  On the other hand, a method for improving the heat stability by blending a hindered amine compound with petroleum resin has been proposed (Patent Document 2). However, although there is a stability effect against heating at a high temperature for a short time, for example, 220 ° C. for several hours, the storage stability of the petroleum resin at a low temperature for a long time, for example, 50 ° C. or less, for several weeks to several months Not proposed at all.

Chemical Economy, March 1976 (page 69) Adhesion Technology 2000 Vol. 20 No. 2 (Page 27) Japanese Examined Patent Publication No. 43-21737 (first page) Japanese Patent Publication No. 3-35335 (first page)

  An object of the present invention is to provide an aliphatic-aromatic copolymer petroleum resin composition having excellent storage stability, in particular, a fat that does not produce a gel-like substance during storage, has little change in physical properties of the resin, and is advantageous in terms of cost. It is an object of the present invention to provide a group-aromatic copolymer petroleum resin composition and a method for producing the same.

  As a result of intensive studies to solve the above problems, the present inventors have blended a specific amount of a hindered amine compound with an aliphatic-aromatic copolymer petroleum resin having an olefinic double bond hydrogen area ratio of a specific value or less. Thus, an aliphatic-aromatic copolymer petroleum resin composition excellent in storage stability, in which no gel-like substance is produced during storage and the change in physical properties with time is small, has been found and the present invention has been completed.

  That is, in the present invention, 0.01 to 2% by weight of a hindered amine compound is blended with an aliphatic-aromatic copolymer petroleum resin having a proton NMR spectrum and an olefinic double bond hydrogen area ratio of 11% or less. The present invention relates to an aliphatic-aromatic copolymer petroleum resin composition and a method for producing the same.

  The aliphatic-aromatic copolymer petroleum resin in the present invention has a spectrum observed when proton NMR is measured, and the area ratio of olefinic double bond hydrogen observed at 4.5 to 6.0 ppm is 11%. It is as follows. If the area ratio of the olefinic double bond hydrogen exceeds 11%, the aliphatic-aromatic copolymer petroleum resin already generates a gel-like substance immediately after production.

  The aliphatic-aromatic copolymer petroleum resin composition of the present invention is 0.01 to 2% by weight, preferably 0.03 to 1.0% by weight, of the hindered amine compound, based on the aliphatic-aromatic copolymer petroleum resin. %. When the amount of the hindered amine compound is less than 0.01% by weight, the resulting aliphatic-aromatic copolymer petroleum resin composition has poor storage stability, and when it exceeds 2% by weight, the storage stability is improved. Is not seen.

  The raw material oil for obtaining the aliphatic-aromatic copolymer petroleum resin in the present invention is not particularly limited, but a fraction having a boiling range of 20 to 110 ° C. obtained by pyrolysis of petroleum (hereinafter referred to as “C5 fraction”). And a mixture consisting of a fraction having a boiling range of 140 to 280 ° C. (hereinafter referred to as “C9 fraction”) is preferably used as the feedstock oil.

  There is no limitation in particular in the component which comprises the C5 fraction which concerns. Representative examples of the constituent components include conjugated diolefinic unsaturated hydrocarbons having 4 to 6 carbon atoms, such as isoprene, trans-1,3-pentadiene, cis-1,3-pentadiene, cyclopentadiene, and methylcyclopentadiene. C 4-6 monoolefinically unsaturated hydrocarbons represented by butene, 2-methyl-1-butene, 2-methyl-2-butene, 1-pentene, 2-pentene, cyclopentene and the like; Examples thereof include aliphatic saturated hydrocarbons such as pentane, 2-methylpentane, 3-methylpentane, and n-hexane.

  Moreover, there is no limitation in particular in the component which comprises the C9 fraction which concerns. As typical examples of the constituent components, styrene, vinyl aromatic hydrocarbons having 8 to 10 carbon atoms typified by α-methylstyrene or β-methylstyrene, vinyltoluene, indene, and alkyl derivatives thereof, which are alkyl derivatives thereof; Examples thereof include cyclic unsaturated hydrocarbons typified by dicyclopentadiene and derivatives thereof; other olefins having 10 or more carbon atoms, saturated aromatics having 9 or more carbon atoms, and the like.

  In addition, when using the mixture which consists of a C5 fraction and a C9 fraction in this invention as a raw material oil of an aliphatic-aromatic copolymer petroleum resin, the mixing ratio of a C5 fraction and a C9 fraction is not specifically limited. In such a mixing ratio, if the C5 fraction is 30% by weight or more, the resulting aliphatic-aromatic copolymer petroleum resin is satisfactory in its hue and tackiness, and if it is 90% by weight or less. Considering that the softening point is satisfactory, the mixing ratio is preferably 70 to 10% by weight of C9 fraction, more preferably 50 to 90% of C5 fraction with respect to 30 to 90% by weight of C5 fraction. The C9 fraction is 50 to 10 wt% with respect to wt%.

Furthermore, when a mixture of C5 fraction and C9 fraction is used as a raw material oil, it is preferable to use a raw material oil having a CPD content defined by the following general formula (1) of 20% by weight or less. It is preferable for obtaining an aliphatic-aromatic copolymer petroleum resin having a heavy bond hydrogen area ratio.
CPD content (% by weight) = (weight of cyclopentadiene + weight of methylcyclopentadiene) / (weight of hydrocarbon component having double bond in raw material oil) × 100 (1)
Here, the hydrocarbon component having a double bond in the feedstock is not particularly limited, but representative examples include conjugated diolefinically unsaturated hydrocarbons and monoolefinic hydrocarbons in the aforementioned C5 fraction. Examples thereof include saturated hydrocarbons, vinyl aromatic hydrocarbons in C9 fraction, cyclic unsaturated hydrocarbons, and olefins having 10 or more carbon atoms.

  Although there is no restriction | limiting in particular about the other physical property of the aliphatic-aromatic copolymer petroleum resin in this invention, A softening point is 60-140 degreeC and a weight average molecular weight (Mw) from the surface of the workability of this petroleum resin composition. Is preferably 500 to 5,000.

There is no restriction | limiting in particular in the manufacturing method of the aliphatic-aromatic copolymer petroleum resin in this invention. For example, it can be produced by adding a catalyst to a mixture of C5 fraction and C9 fraction, heating and polymerizing. As the catalyst used for the polymerization, a Friedel-Crafts type catalyst can be generally used. For example, aluminum trichloride, aluminum tribromide, boron trifluoride or a complex thereof can be used. Of these, a phenol complex of boron trifluoride is preferable. The polymerization temperature is 20 ° C to 100 ° C, preferably 30 ° C to 80 ° C. If the polymerization temperature is less than 20 ° C, the polymerization activity of the catalyst is lowered, and if it exceeds 100 ° C, the hue of the obtained resin may be deteriorated, which is not preferable. The catalyst amount and the polymerization time are preferably in the range of 0.1 to 2.0% by weight of the catalyst and 0.1 to 10 hours with respect to the raw material oil, for example. The reaction pressure is preferably atmospheric pressure to 1 MPa.
As the hindered amine compound used in the present invention, any compound belonging to the category referred to as a hindered amine compound can be used without limitation, and among them, an aliphatic-aromatic copolymer petroleum resin composition having particularly excellent storage stability. Since a product is obtained, a compound having a 2,2,6,6-tetraalkyl-4-piperidyl group represented by the following general formula is preferable.

ここで、一般式中のＲ１〜Ｒ４は炭素数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は互いに同一であっても相違していても良く、その具体例としては、メチル基、エチル基等が挙げられるが、メチル基が好ましい。Ｒ５の具体例としては、水素及びメチル基、オクチル基等が挙げられるが、水素及びメチル基が好ましい。
一般式で示されるヒンダードアミン化合物は分子量４００〜４，０００のものが知られており、ヒンダードアミン系光安定剤（ＨＡＬＳ）として市販されている。具体的な市販品としては、チバ・スペシャルティ・ケミカルズ（株）や旭電化工業（株）で製造されているビス（２，２，６，６−テトラメチル−４−ピペリジル）セバケート、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）セバケート、テトラキス（２，２，６，６−テトラメチル−４−ピペリジル）１，２，３，４−ブタンテトラカルボキシレート、テトラキス（１，２，２，６，６−ペンタメチル−４−ピペリジル）１，２，３，４−ブタンテトラカルボキシレート、ポリ［｛６−（１，１，３，３−テトラメチルブチル）アミノ−１，３，５−トリアジン−２，４−ジイル｝｛（２，２，６，６−テトラメチル−４−ピペリジル）イミノ｝ヘキサメチレン｛（２，２，６，６−テトラメチル−４−ピペリジル）イミノ｝］などが挙げられる。

Here, R1 to R4 in the general formula are alkyl groups having 1 to 4 carbon atoms, and R5 is an alkyl group or alkoxy group having 1 to 8 carbon atoms which may have hydrogen or a substituent. R1 to R4 may be the same as or different from each other. Specific examples thereof include a methyl group and an ethyl group, and a methyl group is preferred. Specific examples of R5 include hydrogen, methyl group, octyl group and the like, and hydrogen and methyl group are preferable.
The hindered amine compound represented by the general formula is known to have a molecular weight of 400 to 4,000, and is commercially available as a hindered amine light stabilizer (HALS). Specific commercial products include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1) manufactured by Ciba Specialty Chemicals Co., Ltd. and Asahi Denka Kogyo Co., Ltd. , 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-piperidyl) Imino ] And the like.

  If the manufacturing method of the aliphatic-aromatic copolymer petroleum resin composition of this invention can mix | blend 0.03 to 2 weight% of hindered amine compounds with respect to aliphatic-aromatic copolymer petroleum resin, it is possible. Any method can be used. Usually, an aliphatic-aromatic copolymer petroleum resin is easily oxidized to form a peroxide even at room temperature, and a peroxide formed when an aliphatic-aromatic copolymer petroleum resin stored for a long time is heated and melted. Decomposition occurs, and it becomes easy to cause a change in the physical properties of the resin such as generation of a gel-like substance and a softening point and a hue. Therefore, in order to obtain an aliphatic-aromatic copolymer petroleum resin composition having more excellent storage stability, the coexisting solvent and low-molecular compound are distilled off after the completion of the polymerization reaction of the aliphatic-aromatic copolymer petroleum resin. A method of blending a melted hindered amine compound with an aliphatic-aromatic copolymer petroleum resin in a molten state immediately after is preferable. Furthermore, the oxygen concentration in the blender at the time of blending is preferably 1000 ppm or less, more preferably 100 ppm or less, and particularly preferably 10 ppm or less. The molten aliphatic-aromatic copolymer petroleum resin at the time of blending This is preferable because it can prevent oxidation of oxygen, especially oxidation by oxygen.

  In addition, the aliphatic-aromatic copolymer petroleum resin composition of the present invention, as long as it does not deviate from the object of the present invention, is usually used as an additive blended in the resin composition, for example, phenol-based antioxidant, phosphorus-based You may mix | blend an antioxidant, a sulfur type antioxidant, a lactone type antioxidant, a ultraviolet absorber, a pigment, calcium carbonate, a glass bead, etc.

  As described above, the aliphatic-aromatic copolymer petroleum resin composition of the present invention is excellent in storage stability, particularly without the formation of a gel-like substance during storage, and the change in the physical properties of the resin is small. It can be suitably used for applications such as a melt adhesive, a pressure sensitive adhesive, an adhesive tape, and a floor adhesive.

  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, the polymerization preparation amount and CPD content rate, an additive, and the obtained composition and a test method are as follows.

1. Raw material (1) Composition of C5 fraction and C9 fraction: Table 1, Table 2
(2) Additive:
Hindered amine compound: ADK STAB light stabilizer LA-77 (Asahi Denka Kogyo Co., Ltd., bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate)
Phenol antioxidant: IRGANOX 1010 (Ciba Specialty Chemicals Co., Ltd.)
(3) Type of raw material oil and polymerization charge, CPD content, additive type and amount added: 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：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：脂肪族−芳香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: Measured by gel permeation chromatography according to JIS K-0124 (1994) using polystyrene as a standard substance.
(3) Olefinic double bond hydrogen area ratio: Aliphatic-aromatic copolymer petroleum resin is dissolved in chloroform-d (manufactured by Wako Pure Chemical Industries, Ltd.) and NMR (nuclear magnetic resonance spectrum) measuring device (model number) GSX270, manufactured by JEOL Ltd.). About the obtained spectrum, the area ratio was calculated | required based on the following formula.

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 an aliphatic-aromatic copolymer petroleum resin composition is put in an aging tester at 50 ° C., and samples are sampled every two weeks at the beginning and every two weeks to dissolve toluene. Determination of gel-like substance formation by gelation (gel-form substance formation time-dependent change), and changes over time in physical properties of the softening point, hue, and molecular weight (physical-characteristic change over time) were measured.
(2) Determination of gel-like substance production 5 g of toluene was dissolved in 5 g of toluene, and then transferred to a flat petri dish. If an unmelted material could be visually confirmed on the petri dish, the gel-like substance was generated. .

Example 1
In a glass autoclave having an internal volume of 2 l, 350 g of the C5 fraction of the composition (1) shown in Table 1 obtained by decomposition of naphtha as a raw oil, and the composition shown in Table 2 obtained by decomposition of naphtha as a raw oil ( 150 g of C9 fraction of 1) was charged. The CPD content of this mixed feedstock was 12%. Next, after heating to 35 ° C. under a nitrogen atmosphere, 0.8 wt% of boron trifluoride phenol complex (Stella Chemifa Co., Ltd., boron trifluoride phenol) was added as a Friedel-Crafts-type catalyst, and 2 Polymerized for 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 aliphatic-aromatic 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, 0.1% by weight of a hindered amine compound (manufactured by Asahi Denka Kogyo Co., Ltd., trade name Adeka Stab Light Stabilizer LA-77) was added to the copolymerized petroleum resin under a nitrogen stream with an oxygen concentration of 2 ppm at 100 ° C. and a stirring speed of 300 rpm. Thus, an aliphatic-aromatic copolymer petroleum resin composition was obtained.
Table 4 shows the storage stability measurement results (softening point, hue, molecular weight, gel substance) of the resulting aliphatic-aromatic copolymer petroleum resin composition. The copolymerized petroleum resin composition did not change with time in physical properties, did not produce a gel-like substance over time, and had good storage stability.

Example 2
An aliphatic-aromatic copolymer petroleum resin composition was obtained in the same manner as in Example 1 except that the amount of hindered amine compound added was 0.05% by weight as shown in Table 3.
Table 4 shows the storage stability measurement results (softening point, hue, molecular weight, gel substance) of the resulting aliphatic-aromatic copolymer petroleum resin composition. The copolymerized petroleum resin composition had no change in physical properties of the petroleum resin, no gel material was formed over time, and the storage stability was good.

Example 3
An aliphatic-aromatic copolymer petroleum resin composition was obtained in the same manner as in Example 1 except that the composition and amount of the C5 fraction and C9 fraction used as the raw material oil were as shown in Table 3. The mixed feedstock oil used had a CPD content of 20%, and the aliphatic-aromatic copolymerized petroleum resin had an olefinic double bond hydrogen area ratio of 11%.
Table 4 shows the storage stability measurement results (softening point, hue, molecular weight, gel substance) of the resulting aliphatic-aromatic copolymer petroleum resin composition. The copolymerized petroleum resin composition did not change with time in physical properties, did not produce a gel-like substance over time, and had good storage stability.

Example 4
An aliphatic-aromatic copolymer petroleum resin composition was obtained in the same manner as in Example 1 except that the composition and amount of the C5 fraction and C9 fraction used as the raw material oil were as shown in Table 3. The mixed feedstock oil used had a CPD content of 7%, and the aliphatic-aromatic copolymerized petroleum resin had an olefinic double bond hydrogen area ratio of 6%.
Table 4 shows the storage stability measurement results (softening point, hue, molecular weight, gel substance) of the resulting aliphatic-aromatic copolymer petroleum resin composition. The copolymerized petroleum resin composition did not change with time in physical properties, did not produce a gel-like substance over time, and had good storage stability.

Example 5
An aliphatic-aromatic copolymer petroleum resin composition was obtained in the same manner as in Example 1 except that the composition and amount of the C5 fraction and C9 fraction used as the raw material oil were as shown in Table 3. The mixed feedstock oil used had a CPD content of 5%, and the aliphatic-aromatic copolymer petroleum resin had an olefinic double bond hydrogen area ratio of 6%.
Table 4 shows the storage stability measurement results (softening point, hue, molecular weight, gel substance) of the resulting aliphatic-aromatic copolymer petroleum resin composition. The copolymerized petroleum resin composition did not change with time in physical properties, did not produce a gel-like substance over time, and had good storage stability.

Example 6
An aliphatic-aromatic copolymer petroleum resin composition was obtained in the same manner as in Example 1 except that the composition and amount of the C5 fraction and C9 fraction used as the raw material oil were as shown in Table 3. The mixed feedstock oil used had a CPD content of 2%, and the aliphatic-aromatic copolymerized petroleum resin had an olefinic double bond hydrogen area ratio of 2%.
Table 4 shows the storage stability measurement results (softening point, hue, molecular weight, gel substance) of the resulting aliphatic-aromatic copolymer petroleum resin composition. The copolymerized petroleum resin composition did not change with time in physical properties, did not produce a gel-like substance over time, and had good storage stability.

比較例１
実施例１で得た脂肪族−芳香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、脂肪族−芳香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、分子量、ゲル状物質）を表５に示した。該共重合石油樹脂は物性が経時的に変化し、ゲル状物質も経時的に生成し、貯蔵安定性が不良であった。

Comparative Example 1
The storage stability of the aliphatic-aromatic copolymer petroleum resin was measured without adding a hindered amine compound to the aliphatic-aromatic copolymer petroleum resin obtained in Example 1. The measurement results (softening point, hue, molecular weight, gel substance) are shown in Table 5. The physical properties of the copolymerized petroleum resin changed with time, and a gel-like substance was formed with time, resulting in poor storage stability.

Comparative Example 2
Aliphatic in the same manner as described in Example 1 except that 0.2% by weight of a phenolic antioxidant (manufactured by Ciba Specialty Chemicals Co., Ltd., IRGANOX 1010) was used instead of the hindered amine compound as an additive. An aromatic copolymer petroleum resin composition was obtained.
The storage stability measurement results (softening point, hue, molecular weight, gel-like substance) of the obtained aliphatic-aromatic copolymer petroleum resin composition are shown in Table 5. The copolymerized petroleum resin composition changed in physical properties over time, and a gel-like substance was formed over time, resulting in poor storage stability.

Comparative Example 3
The storage stability of the aliphatic-aromatic copolymer petroleum resin was measured without adding a hindered amine compound to the aliphatic-aromatic copolymer petroleum resin obtained in Example 3. The measurement results (softening point, hue, molecular weight, gel substance) are shown in Table 5. The physical properties of the copolymerized petroleum resin changed with time, and a gel-like substance was formed with time, resulting in poor storage stability.

Comparative Example 4
The storage stability of the aliphatic-aromatic copolymer petroleum resin was measured without adding a hindered amine compound to the aliphatic-aromatic copolymer petroleum resin obtained in Example 4. The measurement results (softening point, hue, molecular weight, gel substance) are shown in Table 5. The copolymerized petroleum resin composition did not produce a gel-like substance over time, but the physical properties changed over time and the storage stability was poor.

Comparative Example 5
The storage stability of the aliphatic-aromatic copolymer petroleum resin was measured without adding a hindered amine compound to the aliphatic-aromatic copolymer petroleum resin obtained in Example 5. The measurement results (softening point, hue, molecular weight, gel substance) are shown in Table 5. The copolymerized petroleum resin composition did not produce a gel-like substance over time, but the physical properties changed over time and the storage stability was poor.

Comparative Example 6
The storage stability of the aliphatic-aromatic copolymer petroleum resin was measured without adding a hindered amine compound to the aliphatic-aromatic copolymer petroleum resin obtained in Example 6. The measurement results (softening point, hue, molecular weight, gel substance) are shown in Table 5. The copolymerized petroleum resin composition did not produce a gel-like substance over time, but the physical properties changed over time and the storage stability was poor.

Comparative Example 7
The composition of the aliphatic-aromatic copolymer petroleum resin is the same as the production method described in Example 1, except that the composition and amount of the C5 fraction and C9 fraction used as the feedstock are as shown in Table 3. I got a thing. The CPD content of the mixed feedstock used was 27%, and the olefinic double bond hydrogen area ratio of the aliphatic-aromatic copolymer petroleum resin was 13%.
The storage stability measurement results (softening point, hue, molecular weight, gel-like substance) of the obtained aliphatic-aromatic copolymer petroleum resin composition are shown in Table 5. In the copolymerized petroleum resin composition, the formation of a gel-like substance was already confirmed immediately after production, and the copolymerized petroleum resin composition could not be used as an aliphatic-aromatic copolymerized petroleum resin composition.

Claims (4)

Proton NMR spectrum, characterized in that 0.01-2% by weight of a hindered amine compound is blended with an aliphatic-aromatic copolymer petroleum resin having an olefinic double bond hydrogen area ratio of 11% or less. An aliphatic-aromatic copolymer petroleum resin composition. A mixture of 30 to 90% by weight of a fraction having a boiling range of 20 to 110 ° C. and 70 to 10% by weight of a fraction having a boiling range of 140 to 280 ° C. obtained by pyrolysis of petroleum is used as a raw material oil. The aliphatic-aromatic copolymer petroleum resin composition according to claim 1, wherein A feedstock comprising a mixture of a fraction having a boiling range of 20 to 110 ° C. and a fraction having a boiling range of 140 to 280 ° C. has a CPD content defined by the following general formula (1) of 20% by weight or less. The aliphatic-aromatic copolymer petroleum resin composition according to claim 2.
CPD content (% by weight) = (weight of cyclopentadiene + weight of methylcyclopentadiene) / (weight of hydrocarbon component having double bond in raw material oil) × 100 (1) The method for producing an aliphatic-aromatic copolymer petroleum resin composition according to claim 1, wherein the oxygen concentration in the blender when blending the hindered amine compound is controlled to 1000 ppm or less.