JP4882232B2 - Novel aliphatic hydrocarbon resin and process for producing the same - Google Patents

Description

  The present invention relates to a novel aliphatic hydrocarbon resin. More specifically, the present invention relates to a novel aliphatic hydrocarbon resin having excellent performance in hot melt adhesive applications and ink applications.

  In general, aliphatic hydrocarbon resins are made from hydrocarbon oils such as 5-carbon 1-pentene, 2-pentene, 2-methyl-1-butene, 2-methyl-1,3-butadiene, 1,3-pentadiene, etc. Discloses a method obtained by polymerization in a Friedel-Crafts type in the presence of an aluminum chloride catalyst (see, for example, Patent Document 1). The resin obtained by this method is a resin having excellent performance in hot melt adhesive applications and ink applications. However, since an aluminum chloride catalyst is used, the post-treatment of the aluminum chloride catalyst is complicated and a complicated catalytic process is required. There was a problem.

  Also disclosed is a method for thermally polymerizing dicyclopentadiene (hereinafter abbreviated as DCPD) without using a catalyst to obtain a DCPD aliphatic hydrocarbon resin (for example, Patent Document 2 and Non-Patent Document 2). Patent Document 1). However, the resin obtained by this method has a problem that the physical properties of ball tack and hexane tolerance necessary for hot melt adhesive use and ink use are not sufficient. Furthermore, there is a problem that a polymerization process becomes complicated, such as adding a solvent recovery step because a solvent is required during polymerization.

Japanese Patent Publication No. 50-8884 (page 3) JP 49-2344 A (first page) Journal of Petroleum Society, 27, 26 (1984) (first page)

  The present invention has been made in view of the above-mentioned problems, and has a novel performance that is excellent in hot melt adhesive applications and ink applications, and can be polymerized without a complicated process. It is to provide a hydrogen resin.

  As a result of diligent studies to solve the above-mentioned problems, the present inventors have made an aliphatic hydrocarbon resin having excellent performance for hot melt adhesive use and ink use by thermal polymerization using a specific raw material oil and production thereof. The method has been found and the present invention has been completed.

That is, the present invention relates to 25 to 45% by weight of a cyclopentadiene compound selected from the group consisting of cyclopentadiene, dicyclopentadiene and cyclopentadiene multimers , methylcyclopentadiene, methylcyclopentadiene dimer and methylcyclopentadiene. A raw material oil comprising 40 to 60% by weight of a methylcyclopentadiene compound selected from the group consisting of pentadiene multimers and at least 5 to 15% by weight of an aromatic hydrocarbon is thermally polymerized at a temperature of 240 to 260 ° C. , It is related with the manufacturing method of the aliphatic hydrocarbon resin characterized by making it the aliphatic hydrocarbon resin which satisfies following (a)-(c) by concentrating at 200-240 degreeC .
(A) Softening point measured according to JIS K-2207 is 80 to 100 ° C.
(B) Ball tack measured according to JIS Z0237 is 22 or more (c) Hexane tolerance is 20 ml or more The raw material oil used in the present invention is a cyclopentadiene compound, a methylcyclopentadiene compound, and an aromatic hydrocarbon.
Examples of the cyclopentadiene compound of the present invention include cyclopentadiene itself, dicyclopentadiene, which is a dimer of cyclopentadiene, and multimers.
Examples of the methylcyclopentadiene compound of the present invention include methylcyclopentadiene itself, a dimer of methylcyclopentadiene, and a multimer.
Further, the aromatic hydrocarbon of the present invention is not particularly limited, but for example, benzene, toluene, xylene, ethylbenzene, n-propylbenzene, i-propylbenzene, styrene, p-methylstyrene, m-methylstyrene, o-methyl. Examples thereof include styrene, indene, n-butylbenzene, i-butylbenzene, s-butylbenzene, p-dipropylbenzene, m-dipropylbenzene, and o-dipropylbenzene.

  The feedstock oil used in the present invention may be prepared by separately preparing a cyclopentadiene compound, a methylcyclopentadiene compound and an aromatic hydrocarbon, but when the petroleum fraction obtained from crude oil is decomposed or reformed It is preferable to use a fraction produced as a by-product and a residual fraction using specific components from these fractions. Among them, cracked gasoline obtained by pyrolyzing a naphtha fraction in crude oil at a temperature of 800 ° C. or higher is used, and C9 oil having 9 or more carbon atoms obtained by distilling the cracked gasoline is pyrolyzed at 150 to 220 ° C. It is more preferable to use a hydrocarbon oil composed of a cyclopentadiene compound, a methylcyclopentadiene compound and an aromatic hydrocarbon separated in this manner. Since this hydrocarbon oil is an oil that has been substantially disposed of as a fuel so far, it can be used as it is as a raw material oil without synthesizing the raw material oil. This hydrocarbon oil does not need to be further refined, and can be used as a raw material oil for an aliphatic hydrocarbon resin without adding a new solvent.

  In the present invention, the aliphatic hydrocarbon resin is obtained by thermal polymerization of the above raw material oil. The temperature at the time of thermal polymerization is not particularly limited, and is preferably 220 to 300 ° C., more preferably 240 to 260 ° C., because the polymerization can be performed efficiently. The reaction pressure is not particularly limited, and is usually preferably 0.1 to 2.0 MPa in absolute pressure, and more preferably 0.5 to 1.0 MPa. Moreover, the reaction atmosphere at the time of superposition | polymerization is not restrict | limited in particular. 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.

  The aliphatic hydrocarbon resin of the present invention can be produced by any method. For example, a raw material oil composed of 25 to 45% by weight of a cyclopentadiene compound, 40 to 60% by weight of a methylcyclopentadiene compound and 5 to 15% by weight of an aromatic hydrocarbon is thermally polymerized at a temperature of 240 to 260 ° C., and then 200 The method of concentrating at -240 degreeC is mentioned.

  In the production method of the present invention, the aliphatic hydrocarbon resin produced according to the present invention can be obtained by removing unreacted organic substances after the completion of the polymerization reaction. There is no restriction | limiting in particular in the method of removing organic substance from a polymerization solution, For example, the method of distilling organic substance, ie, concentration, 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 distilling the organic matter. 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, and 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 preferably used because the amount of heat and time required for distillation can be reduced.

  The addition amount of the organic solvent 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 aliphatic hydrocarbon resin from the viewpoint that the dissolved product 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 300 ° C. is preferable because the solvent hardly remains and the resin is less susceptible to thermal degradation. Preferably it is 200-240 degreeC. In the case of vacuum distillation, the distillation temperature can be lowered according to the type of solvent and the degree of vacuum.

  The distillation time depends on the type and amount of the obtained aliphatic hydrocarbon resin and the type and addition amount of the organic solvent. For example, in order to suppress residual solvent and resin thermal degradation, 0.05 to 10 hours are required. Preferably, it is 0.4 to 2 hours.

  Since the aliphatic hydrocarbon resin obtained by the production method of the present invention has excellent performance in hot melt adhesive applications and ink applications, the polystyrene-equivalent number average molecular weight is preferably 200 to 600, and further 250 It is preferable that it is -400. The number average molecular weight mentioned here is, for example, after dissolving the aliphatic hydrocarbon resin of the present invention in tetrahydrofuran and adjusting the polymer solution concentration to 50 g / l, and injecting this solution into gel permeation chromatography at room temperature. Can be measured.

The aliphatic hydrocarbon resin obtained by the production method of the present invention has a softening point of 80 to 100 ° C. measured according to (a) JIS K-2207 in order to have excellent performance in hot melt adhesive applications and ink applications. More preferably, it is 85-95 degreeC. When the softening point is less than 80 ° C., deformation and blocking occur during storage of the resin, and handling becomes difficult. Also,
When the temperature exceeds 100 ° C., an insoluble gel is generated, which is not preferable for use as a hot melt adhesive or an ink.

  Further, (b) the ball tack measured according to JIS Z0237 is 22 or more, more preferably 26 or more. When the ball tack is less than 22, the tackiness is insufficient and a good hot melt adhesive cannot be obtained. Furthermore, (c) hexane tolerance is 20 ml or more, more preferably 25 ml or more. When the hexane tolerance is less than 20 ml, the solubility in the ink solvent becomes insufficient, and an ink having good properties cannot be obtained.

  The ball tack here is measured in accordance with the JIS Z0237 pressure-sensitive adhesive tape pressure-sensitive adhesive sheet test method, and is an index of tackiness. The higher the ball tack, the more the aliphatic hydrocarbon resin having better tackiness. 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 index of the solubility of petroleum resin in soybean white squeezed oil. The higher the hexane tolerance, the more the aliphatic hydrocarbon resin becomes more soluble in an aroma-free solvent for ink.

  The hot melt adhesive of the present invention is composed of the above aliphatic hydrocarbon resin, a rubber component, and a hydrocarbon oil for viscosity adjustment.

  Here, the rubber component is not particularly limited, and for example, styrene-isoprene-styrene block copolymer (SIS rubber) and natural rubber are used. Of these, SIS rubber is preferably used because of its high adhesive performance. Any hydrocarbon-based oil can be used as the viscosity-adjusting hydrocarbon-based oil as long as the viscosity of the adhesive can be controlled. For example, naphthene, paraffin, and aromatic hydrocarbon-based oils are used. Of these, naphthene hydrocarbon-based oils are preferably used because of easy viscosity adjustment.

  The ratio of the above components of the hot melt adhesive of the present invention is not particularly limited. For example, the aliphatic hydrocarbon resin is 30 to 60% by weight, the rubber component is 30 to 60% by weight, and the hydrocarbon oil for viscosity adjustment 5 to 20% by weight.

  The aliphatic hydrocarbon resin of the present invention has excellent performance not only for hot melt adhesive applications but also for ink applications.

  ADVANTAGE OF THE INVENTION According to this invention, the novel aliphatic hydrocarbon resin which has the performance outstanding in the hot-melt-adhesive use or the ink use can be provided.

  Such aliphatic hydrocarbon resins are suitable raw materials for hot melt adhesives and suitable raw materials for printing inks that do not contain aromatic solvents.

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. The raw material oil which consists of a raw material cyclopentadiene type compound, a methylcyclopentadiene type compound, and an aromatic hydrocarbon was prepared as follows. C9 oil having 9 or more carbon atoms contained in cracked gasoline obtained at Tosoh Corporation ethylene plant was pyrolyzed at 210 ° C. Next, a hydrocarbon oil (hereinafter, referred to as a fraction A) mainly containing cyclopentadiene and methylcyclopentadiene obtained by distilling the pyrolysis product and separating it from the top of the distillation column was used. The composition of fraction A is shown in Table 1.

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、脂肪族炭化水素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、カラムとして東ソー（株）製、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, after dissolving an aliphatic hydrocarbon resin in tetrahydrofuran and adjusting the resin solution concentration to 50 g / l, this polymer solution was used as a column with two TSKgel2000H (trade name), TSKgel3000H (trade name). ) One and one TSKgel 4000H (trade name) were injected into the GPC apparatus, 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) Ball tack measurement 45 parts by weight of aliphatic hydrocarbon resin, 45 parts by weight of SIS rubber (manufactured by Shell Chemical Co., trade name KRATON D-1107cP), 10 parts by weight of oil (manufactured by Shell Chemical Co., trade name SHELLFLEX 371N) and toluene 100 parts by weight were mixed and homogenized at room temperature, and coated on a polyethylene terephthalate film having a thickness of 25 μm. After coating, the thickness of the pressure-sensitive adhesive after drying at 60 ° C. for 30 minutes was 40 μm. After being left overnight at 23 ° C., a ball tack test was performed according to JIS Z0237.

(4) Hexane Tolerance Measurement An aliphatic hydrocarbon petroleum resin was dissolved in soybean white squeezed oil to prepare a 50% by weight solution. This solution was titrated with n-hexane to obtain a titration amount for starting white turbidity and used as hexane tolerance, which was an index of solubility of the aliphatic hydrocarbon resin in soybean white-drawn oil. The higher the hexane tolerance, the higher the solubility in white soybean oil.

Example 1
After putting 350 g of the fraction A into a 1 l autoclave and sealing it, the mixture was reacted at 260 ° C. for 100 minutes. After completion of the reaction, the autoclave was cooled, and unreacted components were removed by distillation at 220 ° C. for 30 minutes to obtain 188 g of resin. As a result of analyzing the resin with a high-speed GPC apparatus, the number average molecular weight of the obtained resin was 305. Evaluation of the obtained resin was a softening point of 91 ° C., a ball tack 28, and a hexane tolerance of 100 ml or more.

Example 2
175 g of fraction A was placed in a 1 l autoclave, sealed, and reacted at 260 ° C. for 90 minutes. After completion of the reaction, the autoclave was cooled and unreacted components were removed by distillation at 220 ° C. for 30 minutes to obtain 78 g of resin. As a result of analyzing the resin with a high-speed GPC apparatus, the number average molecular weight of the obtained resin was 315. Evaluation of the obtained resin was a softening point of 94 ° C., a ball tack 26, and a hexane tolerance of 35 ml.

Comparative Example 1
250 g of dicyclopentadiene and 250 g of xylene were placed in a 1 l autoclave, sealed, and reacted at 260 ° C. for 75 minutes. After completion of the reaction, the autoclave was cooled, and unreacted components were removed by distillation at 220 ° C. for 30 minutes to obtain 136 g of a resin. As a result of analyzing the resin with a high-speed GPC apparatus, the number average molecular weight of the obtained resin was 270. The evaluation of the obtained resin was a softening point of 95 ° C., but the ball tack was 21 and the tackiness was poor, and the hexane tolerance was 14 ml, and the solubility in the solvent was poor.

Claims (2)

From 25 to 45% by weight of a cyclopentadiene compound selected from the group consisting of cyclopentadiene, dicyclopentadiene and cyclopentadiene multimer, from the group consisting of methylcyclopentadiene, methylcyclopentadiene dimer and methylcyclopentadiene multimer A raw material oil comprising 40 to 60% by weight of a methylcyclopentadiene compound selected from one or more kinds and 5 to 15% by weight of aromatic hydrocarbons is thermally polymerized at a temperature of 240 to 260 ° C. and then concentrated at 200 to 240 ° C. By doing, it is set as the aliphatic hydrocarbon resin which satisfies the following (a)-(c), The manufacturing method of the aliphatic hydrocarbon resin characterized by the above-mentioned.
(A) Softening point measured according to JIS K-2207 is 80 to 100 ° C.
(B) Ball tack measured according to JIS Z0237 is 22 or more (c) Hexane tolerance is 20 ml or more 2. The aliphatic carbonization according to claim 1, wherein the feedstock oil is a hydrocarbon oil obtained by pyrolyzing a C9 oil having 9 or more carbon atoms obtained by distilling cracked gasoline at 150 to 220 ° C. A method for producing a hydrogen resin.