JPH0585564B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Fields] The present invention is a light-colored tackifier with good heat resistance and weather resistance, and water resistance for applications such as adhesives, pressure-sensitive adhesives, paints, rubbers, inks, toners, and semiconductor sealants. The present invention relates to a method for producing hydrogenated hydrocarbon resins useful as anti-blocking agents, anti-blocking agents, and the like. [Prior Art] Most hydrogenated hydrocarbon resins have been conventionally used for petroleum resins. For example, US Pat. No. 2,824,860 proposes a method of catalytically hydrogenating petroleum resins. A large amount of expensive hydrogenation catalyst is used and the reaction is carried out at high temperature and pressure. Petroleum resins are obtained by polymerizing cracked oil fractions obtained when pyrolyzing petroleum fractions such as naphtha, but of these, the fractions with a temperature of about 20°C to 140°C, mainly the _C5 fraction, When used as a raw material, the resin becomes a so-called aliphatic hydrocarbon resin that does not contain aromatic nuclei.
A hydrogenated aliphatic petroleum resin is disclosed in JP-A-61-255918. In this case, since the raw material oil contains a large amount of conjugated diolefin and non-conjugated diolefin, the degree of unsaturation of the resin is high, the hue and heat resistance are poor, and the amount of hydrogen consumed is large. On the other hand, when polymerization is carried out using a cracked oil fraction with a boiling point range of 140 to 280°C as a raw material, the resulting resin will be an aromatic hydrocarbon resin, but in this case as well, the heat resistance stability and hue will be insufficient. Moreover, when used in adhesives and pressure-sensitive adhesives, it was only possible to produce products with poor adhesion and tackiness. A hydrogenated aromatic hydrocarbon resin is disclosed in JP-A-57-16015. According to this publication, clay treatment is performed after the polymerization reaction to remove substances that poison the catalyst in the hydrogenation process, but even when this is applied to coal-based hydrocarbon resin polymerized oil, sulfur compounds are removed. The effect is small, perhaps due to the difference in When hydrogenating petroleum resins and cyclopentadiene resins, increasing the reaction temperature and hydrogen pressure and conducting the reaction under harsh conditions improves the coloring of the resin, but the molecular weight decreases due to molecular chain scission.
The softening point of the resin decreases and the yield decreases. In Japanese Patent Publication No. 45-7064, two-stage hydrogenation of low-temperature hydrogenation and high-temperature hydrogenation was carried out, and in Japanese Patent Publication No. 45-20302,
The catalyst is brought into contact with the unhydrogenated resin only after the preheating step in an attempt to prevent catalyst deactivation. In Japanese Patent Publication No. 45-25709, water is added to the hydrocarbon resin and solvent during the hydrogenation reaction, and
No. 47681 attempts to prevent a decrease in molecular weight and yield by adding alcohol, but this is insufficient. Regarding the hydrogenation of terpene resins, "Adhesion" Magazine 29 , 10, 22-29 (1985) is known.
Conventional literature, with the exception of JP-A-57-16015, does not focus on the reduction in catalyst activity caused by sulfur compounds, and if hydrogenation is performed under harsh conditions with a catalyst with reduced activity, the molecular chain will inevitably deteriorate. It is thought that the cleavage occurs. [Problems to be Solved by the Invention] Although these conventional hydrogenated hydrocarbon resins have good hue, heat discoloration resistance, and weather resistance, they have the following drawbacks. When used as a tackifier for white hot melt adhesives, it has the disadvantage of insufficient cold and heat resistant adhesive strength. That is, there is a problem in that interfacial peeling occurs between the adhesive and the adherend at low and high temperatures. Therefore, for example, applications that require cold-resistant adhesive strength such as ice cream packaging that requires frozen storage, and heat-resistant packaging such as canned beer and canned soft drink packaging that require warehouse storage under high temperatures in the summer. For applications that require adhesive strength, the temperature range in which they can be used is extremely limited. When used as a colorless and transparent hot-melt adhesive used in the production of disposable diapers and sanitary napkins, it has the problem of insufficient holding power. When used as a tackifier for white or colored rubber compounds used for shoe soles, etc., it has the disadvantage of insufficient tackiness. That is, in order to obtain the necessary toughness, it is necessary to blend a large amount of an expensive hydrogenated hydrocarbon resin, which not only increases costs but also causes a decrease in rubber physical properties such as modulus and tensile strength. When used as a vehicle for traffic paint, it has good weather resistance but does not have sufficient adhesion to the road surface. When used as a vehicle for color anticorrosion paint, it has good weather resistance, but does not have sufficient antirust ability. When used as a binder resin for color thermal transfer inks or color toners, the cold and heat resistant adhesive strength is insufficient. Similarly, when used as a modifier for emulsion paints, water resistance is insufficient. Moreover, when used as an internal stress relaxation agent during the curing reaction of semiconductor sealing materials for light emitting diodes, etc., the effect is not sufficient. As a method for producing hydrogenated petroleum resin, a desulfurization method has been proposed in which a part of the polymerized components of petroleum-based hydrocarbon oil as a raw material is prepolymerized to produce a polymer with a concentrated sulfur content. There is (Tokuko 1977-
Publication No. 34812). However, even if this method is directly applied to coal-based hydrocarbon oil produced during coal carbonization and only preliminary polymerization treatment is performed, the desulfurization effect is not sufficient.
In other words, the sulfur concentration where the hydrogenation catalyst is less poisoned
Unable to achieve 50ppm or less. The first object of the present invention is to provide a hydrogenated hydrocarbon resin as a tackifier for hot melt adhesives and adhesives, which has excellent hue, heat discoloration resistance, and weather resistance, as well as heat resistance, cold resistance adhesive strength, and holding power. An object of the present invention is to provide a manufacturing method. A second object of the present invention is to provide a method for producing a hydrogenated hydrocarbon resin as a tackifier for rubber, which has excellent hue, heat discoloration resistance, weather resistance, and tackiness. A third object of the present invention is to provide a method for producing a hydrogenated hydrocarbon resin as a binder for traffic paint, which has excellent hue, heat discoloration resistance, weather resistance, and adhesion to road surfaces. The fourth object of the present invention is to have excellent hue and weather resistance,
Another object of the present invention is to provide a method for producing a hydrogenated hydrocarbon resin as a paint resin that has excellent compatibility and antirust properties. A fifth object of the present invention is to provide a method for producing a hydrogenated hydrocarbon resin as a binder for thermal transfer inks and toners, which has excellent hue, heat discoloration resistance, weather resistance, and blocking resistance. be. The sixth object of the present invention is a method for producing a hydrogenated hydrocarbon resin as a raw material for a resin emulsion, a tackifier for emulsion-based adhesives and adhesives, which has excellent hue and weather resistance, as well as cold resistance, heat-resistant adhesive strength, and water resistance. The goal is to provide the following. The seventh object of the present invention is to have excellent hue and weather resistance,
Another object of the present invention is to provide a method for producing a hydrogenated hydrocarbon resin as a chemical raw material for paper, which has excellent blocking resistance and paper strength. The eighth object of the present invention is to have excellent hue and weather resistance,
Another object of the present invention is to provide a method for producing a hydrogenated hydrocarbon resin as an emulsion raw material for an emulsion-based paint resin that has excellent water resistance. A ninth object of the present invention is to provide a method for producing a hydrogenated hydrocarbon resin as a raw material for an internal stress relaxation agent for semiconductor encapsulation materials, which has excellent hue and heat resistance, and has an excellent internal stress relaxation effect. . [Means for Solving the Problems] The present inventors have conducted extensive research in order to solve the above problems. The above-mentioned heat resistance, cold resistance adhesive strength, holding power, tackiness, adhesion with road surfaces, compatibility as a paint, rust prevention power, emulsion adhesive,
The water resistance of emulsion paints, the blocking resistance of ink and toner binders, the blocking resistance of paper chemicals, and the internal stress-relaxation effect of semiconductor encapsulation materials are all important because they contain polymeric components with oxygen polar groups such as coumaron. It was found that this can be solved by using coumaron indene resin, which is composed of rigid structural units with aromatic rings, as the main raw material.On the other hand, coumaron indene resin is hydrogenated from the viewpoint of hue, heat discoloration resistance, and weather resistance. However, the raw material oil for coumaron indene resin, coal carbonized gas oil and coal tar distilled oil, contains thiophene, monomethylthiophene, dimethylthiophene, trimethylthiophene, thiophene, which are extremely difficult to decompose. 700% of sulfur compounds such as phenol and methylthiophenol
It contains up to 1000ppm, and hydrogenation as it is causes significant deterioration of the catalyst, making it uneconomical.Also, even if some prepolymerization, which is conventionally done with petroleum resins, is carried out, the desulfurization effect is not sufficient. I got it right. As a result of further research, we found that if a fraction with a narrow boiling point range of 170 to 190°C is pre-distilled from coumaron indene raw material oil and pre-processed by partially combining this with a pre-polymerization method, The present invention was completed by discovering that it is possible to produce a hydrogenation raw material hydrocarbon resin that causes less poisoning of the hydrogenation catalyst. That is, the present invention provides coal carbonized gas light oil and/or
Or boiling point 140-190℃ obtained by distilling coal tar
A hydrocarbon oil containing a distillate is subjected to a detar base treatment, and the detar base oil is redistilled to a boiling point of 160~
Separate the middle distillate, which is mainly composed of the 190℃ distillate,
An acid catalyst is added to the fraction to perform light polymerization such that the polymerization rate of resin-forming components such as vinyltoluene, coumaron, and indene contained in the fraction is within the range of 5 to 30% by weight of the entire middle distillate. A hydrocarbon resin with a total sulfur concentration of 50 ppm or less is obtained by ordinary polymerization treatment using low-sulfur treated oil from which catalysts and polymers have been removed as feedstock oil, which is then converted into hydrogen containing metals or metal oxides in the liquid phase. This is a method for producing a hydrogenated hydrocarbon resin in which hydrogenation is carried out in the presence of a hydrogenation catalyst at room temperature to 300° C. and under hydrogen pressure of normal pressure to 350 kg/cm ² G. Coal carbonization gas light oil and/or coal tar is distilled to collect a fraction including a boiling point fraction of 140 to 200°C. Although gas light oil and coal tar may be distilled from each separately, for convenience of the process, usually gas light oil is mixed with tar light oil separated by coal tar distillation as a raw material for distillation.
C ₅ or less FR, benzene, toluene, xylene
A crude distillation process that separates BTX and a fraction containing naphthalene with a boiling point of 140 to 190℃ is used to separate the fraction with a name such as solvent naphtha (SN) or crude naphtha (CN). are doing. This SN is detarred with an acid such as dilute sulfuric acid. The tar bases to be removed become polymerization catalyst poisons in the subsequent polymerization step, and are pyridine, picoline, lutidine, collidine, aniline, etc., and alkyl derivatives thereof. The acid is separated and the remaining acid is washed with water or hydrated in alkaline water and washed with water. The present invention is characterized in that this detarred basic oil is subjected to a combination of redistillation treatment and light polymerization treatment. Usually, in this step, only the pitch component polymerized by the acid is de-pitched and evaporated, and the pre-distillate and the post-distillate are not separated and removed in this step. In the present invention, in this step, organic sulfur compounds such as vinyltoluene, coumaron, and a portion of thiophene, monomethylthiophene, and a portion of dimethylthiophene, which have a boiling point lower than that of indene, are removed as a pre-distillate together with a portion of xylene, styrene, etc., High-boiling organic sulfur compounds such as benzothiophene, which has a boiling point higher than that of vinyltoluene, coumaron, and indene, are removed as an after-distillate together with a portion of duurene, naphthalene, etc. This distillation process separates a fraction whose main component is a fraction with a boiling point of 160 to 190°C. If a large amount of fraction with a boiling point lower than 160°C is included, dimethylthiophene etc. will be mixed in. Also, if it is cut at a boiling point higher than 160°C, vinyltoluene, coumaron, etc. will be lost. If a large amount of fraction with a boiling point higher than 190°C is included, benzothiophene, naphthalene, etc. will be mixed in.
Also, cutting at a boiling point lower than 190°C will result in loss of indene. In any industrial distillation, it is unavoidable that a certain amount of substances above and below the target boiling point will be mixed in. (In other words, those with boiling points lower than 160℃ are
~190℃ fraction is mixed with substances with boiling point higher than 190℃.
Mixed with 160-190℃ fraction. The opposite is also true. ) This distillation treatment may be carried out at normal pressure or reduced pressure, but vacuum distillation is preferred in order to reduce loss of resin-forming components due to thermal polymerization. For example, when recovering vinyltoluene, coumaron, and indene through main distillation,
In the case of vacuum rectification at 100 mmHg, the top temperature range of the collected fraction is preferably within the range of 100 to 120°C. The light polymerization treatment performed after the redistillation treatment is a polymerization process in which the polymerization rate of the resin-forming component contained in the middle distillate obtained by the redistillation treatment is within the range of 5 to 30% by weight of the entire middle distillate. means. Examples of acid catalysts used in this mild polymerization treatment include Brønsted acids such as sulfuric acid, phosphoric acid, pyrophosphoric acid, hydrochloric acid, and nitric acid, boron trifluoride and its complexes, Lewis acid catalysts such as aluminum chloride, stannous chloride, and titanium tetrachloride. Examples include solid acids such as acid, alumina, silica alumina, silica gel, synthetic zeolite, activated clay, and acidic ion exchange resin, and at least one of these acidic compounds is used. When using a solid acid, it is necessary to use a large amount of the solid acid, so it is preferable to use an acidic compound other than the solid acid. Particularly preferred are boron trifluoride complexes and aluminum chloride. The conditions for this mild polymerization treatment vary depending on the type of acid catalyst used, but the amount of acid catalyst used is 0.1 to 0.5% by weight in the case of Lewis acid, 0.5 to 3% by weight in the case of Brønsted acid, and 0.5 to 3% by weight in the case of solid acid. It ranges from 5 to 20% by weight. The reaction time is 0.1 to 3 hours for Lewis acids and Bronsted acids, and 0.1 to 3 hours for solid acids.
It is in the range of 0.5 to 5 hours. However, the conditions are such that the polymerization rate of the resin component is 5 to 30% by weight of the entire middle distillate. If the polymerization rate is less than 5% by weight, the removal of sulfur compounds will be insufficient, and the sulfur concentration of the treated oil will be reduced.
It cannot be reduced to less than 50ppm. If it exceeds 30% by weight, the removal of sulfur compounds is sufficient, but the resin yield decreases, which is not preferable. Organic sulfur compounds that can be removed by this mild polymerization treatment include organic sulfur compounds that have chain transfer reactivity to growing chains, such as thiophene, monomethylthiophene, dimethylthiophene, trimethylthiophene, thiophenol, and tetramethylthiophene. . If necessary, a resin forming component such as styrene, phenol or alkylphenol, and a solvent hydrocarbon such as xylene or toluene are added to the feedstock oil that has been subjected to such low sulfur treatment, and then an ordinary acid catalyst for resin polymerization is added. The resin content is substantially completely polymerized, and the catalyst and solvent are removed by a conventional method to obtain the hydrogenation raw material hydrocarbon resin of the present invention having a total sulfur concentration of 50 ppm or less. In the present invention, in the redistillation step, fractions having a boiling point equal to or lower than styrene, such as thiophene, monomethylthiophene, and dimethylthiophene, are removed, so that most of the styrene component in the raw oil is removed. Therefore, the softening point of the resin obtained tends to be high, and it is extremely preferable to add styrene to this polymerization step in order to control this, increase the amount of resin-forming components, and improve the transparency of the resin. Phenol and alkylphenol can also be added because they improve the compatibility when mixed with other resins such as adhesives, paints, etc., and facilitate emulsion when making an aqueous emulsion. preferable. It is preferable to add a solvent hydrocarbon in order to control the reaction heat of the polymerization reaction, maintain the temperature within an appropriate range, and further facilitate operability. this is
Most of the xylene fraction below 160°C is removed by redistillation treatment, increasing the concentration of the resin-forming component, so it is extremely preferable to add it. The amount of styrene added is 1 to 30% by weight based on the low sulfur treated feedstock, and the amount of phenol or alkylphenol is 1 to 30% by weight.
30% by weight, and the amount of solvent is preferably in a range such that the concentration of the resin forming component is 20 to 50% by weight. As the polymerization catalyst, a normal catalyst used for normal coumaron indene resin raw material oil that is not subjected to sulfur reduction treatment can be used. Examples include Brønsted acids such as sulfuric acid, phosphoric acid, hydrochloric acid and nitric acid; Lewis acids such as boron trifluoride and its complexes and aluminum chloride; solid acids such as acid clay, activated clay, and acidic ion exchange resins. The polymerization conditions vary depending on the type of acid catalyst used, the concentration of the resin-forming component, and the target softening point, but the amount of catalyst used for the component-adjusted low-sulfur treated feedstock oil is 0.8 to 2 in the case of a Lewis acid. % by weight, 5-10% by weight for Brønsted acid and 30-50% by weight for solid acids. Reaction temperature is 50-150℃,
The reaction time is preferably 0.5 to 7 hours. The polymerized oil is decatalyzed by washing with water or an alkali by a conventional method, and the solvent is evaporated by evaporation treatment to obtain a raw material hydrocarbon resin for hydrogenation. This intermediate resin has a total sulfur concentration of 50 ppm or less, so it can be used as is for resin applications that require low sulfur. In addition, it can be used as a raw material resin in the case of hydrogenation treatment by adding and blending other appropriate components at the consumer's end. Subsequently, hydrogenation treatment is performed, but the above evaporation treatment is omitted and the raw material is used as it is, or the hydrogenation raw material hydrocarbon resin is dissolved again in a solvent such as cyclohexane or methylcyclohexane, or the resin is used as it is. Melts nickel, palladium,
at room temperature in the presence of a catalyst containing a metal such as platinum, cobalt, ruthenium, or rhodium or an oxide of the metal.
Hydrogenation is carried out by a conventional method at 300° C. and under a hydrogen pressure of normal pressure to 350 kg/cm ² G. Normal temperature and pressure are for special highly active catalysts such as Raney nickel, and are usually 150 to 300.
Hydrogenation is carried out at a temperature of about 100 to 150 kg/cm ² G. After separating and washing decomposition products such as hydrogen sulfide, the solvent is evaporated from the hydrogenated oil by evaporation treatment to obtain a hydrogenated hydrocarbon resin. As the solvent, hydrogenated hydrocarbons such as cyclohexane are preferred because they consume less hydrogen. The hydrogenation raw material hydrocarbon resin of the present invention has undergone sulfur reduction treatment in advance to have a total sulfur concentration of 50 ppm or less, so the hydrogenation catalyst has extremely little poisoning and deterioration, has a long life, and is extremely suitable for hydrogenation treatment. This can be done at low cost. As the hydrogenation catalyst, any catalyst commonly used as a hydrogenation catalyst can be used, even if it is not a special catalyst with strong sulfur resistance. The hydrogenated hydrocarbon resin of the present invention is almost colorless and transparent, has good weather resistance and heat discoloration resistance, and has the inherent cold resistance, heat resistant adhesive strength, and water resistance of coumaron indene resin.
It maintains excellent properties such as tackiness and blocking resistance, and can be added to various adhesives, pressure-sensitive adhesives, paints, rubbers, inks, toners, etc. as tackifiers,
Extremely useful as a modifier. [Function] Conventionally, the raw material oil for coumarone indene resin, which is made by detarring a fraction containing a boiling point fraction of 140 to 190°C obtained by distilling coal carbonized gas and/or coal tar, contains 700% of organic sulfur compounds. Since it contains up to 1000 ppm, even if we tried to hydrogenate it as it was, the catalyst would be poisoned and inactivated, making it impossible to perform sufficient hydrogenation. Further, even with the conventionally known partial prepolymerization method, sulfur could not be removed sufficiently. This is because the organic sulfur compounds in tar-based feedstock oils are compounds that have sulfur atoms in their cores, such as thiophene, methylthiophene, dimethylthiophene, and benzothiophene, so it is extremely difficult to decompose them. Hydrogenation had to be carried out under harsh conditions using extremely active hydrogenation catalysts. Therefore, decomposition of the molecular chains of the resin components occurred, resulting in lower molecular weight and lowering of the softening point. Furthermore, since the catalyst was highly active, the poisoning effect of sulfur was also large. In the present invention, focusing on the fact that thiophene, monomethylthiophene, dimethylthiophene, tetrahydrothiophene, etc. have a lower boiling point than styrene,
By removing styrene by redistillation at the expense of styrene, and at the same time removing most of the organic sulfur compounds with boiling points above 190°C, such as benzothiophene, we were able to reduce the sulfur concentration to the order of 100 ppm. Thiophenol, trimethylthiophene, and tetramethylthiophene, which have boiling points similar to those of coumarone and indene, were desulfurized by mild polymerization treatment, so this bonding effect caused a reduction in the hydrogenation raw material hydrocarbon resin after the combined treatment. The total sulfur concentration of
We were able to reduce the amount to 50ppm or less. These behaviors were unexpected for petroleum resins with different forms of organic sulfur compounds. The styrene sacrificed in the redistillation process can also be supplemented and added after the light polymerization process and prior to the polymerization of the resin. Hydrogenation of this low-sulfur resin can be carried out without reducing the activity of the catalyst, so the hydrogenation conditions themselves can be relaxed compared to normal hydrogenation conditions, and molecular chains can be cut. However, the fulvene bond (methylcyclopentadiene bond), which has been thought to be the cause of coloring of coal-based hydrocarbon resins, and the terminal double bonds and benzene nuclei, which have been thought to be the cause of discoloration over time, are saturated, and the hue and heat resistance to discoloration are saturated. , weather resistance is thought to be improved. Coal-based coumaron-indene resin is characterized by containing coumaron, a highly polar oxygen-containing compound that is hardly contained in petroleum resins, and it also contains phenol or alkylphenol, which makes it highly polar. It has good compatibility with polymers and has strong tackiness as a tackifier. Furthermore, since it is a resin component with a rigid structure essentially containing an aromatic ring, it has good blocking resistance, heat resistance, and water resistance. However, the resin produced by the method of the present invention has improved these properties and is able to fully exhibit the original excellent properties of coumaron indene resin. It is thought that it has become possible to do so. [Examples] The present invention will be specifically explained below using Examples, Reference Examples, and Comparative Examples, but the present invention is not limited to these Examples in any way. (Example 1) A distillation of light oil obtained by mixing gas light oil produced by coal carbonization with tar light oil produced by tar distillation was carried out, and a fraction with a boiling point of 130 to 200 ° C. was pickled with 40% dilute sulfuric acid. A detarred basic oil was obtained. 2 kg of this detarred base oil was charged into a 33-necked flask, and using a batch vacuum distillation column with 30 theoretical plates, the distillate was heated under a reduced pressure of 100 mmHg, with a reflux ratio of 7, a collected fraction temperature range of 110 to 115°C, and Vacuum distillation was performed under conditions of a yield of 30% by weight to obtain 600g of middle distillate. Corresponds to a normal pressure boiling point of 170-190℃. The compositions of the detarred basic oil (distillation raw material) and the collected middle distillate were investigated using gas chromatography (FID detector), and the total sulfur concentration was measured using oxidative decomposition coulometric titration. The results are shown in Table 1. Sulfur, which was 707 ppm before distillation, is removed by distillation.
Reduced to 115ppm. The morphology of the organic sulfur compounds removed by this distillation process was investigated using gas chromatography (FPD detector), and the results showed that monomethylthiophene and dimethylthiophene were the main components. Next, 500 g of the distilled oil was charged into a 14-neck separable flask equipped with a stirring blade, a reflux condenser, a thermometer, and a temperature controller.
Boron trifluoride ethyl ether complex catalyst
A light polymerization treatment was carried out under the conditions of 0.2% by weight, reaction temperature of 50° C., and reaction time of 3 hours. After the reaction is complete,
26 g of slaked lime was added and stirred to carry out a catalyst decomposition reaction at 60°C for 15 minutes. Catalytic decomposition products and excess slaked lime are then filtered and separated from the polymerized oil, followed by a rotary evaporator to remove the filtrate oil to 10 mm
The temperature was raised to 220°C under reduced pressure of Hg to obtain 417.5 g of light polymerization treated oil as distillate oil. The composition of the polymerized oil (low-sulfur treated oil) thus obtained was examined in the same manner as described above, and the sulfur concentration was also examined. The results are shown in Table 1. Sulfur, which was 115 ppm before light polymerization, was reduced to 31 ppm after light polymerization. The organic sulfur compounds removed by this polymerization treatment were examined using gas chromatography (FPD detector), and the results showed that dimethylthiophene and trimethylthiophene were the main components. The removal rate of organic sulfur compounds through the redistillation treatment and light polymerization treatment was 99% by weight. 400 g of this low sulfur oil, 72 g of styrene, 44 g of phenol, and 352 g of toluene as a solvent were mixed with a stirring blade, a reflux condenser, and a thermometer.
Pour into a 4-neck separable flask and add BF ₃ O.
Add 8.7 g (1.0 wt%) of (C ₂ H ₅ ) ₂ catalyst and reduce the reaction temperature.
The polymerization reaction was carried out at 60° C. for 2 hours. After the reaction is complete, add 26g of slaked lime and stir.
The decomposition reaction of the catalyst was carried out at 60°C for 15 minutes. after that,
Catalytic decomposition products and excess slaked lime are separated by filtration,
Still using the rotary evaporator, 10
The filtrate oil was gradually heated to 220° C. under reduced pressure of mmHg, and the solvent was distilled off to obtain 472 g of hydrogenated raw material resin. The properties of the resin are shown in Table 2. The total sulfur concentration in the resin is 26 ppm, achieving low sulfur content. After dissolving 400g of this hydrogenation raw material hydrocarbon resin in the same amount of cyclohexane, it was
cm ² , into a magnetically stirred autoclave with a capacity of 2, and a nickel-diatomaceous earth catalyst (Ni content 45%).
20g, hydrogen pressure 100-145Kg/cm ² , reaction temperature 220℃,
The hydrogenation reaction was carried out under conditions of a reaction time of 8 hours. After the reaction is complete, the catalyst and resin solution are separated by filtration, and the filtrate oil is charged into a rotary evaporator and heated at 180°C.
The temperature was gradually raised to 5 mmHg, the pressure was reduced, and cyclohexane was distilled off to obtain 400 g of hydrogenated hydrocarbon resin. The total sulfur concentration (oxidative decomposition coulometric titration method), softening point (ring and ball method, JISK2531), nuclear hydrogenation rate, and weather resistance of the above-mentioned low-sulfurized hydrocarbon resins and hydrogenated hydrocarbon resins were measured. Comparison was made with resin {manufactured by Nippon Steel Chemical Co., Ltd., trade name: Esclone V-120}. The results are shown in Table 2. The nuclear hydrogenation rate is 7ppm for ¹ H-NMR.
From the area of the Ar-H spectrum appearing in (This is the spectral area of the resin.)
For weather resistance, a Herige Gardner colorimeter was used to measure the weather resistance at 180°C before the weather resistance test.
The Gardner number of a 50% by weight toluene solution of each sample was measured after a 3-hour heat resistance test and a 17-hour ultraviolet resistance test at a distance of 10 cm. The initial color number, heat discoloration resistance, and ultraviolet discoloration resistance (weather resistance) were all improved by the hydrogenation treatment. (Comparative Example 1) A hydrogenation reaction was carried out using 50 g of the commercially available hydrocarbon resin shown in Table 2 under the same conditions as the hydrogenation reaction in Example 2, but the reaction did not proceed at all. (Comparative Example 2) In Example 1, the polymerization rate was 4% by weight when treated under exactly the same conditions except that 0.08% by weight of BF ₃ ether complex was used in the mild polymerization treatment.
The sulfur content of the treated oil was 60 ppm and could not be reduced to less than 50 ppm. (Comparative Example 3) In Example 1, the process was carried out under exactly the same conditions except that the fraction at 110 to 130°C was collected under a reduced pressure of 100 mmHg in the redistillation process, and the boiling point of the middle distillate was at normal pressure.
The temperature ranged from 170 to 205°C, and benzothiophene increased in the middle distillate, resulting in a sulfur content of 135 ppm.The sulfur concentration of the oil after light polymerization under the same conditions was 55 ppm, and could not be reduced to below 50 ppm. (Reference Example 1) 40 parts of hydrogenated hydrocarbon resin obtained in Example 1, 20 parts of paraffin wax, and 1 part of anti-aging agent were added to 40 parts of ethylene-vinyl acetate copolymer, trade name "Evaflex 220". A hot melt adhesive was prepared by melt mixing. The adhesive composition was applied onto kraft paper to a thickness of 30 μm.
Immediately after melt-coating, another piece of kraft paper was crimped to give the desired result. After crimping, the test piece was left at 20°C and 65% RH for 24 hours, and then a 25 x 150mm test piece was prepared and subjected to a tensile test at three measuring temperatures: -20, 20, and 70°C. The results are shown in Table 3. (Comparative Reference Example 1) In Reference Example 1, an adhesion test was conducted in the same manner as in Reference Example 1, except that a commercially available hydrogenated aromatic petroleum resin was used instead of the hydrogenated hydrocarbon resin obtained in Example 1. Ivy. The results are shown in Table 3.

【table】

【table】

〔Effect of the invention〕

The hydrogenated hydrocarbon resin of the present invention has improved hue, heat discoloration resistance, and weather resistance because the fulvene bonds, terminal double bonds, and benzene nuclei that have been considered to be the cause of discoloration over time are saturated. Also, unlike conventional hydrogenated petroleum resins, its composition contains highly polar oxygen-containing units such as hydrogenated units of coumaron and hydrogenated units of phenol or alkylphenol, so ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVA), styrene-isoprene block polymer (hereinafter abbreviated as SIS), styrene-butadiene block polymer (hereinafter abbreviated as SBS), styrene-isoprene block polymer (hereinafter abbreviated as SBS),
Butadiene block polymer hydride (hereinafter
SEBS), styrene-butadiene rubber (hereinafter referred to as SBR), acrylonitrile-butadiene rubber (hereinafter referred to as NBR), polyvinyl acetate (hereinafter referred to as NBR),
PVA), polymethyl acrylate (PMA), polymethyl methacrylate (PMMA), epoxy resin (ER), urethane resin (UR), and other highly polar polymers. The compatibility of these polymers is superior to that of conventional hydrogenated petroleum resins, resulting in a good plasticizing effect on these polymers over a wide temperature range. Due to this good compatibility and plasticizing effect, EVA,
When used as a tackifier for white hot-melt adhesives and colorless transparent hot-melt adhesives that use SIS, SBS, SEBS, etc. as base polymers, cold resistance,
Improves heat-resistant adhesive strength. It also has excellent tackiness when used as a tackifier for white rubber compounds whose main ingredients are highly polar rubbers such as SBR and NBR. When used as a modifier for paints whose main components are highly polar resins such as PMA, PMMA, ER, and UR,
Improved adhesion to coated objects such as steel plates, water resistance,
Improves rust prevention ability. PVAC emulsion, PMA emulsion,
Paints based on PMMA emulsion,
When an emulsion of the hydrogenated resin of the present invention is used as an adhesive modifier, cold resistance, heat resistance adhesive strength, and water resistance are improved. When used as a modifier for resin encapsulant materials for light emitting diodes that contain ER as a main component, it improves adhesion to the object to be encapsulated, improves water resistance, and also alleviates distortion caused by heat, improving heat resistance. Improves sex. Since it has a highly polar structural unit, when used as a binder resin for traffic paint, it improves wettability with the road surface and improves adhesion to the road surface. When the hydrogenated resin of the present invention is emulsionized and used as a paper chemical, the affinity with cellulose is improved, and thus the paper strength is improved. Since the hydrogenated resin of the present invention is mainly composed of units obtained by hydrogenating coumaron and indene, which are rigid structural units, the glass transition temperature is higher than that of petroleum resins, etc., and the temperature dependence of the melt viscosity is large. .
That is, it changes from a sticky state to a completely non-tacky state when the temperature is slightly lowered, and when used as a binder resin for color thermal transfer inks or color toners, blocking resistance is improved. These effects are as a result of the hydrogenation of coal-based hydrocarbon resin made possible by the present invention, which results in almost colorless,
The resin has been improved to have excellent resistance to heat discoloration and weathering, and this has opened up a wide range of uses for these resins, making it an invention with great practical effects.

Claims (1)

[Claims] 1. A hydrocarbon oil containing a fraction with a boiling point of 140 to 200°C obtained by distilling coal carbonized gas light oil and/or coal tar is detarred and base-treated, and the detarred base oil is subjected to redistillation treatment to have a boiling point of 160 to 190°C. A middle distillate whose main component is a fraction of A hydrocarbon resin with a total sulfur concentration of 50 ppm or less is obtained by carrying out light polymerization within the range of 5 to 30% by weight of the total, using low sulfur treated oil from which catalysts and polymers have been removed as a raw material oil, and carrying out ordinary polymerization treatment, Production of a hydrogenated hydrocarbon resin, characterized in that this is then hydrogenated in the presence of a hydrogenation catalyst containing a metal or a metal oxide at room temperature to 300°C and under hydrogen pressure of normal pressure to 350 kg/cm ² G. Method.