JPH0416486B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a modified hydrocarbon resin, in particular, having a high softening point and low melt viscosity,
In particular, the present invention relates to a method for producing a hydrocarbon resin that can be suitably used as a tackifier, a compounding agent for paint, and the like. Traditionally, pressure sensitive adhesives, hot melt adhesives,
In the field of paint, traffic paint, etc.
As a tackifier (tackifying agent) including adhesive raw materials, rosin resin, alkyd resin,
It is known that epoxy resin etc. can be used. Among these, rosin-based resins are the most popular, but because these resins rely on natural sources of raw materials, they cannot meet the remarkable growth in demand in recent years. Therefore, recently, in order to replace it,
The development of various petroleum-based hydrocarbon resins is progressing, and one of them is the polymerization of C5 _- based fractions such as 1,3-pentadiene, isoprene, and 2-methyl-2-butene using Friedel-Crafts catalysts. Hydrocarbon resins obtained by By the way, with recent hot melt adhesives, there is a need to increase work speed and maintain a uniform coating amount, and also with traffic paint, there is a need to increase work speed and drying speed due to increased traffic volume. Due to the increasing demand for improved workability, etc., there is a need for low melt viscosity tackifiers. However, with the aforementioned C5 _- based hydrocarbon resins, if you try to lower the viscosity, you will be forced to lower the softening point, which will result in poor heat resistance, and if you try to improve the heat resistance, you will have a high Thus, hydrocarbon resins having low melt viscosity and heat resistance (high softening point) have not been known so far. Therefore, the present inventors have found that the softening point is high and
As a result of various studies on hydrocarbon resins with low melt viscosity, at least one selected from the group of chain unsaturated hydrocarbons having 3 to 10 carbon atoms and aromatic hydrocarbons having unsaturated bonds in the side chains having 8 to 16 carbon atoms. One hydrocarbon component (A), 1,2-dihydrodicyclopentadienes, 2-norbornenes, alkylidenenorbornanes, alkylidenecyclohexanes,
A copolymer obtained by polymerizing a monomer mixture consisting essentially of at least one component (B) selected from the group of vinylnorbornanes, vinylcyclohexanes, and cyclohexenes in the presence of a polymerization catalyst. A hydrocarbon resin consisting of
Consisting of 20 to 98 mol% units of component (A) and 2 to 80 mol% units of component (B), and 60 to 98 mol% units of component (B).
A hydrocarbon resin having a softening point of 170°C, a melt viscosity of 10 to 10,000 cps, and a number average molecular weight of 300 to 3,000 satisfies these requirements, has compressive strength,
The present invention was based on the discovery that it has excellent suitability for weather resistance and can be used as a compounding agent for tackifiers and paints. That is, the method for producing a hydrocarbon resin according to the present invention uses a hydrocarbon resin selected from the group of linear unsaturated hydrocarbons having 3 to 10 carbon atoms and aromatic hydrocarbons having unsaturated bonds in the side chains of 8 to 16 carbon atoms. Hydrogen component (A)
and 1,2-dihydrodicyclopentadienes,
At least one component selected from the group of 2-norbornenes, alkylidenenorbornanes, alkylidenecyclohexanes, vinylnorbornanes, vinylcyclohexanes, and cyclohexanes
(B) and is polymerized in the presence of a polymerization catalyst in a proportion of 20 to 98 mol% units of component (A) and 2 to 80 mol% units of component (B). Copolymerized, softening point between 60 and 170℃, 10
Melt viscosity from 10000cps to 300 to 3000
The method is characterized by obtaining a hydrocarbon resin having a number average molecular weight of . In the method of the present invention, the chain unsaturated hydrocarbon having 3 to 10 carbon atoms used as one of the monomer components (A) is preferably a monoolefin or a diolefin. The monoolefin preferably has the general formula R ₁ R ₂ C=CR ₃ R ₄ (wherein R ₁ , R ₂ and R ₃ are each a hydrogen atom or a methyl group, and R ₄ is an alkyl group having 1 to 6 carbon atoms. ), specifically, for example, propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, 3-methyl -1-pentene, 4-methyl-1-pentene, 1-heptene,
Examples include 2-octene. Further _, the diolefin preferably _{has the} general formula _R5R6C = _{CR7 - CR8=CR9R10 or R11R12C} = _CR13 ( _CR14R15 ) _nCR16 = _{CR17R18 (} in the formula , R ₅ , R ₆ , R ₉ , R ₁₁ , R ₁₂ and R ₁₇ each represent a hydrogen atom or a methyl group, and R ₇ , R ₈ ,
R ₁₀ , R ₁₃ to R ₁₆ and R ₁₈ each represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 1 to 4. ) A specific example is a compound represented by
For example, 1,3-butadiene, isoprene, 2,
Examples include 3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2,3-dimethyl-1,3-hexadiene, 1,4-pentadiene, 3,4,5-trimethyl-1,6-heptadiene, etc. It will be done. Similarly, the aromatic hydrocarbon having an unsaturated bond in the side chain having 8 to 16 carbon atoms, which is one of the monomer components (A) forming the hydrocarbon resin, preferably has the following general formula: (In the formula, R ₁ represents a hydrogen atom or a methyl group,
_R21 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, m represents an integer of 0 to 3, and when m is 2 to 3, _R21 may be the same or different,
R ₂₀ represents a saturated or unsaturated hydrocarbon chain, and 1 represents 0 or 1. ) Specific examples of the compound include styrene, vinyltoluene, α-methylstyrene, isopropenyltoluene, tert-butylstyrene, allylbenzene, p-tert-butylallylbenzene, and the like. Among the hydrocarbons exemplified above, those having a carbon number of 4 to 4 are particularly preferable from the viewpoint of resin performance.
6 chain diolefins and aromatic alkenyl compounds having 8 to 10 carbon atoms. These hydrocarbons may be used alone or as a mixture of two or more homologous compounds, as well as monoolefins and diolefins, monoolefins and aromatic hydrocarbons having unsaturated bonds in their side chains, and diolefins and aromatic hydrocarbons having unsaturated bonds in their side chains. It is used as an aromatic hydrocarbon having a saturated bond, a mixture of a monoolefin, a diolefin, and an aromatic hydrocarbon having an unsaturated bond in the side chain. Generally, such mixtures include, for example:
C ₄ fraction, C ₄ fraction of diene extraction residue, C ₅ fraction, C ₅ fraction of isoprene extraction residue, C ₉ fraction, or mixtures of these in arbitrary proportions, etc., which are obtained as naphtha cracked oil fractions. Among them, those that contain a large amount of chain unsaturated hydrocarbons or aromatic hydrocarbons with unsaturated bonds in their side chains, or those that contain 30% by weight or more of these hydrocarbons based on the total polymerizable components. Those adjusted as follows are used. Furthermore, as long as these are the main raw materials, a small amount of other unsaturated compounds may be contained, but if the content is large, the softening point of the resulting hydrocarbon resin may be lowered. The permissible ratio is limited to a range that does not impede the purpose of the present invention. The 1,2-dihydrodicyclopentadiene copolymerized with these hydrocarbons has the following general formula: (In the formula, R ₂₂ located in the 1st to 5th positions and 6 to
R ₂₃ located at the 10th position represents a hydrogen atom or a lower alkyl group. ), specifically, 1,
2-dihydrodicyclopentadiene, 9-methyl-1,2-dihydrodicyclopentadiene, 3,
9-dimethyl-1,2-dihydrodicyclopentadiene, 9-ethyl-1,2-dihydrodicyclopentadiene, 1-ethyl-9-methyl-1,2
-dihydrodicyclopentadiene and the like. These 1,2-dihydrodicyclopentadienes can be obtained by known methods. for example,
U.S. Pat. No. 2,883,372 discloses that cyclopentadiene and six times the amount of cyclopentene are produced by Diels-Alder reaction in the absence of oxygen.
A method for obtaining 1,2-dihydrodicyclopentadiene by reacting at 200° C. for 7 hours is disclosed. By using cyclopentadiene or cyclopentene having a substituent, 1,2-dihydrodicyclopentadiene having a substituent can be obtained. In addition, a method for producing 1,2-dihydrodicyclopentadiene and cyclopentene by thermally decomposing dicyclopentadiene in a gas phase has been published in a US patent.
It is disclosed in the specification of No. 4139569. It goes without saying that it is desirable that the 1,2-dihydrodicyclopentadiene used in the production of hydrocarbon resins be substantially pure, but if these polymerizable components have a purity of about 60% by weight or more If so, in addition to these, hydrides and partially hydrogenated products of cyclopentene, dicyclopentadiene, cyclopentadiene, and cyclopentadiene oligomers (trimer or higher), such as non-polymerizable components such as cyclopentane and tetrahydrodicyclopentadiene. or a derivative thereof. However, these components may worsen the hue of the resulting hydrocarbon resin and may also be accompanied by gel formation.
It is desirable to use cyclopentadiene, dicyclopentadiene, trimeric or higher cyclopentadiene oligomers and their derivatives in an amount of 10% by weight or less in this polymerization component. 2-Norbornenes have the following general formula (In the formula, R ₂₄ located at the 2, 3 or 7 position and R ₂₅ located at the 5 and 6 positions represent a hydrogen atom or a lower alkyl group.) Specifically, for example, , norbornene, 2-methyl-2-norbornene, 5-methyl-2-norbornene, 6-methyl-2-norbornene, 2,5-dimethyl-2-norbornene, 2,6-dimethyl-2-norbornene, 2-ethyl -5-methyl-2-norbornene, 2,6-diethyl-2-norbornene, 2-
Examples include ethyl-5-n-propyl-2-norbornene. These 2-norbornenes can be obtained by known methods. For example, 2-norbornene can be obtained by the Diels-Alder reaction of cyclopentadiene and ethylene (Houben-Weyl, “Methoden der Organischen
Chemie”IVb (1972), p. 445).If olefins are used for cyclopentadiene, propylene, etc., which have substituents, 2-norbornenes having substituents can be obtained. formula (In the formula, R ₂₆ , R ₂₇ located at positions 1 to 5, and 7
and R ₂₈ represents a hydrogen atom or a lower alkyl group. ) Specific examples of the compound include isopropylidenenorbornane, ethylidenenorbornane, methylenenorbornane, isobutylidenenorbornane, and the like. These alkylidene norbornanes can be obtained by partial hydrogen isomerization when producing vinylnorbornanes, which will be described later. Vinyl norbornanes have the following general formula: (In the formula, R ₂₉ and
R ₃₀ to R ₃₂ represent a hydrogen atom or a lower alkyl group, and q represents an integer of 1 to 4. ) Specific examples of the compound include vinylnorbornane, isopropenylnorbornane, 2-methylvinylnorbornane, propenylnorbornane, and the like. These vinylnorbornanes are produced by subjecting conjugated diolefins such as butadiene and isoprene to cyclopentadiene through a Diels-Alder reaction.
It can be obtained by partially hydrogenating the resulting vinyl-2-norbornenes using a palladium catalyst. Vinylcyclohexanes, alkylidenecyclohexanes and cyclohexenes have the following general formulas, respectively. (In the formula, R ₃₃ to R ₄₀ represent a hydrogen atom or a lower alkyl group, and r represents an integer of 1 to 5.) Specifically, examples include vinylcyclohexane, isopropenyl Cyclohexane, 4-methylvinylcyclohexane,
isopropenyl-3-methylcyclohexane, 3
- Vinylcyclohexane such as methylvinylcyclohexane, alkylidenecyclohexane such as methylenecyclohexane, ethylidenecyclohexane, isopropylidenecyclohexane, isobutylidenemethylcyclohexane, cyclohexene, 3-isopropyl-6-methylcyclohexene, 3-isopropylcyclohexene, 4-ethyl -1-methylcyclohexene, 4-ethyl-2
- Cyclohexenes such as methylcyclohexene can be mentioned. These vinylcyclohexanes and cyclohexenes can be obtained by partially hydrogenating vinylcyclohexanes obtained from 1,3-dienes such as butadiene and isoprene by Diels-Alder reaction (Chemical
Abstrachs, 60 , 7925d, 61 , 8200c). Also,
Alkylidenecyclohexanes are produced by partial hydrogen isomerization of vinylcyclohexene (ibid. 73 , 2501e, 82 ,
72660v). Next, in the present invention, 1,2-dihydrodicyclopentadienes, 2-
norbornenes, alkylidene norbornanes,
Alkylidenecyclohexanes, vinylnorbornanes, vinylcyclohexanes and cyclohexenes may be used alone, and
It can also be used as an arbitrary mixture of two or more types. Furthermore, components (B) other than 1,2-dihydrodicyclopentadienes may also contain a small amount of other unsaturated compounds as long as these are used as the main raw materials, but if the content increases, Since there is a risk that the softening point of the resulting hydrocarbon resin may be lowered, the permissible proportion is limited to a range that does not impede the object of the present invention. When copolymerizing the hydrocarbons of component (A) and the hydrocarbons of component (B), generally the reactivity of component (B) is lower than that of component (A), so component (B) By using a method such as using the same amount or more than the same amount as component (A), bringing it into contact with a catalyst in advance, and then blowing or adding component (A) little by little. It is desirable to increase the reactivity of component (B) and increase the proportion of its polymerized units. In terms of high copolymerizability with component (B), the chain unsaturated hydrocarbons having 3 to 10 carbon atoms in component (A) include diolefins, especially conjugated diolefins, and among them,
1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, and the like, which have little steric hindrance, are preferably used. Further, among the aromatic hydrocarbons having an unsaturated group in the side chain, those in which R ₁₉ is a hydrogen atom and 1 is 0 in the general formula (), specifically, styrene,
Vinyltoluene, tert-butylvinyltoluene, etc. are preferably used for the same reason. As the copolymerization catalyst, those known as homopolymerization and copolymerization catalysts for the hydrocarbons can be used as they are. That is, cationic catalysts, anionic catalysts, ionic coordination catalysts, radical catalysts, etc. are used. Examples of cationic polymerization catalysts include those described in Journal of the Japan Petroleum Institute, Vol. 16, No. 10, pp. 865-867 (1973). Specifically, examples include aluminum chloride, aluminum bromide, Examples include boron fluoride, tin tetrachloride, antimony pentachloride, ferric chloride, dichloroalkylaluminum, triethylaluminum-water, trichloroacetic acid, and sulfuric acid. Among these, Lewis acids, particularly aluminum chloride and aluminum bromide, are preferably used because they provide a high yield of hydrocarbon resin, a good hue, and a high softening point. Examples of anionic polymerization catalysts include homopolymerization and copolymerization catalysts described in Japan Petroleum Institute, Vol. 16, No. 9, pp. 779-784 (1973). Specific examples of such anionic polymerization catalysts include:
For example, potassium, alkylpotassium, sodium, alkylsodium, lithium, alkyllithium, SrZn (R ₆ ),
Examples include SrZn (R ₆ ). Among these, lithium and alkyl lithium are component (B)
It is preferably used because it provides a hydrocarbon resin with improved reactivity, good hue, and high softening point. Ionic coordination polymerization catalysts include, for example, the Ziegler catalyst described in Journal of Japan Petroleum Engineering, Vol. 16, No. 8, pp. 699-704 (1973); specific examples include halides such as titanium, vanadium, chromium, zirconium, and β- Diketone salts, alcoholates, etc. and trialkylaluminum, alkyl aluminum halide, alkyl lithium, alkyl magnesium represented by Al(R) _o X _3-o (R is an alkyl group, X is a halogen atom, n is 1 or 2) Combinations with halides, lithium hydride, etc. can be mentioned. Among these, a combination of a titanium or vanadium halide and an alkyl aluminum compound is particularly preferably used because it increases the reactivity of component (B). These ionic coordination polymerization catalysts include propylene,
Butene-1, Pentene-1, Hexene-1, 4-
Monoolefins such as methylpentene-1, 1,3
- It is a particularly preferred catalyst when a linear unsaturated hydrocarbon such as a conjugated diolefin such as butadiene, isoprene, or 1,3-pentadiene is used. Examples of radical polymerization catalysts include those described in Japan Petroleum Institute, Vol. 16, No. 10, pp. 867-871 (1973), specifically peroxides such as benzoyl peroxide and tert-butyl hydroperoxide;
Examples include azo compounds such as azobisisobutyronitrile, hydrogen peroxide-ferrous compounds, and redox catalysts such as potassium persulfate-sodium sulfite. These radical polymerization catalysts are appropriately selected depending on the set polymerization temperature. Generally, these radical polymerization catalysts are preferably used when the hydrocarbon is a conjugated diolefin or a styrene compound. The amount of the above-mentioned polymerization catalyst used varies depending on the type of catalyst, combination of comonomers, polymerization temperature, polymerization time, etc., but usually approximately
It ranges from 0.01 to 10 mol%. Polymerization solvents may or may not be used, but hydrocarbon solvents such as propane, butane, pentane, hexane, heptane, benzene, toluene, xylene, ethylbenzene, etc. can be used for any catalyst system. can. In addition to the above, when using an anionic polymerization catalyst, ether solvents such as diethyl ether, tetrahydrofuran, dioxane, and 1,2-dimethoxyethane can be used. When using a cationic polymerization catalyst, a chlorinated solvent such as dichloromethane, ethyl chloride, 1,2-dichloroethane, chlorobenzene, etc. can be used. Furthermore, when using a radical polymerization catalyst, water can be used as a solvent when emulsion or suspension polymerization is employed. Polymerization temperature generally ranges from several tens of degrees below zero to about 150 degrees Celsius.
can be selected, and the polymerization time is usually in the range of about 0.5 to 10 hours. The reaction pressure is generally normal pressure or elevated pressure. After the copolymerization reaction is completed, the remaining catalyst is treated according to a conventional method, and the unreacted components and reaction solvent are removed by distillation or addition to a poor solvent for the hydrocarbon resin. , the desired hydrocarbon resin can be obtained. The hydrocarbon resin obtained as described above contains about 20 to 98 mol% of units of component (A), preferably about 20 to 98 mol%.
80 mol%, particularly preferably about 40 to 60 mol%, and the unit of component (B) is about 80 to 2 mol%, preferably about 80 to 20 mol%, particularly preferably about 60 to 40 mol%.
Generally, it has a softening point of about 60°C to 170°C, preferably about 80 to 140°C (according to the ring and ball method according to JIS K2531), and a softening point of about 10 to about 10,000 cps, preferably about
It has a melt viscosity (Emiller viscometer, resin temperature 200°C) of 500 to 10 centipoise (cps) and a molecular weight (number average molecular weight by GPC method (polystyrene conversion method)) of about 300 to 3000, preferably about 400 to 1000. ing. When the unit of component (B) is 2 mol% or less, if the viscosity of the obtained hydrocarbon resin is lowered, the softening point will be lowered, and if the softening point is raised, the viscosity will also be higher. When used as a compounding agent for agents, adhesives, or paints, a satisfactory balance between workability and performance cannot be obtained. In addition, when the unit of component (B) is 80 mol% or more, homopolymerization becomes poor due to the structure of component (B), so it is necessary, for example, to make the catalyst concentration abnormally high. This not only increases the difficulty in production, but also makes it difficult to increase the molecular weight in terms of quality, resulting in a low softening point, poor hue, and poor thermal stability. On the other hand, hydrocarbon resins in which the monomer units described above are in the predetermined range, particularly in the preferred range, have a high melt viscosity relative to the softening point, excellent hue and heat resistance, and, The amount of catalyst used can be smaller than when component (B) is homopolymerized. When it has monomer units in a range other than the preferred range above, it does not exhibit the same performance as a hydrocarbon resin that has units in the preferred range above, but it does not exhibit the same performance as the same type of resin that does not have the unit of component (B). , the melt viscosity is high relative to the softening point, and the effect of improving compatibility with other polymers is recognized. Such hydrocarbon resins have excellent properties as tackifiers for hot melt adhesives, pressure sensitive adhesives, and the like. In general, adhesive compositions include hot melt adhesives, which are made by blending a base resin such as ethylene/vinyl acetate copolymer with a tackifier and, if necessary, wax and other additives, and natural rubber or synthetic rubber. There are pressure-sensitive adhesives that are made of a base resin such as tackifier and, if necessary, a solvent and other additives. The former hot melt adhesive is generally used for bookbinding,
It is used as an adhesive or coating agent in fields such as can manufacturing, woodworking, laminating, sealing, and coating processing. Moreover, the latter pressure-sensitive adhesive is generally coated on a base material such as paper, cloth, or plastic film, and is used for applications such as adhesive tapes and labels. In any of these adhesive compositions, a tackifier is blended with the base resin. In particular, in the case of hot melt adhesives, in addition to compatibility with base resins such as ethylene/vinyl acetate copolymer and wax, adhesiveness, melt viscosity, flexibility, etc., heat resistance stability, light resistance stability, Excellent hue, etc. is required. On the other hand, in the case of tackifiers for pressure-sensitive adhesives,
It has excellent compatibility with base resins such as natural rubber and synthetic rubber, has good solubility in solvents, is chemically stable, and has excellent weather resistance.
It is required to have properties such as good color and no strong odor. When the above-mentioned hydrocarbon resin is used as a tackifier in a pressure-sensitive adhesive, examples of the base resin include natural rubber, styrene-butadiene copolymer rubber, polybutadiene, polyisoprene, polyisobutylene, butyl rubber, Polychloroprene, ethylene/propylene copolymer rubber,
Rubber-like polymers such as ethylene/propylene/diene copolymer rubber, styrene/butadiene/styrene block copolymer, and styrene/isoprene/styrene block copolymer are used. When used as a hot melt adhesive, specific examples of the base resin include, for example, ethylene,
Vinyl acetate copolymer, polyethylene, polypropylene, ethylene/propylene copolymer, ethylene/acrylic acid copolymer, polyester, polyamide, polyvinyl acetate, etc. are used. In particular, ethylene/vinyl acetate copolymer is preferably used. When the hydrocarbon resin is used as a tackifier, the blending ratio with the base resin varies somewhat depending on the hot melt adhesive and pressure sensitive adhesive composition. In the case of hot melt adhesives, the blending ratio of tackifier is usually 20 parts by weight based on 100 parts by weight of the base resin.
~300 parts by weight, preferably 30 to 200 parts by weight, and in the case of pressure sensitive adhesives, it is usually 20 to 200 parts by weight, preferably 20 to 200 parts by weight, based on 100 parts by weight of the base resin.
It ranges from 30 to 150 parts by weight. In addition to the essential components of the tackifier and the base resin, various additives may be added to the adhesive composition using the above-mentioned hydrocarbon resin, if necessary.
For example, in the case of a hot melt adhesive composition,
Plasticizers such as dioctyl phthalate and dibutyl phthalate, waxes such as petroleum-based paraffin waxes with melting points of about 40 to 65°C, polyolefin waxes, micro waxes, phenol-based or bisphenol-based organic compounds, metal soaps Antioxidants such as On the other hand, in the case of pressure-sensitive adhesive compositions, dioctyl phthalate, dibutyl phthalate, machine oil, process oil, plasticizers such as polybutene, fillers such as calcium carbonate, zinc white, titanium oxide, silica, amines, ketones, etc. - Examples include amine-based and phenol-based anti-aging agents, stabilizers, and the like. The blending ratio of these additives can be arbitrarily selected. The method for preparing adhesive compositions using the hydrocarbon resins differs for hot melt adhesive compositions and pressure sensitive adhesive compositions. A method for preparing a hot melt adhesive composition is to heat and melt a mixture consisting of a hydrocarbon resin as a tackifier, the base resin, and, if necessary, the various additives described above, while stirring to form a uniform melt. is prepared and shaped into granules, flakes, pellets, rods, etc. while cooling, depending on the purpose. Such a hot melt adhesive composition is melted again and used for adhesion or coating purposes. For example, when used for adhesion, a rod-shaped compound is filled into a solvent gun for corner adhesion of molded products. On the other hand, the pressure-sensitive adhesive can be prepared by mixing on a roll a mixture consisting of a hydrocarbon resin as a tackifier, the base resin and, if necessary, the various additives mentioned above. It can be prepared by a conventional method such as dissolving in a solvent. As described above, when a hot melt adhesive composition is used as an adhesive or a coating agent among the adhesive compositions using the above-mentioned hydrocarbon resin, the above-mentioned hydrocarbon resin has excellent compatibility with the base resin, Furthermore, it has excellent heat resistance stability and color, and has little odor, so it is possible to obtain a uniform hot melt adhesive. It has the advantage of having little odor during preparation and use. Furthermore, even if the above-mentioned hydrocarbon resin is used in a pressure-sensitive adhesive composition, the hydrocarbon resin as a tackifier has excellent weather resistance in addition to the above-mentioned characteristics.
A uniform pressure-sensitive adhesive composition can be obtained, and this pressure-sensitive adhesive composition has excellent color and weather resistance,
Moreover, it has the advantage of having little odor. Adhesive compositions using such hydrocarbon resins will be specifically explained later using Examples. In addition, the evaluation method of the hydrocarbon resin in Examples is as follows. (1) Softening point JIS K5665 (2) Hue ASTM D1544-58T (3) Heat resistance stability 5g of hydrocarbon resin was placed in a test tube (inner diameter 16mm) and immersed in a constant temperature bath heated to 200℃ for 3 hours. After that, the color was expressed using the ASTM D1544-58T method. (4) Odor From mild odor when heated and melted (200℃),
The evaluation was divided into three grades, A, B, and C, including those exhibiting strong irritating odors. Furthermore, the above-mentioned hydrocarbon resins can also be used as additives for paints. That is, the hydrocarbon resin described above can be used as a component of the coating film forming element. When using the hydrocarbon resin for this purpose,
For example, it is dissolved in an aromatic solvent such as benzene, toluene, or xylene, or an aromatic hydrocarbon-containing solvent such as mineral spirits or mineral turpentine, and the pigment is added to this solution, as well as a desiccant, alkyd resin, or polyester as necessary. A coating composition can be prepared by blending resins, epoxy resins, urethane resins, acrylic resins, urea resins, melamine resins, phenolic resins, drying oils, and the like. In particular, the above-mentioned hydrocarbon resins are suitably used in alkyd resin paints and the like. The blending ratio of the hydrocarbon resin in this case depends on other components, but is suitably in the range of 10 to 70% by weight in terms of solid content. When the aforementioned hydrocarbon resin is used in an alkyd resin paint, this hydrocarbon resin has a low viscosity when dissolved in a paint solvent, so it not only has excellent painting workability such as brush painting, but also has a low viscosity when dissolved in a paint solvent. Because of the double bonds, it is affected by a desiccant together with other ingredients such as linseed oil, and has excellent drying properties such as dryness to the touch. Furthermore, such alkyd resin paints also have excellent weather resistance, water resistance, adhesion, and heat resistance. Furthermore, by using a surfactant or the like, the hydrocarbon resin can be used not only for oil-based paints but also for water-based emulsion paints. In this case,
Emulsion can be formed by a conventional method using a surfactant in an amount of 0.1 to 10% by weight, preferably 0.2 to 5% by weight, based on the hydrocarbon resin. The present invention will be explained below with reference to Examples and Reference Examples, but the present invention is not limited to these Examples in any way. Reference Example A A wire mesh catalyst charging basket is fixed in advance to the stirring blade of a 1l capacity autoclave (made of SUS 304). Inside this cage is a palladium catalyst G- manufactured by Nissan Girdler.
Added 5g of 68C. Next, 500 g of 5-vinyl-2-norbornene was added into the autoclave. Next, hydrogen was added into the autoclave from a hydrogen cylinder, and the autoclave was reacted at a temperature of 80° C. and a pressure of 10 Kg/cm ² for about 6 hours, and then allowed to cool, and after depressurizing, the contents were taken out. Then, by distillation, the boiling point is 61-62℃/39mmHg
480g of fraction A was obtained. The composition of this fraction A is as follows. 2-vinylnorbornane 38.5% 2-ethylidenenorbornane 60.1% Unknown components 1.4% Reference example B 272 g of isoprene was placed in a 1 liter autoclave (made of SUS 304) and the temperature was raised to 145°C. 265 g of cyclopentadiene was continuously added thereto over 2 hours, and stirring was continued for 4 hours. The pressure decreased from 14Kg/cm ² to 7Kg/cm ² during that time. After cooling and depressurizing, the contents were taken out. The composition of the resulting reaction mixture is shown. Isoprene 14.2% 5-isopropenyl-2-norbornene 16.4% Dicyclopentadiene 44.7% Others 24.7% Next, 1L capacity autoclave (made of SUS 304)
A wire mesh catalyst charging basket was fixed in advance to the stirring blade of
5 g of -68°C was added, and 500 g of the reaction mixture having the above composition was added thereto. Thereafter, hydrogen was added into the autoclave from a hydrogen cylinder, and the reaction mixture was allowed to react at a temperature of 80° C. and a pressure of 10 kg/cm ² for 8 hours, and then allowed to cool and depressurize, and the resulting reaction mixture was taken out. This reaction mixture was fractionally distilled to obtain 60 g of a B fraction with a boiling point of 105-174°C and 250 g of a C fraction with a boiling point of 174-184°C. The compositions of the obtained fraction B and fraction C are as follows. Dihydroisoprene dimer mainly composed of 4-isopropyl-1-cyclohexene, fraction B 10.9%, fraction C 5.4% Dihydroisoprene-cyclopentadiene codimer mainly composed of 2-isopropenylnorbornane and 2-isopropylidenenorbornane B fraction 72.5%, C fraction 37.7% Dihydrodicyclopentadiene B fraction 11.2%, C fraction 55.2% Tetrahydrodicyclopentadiene B fraction 0.9%, C fraction 1.5% Dihydroisoprene dimer B fraction 4.5%, C fraction: 0.2% (Total amount of both B and C fractions: 100.0% by weight) Examples 1 to 11 A predetermined amount of catalyst and a portion of the solvent (20 ml) were charged into a 1 liter glass autoclave, and stirred. A mixture of the cyclic olefins and various diolefins shown in Table 1 below, and the remainder of the solvent was slowly injected from a pressure cylinder. At this time, heating or cooling was performed to maintain the temperature at 60°C, and each monomer was injected for about 15 minutes. Furthermore, after continuing the polymerization reaction at this temperature for about 2 hours, methanol was added to decompose the catalyst, and the catalyst was washed with water. The obtained polymerized oil was filtered through a glass filter, and the presence or absence of gel formation was examined, and then the filtrate was concentrated to obtain a hydrocarbon resin. Table 1 shows the properties of the obtained hydrocarbon resin.

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[Table] The evaluation method in Table 1 is shown below. 1 Compatibility (1) Mix equal amounts of Mitsui Polychemical product Evaflex 410 (vinyl acetate content: 19% by weight) or Evaflex 210 (vinyl acetate content: 28% by weight) and hydrocarbon resin on a hot plate at 180°C. The coating was applied to a thickness of about 1 mm on a polyester film, and the transparency of the coating film was evaluated. (2) Dissolve an amount of hydrocarbon resin equal to that of natural rubber in a 10% toluene solution of natural rubber, and apply this onto a polyester film to a thickness of approximately 80 μm.
The transparency of the coating film was evaluated. (3) Equal amounts of a commercially available modified rosin for traffic paint (maleated ester type, softening point 94°C, acid value 24, melt viscosity 150 cps) and hydrocarbon resin were placed in a test tube, and the oil at 180°C was heated. The mixture was dissolved and mixed on the bath and cooled to room temperature, and its transparency was evaluated. In the evaluation, ◯ indicates transparency, △ indicates translucent, and × indicates opaque. 2 Heat resistance Hydrocarbon resin in a test tube with an inner diameter of 15 mm and a length of 18 mm
25 g was taken and heated in an oil bath at 200°C for 3 hours, and the hue was measured by the Gardner method. 3 Proportion of cyclic olefin polymerized units in hydrocarbon resin The composition of the raw material mixture before the copolymerization reaction and the composition of the polymerized oil after the copolymerization reaction were determined by gas chromatography, and determined from the reaction amount ratio of each comonomer. . Table 2 shows the polymerized units of each comonomer determined in Example 1.
Shown below.

[Table] In the same manner as in Examples 1 to 11, cyclic olefin-containing fraction homopolymerization and isoprene homopolymerization were carried out. Table 3 shows the properties of the obtained hydrocarbon resin. From these results, it is clear that cyclic olefin alone has extremely low polymerizability, and that the resulting hydrocarbon resin has a low softening point and extremely poor hue and heat resistance.

[Table] Example 12 Cyclic olefin-containing fraction 197 obtained in Reference Example A above was placed in a 1-liter four-necked flask equipped with a stirrer, thermometer, condenser, dropping funnel, and rubber stopper for catalyst injection.
3.9 g of boron trifluoride-phenol complex was added thereto under stirring in a nitrogen gas flow, and slowly heated to 40°C.
Next, 194g of styrene was added dropwise over 2 hours.
Thereafter, the reaction was carried out for 30 minutes while maintaining the temperature at 40 to 45°C, and then the catalyst was decomposed with an aqueous sodium hydroxide solution, washed with water, and concentrated to obtain 280 g of a hydrocarbon resin containing 27 mol% of cyclic olefin units. In the above reaction, no gel was generated. Table 4 shows the properties of the obtained hydrocarbon resin.

[Table] Examples 13 to 15 and Comparative Example 5 In the same manner as Examples 1 to 11, the compositions shown in Table 5 were prepared.
Using the _C5 fraction, copolymerization was carried out with the cyclic olefin-containing fraction obtained in the reference example. Table 6 shows the properties of the obtained hydrocarbon resin.

【table】

【table】

【table】

[Table] Example 16 and Comparative Example 6 Using the hydrocarbon resin obtained in Example 3 (Example 16) and a commercially available resin (Gutdeyer product Wing Tak Plus) (Comparative Example 6), an adhesive was applied. We made adjustments and examined the adhesive tape performance. The results obtained are shown in Table 7.

[Table] It is clear that products using the hydrocarbon resin according to the present invention are superior to commercially available resins in terms of tack and adhesive strength. The evaluation method in Table 7 is as follows. To 100 parts of adhesive raw material resin, 100 parts of Califlex TR-1107 (Ciel product), which is a commercially available SIS block copolymer, 30 parts of mineral oil (Ciel Flex 371N, a Ciel product), and 3 parts of stabilizer (Irganox 1010). was added and kneaded in a kneader at 150°C for 30 minutes to prepare an adhesive. Next, this adhesive was applied to a thickness of 55 μm on a polyester film (Toray product Lumirror, 25 μm thick) using a hot melt coating machine, and
Adhesive force and cohesive force were also measured by the Dow method (20° C.) according to the method described above.

Claims (1)

[Claims] 1 Hydrocarbon component (A) selected from the group of linear unsaturated hydrocarbons having 3 to 10 carbon atoms and aromatic hydrocarbons having an unsaturated bond in the side chain having 8 to 16 carbon atoms
and 1,2-dihydrodicyclopentadienes,
At least one component selected from the group of 2-norbornenes, alkylidenenorbornanes, alkylidenecyclohexanes, vinylnorbornanes, vinylcyclohexanes, and cyclohexanes
20 to 98 mol% of units of component (A) and 2 to 98 mol% of units of component (B), characterized in that a monomer mixture consisting essentially of (B) is polymerized in the presence of a polymerization catalyst.
Copolymerized at a ratio of 80 mol%, 60 to 170
Softening point of ℃, melt viscosity of 10 to 10000cps and
A method for producing a hydrocarbon resin having a number average molecular weight of 300 to 3000.