JPH0217564B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a method for producing a modified dihydrodicyclopentadiene copolymer resin. More specifically, the present invention relates to a method for producing a modified dihydrodicyclopentadiene copolymer resin having a high softening point and low melt viscosity. [Conventional technology] Conventionally, pressure sensitive adhesives, hot melt adhesives,
It is known that rosin resins, alkyd resins, epoxy resins, and the like can be used as tackifiers (tackifiers) including adhesive raw materials in the fields of paints, inks, and traffic paints. Among these, rosin-based resins are the most popular, but because these resins rely on natural products as raw materials, they cannot meet the remarkable growth in demand in recent years. Therefore, recently, various petroleum-based hydrocarbon resins have been developed to replace it, and one of them is _C5 -based fractions such as 1,3-pentadiene, isobrene, and 2-methyl-2-butene. Hydrocarbon resins obtained by polymerization using Friedel-Crafts catalysts and the like have come into use. Furthermore, US Pat. No. 3,310,517 proposes a resin made by thermally polymerizing dicyclopentadiene, and Japanese Patent Publication No. 49-2344 proposes a resin made by copolymerizing dicyclopentadiene and an aromatic alkene. There is. By the way, with recent hot melt adhesives, there is a need to increase work speed and maintain a uniform coating amount, and with traffic paint, there is a need to improve work speed and drying speed due to increased traffic volume. Due to the increasing demand for improved workability, the need for low melt viscosity tackifiers is increasing. 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 end up with a high melt viscosity. Therefore, a hydrocarbon resin having low melt viscosity and heat resistance (high softening point) has not been obtained. In addition, in the field of rubber, in order to improve the cut resistance of tire treads, for example,
Publication No. 38615 proposes a method of blending SBR with a petroleum resin mainly composed of cyclopentadiene or dicyclopentadiene. However, although this method improves tear strength, it has shortcomings such as short scorch time, poor workability, and reduced tensile elongation. [Problems to be Solved by the Invention] Therefore, the present inventors conducted extensive studies on copolymer resins with a high softening point and low melt viscosity, and found that
A modified copolymer resin obtained by modifying a copolymer resin containing a specific proportion of dihydrodicyclopentadienes, dicyclopentadienes, and indenes with an unsaturated carboxylic acid or a derivative thereof satisfies the above requirements and is highly durable. It was discovered that this compound is excellent as a compound for fire, traffic paint, ink, molding rubber, etc., and the present invention was thus completed. [Means for Solving the Problems] That is, the present invention provides a copolymer consisting essentially of dihydrodicyclopentadienes (A), dicyclopentadienes (B) and indenes (C),
A copolymer resin in which the units of (A) are copolymerized at a ratio of 80 to 2 mol%, the units of (B) are 0 to 90 mol%, and the units of (C) are copolymerized in a proportion within the range of 10 to 90 mol%. To,
This is a method for producing a modified dihydrodicyclopentadiene copolymer resin, which comprises graft copolymerizing an unsaturated carboxylic acid or its derivative component. The dihydrodicyclopentadiene (A) used in the present invention includes 9,10-dihydrodicyclopentadiene and 1,2-dihydrodicyclopentadiene. Among these, 9,10-dihydrodicyclopentadiene can be prepared by known methods, for example,
It can be obtained by selectively hydrogenating dicyclopentadienes as described in JP-A-11818. These 9,10-dihydrodicyclopentadienes include, for example, 9-methyl-
9,10-dihydrodicyclopentadiene, 3,9
-dimethyl-9,10-dihydrodicyclopentadiene, 1,9-dimethyl-9,10-dihydrodicyclopentadiene, 1,10-dimethyl-9,10-
Examples include dihydrodicyclopentadiene and 1,6-dimethyl-9,10-dihydrodicyclopentadiene. It goes without saying that the 9,10-dihydrodicyclopentadiene used in the present invention should be substantially pure, but it is essential that these polymerization components have a purity of about 60% by weight or more. In addition, it also contains polymerizable components such as cyclopentene, 1,2-dihydrodicyclopentadiene, partially hydrogenated products of cyclopentadiene oligomers (trimers or more), partially hydrogenated products of isoprene-cyclopentadiene codimers or oligomers. It's okay to stay,
It may also contain a non-polymerizable component such as tetrahydrodicyclopentadiene or a derivative thereof. However, cyclopentadiene, dicyclopentadiene, cyclopentadiene oligomers of trimer or higher, and their derivatives, etc., may worsen the hue of the hydrocarbon resin produced and may be accompanied by the formation of gel. % or less. In addition, the 1,2-dihydrodicyclopentadiene used in the present invention can be prepared by a known method such as
Dales combination of cyclopentenes and cyclopentadienes as described in USP4139569.
Obtained by Alder reaction. These 1,2-dihydrodicyclopentadienes include, for example, 1
-Methyl-1,2-dihydrodicyclopentadiene, 9-methyl-1,2-dihydrodicyclopentadiene, 2,6-dimethyl-1,2-dihydrodicyclopentadiene, 1-methyl-9-ethyl-1, Examples include 2-dihydrodicyclopentadiene. It goes without saying that the 1,2-dihydrodicyclopentadiene used in the present invention is substantially pure, but 60%
It may also contain cyclopentene, dicyclopentadiene, cyclopentadiene oligomer (trimer or higher), isoprene-cyclopentadiene codimer or oligomer, as long as it has a purity of at least % by weight. 1,2-dihydrodicyclopentadiene,
Each of the 9,10-dihydrodicyclopentadienes may be used alone or in combination. Next, dihydrodicyclopentadiene (B) used as a raw material for the modified copolymer resin of the present invention includes dicyclopentadiene derivatives such as dicyclopentadiene, methyldicyclopentadiene, and dimethyldicyclopentadiene. .
One or a mixture of two or more of these dicyclopentadiene components can be used, and a mixed fraction containing these dicyclopentadiene components can also be used. Among these dicyclopentadiene components, dicyclopentadiene or a mixed fraction containing dicyclopentadiene is preferably used in the method of the present invention. These dicyclopentadienes can be easily obtained by a known method, ie, Diels-Alder reaction, and need no explanation. Furthermore, the indenes (C) used as raw materials for the copolymer resin of the present invention are usually contained in the solvent naphtha fraction made from coal tar generated from coke ovens and light oil recovered from coke oven gas, or in petroleum oil. It is contained in the cracked oil that is produced as a by-product during the reforming and field processes. The indenes obtained from these usually contain other polymerization components such as coumaron, styrene, α-methylstyrene, and vinyltoluene. These components may be included in the indenes as long as they do not impede the effects of the present invention. Indenes include indene, 1-methylindene, 2-methylindene, 3-methylindene,
4-methylindene, 5-methylindene, 6-
Methylindene, 7-methylindene, 2,5-
Various alkyl-substituted indenes such as dimethylindene and 3,4-dimethylindene are included. When producing the copolymer resin of the present invention, the components
Since the reactivity of (A) is lower than that of components (B) and (C), the proportion of (A) in the monomer mixture is lower than the units of (A) in the copolymer to be obtained. We need to make sure that there are more of them. The reactivity of component (A) differs depending on the position of the double bond, and when (A) is a 9,10-dihydrodicyclopentadiene, the proportion of (A) in the monomer mixture depends on the polymerization conditions. Although it depends on the situation, it is preferable that the number of units is approximately twice or more than the units of (A) in the copolymer to be obtained, and when (A) is 1,2-dihydrodicyclopentadiene, it is approximately It is preferable to set it to 1.2 times or more. For copolymerization, a catalyst may be added to a monomer mixture of components (A), (B), and (C) in a predetermined ratio, and the mixture may be reacted at a predetermined temperature for a predetermined time. A cationic catalyst is used as the copolymerization catalyst. The cationic polymerization catalyst includes, for example, the cationic catalyst described in Journal of the Japan Petroleum Institute, Vol. 16, No. 10, pp. 865-867 (1973);
_AlCl3 , _AlBr3 , _BF3 , _SrCl4 , _FeCl3 , _AlRCl2
(R: alkyl group), etc. Among these, Lewis acids, especially Lewis acids, have a high yield of copolymer resin, good hue, and easy to obtain products with high softening points.
AlCl ₃ and AlBr ₃ are excellent. The amount of each of the above polymerization catalysts used varies depending on the type of catalyst, combination of comonomers, polymerization temperature, polymerization time, etc., but is generally 0.01 to 10 mol% based on the monomer. Polymerization solvents may or may not be used, but hydrocarbon solvents such as propane, butane, pentane, hexane, heptane, benzene, toluene, xylene, and ethylbenzene can be used for all catalyst systems. . In addition, chlorinated solvents such as dichloromethane, ethyl chloride, 1,2-dichloroethane, and chlorobenzene can be used. The polymerization temperature can be selected from the range of minus several 10℃ to 150℃, and the polymerization time can be selected from 1/2
~10 hours is used. As for the pressure, normal pressure or pressurized conditions are generally used. . 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 the poor solvent of the copolymer resin, and the desired product is removed. A copolymer resin can be obtained. The resulting copolymer resin must contain 80 to 2 mol% units of component (A), preferably 70 to 4 mol%, particularly preferably 60 to 5 mol%.
mol%, and the unit of component (B) is 0 to 90 mol%
, preferably 0 to 80
mol %, particularly preferably 5 to 70 mol %, component
It is necessary that the unit (C) is 10 to 90 mol%, preferably 15 to 85 mol%, particularly preferably 20 to 80 mol%, and generally 60 to 90 mol%.
Softening point of 180℃, preferably 70 to 170℃ (JIS
K-2531 ring and ball method), melt viscosity of 10 to 10,000 cps, preferably 10 to 1,000 cps (Emiller viscometer, resin temperature 200°C), number average molecular weight in the range of 300 to 3,000, preferably 300 to about 2,000 [GPC method (polystyrene conversion method)] and a bromine number of 20 to 90, preferably 25 to 85. When the unit of component (A) in the copolymer resin is less than 2 mol%, attempting to lower the viscosity of the resulting resin will lower the softening point, and conversely, attempting to raise the softening point will increase the viscosity. When used as a tatsuki fire, etc., a satisfactory balance between workability and performance cannot be obtained. On the other hand, if it exceeds 80 mol%, homopolymerization becomes poor due to the structure of dihydrodicyclopentadiene, which requires, for example, an abnormally high catalyst concentration, which only increases the difficulty in production. Moreover, it is difficult to increase the molecular weight in terms of quality, resulting in problems such as a low softening point, poor hue, and poor thermal stability. In addition, the unit of component (B) in the copolymer resin is 90 mol%
If it exceeds this amount, gel will be produced as a by-product during polymerization, the molecular weight distribution of the copolymer will become broader, the melt viscosity will increase, and the compatibility with various polymers will decrease. On the other hand, within the range of each polymerized unit in the proportions defined in the present invention, particularly within its preferred range,
A copolymer resin having a low melt viscosity relative to its softening point and excellent hue and heat resistance can be obtained, and moreover, the amount of catalyst used can be smaller than when homopolymerizing dihydrodicyclopentadienes. Copolymers with defined units outside this preferred range do not exhibit the same performance as copolymer resins with units within the preferred range, but monopolymers of dihydrodicyclopentadienes and 9,10-dihydrodicyclo Compared to the same type of resin that does not have pentadiene units, it has a lower melt viscosity compared to its softening point, and is seen to have improved compatibility with other polymers. The method for controlling the ratio of units of components (A), (B) and (C) in the copolymer within the above range is usually (A),
This can be done by changing the feed amount ratio of (B) and (C). The softening point and molecular weight of copolymer resins can usually be increased by lowering the polymerization temperature. Furthermore, the melt viscosity of the copolymer resin can be lowered by lowering the monomer concentration. The color of the resin can be improved by lowering the polymerization temperature and reducing the catalyst concentration. In order to modify the copolymer resin according to the present invention with an unsaturated carboxylic acid or a derivative thereof, for example, maleic acid, fumaric acid, tetrahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 2-norbornene-5,6- Dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, 3-methyl-
4-Cyclohexene-1,2-dicarboxylic acid, 4
-Unsaturated dicarboxylic acids such as methyl-4-cyclohexene-1,2-dicarboxylic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, glutaconic anhydride, 2-norbornene-5,6-dicarboxylic anhydride, tetrahydro anhydride Acid anhydrides of unsaturated dicarboxylic acids such as phthalic acid, unsaturated dicarboxylic acids such as monomethyl maleate, monomethyl citraconate, monomethyl itaconate, monomethyl glutaconate, dimethyl maleate, dimethyl citraconate, dimethyl itaconate, and dimethyl glutaconate. Although esters of acids are preferred, unsaturated monocarboxylic acids or esters thereof such as acrylic acid, methacrylic acid, ethyl acrylate, methyl methacrylate and the like can also be used. Among the graft copolymerization modification components, α,β-unsaturated dicarboxylic acids or acid anhydrides thereof are preferred;
Particularly preferred is maleic acid or maleic anhydride. The modified copolymer resin can be obtained by reacting the copolymer resin according to the present invention with the unsaturated carboxylic acid, its acid anhydride, or ester exemplified as the graft copolymerization modification component under heating. In this graft copolymerization reaction, the copolymer resin
Usually about 0.01 to about 20 parts by weight per 100 parts by weight,
This is preferably carried out by heating 0.1 to 5 parts by weight of the graft copolymerization modification component.
The temperature during the graft copolymerization reaction is usually 140 to
250°C, preferably in the range of 160 to 220°C,
It is also possible to carry out the reaction in the presence of a conventional radical polymerization initiator in order to accelerate the reaction.
If the unreacted graft copolymerization modified component is present in the mixture after completion of the reaction, it is distilled off,
It is desirable to remove it by other conventional methods.
Moreover, the graft copolymerization reaction can also be carried out in the presence of an aliphatic hydrocarbon solvent or an aromatic hydrocarbon solvent, if necessary. When a modified copolymer resin obtained by modifying the copolymer resin according to the present invention is used in a traffic paint described below, the preferred degree of modification is a saponification number of 0.2 to 60, particularly preferably 0.5 to 30, and a softening point of 60. ~180℃, especially preferably 70-140℃, melt viscosity measured at 200℃ is 10-10000cPs
and particularly preferably 10 to 500 cPs. Hue (Gardner) is 18 or less, preferably 16 or less. The degree of modification can be controlled by the amount of unsaturated carboxylic acid used, the type and amount of radical initiator, reaction temperature, and reaction time, but it is preferably controlled by the feed amount of unsaturated carboxylic acid. In order to maintain the softening point, melt viscosity and hue as closely as possible to the values of the raw resin, the reaction temperature must be adjusted.
The temperature should be kept below 220°C, and the reaction time should be kept to the minimum necessary. The modified copolymer resin according to the present invention has excellent properties as a tackifier for hot melt adhesives, pressure sensitive adhesives, and the like. Adhesive compositions generally 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, as well as natural rubber, synthetic rubber, etc. There are pressure-sensitive adhesives that are made of a base resin mixed with a tackifier and, if necessary, a solvent and other additives. The former hot melt adhesive is generally used for bookbinding, canning, woodworking, laminating, sealing,
It is used as an adhesive or coating agent in fields such as coating processing. The latter pressure-sensitive adhesive is generally coated on a base material such as paper, cloth, or plastic film for use in adhesive tapes, labels, and the like. In each 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 the base resin such as ethylene/vinyl acetate copolymer and wax, adhesiveness, melt viscosity, and flexibility, heat stability, light stability, hue, etc. Good things are required. On the other hand, in the case of tackifiers for pressure-sensitive adhesives,
It must have excellent compatibility with base resins such as natural rubber and synthetic rubber, it must have good solubility in solvents, it must be chemically stable and have excellent weather resistance, and it has a good hue. It is required to have properties such as not having a strong odor. When the modified copolymer resin according to the present invention is used as a tackifier in a pressure-sensitive adhesive, specific examples of the base resin include natural rubber,
Styrene-butadiene copolymer rubber, polybutadiene, polyisoprene, polyisobutylene, butyl rubber, polychloroprene, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-butadiene-styrene block copolymer, styrene-isoprene Rubbery polymers such as styrene block copolymers are used. When used as a hot melt adhesive, specific examples of the base resin include ethylene/vinyl acetate copolymer, polyethylene, polypropylene, ethylene/propylene copolymer,
Ethylene/acrylic acid copolymer, polyester,
Polyamide, polyvinyl acetate, etc. are used.
In the case of hot melt adhesive compositions, it is particularly preferred to use an ethylene/vinyl acetate copolymer as the base resin. When the modified copolymer resin according to the present invention is used as a tackifier, the blending ratio with the base resin varies somewhat depending on the hot melt adhesive composition and the pressure sensitive adhesive composition. In the case of hot melt adhesive compositions, the blending ratio of the tackifier is usually 20 to 300 parts by weight, preferably 20 to 300 parts by weight, based on 100 parts by weight of the base resin.
The amount ranges from 30 to 200 parts by weight, and in the case of pressure-sensitive adhesives, it usually ranges from 20 to 200 parts by weight, preferably from 30 to 150 parts by weight, based on 100 parts by weight of the base resin. In addition to the essential components of the tackifier and the base resin, various additives may be added to the adhesive composition using the modified copolymer resin according to the present invention, 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, microwaxes, and phenols are used. Antioxidants such as organic compounds based on bisphenol or metal soaps, and the like can be mentioned. In addition, in the case of pressure sensitive adhesive compositions, plasticizers such as dioctyl phthalate, dibutyl phthalate, machine oil, process oil, polybutene,
Examples include fillers such as calcium carbonate, zinc white, titanium oxide, and silica, anti-aging agents such as amine-based, ketone-amine-based, and phenol-based anti-aging agents, and stabilizers. The blending ratio of these additives is arbitrary and appropriate. The method for preparing an adhesive composition using the modified copolymer resin according to the present invention differs depending on whether it is a hot melt adhesive composition or a pressure sensitive adhesive.
A hot melt adhesive composition is prepared by stirring a mixture consisting of a tackifier copolymer resin, the base resin, and, if necessary, the various additives described above, while heating and melting the mixture to form a uniform melt. is prepared and shaped under cooling into granules, flakes, pellets, rods, etc. depending on the purpose. This hot melt adhesive composition is melted again and used for adhesion or coating purposes. For example, when used for bonding purposes, a rod-shaped compound is used to bond corners of molded products by filling it into a welding gun. On the other hand, as a method for preparing pressure sensitive adhesives,
A mixture consisting of the modified copolymer resin according to the present invention as a tackifier, the base resin and, if necessary, the various additives described above, is kneaded on a roll or dissolved in a suitable solvent. It can be prepared by the following method. Among the adhesive compositions using the modified copolymer resin according to the present invention, when hot melt adhesive compositions are used as adhesives or coating agents, these resins have excellent compatibility with the base resin and are heat resistant and stable. Because of its excellent properties, a uniform hot melt adhesive composition can be obtained, and this hot melt adhesive composition has the advantage of excellent heat resistance stability and low odor when preparing and using the hot melt adhesive composition. . Furthermore, even if the modified copolymer resin of the present invention is used in a pressure-sensitive adhesive composition, the modified copolymer resin of the tackifier has excellent weather resistance in addition to the above-mentioned characteristics, so that uniform adhesive compositions can be obtained. A pressure sensitive adhesive composition is obtained,
This pressure-sensitive adhesive composition has the advantages of excellent weather resistance and low odor. Next, the modified copolymer resin of the present invention can be used as a compounding agent for molded rubber. Rubbers to which the copolymer resin of the present invention is blended include natural rubber, polybutadiene rubber, SBR, isoprene rubber, butyl rubber, EPDM, CR, chlorosulfonated polyethylene, etc.
SBR is particularly preferred. The blending ratio of the modified copolymer resin of the present invention in these rubbers varies depending on the type of rubber, purpose of addition, and processability depending on the processing method, but is usually 5 to 40 parts by weight per 100 parts by weight of rubber. Preferably it is 5 to 20 parts by weight. Various compounding chemicals generally used for compounding rubber can be used as they are in the rubber to which the modified copolymer resin of the present invention is compounded. That is, vulcanizing agents such as stearic acid, zinc white, carbon black, process oil, sulfur, and peroxide, vulcanization accelerators, deterioration inhibitors, various plasticizers, blowing agents, flame retardants, etc. can be blended. . By using the modified copolymer resin of the present invention as a compounding agent for rubber, the tensile strength of rubber products is improved without reducing the tensile elongation, and the scorch time is not shortened, so there is no problem with workability during processing. Does not cause It is presumed that the above effect is due to the reaction between a vulcanizing agent such as sulfur and the resin of the present invention during vulcanization. Since the resin of the present invention has these effects, it is suitable for improving the cut resistance of tire treads and other rubber products. Furthermore, the modified copolymer resin according to the present invention has a high softening point and low melt viscosity, and is excellent in terms of tack, adhesive strength, and cohesive force, so it can be used in tackifiers, paint formulations, and printing inks. In addition to being used as a raw material for resins, it can also be used as a reactant to improve adhesive strength and cohesive strength. When the modified copolymer resin of the present invention is modified by graft-copolymerizing an unsaturated carboxylic acid or a derivative thereof, when used as a tackifying agent for hot-melt traffic paint, it has the above-mentioned properties and other properties. It exhibits excellent performance in terms of hue, heat stability, weather stability, filler sedimentation, workability, stain resistance, compressive strength, and hair crack resistance. In particular, since the modified copolymer resin of the present invention exhibits low viscosity when melted, workability is significantly improved. Next, a hot-melt traffic paint composition containing a modified copolymer resin as a tackifying agent will be described. In addition to the tackifying agent (a) made of the modified copolymer resin, this hot-melt traffic paint composition usually contains pigments such as titanium white, zinc white, yellow lead, red iron, and phthalocyanine green. (b); Fillers such as calcium carbonate, silica sand, cold water sand, talc, calcium sulfate, etc.; (c); Light reflective substances such as glass beads or cut glass, or anti-slip substances (d); rosin modified products such as maleated rosin, alkyd resins, epoxy resins, polyethylene, polypropylene, ethylene-vinyl acetate copolymers, etc.
Tackifiers other than (a) (e); Plasticizers (f) such as synthetic waxes, paraffin waxes, dioctyl phthalate, dibutyl phthalate, liquid paraffin, diphenyl chloride, alkyd resins, and mineral oils; Heat stabilizers ( g); Weathering stabilizer (h) etc. are blended. When the modified copolymer resin of the present invention is blended into a hot-melt traffic paint composition, the blending ratio is as follows:
For 100 parts by weight of (a), the pigment (b) is in the range of 2 to 200 parts by weight, the filler (c) is in the range of 50 to 1000 parts by weight, and the light-reflecting substance or anti-slip substance (d) is in the range of 2 to 200 parts by weight. 30
The amount of the tackifier (e) other than the modified copolymer resin is in the range of 10 to 1000 parts by weight. Other plasticizers (f), heat stabilizers (g), and weather stabilizers (h) are blended in appropriate amounts as necessary. The hot-melt traffic paint compositions using the modified copolymer resin of the present invention include, for example, the following types depending on the components contained in the composition. That is, a hot-melt traffic paint composition containing a tackifying agent (a) made of a modified copolymer resin, a pigment (b), and a filler (c);
Tackifying agent (a) consisting of modified copolymer resin, pigment
(b), a composition for hot-melt traffic paint containing a filler (c) and a light-reflecting substance or an anti-slip substance (d); a tackifying agent (a) consisting of a modified copolymer resin; Examples include compositions for hot-melting traffic paint containing a pigment (b) and a light-reflecting substance or an anti-slip substance (d). Any of these hot-melt traffic paint compositions may contain a tackifier (e) other than the tackifier (a) comprising the modified copolymer resin of the present invention, if necessary.
Appropriate amounts of a plasticizer (f), a heat stabilizer (g), or a weather stabilizer (h) can be added. As a method for preparing a hot-melt traffic paint composition using the modified copolymer resin of the present invention, the pigment, filler, Examples include a method of blending a light-reflecting substance or an anti-slip substance and other components as necessary, or a method of mixing all the components and then melting them. The hot-melt traffic paint composition using the modified copolymer resin of the present invention can be easily applied using a conventional hot-melt traffic paint application machine. As detailed above, the hot-melt traffic paint composition using the modified copolymer resin of the present invention has excellent physical properties such as filler sedimentation properties and heat-resistant stability, and can be obtained easily. weather resistance of the coating film,
In addition to improving the physical properties of the coating film, such as improved stain resistance and compressive strength, and suppressing the occurrence of hair cracks, it also has the characteristics of improved workability due to its low viscosity when melted. Moreover, the modified copolymer resin according to the present invention can be used as a raw material for a resin for printing ink. When a modified copolymer resin is used as a raw material for printing ink resin, the amount of unsaturated carboxylic acid or derivatives thereof added to the unmodified resin is usually 1 to 20%.
Weight%. If the amount added is less than 1% by weight, the final printing ink resin will not have sufficient drying properties and gloss, and if it is more than 20% by weight, the aliphatic resin used in the printing ink will be insufficient. Solubility in hydrocarbons decreases. In order to produce a printing ink resin from the modified copolymer resin, the modified copolymer resin may be further reacted with a compound having an amino group or a polyhydric alcohol. Compounds having an amino group used in this case include aliphatic, alicyclic and aromatic primary and/or secondary monoamines or polyamines having 1 to 10 carbon atoms, such as methylamine, dimethylamine, Ethylamine, diethylamine, propylamine, dipropylamine, butylamine, dibutylamine, hexylamine, dihexylamine, cyclohexylamine, dicyclohexylamine, aniline, toluidine, xylidine, benzylamine, dibenzylamine, naphthylamine, ethylenediamine, butylene diamine, hexylene These are diamine, phenylene diamine, and xylylene diamine. Compounds having other functional groups in addition to the amino group, such as ethanolamine, diethanolamine, aminoethylethanolamine, morpholine, and 6-aminocapronitrile, can also be used. The reaction between the resin to which an unsaturated carboxylic acid or its derivative has been added and the amino compound is carried out without a solvent or in a solvent inert to the reaction at a temperature of 50 to 300°C at a pressure below or above atmospheric pressure. Do this for 5 minutes to 5 hours. The amount of amino compound added depends on the carboxyl group or acid anhydride group in the resin.
Adjustment is made so that 0.1 equivalent or more disappears. Examples of the polyhydric alcohol include compounds of polyhydric alcohols having 2 to 6 carbon atoms, such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, glycerin, and pentaerythritol. Among these polyhydric alcohols, diethylene glycol is preferably used. As a method for esterifying the copolymer resin modified with the unsaturated carboxylic acid or its derivative with these polyhydric alcohols, the unsaturated carboxylic acid-modified copolymer resin and the polyhydric alcohol are mixed without a solvent or with a hydrocarbon compound. The reaction is carried out by heating in a solvent inert to the reaction at 100 to 300°C for usually 0.01 hour or more, preferably 0.5 to 5 hours. At this time, general esterification catalysts such as sulfuric acid, p-toluenesulfonic acid, and metal halides may be added. In this case, when esterifying the unsaturated carboxylic acid-modified copolymer resin with the polyhydric alcohol, the esterification rate of the carboxyl groups contained in the unsaturated carboxylic acid-modified copolymer resin may be controlled.
The esterification rate is preferably 0.1 to 10%, and particularly preferably 1 to less than 5%. If the esterification rate of carboxyl groups contained in the unsaturated carboxylic acid-modified copolymer resin is greater than 10%, the solubility in aliphatic hydrocarbon solvents and the flow of printing ink will decrease when used as a resin for printing ink. The gloss and hue of the printed surface become poor, and the esterification rate is 0.1%.
If the size is smaller, the fluidity of the printing ink and the gloss and hue of the printed surface will deteriorate. Here, when an anhydride of an unsaturated carboxylic acid such as maleic anhydride or citraconic anhydride is used as the unsaturated carboxylic acid to modify the copolymer resin, the unsaturated carboxylic acid-modified copolymer resin contains Regarding the carboxyl groups included in the formula, one acid anhydride group is calculated as two carboxyl groups. The modified resin for printing ink obtained by the above method and blended into printing ink has improved solubility in aliphatic hydrocarbons, fluidity of ink, and drying of ink film compared to conventionally synthesized resins. It is characterized by its outstanding properties of color, color and gloss, and by the fact that it produces fewer ink droplets during printing. Further, as the pigment to be blended into the printing ink using the above-mentioned modified resin for printing ink, any pigment conventionally blended into printing ink can be used. Further, the blending ratio of the pigment is also an arbitrary ratio that has been conventionally blended into printing inks. Further, in this case, any solvent can be used as long as it is a usual solvent that has been conventionally mixed in printing ink. In addition to the three essential components of the modified resin for printing ink, pigment, and solvent as described above, the printing ink using the above-mentioned modified resin for printing ink may contain components such as auxiliary agents and drying oil as necessary. You can also do it.
It is also possible to mix and use other resins, such as rosin derivatives, phenolic resin alkyd resins, or petroleum resins, as needed with the modified resin for printing ink. [Effects of the Invention] According to the present invention, a copolymer resin containing a specific proportion of dihydrodicyclopentadiene, dicyclopentadiene, and indene is modified with an unsaturated carboxylic acid or a derivative thereof, so that the softening point is lowered. A modified copolymer resin having a high and low melt viscosity and suitable for use in tackifiers, traffic paint formulations, ink formulations, molded rubber formulations, etc. can be obtained. [Example] Hereinafter, the present invention will be specifically explained with reference to Examples. In the examples, percentages are by weight unless otherwise specified. Reference Example A A _C5 fraction obtained by naphtha decomposition was heated at 150°C for 3 hours to convert the cyclopentadiene contained therein into dicyclopentadiene. Next, by removing the light fraction by distillation, the _C5 fraction is 8.3%,
Benzene 0.4%, dicyclopentadiene 78.2%,
Isoprene-cyclopentadiene codimer 5.6
%, crude dicyclopentadiene having a composition consisting of 5.1% cyclopentadiene oligomer and 2.4% unknown components was obtained. In a metal autoclave, 100 parts by weight (1500 g) of this crude dicyclopentadiene and a palladium-based hydrogenation catalyst in the form of tablets (Toyo Sea, Sea,
4 parts by weight of Ai Co. product C31-1A) were charged, and a hydrogenation reaction was carried out under the conditions of a reaction temperature of 50° C. and a hydrogen pressure of 10 Kg/cm ² with stirring for 12 hours. The catalyst was removed by filtration and distilled to obtain 94 parts by weight of a 9,10-dihydrodicyclopentadiene fraction. Gas chromatography analysis results showed a composition of 8.8% pentanes, 79.1% 9,10-dihydrodicyclopentadiene, less than 0.1% dicyclopentadiene, 1.4% tetrahydrodicyclopentadiene, and 6.1% unknown components. Reference example B: Naphtha cracked oil is distilled in an Olderschau type 40-stage distillation column to produce indene with a boiling point of 50-65℃/10mmHg.
A methylindene fraction was obtained. As a result of gas chromatography analysis, its composition was as follows. (%) Styrene 0.2 α-methylstyrene 0.9 Dicyclopentadiene 5.0 Vinyltoluene 8.6 Indene 29.5 Methyl indene 16.4 Total polymerization components 60.6 Production example 1 1 with a stirrer, water-cooled condenser, and thermometer
170 g of the 9,10-dihydrodicyclopentadiene-containing fraction of Reference Example A and 192 g of the indene-containing fraction of Reference Example B were added to a four-necked flask. 4.6 g of a boron trifluoride phenol complex catalyst (boron trifluoride content: 30%) was added to this under a nitrogen atmosphere with stirring using a syringe over about 20 minutes. It was cooled and heated to maintain the temperature at 60°C. After polymerization for 2 hours, aqueous caustic soda solution was added to decompose the catalyst, followed by washing with water and concentration to obtain 127 g of resin. Table 1 shows the composition, resin properties, and compatibility of the copolymer resin.

【table】

〔Evaluation methods〕

1 Compatibility 〇: Transparent, △: Translucent, ×: Opaque (1) Compatibility with natural rubber, styrene-butadiene rubber Natural rubber (RSS#1), styrene-butadiene rubber (1502 manufactured by Japan Synthetic Rubber Co., Ltd.) Each was prepared in a 10% toluene solution, the copolymer resin was dissolved in the same amount as the elastomer, and this was coated on a polyester film to a thickness of about 80μ to evaluate the transparency of the coating after drying. . (2) Compatibility with ethylene-vinyl acetate copolymer and styrene-isoprene-styrene block copolymer Mix equal amounts of these copolymers and copolymer resin on a hot plate at 180°C, and place this on a polyester film. The coating was applied to a thickness of about 1 mm, and the transparency of the coating film was evaluated. The copolymers used are as follows. Ethylene-vinyl acetate copolymer (vinyl acetate
19%): Evaflex 410 manufactured by Mitsui Polychemicals Same as above (vinyl acetate 28%): Evaflex 210 manufactured by Mitsui Polychemicals Styrene-isoprene-styrene block copolymer: Califlex manufactured by Ciel Chemical Co., Ltd.
TR1107 2 Ratio of 9,10-dihydrodicyclopentadiene polymer units in copolymer 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 the amount of each comonomer was determined by gas chromatography. It was determined from the reaction amount ratio of the body. 3 Characteristics of copolymer resin Softening point: JIS K-2531 (ring and ball method) Melt viscosity: Measured at 200°C using an Emiller viscometer. Color: JIS K-5400 (Gardner method) Bromine number: JIS K-2421 Acid number: JIS K-5902 Number average molecular weight (n) and molecular weight distribution (w/
n): Mn and w/n were calculated using GPC using the polystyrene reference method. Example 1 2 parts by weight of maleic anhydride was added to 100 parts by weight of the resin obtained in Production Example 1, and the mixture was heated at 200°C in a nitrogen atmosphere.
The reaction mixture was stirred for hours. Unreacted maleic anhydride was removed by distillation to obtain a modified resin. Softening point 95
°C, melt viscosity 65cP, hue 12, acid value 9.5, saponification value
It was 19.0. Example 2, Comparative Examples 1 and 2 A plasticizer (manufactured by Nippon Sunoil Co., Ltd., Sansen , 4240/
Thumper 150: 17/83) 24 parts, coarse powder calcium carbonate (Nitto Funka Co., Ltd. Kansui Sand #30) 300 parts, fine powder calcium carbonate 160 parts, glass beads (Toshiba Balloteini GB-153T) 100 parts, 36 parts of heat-resistant yellow lead was added and mixed while heating on a 200°C oil bath to prepare a traffic paint composition. The performance is shown in Table 2 in comparison with the case of using a commercially available petroleum resin (Comparative Example 2). From the results in Table 2, it can be seen that the carboxylic acid-modified copolymer resin according to the present invention has low viscosity, excellent fluidity, high compressive strength, and excellent weather resistance.

〔Evaluation methods〕

1 Softening point According to the method of JIS K-5665. 2 Melt viscosity Using an Emiller viscosity type rotational viscometer, shear rate
Measured on a 200°C melt at 176/s. 3 Fluidity Stir the molten material at 200℃ and use a metal ladle (31mm diameter,
24 mm deep), pour it onto a smooth aluminum plate from a height of 30 mm, measure the major and minor axes of the hardened disk on the plate, and calculate the average value. It was also defined as fluidity. 4 Compressive strength According to the method of JIS K-5665. 5 Weather resistance A test piece is prepared by the method described in 5 to 6 of JIS K-5665. Next, the test piece was accelerated for 60 hours using a sunshine weather meter, and the color difference (△E) before and after the acceleration was determined using a color studio.

Claims (1)

[Scope of Claims] 1. A copolymer consisting essentially of dihydrodicyclopentadiene (A), dicyclopentadiene (B) and indene (C), wherein the units of (A) are 80 to 2 mol%, the units of (B) are 0 to 90 mol% and (C)
A modified dihydrodicyclopentadiene copolymer characterized by graft copolymerizing an unsaturated carboxylic acid or its derivative component to a copolymer resin in which units of are copolymerized in a proportion within the range of 10 to 90 mol%. Method for producing combined resin. 2. Claim 1 in which the modified copolymer resin is for use in tackifiers, traffic paint formulations, ink formulations or molded rubber formulations.
Manufacturing method described in section.