JPH01308406A - Manufacture of modified dihydrodicyclopentadiene copolymer resin - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a modified dihydrosyncropentadiene copolymer resin. More specifically, the present invention relates to a method for producing a modified dihydrosyncropentadiene copolymer resin having a high softening point and low melt viscosity.

[Conventional technology]

Traditionally, rosin resins, alkyd resins, epoxy resins, etc. have been used as tackifiers (tackifiers), including adhesive raw materials, in fields such as pressure sensitive adhesives, hot melt adhesives, paints, inks, and traffic paints. is known to be usable. Among these, rosin resins are the most popular, but because these resins rely on natural products as raw materials, they are unable to 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 1,3-pentadiene, isoprene, 2-methyl-
Hydrocarbon resins obtained by polymerizing C6 fractions such as 2-butene using a Friedel-Craft catalyst have come to be used.

Furthermore, U.S. Pat. Proposed.

By the way, with recent hot melt adhesives, there is a need to improve work speed and maintain a uniform coating amount.
In addition, in traffic paint, the need for low melt viscosity tackifiers has been avoided due to the increasing demand for improved workability such as faster work speeds and faster drying speeds due to increased traffic volume. . However, the aforementioned Cs
For 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 melt viscosity. Moreover, a hydrocarbon resin having heat resistance (high softening point) has not been obtained.

Furthermore, in the field of rubber, in order to improve the cut resistance of tire treads, for example, Japanese Patent Publication No. 48-38615 proposes a method of blending SBH with a petroleum resin mainly composed of cyclopentadiene or synchropentadiene. ing.

However, although this method improves tear strength, it has the drawbacks of shortening the scorch time, worsening workability, and decreasing tensile elongation. [Problems to be Solved by the Invention] Therefore, the present inventors As a result of extensive research on copolymer resins with high softening points and low melt viscosity, we have developed copolymer resins containing specific proportions of dihydrosynchropentadienes, synchlopentadienes, and indenes, which are made from unsaturated carboxylic acids or their derivatives. The modified copolymer resin modified with
It was discovered that the composition satisfies the above requirements and is excellent as a tackifier, a composition for traffic paint, a composition for ink, a composition for molded rubber, etc., and the present invention has now been completed.

[Means to solve the problem]

Namely, the present invention provides a copolymer consisting essentially of dihydrosyncropentadienes (A), synclopentadienes (B) and indenes (C), wherein the units of (A) are 80 to 2 mol%, The unit of (B) is 0 to 9
It is characterized by graft copolymerizing an unsaturated carboxylic acid or its derivative component to a copolymer resin in which the units of (C) are copolymerized at a ratio of 0 mol % and 10 to 90 mol %. This is a method for producing a modified dihydrosyncropentadiene copolymer resin.

Dihydrosyncropentadienes used in the present invention (
A) includes 9,10-dihydrocinclopentadiene and 1,2-dihydrocinclopentadiene.

Among these, 9,10-dihydrosyncropentadiene can be obtained by a known method, for example, by selectively hydrogenating synclopentadiene as described in Japanese Patent Publication No. 11818/1983.

These 9,10-dihydrocinclopentadienes include, for example, 9-methyl-9,1O-dihydrocinclopentadiene, 3,9-dimethyl-9,10-dihydrocinclopentadiene, 1,9-dimethyl-9,1
0-dihydrocinclopentadiene, 1.10-dimethyl-9,10-dihydrocinclopentadiene, 1,
Examples include 6-dimethyl-9.10-dihydrocinclopentadiene.

It goes without saying that the 9,10-dihydrosyncropentadiene used in the present invention should be substantially pure, but if it has a purity of about 60% by weight or more in these polymerization components, , In addition to this, cyclopentene, ■,
It may contain polymerizable components such as 2-dihydrocyclopentadiene, partially hydrogenated cyclopentadiene oligomers (trimer or higher), isoprene-cyclopentadiene codimer or partially hydrogenated oligomers, and non-polymerizable components. may contain tetrahydrocinclopentadiene or its derivatives, etc., but,
Cyclopentadiene, synclopentadiene, cyclopentadiene oligomers of trimer or higher and their derivatives should be added in an amount of 10% by weight in this polymerization component, as they may worsen the hue of the produced hydrocarbon flanks and may also be accompanied by gel formation. It is recommended to use the following:

In addition, the 1,2-dihydrocyclopentadiene used in the present invention can be prepared by known methods 1, for example, USP 4.139,5.
It can be obtained by the Diels-Alder reaction between cyclopentenes and cyclopentadiene as described in No. 69. Examples of these 1,2-dihydrocinclopentadienes include 1-methyl-1,2-dihydrocinclopentadiene, 9-methyl-1,2-dihydrocinclopentadiene, and 2,6-dimethyl-1,2-dihydrocinclopentadiene. , l-methyl-9-ethyl-? 1
．． Examples include 2-dihydrocinclopentadiene.

It goes without saying that the 1,2-dihydrosyncropentadiene used in the present invention should be substantially pure, but if the polymerization components have a purity of 60% by weight or more, this It may also contain cyclopentene, synchlopentadiene, cyclopentadiene oligomer (trimer or higher), isoprene-cyclopentadiene codimer or oligomer.

1.2-dihydrocinclopentadiene and 9.10-
The dihydrosynclopentadienes may be used alone or in combination.

Next, examples of the synchropentadiene (B) used as a raw material for the modified copolymer resin of the present invention include synchropentadiene, methyl synchropentadiene, dimethyl synchropentadiene, and other synchropentadiene derivatives. One type or a mixture of two or more of these synchropentadiene components can be used, and a mixed fraction containing these synchropentadiene components can also be used. Among these synchropentadiene components, it is preferable to use synchropentadiene or a mixed fraction containing synchropentadiene in the method of the present invention.

These synchlopentadienes can be easily obtained by a known method, ie, Diels-Alder reaction, and need no explanation.

Furthermore, the indenes (C) used as a raw material for the copolymer resin of the present invention are usually contained in a 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 modification or decomposition of The indenes obtained from these include normal values of polymeric components,
Examples include coumaron, styrene, α-methylstyrene, vinyltoluene, and the like. These components may be included in the indenes as long as they do not impede the effects of the present invention.

Indenes include indene and l-methylindene.

2-methylindene, 3-methylindene, 4-methylindene, 5-methylindene, 6-methylindene,
7-methylindene, 2,5-dimethylindene, 3,
Various alkyl-substituted indenes such as 4-dimethylindene are included.

When producing the copolymer resin of the present invention, since the reactivity of component (A) is lower than that of components (B) and (C),
The proportion of (A) in the monomer mixture must be greater than the units of (A) in the copolymer to be obtained.

Component (A) has different reactivity depending on the position of the double bond, and (A) has 9. In the case of lO-dihydrosyncropentadienes, the proportion of (A) in the monomer mixture depends on the polymerization conditions, but is usually about twice or more the units of (A) in the copolymer to be obtained. In the case where (A) is 1,2-dihydrocinclopentadiene, it is preferably about 1.2 times or more.

For copolymerization, components (A), CB), (C
) A cationic catalyst is used as the copolymerization catalyst. Cationic polymerization catalysts include, for example, Journal of the Japan Petroleum Institute, Vol. 16, No. 10, pp. 865-867 (1
973), specifically the cationic catalyst described in Al2CQ
,,AlBr,,BF3.5rC(1,,FeCQ,,
AQRCQ, (R: alkyl group), etc. Among these, Lewis acids, especially AQ, have a high yield of copolymer resin, good hue, and are easy to obtain products with a high softening point.
C(1,, Al1Br, etc. 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.
Polymerization solvents, generally 0.01 to 10 mol % based on monomer, may or may not be used, but for all catalyst systems propane, butane, pentane, hexane, heptane, benzene, etc. It is possible to use hydrocarbon solvents such as , toluene, xylene, ethylbenzene. In addition, chlorinated solvents such as dichloromethane, ethyl chloride, 1,2-dichloroethane, and chlorobenzene can be used.

The polymerization temperature can be selected from a range of minus several 10° C. to 150° C., and the polymerization time can be selected from a range of 172 to 10 hours. 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 a poor solvent for the copolymer resin, resulting in the desired copolymer resin. can be obtained.

The obtained copolymer resin needs to contain 80 to 2 mol% of units of component (A), preferably 70 to 4 mol%, particularly preferably 60 to 5 mol%, and contains component (B) units of 80 to 2 mol%. ) is required to be O to 90 mol %, preferably O to 80 mol %, particularly preferably 5 to 70 mol %.

It is necessary that the units of component (C) be 10 to 60 mol%, preferably 15 to 85 mol%, particularly preferably 20 to 80 mol%, generally 60 to 180°C, preferably 70 to 170°C. Softening point in °C (
ring and ball method according to JIS K-2531), lO to 10
000 cPS, preferably 10 to 1000 cPS
Melt viscosity (Emiller viscometer, resin temperature 200°C), 3
Number average molecular weight CGPC method (polystyrene conversion method)] within the range of 00 to 3000, preferably 300 to 2000] and 20 to 90, preferably 25 to 8
It has a bromine number of 5.

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 tackifier, 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 dihydrosyncropentadiene, which necessitates, for example, an abnormally high catalyst concentration, which only increases the difficulty in production. In addition, 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, if the unit of component (B) in the copolymer resin exceeds 90 mol%, gel may be formed during polymerization, the molecular weight distribution of the copolymer will become broader, the melt viscosity will increase, and the compatibility with various polymers will be affected. becomes lower.

On the other hand, within the range of the ratio of each polymerized unit specified in the present invention, particularly within the preferred range, a copolymer resin with a low melt viscosity relative to its softening point and excellent hue and heat resistance can be obtained. Moreover, the amount of catalyst used is smaller than when homopolymerizing dihydrosynclopentadienes.

Copolymers of defined units outside this preferred range are
Although it does not show the performance in a copolymer resin having units in a preferable range, the softening point is higher than that of a single dihydrosyncropentadiene resin or a similar resin without a 9.10-dihydrosyncropentadiene unit. It has a relatively low melt viscosity, and has been shown to improve compatibility with other polymers.

The method for controlling the proportion of units of components (A), (B) and (C) in the copolymer within the above range is usually (A)
, (B), and (C) by changing the feed rate ratio.

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,
Unsaturated dicarboxylic acids such as 3-methyl-4-cyclohexene-1,2-dicarboxylic acid and 4-methyl-4-cyclohexene-1,2-dicarboxylic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, glutaconic anhydride acid,
Acid anhydrides of unsaturated dicarboxylic acids such as 2-norbornene-5゜6-dicarboxylic anhydride, tetrahydrophthalic anhydride, monomethyl maleate, monomethyl citraconate, monomethyl itaconate, monomethyl glutaconate, dimethyl maleate, citraconic acid Esters of unsaturated dicarboxylic acids such as dimethyl, dimethyl itaconate, dimethyl glutaconate are preferred, although unsaturated monocarboxylic acids or their esters such as acrylic acid, methacrylic acid, ethyl acrylate, methyl methacrylate may also be used. I can do it. Among the graft copolymerization modified components, α, β-
An unsaturated dicarboxylic acid or an acid anhydride thereof is preferred, and maleic acid or maleic anhydride is particularly preferred.

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 its ester exemplified as the graft copolymerization modification component under heating. This graft copolymerization reaction is usually carried out at about 0.00 parts by weight per 100 parts by weight of the copolymer resin.
This is carried out by heating 0.01 to about 20 parts by weight, preferably 0.01 to 5 parts by weight of the graft copolymerization modification component. The temperature during the graft copolymerization reaction is usually 1
40 to 250°C, preferably 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. In such cases, it is desirable to remove this by distillation or 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 softening. Score is 60-180
℃, particularly preferably 70 to 140℃, 200℃
Melt viscosity measured at °C is 10-too.

One hue (Gardner) in cPs, particularly preferably 10 to 500 cPs, is 18 or less, preferably 16 or less. The degree of modification depends on the amount of unsaturated carboxylic acid used.

Although it can be controlled by the type and amount of the radical initiator, reaction temperature, and reaction time, it is preferable to control by the feed amount of the unsaturated carboxylic acid.

In order to maintain the softening point, melt viscosity and hue as close as possible to the values of the raw resin, the reaction temperature must be kept below 220°C.
Reaction time should be kept to the minimum necessary.

The modified copolymer resin according to the present invention can be used as a tackifier for hot melt adhesives, pressure sensitive adhesives, etc.
It has excellent properties as

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 or synthetic rubber. There are pressure-sensitive adhesives that are made by blending a tackifier and, if necessary, a solvent and other additives with a base resin such as . 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. Moreover, 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 base resins such as ethylene/vinyl acetate copolymer and wax, adhesion, melt viscosity, and flexibility, heat stability, light stability, and color are important. Such good things are required.

On the other hand, also in the case of tackifiers for pressure-sensitive adhesives.

Good compatibility with base resins such as natural rubber and synthetic rubber, good solubility in solvents, chemical stability, and excellent weather resistance.

It is required to have properties such as good hue and no 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, Rubber-like polymers such as polyisobutylene, butyl rubber, polychloroprene, ethylene/propylene copolymer rubber, ethylene/propylene/diene copolymer rubber, styrene/butadiene/styrene block copolymer, styrene/isoprene/styrene block copolymer, etc. 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 a hot melt adhesive composition, the blending ratio of the tackifier is usually 20 to 300 parts by weight per 100 parts by weight of the base resin.
The amount is preferably in the range of 30 to 200 parts by weight, and in the case of pressure sensitive adhesives, it is usually in the range of 20 to 200 parts by weight, preferably 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 hot melt adhesive compositions, plasticizers such as dioctyl phthalate and dibutyl phthalate, waxes such as petroleum-based paraffin wax with a melting point of about 40 to 65°C, polyolefin wax, microwax, and phenol-based or bisphenol-based organic compounds,
Examples include antioxidants such as metal soaps. In addition, 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 and stabilizers.

The blending ratio of these additives is determined as 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 achieve uniform melting. A liquid is prepared and shaped into granules, flakes, pellets, rods, etc. depending on the purpose while cooling. 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 a pressure-sensitive adhesive, a mixture consisting of the modified copolymer resin according to the present invention as a tackifier, the above-mentioned base resin and, if necessary, the above-mentioned various additives, is kneaded on a roll. It can be prepared by conventional methods such as dissolving in a suitable solvent.

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. Due to its excellent stability, a uniform hot melt adhesive composition can be obtained, and this hot melt adhesive composition has excellent heat resistance stability, and has little odor when preparing and using the hot melt adhesive composition. There is an advantage. 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 advantage 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,
Examples include butyl rubber, EPDM, CR, chlorosulfonated polyethylene, and 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, the purpose of addition, and the processability depending on the processing method. 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, stearic acid, zinc white, carbon black, process oil, sulfur, vulcanizing agents such as peroxide, vulcanization accelerators, deterioration inhibitors, various plasticizers, blowing agents,
It is possible to blend refueling agents and the like.

By using the modified copolymer resin of the present invention as a compounding agent for rubber, the tear strength of the rubber product can be improved without reducing the tensile elongation, and the scorch time will not be shortened, so it will not interfere 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 according to the present invention is modified by graft copolymerizing an unsaturated carboxylic acid or its derivative to the copolymer resin, when used as a tackifying agent for hot-melt traffic paint, it has the above-mentioned 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 above-mentioned modified copolymer resin, the hot-melt traffic paint composition also contains pigments such as titanium white, zinc white, yellow lead, red iron oxide, and phthalocyanine green. b); Calcium carbonate, silica sand, cold water sand.

Fillers such as talc and calcium sulfate (C); light-reflective substances such as glass beads or cut glass, or anti-slip substances (d), etc. are added, and if necessary, rosin such as maleated rosin is added. Tackifying agents (e) other than the above-mentioned modified copolymer resins (a) such as modified products, alkyd resins, epoxy resins, polyethylene, polypropylene, ethylene-vinyl acetate copolymers, etc.; synthetic waxes, paraffins; Plasticizers (f) such as wax, dioctyl phthalate, dibutyl phthalate, liquid paraffin, diphenyl chloride, alkyd resin, mineral oil;
A heat stabilizer (g); a weather 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: Pigment (b) ranges from 2 to 200 parts by weight, filler (c) ranges from 50 to 1000 parts by weight, light reflective or anti-slip substance (d) ranges from 30 to 20 parts by weight.
Within the range of 0 parts by weight, tackifiers other than modified copolymer resins (
, ) ranges from 10 to 1000 parts by weight. Other plasticizers (f), heat stabilizers (g) and weather stabilizers (
h) is blended in an appropriate amount as required.

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 tackifier (a) made of a modified copolymer resin, a pigment (b), and a filler (c); a tackifier made of a modified copolymer resin; A composition for a hot-melt traffic paint containing (a), a pigment (b), a filler (c), and a light-reflecting substance or an anti-slip substance (d); a tackifier made of a modified copolymer resin (a), a pigment (b), and a composition for hot-melt traffic paint containing 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) made of the modified copolymer resin of the present invention, a plasticizer (f), if necessary. ), heat stabilizer (g) or weather stabilizer (h)
An appropriate amount of each can be blended.

A method for preparing a composition for hot-melt traffic paint using the modified copolymer resin of the present invention involves stirring the tackifying agent made of the modified copolymer resin in a molten state while adding the pigment, filler, and light. Examples include a method of blending a reflective material or an anti-slip material 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 settling properties and heat-resistant stability, and The weather resistance, stain resistance, and compressive strength of the paint film are improved, and the physical properties of the paint film are improved, such as suppressing the occurrence of hair cracks.In addition, the viscosity when melted is low, which improves workability. have.

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 a resin for printing ink, the amount of unsaturated carboxylic acid or derivatives thereof added to the unmodified resin is generally from 1 to 20% by 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 fat used in the printing ink will be insufficient. Solubility in group 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, diethylamine, cyclohexylamine, dicyclohexylamine, aniline, toluidine, xylidine,
benzylamine, dibenzylamine, naphthylamine,
These are ethylene diamine, butylene diamine, hexylene diamine, phenylene diamine, and xylylene diamine. Also, ethanolamine.

jetanolamine, aminoethylethanolamine,
Compounds having other functional groups in addition to the amino group, such as 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 under a pressure below atmospheric pressure or above atmospheric pressure. Do this for 5 minutes to 5 hours.

The amount of the amino compound added is adjusted so that 0.1 equivalent or more of carboxyl groups or acid anhydride groups in the resin disappear.

Examples of the polyhydric alcohol include compounds of polyhydric alcohols having 2 to 6 carbon atoms, such as ethylene glycol, propylene glycol, butylene gellicol, 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. in a solvent inert to reactions such as, at 100 to 300°C for usually 0.01 hour or more, preferably 0.5
Heat it for 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 the unsaturated carboxylic acid-modified copolymer resin is esterified with the polyhydric alcohol, the esterification rate of the carboxyl groups contained in the unsaturated carboxylic acid-modified copolymer resin is set to 0.1 to 10. %, and particularly preferably the esterification rate is in the range of 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 becomes 0.1.
If it is less than %, the fluidity of the printing ink and the gloss and hue of the printed surface will be poor. 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 As the carboxyl group, one acid anhydride group has two
It shall be calculated as 1 carboxyl group.

The modified resin for printing ink obtained by the above method and blended into printing ink has a particularly high solubility in aliphatic hydrocarbons compared to conventionally synthesized resins.

It is characterized by extremely excellent ink fluidity, ink film drying properties, hue and gloss, and little generation of 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, phenol resins, alkyd resins, or petroleum resins, as needed with the modified resin for printing ink.

〔Effect of the invention〕

According to the present invention, a copolymer resin containing dihydrosyncropentadienes, syncropentadienes, and indenes in a specific proportion is modified with an unsaturated carboxylic acid or a derivative thereof, so that it has a high softening point and a low melt viscosity. Yes, tackifier, traffic paint formulation,
A modified copolymer resin suitable for ink formulations, molded rubber formulations, etc. is 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 C6 fraction obtained by naphtha decomposition was heated at 150° C. for 3 hours to convert the cyclopentadiene contained therein into synchropentadiene. Next, the light fraction was removed by distillation, resulting in a C5 fraction of 8.3%.

Benzene 0.4%, synchropentadiene 78.2%,
Isoprene-cyclopentadiene codimer-5.6%,
Crude synchropentadiene 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 synchropentadiene and a palladium-based hydrogenation catalyst in the form of tablets (Toyo C.C.I. product C3) were placed in a metal autoclave.
1-IA) was 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/aJ, with stirring for 12 hours. Filter to remove the catalyst and distill.9.
94 parts by weight of a 10-dihydrosyncropentadiene fraction was obtained. Gas chromatography analysis results showed 8.8% of pentanes, 79.1% of 9,10-dihydrocinclopentadiene, less than 0.1% of synclopentadiene, 1.4% of tetrahydrocinclopentadiene, and 6.1% of unknown components. The composition is shown.

Reference Example B Naphtha cracked oil was distilled in an Oldershaw-type 40-stage distillation column to obtain indene and methylindene fractions with a boiling point of 50 to 65°C and 710 mmHg. Its composition was as determined by gas chromatography analysis.

(%) 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 Stirrer, water-cooled condenser, thermometer 170 g of the 9.10-dihydrosynchlopentadiene-containing fraction of Reference Example A and 192 g of the indene-containing fraction of Reference Example B were added to a 4-day flask (Ia) equipped with a 1a. 4.6 g of boron trifluoride phenol complex catalyst (containing boron trifluoride 30%) was added dropwise to the mixture using a syringe over about 20 minutes while stirring under a nitrogen atmosphere. It was cooled and heated to maintain the temperature at 60°C. After polymerization for 2 hours, a caustic soda aqueous solution was added to decompose the catalyst, followed by water washing and concentration to obtain 127 g of resin. Table 1 shows the composition, resin properties, and compatibility of the copolymer resin.

〔Evaluation methods〕

1. Compatibility 0: Transparent, Δ: Translucent, ×: Opaque (1) Compatibility with natural rubber and styrene-butadiene rubber Natural rubber (R8S #1) and styrene-butadiene rubber (1502 manufactured by Japan Synthetic Rubber Co., Ltd.) were each mixed with toluene 10
% solution and dissolve an equal amount of copolymer resin to the elastomer.

This was coated on a polyester film to a thickness of about 80 μm, and the transparency of the coated film after drying was evaluated.

(2) Compatibility with ethylene-vinyl acetate copolymer and styrene-isoprene-styrene block copolymer.
The mixture was mixed on a hot plate at 0.degree. C. and coated on a polyester film 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 Nimitsui Polychemicals Same as above (vinyl acetate 28%) Evaflex 210 manufactured by Nimitsui Polychemicals Styrene-isoprene-styrene block copolymer:
Cariflex TR1107 manufactured by Shell Chemical Co., Ltd. 2. Proportion of 9.10-dihydrosynchropentadiene polymer units in the 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. It was determined from the reaction amount ratio of each comonomer.

3. Characteristics of copolymer resin Softening point: JIS K-2531 (ring and ball method) Melt viscosity:
It was measured at 200°C using an Emiller viscometer.

Hue: JIS K-5400 (Gardner method) Bromine number: JIS-2421 Acid number: JIS K-5902 Number average molecular weight (Mn) and molecular weight distribution (My/Mn): G
PC was used to calculate Mn and Mv/Mn with the polystyrene reference method.

Example 1 Anhydrous maleic W was added to 100 parts by weight of the resin obtained in Production Example 1.
2 parts by weight of i was added, and the mixture was stirred and reacted at 200° C. for 2 hours in a nitrogen atmosphere. Unreacted maleic anhydride was removed by distillation to obtain a modified resin. Softening point: 95℃, melt viscosity: 65cP
, hue 12, acid value 9.5, and saponification value 19.0.

Example 2. Comparative Example 1.2 Plasticizer (manufactured by Nippon Sunoil Co., Ltd., Sansen 4240/Samper 150
: 17/83) 24 parts, 300 parts of coarse powdered calcium carbonate (Madozusand #30, manufactured by Nitto Funka Co., Ltd.), 160 parts of finely powdered calcium carbonate, 100 parts of Glass Peas (GB-1537, manufactured by Toshiba Barotini Co., Ltd.), Add 36 parts of heat-resistant yellow lead,
A traffic paint composition was prepared by heating and mixing on an oil bath at 00°C. Commercially available petroleum resin (comparative example 2)
Table 2 shows a comparison with the case where .

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 Measured on a melt at 200°C at a shear rate of 1767 seconds using an Emiller viscosity type rotational viscometer.

3. Stir the melt at 200°C and quickly scoop out a portion of it with a metal ladle (31cm diameter, 24mm depth).

The material was poured onto a smooth aluminum plate from a height of 30 mm, and the long axis and short axis of the disk-shaped material cured on the plate were measured, and the average value was taken as the 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 before and after acceleration (Δ
E) was obtained at Color Studio.

Agent: Patent attorney Sei Yanagi Hara

Claims (2)

[Claims] (1) A copolymer consisting essentially of dihydrodicyclopentadienes (A), synchropentadienes (B) and indenes (C), in which the units of (A) are 80 to 2 mol%, and the units of (B) are Graft copolymerization of an unsaturated carboxylic acid or its derivative component to a copolymer resin in which units of (C) are copolymerized in a ratio of 0 to 90 mol% and units of (C) are copolymerized in a ratio within the range of 10 to 90 mol%. A method for producing a modified dihydrodicyclopentadiene copolymer resin, the method comprising: (2) The method according to claim 1, wherein the modified copolymer resin is used for tackifiers, traffic paint formulations, ink formulations, or molded rubber formulations.