JPS6211704A - Production of modified hydrocarbon resin - Google Patents

Abstract

PURPOSE:To obtain a modified hydrocarbon resin, useful as a tackifier, etc., and having a high softening point and low melt viscosity, by subjecting a copolymer of a chain unsaturated hydrocarbon, a cyclic hydrocarbon having vinylidene group, etc., in a specific proportion to addition reaction of an alpha,beta-unsaturated carboxylic acid, etc. CONSTITUTION:A copolymer, consisting (A) 20-98mol% chain unsaturated hydrocarbon, e.g. ethylene or 2,3-dimethyl-1,3-butadiene, and/or cyclic hydrocarbon having vinylidene group, e.g. 1,2-dimethylcyclohexane, and (B) 80-2mol% 9,10-dihydrodicyclopentadiene, or a derivative thereof and having preferably >=60 deg.C softening point, <=10,000 cP melt viscosity and 300-3,000 molecular weight is subjected to addition reaction of an alpha,beta-unsaturated carboxylic acid or derivative thereof, e.g. maleic acid, in an amount of normally 0.01-50pts.wt. based on 100pts.wt. hydrocarbon resin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a modified hydrocarbon resin. More specifically, the present invention relates to a method for producing a novel modified hydrocarbon resin having a high softening point and low melt viscosity.

It has long been known that rosin resins, alkyd resins, epoxy resins, etc. can be used as tackifiers, including adhesive raw materials, in fields such as pressure sensitive adhesives, hot melt adhesives, paints, and traffic paints. There is. 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, in recent years, various petroleum-based hydrocarbon resins have been developed to replace them, and one of them is a method that is free of C5 fractions such as 1,3-pentadiene, isoprene, and 2-methyl-2-butene. Hydrocarbon resins obtained by polymerization using Dell-Krauch catalysts and the like have come to be used.

By the way, in the hot melt adhesive [L], due to the need to improve work speed and maintain a uniform coating amount,
In addition, in traffic paint, the need for low melt viscosity tackifiers is increasing due to increasing demands for improved workability such as faster work speeds and faster drying speeds due to increased traffic volume. ing. However, the aforementioned 0
For 5-series hydrocarbon 4iIIJ 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, the melt viscosity will be high, and the softening point will be lowered. A hydrocarbon resin having a high melt viscosity and heat resistance (high softening point) has not been obtained.

Therefore, as a result of various studies on hydrocarbon resins with a high softening point and low melt viscosity, the present inventors found that a chain unsaturated hydrocarbon and/or a cyclic hydrocarbon having a vinylidene group and a 9,10-dihydrodicyclo A modified product of a copolymer with a specific proportion of pentadiene or a derivative thereof satisfies such requirements, and a modified hydrocarbon resin made of a modified product of such a copolymer has excellent suitability for compressive strength, weather resistance, etc. The present invention was completed based on the discovery that the present invention can be used as a tackifier.

Therefore, the present invention relates to a novel method for producing a modified hydrocarbon resin, in which a chain unsaturated hydrocarbon and/or a cyclic hydrocarbon having a vinylidene group and a 9,10- A copolymer consisting essentially of dihydrodicyclopentadiene or a derivative thereof, wherein the polymerized units of the hydrocarbons are 20 to 98 mol%, and 9, 1
80 polymerized units of 0-dihydrodicyclopentadiene
It is copolymerized at a ratio within the range of ~2 mol%, and generally 6
Addition reaction of an α,β-unsaturated carboxylic acid or a derivative thereof to a hydrocarbon resin having a softening point of 0°C or higher, a melt viscosity of 10,000 cps or lower, and a molecular weight within the range of 300 to 3,000. This is done by

The chain unsaturated hydrocarbon forming the hydrocarbon resin used in the present invention is preferably a monoolefin or diolefin. The monoolefin preferably has the general formula R
A compound represented by RC=CR3R4 (where R to R3 are each a hydrogen atom or a methyl group, and R4 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms),
Specifically, for example, ethylene, 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. In addition, the diolefin preferably has the general formula % where R1□ is a hydrogen atom or a methyl group, R,
R, R, R to R and R18 are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 4), and specifically, for example, 1
, 3-butadiene, isoprene, 2,3-dimethyl-1
, 3-butadiene, 1,3-pentadiene, 2.3-dimethyl-1,3-hexadiene, 1.4-pentadiene, 3.4.5-trimethyl-1,6-heptadiene, and the like.

In addition, nylidene groups (C
The cyclic hydrocarbon having H2=C<group) is preferably a compound represented by each of the following general formulas, [I), U)Cu1l)
(Here, R19 to R22 are each a hydrogen atom or a methyl group, R23 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, m is an integer of O to 3, and when m is 2 to 3, R23 may be the same or different, R24 is a saturated or unsaturated hydrocarbon chain, J is O or 1, X is a saturated or unsaturated hydrocarbon chain having 2 to 6 carbon atoms, and Y is a carbon 3 to 7 saturated or unsaturated hydrocarbon chains, the hydrocarbon chains represented by X and Y may be substituted with an alkyl group, a halogen atom, etc.), specifically, for example, 1.2- dimethylidenecyclohexane,
Examples include 1,2-dimethylidenecyclopentane, vinylcyclohexane, limonene, styrene, vinyltoluene, α-methylstyrene, isopropenyltoluene, tert-butylstyrene, allylbenzene, p-tert-butylallylbenzene, and the like.

Among the hydrocarbons listed above, particularly preferred from the viewpoint of resin performance are chain diolefins having 4 to 6 carbon atoms, aromatic alkenyl compounds having 8 to 10 carbon atoms, and carbon atoms having 8 to 10 carbon atoms. Examples include 1,2-dimethylidene compounds.

These hydrocarbons may be used singly or as a mixture of two or more homologous compounds, as well as monoolefins and diolefins, monoolefins and vinylidene group-containing cyclic hydrocarbons, diolefins and vinylidene group-containing cyclic hydrocarbons, and monoolefins and vinylidene group-containing cyclic hydrocarbons. It is used as a mixture of olefins, diolefins, and vinylidene group-containing hydrocarbons. Generally, such mixtures include, for example, a C4 fraction, a C4 fraction of diene extraction residue, a C5 fraction, a C5 fraction of isoprene extraction residue, and a C5 fraction of isoprene extraction residue.
Among those obtained as naphtha cracked oil fractions such as 9 fractions or a mixture of these in arbitrary proportions, those containing a large amount of chain unsaturated hydrocarbons or vinylidene group-containing cyclic hydrocarbons, or those containing 30% of the total polymerized components. Those adjusted to contain at least % by weight of these hydrocarbons 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.

9,10-dihydrodicyclopentadiene or a derivative thereof copolymerized with these hydrocarbons is a compound represented by the following general formula, [IV] [wherein the 1- or 2-position R25 is a hydrogen atom, a halogen atom, a methyl group or a methoxy group,
R26 located at the 3-10-positions is a hydrogen atom, a halogen atom, a hydroxyl group, -R27, -OR, -R290R
3o, -R310H1-co.

(However, R2□, R28, R3o, R3□, and R33 represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group, and R and R each have 1 to 10 carbon atoms.)
~10 alkylene group, R34 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group or an aralkyl group having 6 to 10 carbon atoms), an isocyanate group or an aldehyde group, specifically 1 , for example 9-methyl-9,10-dihydrodicyclopentadiene, 3,
9-dimethyl-9゜10-dihydrodicyclopentadiene, 9-and-droxy-9,10-dihydrodicyclopentadiene, 9-methoxy-9,10-dihydrodicyclopentadiene, 9-acetyl-9,10-dihydrodicyclopentadiene Cyclopentadiene, 9-phenoxy-9,10-dihydrodicyclopentadiene, 9-isocyanate-9,1
0-dihydrodicyclopentadiene, bishydrogen phosphate (
g, io-dihydrodicyclopentagenyl), and the like.

These 9,10-dihydrodicyclopentadienes can be obtained, for example, as follows. First, 9.10-dihydrodicyclopentadiene is produced by heat treating cyclopentadiene in 05m produced by naphtha decomposition etc. to form dicyclopentadiene, and then hydrogenating the double bond of the norbornene ring. can get. Hydrogenation h0 can be carried out using a known method, for example, using one or more of nickel, palladium, cobalt, platinum, ruthenium, rhodium, copper, etc., or oxides of these metals as a hydrogenation catalyst, at room temperature or with heating. This is carried out by adding hydrogen gas at a predetermined molar ratio under normal pressure or increased pressure. Further, a derivative of 9,10-dihydrodicyclopentadiene is synthesized by a method of thermally dimerizing a cyclopentadiene derivative and partially hydrogenating the same. Furthermore, alcohols, carboxylic acids, isocyanic acids,
The P 1 form of 9,10-dihydrodicyclopentadiene can also be synthesized by a method of adding sulfuric acid or the like.

It goes without saying that the 9,10-dihydrodicyclopentadiene used should be substantially pure, but other substances may be used as long as they have a purity of 60% by weight or more in these polymerization components. It may also contain polymerizable components such as cyclopentene, partially hydrogenated cyclopentadiene oligomer (trimer or higher), isoprene-cyclopentadiene codimer or partially hydrogenated oligomer,
It may also contain a non-polymerizable component such as tetrahydrodicyclopentadiene or a derivative thereof.

However, cyclopentadiene,
Dicyclopentadiene, cyclopentadiene oligomers with three or more rings, and derivatives thereof, etc., account for 10% of this polymerization component.
It is desirable to use one that weighs less than 100 lbs.

When copolymerizing hydrocarbons and 9,10-dihydrodicyclopentadiene, 9,10-dihydrodicyclopentadiene generally has low reactivity, so a large amount of 9,10-dihydrodicyclopentadiene is used, and it is brought into contact with a catalyst in advance. Then, by blowing or adding a small amount of hydrocarbons, it is possible to increase the reactivity of 9,10-dihydrodicyclopentadiene and increase the proportion of its polymerization medium. desirable.

9. Diolefins, especially conjugated diolefins, have low neutral hindrance as chain unsaturated hydrocarbons because of their high copolymerizability with 10-dihydrodicyclopentadienes
, 3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-butadiene are preferably used. Furthermore, among vinylidene group-containing cyclic hydrocarbons, those in the general formula [I] in which R1° and R2o are hydrogen atoms, those in the general formula [I[] in which R21 is a hydrogen atom, and those in the general formula [I[ In [], R22 is a hydrogen atom and 1 is O
specifically, 1,2-dimethylidenecyclohexene, vinylcyclohexene, vinylcyclohexane,
Vinyltoluene, tert-butylvinyltoluene, and the like are preferably used for similar reasons.

As the copolymerization catalyst, those known as homopolymerization and copolymerization catalysts for the above-mentioned hydrocarbons can be used as they are. That is, cationic catalysts, anionic catalysts, ionic coordination catalysts, radical catalysts, etc. are used.

Examples of the cationic polymerization catalyst include the cationic polymerization catalyst described in the Japan Petroleum Institute, Vol. 16, No. 10, pp. 865-867 (1973), specifically AJCJ, A, I! Br3
, 8F , 5nCJ , 5bCJ , FeCJ
3. AJRC, Q, (R: alkyl group), AJIEt3
-R20, CCfJ3COOH1H2SO4, etc. Among these, Lewis acid,
Especially AJCJ, A-1! B r 3 etc. are excellent. Furthermore, complexes of these Lewis acids with alcohols, esters, ethers, alkyl halides, etc. can also be suitably used. These polymerization catalysts reduce the catalytic activity of 9.10-dihydrodicyclopentadiene when it contains a hydroxyl group or carbonyl group, but they also reduce the catalytic activity when the 9.10-dihydrodicyclopentadiene does not contain these groups. It can be used without any trouble.

Examples of anionic polymerization catalysts include catalysts for the homopolymerization and copolymerization of hydrocarbons described in Journal of the Japan Petroleum Institute, Vol. 16, No. 9, pp. 779-784 (1973), specifically, KRl
Na, NaR, Li, LiR, 5rZn(R>
, CuZn (R)4 [R: alkyl group], etc. Among these, li and LiR increase the reactivity of 9,10-dihydrodicyclopentadiene, making it a hydrocarbon with a good hue and a high softening point. This is preferred because it provides a resin. These polymerization catalysts are particularly preferably used when the 9,10-dihydrodicyclopentadiene is a derivative containing a carbonyl group.

Examples of ionic coordination polymerization catalysts include Ziegler catalysts described in Japan Petroleum Institute, Vol. 16, No. 8, pp. 699-704 (1973), specifically halides of li, VlCr, and Zr, β-diketone salts, With Alcorado etc./1(R)
,△,Q (R) ,X3-,,LiR1MCIRX
[R: alkyl group; .10-Dihydrodicyclopentadiene is particularly preferred since it increases the reactivity thereof.

These ionic coordination polymerization catalysts include monoolefins such as ethylene, propylene, butene-1, pentene-1, hexene-1,4-methylpentene-1, 1,3-butadiene, isoprene, 1,3-pentadiene, etc. It is a particularly preferred catalyst when a linear unsaturated hydrocarbon such as a conjugated diolefin is used, or when 9,10-dihydrodicyclopentadiene does not contain a hydroxyl group or a carbonyl group.

Radical polymerization catalysts include, for example, Journal of the Japan Petroleum Institute, Vol. 16, No. 1.
Radical polymerization catalysts described in No. 0, pp. 867-871 (1973), specifically peroxides such as benzoyl peroxide and tert-butyl hydroperoxide, azo compounds such as azobisisobutyroni-1-lyl, Hydrogen oxide - 1st
There are 6 compounds, potassium persulfate-sulfur 1 helium sulfite, and other redox catalysts, and these radical polymerization catalysts are appropriately selected from these depending on the set polymerization temperature.

-In particular, these radical polymerization catalysts are particularly preferred as catalysts when the hydrocarbon is a conjugated diolefin or styrenic compound, or when the 9,10-dihydrodicyclopentadiene derivative contains a polar group such as a hydroxyl group. used.

That is, even if the 9.10-dihydrodicyclopentadiene derivative has a polar group, the polymerization performance of the radical polymerization catalyst does not deteriorate as in the case of the ionic coordination polymerization catalyst.

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.
Generally from about 0.01 to 10 mole percent based on 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, anionic polymerization catalysts include ethers such as diethyl ether, tetrahydrofuran, dioxane, and 1,2-dimethoxyethane, and cationic polymerization catalysts include dichloromethane, ethyl chloride, 1,2-dichloroethane, and chlorobenzene. A chlorine compound solvent can be used, and in the case of a radical polymerization catalyst, water can be used if an emulsion or suspension polymerization method is employed.

The polymerization temperature can be selected from the range of -vi10''C to about 150''C, and the polymerization time can be selected from about 1/2 to about 150''C.
A value within the range of 0 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 a poor solvent for the hydrocarbon resin to obtain the desired hydrocarbon resin. be able to.

The obtained hydrocarbon resin contains chain unsaturated hydrocarbons and/or
or 20 to 98 mol%, preferably 30 to 9 mol% of polymerized units of hydrocarbons consisting of vinylidene-containing cyclic hydrocarbons.
6 mol%, particularly preferably 40 to 95 mol%, and 80 to 2 mol%, preferably 80 to 2 mol% of polymerized units of 9,10-dihydrodicyclopentadiene consisting of 9,10-dihydrodicyclopentadiene or its derivatives. 70-4
mol %, particularly preferably 60 to 5 mol %, and generally has a softening point (J
Ring and ball method according to IS K-2531>, 10,0OO
CI) S or less, preferably a melt viscosity of 500 to 10 cps (Emiller viscometer, resin temperature 200 °C) and a melt viscosity of 300
~3,000, preferably 400 to 1°000 molecules 1l GPc method (polystyrene conversion method: number average molecular weight)]
have.

9. When the polymerized unit of 10-dihydrodicyclopentadiene is 2 mol% or less, the softening point of the resulting hydrocarbon resin will decrease if the viscosity is lowered, and conversely, if the softening point is raised, the viscosity will also increase. Therefore, when the modified product is used as a pressure-sensitive adhesive, an adhesive, or a compounding agent for paint, a satisfactory balance between workability and performance cannot be obtained.

Moreover, if this polymerized unit is 80 mol% or more, 9.10-
Due to the structure of dihydrodicyclopentadiene, homopolymerization is poor, making it necessary, for example, to use an abnormally high catalyst concentration, which not only increases manufacturing difficulties but also reduces molecular weight in terms of quality. Since it is difficult to increase the amount, problems arise such as a low softening point, poor hue, and poor thermal stability.

On the other hand, within the range of each polymerization unit for vj polymerization defined in the present invention, particularly within the preferred range, a hydrocarbon 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 9,10-dihydrodicyclopentadiene. Copolymers with defined polymerized units outside this preferred range do not exhibit the same performance as hydrocarbon resins with polymerized units in the preferred range, but 9.10-dihydrodicyclopentadiene copolymers without polymerized units It has a lower melt viscosity in comparison to its softening point, and has been shown to improve compatibility with other polymers.

The modified hydrocarbon resin according to the present invention has tack, adhesive strength,
Because it has superior cohesive strength, it can be used as a reactive agent to improve the Tackifier-1 adhesive strength and cohesive strength of adhesives and adhesives.

When modifying the hydrocarbon resin with α, β-unsaturated carboxylic acid or its derivatives, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid,
Maleic anhydride, itaconic anhydride, citraconic anhydride, etc. are generally used, but esters and other derivatives can also be used as appropriate. Among these α,β-unsaturated carboxylic acids, α,β-unsaturated dicarboxylic acids or acid anhydrides thereof are preferred, and maleic acid or maleic anhydride is particularly preferred. The modification reaction is a hydrocarbon tree W
ii) Addition reaction is carried out by adding preferably about 0.01 to 50 parts by weight of α,β-unsaturated carboxylic acids to 100 parts by weight under heating, but it is possible to carry out an addition reaction by lowering the reaction temperature or shortening the reaction time. In this case, a conventional radical initiator may be used.

If there are many unreacted α,β-unsaturated carboxylic acids,
It is desirable to remove it by concentration.

The acid value obtained in this way is about 0.1 to 150, preferably about 0.2 to 20, particularly preferably about 0.5 to 1.
α, β-Unsaturated carboxylic acid modified hydrocarbon resins in the range of 5 have increased affinity with pigments, so when used in paints such as traffic paint, fluidity and film properties are improved, and adhesives When used in adhesives and adhesives, adhesive strength and cohesive strength are improved.

When used as a tackifier component for adhesives and adhesives, natural rubber, styrene-butadiene rubber,
Butyl rubber, isoprene rubber, styrene-butadiene-
This hydrocarbon resin modified product is blended with a styrene block copolymer, a styrene-isoprene-styrene block copolymer, an acrylic resin, an ethylene-polar monomer copolymer, an epoxy resin, a urethane resin, and the like. When blending, since the viscosity of the modified hydrocarbon resin is low,
The solution blending method can reduce the amount of solvent used, and the heat melting method can reduce energy costs by reducing melting humidity and melting time.

Furthermore, when used as a reactive pressure-sensitive adhesive or adhesive, due to the low viscosity of this modified hydrocarbon resin, it is not necessary to use a commonly used reactive or non-reactive diluent. Therefore, it has excellent performance as an adhesive.

The modified hydrocarbon resin according to the present invention is also suitably used as a compounding agent for traffic paint and other paints. In other words, by blending this hydrocarbon resin or its modified product with alkyd resin, polyester resin, epoxy resin, urethane resin, acrylic resin, urea resin, melamine resin, phenol resin, etc., the balance between workability and coating performance can be improved. We can produce good paints.

Next, the present invention will be explained with reference to examples.

Reference example A Commercially available dicyclopentadiene (purity 94.6%) 171
0g of palladium-carbon catalyst (palladium 5% by weight)2
5 g of octane and 2000 q of octane were added, and hydrogen gas was aerated at room temperature and pressure at a flow rate of 10 ml/min for 15 hours. Pass through the mouth to remove the catalyst and distill to a boiling point of 180-184
1500 g of a °C fraction was obtained. Gas chromatography analysis results showed that 9,10-dihydrodicyclopentadiene was 84.5% and tetrahydrodicyclopentadiene was 10%.
．． 0%, unreacted dicyclopentadiene 0.2%, and unknown components 5.3%.

Reference Example B A C5 fraction obtained by naphtha decomposition was heated at 160° C. for 5 hours to convert the cyclopentadiene contained therein into dicyclopentadiene. Next, by removing the light fraction by distillation, the C5 fraction was 1460% and the benzene 2.6%.
%, dicyclopentadiene 69.1%, isoprene-cyclopentadiene codyne -7.3%, cyclopentadiene oligomer (trimer or more) 4.7%, and unknown component 2.3%. Dicyclopentadiene was obtained.

This crude dicyclopentadiene 1710!7 was used as Reference Example A
Hydrogenated in the same way as 1420, a colorless and transparent slightly viscous liquid
! I got J. The analysis result of gas chromatography is 9
, 10-dihydrodicyclopentadiene 71.2%, tetrahydrodicyclopentadiene 10.7%, unreacted dicyclopentadiene 0.5% and unknown components 17.6%
The composition of

Reference Example C 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 was 4.8% and the benzene 0.5%.
, crude dicyclopentadiene was obtained with a composition consisting of 77.1% dicyclopentadiene, 7.2% isobrene-citalobentadiene codimer, 8.2% cyclopentadiene oligomer, and 2.2% unknown components. Ta.

In a metal autoclave, 100 parts by weight of this crude dicyclopentadiene (17107) and a palladium-based hydrogenation catalyst in tablet form (Toyo C.C.I. product C) were placed in a metal autoclave.
3l-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 h/ci with stirring for 12 hours. The catalyst was removed by filtration and distilled to obtain 90 parts by weight of a 9,10-dihydrodicyclopentadiene fraction. The gas chromatography analysis results show that pentanes 19. θ%, 77.0% of 9.10-dihydrodicyclopentadiene, 0.1% or less of dicyclopentadiene, 0.8% of tetrabitolodicyclopentadiene, and 3.2% of unknown components.

Reference Example 1 A catalyst of a predetermined width and a portion of a solvent (20d>) were charged into a glass autoclave of 11 sizes in each city, and the 9,10-dihydrodicyclopentadiene-containing distillate of a predetermined width obtained in Reference Example B was placed under stirring. The mixture of monomers, various diolefins, and the remainder of the solvent is slowly injected from a pressure-resistant cylinder as a mixture. At this time, heating or cooling is performed to maintain the temperature at 60°C, and each monomer is injected for about 15 minutes. After continuing the polymerization reaction at this temperature for about 2 hours,
The catalyst was decomposed by adding methanol and washed with water. After passing the polymerized oil through a glass filter and checking for the presence or absence of gel formation, the 0 liquid was concentrated to obtain a hydrocarbon resin. The properties of the obtained hydrocarbon resin are shown in Table 1 below.

Margin below [Evaluation method] 1. Compatibility: ○: Transparent, Δ: Translucent, X: Opaque (1) Mitsui Polychemical product Evaflex 410 (vinyl acetate content: 19% by weight) or Evaflex 210 (vinyl acetate content: 28% by weight) and a hydrocarbon resin, Mix equal amounts on a hot plate at 180°C, and spread this onto a polyester film for about 1 rat
The film was coated to a thickness of n and its transparency was evaluated.

(2) A hydrocarbon resin in an amount equal to that of natural rubber was dissolved in a 10% solution of natural rubber in toluene, and this was coated on a polyester film to a thickness of approximately 80 μm, and the transparency of the coating film was evaluated. .

(3) Modified rosin commercially available for traffic paint (maleated ester type: softening point 94°C,
(acid value: 24, melt viscosity: 150 cps) and hydrocarbon resin were placed in equal amounts in a test tube, dissolved and mixed on a 180° C. hot bath, and the mixture was cooled to room temperature and its transparency was evaluated.

2. Heat resistance: 2.5 g of hydrocarbon resin was placed in a test tube with an inner diameter of 15 mm and a length of 18 mtn, heated in an oil bath at 200° C. for 3 hours, and the hue was measured by the Gardner method.

3. Ratio of 9.10-dihydrodicyclopentadiene polymer units in hydrocarbon tjJ fat: 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 each comonomer was determined by gas chromatography. It was determined from the reaction amount ratio of the polymers.

Reference Example 2, Reference Comparative Example 1 In the same manner as Reference Example 1, the 9,10-dihydrodicyclopentadiene-containing product obtained in Reference Example A above using the C5 fraction having the composition shown in Table 2 below. Copolymerization with the fraction was carried out.

Margin Table 2 Below: Butenes 1.0% by weight 1,4-pentadiene 2.2% by weight Butadiene 1
．． 0 Cyclopentadiene 1.2 Chain C5 monoolefin 14.6 Dicyclopentadiene 1.1 Cyclopentene 4.3 (polymerization component total) 46.0% by weight isoprene
7.4 1.3-pentadiene 13.204-C6 non-polymerized component 54.0 weight 8% The properties of the obtained hydrocarbon resin are as follows:
It is shown in Table 3 below.

Margins below Example 1, Comparative Examples 1 to 2 100 parts of the hydrocarbon resin obtained in Reference Example 1 (weight,
(same below), add 0.5 part of maleic anhydride, and heat to 200°C.
The maleated hydrocarbon resin (softening point 9) was reacted for 2 hours.
9°C, hue 7, acid 1d[i2. o) was obtained.

To 100 parts of this maleated hydrocarbon resin, a plasticizer ('a
Island essential oil product Toxinol TS-110) 12 parts, coarse powder calcium carbonate (Nitto powdered product Kansui Sand #30) 20 parts
0 parts, 200 parts of finely powdered calcium carbonate (Shiraishi Calcium Product Whiten H), 66 parts of titanium oxide (Ishito Sangyo Product Tybake A-220) and 100 parts of Glass Peas (Toshiba Parody Product GB-153T) were added,
A composition for traffic paint was prepared by melt-mixing on an oil bath at 200°C. Its properties are shown in Table 4 below, and for comparison, the property values of commercially available traffic paints based on petroleum resin (Comparative Example 1) or modified rosin (Comparative Example 2) are also listed.

From these results, the traffic paint composition using the maleated hydrocarbon resin according to the present invention not only has low viscosity and excellent workability, but also has high compressive strength, no filler sedimentation, and weather resistance. It can be seen that it has excellent quality not found in conventional products, such as good elasticity.

Table 4 Softening point ('C) 107 104 1
06 Melt viscosity (cps) 200℃ 2350 3600 410
0180℃ 4750 6700 85
00 style charter (rRn) 60 60
57 Compressive strength (Kg/cti) 552 285
320 Filler sedimentation (%) None 15 None Paint whiteness 89 89 86 Whiteness after promotion 90 89 83 Arc crack A CB [Evaluation method] 1. Softening point: According to the method of JIS K-5665 2. Melt viscosity : Using an Emiller viscosity type rotational viscometer, measure a melt at 200°C at a shear rate of 176/sec. 3. Stir the melt with a fluidity of 200°C,
A portion of the disc was quickly scooped out with a diameter and depth of 24 m (#I), poured down from a height of 30 mtn onto a smooth aluminum plate, and the long and short axes of the disc-shaped material hardened with root soil were measured. 4. Compressive strength: Based on the method of JIS K-5665 5. Filler sedimentation property: Fill a 50 degree beaker with the unmolten mixture, let it stand at 240°C for 2 hours, and then cool it. 6. Paint film whiteness: A test piece was prepared according to the method described in JIS K-5665 5 to 6, and was cured at a color studio. Then, the a and b values were measured, and the whiteness (W%) was calculated from these values.

W=100- [(100-L)2+a2+b211/
2 7. Whiteness after acceleration and hair cracks: The test piece used to measure the whiteness of the coating film was accelerated for 100 hours with a Sunshine Weather-Ometer, and its whiteness was measured. The appearance of the surface was observed, and the degree of hair cracks was evaluated as follows: A: No change at all B: Slight hair cracks observed C: Hair cracks have grown and are clearly observed D: Hair The cracks are growing and continuous on the panel (
Complete rack) Example 2, Comparative Example 3 Maleinated hydrocarbon resin obtained in Example 1 (Example 2
) and a commercially available resin (Guttoyer product Wing Tack Plus) (Comparative Example 3) were used to prepare adhesives, and the adhesive tape performance was examined. The results obtained are shown in Table 5 below, and it can be seen that the maleated hydrocarbon resin according to the present invention is superior to commercially available resins in terms of tack and adhesive strength.

Table 5 Tack (Ball No.) 17
12 Adhesive strength (g/25rR#I) 335
7 2600 cohesive force (rRIn/2hr)
0.1 0.1 [Evaluation method] To 100 parts of adhesive raw resin, 100 parts of commercially available SIS-based block copolymer Cauliflex TR-1107 (Shell product), mineral oil (Shell product Shelflex 371 N) ) and 3 parts of a stabilizer (Irganox 1010) were added, and the mixture was heated in a kneader at 150°C for 30
The adhesive was prepared by mixing the mixture for 1 minute.

Next, apply this adhesive onto a polyester film (Toshi product Lumirror, thickness 25 μm) using a hot melt coating machine for 5 minutes.
It was coated to a thickness of 5 μm, and the adhesive force and cohesive force were measured by the method of JIS Z-1522, and the tack was measured by the Dow method (20° C.).

Reference Examples 3 to 5, Reference Comparative Example 2 In the same manner as Reference Example 1, isoprene, pentane, and cyclopentadiene were extracted from the C fraction (C5 fraction obtained by naphtha cracking) having the composition shown in Table 6 below. Using the fraction with high 1,3-pentadiene concentration obtained by removing
Copolymerization with the 9,10-dihydrodicyclopentadiene-containing fraction obtained in Reference Example C was performed.

Table 6 Butenes 0.1% cyclopentadiene 1.21ffi Chain C5 monoolefin 1
3.1 Dicyclopentadiene 0.1 Cyclopentene 12.6 (Polymerization component meter
69.2% by weight) Isoprene 0
．． 2 1.3-Pentadiene 41.9 04~C
6 Non-polymerized component: 30.8% by weight The properties of the obtained hydrocarbon resin are shown in Table 7 below.

Examples 3 to 6, Comparative Examples 4 to 5 Regarding the hydrocarbon resins obtained in Reference Examples 2 to 5 and Reference Comparative Examples 1 to 2, various α, β-unsaturated carpons shown in Table 8 below were used. An acid or its acid anhydride was reacted in the same manner as in Example 1 to obtain the corresponding modified hydrocarbon resin.

Using the obtained modified hydrocarbon resin, a traffic paint composition was prepared in the same manner as in Example 1, and its properties are shown in Table 8.

Example 7 2.5 parts of maleic anhydride and 1 part of di-tert-butyl peroxide were added to 100 parts of the hydrocarbon resin obtained in Reference Example 3, and after melting and stirring at 180'C for 5 hours, the mixture was lowered under reduced pressure. The Buddha's dots were removed to obtain 102 parts of maleated hydrocarbon resin.

Using the obtained maleated hydrocarbon resin, a composition for traffic paint was prepared in the same manner as in Example 1, and its properties are shown in Table 8.

Examples 8 to 12, Comparative Examples 6 to 7 The modified hydrocarbon resins obtained in Examples 3 to 7 and Comparative Examples 4 to 5, respectively, were tackified. An adhesive was prepared in the same manner as in Example 2, and the performance of the adhesive tape was examined. The results obtained are shown in Table 9 below.

Below margin 130-

Claims (1)

[Scope of Claims] 1. Consists essentially of a linear unsaturated hydrocarbon and/or a cyclic hydrocarbon having a vinylidene group and 9,10-dihydrodicyclopentadiene or a derivative thereof, and polymerized units of the hydrocarbons; is 20 to 98 mol%, and 9,10
-Polymerized units of dihydrodicyclopentadiene are 80 or more
1. A method for producing a modified hydrocarbon resin, which comprises adding an α,β-unsaturated carboxylic acid or a derivative thereof to a copolymer in a proportion within the range of 2 mol %. 2. The modified hydrocarbon resin according to claim 1, wherein a copolymer having a softening point of 60° C. or higher, a melt viscosity of 10,000 cps or lower, and a molecular weight within the range of 300 to 3,000 is used. Manufacturing method.