JPH07188352A - Modified hydrocarbon resin and its aqueous dispersion - Google Patents

Abstract

PURPOSE:To obtain a resin, having a specific acid value, a specified molecular weight and good melt viscosity, excellent in heat and light stabilities and water dispersibility and suitable as a tackifier, etc., by carrying out the graft copolymerization of a specific hydrocarbon resin with a monoolefindicarboxylic acid (anhydride). CONSTITUTION:This resin is obtained by carrying out the graft copolymerization of (A) a hydrocarbon resin prepared by copolymerizing 100 pts.wt. vinylaromatic hydrocarbon such as (o-methyl)styrene or isopropenyltoluene with 5-100 pts.wt. hydrocarbon component consisting essentially of a 4-5C unsaturated hydrocarbon such as 1-butene with (B) a monoolefindicarboxylic acid (anhydride) such as maleic acid (anhydride) and has 1-150mg KOH/g acid value and 300-5000 weight- average molecular weight.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a modified hydrocarbon resin and an aqueous dispersion thereof.

[0002]

2. Description of the Related Art Tackifying resins are used to impart tackiness to pressure sensitive adhesives, adhesives and the like. For example, as a resin for imparting tackiness to rubber-based pressure-sensitive adhesives and hot-melt adhesives of ethylene / vinyl acetate copolymer system and styrene block copolymer system, styrene, vinyltoluene, α-methylstyrene, etc. Attempts have been made to use molecular weight polymers and petroleum resins. However, the above-mentioned low molecular weight polymer and petroleum resin do not provide sufficient adhesive force or adhesive force even when used in a rubber pressure-sensitive adhesive, and when used in a hot melt adhesive, It has the drawback of poor compatibility with the ethylene / vinyl acetate copolymer as the main component. Further, petroleum resins produced from ordinary unsaturated hydrocarbon-containing fractions have problems in color, thermal stability and the like.

The present inventors have previously selected, as a tackifying resin for improving these problems, isopropenyltoluene and a fraction having 4 to 5 carbon atoms, which is a by-product during petroleum refining or petroleum cracking. And a homopolymer of isopropenyltoluene have been proposed (JP-A-49-118729, JP-A-49-128945, JP-B-Sho). 54-34033
Issue).

On the other hand, organic solvent type pressure-sensitive adhesives have been widely used in this field. Since this organic solvent type pressure-sensitive adhesive uses an organic solvent, it has problems in terms of safety and hygiene in the manufacturing process, workability and pollution, and a solvent recovery facility was required to prevent this.

Therefore, for example, an aqueous dispersion (acrylic emulsion) of an acrylic resin has been proposed as a non-organic solvent type, that is, a water dispersion type pressure-sensitive adhesive. Since the water-dispersed adhesive does not use an organic solvent, the safety and pollution problems in the manufacturing process are solved, and the facility for recovering the organic solvent is not required, which simplifies the manufacturing facility. There is. For this reason, acrylic emulsions are widely used in the market. However, in recent years, the performance required for adhesives and adhesives has increased, and the adhesive strength of conventional acrylic emulsions
It has become impossible to sufficiently meet these demands.

In order to improve the adhesive strength of the aqueous dispersion type pressure-sensitive adhesive, a rosin-based tackifier which is a natural raw material is used, and its emulsion is also commercially available. However, rosin-based tackifiers have an odor generation during work, and have poor heat stability, light stability, etc.
Attempts have been made in the past to substitute synthetic resins.

Further, the above-mentioned isopropenyltoluene,
A copolymer obtained by polymerizing a fraction selected from fractions having 4 to 5 carbon atoms, which is a by-product during petroleum refining or petroleum decomposition, in a specific ratio, and a homopolymer of isopropenyltoluene are acrylic. Although excellent in compatibility with resins, emulsification of these resins is generally extremely difficult, and an aqueous dispersion that can be actually used has not been obtained.

Therefore, the present inventors previously prepared an aqueous dispersion obtained by dispersing an isopropenyltoluene copolymer, which is a copolymer of isopropenyltoluene and an unsaturated hydrocarbon having 4 to 5 carbon atoms, in an aqueous medium. I proposed a body
1509).

[0009]

However, the production of this aqueous dispersion requires a nonionic surfactant, and there is a possibility that sufficient adhesive force may not be obtained for applications requiring water-resistant adhesiveness. there were.

Therefore, an object of the present invention is to provide a modified hydrocarbon resin having a good melt viscosity, excellent thermal stability and light stability and suitable as a tackifier or a tackifying resin for an adhesive, and a non-organic solvent. It is a tackifier of a mold, and an object thereof is to provide an aqueous dispersion having excellent water-resistant adhesiveness.

[0011]

In order to solve the above problems, the present invention provides a hydrocarbon component containing 100 parts by weight of vinyl aromatic hydrocarbon and an unsaturated hydrocarbon having 4 to 5 carbon atoms as main components. Hydrocarbon resin copolymerized with 5-100 parts by weight, graft-copolymerized at least one selected from monoolefin dicarboxylic acid and its anhydride, an acid value of 1-150 (mgKOH / g), And a modified hydrocarbon resin having a weight average molecular weight of 300 to 5,000 is provided.

The present invention also provides an aqueous dispersion obtained by dispersing the modified hydrocarbon resin in an aqueous medium.

Hereinafter, the modified hydrocarbon resin of the present invention (hereinafter,
The "modified resin of the present invention" and its aqueous dispersion (hereinafter referred to as "aqueous dispersion of the present invention") will be described in detail.

The hydrocarbon resin as the main component of the modified resin of the present invention is obtained by copolymerizing a vinyl aromatic hydrocarbon and a hydrocarbon component containing an unsaturated hydrocarbon having 4 to 5 carbon atoms as a main component. Is.

Examples of the vinyl aromatic compound which is the main component of the hydrocarbon resin include styrene, o-methylstyrene, vinyltoluene, isopropenyltoluene and the like. These may be contained singly or in combination of two or more in the hydrocarbon resin. Among these, isopropenyltoluene is particularly preferable because a hydrocarbon resin having a narrow molecular weight distribution and good compatibility with other resins can be obtained.

This isopropenyltoluene includes ortho, meta and para isomers, and these may be used alone or as a mixture. In terms of high reaction efficiency and high yield of a hydrocarbon resin, the ratio of para isomer 20 to 60% by weight, meta isomer 40 to 80% by weight, ortho isomer 0 to 10% by weight is particularly preferable. A mixture consisting of is preferred.

Further, the hydrocarbon component (hereinafter, abbreviated as "hydrocarbon component") containing an unsaturated hydrocarbon having 4 to 5 carbon atoms as the main component, which is the other main component of the hydrocarbon resin, is 1-butene. , Isobutene, 2-butene, 1,3-butadiene, 1
-Pentene, 2-methyl-1-butene, 3-methyl-1
-One or more kinds of various unsaturated hydrocarbons such as butene, 2-pentene, isoprene, 1,3-pentadiene, and cyclopentadiene. Further, this hydrocarbon content may contain saturated hydrocarbons within a range not impairing the object of the present invention. As a specific example of this hydrocarbon component,
Examples thereof include those composed of a fraction containing an unsaturated hydrocarbon having 4 to 5 carbon atoms, which is a by-product in petroleum refining, petroleum cracking and the like. A fraction containing an unsaturated hydrocarbon having 4 to 5 carbon atoms (hereinafter referred to as “C ₄ ,
The "C ₅ fraction" is a fraction whose boiling point range under normal pressure is usually -15 to + 45 ° C. In the present invention,
The hydrocarbon content of the main component of the hydrocarbon resin is C ₄ ,
Various polymerizable monomers in the C ₅ fraction may be used alone or in combination.
Combinations of more than one species may be included. For example, C ₄ , C
Intact ₅ fraction, C ₄ fraction, C ₄ excluding butadiene
Fraction, can be used C ₅ fraction, C ₅ fraction excluding isoprene, C ₅ fraction and the like excluding cyclopentadiene.

The hydrocarbon resin as the main component of the modified resin of the present invention is obtained by copolymerizing 100 parts by weight of the vinyl aromatic compound with 5 to 100 parts by weight of the hydrocarbon content. .

The copolymerization reaction of the vinyl aromatic compound and the hydrocarbon component is preferably carried out in the presence of a Friedel-Crafts catalyst.

As the Friedel-Crafts catalyst, known Friedel-Crafts catalysts can be used. Examples thereof include aluminum chloride, aluminum bromide, dichloromonoethylaluminum, titanium tetrachloride, tin tetrachloride, and various complexes of boron trifluoride. Can be mentioned.

The amount of this Friedel-Crafts catalyst used is
The amount is usually 0.05 to 5 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the total amount of the vinyl aromatic compound and the hydrocarbon.

This copolymerization reaction is carried out using a solvent so that the concentration of the polymerizable monomer is about 10 to 60% by weight in order to remove the heat of reaction, suppress the viscosity of the reaction solution, and adjust the molecular weight. Is preferred.

Examples of the solvent used include aliphatic hydrocarbons such as pentane, hexane, heptane and octane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane; aromatics such as toluene, xylene, ethylbenzene and mesitylene. Group hydrocarbons; and mixtures thereof.

The polymerization temperature depends on the raw material composition,
Usually, the range of −50 to + 50 ° C. is preferable. In addition, the reaction time is usually preferably in the range of 10 minutes to 10 hours.

After completion of the polymerization, the catalyst is decomposed with an aqueous alkali solution or methanol, and then washed with water to remove unreacted monomers,
The target hydrocarbon resin can be obtained by stripping off the solvent and the like.

The hydrocarbon resin has a softening point (ring and ball method) of usually about 30 to 150 ° C. The weight average molecular weight is usually in the range of 300 to 5000.

The modified resin of the present invention is obtained by graft-copolymerizing the above hydrocarbon resin with at least one modified monomer selected from monoolefin dicarboxylic acid and its anhydride.

Examples of the monoolefin dicarboxylic acid include maleic acid, citraconic acid, itaconic acid, glutaconic acid, 3-methyl-2-pentene diacid, 2-methyl-2-pentene diacid and the like. it can. Of these, maleic acid and its anhydride are particularly preferable.

The amount of grafting of at least one modifying monomer selected from the monoolefin dicarboxylic acid and its anhydride in the modified resin of the present invention, that is, the content in the modified resin is such that the emulsifying property is good and the self-sufficiency is sufficient. Has emulsifying properties,
The acid value of the modified resin is 1 to 1 because it becomes a modified resin with excellent hue.
150 (mgKOH / g), more preferably 5-10
An amount in the range of 0 (mgKOH / g) is preferable.

The modified resin of the present invention can be produced by any method as long as it is a method of graft-copolymerizing the hydrocarbon resin with at least one modified monomer selected from monoolefin dicarboxylic acid and its anhydride. You may follow. For example, a method in which the above-mentioned hydrocarbon resin is dissolved in an organic solvent, and then a modified monomer and a radical polymerization initiator are sequentially added, followed by heating and stirring to carry out a graft copolymerization reaction; A method of adding a modified monomer and a radical polymerization initiator to a melt to be stirred and carrying out a graft copolymerization reaction by stirring; a hydrocarbon resin, a modified monomer and a radical initiator are mixed in advance, and the resulting mixture is an extruder. And the mixture is heated and kneaded to carry out a graft copolymerization reaction; a tablet-shaped hydrocarbon resin is impregnated with a solution of a modified monomer and a radical polymerization initiator dissolved in an organic solvent, and then the tablet-shaped hydrocarbon resin is Examples include a method in which the graft copolymerization reaction is performed by heating to the highest temperature at which the hydrocarbon resin does not dissolve. Further, when the unsaturated bond remains in the hydrocarbon resin used, the radical polymerization initiator is not always necessary, and the graft copolymerization reaction may be performed in the absence of the radical polymerization initiator. it can.

The reaction temperature is 50 ° C. or higher, especially 80 to 20.
The range of 0 ° C. is suitable, and the reaction time is about 2 to 10 hours. The reaction system may be either a batch system or a continuous system, but the batch system is preferred in order to uniformly carry out the graft copolymerization.

When the graft copolymerization reaction is carried out using a radical polymerization initiator, the radical polymerization initiator used may be any one as long as it promotes the reaction between the block copolymer and the graft copolymerized unit. However, organic peroxide compounds, organic perester compounds, azo compounds and the like can be mentioned. Specific examples of the organic peroxide include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoate) hexyne-3,1,4- Bis (tert
-Butylperoxyisopropyl) benzene, lauroyl peroxide, 2,5-dimethyl-2,5-di (te
Examples thereof include rt-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (tert-butylperoxy) hexane. Further, specific examples of the organic perester include tert-butyl peracetate and tert.
-Butyl benzoate, tert-butyl perphenyl acetate, tert-butyl perisobutyrate, t
ert-butyl per-sec-octoate, tert
-Butyl perpivalate, cumyl perpivalate, te
Examples thereof include rt-butyl perdiethyl acetate.
Furthermore, specific examples of the azo compound include azobis-isobutylnitrile and dimethylylazoisobutyrate. Organic peroxides and organic peresters are particularly preferable. Furthermore, dicumyl peroxide, di-ter
t-butyl peroxide, 2,5-dimethyl-2,5-
Di (tert-butylperoxy) hexyne-3,2
Dialkyl peroxides such as 5-dimethyl-2,5-di (tert-butylperoxyisopropyl) benzene are preferred.

The modified resin of the present invention has a weight average molecular weight of 3
Those in the range of 00 to 5000 are easy to handle,
And since the melt viscosity is in an appropriate range, workability during preparation of adhesives and pressure-sensitive adhesives and coating thereof becomes good,
It is preferable because emulsification becomes easy and tackiness is excellent.

The present invention also provides an aqueous dispersion obtained by dispersing the above modified resin in an aqueous medium.

The aqueous medium in the aqueous dispersion of the present invention includes, for example, a medium composed of a basic substance and water. The basic substance used is an alkali metal,
Alkaline earth metals, substances that act as bases in water such as ammonia and amines, alkali metal oxides, hydroxides, weak acid salts, hydrides, alkaline earth metal oxides, hydroxides, weak acid salts, hydrogen Examples thereof include substances that act as a base in water, such as compounds, alkoxides of these metals, and the like.
These may be used alone or in combination of two or more.

The amount of these basic substances used is usually 0.2 chemical equivalent or more with respect to the carboxyl group in the modified resin (an acid anhydride group has a carboxyl group of 2 in order to obtain a good emulsion). The number is equal to or greater than 0.4 chemical equivalent.

The proportion of the modified resin in the aqueous dispersion is usually 10 to 80% by weight, preferably 30 to 70% by weight.

The aqueous dispersion of the present invention can be produced by, for example, mixing a modified resin, a basic substance and water and stirring the mixture at a temperature not lower than the softening point of the modified hydrocarbon resin. The temperature at the time of dispersion may be equal to or higher than the softening point of the modified hydrocarbon resin as described above, but is usually 120 to 200 ° C.
Is the range. The time required for dispersion varies depending on the resin composition, but is usually preferably 15 minutes to 3 hours.

The aqueous dispersion of the present invention can be used as a water-dispersible adhesive and a tackifier for adhesives by mixing with various emulsions. As the emulsion to be used, various commercially available products can be used and are not particularly limited, but particularly acrylic emulsion, ethylene-
Good performance can be exhibited by mixing with an emulsion such as a vinyl acetate copolymer.

The modified resin of the present invention can also be used as a tackifier for hot melt adhesives. As the base resin of the adhesive, polyolefin-based,
Examples thereof include polymers made of polyamides, polyesters, vinyl acetate copolymers, cellulose derivatives, polymethylmethacrylates, polyvinyl ethers, polyurethanes and the like. In particular, when the modified resin of the present invention is used as a tackifier in an ethylene-vinyl acetate hot melt adhesive, an adhesive having good peel strength can be obtained.

[0041]

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded.

Example 1 Production of Hydrocarbon Resin Cimcresol Production Process
The acid fission products of cymene hydroperoxide in water
Isolation of the composition shown below obtained by separation by distillation
100 g of propenyltoluene (purity: 99.2%), stone
Containing unsaturated hydrocarbons obtained by the thermal decomposition of oil naphtha
Mu, C of the following composition_Four, C_FiveFraction 10g, and toluene
Charge 150 g into an autoclave and keep the temperature under stirring.
BF as catalyst while keeping at 0 ℃ ₃Phenol complex 1.
5 g was added dropwise for about 10 minutes to react. afterwards,
Stirring was continued for another 3 hours. Next, 5 wt% sodium hydroxide
Add 50 ml of liquor solution and stir vigorously for 30 minutes.
After decomposing the catalyst, the aqueous phase was separated to obtain an oily polymer.
It was Further, the oily polymer was washed with water until it became neutral.
After that, the unreacted oil and the solvent toluene were distilled off under reduced pressure with heating and white.
A lumpy hydrocarbon resin was obtained. Also, the obtained hydrocarbon
Properties of resin (hue, softening point, weight average molecular weight, acid value)
Was measured according to the following method. The results are shown in Table 1.
You

Composition of isopropenyltoluene o-isopropenyltoluene 5.3% by weight m-isopropenyltoluene 60.4% by weight p-isopropenyltoluene 33.5% by weight cymene 0.8% by weight

Composition of C ₄ and C ₅ cuts C ₃ cut 1.5% by weight isobutane 0.4% by weight n-butane 1.3% by weight 1-butene 10.5% by weight isobutylene 19.8% by weight trans -2-butene 8.7 wt% cis-2-butene 4.4 wt% 1,3-butadiene 20.9 wt% n-pentane 5.1 wt% isoprene 5.6 wt% 1,3-pentadiene 2. 8% by weight Cyclopentadiene 3.1% by weight Others (fraction with boiling point of 80 ° C. or lower) 15.9% by weight

Method for measuring properties of resin Hue: Gardner ASTM D154-58 Softening point: Ring and ball method Molecular weight: GPC (styrene conversion) Acid value: JIS K5902

Reference Example 2 A hydrocarbon resin was produced in the same manner as in Reference Example 1 except that the amount of BF ₃ phenol complex used was 2.1 g. The properties of the obtained hydrocarbon resin were measured. The results are shown in Table 1.

[0047]

(Example 1) The hydrocarbon resin 4 produced in Reference Example 1 was placed in a 1 liter autoclave equipped with a stirring blade.
05g was put and it heated at 160 degreeC and was made to melt | dissolve. Further, nitrogen gas was blown from the bottom of the autoclave at a flow rate of 40 l / hr to replace the inside of the autoclave with nitrogen. Then, while maintaining the temperature, maleic anhydride 45
g and 13.5 g of di-tert-butyl peroxide were added dropwise over 4 hours. After the dropping was completed, the reaction was further performed for 1 hour. Further, the reaction mixture was subjected to reduced pressure treatment at 160 ° C. to remove unreacted maleic anhydride to obtain a modified hydrocarbon resin. The modified hydrocarbon resin thus obtained was dissolved in xylene, and then a large amount of methyl alcohol was added for precipitation.
The precipitated modified hydrocarbon resin was repeatedly washed with methanol and then dried to obtain a sample. The hue, softening point, weight average molecular weight and acid value of this sample were measured. The results are shown in Table 3.
Shown in.

(Examples 2 to 5) The modification reaction was conducted in the same manner as in Example 1 except that the amounts of maleic anhydride and di-tert-butyl peroxide used in Example 1 were changed to the amounts shown in Table 2. A modified hydrocarbon resin was obtained. The hue, softening point, weight average molecular weight and acid value of the resulting modified hydrocarbon resin were measured. The results are shown in Table 3.

[0050]

[0051]

(Example 6) Ethylene-vinyl acetate copolymer (EVA # 220, manufactured by Mitsui DuPont Polychemical Co., Ltd.)
40 g, 40 g of the modified hydrocarbon resin obtained in Example 3,
And wax (Sazol Wax H, manufactured by Sazol Corporation)
-1) 20g was melt-mixed at 180 degreeC and the hot-melt type adhesive agent was prepared. The melt viscosity of the obtained hot-melt type adhesive was measured with an Emirer viscometer to find that it was 160 ° C.
It was 4350 cp at 180 ° C. and 250 cp at 180 ° C.

This hot melt adhesive was applied to an aluminum foil (thickness: 50 μm) to a thickness of 15 μm. Next, the coated surfaces are stuck together and heat-sealed using a heat-sealing device having an upper bar temperature of 170 ° C. and a lower bar temperature of 70 ° C. under a pressing force of 1 kg / cm ² for 2 seconds to bond with a hot-melt adhesive. An adhesive piece was obtained in which aluminum foil was laminated on both sides of the layer. This adhesive piece was cut into a width of 25 mm to prepare a test piece. This test piece was subjected to a T-type peel test at a tensile temperature of 300 mm / min at a measurement temperature of 0 to 80 ° C. to measure the peel strength. The results are shown in Table 4.

Example 7 A hot melt adhesive was prepared in the same manner as in Example 6 except that the modified hydrocarbon resin obtained in Example 4 was used, and its melt viscosity was measured. Was prepared and the peel strength was measured. The results are shown in Table 4.
Shown in.

Comparative Example 1 A hot melt adhesive was prepared in the same manner as in Example 6 except that the modified hydrocarbon resin obtained in Reference Example 1 was used, and its melt viscosity was measured. Was prepared and its peel strength was measured. The results are shown in Table 4.

[0056]

(Embodiment 8) Internal volume 1.5 equipped with a stirring blade
Into a liter autoclave, 400 g of the modified hydrocarbon resin obtained in Example 1, 16 g of sodium hydroxide and 600 g of water were charged all at once, and the temperature was raised to 150 ° C. The mixture was emulsified at 150 ° C. for 2 hours with stirring to obtain an aqueous dispersion. Table 5 shows the physical properties of the obtained aqueous dispersion (solid content concentration, viscosity, pH, particle size, 100 mesh sieve amount).

(Examples 9 to 11) Emulsification was carried out in the same manner as in Example 8 except that the amounts of the modified hydrocarbon resin and sodium hydroxide used as raw materials were changed to the amounts shown in Table 5, to obtain an aqueous dispersion. It was Table 5 shows the physical properties (solid content concentration, viscosity, pH, particle size, 100 mesh sieve amount) of the obtained aqueous dispersion.
Shown in.

Comparative Example 2 When emulsification was carried out in the same manner as in Example 8 except that the unmodified hydrocarbon resin obtained in Reference Example 1 was used, no emulsion was obtained.

(Comparative Example 3) Internal volume 1.5 equipped with a stirring blade
Into a liter autoclave, 540 g of the hydrocarbon resin obtained in Reference Example 1, 60 g of a surfactant (Emulgen 420, manufactured by Kao Corporation), and 400 g of water were charged all at once, and the temperature was raised to 150 ° C. The mixture was emulsified at 150 ° C. for 2 hours with stirring to obtain an aqueous dispersion. Table 5 shows the physical properties of the obtained aqueous dispersion (solid content concentration, viscosity, pH, particle size, 100 mesh sieve amount).

[0061] Particle size: Microtrac particle size analyzer (LEEDS '& NORTHRO
P INSTRUMENTS ') 100 mesh sieve amount: 100
It is passed through a sieve of a mesh and expressed as% of the amount of the resin not passed through.

Example 12 The aqueous dispersion obtained in Example 8 and an acrylic emulsion (Nikkasol TS-80) were used.
5 and Nippon Carbide Industry Co., Ltd.) were mixed at a ratio of 50/50 (weight ratio) and stirred to obtain an adhesive mixture. 10 g / m of this mixture was applied to a PET film (25 μm).
² was applied. Next, this PET film was brought into contact with the surface of the adhesive mixture on which a stainless steel plate was applied, and was reciprocated once with a 2 kg rubber roller at a speed of 300 mm / min to obtain a bonded sample. This adhesive sample was subjected to 1 at a tensile speed of 300 mm / min using a tensile tester.
It was subjected to an 80 ° peel test. Also, after the adhesive sample was immersed in water at 40 ° C. for 240 hours, a similar peeling test was performed,
The water resistant adhesion performance was investigated. The results are shown in Table 6.

Comparative Example 4 An adhesive sample was prepared and an adhesive test was conducted in the same manner as in Example 12 except that the aqueous dispersion obtained in Comparative Example 3 was used. The results are shown in Table 6.

Comparative Example 5 An adhesive sample was prepared in the same manner as in Example 12 using only the acrylic emulsion, and the adhesion test was conducted. The results are shown in Table 6.

[0065]

[0066]

INDUSTRIAL APPLICABILITY The modified hydrocarbon resin of the present invention has a good melt viscosity, is excellent in heat stability and light stability, and is suitable as a tackifier or a tackifying resin for an adhesive.

Further, the aqueous dispersion of the present invention is excellent in water-resistant adhesion and emulsified without the use of a surfactant, so that it is suitable as a non-organic solvent type tackifier. .

Claims (3)

[Claims] 1. A hydrocarbon resin obtained by copolymerizing 100 parts by weight of a vinyl aromatic hydrocarbon and 5 to 100 parts by weight of a hydrocarbon component containing an unsaturated hydrocarbon having 4 to 5 carbon atoms as a main component, Formed by graft copolymerizing at least one selected from monoolefin dicarboxylic acid and its anhydride,
A modified hydrocarbon resin having an acid value of 1 to 150 (mgKOH / g) and a weight average molecular weight of 300 to 5000. 2. The modified hydrocarbon resin according to claim 1, wherein the vinyl aromatic hydrocarbon is isopropenyltoluene. 3. An aqueous dispersion obtained by dispersing the modified hydrocarbon resin according to claim 1 in an aqueous medium.