JPS6128508A - Novel hydrocarbon resin and adhesive additive formed therefrom - Google Patents

Abstract

PURPOSE:A hydrocarbon resin low in melt viscosity and odor and excellent in color, heat resistance and compatibility with other base polymers, comprising a specified hydrogenated styrenic hydrocarbon/cycloalkene copolymer. CONSTITUTION:A hydrocarbon resin obtained by hydrogenating a copolymer comprising about 50-99mol% structure units of a styrenic hydrocarbon (e.g., styrene) and about 50-1mol% structural units of a cycloalkene (e.g., cyclopentene). Said hydrocabon resin should have a number-average MW of about 200- 10,000, an iodine value <=10 and a rate of hydrogenation of benzene nuclei <=20%. This hydrocarbon resin can be suitably used as a tackifier or a softener which is added to a hot-melt adhesive in which the base resin is an ethylene/ vinyl acetate copolymer or the like, or a pressure-sensitive adhesive in which the base resin is a styrene/butadiene/styrene block copolymer rubber or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to hydrocarbon resins. More specifically, it is excellent as an additive such as a tackifier for hot melt adhesives or pressure sensitive adhesives, has a low melt viscosity, and has excellent compatibility with the base polymer of adhesives. This invention relates to a new hydrocarbon resin that has little odor, good heat resistance stability, and good color.

[Problems to be solved by conventional technology/invention]

Traditionally, rosin resins, alkyd resins, epoxy resins, etc. have been used as tackifiers, including adhesive raw materials, in fields such as pressure sensitive adhesives, hot melt adhesives, paints, and traffic paints. It is known that it can be done. 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 it. However, with recent hot melt adhesives, there is a need to improve work speed and maintain a uniform coating amount. From etc.
There is a growing need for low melt viscosity tackifiers.

However, the styrene resins conventionally used for this purpose generally exhibit high melt viscosity and often exhibit a pungent odor when heated and melted.

For example, Japanese Patent Application Laid-Open No. 58-42610
6, a copolymer of a chain unsaturated hydrocarbon and/or a cyclic hydrocarbon having a vinylidene group and 9,10-dihydrodicyclopentadiene has been proposed. According to this proposal, although the melt viscosity and odor are satisfactory, the hydrocarbon resin obtained by the above-mentioned process has a yellowish tinge in some cases, so when this resin is used as a tackifier, it cannot be used as an adhesive. There remained the problem that the product value of the product could be damaged.

[Summary of the invention]

As a result of extensive research into hydrocarbon resins that exhibit low melt viscosity, excellent compatibility with adhesives and adhesive base polymers, brown hue, heat resistance stability, and good odor, we found that styrene It was discovered that a specific new hydrocarbon resin derived from a hydrocarbon-based hydrocarbon and a cycloalkene satisfies the above requirements, and the present invention was completed.

That is, the present invention provides a hydrogenated product of a copolymer consisting essentially of a styrenic hydrocarbon (A) and a cycloalkene CB, in which the proportion of structural units derived from (A) is about 50 to about 99 moles. The proportion of structural units derived from arc, (to)) is about 1 to about 50 mol% [total of both is 100 mol arc]
with a number average molecular weight of about 200 to about 10,
A hydrocarbon resin (0) which is within the range of
The application invention is an additive for hot melt adhesives or pressure sensitive adhesives consisting of the following. Hereinafter, each invention of the present application will be explained in detail.

[Hydrocarbon Resin 0] Specifically, the styrenic hydrocarbon particles forming the hydrocarbon resin (0) according to the present invention include, for example, styrene, α-methylstyrene, O-methylstyrene, m-
Examples include methylstyrene, p-methylstyrene, m-impropyltoluene, and p-isopropenyltoluene. Each of these may be used alone to form the hydrocarbon resin (0) together with the cycloalkene CB) described later, or the secondary and upper components may be used together with the cycloalkene ω) in any proportion to form the hydrocarbon resin (0). ) may be the source of formation. Cycloalkene aB) is another component that forms the hydrocarbon resin (0).
is substantially a monocycloalkene, specifically, for example, cyclononene, cyclopentene, cycloheptene, cyclooctene, cyclononene, etc., as well as those in which one or more of the hydrogen atoms in these rings is a methyl group, an ethyl group,
Examples include those substituted with lower alkyl groups such as propyl group and isopropyl group. These cycloalkenes (B) may also be used alone to form the hydrocarbon resin (0) together with the styrenic hydrocarbon (A), or the secondary and upper components may be used in any ratio to form cycloalkenes CB. ) may be the source of forming the hydrocarbon resin (0).

The proportion of structural units derived from the above-mentioned styrene A hydrocarbon (A) and cycloalkene (B) contained in the hydrocarbon resin (a) according to the present invention is approximately 50 to 99 mol% derived from (A). , about 1 to 50 derived from (B)
mol% (total of both is 100 mol-. The same applies hereinafter), preferably about 60 to 98 mol% of the material derived from (A) and about 98 mol% of the material derived from (B). is about 2 to 40 mol%, more preferably about 5 to 30 mol% is derived from (A), and more preferably about 5 to 30 mol% is derived from (A). If the proportion derived from (A) exceeds the above range, the melt viscosity will increase and the compatibility with the adhesive or the base polymer of the adhesive will deteriorate; If the amount derived from (A) decreases, the molecular weight will be low, resulting in weight loss and odor generation during heating, which is not preferable.

Incidentally, it is preferable that the basic components constituting the hydrocarbon resin (0) are only the styrene hydrocarbon (A) and the cycloalkene (B), but these may be used within the range that does not impair the effects of the present invention. In addition to components (A) and (B), pentene-2,2
-Alkenes such as methyl-2-butene and butene-2 are 1
0 mol% or less, butadiene, isoprene, 1,6-
It does not matter if an alkaline diene such as pentadiene is the source of the constituent component in an amount of 10 mol% or less. Furthermore, the amount of aromatic hydrocarbon taken in from the solvent by chain transfer reaction during the polymerization of A and B may be 10 mol % or less as a source of the constituent components.

The number average molecular weight of the hydrocarbon resin (0) according to the present invention must be in the range of about 200'' to 10,000, and preferably in the range of about 500 to 700. The average molecular weight is a value converted to polystyrene using the GPO method.
0) generally has a softening point of 200°C or less, preferably about 150°C or less (ring and ball method according to J.E.S. K-2531), including those that are liquid at room temperature, and about 10.0OOOPS or less, preferably about 2000PS or less. It has the following melt viscosity (Emiller viscometer, resin temperature 200°C), and the ratio of weight average molecular weight (MW) (measured in the same manner as Mn) to 1n yw
The molecular weight distribution expressed as /Mn is about 1.0 to 5.0,
preferably about 1.0 to 5.0, and further has Gar
The hue by the dner method (ASTM D1544-68) is 3 or less.

Further, the hydrocarbon resin (0) according to the present invention has an iodine value [by Rice method]. ] is required to be 10 or less, preferably 5 or less, and the hydrogenation rate of benzene nuclei [measure the absorbance of ultraviolet rays at wavelengths of 274 nm and 274 nm with a tetrahydrofuran solution for the sample before and after hydrogenation, and Hail to the rate of change. ] is required to be 20 or more, preferably 30% or more. If these two conditions are not met, the elastomer will have a strong odor and poor heat resistance, making it unsuitable for applications where odor and coloring are averse, and the elastomer will not be able to sufficiently exhibit its softening effect.

[Production method of hydrocarbon resin (C)]

The hydrocarbon resin (0) of the present invention is a styrenic hydrocarbon (A
) and cycloalkene (, B), and then hydrogenating the product. First, the method for producing the copolymer in the first stage will be explained.

The catalyst used in the polymerization of the copolymer is generally known as a free sol fluoride catalyst, and includes, for example, aluminum chloride, aluminum bromide, dichloromonoethylaluminum, titanium tetrachloride, tin tetrachloride,
Examples include boron trifluoride and various complexes of boron trifluoride. The amount of the catalyst to be used is preferably in the range of usually 0.01 to 5.0 weight (%), and 0.05 to 3.0 weight (%) based on the total of component (A) and component (B). ) is particularly preferable.

It is preferable to use a polymerization solvent to remove the heat of two reactions during the polymerization and to suppress the viscosity of the polymerization solution. Suitable solvents include the above-mentioned cycloalkene CB) itself, which is a polymerization component, as well as aromatic hydrocarbons such as toluene, xylene, ethylbenzene, mesitylene, cumene, and cymene, or mixtures thereof, or combinations thereof with pentane, hexane, Examples include mixtures with aliphatic hydrocarbons such as heptane and octane and/or alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane. When using cycloalkene ω) itself as a solvent,
It is preferable that the concentration of the above-mentioned styrenic hydrocarbons, which is another comonomer, is adjusted to about 20 to 80% by weight (A), (B). ) is added to the mixture, and the initial polymerization concentration of the total of component (A) and component (B) is usually 60 to 70 weight (%), preferably 40 to 60 weight (%). More preferably. Polymerization can be carried out either batchwise or continuously, and multi-stage polymerization can also be carried out. In either method, the initial concentration of the component (A) and component CB) is usually preferably carried out within the above-mentioned range. . Although it is preferable that the raw material monomers (A) and (2) are pure, they may contain polymerization components such as those mentioned above as long as the effects of the present invention are not impaired.

The polymerization temperature varies depending on the proportions of component method) and component ω) used, the type and amount of the catalyst, and the type and amount of the solvent, but it is usually preferably carried out within the range of -20 to 60°C.

The polymerization time is selected in the range of 0.5 to 5 hours,
Polymerization is usually almost complete in 1 to 2 hours.

After the polymerization is completed, the catalyst is decomposed with an aqueous alkali solution or methanol, washed with water, and unreacted monomers, solvent, etc. are distilled off to obtain the desired copolymer resin in the first step. However, it is also possible to directly perform the hydrogenation described below without distilling off the solvent.

In the hydrogenated copolymer that is the hydrocarbon resin (0) according to the present invention, the proportion of structural units derived from Bl is adjusted according to the proportions of component monomers 5 and aS> used and the above conditions. This can be done by adjusting.

The number average molecular weight (Mn) and molecular weight distribution (MW/Mn) of the copolymer (0) of the present invention can generally be adjusted as follows. That is, if the polymerization temperature in the first stage of copolymerization is lowered, the Mn of the copolymer will increase, and conversely, if the polymerization temperature is increased, the Mn will be decreased. Cycloalkene as a solvent
and other hydrocarbon solvents to increase the molar ratio (A)/(B) of the raw material monomers, the copolymer (0
) becomes larger, and the same raw material monomer molar ratio (A)/
When a3) is lowered, Mn of the copolymer (0) becomes smaller. Further, when the concentration of the Friedel-Crauch catalyst is decreased, the Mn of the copolymer is decreased, and when the concentration of the catalyst is increased, the Mu of the copolymer is decreased. Among the three conditions mentioned above, by conducting the polymerization under conditions where the concentration of the free sol colloidal fluoride catalyst and the raw material monomer molar ratio (A)/tB) are relatively low, yw/n is 1.1 to 2.5. Copolymers are easily obtained.

Adjustment of the softening point can likewise be achieved relatively easily by varying the pre-polymerization temperature. In other words, if the polymerization temperature is lowered, the softening point of the resin (0) finally obtained will be higher, and if the polymerization temperature is raised, the softening point of the resin will be lower. After determining the type and amount of the polymer, the softening point of the final resin (0) can be adjusted to a desired range by appropriately selecting the polymerization temperature. Note that the softening point usually hardly changes depending on the hydrogenation described below.

Next, the hydrogenation stage will be explained. Hydrogenation is carried out using a solvent in the presence of a suitable hydrogenation catalyst. Catalysts include metals from groups ■ and ■ of the periodic table, such as nickel, chromium, palladium, platinum, cobalt, osmium, rhenium, ruthenium, Raney nickel, nickel sulfide, nickel oxide, and chromium submersible! [,
Cobalt-molybdenum, molybdenum oxide, molybdenum sulfide, platinum oxide, cobalt oxide, rhenium oxide, ruthenium oxide, sponge iron, iron oxide, etc. are used.

In addition, various solvents can be used, such as pentane, hexane, heptane, isohebutane, octane,
Various aliphatic, alicyclic, and aromatic solvents such as isooctane, cyclohexane, methylcyclohexane, decalin, tetralin, benzene, toluene, xylene, and dioxane are used. Therefore, as described above, hydrogenation can be carried out as is after removing the catalyst from the polymerization solution in the first stage.

Hydrogenation is carried out by a patch method or a continuous method at a temperature below the thermal deterioration temperature of the resin, preferably about 100 to 240°C, under reduced pressure to increased pressure, generally from atmospheric pressure to about 600°C.
VαG, preferably about 10-150 kg/aI? The treatment is carried out by treating with hydrogen gas under a pressure condition of G for about 10 minutes to about 24 hours, preferably about 10 minutes to about 7 hours.

[Use invention]

The novel hydrocarbon resin of the present invention obtained by hydrogenation (
No. 0) has excellent properties as an additive for hot-melt adhesives and pressure-sensitive adhesives, that is, as a tackifier and a softener.

Adhesive compositions include - hot melt adhesives, which are generally made of a base resin such as ethylene-vinyl acetate copolymer, tackifier and optionally wax and other additives, and natural 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, sheets,
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, in the case of tackifiers for pressure-sensitive adhesives, they must have excellent compatibility with base resins such as natural rubber and synthetic rubber, good solubility in solvents, and chemical It must be stable, have excellent weather resistance, and have a good hue.
It is required to have properties such as not having a strong odor.

When the hydrocarbon resin (0) according to the present invention is used as a tackifier or softener in a pressure-sensitive adhesive, specific examples of the base resin include natural rubber, styrene-butadiene copolymer rubber, Polybutadiene, polyisoprene, polyisobutylene, butyl rubber, polychloroprene, ethylene/propylene copolymer rubber, ethylene/propylene α-olefin copolymer rubber, ethylene/propylene self-diene copolymer rubber, styrene/butadiene-styrene block copolymer, Rubber-like polymers such as styrene/isoprene/styrene block copolymer, hydrogenated styrene/butadiene styrene block copolymer (sxns), and hydrogenated styrene/isoprene/styrene block copolymer are used. In particular, styrene-e-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, and hydrogenated copolymers thereof are preferred.
When used as a tackifier or softener for hot melt adhesives, specific examples of the base resin include, for example, ethylene/vinyl acetate copolymer, polyethylene, polypropylene, ethylene/propylene copolymer, Ethylene/ac IJ/Lit copolymerization 1. ethylene·
Acrylic ester copolymers, polyesters, polyamides, polyvinyl acetate, etc. are used. In the case of hot melt adhesive compositions, it is particularly preferred to use ethylene/vinyl acetate copolymers and ethylene/acrylic acid ester copolymers as base resins.

When the hydrocarbon resin (0) 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, preferably 50 to 200 parts by weight, based on 100 parts by weight of the base resin. In the case of
It ranges from 0 to 150 parts by weight. Similarly, when used as a softener, the blending ratio with the base resin is usually 2 to 60 parts by weight per 100 parts by weight of the base resin in the case of hot melt adhesive compositions, and 1 part by weight of the base resin in the case of pressure sensitive adhesives.
It is usually in the range of 10 to 100 parts by weight per 00 parts by weight. For any type of adhesive, if hydrocarbon resin (0) is used as a tackifier, other softeners listed below may be used; 1 For example, rosin and its derivatives, terpene resins, alicyclic resins, aliphatic resins,
Aromatic resins, aliphatic-aromatic copolymer resins, and the like may also be used.

In addition to the essential components of the tackifier or softener and the base resin, various additives may be added to the adhesive composition using the hydrocarbon resin (0) according to the present invention, if necessary. For example, in the case of hot melt adhesive compositions,
Softeners such as dioctyl phthalate and dibutyl phthalate, waxes such as petroleum-based paraffin waxes with melting points varying from 40 to 65"C, polyolefin waxes, micro waxes, phenol-based or bisphenol-based organic compounds, metal soaps, etc. Antioxidants, etc. In the case of pressure-sensitive adhesive compositions, dioctyl phthalate, dibutyl phthalate, machine oil,
Examples include process oil, softeners such as polybutene, fillers such as calcium carbonate, zinc white, titanium oxide, and silica, anti-aging agents such as amine-based, ketone-amine-based, and phenol-based anti-aging agents, and stabilizers. The blending ratio of these additives is arbitrary and appropriate.

The method for preparing an adhesive composition using the hydrocarbon resin (0) according to the present invention differs depending on whether it is a hot melt adhesive composition or a pressure sensitive adhesive. The hot melt adhesive composition is prepared by stirring a mixture consisting of the tackifier hydrocarbon resin (0), the base resin and, if necessary, the various additives described above, while heating and melting the mixture. A molten liquid is prepared and, depending on the application, it is shaped into granules, flakes, pellets, rods, etc. while being cooled. This hot melt adhesive composition is melted again and used for adhesion or coating purposes. For example, when used for adhesion, a method such as filling a rod-shaped compound into a welding gun is used for corner adhesion of molded products.

On the other hand, as a method for preparing a pressure-sensitive adhesive, a mixture consisting of the hydrocarbon resin (0) according to the present invention as a tackifier, the base resin and, if necessary, the various additives described above, is rolled on a roll. H can be prepared by conventional methods such as kneading or dissolving in a suitable solvent.

When a hot melt adhesive composition is used as an adhesive or a coating agent in an adhesive composition using the hydrocarbon resin (C1) according to the present invention, the hydrocarbon resin (0) according to the present invention is a base resin. This hot melt composition has excellent heat resistance stability, color, and odor, and has excellent heat resistance stability, color, and odor. It has the advantage that there is little odor during use and during use. Furthermore, even if the hydrocarbon resin (a) of the present invention is used in a pressure-sensitive adhesive composition, since the hydrocarbon resin of the tackifier has excellent weather resistance in addition to the above-mentioned characteristics, it is possible to obtain a uniform pressure-sensitive adhesive composition. An adhesive composition is obtained, and this pressure-sensitive adhesive composition has the advantages of excellent color and weather resistance, and low odor.

・Adhesive compositions using the hydrocarbon resin of the present invention will be specifically explained later by examples. In addition, in the examples, evaluation of the hydrocarbon resin was performed by the following method.

(1) Softening point J-5K-5665 (2) Hue ASTM D 1544-5BT (5)
Try 5g of heat-resistant and stable hydrocarbon resin 1/&! After taking a tube (inner diameter 16 mm) and immersing it in a constant temperature bath maintained at 200° C. for 3 hours, the color was expressed by the method of ASTM D 1544-5BT.

(A) Odor The odor during heating and melting (200° C.) was divided into five grades from weak odor to strongly irritating odor, A% B, and G.

(5) Cloudy point 140″F paraffin wax 2g and hydrocarbon resin 2g
Put into a test tube, melt at an oil bath temperature of 200°C, and mix well. Set the thermometer so that the temperature sensitive part is located in the center of the melt, and let it cool at room temperature.The temperature when it becomes cloudy is read as the cloudy point.

(6) Compatible with gvA 0.1 g each of ethylene-vinyl acetate copolymer (Evaflex 22o manufactured by DuPont Mitsui) and hydrocarbon resin were added to 200
Melt mix for 1 minute on a ℃ hot plate and apply to a polyester film to a thickness of about 1 mm.

The transparency was compared at room temperature and evaluated by dividing the transparent ones into A, the translucent ones into B, and the opaque ones into C.

(73200℃ melt viscosity Measured using an Emiller rotational viscometer.

(8) Number average molecular weight (Mn), molecular weight distribution (M w/M
r1) Calculated based on polystyrene using gel permeation chromatography [Example] [Effect of the invention] Example 1 Freshly distilled styrene in a 500 tJ 40 flask equipped with a stirrer, condenser, thermometer and rubber cap for catalyst injection. 50 g, 11 g of clopentene, and 39 g of toluene were added, stirred under a nitrogen atmosphere, and kept at 5°C. To this, 0.3 g of boron trifluoride phenol complex salt was added through a rubber cap using a syringe while cooling the mixture to maintain the temperature at 5° C., and stirring was continued for 2 hours. At this point, gas chromatography analysis of the polymerization solution revealed that styrene was 99.8%.
80.0% of cyclopentene was reacted, and toluene was not changed at all. The catalyst was analyzed using a 10% aqueous sodium hydroxide solution, washed with water until neutral, and concentrated. The obtained total amount of resin, the same weight of hexane, and a sulfur-resistant nickel catalyst (manufactured by Koku Kagaku, brand NN-113) 6 were mixed into a 500 mJ? The mixture was placed in an autoclave and hydrogenated under the conditions listed in Table 1. After cooling, depressurizing, and purging with nitrogen, the catalyst was separated and the p liquid was concentrated to obtain 57.8 g of hydrocarbon resin (corrected sampling amount for gas chromad analysis).

Table 1 shows the resin composition (indicated by monomer before hydrogenation)', nuclear hydrogenation rate, and resin properties calculated from gas chromatography analysis of the polymerization solution.

Examples 2 to 4.6.8.9, Comparative Example 1.2 Polymerization was carried out in the same manner as in Example 1 using the monomers and polymerization conditions listed in Table 1, followed by hydrogenation and post-treatment under the hydrogenation conditions listed in Table 1. The results are shown in Table 1.

In Comparative Example 2, the hydrogenation reaction was not possible because the resin yield in the polymerization reaction was as small as 2 g. The following hydrogenation catalysts were used.

Sulfur-resistant nickel: 8Kokugakusha [N-11! IJ Palladium Carbon Futagawa Lab made by Fine Chemical Co., Ltd. "o-12"
J Ranney Nickel: 8 Manufactured by Kiku Kagaku Co., Ltd. [N-154J Example 5 Boiling point of 05 fraction of isoprene extraction diameter 36 to 44 °C
The fraction was used as a raw material for petroleum resin, and the recovered unreacted fraction was converted into a cyclopentene fraction (boiling point 6) with the composition shown in Table 2.
6-44°C) was recovered.

Table 2 Composition of cyclopentene fraction (wt%) Cyclopentene 15.42-Methyl-siebutene
1.61.3-Pentadiene 2,
2 Pentene-29, Fisoprene 0.2 500 mJ with stirrer, condenser, thermometer and dropping funnel.
20 g of hexane and 0.8 g of anhydrous aluminum chloride powder are placed in a 40 flask, stirred under a nitrogen atmosphere, and kept at 60°C. A mixture of 50 g of styrene and 50 g of cyclopentene fraction was added to the mixture through a dropping funnel while being cooled to maintain the temperature at 50°C.
x Mado A-We 1. ? -This JL x 4t,
y L → 99.9%, 50.5% of cyclopentene and 34.0% of other unsaturated compounds were reacted. The catalyst was decomposed with methanol, washed with water until neutral, and concentrated. Hydrogenation was carried out under the conditions listed in Table 1, and post-treatment was carried out in the same manner as in Example 1 to obtain 58.6 g of hydrocarbon resin (sample corrected for gas chromad analysis). Table 1 shows the physical properties of the hydrocarbon resin.

Example 7 Styrene and the cyclopentene fraction listed in Table 2 were polymerized under the conditions listed in Table 1 in the same manner as in Example 1, and then hydrogenated and treated under the conditions listed in Table 1. The results are shown in Table 1.

Comparative Example 6 9 obtained by partially hydrogenating dicyclopentadiene fraction
, 10-E) Hydrodicyclopentadiene content Table 3.
9.10-dihydrodicyclopentadiene 9.10-dihydrodicyclopentadiene 79.1 Dicyclopentadiene 0.12-isopropenyl-norbornane, cyclopentadiene codimer tetrahydrodicyclopentadiene 9+6 Other polymerization components 5.7 Styrene and 9,10-dicyclopentadiene were polymerized in the same manner as in Example 1 under the conditions listed in Table 1, and hydrogenated and post-treated under the conditions listed in Table 1. The results are shown in Table 1.

Comparative Example 4 500 mJ with stirrer, condenser, thermometer and rubber cap for catalyst injection. 50 g of freshly distilled styrene and 30 g of cyclopentene were placed in a 40 flask, stirred under a nitrogen atmosphere, and kept at 30°C. Add 0.5 g of boron trifluoride phenol complex salt to this via a syringe through the rubber cap while cooling to maintain the temperature at 30°C.
Stirring was continued for an hour. At this point, gas chromatography analysis of the polymerization solution revealed that styrene was 99.9% and cyclopentene was 2%.
The reaction rate was 5.8%. The catalyst was decomposed with a 10% caustic soda aqueous solution, washed with water until neutral, and concentrated to obtain 62.8 g of a colorless and transparent hydrocarbon resin (corrected sampling amount for gas chromad analysis). Therefore, it can be seen that the conversion rate of the reaction monomer into resin is 99.9%, which is almost quantitative. The hydrocarbon resin has a softening point of 60.0°C, a hue of 1 or less, a melt viscosity of i'5 cp, Mn 452, Mw/Mn
It was 1.2.

Comparative Example 5 Commercially available hydrogenated petroleum resin (“Alcon P-10” manufactured by Hazuki Chemical Co., Ltd.
The resin properties of 0J) are shown in Table 1 for comparison. I understand.

Example 10.11, Comparative Examples 6 to B 40 parts of the hydrocarbon resin listed in Table 4, ethylene-acetate picopolymer (Evaflex 210 manufactured by Mitsui Polychemical Co., Ltd.)
)401! fi, 20 parts of 140″F paraffin wax was melted and stirred for 1 hour at an oil bath temperature of 180°C.
The mixture was allowed to stand in an air oven at 0° C. for 24 hours, and examined for phase separation. The color and peel strength of adhesives that did not undergo phase separation were measured using the following methods. The results are shown in Table 4.

(Al　adhesive color The color of the adhesive at room temperature was evaluated as follows.

A: white, B: pale yellow, C: tan (b) Peel strength: Apply adhesive to aluminum foil (thickness 50 microns) to a thickness of 15 microns, and heat seal the adhesive surfaces together (temperature 170°C, pressure 1 tq 7 aw) ', time 1 second). Next, using an Instron universal testing machine, T-peel was performed at a temperature of 25° C. and a speed of 500 mm/min to determine the peel strength.

The results are shown in Table 4.

Example 12.13, Comparative Examples 9 to 11 S engineering S block copolymer (Shell Chemical Co., Ltd. "rR-1'
1o7J) 100 parts by weight, softener (Shell Chemical Co., Ltd. [Shelf Flex 22RJ) 50 g, stabilizer (Geigy Co., Ltd. "Irganox 1010J") 3 parts by weight, Examples 2.5 to Comparative Examples 1.6.4. Resin 10 obtained
0 parts by weight was blended as a tackifier and heated at 150℃5
The mixture was kneaded using a kneader for 0 minutes to prepare an adhesive. This adhesive was applied to a polyester film (25μ) on a 195℃ heating plate.
An adhesive tape was prepared by applying the adhesive tape to a thickness of 50±5 μm using an applicator (for 20 minutes) on a 50±5 μm thick film.

Next, adhesive performance was evaluated using the test method shown below.〇+1) Corrugated cardboard adhesion = Adhesive tape was crimped onto corrugated paper (J-5x-7) by rolling an 850g rubber roller at a temperature of 5°C. Immediately peel it off and examine the surface condition of the corrugated paperboard. 〇Rating 5: The entire surface of the corrugated paperboard is destroyed.

4: The surface of the cardboard! IOS or higher will be destroyed.

6; Destruction of the surface of the corrugated paperboard was clearly observed.

2: Slight damage to the surface of the cardboard was observed.

12 No surface damage of corrugated paperboard was observed 10 (2) Tack (ball shop): Measured at 20°C by T, Dow method (5) Adhesive force (g/25 mm width: JIS Z-152
Measurement was performed at 20°C using method 4.

(A) Cohesive force (mm/2HR): , r engineering S Z
-1524 method at 20°C.

(5) Corrugated board retention strength (HR): Corrugated paper (JIS K-7) was used as an adherend, a single load was hung at the end, and the time until the load slipped off was measured at 20°C.

The results obtained by the above test method are shown in Table 5. Comparative Example 12 Instead of using the hydrocarbon resin of the present invention, a commercially available hydrogenated petroleum resin ("Alcon P-100J" manufactured by Buyo Kagaku Co., Ltd.) was used. Except for this, the same procedure as in Example 16 was carried out.

As a result, when the hydrocarbon polymer obtained according to the present invention is used as a tackifier for a hot-melt pressure-sensitive adhesive, the resulting adhesive composition exhibits superior adhesive performance compared to the comparative example. Example 14: SIBS Block Fuborimer (Shell Chemical Co., Ltd. rGX-1)
657J), 120 parts by weight of the resin obtained in Example 7 as a tackifier, 33 parts by weight of a stabilizer (Irganox 1010J manufactured by Geigy), and 30 parts by weight of the resin obtained in Example 9 as a softener. Parts by weight were blended, an adhesive was prepared in the same manner as in Example 13, and the adhesive performance was evaluated.

Comparative Example 15 Using the polymer of the present invention (Example 9)! Add softener A to
An adhesive ("Shell Flex 22RJ" manufactured by Shell Chemical Co., Ltd.) was prepared in the same manner as in Example 15, and the performance of the adhesive was evaluated.

As a result, all the adhesives obtained from C1 using the polymer of the present invention exhibited superior adhesive performance compared to the comparative series, and the hydrocarbon resin of the present invention was found to be a softener for i-melt type pressure-sensitive adhesives. It can be seen that it also exhibits excellent performance as an agent.

to Table 6 the law of nature death the law of nature

Claims (2)

[Claims] (1) Styrenic hydrocarbon (A) and cycloalkene (B)
), which is a hydrogenated copolymer consisting essentially of
The proportion of structural units derived from (A) is about 50 to about 99 mol%, and the proportion of structural units derived from (B) is about 1 to about 5
The range is 0 mol% [total of both is 100 mol%],
A hydrocarbon resin having a number average molecular weight in the range of about 200 to 10,000, an iodine value of 10 or less, and a hydrogenation rate of benzene nuclei of 20% or more. (2) Styrenic hydrocarbon (A) and cycloalkene (B)
), which is a hydrogenated copolymer consisting essentially of
The proportion of structural units derived from (A) is about 50 to about 99 mol%, and the proportion of structural units derived from (B) is about 1 to about 5
The range is 0 mol% [total of both is 100 mol%],
A hot melt adhesive or pressure sensitive adhesive comprising a hydrocarbon resin having a number average molecular weight in the range of about 200 to about 10,000, an iodine value of 10 or less, and a hydrogenation rate of benzene nuclei of 20% or more. Additive for agents.