JPH051268A - Tackifier - Google Patents

Abstract

(57) [Summary] [Object] To provide a tacky fire having a low melt viscosity while having a high softening point. A hydrocarbon component (A) selected from the group consisting of a chain unsaturated hydrocarbon having 3 to 10 carbon atoms and an aromatic hydrocarbon having an unsaturated bond in a side chain having 8 to 16 carbon atoms,
Substantially consisting of at least one component (B) selected from the group of 1,2-dihydrodicyclopentadiene, 2-norbornene, alkylidene norbornane, alkylidene cyclohexanes, vinyl norbornanes, vinyl cyclohexanes and cyclohexenes A hydrocarbon resin comprising a copolymer obtained by polymerizing a monomer mixture in the presence of a polymerization catalyst, comprising 20 units of the component (A).
To 98 mol% and units of component (B) from 2 to 8
Within the range of 0 mol%, having a softening point of 60 to 170 ° C., a melt viscosity of 10 to 10,000 cps, and 30
It consists of a hydrocarbon tree having a number average molecular weight of 0 to 3000.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low melt viscosity type tacky fire.

[0002]

2. Description of the Related Art Conventionally, in the fields of pressure-sensitive adhesives, hot melt adhesives, paints, and traffic paints,
Tatsuki Fire including tackifier raw material (tackifier)
It is known that a rosin resin, an alkyd resin, an epoxy resin or the like can be used as the resin. Of these, rosin-based resins have been the most prized, but these resins cannot cope with the recent remarkable growth in demand because they rely on natural materials as raw materials. Therefore, recently, in order to replace it, various petroleum hydrocarbon resins have been developed, and as one of them, 1,5-pentadiene, isoprene, 2-methyl-2-butene and other C ₅ -based distillates have been developed. Hydrocarbon resins and the like obtained by polymerizing the components with a Friedel-Crafts catalyst or the like have come to be used.

By the way, in recent hot-melt adhesives, the work speed is improved and it is necessary to maintain a uniform coating amount. Also, in the traffic paint, the work speed is improved and the drying is accompanied by an increase in traffic volume. The demand for low melt viscosity type tackifiers has been emphasized due to increasing demands for workability improvement such as speed improvement.

[0004]

However, in the above-mentioned C ₅ hydrocarbon resin and the like, if the viscosity is reduced, the softening point is unavoidably lowered, and accordingly, the heat resistance is also deteriorated. When the heat resistance is improved, the melt viscosity becomes high. Thus, conventionally, a hydrocarbon resin having a low melt viscosity and heat resistance (high softening point) has not been known.

Therefore, as a result of various studies on the hydrocarbon resin having a high softening point and a low melt viscosity, the present inventors have found that a chain unsaturated hydrocarbon having 3 to 10 carbon atoms and 8 to 16 carbon atoms. At least one hydrocarbon component (A) selected from the group of aromatic hydrocarbons having an unsaturated bond in the side chain
And at least one component (B) selected from the group consisting of 1,2-dihydrodicyclopentadiene, 2-norbornene, alkylidene norbornane, alkylidene cyclohexane, vinyl norbornane, vinyl cyclohexane and cyclohexene. That the specific ratio of the copolymer satisfies such requirements, that the hydrocarbon resin comprising the copolymer can be suitably used as a tacky fire having suitable properties such as compressive strength and weather resistance. The inventors of the present invention have found out what can be done and have reached the present invention.

[0006]

The tacky fire according to the present invention is a group of chain unsaturated hydrocarbons having 3 to 10 carbon atoms and aromatic hydrocarbons having unsaturated bonds in the side chains having 8 to 16 carbon atoms. A hydrocarbon component (A) selected from
Substantially consisting of at least one component (B) selected from the group of 1,2-dihydrodicyclopentadiene, 2-norbornene, alkylidene norbornane, alkylidene cyclohexanes, vinyl norbornanes, vinyl cyclohexanes and cyclohexenes A hydrocarbon resin comprising a copolymer obtained by polymerizing a monomer mixture in the presence of a polymerization catalyst, comprising 20 units of the component (A).
To 98 mol% and units of component (B) from 2 to 8
Within the range of 0 mol%, having a softening point of 60 to 170 ° C., a melt viscosity of 10 to 10,000 cps, and 30
It is characterized by comprising a hydrocarbon resin having a number average molecular weight of 0 to 3000.

In the present invention, the chain unsaturated hydrocarbon having 3 to 10 carbon atoms, which is used as one of the monomer components (A) for forming the hydrocarbon resin, is preferably monoolein or diolephine. is there. Monoolefins are preferably of the general formula

[0008]

[Chemical 1] (In the formula, R ₁ , R ₂ and R ₃ are each a hydrogen atom or a methyl group, and R ₄ represents an alkyl group having 1 to 6 carbon atoms.) Specifically, for example, , Propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene, 1-hexene, 2-
Hexene, 3-methyl-1-pentene, 4-methyl-1
-Pentene, 1-heptene, 2-octene and the like.

Further, diolefin is preferably of the general formula

[0010]

[Chemical 2] Or

[0011]

[Chemical 3] (In the formula, R ₅ , R ₆ , R ₉ , R ₁₁ , R ₁₂ and R ₁₇
Each represents a hydrogen atom or a methyl group, and R ₇ , R ₈ and
R ₁₀ , R _{13 to} R ₁₆ and R ₁₈ each represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 1 to 4. ), Specific examples include 1,3-butadiene, isoprene, and 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 etc. are mentioned.

Similarly, the aromatic hydrocarbon having an unsaturated bond in the side chain having 8 to 16 carbon atoms, which is one of the monomer components (A) forming the hydrocarbon resin, is preferably the following: General formula (I)

[0013]

[Chemical 4] (In the formula, R ₁ represents a hydrogen atom or a methyl group, R ₂₁ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and m is 0.
Represents an integer of 3 and when m is 2 to 3, R ₂₁ may be the same or different, R ₂₀ represents a saturated or unsaturated hydrocarbon chain, and 1 represents 0 or 1. Specific examples of the compound represented by) include styrene, vinyltoluene, α-methylstyrene, isopropenyltoluene, tert-butylstyrene, allylbenzene and p-tert-butylallylbenzene.

Among the hydrocarbons exemplified above, those having 4 to 6 carbon atoms are particularly preferable from the viewpoint of resin performance.
The chain diolefin and the aromatic alkenyl compound having 8 to 10 carbon atoms can be mentioned. These hydrocarbons may be used alone or as a mixture of two or more homologous compounds, and further, monoolephine and diolephine, monoolefin and aromatic hydrocarbon having an unsaturated bond in the side chain, and diolephine and the side chain having no unsaturated bond. It is used as an aromatic hydrocarbon having a saturated bond, a mixture of monoolefin, diolefin and an aromatic hydrocarbon having an unsaturated bond in the side chain.

[0015] The general such mixtures, for example, _{C 4} fraction, _{C 4} fraction of a diene extraction residue, _{C 5} fraction, _{C 5} fraction of isoprene extraction residue, _{C 9} fraction, or these optional Among those obtained as a naphtha cracked oil fraction, such as a mixture of proportions, those containing a large amount of chain unsaturated hydrocarbon or aromatic hydrocarbon having an unsaturated bond in the side chain, or all polymerizable components On the other hand, those prepared to contain 30% by weight or more of these hydrocarbons are used. Further, as long as these are the main raw materials, a small amount of other unsaturated compounds may be contained, but if the content thereof is large, the softening point of the resulting hydrocarbon resin may decrease, so that The permissible rate is limited to a range that does not impair the object of the present invention.

1,2 copolymerized with these hydrocarbons
-Dihydrodicyclopentadiene is represented by the following general formula (I
I)

[0017]

[Chemical 5] (Wherein R ₂₂ located at the 1 to 5 position and R ₂₃ located at the 6 to 10 position represent a hydrogen atom or a lower alkyl group), and specifically,
2-dihydrodicyclopentadiene, 9-methyl-1,
2-dihydrodicyclopentadiene, 3,9-dimethyl-1,2-dihydrodicyclopentadiene, 9-ethyl-1,2-dihydrodicyclopentadiene, 1-ethyl-9-methyl-1,2-dihydrodicyclo Examples include pentadiene.

These 1,2-dihydrodicyclopentadiene compounds can be obtained by a known method. For example, U.S. Pat. No. 2,883,372 describes cyclopentadiene and its 6-fold amount of cyclopentene at 200 ° C. by the Diels-Alder reaction in the absence of oxygen.
A method for obtaining 1,2-dihydrodicyclopentadiene by reacting for a time is disclosed. If cyclopentadiene or cyclopentene having a substituent is used, 1,2-dihydrodicyclopentadiene having a substituent can be obtained. Also, a method of thermally decomposing dicyclopentadiene in a gas phase to produce 1,2-dihydrodicyclopentadiene and cyclopentene is disclosed in US Pat. No. 4,139,56.
No. 9 specification.

1, 2 used in the production of hydrocarbon resins
Of course, it is desirable that the dihydrodicyclopentadiene is substantially pure. However, if the dihydrodicyclopentadiene has a purity of about 60% by weight or more in these polymerizable components, it is possible to use cyclopentene. , Dicyclopentadiene, cyclopentadiene, cyclopentadiene oligomer (trimer or higher) hydride or partial hydride, for example, non-polymerizable components such as cyclopentane, tetrahydrodicyclopentadiene or derivatives thereof may be included. .. However, since these components deteriorate the hue of the resulting hydrocarbon resin and may cause gel formation, cyclopentadiene, dicyclopentadiene, cyclopentadiene oligomer of trimer or more and its derivatives, etc. It is desirable to use 10% by weight or less of this polymerization component.

The 2-norbornenes are represented by the following general formula (II
I)

[0021]

[Chemical 6] (Wherein R ₂₄ located at the 2, 3 or 7-position and R ₂₅ located at the 5 and 6-positions represent a hydrogen atom or a lower alkyl group), and specifically, for example, , Norbornene, 2-methyl-2-norbornene,
5-methyl-2-norbornene, 6-methyl-2-norbornene, 2,5-dimethyl-2-norbornene, 2,
6-dimethyl-2-norbornene, 2-ethyl-5-methyl-2-norbornene, 2,6-diethyl-2-norbornene, 2-ethyl-5-n-propyl-2-norbornene and the like can be mentioned.

These 2-norbornenes can be obtained by a known method. For example, 2-norbornene can be obtained by the Diels-Alder reaction of cyclopentadiene and ethylene (Houben-
Weyl, "Methoden der Organi"
schen Chemie "IVb (1972), 4th
45). When olefins such as cyclopentadiene and propylene having a substituent are used, 2-
Norbornenes can be obtained.

Alkylidene norbornanes are represented by the following general formula (IV)

[0024]

[Chemical 7] (Wherein R ₂₆ , R ₂₇ and R ₂₈ located at the 1 to 5 and 7 positions represent a hydrogen atom or a lower alkyl group), and specific examples thereof include isopropylidene norbornane. , Ethylidene norbornane, methylene norbornane, isobutylidene norbornane and the like.

These alkylidene norbornanes can be obtained by partial hydroisomerization during the production of vinyl norbornanes described below. Vinyl norbornanes are represented by the following general formula (V)

[0026]

[Chemical 8] (In the formula, R ₂₉ and R ₃₀ located at the 2, 3, 5, 7 positions
To R ₃₂ represent a hydrogen atom or a lower alkyl group, and q represents an integer of 1 to 4. Specific examples of the compound represented by) include vinylnorbornane, isopropenylnorbornane, 2-methylvinylnorbornane, propenylnorbornane and the like.

These vinyl norbornanes are obtained by subjecting conjugated diolephines such as butadiene and isoprene to cyclopentadiene reaction with a Diels-Alder reaction, and partially hydrogenating the obtained vinyl-2-norbornenes with a palladium catalyst. Can be obtained. Vinylcyclohexanes, alkylidenecyclohexanes and cyclohexenes are each represented by the following general formula (VI)

[0028]

[Chemical 9] General formula (VII)

[0029]

[Chemical 10] General formula (VIII)

[0030]

[Chemical 11] (In the formula, R _{33 to} R ₄₀ represent a hydrogen atom or a lower alkyl group, and r represents an integer of 1 to 5.), and specific examples thereof include vinylcyclohexane and isopropenyl. Cyclohexane, 4-methylvinylcyclohexane, isopropenyl-3-methylcyclohexane, vinylcyclohexane such as 3-methylvinylcyclohexane, methylenecyclohexane, ethylidene cyclohexane, isopropylidene cyclohexane, alkylidene cyclohexane such as isobutylidenemethylcyclohexane, cyclohexene, Examples of cyclohexenes such as 3-isopropyl-6-methylcyclohexene, 3-isopropylcyclohexene, 4-ethyl-1-methylcyclohexene, 4-ethyl-2-methylcyclohexene and the like. Door can be.

These vinylcyclohexanes and cyclohexenes can be obtained by partially hydrogenating vinylcyclohexenes obtained by the Diels-Alder reaction from 1,3-dienes such as butadiene and isoprene (Chemical Abstracts). ，
60, 7925d and 61, 8200c). Further, alkylidene cyclohexanes are partially hydroisomerized of vinyl cyclohexenes (73,2501e, 82,726).
60v).

Next, in the present invention, the monomer component (B)
1,2-dihydrodicyclopentadiene as a compound, 2
-Norbornenes, alkylidene norbornanes, alkylidene cyclohexanes, vinyl norbornanes, vinyl cyclohexanes and cyclohexenes may be used alone or as an arbitrary mixture of 2 or more kinds. Further, in the component (B) other than 1,2-dihydrodicyclopentadiene, a small amount of other unsaturated compound may be contained as long as these are the main raw materials, but if the content becomes large, Since the softening point of the obtained hydrocarbon resin may be lowered, the permissible ratio is limited to the range that does not impair the object of the present invention.

In copolymerizing the hydrocarbons of the component (A) with the hydrocarbons of the component (B), the reactivity of the component (B) is generally lower than that of the component (A). (B) is used in an amount equal to or greater than that of component (A), and this is brought into contact with the catalyst in advance, and then component (A) is blown in little by little or added. Therefore, it is desirable to increase the reactivity of the component (B) and increase the proportion of its polymerized units.

In view of its high copolymerizability with the component (B), the chain unsaturated hydrocarbon having 3 to 10 carbon atoms of the component (A) is a diolephine, particularly a conjugated diolephine, among which steric hindrance. A small amount of 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene and the like are preferably used. Further, among the aromatic hydrocarbons having an unsaturated group in the side chain, in the general formula (I), R ₁₉ is a hydrogen atom and 1 is 0, specifically, styrene and vinyltoluene. , Tert-butyl vinyltoluene and the like are preferably used for the same reason.

As the copolymerization catalyst, those known as homopolymerization and copolymerization catalysts of the above hydrocarbons can be used as they are. That is, a cationic catalyst, an anionic catalyst, an ion coordination catalyst, a radical catalyst or the like is used. Examples of the cationic polymerization catalyst include, for example, Journal of Japan Petroleum Institute, No. 16
Volume No. 10, pages 865-867 (1973) can be mentioned. Specific examples include aluminum chloride, aluminum bromide, boron trifluoride, tin tetrachloride, antimony pentachloride, ferric chloride, dichloroalkylaluminum, triethylaluminum-water, trichloroacetic acid, sulfuric acid and the like. it can. Among these, Lewis acids, particularly aluminum chloride and aluminum bromide, are preferably used from the viewpoints of high yield of hydrocarbon resin, good hue and high softening point.

Examples of the anionic polymerization catalyst include, for example, Journal of Japan Petroleum Institute, Vol. 16, No. 9, pages 779 to 784 (197).
The homopolymerization and copolymerization catalysts described in 3) can be mentioned. Specific examples of such an anionic polymerization catalyst include, for example, potassium, alkyl potassium, sodium, alkyl sodium, lithium, alkyl lithium, and SrZn (R ₆ ) or CuZ with R as an alkyl group.
n (R ₄ ) and the like can be mentioned. Among these, lithium and alkyllithium are preferably used because they enhance the reactivity of the component (B) and give a hydrocarbon resin having a good hue and a high softening point.

Examples of the ion coordination polymerization catalyst include, for example, Journal of Japan Petroleum Institute, Vol. 16, No. 8, pages 699 to 704 (197).
3) The Ziegler catalyst described, specifically, halides of titanium, vanadium, chromium, zirconium, etc., β-diketone salts, alcoholates, etc. and trialkylaluminum,

[0038]

[Chemical 12] (R is an alkyl group, X is a halogen atom, and n is 1 or 2) and a combination with an alkylaluminum halide, an alkyllithium, an alkylmagnesium halide, lithium hydride and the like can be mentioned. Among these, a combination of a titanium or vanadium halide and an alkylaluminum compound enhances the reactivity of the component (B), and is therefore particularly preferably used.

These ion coordination polymerization catalysts include monoolefins such as propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1, 1,3-butadiene, isoprene and 1,3-pentadiene. Is a particularly preferable catalyst when a chain unsaturated hydrocarbon such as conjugated diolephine is used. Examples of the radical polymerization catalyst include those described in Journal of Japan Petroleum Institute Vol. 16, No. 10, pages 867 to 871 (1973), specifically, peroxides such as benzoyl peroxide and tert-butyl hydroperoxide. Azo compounds such as azobisisobutyronitrile,
Examples thereof include redox catalysts such as hydrogen peroxide-ferrous iron compound, potassium persulfate-sodium sulfite and the like. These radical polymerization catalysts are appropriately selected according to the set polymerization temperature.

Generally, these radical polymerization catalysts are preferably used when the hydrocarbon is a conjugated diolephine or a styrene compound. The amount of the above-mentioned polymerization catalyst used varies depending on the kind of the catalyst, the combination of the comonomer, the polymerization temperature, the polymerization time, etc. It is in the range of 10 mol%. The polymerization solvent may or may not be used, but hydrocarbon solvents such as propane, butane, pentane, hexane, heptane, benzene, toluene, xylene and ethylbenzene may be used for any catalyst system. it can.

In addition to the above, when an anionic polymerization catalyst is used, an ether solvent such as diethyl ether, tetrahydrofuran, dioxane or 1,2-dimethoxyethane can be used. When using a cationic polymerization catalyst, a chlorinated solvent such as dichloromethane, ethyl chloride, 1,2-dichloroethane, chlorobenzene can be used. When a radical polymerization catalyst is used, water can be used as a solvent when the emulsion or suspension polymerization method is adopted.

The polymerization temperature is generally from several tens of degrees Celsius below zero to about 1.
The range of 50 ° C. can be selected, and the polymerization time is usually in the range of about 0.5 to 10 hours. The reaction pressure is generally atmospheric pressure or under pressure. After the completion of the copolymerization reaction, the remaining catalyst is treated by a conventional method, and the unreacted components and the reaction solvent are distilled off or removed by adding them to the poor solvent of the hydrocarbon resin. Thus, the desired hydrocarbon resin can be obtained.

The hydrocarbon resin obtained as described above has a component (A) unit of about 20 to 98 mol%, preferably about 20 to 80 mol%, particularly preferably about 40 to 60 mol%, The unit of component (B) is about 80 to 2 mol%, preferably about 80 to 20 mol%, particularly preferably about 60 to
40 mol% and generally has a softening point (JIS K253 of about 60 to 170 ° C., preferably about 80 to 140 ° C.).
According to the ring and ball method according to 1. ), About 10 to about 10,000 centipoise (cps), preferably about 500-10 cp.
s melt viscosity (Emmer viscometer, resin temperature 200 ° C.) and about 300-3000, preferably about 400-1000.
(Number average molecular weight by GPC method (polystyrene conversion method)).

When the unit of the component (B) is 2 mol% or less,
When the viscosity of the resulting hydrocarbon resin is reduced, the softening point is lowered, and when the softening point is increased, the viscosity is also increased. Therefore, for use as a pressure-sensitive adhesive, an adhesive or a compounding agent for paint, A satisfactory balance between workability and performance cannot be obtained. Further, when the unit of the component (B) is 80 mol% or more, the homopolymerizability becomes poor due to the structure of the component (B), and therefore, for example, it is necessary to increase the catalyst concentration abnormally. In addition to the difficulty in production, it is difficult to increase the molecular weight in terms of quality, so that the softening point is low, the hue is poor, and the thermal stability is poor.

On the other hand, a hydrocarbon resin having the above-mentioned monomer unit in the above-mentioned predetermined range, particularly in the preferable range thereof, has a high melt viscosity for its softening point and is excellent in both hue and heat resistance. Moreover, the amount of the catalyst used can be smaller than when the component (B) is homopolymerized. When it has a monomer unit in a range other than the above-mentioned preferred range, it does not show the performance as a hydrocarbon resin having a unit in the above-mentioned preferred range, but is compared with a resin of the same kind having no unit (B). The melt viscosity is high relative to the softening point, and the effect of improving the compatibility with other polymers is recognized.

Such a hydrocarbon resin has excellent properties as a tacky fire (tackifier) such as a hot melt adhesive or a pressure sensitive adhesive. Generally, a composition for an adhesive includes a hot melt adhesive prepared by adding a tackifier to a base resin such as an ethylene / vinyl acetate copolymer and, if necessary, wax and other additives, a natural rubber or a synthetic rubber. There is a pressure-sensitive adhesive obtained by adding a tackifier and, if necessary, a solvent and other additives to a base resin such as.

The former hot melt adhesive is generally used as an adhesive or a coating agent in the fields of bookbinding, can manufacturing, woodworking, laminating, sealing, coating and the like. The latter pressure-sensitive adhesive is generally coated on a base material such as paper, cloth, plastic film and the like, and is used for adhesive tapes and labels. In any of these adhesive compositions, a tackifier is added to the base resin. In particular, in the case of a hot melt adhesive, compatibility with base resins such as ethylene / vinyl acetate copolymer and wax, adhesiveness, melt viscosity, flexibility, heat resistance stability, light stability, Excellent hue is required.

On the other hand, also in the case of a tackifier for a pressure sensitive adhesive, it has excellent compatibility with base resins such as natural rubber and synthetic rubber, has good solubility in a solvent, and chemically It is required to have properties such as stability, excellent weather resistance, good hue, and strong odor. When the above-mentioned hydrocarbon resin is used as a tacky fire in a pressure-sensitive adhesive, the base resin is specifically natural rubber, styrene-butadiene copolymer rubber, polybutadiene, polyisoprene, polyisobutylene, butyl rubber. A rubber-like polymer such as polychloroprene, ethylene / propylene copolymer rubber, ethylene / propylene / diene copolymer rubber, styrene / butadiene / styrene block copolymer, styrene / isoprene / styrene block copolymer is used.

When used as a hot melt adhesive,
Specific examples of the base resin include ethylene / vinyl acetate copolymer, polyethylene, polypropylene, ethylene / propylene copolymer, ethylene / acrylic acid copolymer, polyester, polyamide, polyvinyl acetate, etc. . In particular, ethylene / vinyl acetate copolymer is preferably used.

When the above hydrocarbon resin is used as a tackifier, the blending ratio with the base resin is somewhat different depending on the hot melt adhesive and the pressure sensitive adhesive composition. In the case of a hot melt adhesive, the compounding ratio of the tackifier is usually 20 to 300 parts by weight with respect to 100 parts by weight of the base resin,
It is preferably in the range of 30 to 200 parts by weight, and in the case of a pressure-sensitive adhesive, it is usually added to 100 parts by weight of the base resin.
It is in the range of 20 to 200 parts by weight, preferably 30 to 150 parts by weight.

In the adhesive composition using the above-mentioned hydrocarbon resin, in addition to the essential components of the tackifier and the base resin,
If necessary, various additives are mixed. For example, in the case of a hot melt adhesive composition, a plasticizer such as dioctyl phthalate or dibutyl phthalate, a melting point of 40 to 6
Examples include waxes such as petroleum paraffin waxes, polyolefin waxes, and micro waxes at about 5 ° C., phenol- or bisphenol-based organic compounds, and antioxidants such as metal soaps.

On the other hand, in the case of the pressure-sensitive adhesive composition, dioctyl phthalate, dibutyl phthalate, machine oil, process oil, plasticizer such as polybutene, filler such as calcium carbonate, zinc white, titanium oxide and silica, amine Examples thereof include anti-aging agents, stabilizers, and the like such as system, ketone-amine system, and phenol system. The mixing ratio of these additives is arbitrarily selected.

The method of preparing an adhesive composition using the above hydrocarbon resin differs between the case of the hot melt adhesive composition and the case of the pressure sensitive adhesive composition. As a method for preparing the hot-melt adhesive composition, a hydrocarbon resin as a tackifier, a mixture of the above-mentioned base resin and, if necessary, the above-mentioned various additives is stirred while being heated and melted to obtain a uniform melt. Is prepared, and this is molded into a granular shape, a flake shape, a pellet shape, a rod shape, or the like under cooling depending on the intended use.

Such a hot melt adhesive composition is
It is melted again and used for adhesion or coating. For example, in the case of being used for bonding, in the corner bonding of a molded product, a rod-shaped compound is used by filling it in a solvent gun. On the other hand, as a method for preparing the pressure-sensitive adhesive, a mixture of a hydrocarbon resin as a tackifier, the base resin and, if necessary, various additives described above is mixed on a roll, or a suitable mixture is prepared. It can be prepared by a usual method such as dissolution in a solvent.

As described above, among the adhesive compositions using the above-mentioned hydrocarbon resin, when the hot-melt adhesive composition is used as an adhesive or a coating agent, the above-mentioned hydrocarbon resin is compatible with the base resin. Excellent heat resistance and hue, and less odor, so that a uniform hot melt adhesive can be obtained.This hot melt adhesive also has excellent heat stability and hue, and It has an advantage that the odor during preparation or use of the hot melt adhesive composition is small.

Further, even if the above-mentioned hydrocarbon resin is used in the pressure-sensitive adhesive composition, the hydrocarbon resin as the tackifier has not only the above-mentioned characteristics but also excellent weather resistance, so that a uniform pressure-sensitive adhesive can be obtained. An adhesive composition can be obtained, and this pressure-sensitive adhesive composition has an advantage that it is excellent in hue and weather resistance and has less odor. An adhesive composition using such a hydrocarbon resin will be specifically described later with reference to Examples. The method for evaluating the hydrocarbon resin in the examples is as follows.

(1) Softening point JIS K5665 (2) Hue ASTM D1544-58T (3) Heat resistance stability 5 g of a hydrocarbon resin was placed in a test tube (inner diameter 16 mm) and placed in a constant temperature bath maintained at 200 ° C. After soaking for a time,
The hue is shown by the method of ASTM D1544-58T.

(4) Odor From the weak odor at the time of heating and melting (200 ° C.) to the one exhibiting a strong irritating odor, the evaluation was divided into three grades of A, B and C. The present invention will be described below with reference to examples and reference examples, but the present invention is not limited to these examples. Reference Example A A wire mesh catalyst charging basket is fixed in advance to a stirring blade of a 1-liter capacity autoclave (SUS304). 5 g of a palladium-based catalyst G-68C manufactured by Nissan Gardler Co. was placed in the basket. Next, into the autoclave 5-vinyl-
500 g of 2-norbornene was added.

Then, hydrogen was added from the hydrogen cylinder into the autoclave, and the mixture was reacted at a temperature of 80 ° C. and a pressure of 10 Kg / cm ² for about 6 hours, then allowed to cool and depressurized, and then the contents were taken out. Then, by distillation, boiling point 61-62 ° C / 3
480 g of A fraction of 9 mmHg was obtained. The composition of this fraction A is as follows. 2-Vinylnorbornane 38.5% 2-Ethylidenenorbornane 60.1% Unknown component 1.4% Reference Example B 1-liter capacity autoclave (manufactured by SUS304) was charged with 272 g of isoprene and heated to 145 ° C. 265 g of cyclopentadiene was continuously added thereto over 2 hours, and then stirring was continued for 4 hours. The pressure is 14
It fell from Kg / cm ² to 7 Kg / cm ² . The contents were taken out after cooling and depressurizing. The composition of the resulting reaction mixture is shown below.

Isoprene 14.2% 5-Isopropenyl-2-norbornene 16.4% Dicyclopentadiene 44.7% Others 24.7% Next, 1 liter capacity autoclave (SUS304
Wire cage catalyst charging basket was fixed in advance to the stirring blade of (made by), and in the basket the Nissan Gardler Palladium catalyst G-68C.
5 g of the reaction mixture, and the reaction mixture 50
0 g was added.

Thereafter, hydrogen was added from a hydrogen cylinder into the autoclave, and the temperature was 80 ° C. and the pressure was 10 Kg / cm ² .
After reacting for a period of time, the mixture was allowed to cool and depressurized, and the obtained reaction mixture was taken out. The reaction mixture is fractionally distilled to a boiling point of 10
60 g of B fraction of 5 to 174 ° C and boiling point of 174 to 184 ° C
250 g of C fraction was obtained. The composition (% by weight) of the obtained B fraction and C fraction is as follows.

[0062] Examples 1 to 11 A 1 liter glass autoclave was charged with a predetermined amount of catalyst and a part of the solvent (20 ml), and the mixture was stirred under stirring.
The cyclic olefin and various diolefins shown in (4) and the rest of the solvent were mixed together and injected from a pressure-resistant cylinder. At this time, heating or cooling was carried out so as to keep the temperature at 60 ° C., and each monomer was injected in about 15 minutes.

After continuing the polymerization reaction at this temperature for about 2 hours, methanol was added to decompose the catalyst, and the catalyst was washed with water.
The resulting polymerized oil was filtered through a glass filter to check for gel formation, and then the filtrate was concentrated to obtain a hydrocarbon resin. The properties of the obtained hydrocarbon resin are shown in Tables 1 and 2.

[0064]

[Table 1]

[0065]

[Table 2] The evaluation methods in Table 1 and Table 2 are shown below. 1. Compatibility (1) Evaflex 410 (vinyl acetate content 19% by weight) or 210 (28% by weight) of Mitsui Polychemical Products and hydrocarbon resin are mixed in equal amounts on a hot plate at 180 ° C, and this is mixed with polyester. It was applied on a film to a thickness of about 1 mm and the transparency of the coating film was evaluated.

(2) A hydrocarbon resin in an amount equal to that of natural rubber is dissolved in a 10% solution of natural rubber in toluene, and this is coated on a polyester film to a thickness of about 80 μm to make the coating film transparent. evaluated. (3) Modified rosin (maleated ester type, softening point 94) commercially available for traffic paint
℃, acid value 24, melt viscosity 150 cps) and hydrocarbon tree in equal amount into a test tube, melted in an oil bath at 180 ℃,
The transparency of the mixture mixed and cooled to room temperature was evaluated.

In the evaluation, ◯ means transparent, Δ means semi-transparent, and × means opaque. 2. Heat resistance Hydrocarbon resin 2 in a test tube with an inner diameter of 15 mm and a length of 18 mm
5 g was taken and heated in an oil bath at 200 ° C. for 3 hours, and the hue was measured by the Gardner method. 3. Ratio of Polymerized Cyclic Olefin Unit in Hydrocarbon Resin The composition of the raw material mixture before the copolymerization reaction and the composition of the polymerized oil after the copolymerization reaction were determined by gas chromatography and determined from the reaction amount ratio of each comonomer. Table 3 shows the polymerized units of each comonomer obtained in Example 1.

[0068]

[Table 3] Comparative Examples 1 to 4 In the same manner as in Examples 1 to 11, cyclic olefin-containing fraction homopolymerization and isoprene homopolymerization were carried out. Table 4 shows the properties of the obtained hydrocarbon resin. From this result, the cyclic olefin alone has extremely low polymerizability, and
It is clear that the resulting hydrocarbon resin has a low softening point and has extremely poor hue and heat resistance.

[0069]

[Table 4] Example 12 In a 4-liter flask having a capacity of 1 liter equipped with a stirrer, a thermometer, a condenser, a dropping funnel and a rubber stopper for injecting a catalyst, 197 g of the cyclic olefin-containing fraction obtained in Reference Example A and 78 g of benzene as a solvent. Was charged, 3.9 g of boron trifluoride-phenol complex was added under stirring in a nitrogen gas stream, and the mixture was gently heated to 40 ° C. and heated. Then styrene 1
94 g was added dropwise over 2 hours, and then the temperature was adjusted to 40-4.
After the reaction was carried out for 30 minutes while maintaining the temperature at 5 ° C., the catalyst was decomposed with an aqueous sodium hydroxide solution, washed with water and concentrated to obtain 280 g of a hydrocarbon resin having a cyclic olefin unit of 27 mol%.
No gel was formed in the above reaction. The properties of the resulting hydrocarbon resin are shown in Table 5.

[0070]

[Table 5] Examples 13 to 15 and Comparative Example 5 In the same manner as in Examples 1 to 11, the C ₅ fraction having the composition shown in Table 6 was used to perform copolymerization with the cyclic olefin-containing fraction obtained in the Reference Example. Done. Table 7 shows the properties of the obtained hydrocarbon resin.

[0071]

[Table 6]

[0072]

[Table 7] Example 16 and Comparative Example 6 The hydrocarbon resin obtained in Example 3 (Example 16)
And commercially available resins (goodyear wing, tack,
Plus) (Comparative Example 6) was used to adjust the pressure-sensitive adhesive, and the pressure-sensitive adhesive tape performance was examined. The results obtained are shown in Table 8.

It is apparent that the one using the hydrocarbon resin according to the present invention is superior to the commercially available resin in terms of tack and adhesive strength.

[0074]

[Table 8] The evaluation methods in Table 8 are as follows. Caliperex TR-1107 (Ciel product), which is a commercially available SIS block copolymer, is added to 100 parts of the adhesive raw material resin.
00 parts, mineral oil (Ciel products Chelflex 371
N) 30 parts and a stabilizer (Irganox 1010) 3 parts were added, and kneading was performed at 150 ° C. for 30 minutes with a kneader to adjust the pressure-sensitive adhesive.

Next, this adhesive was applied to a polyester film (Lumirror manufactured by Toray Industries Co., Ltd., thickness: 25 μm) by a hot-melt applicator to a thickness of 55 μm, and JISZ-15 was used.
Adhesion and cohesion were also measured by the Dow method (20 ° C.), respectively, according to the method of No. 22.

Claims (1)

1. A hydrocarbon component selected from the group consisting of a chain unsaturated hydrocarbon having 3 to 10 carbon atoms and an aromatic hydrocarbon having an unsaturated bond in a side chain having 8 to 16 carbon atoms. (A)
And at least one component (B) selected from the group consisting of 1,2-dihydrodicyclopentadiene, 2-norbornene, alkylidenenorbornane, alkylidenecyclohexanes, vinylnorbornanes, vinylcyclohexanes and cyclohexenes. A hydrocarbon resin comprising a copolymer obtained by polymerizing a monomer mixture of the following formula in the presence of a polymerization catalyst, wherein the unit (A) is 20 to 98 mol% and the unit (B) is Having a softening point of 60 to 170 ° C., a melt viscosity of 10 to 10,000 cps, and 3
A tacky fire made of a hydrocarbon resin having a number average molecular weight of 00 to 3000.