JPH11172214A - Tacky adhesive composition containing hydrocarbon tackifier - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a tacky adhesive having good initial adhesion, tackiness and retention and a hot melt adhesive showing good heat resistance and good adhesiveness over a wise range of temperatures. SOLUTION: This tacky adhesive composition is obtained by compounding at least one base polymer selected from elastomers and thermoplastic resins with a hydrocarbon resin having a softening point of 60-130 deg.C obtained by the cationic polymerization of a monoolefin and a 4-5C conjugated diene with the use of an acidic halogenated metal catalyst as a tackifier. The acidic halogenated metal catalyst is brought into contact with a monocyclic monoolefin in an amount of at least 5 times (by weight ratio) the catalyst prior to the polymerization.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a pressure-sensitive adhesive composition containing a specific hydrocarbon resin as a tackifier and containing an elastomer and / or a thermoplastic resin as a base polymer. The adhesive compositions of the present invention exhibit improved adhesive properties and are particularly useful as pressure sensitive adhesives and hot melt adhesives.

[0002]

2. Description of the Related Art Conventionally, as an adhesive or a hot melt adhesive, a composition in which a tackifier is blended with a base polymer such as an elastomer or a thermoplastic resin has been used.
For example, pressure-sensitive adhesive tapes or labels such as pressure-sensitive adhesive tapes, kraft tapes, and price labels use a pressure-sensitive adhesive obtained by compounding a tackifier with an elastomer. Natural rubber, polyisoprene, styrene-butadiene rubber (SBR),
Styrene-isobutylene-based block copolymers and hydrides thereof, styrene-butadiene-based block copolymers and hydrides thereof are used, and as a tackifier, natural resins such as polyterpene resins and rosin esters and petroleum-based resins are used. Hydrocarbon resins are used. on the other hand,
Hot melt adhesives widely used for bonding paper, wood, metal, plastic, etc. include thermoplastic resins such as polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and styrene-
A thermoplastic elastomer such as an isoprene-based block copolymer or a styrene-butadiene-based block copolymer is blended with a petroleum hydrocarbon resin as a tackifier.

[0003] Among petroleum hydrocarbon resins, a hydrocarbon resin obtained by cationic polymerization of a monoolefin and a conjugated diene having 4 to 5 carbon atoms using an acidic metal halide catalyst is blended as a tackifier. The pressure-sensitive adhesive composition is particularly excellent in initial adhesive strength, and the hot-melt adhesive containing the same hydrocarbon resin has good heat resistance and exhibits good adhesiveness over a relatively wide temperature range. Have. As a specific example of such a hydrocarbon resin tackifier, a monomer mixture comprising isoprene, an aromatic monoolefin and an aliphatic monoolefin is cationically polymerized using an aluminum halide-based catalyst in the presence of a solvent. And a monomer mixture comprising 1,3-butadiene, styrene, cyclopentene and 1,3-butadiene in the presence of a solvent. And hydrocarbon resins obtained by cationic polymerization in the presence of an aluminum halide-based catalyst (JP-A-60-118777).

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an adhesive comprising a hydrocarbon resin tackifier obtained by cationic polymerization of a monoolefin and a conjugated diene as described above using an acidic metal halide catalyst. It is an object of the present invention to provide a pressure-sensitive adhesive composition exhibiting even more excellent pressure-sensitive adhesive properties as compared with an adhesive composition. More specifically, (1) a pressure-sensitive adhesive composition having excellent initial adhesive strength together with good adhesive strength and holding power, and (2) good heat resistance, over a relatively wide temperature range. To provide a hot-melt adhesive composition exhibiting excellent adhesiveness.

The present inventors have conducted intensive studies on hydrocarbon resin tackifiers. As a result, when cation polymerization of a conjugated diene and a monoolefin using an aluminum chloride catalyst was carried out, the aluminum chloride catalyst and cyclopentene were added prior to the initiation of the polymerization. It has been found that the hydrocarbon resin obtained as a result of the polymerization is more excellent as a tackifier by contacting with a monocyclic monoolefin such as the above, and the present invention has been completed based on this finding.

[0006]

According to the present invention, at least one base polymer selected from the group consisting of (a) an elastomer and a thermoplastic resin, and (b) a monoolefin and a carbon An adhesive composition comprising a hydrocarbon resin having a softening point of 60 to 130 ° C. obtained by cationically polymerizing 4 to 5 conjugated dienes using an acidic metal halide catalyst, A pressure-sensitive adhesive composition is provided, which comprises contacting an acidic metal halide catalyst with a monocyclic monoolefin at least 5 times (by weight) the polymerization catalyst before polymerization.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The adhesive composition of the present invention comprises:
(A) at least one base polymer selected from an elastomer and a thermoplastic resin, and (b) a monoolefin using an acidic metal halide catalyst contact-treated with a monocyclic monoolefin as a tackifier. And a conjugated diene having 4 to 5 carbon atoms and a hydrocarbon resin having a softening point of 60 to 130 ° C. obtained by cationic polymerization.

Hydrocarbon Resin Tackifier The hydrocarbon resin used as the tackifier in the present invention comprises a polymerization catalyst comprising an acidic metal halide and a monocyclic monoolefin at least 5 times (weight ratio) the catalyst. After contacting, it is produced by cationic polymerization of a monoolefin and a conjugated diene having 4 to 5 carbon atoms.

The monocyclic monoolefin to be brought into contact with the acidic metal halide catalyst is a cyclic monoolefin having 5 to 6 carbon atoms, and examples thereof include cyclopentene, methylcyclopentene and cyclohexene. Cyclohexene is preferred.

The acidic metal halide catalyst is a Friedel-Crafts type catalyst, which is in a gaseous or solid state at room temperature. Typical examples thereof include fluorides, chlorides, and the like of metals such as aluminum, boron and iron. Examples thereof include bromide and iodide, and among them, aluminum halide such as aluminum chloride and aluminum bromide is preferable. Aluminum halide is usually used as 5-200 mesh particles, but is not limited thereto, and can be used as larger particles or smaller particles. The amount of the acidic metal halide catalyst used is 0.1 to 1 with respect to the total amount of the monomer mixture containing the monoolefin and the conjugated diene having 4 to 5 carbon atoms and the monocyclic monoolefin.
0% by weight.

The amount of the monocyclic monoolefin to be brought into contact with the acidic metal halide catalyst must be at least 5 times (weight ratio) the amount of the acidic metal halide catalyst. If the amount of the monocyclic monoolefin is too small, the effects of preventing gel formation and improving the hue are insufficient. The weight ratio between the monocyclic monoolefin and the acidic metal halide catalyst is preferably from 5: 1 to 120:
1, more preferably from 10: 1 to 100: 1, even more preferably from 15: 1 to 80: 1. Use of an excessively large amount of the monocyclic monoolefin in this proportion is not preferable because the catalytic activity decreases and the polymerization does not proceed sufficiently.

In order to bring the acidic metal halide catalyst into contact with the monocyclic monoolefin, a method of mixing and stirring the two is employed. When mixing the two, the order of introduction is not particularly limited, and even if the acidic metal halide catalyst is introduced into the monocyclic monoolefin, or conversely, the monocyclic monoolefin is introduced into the acidic metal halide catalyst. It does not matter. Since mixing is usually exothermic, a suitable diluent can be used. Examples of the diluent include aliphatic hydrocarbons such as pentane, hexane, heptane, cyclopentane, cyclohexane, isopentane, and methylpentane; and aromatic hydrocarbons such as benzene, toluene, and xylene. Can be used. The mixing is usually performed at a temperature of -20 ° C to + 100 ° C, preferably 0 to + 80 ° C, and the mixing time is generally performed within 3 hours, preferably within 1 hour. The amount of the diluent used is usually not more than 19 times the weight of the monocyclic monoolefin.

Preferred examples of the conjugated diene having 4 to 5 carbon atoms used as a raw material for producing a hydrocarbon resin include 1,3
-Pentadiene, isoprene and 1,3-butadiene. The monoolefin used as a hydrocarbon resin production raw material is a monoolefinically unsaturated hydrocarbon having 4 to 10 carbon atoms (including a cyclic monoolefin). Preferred examples of the monoolefin include linear monoolefins such as butenes, pentenes, methylbutenes, methylpentenes, and diisobutylene; cyclic monoolefins such as cyclopentene, cyclohexene, and methylcyclopentene; and styrene and methylstyrenes And other aromatic monoolefins.

The ratio between the monoolefin and the conjugated diene having 4 to 5 carbon atoms is usually in the range of 90/10 to 15/85 (weight ratio). Since the monocyclic monoolefin used in contact with the acidic metal halide catalyst is also polymerizable, when the monocyclic monoolefin is present in the polymerization system, one of the monoolefins used in the above ratio is used. Make up the part. A typical monomer mixture containing a monoolefin and a conjugated diene having 4 to 5 carbon atoms in this ratio is generally -20.
It is obtained as a naphtha cracking fraction at ~ 60 ° C or, if desired, by combining this fraction with various olefinically unsaturated hydrocarbon fractions. Such monomer mixtures obtained industrially usually contain considerable amounts of saturated hydrocarbons such as butanes, pentanes, cyclopentane, etc. It does not hinder the production of the hydrogen resin. Further, the monomer mixture may contain cyclopentadiene, a dimer thereof, a co-dimer of cyclopentadiene and a chain conjugated diene, and the like, but since these lower the hue of the hydrocarbon resin, Preferably, it is not substantially contained in the monomer mixture.

The preparation of the acidic metal halide catalyst may be carried out in the same reactor as the polymerization reaction or separately. Conducting a polymerization reaction by bringing an acidic metal halide catalyst and a monocyclic monoolefin into contact with each other before the start of polymerization, and then gradually adding a monomer mixture of a conjugated diene and a monoolefin to the mixture. Can be.
Further, after the acidic metal halide catalyst and the monocyclic monoolefin are brought into contact with each other before the start of the polymerization, the mixture may be added to a monomer mixture of a conjugated diene and a monoolefin, or Both can be simultaneously introduced into the reactor. The reaction is carried out according to a known method regardless of a batch type or a continuous type.

The polymerization reaction is carried out using a suitable solvent if desired. It is preferable to use a solvent for the purpose of suppressing the heat of reaction during the polymerization. Examples of the solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, cyclopentane, cyclohexane, isopentane, and methylpentane; and aromatic hydrocarbons such as benzene, toluene, and xylene. However, in consideration of the problem of environmental pollution, it is preferable to avoid aromatic hydrocarbons and use aliphatic hydrocarbons. Even when aromatic hydrocarbons are not used as solvents,
By avoiding the formation of a large amount of gel, a hydrocarbon resin having an excellent hue can be obtained. The amount of the solvent to be used is generally 1,000 parts by weight or less, preferably 50 to 500 parts by weight, per 100 parts by weight of the monomer.

The polymerization is usually carried out at a temperature of -20.degree. C. to + 100.degree. C., preferably 0 to + 80.degree. C., and the pressure of the reaction system may be higher or lower than atmospheric pressure. The reaction time is also not critical and can generally vary from a few seconds to 12 hours or more. The polymer thus obtained is treated according to a conventional method and dried.

The hydrocarbon resin thus obtained is ASTM
JI having a Gardner chromaticity of 6 or less as measured by D-1544-63T, a number average molecular weight of 500 to 3,000, and 60 to 130C, preferably 70 to 120C.
It has a softening point specified in SK-2531 and is soluble in aliphatic and aromatic hydrocarbons such as pentane, hexane, benzene, toluene, xylene, chloroform, carbon tetrachloride or halogenated hydrocarbon solvents. And a resinous polymer having a low melt viscosity.

Elastomer and Thermoplastic Resin As the base polymer of the adhesive composition of the present invention, at least one selected from elastomers and thermoplastic resins is used. Elastomers and thermoplastics include those elastomers and thermoplastics used in the preparation of adhesive compositions in combination with conventional hydrocarbon resin tackifiers. The preferred base polymer used in the preparation of the adhesive composition used as a pressure-sensitive adhesive is an elastomer. As an elastomer,
Examples thereof include a conjugated diene rubber and a thermoplastic elastomer composed of an aromatic monoolefin polymer block and a conjugated diolefin polymer block.

As the conjugated diene rubber, natural rubber, S
Examples thereof include BR, synthetic polyisoprene rubber, and polybutadiene rubber, and those having a Mooney viscosity of 20 to 100, preferably 30 to 80 are usually used. Of these, natural rubber and SBR are preferred. In the case of SBR, the amount of bound styrene is usually 15 to 55% by weight, preferably 20 to 50% by weight, and the number average molecular weight is 100,000 to 1,1.
1,000,000, preferably 200,000-500,
000 random copolymers.

As the thermoplastic elastomer comprising an aromatic monoolefin polymer block and a conjugated diolefin polymer block, the thermoplastic elastomer represented by the general formula (AB) _n or (AB)
_n-1 A (where A is substantially an aromatic monoolefin polymer block, B is substantially a conjugated diolefin polymer block, and n is an integer from 2 to 10) Olefin polymer block content 10-7
0% by weight, preferably 10-55% by weight and an average molecular weight of 25,000-500,000, preferably 40,000.
0 to 200,000 block copolymers.

Specific examples of the aromatic monoolefin constituting the block copolymer include styrene, α-methylstyrene, vinyltoluene and the like, and usually styrene is used. Further, specific examples of the conjugated diolefin include 1,3-butadiene, isoprene, 1,3-pentadiene and the like. Specific examples of the block copolymer include, for example, a styrene-isoprene-based block copolymer, a styrene-butadiene-based block copolymer,
And hydrogenated products thereof.

In addition, a copolymer containing a small amount of an aromatic monoolefin unit at a gradually increasing ratio from one end to the other end of the conjugated diene block is referred to as a “substantial conjugated diolefin polymer block”. So-called “tapered block copolymer”. In addition, a “tapered block copolymer” containing a copolymer containing a small amount of a conjugated diene unit in a ratio that gradually increases from one end to the other end of the aromatic monoolefin block as a “substantial aromatic monoolefin polymer block” Is also included. Further, if necessary, an AB type block copolymer may be appropriately blended.

Each of these block copolymers is a known substance, and is a known method using a lithium-based initiator, for example, JP-B-36-19286 and JP-B-40-2.
3798, JP-B-43-17979, JP-B-43-
It is manufactured according to the method described in No. 2394 or the like.

The base polymer used for preparing the adhesive composition used as a hot melt adhesive is a thermoplastic resin; a styrene-butadiene block copolymer, a styrene-isoprene block copolymer, or the like. Thermoplastic elastomers. Examples of the thermoplastic resin include polyethylene; ethylene copolymers such as ethylene-vinyl acetate copolymer and ethylene-ethyl acrylate copolymer; polyamide; polyester; and the like. Polymers are preferred.

Among such ethylene polymers, ethylene copolymers are preferred. Specific examples of the comonomer constituting the copolymer include vinyl acetate, vinyl propionate,
Unsaturated esters such as ethyl acrylate, butyl acrylate, methyl methacrylate and ethyl methacrylate; unsaturated acids such as acrylic acid and methacrylic acid; Particularly, an ethylene-unsaturated ester copolymer having an unsaturated ester content of 10 to 50% by weight and a melt index of 0.5 to 2,500 is best.

Adhesive composition The adhesive composition of the present invention comprises at least one base polymer selected from the above-mentioned elastomers and thermoplastic resins and the above-mentioned hydrocarbon resin tackifier. And is prepared by blending The proportions of the base polymer and the hydrocarbon resin tackifier can vary depending on the desired use of the adhesive composition, but generally the base polymer 10
5 to 300 parts by weight, preferably 40 to 200 parts by weight, of the hydrocarbon resin tackifier is added to 0 parts by weight.

[0028] Other tackifiers and various additives can be blended depending on the use as long as the properties of the desired adhesive composition are not essentially hindered. For example, a process oil, a softener such as polybutene, a plasticizer, an antioxidant, a filler, and the like are added. In the hot-melt adhesive composition, waxes such as paraffin wax, microcrystalline wax, and polyethylene wax, which are generally used, can be added at a ratio of 5 to 500 parts by weight based on 100 parts by weight of the base polymer.

The adhesive composition of the present invention is produced according to a method similar to that of the conventional adhesive composition. For example, in the case of a pressure-sensitive adhesive composition, each compounded component can be stirred and mixed in the presence of a solvent such as toluene to form a pressure-sensitive adhesive solution, or a hydrocarbon resin tackifier previously emulsified in a base elastomer latex. Can be mixed with stirring to form an adhesive emulsion. These pressure-sensitive adhesive solutions or pressure-sensitive adhesive emulsions are usually uniformly coated on a desired substrate using a coating machine, dried in an oven, and then wound up to produce various pressure-sensitive adhesive tapes or pressure-sensitive label products. Is done. In the case of a hot-melt adhesive composition, the respective components are simultaneously charged into a melting pot or sequentially from those having a low melt viscosity, and then heated and melt-mixed at 100 to 200 ° C., and then a block, a rod, and a powder are formed. It can be processed into a suitable shape such as a film, a sheet, or the like, or can be produced continuously using a single-screw or twin-screw extruder.

[0030]

The present invention will be described more specifically with reference to the following examples. Parts and% in Examples and Comparative Examples
Unless otherwise specified, weight is based on weight. Polymerization Example 1 (Preparation of Hydrocarbon Resin A) 1.0 part of aluminum chloride was placed in a SUS autoclave,
31.1 parts of cyclopentene and 57.7 parts of cyclopentane (diluent) are added, and the mixture is stirred and the temperature of the system is reduced to 60 ° C. and 1 part.
Maintained for 0 minutes.

Next, 111.2 parts of the monomer mixture having the following composition (the total amount of 1,3-pentadiene, cyclopentene and diisobutylene is 100 parts) is gradually and continuously added to the above solution over 60 minutes. Was added. Monomer mixture 1,3-pentadiene 42.8 parts by weight 38.5% Cyclopentene 13.2 parts by weight 11.9% Diisobutylene 44.0 parts by weight 39.6% C _4-6 unsaturated hydrocarbon 3.4 Parts by weight 3.1% C _4-6 saturated hydrocarbon 7.8 parts by weight 7.0%

Since the temperature of the system rises due to the heat generated by the reaction, the heating temperature was adjusted to maintain the internal temperature at 70 ° C. After completion of the addition, the polymerization system was maintained at 70 ° C., and the mixture was further stirred for 10 minutes. Then, an equal volume mixture of methanol and 28% aqueous ammonia was added to decompose aluminum chloride. The catalyst particles deactivated by the decomposition were removed by filtration, the filtrate was transferred to a glass flask, and heated while blowing in nitrogen to distill off unreacted hydrocarbons, and then heated to 240 ° C. . Next, saturated steam was blown into the system to remove the oily polymer generated by the polymerization reaction, and after confirming that almost no oil layer was present in the distillate, the blowing of steam was stopped to melt the residue. Was taken out and cooled to room temperature to obtain a yellow resinous substance (hydrocarbon resin A).

With respect to the obtained hydrocarbon resin A, the resin yield (1 in the monocyclic monoolefin and monomer mixture)
Yield based on the total weight of 3-pentadiene, cyclopentene, styrene and diisobutylene), softening point (JIS
Measured by the ring and ball method specified by K-2531),
The weight average molecular weight, number average molecular weight, and Gardner chromaticity were determined. The weight average molecular weight and the number average molecular weight are measured by gel permeation chromatography and converted to standard polystyrene. Gardner chromaticity is A
It was measured by STM D-1544-63T and expressed as a measured value for a solution obtained by dissolving the resin in an equal amount of toluene. Table 1 shows the results.

Polymerization Examples 2 to 6 (Preparation of Hydrocarbon Resins BF) Using the cyclic monoolefin, diluent and monomer mixture shown in Table 1, the same operation as in Polymerization Example 1 was carried out, and Hydrogen resins BF were obtained.

[0035]

[Table 1]

Comparative Polymerization Examples 1 to 6 (Preparation of Hydrocarbon Resins GL) Using benzene as a diluent without contacting the catalyst with a monocyclic monoolefin in advance, and using a monomer mixture shown in Table 2 The same operation as in Polymerization Example 1 was performed to obtain hydrocarbon resins G to
L was obtained.

[0037]

[Table 2]

The resins obtained in Polymerization Examples 1 to 3 in Table 1 and the resins obtained in Comparative Polymerization Examples 1 to 3 in Table 2 are resins having almost the same softening point. However, the resins obtained in Polymerization Examples 1 to 3 in which the catalyst was previously contacted with cyclopentene, which is a monocyclic monoolefin, had a smaller weight average molecular weight than the resins in Comparative Polymerization Examples 1 to 3 in which this operation was not performed. It is clear that it is. Similar results were obtained when styrene was copolymerized (polymerization examples 4 to 6 in Table 1 and comparative polymerization examples 4 to 6 in Table 2).

Examples 1-4 and Comparative Examples 1-4 (Evaluation as a conjugated diene rubber-based pressure-sensitive adhesive) Polymerization Examples 1-3 and Polymerization Example 5 and Comparative Polymerization Examples 1
The following pressure-sensitive adhesives were prepared using the resins obtained in Comparative Example 3 and Comparative Polymerization Example 5, and the pressure-sensitive adhesive properties were measured. 100 parts of natural rubber (pale crepe, Mooney viscosity 60), 100 parts of the hydrocarbon resin A to C, E, GI or K and 1 part of an antioxidant are dissolved and mixed in toluene, and an adhesive solution having a nonvolatile content of 17% is prepared. Was prepared. Next, this solution was applied on a 25 μm-thick polyester film so as to have a paste thickness of 25 μm to prepare an adhesive tape, and its initial adhesive strength, adhesive strength, and holding power were measured according to the following methods. Table 3 shows the results.

[0040]

[Table 3]

(1) Initial adhesive strength: JIS Z-0237
At 23 ° C, a 10 cm long adhesive surface is stuck on a slope on a stainless steel plate with a slope angle of 30 degrees at 23 ° C, and steel balls of 30 sizes from 3/32 inch to 1 inch in diameter are sloped. The size of the sphere having the largest diameter that stops at 10 cm from the position 10 cm above and stops on the adhesive tape (unit: ball number [= × 1/32 inch]).

(2) Adhesive strength: According to JIS Z-0237, an adhesive tape having a width of 10 mm and a length of 100 mm was attached to a stainless steel plate polished with a water-resistant abrasive paper of No. 280 at a speed of 200 mm / min at 23 ° C. , And the peeling force (unit: N / m) was measured. (3) Holding force: 10 mm × 10 mm on a stainless steel plate polished with No. 280 water-resistant abrasive paper according to JIS Z-0237.
paste the adhesive tape so that the area of
The time (unit: minute) required for the pressure-sensitive adhesive tape to fall off the stainless steel plate by applying a load of 1 kg at ℃ was measured.

Examples 5 to 8 and Comparative Examples 5 to 8 (Evaluation as a styrene-isoprene-based block copolymer-based pressure-sensitive adhesive) Polymerization Examples 1 to 3, Polymerization Example 5, and Comparative Polymerization Examples 1 to
Using the resins obtained in Comparative Example 3 and Comparative Polymerization Example 5, a pressure-sensitive adhesive was prepared by the following operation, and pressure-sensitive adhesive properties were measured. Styrene-isoprene block copolymer (Quintac 34
21, 100 parts of Zeon Corporation), 100 parts of the hydrocarbon resins A to C, E and G to I, K, 20 parts of naphthenic process oil (Shellflex 371N, manufactured by Shell Chemical Company), antioxidant One part of the agent was dissolved and mixed in toluene to prepare an adhesive solution having a nonvolatile content of 40%. Next, this solution was applied on a 25 μm-thick polyester film so as to have a glue thickness of 25 μm to prepare an adhesive tape,
The initial adhesive strength, adhesive strength and holding power were measured. Except that the measurement of the holding force was performed at 50 ° C., the measuring method and the unit of each physical property were the same as described above. Table 4 shows the results.

[0044]

[Table 4]

Examples 9 to 12 and Comparative Examples 9 to 12 (Evaluation as Hot Melt Adhesive Based on Ethylene-Vinyl Acetate Copolymer) Polymerization Examples 4 to 6, Polymerization Example 2, and Comparative Polymerization Examples 4 to 6
Using the resin obtained in Comparative Polymerization Example 2, an adhesive was prepared by the operation described below, and the adhesive properties were measured. Ethylene-
Vinyl acetate (EVA) copolymer (vinyl acetate content 28
%, Melt index 150g / 10min)
Part, microcrystalline wax (melting point 173 ° F)
50 parts, and the hydrocarbon resins B, D to F, H, J
~ L to make a mixture of 100 parts, JIS K-
The cloud point of each formulation was measured according to the method specified in 2266.

The composition melted at 180 ° C.
After applying 0.2 mm thickness to an aluminum plate having a thickness of 0.2 mm, another aluminum plate is superimposed and a pressure of 1.0 kg / c is applied.
Sealing and fusion were performed for 2 seconds under conditions of m ² and a temperature of 140 ° C. to produce a laminated sample. This sample is cut into 25 mm-width pieces to form test pieces, and the test pieces are pulled at 5 ° C., 20 ° C., and 35 ° C. at a speed of 200 mm / min, and adhered by a 90 ° peeling method (unit: g / inch). ) Was measured. Table 5 shows the results.

[0047]

[Table 5]

[0048]

The adhesive composition containing a specific hydrocarbon resin tackifier used in the present invention exhibits excellent adhesive properties. More specifically, as a pressure-sensitive adhesive composition, it has excellent initial adhesive strength and good adhesive strength, holding power, and, as a hot melt adhesive composition, has good heat resistance, Shows good adhesion over a relatively wide temperature range.

(Preferred Embodiment of the Invention) (a) At least one base polymer selected from an elastomer and a thermoplastic resin, and (b) a monoolefin and a conjugated diene having 4 to 5 carbon atoms as a tackifier. And an adhesive composition comprising a hydrocarbon resin having a softening point of 60 to 130 ° C. obtained by cationically polymerizing the acid metal halide catalyst with the acid metal halide catalyst. Preferred embodiments of the adhesive composition of the present invention, which is characterized in that it is brought into contact with a monocyclic monoolefin 5 times or more (weight ratio) of the catalyst before the polymerization, are summarized as follows.

1. The weight ratio of the monocyclic monoolefin contacted with the acidic metal halide catalyst to the catalyst is 5: 1 to 1: 1.
120: 1, more preferably 10: 1 to 100: 1. 2. The monocyclic monoolefin contacted with the acidic metal halide catalyst is a cyclic monoolefin having 5 to 6 carbon atoms, more preferably cyclopentene or cyclohexene.

3. The acidic metal halide catalyst is an aluminum, boron or iron fluoride, chloride, bromide or iodide, more preferably an aluminum halide. 4. The contact between the acidic metal halide catalyst and the monocyclic monoolefin is performed in the presence of a diluent selected from aliphatic hydrocarbons and aromatic hydrocarbons. 5. The conjugated diene having 4 to 5 carbon atoms is at least one selected from 1,3-pentadiene, isoprene and butadiene.

6. The monoolefin to be polymerized with the conjugated diene having 4 to 5 carbon atoms is at least one selected from monoolefinically unsaturated hydrocarbons having 4 to 10 carbon atoms. 7. The monoolefin to be polymerized with the conjugated diene having 4 to 5 units is at least one selected from butenes, pentenes, methylbutenes, methylpentenes, diisobutylene, cyclopentene, cyclohexene, methylcyclopentenes, styrene and methylstyrenes. It is a kind.

8. When the ratio of the monoolefin (including the monocyclic monoolefin used in contact with the acidic metal halide catalyst to the polymerization system, the monocyclic monoolefin is included) and the conjugated diene having 4 to 5 carbon atoms is satisfied. 90/10 to 15/8
5 (weight ratio). 9. The copolymerization of the monoolefin and the conjugated diene having 4 to 5 carbon atoms is performed in an aliphatic hydrocarbon solvent. 10. The softening point of the hydrocarbon resin produced by polymerization is 70
~ 120 ° C.

11. The adhesive composition has a tackifier composed of a hydrocarbon resin in an amount of 5 to 300 parts by weight, more preferably 100 parts by weight of at least one base polymer selected from an elastomer and a thermoplastic resin. 40
-200 parts by weight. 12. The adhesive composition is a pressure-sensitive adhesive containing, as a base polymer, a conjugated diene rubber or a thermoplastic elastomer composed of an aromatic monoolefin polymer block and a conjugated diolefin polymer block.

13. The conjugated diene rubber of the above 12 is a natural rubber, a styrene-butadiene copolymer rubber (SB
R), selected from synthetic polyisoprene rubber and polybutadiene rubber, more preferably natural rubber or SB
R and usually has a Mooney viscosity of 20 to 100, more preferably 30 to 80. 14． The above 13 SBR has a bound styrene content of 15 to 5
It is a random copolymer having 5% by weight, more preferably 20 to 50% by weight, a number average molecular weight of 100,000 to 1,000,000, and more preferably 200,000 to 500,000.

15. The thermoplastic elastomer comprising the aromatic monoolefin polymer block and the conjugated diolefin polymer block of the above 12 is a compound represented by the general formula (AB) _n or (AB) _n-1 A (where A is substantially , An aromatic monoolefin polymer block, B is a substantially conjugated diolefin polymer block, and n represents an integer of 2 to 10.)
10 to 70% by weight, more preferably 10 to 55% by weight of an aromatic monoolefin polymer block content represented by
And a block copolymer having an average molecular weight of 25,000 to 500,000, more preferably 40,000 to 200,000.

16. The adhesive composition is a hot melt adhesive containing, as a base polymer, a thermoplastic resin; or a thermoplastic elastomer selected from styrene-butadiene-based block copolymers and styrene-isoprene-based block copolymers. is there. 17． The above-mentioned thermoplastic polymer is an ethylene polymer.

18. The ethylene polymer of the above 17 is a homopolymer of ethylene, or ethylene and an unsaturated selected from vinyl acetate, vinyl propionate, ethyl acrylate, butyl acrylate, methyl methacrylate, and ethyl methacrylate. It is a copolymer with an ester and a monomer selected from the group consisting of unsaturated acids selected from acrylic acid and methacrylic acid. 19. The adhesive composition is a hot melt adhesive containing, as a base polymer, an ethylene-unsaturated ester copolymer having an unsaturated ester content of 10 to 50% by weight and a melt index of 0.5 to 2,500.

Claims (1)

[Claims] (1) at least one base polymer selected from an elastomer and a thermoplastic resin,
(B) Monoolefin and carbon number 4 or more as tackifiers
Softening point 60-130 obtained by cationic polymerization of conjugated diene of No. 5 with an acidic metal halide catalyst.
C. A pressure-sensitive adhesive composition containing a hydrocarbon resin at a temperature of 5 ° C., wherein the acidic metal halide catalyst is brought into contact with a monocyclic monoolefin at least 5 times (by weight) the catalyst before polymerization. An adhesive composition comprising: