JPS6128516A - Low-softening point hydrocarbon polymer and its use - Google Patents

Abstract

PURPOSE:The titled polymer having excellent heat stability and low odor and being useful as, for example, a softener for a hot-melt or solvent-type pressure-sensitive tackifier, comprising a hydrogenated product of an unsaturated hydrocarbon/9,10-dihydrodicyclopentadiene copolymer. CONSTITUTION:A hydrocarbon polymer obtained by hydrogenating a copolymer comprising (A) an unsaturated hydrocarbon (e.g., 1,3-butadiene or 1,3-pentadiene) and (B) 9,10-dihydrodicyclopentadiene or its derivative and having a content of structural units derived from compound A of about 20-98mol%, a content of structural units derived from compound B of about 80-2mol%, a softening point <=60 deg.C and an iodine value <=100. This polymer is excellent in heat stability and low odor and useful as a tackifier or softener for a pressure-sensitive adhesive, especially, a hot-melt or solvent-type pressure-sensitive adhesive.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to low softening point hydrocarbon polymers.

More specifically, low softening point hydrocarbons useful as tackifiers or softeners for pressure-sensitive adhesives with excellent heat resistance stability and low odor, especially hot-melt pressure-sensitive adhesives or solvent-type pressure-sensitive adhesives. Relating to polymers.

[Problems to be solved by conventional technology/invention]

In recent years, in addition to conventional pressure-sensitive adhesives such as solvent-based and emulsion-based adhesives, hot-melt adhesives have come into widespread use. The main uses of hot-melt pressure-sensitive adhesives include labels, craft tapes, and cloth tapes. Among these tapes, which are frequently used in the packaging field such as cardboard, they have a well-balanced adhesive performance such as cardboard adhesion at low temperatures, tack, adhesion, cohesive force, and cardboard retention strength, and are heat resistant and stable. A material with excellent properties and low odor is required. These performances are highly dependent on the elastomer, which is the main component of hot-melt pressure-sensitive adhesives, and in particular on the tackifier (tackifier). There was no.

[Means to try to solve problems]

By the way, recently, hydrocarbon resins have been increasingly used as tackifiers for hot-melt pressure-sensitive adhesives, instead of rosin resins, terpene resins, etc. As such, the present applicant previously proposed a hydrocarbon resin having specific compositional properties (Japanese Patent Laid-Open No. 58-42610).

As a result of further studies on the resin, the present inventors found that a resin having a specific composition and properties is surprisingly extremely effective in solving the above problems, and that a hot melt pressure sensitive adhesive and a solvent. We have discovered that it is also excellent as a softener for bulk and positive adhesives, and have completed the present invention.

That is, the present invention is characterized by the unsaturated hydrocarbon (A) and 9.10
-dihydrodicyclopentadiene or its derivative (B
) A hydrogenated copolymer consisting essentially of
The proportion of structural units derived from (A) is in the range of about 20 to 98 mol%, the proportion of structural units derived from (B) is in the range of about 80 to 2 mol% [the total of both is 100 mol%], and the softening point is The invention relates to a hydrocarbon polymer (C) having a temperature of about 60°C or less and an iodine value of 100 or less, and furthermore, an additive for a pressure-sensitive adhesive comprising the polymer (C).

[Production method of hydrocarbon polymer (C)]

[Component (A)] Specifically, the unsaturated hydrocarbon (A) that forms the hydrocarbon polymer according to the present invention is, for example, ethylene, propylene, 1-butene, 2-butene, isobutylene, 1 −
Chain monoolefins such as pentene, 2-pentene, 1-hexene, 2-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-heptene, 2-octene, 1,3-butadiene, Isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2
．． diolefins such as 3-dimethyl-lI3-hexadiene, lI4-pentadiene, 3,4.5-trimethyl-1,6-heptadiene, 1,2-dimethylidenecyclohexane, 1,2-dimethylidenecyclopentane, Examples include cyclic hydrocarbons having unsaturated bonds in side lines such as vinylcyclohexane, limonene, styrene, vinyltoluene, α-methylstyrene, isopropenyltoluene, tert-butylstyrene, allylbenzene, and p-tert-butylallylbenzene.

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

These hydrocarbons can be used individually or as a mixture of two or more homologous compounds, as well as monoolefins and diolefins, monoolefins and cyclic hydrocarbons having unsaturated bonds in their side chains, and diolefins and side chains. It is used as a cyclic hydrocarbon having an unsaturated bond in its side chain, or a mixture of a monoolefin, a diolefin, and a cyclic hydrocarbon having an unsaturated bond in its side chain.

[(B) component]

9,10-dihydrodicyclopentadiene or its derivative (B) to be copolymerized with these hydrocarbons is a compound represented by the following general formula; is a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and R located at the 3-10-position is a hydrogen atom, a halogen atom, a hydroxyl group, -R
3, -0R4, (However, R3, R+, R6, R8, R
6 represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group, R5, R7,
represents an alkylene group having 1 to 10 carbon atoms, R1° is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkylene group having 6 to 10 carbon atoms.
aryl group or aralkyl group), isocyanate group or aldehyde group], specifically, for example, 9-methyl-9,10-dihydrodicyclopentadiene, 3,9-dimethyl-9,10-dihydrodicyclopentadiene, Cyclopentadiene, 9-hydroxy-9,10-dihydrodicyclopentadiene, 9-methoxy-9,10-dihydrodicyclopentadiene, 9-acetyl-9,10-dihydrodicyclopentadiene, 9-phenoxy-9,1
Examples thereof include 0-dihydrodicyclopentadiene, 9-isocythyl-1--9.10-dihydrodicyclopentadiene, and phosphorous bis(9,10-dihydrodicyclopentadienyl).

These 9. lO-dihydrodicyclopentadiene can be obtained, for example, as follows. First, 9.10-dihydrodicyclopentadiene is obtained by heat-treating cyclopentadiene in the C5 fraction produced by naphtha decomposition to form dicyclopentadiene, and then hydrogenating the double bond of the norbornene ring. It is obtained by Hydrogenation is
A known method, for example, using one or more of nickel, palladium, cobalt, platinum, ruthenium, rhodium, copper, etc., or oxides of these metals as a hydrogenation catalyst, at room temperature or under elevated pressure, Alternatively, it is carried out by adding hydrogen gas at a predetermined molar ratio under pressure. In addition, 9,10-dihydrodicyclopentadiene derivatives can be obtained by thermally dimerizing cyclopentadiene derivatives,
It is synthesized by partially hydrogenating this. Furthermore,
Derivatives of 9.10-dihydrodicyclopentadiene can also be synthesized by adding alcohols, carboxylic acids, isocyanic acid, phosphoric acid, etc. to dicyclopentadiene or its derivatives in the presence of an acid catalyst. .

It goes without saying that the 49.10-dihydrodicyclopentadiene used is substantially pure, but if it has a purity of about 60% by weight or more in these polymerization components, In addition, cyclopentene, cyclopentadiene oligomer (trimer or more) partially hydrogenated products,
It may contain a polymerizable component such as a partially hydrogenated product of an isoprene-cyclopentadiene codimer or an oligomer, and may also contain a non-polymerizable component such as tetrahydrodicyclopentadiene or a derivative thereof.

However, since this may worsen the hue of the hydrocarbon polymer produced by the reaction with (A) and even the final hydrocarbon polymer C, and may still be accompanied by the formation of gel, cyclopentadiene, dicyclopentadiene, It is desirable to use 10% by weight or less of the cyclopentadiene oligomer and its derivatives in this polymerization component.

[Polymerization method]

When copolymerizing hydrocarbons and 9.10-dihydrodicyclopentadiene, 9.10-dihydrodicyclopentadiene generally has low reactivity, so a large amount of 9.10-dihydrodicyclopentadiene is used, and it is brought into contact with a catalyst in advance. Then, by blowing or adding a small amount of hydrocarbons, it is possible to increase the reactivity of 9,10-dihydrodicyclopentadiene and increase the proportion of its polymerized units. desirable.

9. 1,3-Butadiene, which has a high degree of copolymerizability with 10-dihydrodicyclopentadiene, is used as unsaturated hydrocarbons such as quenched diolefins, especially quenched conjugated diolefins, and 1,3-butadiene, which has little neutral hindrance. , isoprene, 1,3-pentadiene, 2,3-dimethyl-butadiene are preferably used.

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

Examples of cationic polymerization catalysts include cationic polymerization catalysts described in Petroleum Engineering, Journal of Japan, Vol. 16, No. 10, pp. 865-867 (1973), specifically ^1C13, ^lBr3,
BF3, BF, phenol, 5nC14, 5bC15
, FeC1'3, AIRCI 2 (R: alkyl group)
, Alt! t3-120, CCl5COOH1H2S
Among these, ICl3 and AlBr3 have a high yield of hydrocarbon polymers and a good hue.
, BF3, BP, 'Lewis acids, especially BP, 'phenol, etc. are excellent, and it is easy to obtain products with a low softening point.
, BP, and phenol are excellent. These polymerization catalysts reduce the catalytic activity when the 9.10-dihydrodicyclopentadiene contains a hydroxyl group or carbonyl group, but when it does not contain these groups, the catalytic activity is reduced. It can be used without any problems.

The amount of each of the above polymerization catalysts used varies depending on the type of catalyst, combination of comonomers, polymerization temperature, polymerization time, etc., but generally it is about 0.01 to 10 mol% based on the monomer. be. The polymerization solvent may or may not be used, but
For all catalyst systems, propane, butane, pentane,
hexane, heptane, benzene, toluene, xylene,
Hydrocarbon solvents such as ethylbenzene can be used. In addition, anionic polymerization catalysts include ethers such as diethyl ether, tetrahydrofuran, dioxane, and 1,2-dimethoxyethane, and cationic polymerization catalysts include dichloromethane, ethyl chloride, l,2-dichloroethane, and chlorobenzene. Chlorinated solvents can be used, and in radical polymerization catalysts, water can be used if emulsion or suspension polymerization methods are employed.

The polymerization temperature can be selected from a range of -0°C to about 150°C, and the polymerization time is about 1/2 to 10 hours. As for the pressure, normal pressure or pressurized conditions are generally used. After the copolymerization reaction is completed, the remaining catalyst is treated according to a conventional method, and the unreacted components and reaction solvent are removed by distillation or addition to a poor solvent for the hydrocarbon polymer. Polymers can be obtained. However, the hydrogenation described below may be performed without isolating the hydrocarbon polymer in the first stage.

(A) and (B) of the novel hydrocarbon polymer (C) of the present invention
) is used in the first stage polymerization.
It can be controlled by the ratio of amounts of A) and (B). Furthermore, the softening point can be easily controlled by controlling the polymerization temperature, monomer concentration, and catalyst concentration in the first stage. For example, increasing the polymerization temperature, decreasing the monomer concentration, and increasing the catalyst concentration generally lowers the softening point.

An alternative method of obtaining a hydrocarbon polymer before hydrogenation is
When producing a high softening point hydrocarbon polymer having a similar resin composition, the low softening point hydrocarbon polymer partially contained in the fraction that is removed as a solvent and unreacted monomer is further separated by distillation, etc. You can also get it.

[Hydrogenation catalyst]

The hydrocarbon polymer (C) of the present application can be obtained by hydrogenating the hydrocarbon polymer obtained as described above. Hydrogenation is carried out using a solvent in the presence of a suitable hydrogenation catalyst. Catalysts include metals of groups I and II of the periodic table or their compounds, such as nickel, chromium, palladium, platinum, cobalt, osmium, rhenium, ruthenium, Raney nickel, nickel sulfide, nickel oxide, copper chromite, 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, including aliphatic and alicyclic solvents such as pentane, hexane, heptane, isohbutane, octane, isooctane, cyclohexane, methylcyclohexane, decalin, tetralin, benzene, toluene, xylene, and dioxane. system,
Various solvents such as aromatic solvents are used. Therefore, after removing the catalyst from the polymerization solution in the first stage, hydrogenation can be carried out as it is.

Hydrogenation is carried out at approximately 20°C by a batch method or a continuous method.
At a temperature below the thermal deterioration temperature of the polymer, preferably below 300°C, under reduced pressure to increased pressure, generally at atmospheric pressure to about 300 kg/ajc, preferably about 10 to 150 kg/ajc.
This is carried out by treatment with hydrogen gas under aaG pressure conditions for about 10 minutes to about 24 hours, preferably about 10 minutes to about 10 hours.

Note that, as long as the hydrogenation conditions are below the thermal deterioration temperature, the softening point and melt viscosity of the hydrocarbon polymer usually hardly change even after hydrogenation.

[Properties of hydrocarbon polymer (C)]

The hydrocarbon polymer (C) obtained as described above has a proportion of structural units derived from the unsaturated hydrocarbon (A) of about 20 to 98 mol%, preferably about 40 to 98 mol%, particularly preferably about 45 to 95 mol%. 9,10 mol % and also consists of 9,10-dihydrodicyclopentadiene or its derivatives
- The proportion of structural units derived from dihydrodicyclopentadiene (B) is about 80 to 2 mol%, preferably about 60 to 2 mol%
mol%, particularly preferably about 55 to 5 mol%, and is liquid at a softening point (ring and ball method according to JIS K-2531) of about 60°C or lower, preferably about 30°C or lower as an essential range, and preferably about 50cps. Hereinafter, a melt viscosity of about 20 to 1 cps (Emirer viscosity needle, polymer temperature of 200° C.) and a molecular weight of preferably about 200 to 500, particularly preferably about 250 to 450 are used.
polystyrene conversion method: number average molecular weight)].

9. When the proportion of structural units derived from 10-dihydrodicyclopentadiene is 2 mol% or less, the molecular weight of the resulting hydrocarbon polymer increases, and sufficient plasticizing effect and adhesive performance (corrugated board adhesion, tack, If the structural unit ratio is 80 mol% or more, homopolymerizability will be poor due to the structure of 9,10-dihydrodicyclopentadiene. It is necessary to raise the temperature to an abnormally high temperature, which not only increases the difficulty in manufacturing, but also causes problems such as poor quality, poor hue, and poor thermal stability. It is necessary that the structural unit ratio is within the above-mentioned essential range. Moreover, the hydrocarbon polymer (C) of the present invention
If the softening point exceeds 60°C, the adhesive properties such as cardboard adhesion and tack at low temperatures will be poor, so it is necessary that the softening point be within this range.

Furthermore, the hydrocarbon polymer (C) of the present invention needs to have an iodine value (Rice method (Ig/100g)) of 100 or less, preferably 60 or less, particularly preferably 30 or less. . If the iodine value exceeds 100, odor during heating and heat resistance stability will be poor.

[Use invention]

Next, an additive for pressure-sensitive adhesives comprising the polymer (C) according to the present invention, and as a tackifier or softener for hot-melt pressure-sensitive adhesives or solvent-type pressure-sensitive adhesives. The additives will be explained below.

[Hot melt pressure sensitive adhesive]

Hot-melt pressure-sensitive adhesives usually consist of a base resin, a Tackifier-1 softener, and other additives. The polymer (C) of the present invention is extremely useful both as a tackifier and as a softener in this case, and when applied to adhesive tapes for packaging, it improves corrugated board adhesion, tack, adhesive strength, and cohesion. A product with well-balanced adhesive properties such as strength and cardboard holding power can be obtained. Furthermore, the polymer (C) of the present invention also has excellent compatibility with the base resin.

When the hydrocarbon polymer (C) according to the present invention is added as a tackifier to a hot-melt pressure-sensitive adhesive, specific examples of the base resin include styrene-butadiene copolymer, polybutadiene, Isobutylene, butyl rubber, ethylene/propylene copolymer rubber, ethylene/propylene/diene copolymer rubber, styrene/butadiene/styrene block copolymer, styrene/isoprene/styrene block copolymer, styrene/butadiene/styrene block copolymer water Rubber-like polymers such as additives and hydrogenated styrene/isoprene/styrene block copolymers are used.

When the polymer (C) of the present invention is used as a tackifier for a hot-melt pressure-sensitive adhesive, the blending ratio is usually 5 to 200 parts by weight, preferably 5 to 200 parts by weight, based on 100 parts by weight of the base resin, although it depends on other conditions. is in the range of 10 to 150 parts by weight, and when used as a softener, it is usually in the range of 5 to 100 parts by weight, preferably 10 to 50 parts by weight.

In addition, when the polymer (C) of the present invention is added as a tackifier or softener for a hot-melt pressure-sensitive adhesive, other softeners or tackifiers can also be used together. As the softening agent in this case, dioctyl phthalate, dibutyl phthalate, machine oil, process oil, polybutene, etc. can be used. Other tackifiers that can be used include rosin and derivatives thereof, terpene resins, alicyclic resins, aliphatic resins, aromatic resins, and aliphatic-aromatic copolymer resins. Examples of other additives include fillers such as calcium carbonate, zinc white, titanium oxide, and silica, anti-aging agents such as amine-based, ketone-amine-based, and phenol-based antioxidants, and stabilizers. The blending ratio of these additives is arbitrary and appropriate.

To prepare a hot-melt pressure-sensitive adhesive composition, the base resin and, if necessary, other tackifiers 1.
A mixture of the polymer of the present invention together with a softener and additives may be heated and stirred to form a uniform melt. A pressure-sensitive adhesive tape can be obtained by applying the melt onto cloth, kraft paper, synthetic film, etc. using a hot-melt coating machine.

[Solvent-based pressure-sensitive adhesive]

Next, the use of the polymer (C) of the present invention as a softener for a solvent-type pressure-sensitive adhesive will be explained.

Specific examples of the base resin in this case include natural rubber, styrene-butadiene copolymer rubber, polybutadiene, polyisoprene, polyisobutylene, butyl rubber, polychloroprene, ethylene-propylene copolymer rubber, and ethylene-propylene-diene. Copolymer rubber, styrene/butadiene/styrene block copolymer, styrene/
Rubber-like polymers such as isoprene/styrene block copolymer, hydrogenated styrene/butadiene/styrene block copolymer, and hydrogenated styrene/isoprene/styrene block copolymer are used.

The proportion of the polymer of the present invention to be used depends on various conditions, but is usually 5 to 100 parts by weight per 100 parts by weight of the base resin.
Preferably it is in the range of 10 to 50 parts by weight.

In addition, other softeners such as dioctyl phthalate, dibutyl phthalate, machine oil, process oil, polybutene, etc. may be used together with the polymer of the present invention, and other additives such as calcium carbonate, zinc white,
Titanium oxide; fillers selected from silica, anti-aging agents such as amine-based, ketone-amine-based, and phenol-based;
Stabilizers are added. The blending ratio of these additives is arbitrary and appropriate.

The method for preparing a solvent-type pressure-sensitive adhesive using the polymer (C) of the present invention as a softener includes the polymer (C) according to the present invention as a tackifier and softener, the above-mentioned base resin and the necessary It can be prepared by a conventional method such as dissolving a mixture of the various additives mentioned above in a suitable solvent depending on the purpose.

[Example] [Effect of the invention] Reference example 1 The cg fraction obtained by naphtha decomposition was heated at 150°C for 3 hours, and the cyclo'pene'tadiene contained therein was converted to dicyclopentadiene.Next Then, by removing the light fraction by distillation, the C,S fraction was 4.8% and the benzene was 0.
．． 5%, dicyclopentadiene 77.1%, isoprene-cyclopentadiene codimer 7.2%, cyclopentadiene oligomer 8.2% and unknown component 2.2%. .

In a metal autoclave, 100 parts by weight (1710 g) of this crude dicyclopentadiene and a palladium-based hydrogenation catalyst in the form of tablets (Toyo C.C.I. product C3) were placed in a metal autoclave.
1-IA) was charged, and a hydrogenation reaction was carried out under the conditions of a reaction temperature of 50° C. and a hydrogen pressure of 10 kg/− for 12 hours with stirring. Pass through the mouth to remove the catalyst, distill and 9.1
90 parts by weight of a 0-dihydrodicyclopentadiene fraction was obtained. The gas chromatography analysis results show that pentane I
I 19.0%, 9.10-dihydrodicyclopentadiene 77.0%, dicyclopentadiene 0.1% or less,
It showed a composition of 0.8% tetrahydrodicyclopentadiene and 3.2% unknown components.

Reference Example 2.3 A predetermined amount of the catalyst and a portion of the solvent (20++j) were placed in a glass autoclave with a capacity of 11, and while stirring, a predetermined amount of the 9.1 O-dihydrodicyclopentadiene-containing fraction obtained in the above reference example was added. The 1.3-pentadiene-containing fraction shown in Table 1 and the remainder of the solvent are slowly injected as a mixture from a pressure cylinder.At this time, heating or cooling is performed to maintain the temperature at 60°C, and each monomer is The injection was carried out over a period of about 15 minutes.

Furthermore, after continuing the polymerization reaction at this temperature for about 2 hours, methanol was added to separate the catalyst, and the catalyst was washed with water. The entire amount of hydrocarbon resin obtained by concentrating the polymerized oil, an equal weight of hexane, and a sulfur-resistant nickel catalyst (8 volatile chemical rN-113BJ) listed in Table 2 as a hydrogenation catalyst were placed in a steel 500+sl autoclave. Reaction temperature 200℃, reaction pressure 48
Hydrogenation was carried out at kg/cjG for a reaction time of 7 hours. cooling,
After the expansion pressure and nitrogen substitution, the catalyst was reduced and the filtrate was concentrated to obtain a hydrogenated carbonized water curtain resin. The properties of the obtained hydrocarbon resin are shown in Table 2 below. A predetermined amount of the fraction containing 9.10-dihydrodicyclopentadiene, various unsaturated hydrocarbons, and the remainder of the solvent are slowly injected as a mixture from a pressure cylinder. At this time, heating or cooling was performed to maintain a predetermined temperature, and each monomer was injected for about 15 minutes.

Furthermore, 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 polymerized oil was filtered through a glass filter, and the filtrate was concentrated. Hexane in an amount equal to the total weight of the obtained hydrocarbon resin and the hydrogenation catalyst shown in Table 4 were placed in a steel autoclave (container 500+nl), and a hydrogenation reaction was carried out under the conditions shown in Table 4. cooling, depressurization,
After purging with nitrogen, the catalyst was filtered off, and the filtrate was concentrated to obtain a hydrocarbon resin. The properties of the obtained hydrocarbon resin are shown in Table 4 below. The hydrogenation catalysts listed in Table 4 were from the following manufacturers.

Sulfur-resistant nickel (rN113BJ manufactured by 8 Volatile Chemical) Raney nickel (rN152J manufactured by 8 Volatile Chemical) Palladium carbon (manufactured by Yoken Fine Chemical) Example 5 Example 1 except for using the C5 fraction shown in Table 3 as the unsaturated hydrocarbon Polymerization was carried out in the same manner as above to obtain the hydrocarbon resins shown in Table 4.

Example 6 The same procedure as in Example 1 was carried out except that α-methylstyrene was used as the unsaturated hydrocarbon. Homopolymerization of a pentadiene-containing fraction, homopolymerization of a 1,3-pentadiene-containing fraction, copolymerization of a 9,10-dihydrodicyclopentadiene-containing fraction and a 1,3-pentadiene-containing fraction, and homopolymerization of butadiene were carried out. The properties of the obtained hydrocarbon resin are shown in Table 5 below.

Comparative Examples 5 to 6 After homopolymerization of a 1,3-pentadiene-containing fraction and homopolymerization of butadiene in the same manner as in Example 1, hydrogenation was further performed in the same manner as in Example 1. The properties of the obtained hydrocarbon resin are shown in Table 5 below.

Examples 7-12. Comparative Examples 7 to 10 SIS block copolymer (shell chemistry, TR-
1107J) 100 parts by weight, 30 parts by weight of softener (Shell Kagakuten [Shell Flex 22RJ), stabilizer (
Example 1 to 3 parts by weight of Geigy [Irganox 10IOJ] and 70 parts by weight of the resin obtained in Reference Example 2 were added.
6 to Resin 30 obtained in Comparative Examples 2.4.5 and 6
Mix parts by weight as tackifier and heat at 150℃30
The adhesive was prepared by kneading for a minute using a niegu. This adhesive was melted and applied to a thickness of 50±5 μm using an applicator on a polyester film (25 μm thick) on a 195° C. heating plate for 20 minutes to prepare an adhesive tape.

Next, adhesive performance was evaluated using the test method shown below.

(11 Corrugated board adhesion: Press the adhesive tape onto corrugated paper (JIS K-7) at 5°C by rolling it with an 850 g rubber roller, immediately peel it off, and examine the surface condition of the corrugated paper.

Rating 5: The entire surface of the corrugated paperboard is destroyed.

4: 30% or more of the surface of the corrugated paperboard is destroyed.

3: Destruction of the surface of the corrugated paperboard is clearly observed.

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

1: No surface damage to the corrugated paperboard was observed.

(2) Tuck (ball number, ): J, D
It was measured at 20°C by the o-method.

(3) Adhesive strength (g/25mm) + JIS Z-
Measurements were made at 20° C. using the method No. 1524.

(4) Cohesive force (am/2)lR): JIS Z
-1524(7) method at 20°C.

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

Table 6 shows the results obtained by the above test method.

Comparative Example 11 Instead of using the polymer of the present invention, commercially available liquid resin A (
The same procedure as in Example 7 was carried out except that rYs resin P

Comparative Example 12 Instead of using the polymer of the present invention, commercially available liquid resin B (
The same procedure as in Example 7 was carried out except that "Dymaron" manufactured by Cheap Oil was used.

As a result, when the low softening point hydrocarbon polymer hydrogenated product obtained according to the present invention is used as a tackifier for hot-melt pressure-sensitive adhesives, the resulting adhesive composition has excellent adhesiveness compared to the comparative example. It can be seen that the balance of adhesive performance, which had been a problem until now, has been greatly improved.

Examples 13-14. Comparative Examples 13-14 SIS block copolymer (rTR-11 manufactured by Shell Chemical Co., Ltd.
07J) 100 parts by weight, 80 parts by weight of the resin obtained in Reference Example 3 as a tackifier, 3 parts by weight of stabilizer (Irganox 10IOJ manufactured by Geigy), Example 1, Example 4, Comparative as a softener. 30 parts by weight of the resins obtained in Example 2 and Comparative Example 6 were blended, an adhesive was prepared in the same manner as in Example 7, and the performance of the adhesive was evaluated.

Comparative Example 15 Instead of using the polymer of the present invention, softener A (Shell Chemical Co., Ltd. "Shell Flex 22RJ") was used, and Example 13
An adhesive was prepared in the same manner as above, and the adhesive performance was evaluated.

Comparative Example 16 Instead of using the resin of the present invention, a softener B″ (Shell Chemical Co., Ltd. “Shell Flex 371NJ” was used, and Example 1
An adhesive was prepared in the same manner as in Example 3, and the performance of the adhesive was evaluated.

Example 15, Comparative Example 17 SEBS block copolymer (Shell Chemical WJ rGX
-1657J) 100 parts by weight, tackifier
120 parts by weight of the resin obtained in Reference Example 3, stabilizer (
Resin 3 obtained in Example 1 and Comparative Example 5 was added as a softening agent to 3 parts by weight of "Irganox 10IOJ" manufactured by Geigy.
0! A pressure-sensitive adhesive was prepared in the same manner as in Example 7,
Adhesive performance evaluation was performed.

Comparative Example 18 Instead of using the polymer of the present invention, softener A (Shell Chemical Department "Shell Flex 22RJ") was used, and Example 1
Adhesives were prepared in the same manner as in 3, and the results showed that all the adhesives obtained by using the polymer of the present invention showed excellent adhesive performance compared to the comparative example, and the low softening point of the present invention It can be seen that the hydrogenated hydrocarbon polymer exhibits excellent performance as a softener for hot-melt pressure-sensitive adhesives.

Examples 16-17, Comparative Examples 19-20 Natural rubber (R3S'l, Mooney viscosity liver, Ya. (100
℃) 76) 30 g, 24 g of the resin obtained in Reference Example 3 as a tackifier, and 9 g each of the polymers obtained in Example 1, Example 4, Comparative Examples 2 and 6 as a softener, #
and toluene 250. A solvent-type pressure-sensitive adhesive was prepared by mixing the following. Polyvarnish each of these adhesives.

Apply it on the chill film with an applicator and heat it at 80℃ for 2 hours.
The adhesive tape was prepared by drying for 0 minutes. The thickness of the adhesive in the adhesive tape was 20±5μ. Thereafter, the adhesive performance of these adhesive tapes was evaluated using the same test method as in Example 7.

Comparative Example 21 Instead of using the polymer of the present invention, an adhesive was prepared in the same manner as in Example 16 using softener A (Sansen Oil 450J, manufactured by Sun Oil Co., Ltd.), and the adhesive performance was evaluated. .

Comparative Example 22 Instead of using the polymer of the present invention, a PSA was prepared in the same manner as in Example 16 using softener B (Shell Flex 371NJ manufactured by Shell Chemical Co., Ltd.), and the performance of the PSA was evaluated.

The results of Examples 16-17 and Comparative Examples 19-22 are shown in Table 9.

As a result, all the adhesives obtained by using the polymer of the present invention as a softener showed excellent adhesive performance compared to the comparative examples, and the low softening point hydrocarbon polymer hydrogenated product of the present invention It can be seen that it also exhibits excellent performance as a softener for solvent-based pressure-sensitive adhesives.

Claims (2)

[Claims] (1) A hydrogenated product of a copolymer consisting essentially of an unsaturated hydrocarbon (A) and 9,10-dihydrodicyclopentadiene or a derivative thereof (B), with a structural unit derived from (A) The proportion is in the range of about 20 to 98 mol%, the proportion of structural units derived from (B) is in the range of about 80 to 2 mol% [the total of both is 100 mol%], the softening point is 60°C or less, and the iodine value is 100. A hydrocarbon polymer that is: (2) A copolymer consisting essentially of an unsaturated hydrocarbon (A) and 9,10-dihydrodicyclopentadiene or a derivative thereof (B), wherein the proportion of structural units derived from (A) is about 20 to 98 mol%, the proportion of structural units derived from (B) is in the range of about 80 to 2 mol% [total of both is 100 mol%], and the softening point is 60°C or less and the iodine value is 100 or less. Additive for pressure-sensitive adhesives made of hydrogen polymer.