JPS61137829A - Substituted aromatic hydrocarbon hydrogenated at aromatic nucleus and additive for adhesive produced by use thereof - Google Patents

Abstract

NEW MATERIAL:The hydrogenated and substituted aromatic hydrocarbon obtained by the hydrogenation of an aromatic hydrocarbon wherein the nucleus H atom is substituted with a lower alkyl-substituted or unsubstituted tricyclo[5.2.1.0<2.6>]deca-3- or 4-yl group. EXAMPLE:Tricyclo[5.2.1.0<2.6>]dec-4-ylcylohexane. USE:Softener and tackifier for adhesive. PREPARATION:The objective compound can be produced by reacting 1mol of an aromatic hydrocarbon with 1.2-10mol of tricyclo[5.2.1.0<2.6>]dec-3-ene, if necessary in a reaction solvent such as pentane, ethyl chloride, etc., in the presence of a Friedel-Crafts catalyst such as AlCl3, TiCl4, etc., at 0-150 deg.C for 1-10hr.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to hydrogenated substituted aromatic hydrocarbons, a method for producing the same, and an additive for adhesives using the same. More specifically, hydrogenated substituted aromatic hydrocarbons obtained by further hydrogenating substituted aromatic hydrocarbons in which a tricyclodecyl group is substituted with a hydrogen atom, and a softener for adhesives using the same. Or it relates to an additive as a tackifier.

[Background of the invention]

The present inventor has discovered that tricyclo(5,2,1,0''6)
Derivation of aromatic hydrocarbons using 3-enes.

In the process of research on the body, the tricyclo(5,
2,1,0''') to provide novel hydrogenated substituted aromatic hydrocarbons by further hydrogenating the reaction product of deca-3-enes and aromatic hydrocarbons, and to provide the hydrogenated substituted aromatic hydrocarbons. We have discovered that aromatic hydrocarbons are extremely useful as additives for adhesives, ie, softeners or tackifiers, and have completed the present invention.

[Summary of the invention]

Therefore, the first aspect of the present invention provides aromatic hydrocarbons in which at least one nuclear hydrogen atom is lower alkyl-substituted or unsubstituted tricyclo(5,2,1,0''')dec-3-yl. It relates to hydrogenated aromatic hydrocarbons which are hydrogenated products substituted with a group ([) or a tricyclo(5,2,1,0'''6]deca,-4-yl group ('II).

(1) (II) However, R1: is a lower alkyl group located at the 1st and 7th to 10th positions, and n R1's are the same or different.

R2: lower alkyl group located at the 2nd to 6th positions, m
The R2's are the same or different.

n: 0 to 5 m2 0 to 5 The second aspect of the present invention is an additive for adhesives comprising a hydrogenated substituted aromatic hydrocarbon.

[Manufacturing raw materials] The aromatic hydrocarbons that are one of the manufacturing raw materials for the hydrogenated aromatic hydrocarbons according to the present invention usually have 6 to 14 carbon atoms, preferably 6 to 9 carbon atoms, and have carbon atoms in the side chain. It does not have an unsaturated group, such as benzene, naphthalene, anthracene, and various alkyl group substituted products of these, specifically toluene, 0-xylene, m-ethyltoluene, p-ethyltoluene, Lobethylbenzene, isobutylbenzene, 5ec-butylbenzene, L
-butylbenzene, various diethylbenzenes, 1=methylnaphthalene, 2-methylnaphthalene, 9-methylanthracene, and the like. Other aromatic hydrocarbons used in the present invention include biphenyl, terphenyl, indane, and the like.

Among these aromatic hydrocarbons, benzene and mono- or dialkyl-substituted benzenes are preferred, especially toluene, ethylbenzene and xylene.

Tricyclo(5
, 2,1,0"" J decar-3-ene is preferably unsubstituted, but it is also preferable that the 1-position, 7-10th position, or 2-6th position has at least one lower alkyl group, such as methyl. Substituted groups such as ethyl group, propyl group, isopropyl group, butyl group, etc. are used. Substitution positions of the lower alkyl group include, for example, monosubstitution at the 3- to 10-positions excluding the 6-position, the 5,7-position, the 5,8-position,
5.9-position, 5,10-position, 4.7-position, 4.8-position,
Examples include di-substituted compounds at the 4.9-position, 3.8-position, 3.9-position, ■, and 4-position.

(However, R', R2, n, m: the same as the above definitions.) Such tricyclo(5,2,1,0cadeca-3-ene) is can be obtained by selective hydrogenation of dicyclopentadines. When used in the present invention, this material is preferably pure, but contains about 60% by weight.
It can be used if it has the following purity,
In addition to this, cyclopentene, tricyclo(5,2,1,
Polymerizable components such as partially hydrogenated products of 0'''3decac-8-ene and cyclopentadiene oligomers (dimer or higher) and non-polymerizable components such as tricyclo(5,2,1,0'')decane or its derivatives. It may contain ingredients.

[Production of substituted aromatic hydrocarbons]

The reaction is carried out at a molar ratio of about 1 to 5 with respect to the aromatic hydrocarbons.
Using 0 times the amount, preferably about 1.2 to 10 times the amount of tricyclo(5,2,t,o''*deca-3-ene, pentane, hexane, heptane, dichloromethane,
The reaction is carried out using a Friedel-Krach type catalyst in the presence of a reaction solvent such as ethyl chloride or 1,2-dichloroethane.

As a Friedel-Krauch type catalyst, for example, AlCl
3, AlBr3, BF3.5nC14, SnBr4
, FeC1,, Be112% CdC]□, ZnCl2
, BCl3, B Br, , TiCl4, TiBr4
, zrCI4, Lewis acids such as alkyl aluminum dichlorides, complexes of BF3 with alcohols, phenols, ethers, ternary complexes of AlCl with aromatic hydrocarbons and hydrogen halides, among others. BF, AlCl, or complexes thereof are preferably used. The amount of these catalysts used varies depending on the type of catalyst, the type and purity of both reaction raw materials, reaction temperature, etc., but generally it is about 1 to 50 mol% of the aromatic hydrocarbons that are the reaction raw materials. used.

The reaction is generally carried out at a temperature of about -10 to 200°C, preferably about 0 to 200°C.
At a temperature of 150°C, under normal pressure or pressurized conditions, about 1 to 1
Runs for 0 hours. As for the order of operation, first, both the reaction raw materials and the reaction solvent used as necessary are maintained at a predetermined temperature and pressure, and a catalyst is added while stirring to start the reaction. After reacting for a specified time,
The remaining catalyst is removed according to a conventional method, and the unreacted components and reaction solvent are removed by distillation to obtain the desired novel substituted aromatic hydrocarbons. Note that tricyclo(5,2,1,0"")dec-3-ene, which is used as a raw material, hardly polymerizes by itself, so the target substituted aromatic hydrocarbons can be obtained with relatively high purity. be able to.

According to the example of the above-mentioned Japanese Patent Publication No. 47-11818,
Dihydrodicyclopentadiene (tricyclo(5,2,
1,0" (deca-3-ene) was polymerized in toluene using anhydrous aluminum chloride as a catalyst to obtain a pale yellow resin with a softening point of 75°C and a bromine number of 32, that is, a polymer of dihydrodicyclopentadiene. There is a statement to that effect.However,
As shown in the Reference Examples described below, the present inventors conducted a similar reaction and obtained a colorless liquid product instead of a solid resinous product, which was also used in the above-mentioned substituted aromatic hydrocarbons used in the present invention. It has also been confirmed that Tokuko Sho 47-1181
The reason why a resinous polymer was obtained in Example No. 8 is presumed to be due to reactive impurities in the raw materials.

[Production of hydrogenated aromatic hydrocarbons]

The hydrogenated substituted aromatic hydrocarbons that are the substances of the present invention can be produced by hydrogenating the benzene nucleus contained in the structure of the substituted aromatic hydrocarbons. 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 sulfide, platinum oxide, cobalt oxide, rhenium oxide, ruthenium oxide, sponge iron, iron oxide, etc. are used. In addition, various solvents can be used, including various aliphatic and alicyclic solvents such as pentane, hexane, heptane, isohbutane, octane, isooctane, cyclohexane, methylcyclohexane, and decalin.

Furthermore, if the substituted aromatic hydrocarbon has a low viscosity in liquid form at a predetermined reaction temperature, it can be directly hydrogenated without a solvent.

Hydrogenation is usually carried out in a batch or continuous manner over 20 minutes.
at a temperature of from 100 to 300°C, preferably from about 100 to 240°C, under reduced pressure to increased pressure, generally from atmospheric pressure to about 30°C.
0kg/cdG, preferably about 10-150kg/
d for about 10 minutes to about 24 hours under pressure conditions of G.
Preferably from about 10 minutes to about 24 hours, preferably about 1
This is done by treating with hydrogen gas for 0 minutes to about 7 hours.

After hydrogenation, the solvent, unhydrogenated substituted aromatic hydrocarbons, and hydrogenated substituted aromatic hydrocarbons can be separated by a conventional method such as distillation. However, when hydrogenated substituted aromatic hydrocarbons are used as additives for adhesives as described below, it is not necessary to separate the unhydrogenated substituted aromatic hydrocarbons, and the two may be used as a mixture. can. In this case, the total hydrogenation rate of the mixture is preferably 10% or more, particularly preferably 40% or more.

[Substance of the present invention]

Preferred novel hydrogenated substituted aromatic hydrocarbons obtained in this way include, for example, the following general formula C+V
) can be shown. However, tricyclo(5,2
, 1,0'°cadec3-yl group or tricyclo(5
,2,1,02,6]dec-4-yl group (all of which are substituted or unsubstituted with lower alkyl) is simply abbreviated as X.

t (In the formula, R is a lower alkyl group, S is an integer from 1 to 3, and when X is 2 or more, they are in the meta position with respect to each other, and t is 1
An integer between 1 and 2. ) The substances of the present invention including those represented by general formula (IV) are illustrated below.

X X For compounds with one benzene ring, a cyclohexadiene ring where the benzene ring is not completely hydrogenated,
Substantially no cyclohexene ring was produced.

[Use invention]

Novel hydrogenated substituted aromatic hydrocarbons A (hereinafter referred to as A) of the present invention
It is sometimes abbreviated as ) has excellent properties as an additive for hot-melt adhesives and pressure-sensitive adhesives, that is, as a tackifier and a softener. Note that the hydrogenated substituted aromatic hydrocarbons can be used alone or in a mixture of two or more kinds for this purpose.

Adhesive compositions generally include hot-melt adhesives that are made by blending a base resin such as ethylene/vinyl acetate copolymer with a tackifier and, if necessary, wax and other additives, as well as natural rubber, synthetic rubber, etc. There are pressure-sensitive adhesives that are made of a base resin mixed with a tackifier and, if necessary, a solvent and other additives. The former hot melt adhesive is generally used as an adhesive or coating agent in the fields of bookbinding, can manufacturing, woodworking, lamination, sheeting, coating processing, etc. Moreover, the latter pressure-sensitive adhesive is generally coated on a base material such as paper, cloth, or plastic film for use in adhesive tapes, labels, and the like. In each of these adhesive compositions, a tackifier is blended with the base resin. In the case of hot melt adhesives, in addition to compatibility with base resins such as ethylene/vinyl acetate copolymer and wax, adhesion, melt viscosity, and flexibility, heat stability and tip stability are also important. Good qualities such as gender and hue are required.

On the other hand, in the case of tackifiers for pressure-sensitive adhesives, they must have excellent compatibility with base resins such as natural rubber and synthetic rubber, have good solubility in solvents, and be chemically stable. It is required to have properties such as excellent weather resistance, good hue, and no strong odor.

When A according to the present invention is used as a tackifier or softener in a pressure-sensitive adhesive, examples of the base resin include natural rubber, styrene-butadiene copolymer rubber, polybutadiene, polyisopropylene, etc. polyisobutylene, butyl rubber, polychloroprene, ethylene/propylene copolymer rubber, ethylene/propylene/α
-Olefin copolymer rubber, ethylene/propylene/diene copolymer rubber, styrene/butadiene/styrene block copolymer, styrene/isoprene/styrene block copolymer, hydrogenated styrene/butadiene/styrene block copolymer (SEBS) ), rubber-like polymers such as hydrogenated styrene/isoprene/styrene block copolymers are used. Particularly preferred are styrene/butadiene/styrene block copolymers, styrene/isoprene/styrene block copolymers, and hydrogenated copolymers thereof.

In addition, when used as a tackifier or softener for hot melt adhesives, specific examples of the base resin include ethylene/vinyl acetate copolymer, polyethylene, polypropylene 1, ethylene/propylene copolymer, etc. °, ethylene/acrylic acid copolymer, ethylene/acrylic acid ester copolymer, polyester, polyamide, polyvinyl acetate, etc. are used. In the case of a hot melt adhesive composition, it is preferable to use an ethylene/vinyl acetate copolymer and an ethylene/acrylic acid ester copolymer as the base resin.

When A according to the present invention is used as a tackifier, the blending ratio with the base resin varies somewhat depending on the hot melt adhesive composition and the pressure sensitive adhesive composition. In the case of a hot melt adhesive composition, the blending ratio of the tackifier is usually 20 to 300 parts by weight, preferably 30 to 200 parts by weight, based on 100 parts by weight of the base resin. In some cases, it is usually 20 parts by weight per 100 parts by weight of the base resin.
It ranges from 30 to 200 parts by weight, preferably from 30 to 150 parts by weight. Similarly, when used as a softener, the blending ratio with the base resin is usually 2 to 30 parts by weight per 100 parts by weight of the base resin in the case of hot melt adhesive compositions, and the proportion of the base resin in the case of pressure sensitive adhesives. It is usually in the range of 10 to 200 parts by weight per 100 parts by weight. For any type of adhesive, when using A as a tackifier, other softeners listed below may be used, or when using as a softener, other tackifiers 1
For example, rosin and derivatives thereof, terpene resins, alicyclic resins, aliphatic resins, aromatic resins, aliphatic-aromatic copolymer resins, and the like may be used.

In addition to the tackifier or softener and the essential components of the base resin, the adhesive composition using A according to the present invention includes:
Various additives are blended as necessary. For example, in the case of a hot melt adhesive composition, softeners such as dioctyl phthalate and dibutyl phthalate, waxes such as petroleum-based paraffin wax with a melting point of about 40 to 65°C, polyolefin wax, microwax, and phenol-based Alternatively, antioxidants such as bisphenol-based organic compounds and metal soaps may be mentioned. In the case of pressure-sensitive adhesives, dioctyl phthalate, dibutyl phthalate, machine oil, process oil, softeners such as polybutene, fillers such as calcium carbonate, zinc white, titanium oxide, silica, amine-based adhesives, ketone-based adhesives, etc. amine type,
Examples include phenol-based anti-aging agents and stabilizers. The blending ratio of these additives is arbitrary and appropriate.

The method for preparing an adhesive composition using A according to the present invention differs depending on whether it is a hot melt adhesive composition or a pressure sensitive adhesive. The hot melt adhesive composition is prepared by stirring a mixture of the tackifier A, the base resin, and optionally the various additives described above while heating to prepare a uniform melt. This is then cooled and formed into granules, flakes, pellets, rods, etc. depending on the application. This hot melt adhesive composition is again used for melting or coating. For example, when used for bonding purposes, a rod-shaped compound is used to fill a welding gun in corner bonding of molded products. On the other hand, as a method for preparing a pressure-sensitive adhesive, a mixture consisting of A according to the present invention as a tackifier, the above-mentioned base resin, and optionally the above-mentioned various additives is kneaded on a roll, or a suitable It can be prepared by a conventional method such as dissolving in a suitable solvent.

When a hot melt adhesive composition is used as an adhesive or a coating agent in an adhesive composition using A according to the present invention, A according to the present invention has excellent compatibility with the base resin and has high heat resistance stability. , excellent in color and odor, a uniform hot melt adhesive composition can be obtained, and this hot melt composition has excellent heat resistance stability and color, and has little odor during preparation and use of the hot melt composition. There is an advantage. Furthermore, even if A of the present invention is used in a pressure-sensitive adhesive composition, the hydrocarbon resin of the tackifier has excellent weather resistance in addition to the above-mentioned characteristics, so that a uniform pressure-sensitive adhesive composition can be obtained. This pressure-sensitive adhesive composition has the advantage of being excellent in color and weather resistance, and having little odor.

The adhesive composition using the hydrogenated substituted aromatic hydrocarbon A of the present invention will be specifically explained later with reference to Examples. In addition,
In the examples, evaluation of A was performed by the following method.

(11 Softening point JIS K-5665 (2) Hue ASTM D 1544-58T Gardner number (G, No).

(3) Molecular weight Measured by field desorption ionization mass spectrometry.

(4) Refractive index Measured at 25°C using an Atsube refractometer.

(5) Viscosity: 25°C using Bismetron manufactured by Niura System Co., Ltd.
It was measured with

〔Example〕

Reference Example 1 The fraction obtained by naphtha decomposition was heated at 150"C for 3 hours to convert the cyclopentadiene contained therein into dicyclopentadiene, producing pentane and pentenes 20.1
%, benzene 0.5%, dicyclopencudiene 72.1
%, isoprene-cyclopentadiene codimer-4,8
%, crude dicyclopentadiene having a composition of 2.5% cyclopentadiene oligomer was obtained. In a metal autoclave, this crude dicyclopentadiene 100
i part (1710g) and palladium-based tablet hydrogenation catalyst (product of Toyo Sea, Sea, A.F. Co., Ltd. C3l)
-LA) 4 parts by weight were 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/cnl with stirring for 12 hours. The filtered catalyst was removed and distilled to give tricyclo(5,2,1,02,6]dec-3-ene(9,
90 parts by weight of a fraction (10-dihydrodicyclopentadiene) was obtained. Gas chromatography analysis results showed that pentanes were 19.9%, tricyclo(5,2,1,0"Edec-3-ene 70.9%, dicyclopentadiene 0.1%).
Below, isoprene-cyclopentadiene codimer hydrogenation reaction #4.5%, tricyclo(5,2,1,02″6)
The composition was 2.1% decane and 2.6% unknown components.

Reference example 2: Equipped with a thermometer, stirring material, cooler and dropping funnel, capacity i15
195 g (2.5 mol) of benzene and 2 g of powdered anhydrous aluminum chloride are added to a 00 ml four-day flask under a nitrogen atmosphere. A tricyclo(5,2,1,0'°6)dec-3-ene-containing fraction (purity 70-9%, obtained in Reference Example 1) was added from the dropping funnel while stirring. ) 94.5g (0.5 mol) was added,
Heat and stir at 70°C for 2 hours. The reaction was terminated by adding methanol, and the reaction solution was washed until it became neutral. Then, distillation was carried out at a top temperature of 150 to 155°C, a pressure of 5 mm, and 1 g.
12.5 g of an almost colorless distillate was obtained. Molecular weight 212 (
From the infrared spectrum (shown in Figure 1), tricyclo[5,2. t, o”t deca-4
- It turned out to be ylbenzene. The refractive index Pf) was 1.5558.

Reference example 3 Capacity 11 equipped with thermometer, stirring material, cooler and dropping funnel
400 g (4.35 mol) of toluene and 5 g of powdered anhydrous aluminum chloride are added to a four-day flask under a nitrogen atmosphere. While stirring, add tricyclo(5 ml) from the dropping funnel.
, 2,1,0'cadec-3-ene-containing fraction (purity 70.
9%) 126.9 g (0.67 mol) was added dropwise to 70
The reaction was carried out at ℃ for 5 hours. The reaction was terminated by adding methanol, and the mixture was washed with water. The reaction solution was distilled to a boiling point of 158-162
90 g of a colorless distillate was obtained at 15 wm. Molecule Jl
226 (theoretical value 226 as the formula It turned out to be.

The refractive index ('sho) was 1.5582.

Reference Example 4 461 g of ethylbenzene (4,3
5 mol) and 5 g of powdered anhydrous aluminum are added under a nitrogen atmosphere. While stirring, add tricyclo(
5,2,1,0) deca-3-ene-containing fraction (purity 70.
9%) 126.6g (0.67 mol) was added, and 60
Heat the reaction at ℃ for 2 hours. The reaction was terminated by adding methanol, and the reaction solution was washed until it became neutral.

It was then distilled to obtain 115 g of a fraction with a boiling point of 170-174°C/5 ml/g. The molecular weight is 240 (theoretical value 240 as the following formula), and the infrared spectrum shows that it is mainly a mixture of 2-, 3-, and 4-tricyclo(5,2,1,0)dec-4-yl-ethylbenzene. Ta.

Reference Example 5 Mixed xylene (m-xylene 45%,
51'% ethylbenzene, 4% 0- and p-xylene
) 3 g of powdered anhydrous aluminum chloride are added to 79.5 g (0.75 mol) under a nitrogen atmosphere. Tricyclo(5,2,1,0'°cadecar-3-ene-containing fraction (purity 70.9%) 283.5
g (1.5 mol) was added thereto, and the mixture was heated and stirred at 60° C. for 2 hours.

The reaction was terminated by adding methanol, and the reaction solution was washed until it became neutral. Next, the pot temperature was 150°C and the pressure was 2Qmmt.
Remove unreacted substances with 1 g, Gardner hue: 10.25°C
Viscosity 10,800 cp, refractive index (7L#) 1.548
49 g of viscous liquid of No. 2 was obtained. As a result of the analysis, tricyclo(
5,2,1,0”]]Deca-3-nin: 1 of mixed xylem
It was found that the composition consisted of 59% by weight of /1 adduct, 33% by weight of 2/1 adduct, and 8% by weight of others.

Reference Example 6 Mixed xylene (m-xylene 45%,
ethylbenzene 51%, 0- and hypo-xylene 4%)
3 g of powdered anhydrous aluminum chloride are added to 63.6 g (0.60 mol) under a nitrogen atmosphere. While stirring, add tricyclo(5,2,1,0'') from the lower funnel.
Dec-3-ene-containing fraction (purity 70.9%) 283
．． 5 g (1.5 mol) was added, and the mixture was heated and stirred at 90°C for 2 hours.

The reaction was terminated by adding methanol, and the reaction solution was washed until it became neutral. Next, the pot temperature was 150°C and the pressure was 20+u+.
Unreacted substances were removed with Hg, and the Gardner hue was 11.25°C.
73 g of a viscous liquid with a viscosity of 40,300 cp was obtained. As a result of the analysis, tricyclo[5,2. It was found to consist of 37% by weight of a 1/1 adduct of x, o"'r deca-3-ene: mixed xylenes.

Reference Example 7 Mixed xylene (m-xylene 45%,
ethylbenzene 51%, 0- and p-xylene 4%)
3 g of powdered anhydrous aluminum chloride are added to 45.4 g (0.43 mol) under a nitrogen atmosphere. Tricyclo(5,2,1,0''')dec-3-ene-containing fraction (purity 70.9%) 283.
5 g (1.5 mol) was added, and the mixture was heated and stirred at 90°C for 2 hours.

The reaction was terminated by adding methanol, and the reaction solution was washed until it became neutral. Next, the pot temperature was 150”C1 and the pressure was 20mi.
Unreacted substances were removed with aHg and the Gardner hue was 12.5.
75 g of a viscous liquid with a viscosity of 57,800 cp at 25° C. was obtained.

As a result of analysis, tricyclo + 5, z, t, o'' + dekar 3
-Ene: It was found to consist of 33% by weight of a 1/1 adduct of mixed xylenes.

Example 1 Tricyclo(5,2,1,0'°6) obtained in Reference Example 2
] Dec-4-ylbenzene 34 g 1 Mitsui hexane (Mitsui Petrochemical) 118 g and a sulfur-resistant nickel catalyst (Nikki Chemical rN-113BJ) as a hydrogenation catalyst
Put 2.5g into a 500ml steel autoclave,
Reaction temperature 200°C1 reaction pressure 40kg/cfflG
, hydrogenation was carried out for a reaction time of 5 hours. After cooling, depressurizing, and purging with nitrogen, the catalyst is filtered off, the filtrate is distilled, and the top temperature is 144-
33 g of colorless distillate was obtained at 150° C. and pressure cuff mHg.

From the molecular weight 218 (theoretical value 218 as the following formula) and the infrared spectrum (shown in Figure 2), tricyclo(5,2
,1,0'"]] was found to be deca-4-ylcyclohexane.

The refractive index (H Company) was 15,110.

Example 2 80 g of the mixture of 2-, 3- and 4-tricyclo(5,2,1,02'6)dec-4-yltoluene obtained in Reference Example 3 was treated in the same manner as in Example 1 to obtain the results shown in Table 1. The hydrogenation reaction was carried out under the conditions shown below. After the hydrogenation, the catalyst was filtered off, and the filtrate was distilled at a top temperature of 154-158° C. and a pressure cuff of mHg to obtain 78 g of a colorless distillate. 2-, 3- and 4 from the molecular weight 232 (theoretical value 232 as the following formula) etc.
-tricyclo(5,2,1,0'°)dec-4-ylmethylcyclohexane.

The refractive index (nine function was 1.5080).

Example 3 A mixture of 2-, 3- and 4-tricyclo(5,2,1,02,6]dec-4-yl-ethylbenzene obtained in Reference Example 4 was treated as in Example 1 under the conditions listed in Table 1. A hydrogenation reaction was carried out in the same manner. After hydrogenation, the catalyst was filtered off, and the filtrate was collected at a tower top temperature of 163-168°C and a pressure cuff of 1n 1.
1 g was distilled to obtain 98 g of a colorless distillate. Molecular weight 24
6 (theoretical value 246 as the following formula) etc., 2- and 3
- and 4-tricyclo(5,2,1,0'cadecar4
It was found that the mixture consisted mainly of -yl-ethylcyclohexane.

Example 4 Tricyclo(5,2,1,0''3) obtained in Reference Example 5
Dec-3-ene: A mixture consisting of 59% by weight of a 1/1 adduct of mixed xylene, 33% by weight of a 2/1 adduct of mixed xylene, and 8% by weight of the same was prepared in the same manner as in Example 1 under the conditions listed in Table 1. A hydrogenation reaction was carried out by operation. After hydrogenation, the catalyst was separated by filtration, and the solvent was removed from the filtrate in a pot temperature of 150°C and a pressure of 2Q mml 1g.
39 g of a viscous liquid of 028 was obtained.

As a result of analysis, tricyclo(5,2,1,02,6]dec-3-ene: 1/1 addition hydrogenated product of mixed xylene 59% by weight
, 33% by weight of the 2/1 adduct and 8% by weight of its compound.

Examples 5 to 6 The reaction was carried out in the same manner as in Example 4 under the conditions shown in Table 1, and the yield and physical properties of the reactants obtained by removing unreacted substances are shown in Table 21.

Example 7 SUBS block copolymer (Shell Chemical 11 rG-
1657J) 100f! Quantity parts, commercially available hydrogenated petroleum resin (
57 parts by weight of “Alcon P-70J” manufactured by Arayo Kagakusha,
Stabilizer (Geigy “Irganox 10IOJ”)
To 1 part by weight, 129 parts by weight of the novel hydrogenated substituted aromatic hydrocarbon of the present invention obtained in Examples 1 to 6 was blended as a tackifier, and kneaded at 150°C for 30 minutes in a niegu to prepare an adhesive.

This adhesive is applied to a polyester film (
25μyi> for 20 minutes) and applied to a thickness of 30±5μ using an applicator to prepare an adhesive tape.

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

(1) Compatibility of Compounds A hot-melted adhesive was applied to a glass plate to a thickness of 2 to 31 m, and the transparency of the adhesive was evaluated. O: Good compatibility (transparent), Δ: Slightly poor compatibility (semi-transparent), ×: Poor compatibility (opaque) (2) Tack (Ball N11): J, Do
-Measured at 20°C by method.

(3) Adhesive strength (g/25mm): JIS Z-
1524 at 20°C.

(4) Cohesive force (Tsuru/2 HR): JIS Z-
1524 at 20°C.

Table 3 shows the results obtained by the above test method.

Comparative Example 1 The same procedure as in Example 7 was carried out except that commercially available liquid resin A ("Wingtac 10" manufactured by Gutdeyer Co., Ltd.) was used instead of using the novel hydrogenated substituted aromatic hydrocarbons of the present invention.

Comparative Example 2 Instead of using the novel hydrogenated substituted aromatic hydrocarbons of the present invention, commercially available liquid resin D (Idemitsu Petrochemical type “Polybutene 1
The same procedure as in Example 7 was carried out except that 0+1-T J ) was used.

Comparative Example 3 The same procedure as in Example 7 was carried out except that commercially available liquid resin E (Kuraprene LIR-50J manufactured by Clareisoprene Chemical Co., Ltd.) was used instead of the novel hydrogenated substituted aromatic hydrocarbon of the present invention. Ta.

As a result, when the novel hydrogenated substituted aromatic hydrocarbons obtained according to the present invention are used as a softener for hot-melt pressure-sensitive adhesives, the resulting adhesive composition exhibits superior adhesive performance compared to comparative examples. I understand what is shown.

[Brief explanation of drawings]

Figure 1 shows the infrared absorption spectrum of the reaction product obtained in Reference Example 2, and Figure 2 shows the infrared absorption spectrum of the reaction product obtained in Example 1, with the horizontal axis representing the wave number. be. Applicant Mitsui Petrochemical Industries Co., Ltd. Agent Kazudai Yamaguchi Figure 1 Figure 2

Claims (2)

[Claims] (1) At least one nuclear hydrogen atom of aromatic hydrocarbons is lower alkyl substituted or unsubstituted tricyclo[5,
Hydrogenation of those substituted by 2,1,0^2^,^6]dec-3-yl group or tricyclo[5,2,1,0^2^,^6]dec-4-yl group hydrogenated aromatic hydrocarbons. (2) At least one nuclear hydrogen atom of aromatic hydrocarbons is lower alkyl substituted or unsubstituted tricyclo
Hydrogenation of those substituted by 2,1,0^2^,^6]dec-3-yl group or tricyclo[5,2,1,0^2^,^6]dec-4-yl group An additive for adhesives consisting of hydrogenated aromatic hydrocarbons.