JPS61122233A - Novel susbtituted aromatic hydrocarbon, production thereof, and additive for adhesive produced by using same - Google Patents

Abstract

NEW MATERIAL:The novel substituted aromatic hydrocarbon wherein at least one of the nucleus hydrogen atom of the aromatic hydrocarbon is substituted with tricyclo[5,2,1,0<2.6>]dec-3-yl group or tricyclo[5,2,1,0<2.6>]dec-4-yl group which may be substituted with lower alkyl. EXAMPLE:Tricyclo[5,2,1,0<2.6>]dec-4-ylbenzene. USE:Additive useful as a softener or tackifier for adhesives. PREPARATION:A novel substituted aromatic hydrocarbon can be prepared by reacting an aromatic hydrocarbon and a lower alkyl-substituted or unsubstituted tricyclo[5,2,1,0<2.6>]dec-3-ene in the presence of a Friedel-Crafts catalyst.

Description

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

[Background of the invention]

The present inventor has discovered that tricyclo[s, z, t, o''*deca, 3
In the course of research on derivatives of aromatic hydrocarbons using -enes, the tricyclo[5.2,1,0''
that deca-3-enes react with aromatic hydrocarbons to give novel substituted aromatic hydrocarbons, and that the novel substituted aromatic hydrocarbons are useful as additives for adhesives; It has been discovered that hydrocarbons are extremely useful as additives for adhesives, ie, softeners or tackifiers, leading to the completion of the present invention.

[Summary of the invention]

Therefore, the first aspect of the present invention is that at least one nuclear hydrogen atom of an aromatic hydrocarbon is a lower alkyl-substituted or unsubstituted tricyclo[5.2,1,0""J decar-3-yl group (
1) or tricyclo[5.2,1,0”1deca-4-
The present invention relates to novel substituted aromatic hydrocarbons substituted by an yl group (n).

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

R: A lower alkyl group located at the 2nd to 6th positions, and n R2's are the same or different.

n: 0-5 m: 0-5 The second aspect of the present invention relates to a method for producing such novel substituted aromatic hydrocarbons, and the novel substituted aromatic hydrocarbons are composed of aromatic hydrocarbons and the following general formula Lower alkyl substituted or unsubstituted tricyclo[5.2,1
,0'' is prepared by reacting deca-3-ene in the presence of a Friedel-Crafts type catalyst.

(However, R1, RL, R, n, m are the same as defined above.) The third aspect of the present invention is an additive for adhesives comprising such novel substituted aromatic hydrocarbons.

〔Production method〕

Examples of aromatic hydrocarbons that are raw materials for producing one of the novel substituted aromatic hydrocarbons according to the present invention include benzene,
Naphthalene, anthracene, and various alkyl group substituted products of these, specifically toluene, O-xylene, m-xylene, paraxylene, ethylbenzene, n
-Propylbenzene, isopropylbenzene, 0-ethyltoluene, m-ethyltoluene, p-ethyltoluene, n-butylbenzene, isobutylbenzene, 5eC-
Examples include butylbenzene, t-butylbenzene, various diethylbenzenes, 1-methylnaphthalene, 2-methylnaphthalene, and 9-methylanthracene.

Other aromatic hydrocarbons include biphenyl, terphenyl, and indanna (!'). Among these aromatic hydrocarbons, benzene and mono- or dialkyl-substituted benzenes, particularly toluene, ethylbenzene, and xylene are preferred.

Tricyclo[5
．． As 2,1,0-cadec-3-ene, unsubstituted one is preferable, but in addition to that, 2,1,0-cadec-3-ene is
- 6th position is substituted with a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc. The substitution position of the lower alkyl group is as follows: For example, mono-substituted products at the 3- to 10-positions excluding the 6-position, the 5.7-position, the 5,8-position,
position, 5.9-position, 5.10-position, 4,7-position, 4.8-position
Examples include di-substituted compounds at the 4, 9-, 3.8-, 3.9-, and 1.4-positions.

Such tricyclo[5.2,1ryu')dec-3-ene can be obtained by selectively hydrogenating dicyclopentadiene, as described in, for example, Japanese Patent Publication No. 11818/1983. . When used in the present invention, this material is preferably pure, but approximately 60% by weight
It can be used as long as it has a purity higher than that; other than this, cyclopentene, tricyclo[5.2,1,0
″] Dec-8-ene, cyclopentadiene oligomer (
It may contain a polymerizable component such as a partially hydrogenated product (dimer or more) and a non-polymerizable component such as tricyclo[5.2,1,6]decane or a derivative thereof.

The reaction is in molar ratio to aromatic hydrocarbons.

about 1 to 50 times the amount, preferably about 1.2 to 10 times the amount of tricyclo rs, 2. It is carried out using a Friedel-Crafts type catalyst using x,o7lidecar-3-ene, optionally in the coexistence of a reaction solvent such as pentane, hexane, heptane, dichloromethane, ethyl chloride, 1,2-dichloroethane, etc. .

As a Friedel-Crafts type catalyst, for example, AlC
l1, AlBr1, BFI, 5nC14, Sn
Br4 1, FeC13, BeCl2,
CdCl2-, ZnC1z, BCl3, BBrv,
TiCl4, TiBr4, ZrCl4, Lewis acids such as alkyl aluminum dichlorides, complexes of BP with alcohols, phenols, ethers, AlCl,
Complexes of Lewis acids such as ternary complexes with aromatic hydrocarbons and hydrogen halides are used, among which BF3, AlC
l, 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 O to 200°C.
At a temperature of 150°C and under normal or pressurized conditions, approximately 1 to
It will be held for 10 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 predetermined period of time, the remaining catalyst is removed according to a conventional method, and unreacted components and reaction solvent are removed by distillation to obtain the desired novel substituted aromatic hydrocarbons. In addition, since tricyclo[5.2,1,0"1dec-3-ene used as a raw material hardly polymerizes alone, it is difficult to obtain the target substituted aromatic hydrocarbons with relatively high purity. I can do it.

According to the example of the above-mentioned Japanese Patent Publication No. 47-11818,
Dihydrodicyclopentadiene (tricyclo[5.2,
1,0"1dec-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 Example 2 of the present invention described below, the present inventors conducted a similar reaction and obtained a colorless liquid product instead of a resin-like product, and also confirmed that this was the compound of the present invention. are doing. The reason why a resinous polymer was obtained in the example of Japanese Patent Publication No. 47-11818 is presumed to be due to reactive impurities in the raw materials.

[Substance of the present invention]

Examples of the novel substituted aromatic hydrocarbons obtained in this way include the following. However, tricyclo[5.2,1,0''3dec-3-yl group or tricyclo[5.2,1,02''dec-4-yl group is simply abbreviated as X.

The novel substituted aromatic hydrocarbons A (hereinafter sometimes abbreviated as A) of the present invention can be used as additives for hot melt adhesives and pressure sensitive adhesives, that is, as tackifiers and softeners. Has excellent properties.

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 particular, in the case of hot melt adhesives, in addition to compatibility with base resins such as ethylene/vinyl acetate copolymer and wax, adhesion, melt viscosity, and flexibility, heat stability, tip stability, Good things such as 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, specific examples of the base resin include natural rubber, styrene-butadiene copolymer rubber, polybutadiene, polyisoprene, Polyisobutylene, butyl rubber, polychloroprene, ethylene/propylene copolymer rubber, ethylene/propylene/α-olefin copolymer rubber, ethylene/propylene/diene copolymer rubber, styrene/butadiene/styrene block copolymer, styrene/isoprene/styrene Rubber-like polymers such as block copolymers, hydrogenated styrene-butadiene-styrene block copolymers (SEBS), and 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, and ethylene/propylene copolymer. , ethylene/acrylic acid copolymer, ethylene/acrylic ester copolymer, polyester, polyamide,
Polyvinyl acetate etc. are used. In the case of hot melt adhesive compositions, it is particularly preferred to use ethylene/vinyl acetate copolymers and ethylene/acrylic acid varnishes (chill copolymers) as base resins.

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 a hot melt adhesive composition, and 100N of the base resin in the case of a pressure sensitive adhesive. It is usually in the range of 10 to 100 parts by weight. For any type of adhesive, when A is used as a tackifier, other softeners listed below may be used, or when used as a softener, other tackifiers such as rosin and its derivatives may be used. , terpene resin, alicyclic resin,
Aliphatic resins, aromatic resins, aliphatic-aromatic copolymer resins, etc. may also 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, amines, ketone-amines, etc. system,
Examples include phenol-based anti-aging agents and stabilizers. The blending ratio of these additives is arbitrary and appropriate.

The method for producing 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. A method for producing a hot melt adhesive composition is to prepare a homogeneous molten liquid by stirring a mixture consisting of the tackifier A, the base resin and, if necessary, the various additives described above while heating. 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 conventional methods such as dissolving in a suitable solvent.

When a hot melt adhesive composition is used as an adhesive or 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 is heat resistant and stable. This hot melt adhesive composition has excellent heat stability, color and odor, so a uniform hot melt adhesive composition can be obtained.
Moreover, there is an advantage that there is little odor during the preparation and use of the hot melt composition. 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.

Adhesive compositions using the novel substituted aromatic hydrocarbons 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.

(1) Softening point JIS K-5665 (2) Hue A
STM 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 refractor needle.

(5) Viscosity Measured at 25°C using Vismetron manufactured by Shibaura Systems.

〔Example〕

Reference Example 1 The CS fraction obtained by naphtha decomposition was heated at 150"C for 3 hours, and the cyclopentadiene contained therein was converted to dicyclopentadiene, resulting in 20.1% and 0.5% benzene.
, crude dicyclopentadiene having a composition of 72.1% dicyclopentadiene, 4.8% isoprene-cyclopentadiene codimer, and 2.5% cyclopentadiene oligomer was obtained. 100 parts by weight (1710 g) of this crude dicyclopentadiene and 4 parts by weight of a palladium-based tablet hydrogenation catalyst (C3l-IA manufactured by Toyo C.C.I.) were placed in a metal autoclave, and the reaction temperature was 50°C. Under the condition of pressure 10 kg/cA, 12
The hydrogenation reaction was carried out while stirring for hours. The catalyst was removed by filtration, and the mixture was distilled to obtain 90 parts by weight of tricyclo[5,2,1,0'')dec-3-ene (9,10-dihydrodicyclopentadiene) fraction. Gas chromatography analysis results showed 19.9% pentanes, 5.2% tricyclo
, 1,0"]] Decal-3-ene 70.9% Dicyclopentadiene 0.1% or less, Isoprene-cyclopentadiene codimer hydrogenation reaction product 4.5%, Tricyclo[5.2
, 1,6] decane 2.1% and unknown component 2.6%.

〔Example〕

Example 1 Capacity 50 with temperature needle, stirring material, cooler and dropping funnel
195 g (2.5 mol) of benzene and 2 g of powdered anhydrous aluminum chloride are added to a 0 ml four-hole flask under a nitrogen atmosphere. While stirring, add tricyclo from the dropping funnel.
5.2,1”) Deca-3-ene-containing fraction (purity 70.9
% Obtained in Reference Example 1. The same applies to later examples.

) 94.5 g (0.5 mol) was added, and the mixture was heated and stirred at 70° C. for 2 hours. Terminate the reaction by adding methanol,
The reaction solution was washed until it became neutral. Then, the mixture was distilled to obtain 12.5 g of an almost colorless distillate at a top temperature of 150 to 155° C. and a pressure of 5+nHg. The molecular weight was 212 (theoretical value 212 as the formula below), and the infrared spectrum (shown in Figure 1) revealed that it was tricyclo[5.2,1,0''l dec-4-ylbenzene.Refractive index ( N is 1.555
It was 8.

Example 2 Capacity 11 with thermometer, stirring material, condenser and dropping funnel
400 g (4.35 mol) of toluene and 5 g of powdered anhydrous aluminum oxide are added to a four-hole flask under a nitrogen atmosphere. Add tricyclo[5] from the dropping funnel while stirring.
．． 2,1,0'''cadec-3-ene-containing fraction (purity 70
．． 9%) 126.9 g (0.67 mol) was added dropwise.7
The reaction was carried out at 0°C for 5 hours. The reaction was terminated by adding methanol, and the mixture was washed with water. The reaction solution was distilled and boiled to 158-16
90 g of colorless distillate was obtained at 2° C./5 miHg. Molecular weight 226 (theoretical value 226 as the following formula), 2-, 3- and 4-tricyclo[5
．． It turned out to be a mixture of 2,1,0'° deca-4-yltoluene. Refractive index <N'J,,C> is 1.5
It was 582.

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

2-, 3- and 4- from the infrared spectrum
It was found that the main component was a mixture of dolicycloC5,2°1.0"1dec-4-yl-ethylbenzene.

Example 4 Mixed xylene (m-xylene 45%,
51% ethylbenzene, 0- and p-xylene,
4%) 79.5 g (0.75 mol) are added with 3 g of powdered anhydrous aluminum chloride under a nitrogen atmosphere. Tricyclo from the dropping funnel while stirring [5.2,
1,0'''J deca-3-ene-containing fraction (purity 70.9%
) 283.5 g (1.5 mol) was added, and 283.5 g (1.5 mol) was added, and the
Heat and stir for an hour.

The reaction was terminated by adding methanol, and the reaction solution was washed until it became neutral. Next, the pot temperature was 150℃ and the pressure was 20snH.
Unreacted substances were removed at 10.g to obtain 49 g of a viscous liquid having a Gardner hue of 10.25° C., a viscosity of 10.800 cp, and a refractive index of <N:> 1.5482. As a result of the analysis, tricyclo(s,
z, t, o” + deca-3-ene: 171 of mixed xylene
It was found that the composition consisted of 59% by weight of adducts, 33% by weight of 2/1 adducts, and 8% by weight of others.

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 1.

Table 1 Example 7 1e capacity 4 with cooler, stirrer, temperature needle and gas inlet pipe
400 g (4.35 mol) of toluene and 1 g (0.1 mol) of anhydrous aluminum chloride are placed in a flask, and then hydrogen chloride gas is blown into the flask while stirring. When the anhydrous aluminum chloride was completely dissolved to become a uniform red liquid (a ternary complex of aluminum chloride-hydrogen chloride-toluene was formed), the supply of hydrogen chloride gas was stopped. Next, while maintaining the temperature at 20°C, 126.9 g (0.67 mol) of tricyclo[5.2,1,0''1-dec-3-ene-containing fraction (purity 70.9%)
was added dropwise and reacted at 20°C for 2 hours, then at 70°C for 2 hours, and then at 70°C for 2 hours.

After pouring the reaction solution into ice water, the oil layer was washed with water until it became neutral. The reaction solution was distilled to a boiling point of 158-162"C/5
121 g of a fraction of u+l1 g was obtained. This is Example 2
(infrared absorption spectrum).

Example 8 To the same apparatus as in Example 2, 400 g (4.35 mol) of toluene and 5 g of boron trifluoride diethyl ether complex are added in a nitrogen atmosphere. While stirring, add tricycloC5,2,1,
02° Cadec-3-ene-containing fraction (purity 70.9%) 1
26.9 g (0.67 mol) was added dropwise, and the reaction was carried out at 20°C for 2 hours, and further at 70°C for 3 hours. 10%
The catalyst was decomposed with an aqueous solution of caustic soda and washed with water until it became neutral. The reaction solution was distilled to a boiling point of 158-162°C and 15°Hg.
70g of fraction was obtained. This was consistent with the product of Example 2 (infrared absorption spectrum).

Examples 9 to 14 SIS block copolymer (Shell Chemical Department rTR-11
07J) 100 parts by weight, softener (Shell Chemical Department [
Shelfflex 22RJ') 30 parts by weight, stabilizer (Geigy "Irganox 10IOJ") '3
30 parts by weight of the resins obtained in Examples 1 to 6 were added to 70 parts by weight of a commercially available aliphatic petroleum resin (Hiretsu T-300XJ manufactured by Mitsui Petrochemical Industries) using a tackifier.
The mixture was blended as follows and kneaded in a niegu at 150°C for 30 minutes to prepare an adhesive. Melt this adhesive on a polyester film (25μ thick) on a 195°C heating plate for 2 hours.
0 minutes) using an applicator to a thickness of 30±5μ to prepare an adhesive tape.

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

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

Evaluation 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.

No surface damage was observed on the corrugated paper. stomach.

(2) Tuck (ball position): J, Do%1
It was measured at 20°C by the method.

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

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

(5) Corrugated cardboard holding power (HR): Corrugated paper (JIS K-7) was used as the adherend, a load of 1 kg was suspended at the end, and the time until the load slipped off was measured at 20°C.

Table 2 shows the results obtained by the above test method.

Comparative Example 1 The same procedure as in Example 9 was carried out, except that commercially available liquid resin A ("Wingtack 1O" manufactured by Gutdeyer Co., Ltd.) was used instead of the novel substituted aromatic hydrocarbons of the present invention.

Comparative Example 2 Instead of using the novel substituted aromatic hydrocarbons of the present invention, commercially available liquid resin A (YS Resin P
The procedure was the same as in Example 9 except that 200J) was used.

Comparative Example 3 The same procedure as in Example 9 was carried out except that commercially available liquid resin B ("Guimaron" manufactured by Yaskawa Oil Co., Ltd.) was used instead of the novel substituted aromatic hydrocarbons of the present invention.

As a result, when the novel substituted aromatic hydrocarbons obtained according to the present invention are used as a tackifier for hot-melt pressure-sensitive adhesives, the resulting adhesive composition exhibits superior adhesive performance compared to comparative examples. It can be seen that the balance of adhesive performance (cardboard adhesion, cardboard holding power), which had been a problem until now, has been greatly improved.

Examples 15-20 SRBS block copolymer (Shell Chemical Department rGX-1
657J) 100 parts by weight, commercially available hydrogenated petroleum resin (Arayo Kagaku Co., Ltd. [Alcon P-70J]) 57 parts by weight, stabilizer (Geigy Co., Ltd. "Irganox 1o10j")
129ffi of the resin obtained in Examples 1 to 6 to 1 part by weight
Add ffi part as a tackifier and heat at 150°C.
An adhesive was prepared by kneading the mixture for 30 minutes using a niegu.

The adhesive tape preparation method and adhesive performance evaluation were performed in the same manner as in Example 9. These results are shown in Table 3.

The compatibility of the compounds was evaluated by coating a glass plate with a hot-melted adhesive at a thickness of 2 to 3 thick and evaluating the transparency of the adhesive. ○: Good compatibility (retired), △: Slightly poor compatibility (semi-transparent), ×: Poor compatibility (opaque) Comparative Example 4 Instead of using the novel substituted aromatic hydrocarbons of the present invention, a commercially available liquid resin was used. The same procedure as in Example 15 was carried out except that A (Wing Tack 10J manufactured by Gutdeyer) was used.

Comparative Example 5 Instead of using the novel substituted aromatic hydrocarbons of the present invention, commercially available liquid resin D (Idemitsu petrochemical group [polybutene 108
-TJ) was carried out in the same manner as in Example 15, except that TJ) was used.

Comparative Example 6 The same procedure as in Example 15 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 substituted aromatic hydrocarbons of the present invention.

[Brief explanation of the drawing]

FIG. 1 shows a liquid chromatogram of the reaction product obtained in Example I, with the horizontal axis representing the count number. FIG. 2 shows an infrared absorption spectrum of the reaction product obtained in Example 1, with the horizontal axis representing wave numbers. Applicant Mitsui Petrochemical Industries Co., Ltd. Agent Kazudai Yamaguchi 1 Figure Count Black

Claims (3)

[Claims] (1) At least one nuclear hydrogen atom of the aromatic hydrocarbon is lower alkyl substituted or unsubstituted tricyclo [5.
Novel substituted aromatics substituted by 2.1.0^2^,^6]dec-3-yl group or tricyclo[5.2.1.0^2^,^6]dec-4-yl group Group hydrocarbons. (2) Reacting aromatic hydrocarbons and lower alkyl substituted or unsubstituted tricyclo[5.2.1.0^2^,^6]dec-3-ene in the presence of a Friedel-Crafts type catalyst At least one nuclear hydrogen atom of the aromatic hydrocarbons is a lower alkyl substituted or unsubstituted tricyclo[5.2.1.0^2^,^6]dec-3-yl group or Tricyclo [5.2.1.0^2^,^6] Deka-4
-Process for producing novel substituted aromatic hydrocarbons substituted with an yl group. (3) At least one nuclear hydrogen atom of the aromatic hydrocarbon is lower alkyl substituted or unsubstituted tricyclo [5.
Novel substituted aromatics substituted by 2.1.0^2^,^6]dec-3-yl group or tricyclo[5.2.1.0^2^,^6]dec-4-yl group Additive for adhesives consisting of group hydrocarbons.