Adhesive composition

The present invention relates to an adhesive composition comprising 100 parts by weight of a polyester-polyurethane having an isocyanate group (--NCO) and 0.002-20 parts by weight of a halogenating agent, suitably used for the adhesion of polyolefin materials which are difficult to glue, such as car molding and base materials for electrostatic flocked products, the adhesion of trimming, the adhesion of rubber products and others.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to adhesive compositions to be utilized for 
the adhesion of polyolefin materials which are used in automotive parts 
and which adhere with other materials with difficulty, the adhesion of 
materials for electrostatic flocked products, and the adhesion and coating 
of products made of rubber or synthetic resin. 
2. Description of the Related Art 
As the usual methods of adhesion of polyolefin materials such as 
polypropylene and others, which adhere with other materials with 
difficulty, there is a method of applying an adhesive subsequent to 
performing a surface treatment with primers such as chloroprene rubbers 
and others, and a method of applying an adhesive after treatment by corona 
discharge. 
Also, previously, a resin coating such as nylon, epoxy, acrylic, acrylic 
ethylene copolymers and others, or a rubber coating such as butadiene 
rubber (BR), chloroprene rubber (CR), and styrene-butadiene copolymer 
rubber (SBR) and others, is the usual material used in surface coating 
such as natural rubber (NR) and synthetic rubbers such as 
styrene-butadiene copolymer rubber (SBR), butadiene rubber (BR), 
isobutylene-isoprene copolymer rubber (IIR), chloroprene rubber (CR), 
acrylonitrile-butadiene copolymer rubber (NBR), isoprene rubber (IR), 
ethylene-propylene-diene terpolymer rubber (EPDM), and ethylene-propylene 
copolymer rubber (EPM), fibers such as cotton and rayon, and synthetic 
resins such as acrylonitrile-butadiene-styrene terpolymer (ABS) and 
polystyrene (PS). 
Also, as a means for improving the endurance to abrasion of the weather 
strip of automobiles, there is a method of providing on its surface, a 
film of chloroprene rubber by applying a urethane coating containing 
chloroprene rubber, or providing a film of silicon coating. 
Further, the side protection molding furnished on the sides of the car body 
are attached by means of an adhesive tape that is adhesive on both of its 
surfaces. A wax is applied on the car body to preserve the coating. In 
order to remove this wax, the car has to be washed using a wax remover. 
Also, when fuel, such as gasoline, is being supplied to the fuel tank of 
the automobile, there is the possibility that the fuel may spill. 
In the methods of adhesion mentioned above, since previous treatment with a 
primer or by corona discharge is required for the adhesion of polyolefin 
materials, there is an increase in the number of the required processes, 
resulting in poor operating efficiency, aside from the fact that the 
adhesive strength acquired with these methods is low. 
Also, prior to the present invention, there has been the problems of poor 
adhesion of the resin coating and the rubber coating with the material to 
be adhered, and, moreover, the problem of the deterioration of the 
endurance to abrasion of the coat thus formed. 
Further, in the methods where a film of chloroprene rubber or a silicon 
coating is applied on the weather strip of a car, there is still the 
problem of the deterioration of the endurance to abrasion. 
Finally, in the case where the car is washed using a wax remover, or when 
fuel is split on the car body as mentioned earlier, there is the problem 
of the deterioration of the strength of the adhesion between the tape 
having two adhesive surfaces and the car body, or between the tape and the 
molding, when the wax remover or the split fuel is absorbed by the 
adhesive tape. 
SUMMARY OF THE INVENTION 
An object of the present invention is to provide a solution to the problems 
related to the prior art mentioned above, by providing an adhesive 
composition that has strong adhesive properties, and, without the need for 
a prior treatment, enables the adhesion of polyolefin materials which 
adheres with other materials with difficulty. 
One other object of the present invention is to solve the problems 
mentioned above, by providing an adhesive composition that provides a 
coating with excellent endurance to abrasion, and has a strong adhesion 
with the coated material. 
In order to realize the objects mentioned above, the adhesive composition 
of the present invention has a constitution comprising 100 parts by weight 
of a polyester-polyurethane that has an isocyanate group (--NCO) and 
0.002-20 parts by weight of a halogenating agent. 
Also, the adhesive composition of the present invention has a constitution 
comprising 100 parts by weight of a polyurethane containing a hydroxyl 
group (--OH) or an isocyanate group (--NCO) formed by the reaction of a 
low molecular-weight diol with the product of the reaction of a 
diisocyanate with a mixture of polyester diol and polyether diol, and 
0.002-20 parts by weight of a halogenating agent. 
The specific nature of the invention, as well as other objects, uses and 
advantages thereof, will become clear with an understanding of the 
described embodiments and the appended claims. Also, many other advantages 
not mentioned in this specification will become apparent to one skilled in 
the art upon application of the present invention. 
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
First, the constitution of the adhesive composition related to the first 
aspect of the invention is explained in detail. 
Polyester-polyurethane comprises a polyisocyanate and a polyester polyol. A 
polyisocyanate is a compound containing a plurality of isocyanate groups, 
for example, there are the aromatic polyisocyanates such as tolylene 
diisocyanate (TDI), 1,5-naphthalene diisocynate (NDI), xylilene 
diisocyanate (XDI), 4,4'-diphenylmethane diisocyanate (MDI), 
4,4',4"-triphenylmethane triisocyanate (TPMI), isophorone diisocyanate 
(IPDI) and others, the alicyclic polyisocyanates such as 4,4'-methylenebis 
(cyclohexyl isocyanate) (H-MDI), hexahydroxylilene diisocyanate and 
others, and the aliphatic polyisocyanates such as 1,6-hexamethylene 
diisocyanate (1,6-HMDI) and others. 
As examples of a polyester polyol, there are polybutylene adipate (PBA), 
polyethylene butylene adipate (PEBA), polyethylene adipate (PEA), 
polyethylene sebacate (PESe) and others. 
As a halogenating agent, for example, there are alkyl hypohalides such as 
t-butyl hypochloride (t-BHC), hypohalogenous acids such as sodium 
hypochlorite and potassium hypochlorite, compounds that have a -CONX-bond 
in a molecule such as N-bromosuccinimide (NSBI), trichloroisocyanuric acid 
(TCIA), dichloroisocyanuric acid (DiCIA) and others, and a mixed solution 
comprising antimony pentafluoride, sulfur fluoride and bromine. Among the 
halogenating agents mentioned above, alkyl hypohalide, hypohalogenous acid 
or the compound having a -CONX-bond in a molecule is preferred. 
The mixing ratio of the halogenating agent is in the range of 0.002-20 
parts by weight to 100 parts by weight of polyester-polyurethane. When the 
mixing ratio is less than 0.002 part by weight, the degree of 
halogenization is low, resulting in a small improvement in the adhesive 
strength, whereas when the mixing ratio is more than 20 parts by weight, 
the stability of the adhesive composition is impaired. 
Solvents and chain extending agents may be used as desired. As chain 
extending agents, the examples are dihydric alcohols such as butylene 
glycol (BG), 1,6-hexanediol (1,6-HD), ethylene glycol (EG) and others. 
As solvents, there are aliphatic hydrocarbons such as n-hexane, n-heptane 
and n-octane, alicyclic hydrocarbons such as cyclohexane and cyclooctane, 
aromatic hydrocarbons such as benzene, ethyl benzene, toluene and xylene, 
ketones such as acetone, methyl ethyl ketone, ethyl propyl ketone and 
methyl butyl ketone, ethers such as tetrahydrofuran, acetic esters such as 
methyl acetate, ethyl acetate, and isopropyl acetate, halogenated 
hydrocarbons such as methylene chloride, 1,1,1-trichloroethane and 
trichloroethylene, and aside from the above, there are dimethyl sulfoxide 
(DMSO), dimethyl formamide (DMF) and others. These solvents can be used 
alone or as a mixed solution of two or more kinds of the above solvents, 
the mixing ratio of the adhesive composition with these solvents being 
determined accordingly and appropriately. 
Next, the constitution of the adhesive composition related to the second 
aspect of the invention is described. 
As a polyester diol used in the present invention, there are substances 
synthesized by the reaction of a type of diol, or a mixture of two or more 
types of diols, such as EG as mentioned earlier, propylene glycol, 
1,4-butanediol, 1,3-butanediol, 2,3-butanediol, diethylene glycol, 
dipropylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-HD mentioned 
earlier, neopentyl glycol and others, and a type of carbonic acid, or a 
mixture of two or more types of carbonic acids, such as succinic acid, 
adipic acid, azelaic acid, sebacic acid, phthalic acid and isophthalic 
acid and others. 
As a polyether diol, polyoxypropylene glycol (PPG), polyoxyethylene glycol, 
polytetramethylene oxide glycol and others are used. 
These polyester diols and polyether diols are used in the form of mixtures. 
The mixing ratio can be set appropriately over a wide range of ratios of 
the polyester diol and polyether diol. 
Among the substances used as a diisocyanate, there are 2,4-tolylene 
diisocyanate, 65/35 (the ratio of 2,4-tolylene diisocyanate to 
2,6-tolylene diisocyanate, the same hereinafter) tolylene diisocyanate, 
80/20 tolylene diisocyanate, MDI mentioned earlier, dianisidine 
diisocyanate, tolidene diisocyanate, hexamethylene diisocyanate, 
metaxylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated 
diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, 
hydrogenated 2,4-tolylene diisocyanate, hydrogenated 65/35 tolylene 
diisocyanate, hydrogenated 80/20 tolylene diisocyanate, isophorone 
diisocyanate and others. 
The diisocyanate is made to react with a mixture of a polyester diol and a 
polyether diol mentioned earlier. In this reaction, an appropriate ratio 
of the mixture and the diisocyanate mentioned above in terms of hydroxyl 
group (--OH):isocyanate group (--NCO) is a mole ratio in the range of 
1:2-10. When the proportion of the --NCO is less than 2, the polyurethane 
generated by the reaction becomes too soft, becoming not suitable for use 
as a coating. Also, when the proportion of the --NCO is more than 10, the 
polyurethane becomes too hard and brittle, and neither is it suitable for 
use as a coating. 
As a low molecular-weight diol, there are substances which can be used 
alone, or as a mixture of two or more types, such as EG, propylene glycol, 
1,4-butanediol, 1,3-butanediol, 2,3-butanediol, diethylene glycol, 
dipropylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-HD, neopentyl 
glycol, and others. 
This low molecular-weight diol is added to the product generated by the 
reaction of the mixture of polyester diol and polyether diol with a 
diisocyanate. As the proportion of this low molecular-weight diol becomes 
high, the proportion of --OH becomes high compared to the proportion of 
--NCO, generating a polyurethane of terminal --OH. On the other hand, when 
the proportion of the low molecular-weight diol is small, the proportion 
of --NCO becomes relatively high compared to the proportion of --OH, and a 
polyurethane of terminal --NCO is generated. In the present invention, as 
any of the substances generated can be used, one may be chosen 
appropriately according to usage. 
As mentioned above, the polyurethane having an isocyanate group or a 
hydroxyl group is generated by first making a mixture of polyester diol 
and polyether diol react with a diisocyanate, then making the product of 
this reaction further react with the low molecular-weight diol. 
In this process, a solvent may be used as desired. Among the solvents that 
can be used are n-hexane, cyclohexane, benzene, toluene, xylene, ethyl 
benzene, acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl 
isobutyl ketone, tetrahydrofuran, methyl acetate, ethyl acetate, isopropyl 
acetate, isobutyl acetate, methylene chloride, 1,1,1-trichloroethane, DMSO 
mentioned earlier, DMF and others. 
As a halogenating agent, the ones in use are acid imido halogen compounds 
such as NBSI mentioned earlier, N-bromophthalimide and others, isocyanuric 
acid halides such as TCIA, DiCIA and others, halogenized hydantoins such 
as dichlorodimethyl hydantoin, and alkyl hypohalides and others. 
The alkyl hypohalide mentioned above is a normal, secondary or tertiary 
alkyl hypohalide, the preferred ones being a chloride and a bromide of a 
particularly stable tertiary alkyl hypohalide, that is, the t-BHC 
mentioned earlier, tertiary butyl hypobromide, tertiary amyl hypobromide 
and others. Aside from these, halogen substituted alkyl hypochlorides such 
as dichloro-, trichloro-, fluoromethyl hypochloride or others can also be 
used. 
The mixing ratio of the halogenating agent and its grounds are the same as 
those of the first case of the invention.

EMBODIMENTS 1 TO 5 AND COMATIVE EXAMPLES 1 AND 2 
Embodiments using the adhesive composition of the first aspect of the 
present invention is described below and compared with comparative 
examples. 
First, a polyester-polyurethane having an isocyanate group was synthesized 
according to the mixing ratio described below. 
Polyester-polyurethane [1] 
A polyurethane prepolymer was synthesized by mixing 100 parts by weight 
(hereinafter referred to as parts only) of MDI with 66.56 parts of PBA 
(average molecular weight 500) in trichloroethylene and making them 
undergo reaction for three hours in a dry nitrogen gas atmosphere at a 
temperature of 80.degree. C. Afterward, polyester-polyurethane was 
synthesized by adding 20.40 parts of BG to this polyurethane prepolymer 
and making them undergo reaction for 20 minutes at a temperature of 
80.degree. C. The polyester-polyurethane obtained was 25% solid and 75% 
trichloroethylene. 
Polyester-polyurethane [2] 
A polyurethane prepolymer was synthesized by mixing 100 parts of MDI with 
266.31 parts of PEBA (average molecular weight 2000) in trichloroethylene 
and making them undergo reaction for three hours in a dry nitrogen gas 
atmosphere at a temperature of 80.degree. C. Afterward, 
polyester-polyurethane was synthesized by adding 26.76 parts of 1,6-HD to 
this polyurethane prepolymer and making them undergo the reaction for 20 
minutes at a temperature of 80.degree. C. The polyester-polyurethane 
obtained was 25% solid and 75% trichloroethylene. 
Polyester-polyurethane [3] 
A polyurethane prepolymer was synthesized by mixing 100 parts of XDI with 
191.94 parts of PEA (average molecular weight 1000) in trichloroethylene 
and making them undergo reaction for three hours in a dry nitrogen gas 
atmosphere at a temperature of 80.degree. C. Then, polyester-polyurethane 
was synthesized by adding 44.09 parts of EG to this polyurethane 
prepolymer and making them undergo reaction for 20 minutes at a 
temperature of 80.degree. C. The polyester-polyurethane obtained was 25% 
solid and 75% trichloroethylene. 
Polyester-polyurethane [4] 
A polyurethane prepolymer was synthesized by mixing 100 parts of 1,6-HMDI 
with 99.10 parts of PESe (average molecular weight 1000) in 
trichloroethylene and making them undergo reaction for three hours in a 
dry nitrogen gas atmosphere at a temperature of 80.degree. C. Afterward, 
polyester-polyurethane was synthesized by adding 28.92 parts of EG to this 
polyurethane prepolymer and making them undergo reaction for 20 minutes at 
a temperature of 80.degree. C. The polyester-polyurethane obtained was 25% 
solid and 75% trichloroethylene. 
Polyester-polyurethane [5] 
A polyurethane prepolymer was synthesized by mixing 100 parts of MDI with 
266.31 parts of PEA (average molecular weight 1000) in trichloroethylene 
and making them undergo reaction for three hours in a dry nitrogen gas 
atmosphere at a temperature of 80.degree. C. Afterward, 
polyester-polyurethane was synthesized by adding 5.79 parts of EG to this 
polyurethane prepolymer and making them undergo reaction for 20 minutes at 
a temperature of 80.degree. C. The polyester-polyurethane obtained was 25% 
solid and 75% trichloroethylene. 
Next, using adhesive compositions combining 100 parts of the solid portions 
of the polyurethanes [1]-[5] obtained above and a halogenating agent at 
the mixing ratios shown in Table 1, the adhesive strengths of these 
adhesive compositions were measured using a five-times magnification 
polyethylene foam as the material to be glued. 
In the adhesive strength measurement, two pieces of five-times 
magnification polyethylene foams, serving as test pieces, were applied 
with the adhesive composition on an adhesion area of 25.times.25 mm, 
heated for two minutes at a temperature of 100.degree. C. to let the 
solvent evaporate, then glued and formed together under a load of 5 
kg/cm.sup.2. The tensile shear strength (kg/cm.sup.2) was measured by a 
tension test of the test piece thus prepared, at a pulling speed of 50 
mm/min. The results are shown in Table 1. 
TABLE 1 
______________________________________ 
Embodiment or 
Comparative 
Polyester- Halogenating 
Tensile Shear 
Example Polyurethane 
Agent Strength 
______________________________________ 
Embodiment 1 
[1] (100) t-BHC (0.002) 
6.1* 
Embodiment 2 
[2] (100) t-BHC (1) 5.9* 
Embodiment 3 
[3] (100) NBSI (1) 6.1* 
Embodiment 4 
[4] (100) TCIA (1) 6.0* 
Embodiment 5 
[5] (100) TCIA (20) 5.8* 
Comparative 
[1] (100) TCIA (30) Gelled 
Example 1 
Comparative 
[1] (100) TCIA (0.001) 
0.2 
Example 2 
______________________________________ 
The abbreviations in the table stand for the following: 
tBHC: tbutyl hypochloride 
NBSI: Nbromosuccinimide 
TCIA: trichloroisocyanuric acid 
[1] to [5] under the column polyesterpolyurethane oorrespond to the 
polyesterpolyurethanes [1] to [5] which are polyurethanes that contain an 
isocyanate group, as mentioned earlier, and the symbol "*" under the 
column tensile shear strength denotes the collapse of the polyethylene 
foam used as the test piece. 
As shown in Table 1, with the mixing proportion of the halogenating agent 
with the polyester-polyurethane containing an isocyanate group in the 
range of 0.002-20 parts, it is observed that the five-times magnification 
polyethylene foam used as the test piece collapses at a higher tensile 
shear strength. 
That the adhesive composition of the present invention exhibits such a 
superior adhesive strength is due to the fact that the halogen in the 
halogenating agent halogenizes the non-polarized polyolefin in the test 
piece, as well as halogenizes the polyurethane in the adhesive 
composition, resulting in a strengthening of the intermolecular forces. 
On the other hand, as shown in Comparative Examples 1 and 2, it can be 
observed that when the mixing proportion of the halogenating agent is not 
within the range prescribed in the present invention, either the stability 
of the adhesive composition is poor or the adhesive strength is very weak. 
Thus, in this embodiment, not only is the adhesion of difficult to adhere 
polyethylene materials easily accomplished without the use of any primers 
as in the prior methods, but, moreover, the adhesive strength obtained is 
very high. Therefore, the adhesive composition of the present invention 
can be suitably used, for example, for products using polyolefin materials 
such as car molding, base material for electrostatic flocked products, 
interior trims, rubber products and others. 
EMBODIMENTS 6 TO 11 AND COMATIVE EXAMPLES 3 TO 12 
An embodiment of the second aspect of the invention applied as a coating 
composition is described below and compared with comparative examples. 
First, the material to be coated is a vulcanized material as described in 
the following. 
The vulcanized material is obtained by vulcanizing a composition of 100 
parts of EPDM, 70 parts of carbon black, 35 part of mineral oil, 7 parts 
of zinc oxide, 2 parts of stearic acid, 2 parts of a vulcanizing 
accelerator and 1.5 parts of sulfur for 30 minutes at a temperature of 
160.degree. C. 
Also, an abrasion endurance test is performed according to the method and 
conditions described below, with the evaluation of the endurance to 
abrasion being measured in terms of the amount of abrasion. 
Abrasive Wheel: H-22, load: 1 kg 
Abrasion Speed of Rotation: 60 rpm 
Test Area: 100 mm.times.100 mm 
Abrasion Cycle: 1000 cycles 
EMBODIMENT 6 
A mixture of 120 parts of PPG (molecular weight about 2000), 44 parts of 
polyethylene adipate (molecular weight about 2000), 100 parts of MDI and 
264 parts of trichloroethylene was heated for three hours in an 
atmospheric current of dry nitrogen at a temperature of 80.degree. C. 
Further, 24.8 parts of 1,6-hexanediol and 170 parts of DMF were added and 
then heated for 20 minutes in an atmospheric current of dry nitrogen at a 
temperature of 80.degree. C. Polyurethane was obtained as a result of 
these processes. 
A coating composition was then obtained by mixing 30 parts of carbon black, 
100 parts of toluene, 40 parts of DMF and 0.002 part of TCIA to 100 parts 
of the polyurethane obtained above. 
This coating composition was applied on the material to be coated mentioned 
earlier and hardened by heating for 2 minutes at a temperature of 
100.degree. C. to produce a test material. Then the abrasion endurance 
test mentioned earlier was performed on this test material. The result of 
this test is shown in Table 2. 
EMBODIMENT 7 
A coating composition was obtained by mixing 10 parts of carbon black, 80 
parts of toluene, 50 parts of DMF and 0.4 part of NBSI to 100 parts of a 
polyurethane prepared in the same manner as in Embodiment 6. 
This coating composition was applied on the material to be coated mentioned 
above and hardened by heating for 5 minutes at a temperature of 
100.degree. C. to produce a test material. Then the abrasion endurance 
test mentioned above was performed on this test material. The result of 
this test is shown in Table 2. 
EMBODIMENT 8 
140 parts of PPG (molecular weight about 2000), 60 parts of polyethylene 
adipate (molecular weight about 2000), 100 parts of MDI and 300 parts of 
trichloroethylene were made to undergo reaction according to the same 
method used for Embodiment 6. After this, polyurethane was synthesized by 
adding 24.2 parts of 1,6-HD and 246 parts of DMF and making the mixture 
undergo reaction in the same manner as in Embodiment 6. 
A coating composition was prepared by mixing 30 parts of carbon black, 100 
parts of benzene, 50 parts of DMF and 0.1 part of TCIA to 100 parts of 
this polyurethane. 
This coating composition was applied on the material to be coated mentioned 
above and hardened by heating for 5 minutes at a temperature of 
100.degree. C. to produce a test material. Then the abrasive endurance 
test mentioned above was performed on this test material. The result of 
this test is shown in Table 2. 
EMBODIMENT 9 
Polyurethane was obtained by mixing 60 parts of PPG (molecular weight about 
2000), 140 parts of PEBA (molecular weight about 2000), 100 parts of MDI 
and 300 parts of trichloroethylene and then letting the mixture undergo 
reaction according to the same method used for Embodiment 6. 
A coating composition was prepared by mixing 189 parts of 1,4-butanediol, 
246 parts of DMF and 10 parts of TCIA to 100 parts of this polyurethane. 
Using this coating composition, a test material was produced in the same 
manner as in Embodiment 8 mentioned above. The abrasion endurance test 
mentioned above was performed on this test material. The result of this 
test is shown in Table 2. 
EMBODIMENT 10 
Polyurethane was obtained by mixing 60 parts of PPG (molecular weight about 
2000), 140 parts of PBA (molecular weight about 2000), 100 parts of MDI 
and 300 parts of trichloroethylene and then letting this mixture undergo 
reaction according to the same method used for Embodiment 6. 
A coating composition was prepared by mixing 12.2 parts of ethylene glycol, 
300 parts of DMF and 20 parts of TCIA to 100 parts of this polyurethane. 
Using this coating composition, a test material was produced in the same 
manner as in Embodiment 6 mentioned above. Then, the abrasion endurance 
test mentioned earlier was performed on this test material. The result of 
this test is shown in Table 2. 
EMBODIMENT 11 
Polyurethane was obtained by mixing 140 parts of PPG (molecular weight 
about 2000), 60 parts of PEBA (molecular weight about 2000), 100 parts of 
MDI and 300 parts of trichloroethylene and letting this mixture undergo 
reaction as in Embodiment 6 mentioned earlier. 
A coating composition was prepared by mixing 12.2 parts of ethylene glycol, 
300 parts of DMF and 10 parts of TCIA to 100 parts of this polyurethane. 
Using this coating composition, a test material was produced in the same 
manner as in Embodiment 6 mentioned earlier. The abrasion endurance test 
was then performed on this test material. The result of this test is shown 
in Table 2. 
COMATIVE EXAMPLE 3 
A coating was prepared by mixing 100 parts of liquid polybutadiene (a 
product of Idemitsu Sekiyu Kagaku Kogyo Kabushikigaisha with the brand 
name Idemitsu Seal AB-700W) and 10 parts of MDI. This coating was applied 
on the material to be coated and then hardened at room temperature to 
produce a test material. The abrasion endurance test was performed on this 
test material and the result of this test is shown in Table 2. 
COMATIVE EXAMPLE 4 
A coating was prepared by mixing 100 parts of liquid polybutadiene (a 
product of Idemitsu Sekiyu Kagaku Kogyo kabushikigaisha with the brand 
name Idemitsu Seal AB-100) and 10 parts of MDI. This coating was applied 
on the material to be coated and hardened at room temperature to produce a 
test material. The abrasion endurance test was then performed on this test 
material. The result of this test is shown in Table 2. 
COMATIVE EXAMPLE 5 
A 70% solution of N-metoxymethylized nylon (a product of Teikoku Kagaku 
Sangyo Kabushikigaisha with the brand name Trejin M-20) was applied on the 
material to be coated and made to harden at room temperature to produce a 
test material. The abrasion endurance test was performed on this test 
material. The result of this test is shown in Table 2. 
COMATIVE EXAMPLE 6 
A coating was prepared by mixing 100 parts of epoxy resin (a product of 
Nippon Ciba-Geigy Kabushikigaisha with the brand name Alardite PZ820) and 
100 parts of polyaminoamide (a product of Nippon Ciba-Geigy 
Kabushikigaisha with the brand name Hardener HZ). This coating was applied 
on the material to be coated and made to harden at room temperature to 
produce a test material. The abrasion endurance test was performed on this 
test material. The result of this test is shown in Table 2. 
COMATIVE EXPERIMENT 7 
A coating was prepared by mixing 100 parts of epoxy resin (a product of 
Nippon Ciba-Geigy Kabushikigaisha with the brand name Alardite GY250) and 
30 parts of polyaminoamide (a product of Nippon Ciba-Geigy Kabushikigaisha 
with the brand name Hardener HZ). This coating was applied on the material 
to be coated and made to harden at room temperature to produce a test 
material. The abrasion endurance test was performed on this test material 
and the result of this test is shown in Table 2. 
COMATIVE EXPERIMENT 8 
As a coating, a solution containing 74% toluene of a chloroprene rubber (a 
product of Konishi Kabushikigaisha with the brand name Bond G.sub.2) was 
applied on the material to be coated and then made to harden at room 
temperature to produce a test material. The abrasion endurance test was 
performed on this material. The result of this test is shown in Table 2. 
COMATIVE EXAMPLE 9 
SBR (a product of Nogawa Chemical Kabushikigaisha with the brand name 
Diabond 5010) was applied on the material to be coated and made to harden 
at room temperature to produce a test material. The abrasion endurance 
test was performed on this material. The result of this test is shown in 
Table 2. 
COMATIVE EXAMPLE 10 
As a coating, a 70% non-volatile acrylic resin emulsion (a product of 
Nogawa Chemical Kabushikigaisha with the brand name Diabond DA--830A) was 
applied on the material to be coated and made to harden at room 
temperature to produce a test material. The abrasion endurance test was 
performed on this test material. The result of this test is shown in Table 
2. 
COMATIVE EXAMPLE 11 
As a coating, a 55% non-volatile denatured acrylic ethylene emulsion (a 
product of Sunstar Kagaku Kabushikigaisha with the brand name Penguin 
Cement 138) was applied on the material to be coated and made to harden at 
room temperature to produce a test material. The result of this test is 
shown in Table 2. 
COMATIVE EXAMPLE 12 
As a coating, a polyurethane coating (a product of Nogawa Chemical 
Kabushikigaisha with the brand name Diabond DA700E) was applied on the 
material to be coated and made to harden at room temperature to produce a 
test material. The abrasion endurance test was performed on this test 
material. The result of this test is shown in Table 2. 
TABLE 2 
______________________________________ 
Embodiment or Amount of Abrasion 
Comparative Example 
(mg/1000 cycles) 
______________________________________ 
Embodiment 6 25 
Embodiment 7 28 
Embodiment 8 20 
Embodiment 9 10 
Embodiment 10 9 
Embodiment 11 11 
Comparative Example 3 
2252 
Comparative Example 4 
2290 
Comparative Example 5 
631 
Comparative Example 6 
692 
Comparative Example 7 
572 
Comparative Example 8 
691 
Comparative Example 9 
1950 
Comparative Example 10 
671 
Comparative Example 11 
624 
Comparative Example 12 
482 
______________________________________ 
As shown in Table 2, in the abrasion tests at 1000 cycles of the abrasion 
wheel, the amounts of abrasion of the test materials applied with the 
coating of each of the comparative examples are all greater than or equal 
to 482 mg. On the other hand, the amounts of abrasion of the test 
materials applied with the coating compositions of the present invention 
are all less than or equal to 28 mg, very much smaller than those of the 
comparative examples, thus showing that the coating compositions of the 
present invention have good endurance to abrasion. This is due to the 
combined usage of polyester diol and polyether diol and, moreover, to the 
hardness and other properties of the polyurethane having an increased 
molecular weight, which was obtained as a result of the reaction with a 
low molecular-weight polyol as a chain extending agent. 
Also, for the coating compositions of Embodiments 6 to 11, the acquired 
coating exhibited good adhesion with the material to be coated. This is 
due to the fact that the halogenating agent halogenates the coating 
composition itself, as well as halogenating the material to be coated, 
thus improving their mutual binding forces. 
EMBODIMENTS 12 TO 17 AND COMATIVE EXAMPLES 13 AND 14 
An embodiment of the coating composition of the second aspect of the 
present invention for use in weather strips of cars is described below. 
The base material normally used for weather strips is a vulcanized 
polyolefin rubber. Specific examples are EPDM, EPM and others. Further, 
these polyolefin rubbers can be used with a mixture of other rubber 
materials, as long as the mixing proportion of these other materials is 
within a range in which the properties of these polyolefin rubbers are not 
lost. For example, for the vulcanized polyolefin rubber, the mixing 
proportion of the other rubber material must be less than or equal to 1/2 
parts by weight of the vulcanized polyolefin rubber. Examples of these 
other rubber materials are NR, SBR, NBR, IR, CR, IIR, all mentioned 
earlier, and others. 
Depending on the object, the various vulcanized rubbers mentioned above can 
be mixed with other mixing substances that are normally used, such as 
vulcanizing agents, vulcanizing accelerators, age resisters, antioxidants, 
antiozonants, fillers, plasticizers, foaming agents, auxiliary foaming 
agents and others. 
Examples of vulcanizing agents are sulfur, morpholinedisulfide, dicumyl 
peroxide and others. 
As examples of vulcanizing accelerators, there are 2-mercaptobenzothiazole, 
zinc dimethyl dithiocarbamate, tetramethylthiuram disulfide and others. 
As examples of age resisters, antioxidants and antiozonants, there are 
phenyl-.alpha.-naphthylamine, 2,6-di-t-butyl-p-cresol and others. 
As examples of fillers, there are carbon black, hydrosilicate, magnesium 
carbonate, clay and others. 
As examples of plasticizers, there are dioctyl sebacate, mineral oil and 
others. 
As foaming agents, there are N,N'-dinitrosopentamethylene tetramine, 
N,N'-dimethyl-N,N'-dinitrosotelephthalamide, azodicarbonamide, 
azobisisobutyronitrile, benzene sulfonyl hydrazide, p,p'-oxybis (benzene 
sulfonyl hydrazide), toluene sulfonyl hydrazide and others. 
As examples of auxiliary foaming agents, there are urea, salicylic acid and 
others. 
After forming the weather strip by an extrusion process using as base 
material the substance containing EPDM and other materials as shown in the 
composition in Table 3, it was vulcanized for 30 minutes at a temperature 
of 160.degree. C. to produce a weather strip for an automobile. A test 
material was prepared by applying a coating composition of each of the 
embodiments shown below. 
TABLE 3 
______________________________________ 
Mixing Proportion 
Composition (parts by weight) 
______________________________________ 
EPDM 100 
carbon black 70 
mineral oil 35 
zinc oxide 5 
stearic acid 1 
vulcanizing 2 
accelerator 
sulfur 1.5 
______________________________________ 
EMBODIMENT 12 
The coating composition of Embodiment 6 was used. 
EMBODIMENT 13 
The coating composition of Embodiment 7 was used. 
EMBODIMENT 14 
The coating composition of Embodiment 8 was used. 
EMBODIMENT 15 
The coating composition of Embodiment 9 was used. 
EMBODIMENT 16 
The coating composition of Embodiment 10 was used. 
EMBODIMENT 17 
The coating composition of Embodiment 11 was used. 
COMATIVE EXAMPLE 13 
Instead of using 0.002 part of TCIA as a halogenating agent as in 
Embodiment 6, 25 parts of the same TCIA was used. A coating composition, 
whose other aspects are the same as those in Embodiment 6, was then 
prepared. 
COMATIVE EXAMPLE 14 
Instead of using 0.4 part of NBSI as a halogenating agent as in Embodiment 
7, 30 parts of the same NBSI was used. A coating composition, whose other 
aspects are the same as those in Embodiment 7, was then prepared. 
Next, an abrasion endurance test, using a glass edge abrasion testing 
machine which is an improved version of the Gakushin style abrasion 
testing machine, was performed on the test materials obtained in the 
Embodiments 12 to 17 and Comparative Examples 13 and 14 mentioned above, 
under the following conditions: 
TESTING CONDITIONS 
Abrasive: glass (thickness, 5 mm) 
Cycle of Abrasive: 60 cycles/min 
Stroke of Abrasive: 70 mm 
TESTING METHOD 
Normal State Abrasion: The base is mounted on the testing machine and the 
base is abraded and the amount of abrasion in the normal condition is 
tested. 
TABLE 4 
______________________________________ 
Embodiment or Abrasion Endurance Test 
Comparative Example 
(50,000 cycles) 
______________________________________ 
Embodiment 12 O 
Embodiment 13 O 
Embodiment 14 O 
Embodiment 15 O 
Embodiment 16 O 
Embodiment 17 O 
Comparative Example 13 
Gelled 
Comparative Example 14 
Gelled 
______________________________________ 
The symbol "O" in Table 4 a denotes a small amount of abrasion, that is, a 
strong endurance to abrasion. 
As observed in Table 4, in Comparative Examples 13 and 14, the coating 
compositions themselves gelled, whereas in Embodiments 12 to 17, the 
coating composition was able to endure an abrasion of 50,000 cycles, thus 
showing that there is no problem with regard to abrasion. Also, the film 
of coating obtained exhibited good adhesion with the coated material. 
Aside from the above tests, the weather strip processed with the coating 
compositions of Embodiments 12 to 17 was bent 180 degrees, and the 
pliability was observed. 
The result of this was that the vulcanized polyolefin rubber used as base 
material for the weather strip retained its flexibility, and the weather 
strip exhibited good pliability. The properties of endurance to abrasion 
and pliability mentioned above are due to the properties of the high 
molecular-weight polyurethane that has a special structure. 
Therefore, the coating compositions of Embodiments 12 to 17 are suitable 
for use as coating compositions for weather strips. 
EMBODIMENTS 18 TO 23 AND COMATIVE EXAMPLES 15 AND 16 
Next, embodiments of the second aspect of the invention used as an adhesive 
composition for electrostatic flocked materials are described and compared 
with comparative examples. 
In the various examples below, it is either that electrostatic flocking was 
performed by applying the adhesive composition of each embodiment below on 
a base made of EPDM (Embodiments 18 to 20), or, a test material was made 
by applying the adhesive composition, then forming a pile, after 
electrostatic flocking (Embodiments 21 to 23). An abrasion endurance test 
with the conditions below was performed on this test material. The results 
of this test are shown in Table 5 to be mentioned later. 
TEST CONDITIONS 
Abrasive Wheel: H-22, load: 5 kg 
Speed of Rotation of Abrasion: 60 rpm 
Size of Test Material: 100 mm.times.100 mm 
Abrasion Cycle: 1000 cycles 
EMBODIMENT 18 
The composition mentioned in Embodiment 6 was used. 
EMBODIMENT 19 
The composition mentioned in Embodiment 7 was used. 
EMBODIMENT 20 
The composition mentioned in Embodiment 8 was used. 
EMBODIMENT 21 
The composition mentioned in Embodiment 9 was used. 
EMBODIMENT 22 
The composition mentioned in Embodiment 10 was used. 
EMBODIMENT 23 
The composition mentioned in Embodiment 11 was used. 
COMATIVE EXAMPLE 15 
The composition mentioned in Comparative Example 13 was used. 
COMATIVE EXAMPLE 16 
The composition mentioned in Comparative Example 14 was used. 
TABLE 5 
______________________________________ 
Embodiment or Abrasion Endurance Test 
Comparative Example 
(30,000 cycles) 
______________________________________ 
Embodiment 18 O 
Embodiment 19 O 
Embodiment 20 O 
Embodiment 21 O 
Embodiment 22 O 
Embodiment 23 O 
Comparative Example 15 
X 
Comparative Example 16 
X 
______________________________________ 
The symbol "O" used under the column Abrasion Endurance Test in Table 5 
means that the amount of abrasion was small, that is, the result was good, 
while the symbol "X" denotes that the amount of abrasion was great and 
that the result was bad. 
As observed in Table 5, for Comparative Examples 15 and 16, the result was 
bad for both in the 30,000 cycle abrasion endurance test, whereas for 
Embodiments 18 to 23, the material was able to endure 30,000 cycles of 
abrasion, thus showing that there is no problem with regard to abrasion. 
This is due to the high molecular-weight polyurethane that has a special 
structure. Also, the film of coating obtained exhibited excellent adhesion 
with the base material. 
Therefore, the adhesive compositions in Embodiments 18 to 23 are suitable 
for use as an adhesive composition for electrostatic flocked materials. 
EMBODIMENTS 24 TO 29 AND COMATIVE EXAMPLES 17 AND 18 
Next, embodiments of the adhesive composition of the second aspect of the 
present invention as used in adhesive tapes is described. 
The following substances were used as adhesive compositions: 
EMBODIMENT 24 
The adhesive composition was made by adding 0.002 part of t-BHC as a 
halogenating agent to 100 parts of the polyurethane described in 
Embodiment 6. 
EMBODIMENT 25 
A mixture of 60 parts of PPG (molecular weight about 1000), 22 parts of 
polyethylene butylene adipate (molecular weight 1000), 100 parts of MDI 
and 264 parts of trichloroethylene was made to undergo reaction for 3 
hours in an atmospheric current of dry nitrogen at a temperature of 
80.degree. C. 
Afterward, polyurethane was obtained by adding 24.8 parts of 1,6-HD and 170 
parts of DMF and then letting the mixture undergo reaction for 20 minutes 
in an atmospheric current of nitrogen at a temperature of 80.degree. C. 
Finally, an adhesive composition was made by adding 0.4 part of NBSI as a 
halogenating agent to 100 parts of this polyurethane. 
EMBODIMENT 26 
An adhesive composition was made by adding 20 parts of TCIA as a 
halogenating agent to 100 parts of the polyurethane described in 
Embodiment 8. 
EMBODIMENT 27 
An adhesive composition was made by adding 0.002 part of t-BHC as a 
halogenating agent to 100 parts of the polyurethane described in 
Embodiment 9. 
EMBODIMENT 28 
An adhesive composition was made by adding 0.4 part of NBSI as a 
halogenating agent to 100 parts of the polyurethane described in 
Embodiment 10. 
EMBODIMENT 29 
An adhesive composition was made by adding 20 parts of TCIA as a 
halogenating agent to 100 parts of the polyurethane described in 
Embodiment 11. 
Next, the adhesive composition of each embodiment and comparative example 
mentioned above were used and the area of adhesion and tensile shear 
strength were measured. 
A test material was made by using an 8-times magnification polyethylene 
foam as the base material for the two-surface adhesive tape. The 
two-surface adhesive tape was taped on one surface of the polyethylene 
foam, then glued to a solid coating steel plate. The other surface of the 
polyethylene foam was applied with an adhesive and then glued to a vinyl 
chloride resin plate. This test material was immersed in gasoline or wax 
remover, serving as a solvent, for one hour. Then, the area of adhesion 
and the tensile shear strength were measured. The test on the tensile 
shear strength was performed at a pulling speed of 30 mm/min. The results 
are shown in Table 6. 
TABLE 6 
______________________________________ 
Embodiment or Tensile Shear 
Comparative Adhesion Area Strength 
Example Solvent (%) (kg/cm.sup.2) 
______________________________________ 
Embodiment 24 
G 89 7.5 
Embodiment 25 
G 92 7.8 
Embodiment 26 
G 92 8.0 
Embodiment 27 
W 90 7.6 
Embodiment 28 
W 91 7.6 
Embodiment 29 
W 90 7.9 
Comparative 
G 25 1.5 
Example 17 
Comparative 
W 25 1.5 
Example 18 
______________________________________ 
In Table 6, adhesive compositions were not used in Comparative Examples 17 
and 18. In the column for solvent, "G" stands for gasoline and "W" stands 
for wax remover. 
As observed in Table 6, for both Comparative Examples 17 and 18, the area 
of adhesion was 25%, and the tensile shear strength was 1.5 kg/cm.sup.2, 
whereas for Embodiments 24 to 29, the area of adhesion was satisfactorily 
maintained in the range of 89 to 92%, while the tensile shear strength was 
within 7.5 to 8.0, showing a high strength. This is particularly due to 
the fact that the halogenating agent halogenates the adhesive composition 
itself as well as the polyethylene base of the adhesive tape, thus 
improving the mutual bonding forces. 
Therefore, the adhesive compositions in Embodiments 24 to 29 are suitable 
for application in adhesive tapes used for mounting moldings onto car 
bodies, and in adhesive tapes used in chemical apparatus which are prone 
to being spilled with solvents. 
As many apparently widely different embodiments of this invention may be 
made without departing from the spirit and scope thereof, it is to be 
understood that the invention is not limited to the specific embodiments 
thereof except as defined in the appended claims.