JPH021791A - Adhesive composition - Google Patents

Abstract

PURPOSE:To obtain an adhesive composition giving a coating film having excellent abrasion resistance and suitable for the bonding and coating of a rubber product or synthetic resin product, etc., by compounding a specific amount of a halogenation agent to a polyurethane containing isocyanate group or hydroxyl group. CONSTITUTION:The objective composition is produced by compounding (A) 100 pts.wt. of a polyurethane having isocyanate group or hydroxyl group and produced by reacting (i) a reaction product of a diisocyanate with a mixture of a polyester diol and a polyether diol with (ii) a low-molecular weight diol such as ethylene glycol or 1,6-hexanediol and (B) 0.002-20 pts.wt. of a halogenation agent such as an acid imide halide compound, an isocyanuric acid halide or halogenated hydantoin.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an adhesive composition suitable for adhering and painting rubber products, synthetic resin products, etc.

[Prior art] Conventionally, natural rubber (NR), styrene-butadiene copolymer rubber (SBR), butadiene rubber (BR), isobutylene-isoprene copolymer rubber (IR), chloroprene rubber (CR), acrylonitrile-butadiene copolymer rubber Polymer rubber (NBR), isoprene rubber (IR), ethylene-propylene-diene copolymer rubber (EPDM), ethylene-
Surface coatings for synthetic rubber such as propylene copolymer rubber (EPM), fibers such as cotton and rayon, and synthetic resins such as ABS resin and PS resin are nylon, epoxy, acrylic, and acrylic-ethylene copolymer. resin paint or BR
Rubber paints such as , CR, and SBR are used.

In addition, as a means of imparting wear resistance to automobile weather strips, a urethane paint containing chloroprene rubber is applied to the surface to provide a chloroprene rubber film, or a silicone coating layer is provided. There is a way.

Further, the side protection molding attached to the side surface of the car body is fixed with double-sided adhesive tape. On the other hand, car bodies are coated with wax to protect the paint. In order to remove this wax, cars are washed using a Waraku rim bar. Furthermore, when refilling a fuel tank of a vehicle with fuel such as gasoline, the fuel may spill.

[Problems to be Solved by the Invention] The above-mentioned conventional resin-based paints and rubber-based paints have problems in that they have poor adhesion to adherends and the resulting coating films have poor abrasion resistance.

Further, the methods of providing a chloroprene rubber coating or a silicon coating layer on the weather strip still have the problem of poor abrasion resistance.

Furthermore, if the wax remover is used to wash the car or fuel is spilled, the wax remover or fuel may get on the double-sided adhesive tape, and between the double-sided adhesive tape and the molding, and between the double-sided adhesive tape and the body. There was a problem in that the adhesive strength of the material decreased.

An object of the present invention is to solve the above-mentioned problems and to provide an adhesive composition whose resulting film has excellent abrasion resistance and good adhesion to adherends.

[Means for Solving the Problems] In order to achieve the above object, the present invention provides an isocyanate group or 0.0 parts by weight of halogenating agent per 100 parts by weight of polyurethane having hydroxyl groups
02 to 20 parts by weight is used.

[Detailed Description of Means] The polyester diols used in the present invention include ethylene glycol, propylene glycol, butanediol-1,4, butanediol-1°3, butanediol-2,3, diethylene glycol, dipropylene glycol, Triethylene glycol, pentanediol 1
．． 5. One type or mixture of two or more diols such as hexanediol-1,6 and neopentyl glycol, and one type of carboxylic acid such as succinic acid, adipic acid, azelaic acid, sebacic acid, phthalic acid, and isophthalic acid. Alternatively, those synthesized by reacting a mixture of two or more types are used.

As the polyether diol, polyoxypropylene glycol (PPG), polyoxyethylene glycol, polytetramethylene oxide glycol, etc. are used.

These polyester diols and polyether diols are used in combination. The mixing ratio of the polyester diol and the polyether diol can be set at an appropriate ratio over a wide range.

The diisocyanates include 2.4-) lylene diisocyanate, 65/35 (ratio of (2,4-) lylene diisocyanate and 2.6-) lylene diisocyanate, the same applies hereinafter) tolylene diisocyanate, 80/20) lylene diisocyanate, 4.4'-diphenylmethane diisocyanate (MDI>, dianisidine diisocyanate, tridene diisocyanate, hexamethylene diisocyanate, metaxylene diisocyanate, 1°5
- Naphthalene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated 2,4-tolylene diisocyanate, hydrogenated 65/35) lylene diisocyanate, hydrogenated 80/2
0) Lylene diisocyanate, isophorone diisocyanate, etc. are used.

This diisocyanate is reacted with the mixture of the polyester diol and polyether diol. At that time, the ratio of the above mixture and diisocyanate used is hydroxyl group (-0H): isocyanate group (-
The molar ratio of N2CO) is preferably in the range of 1:2 to 10. If the -NCO ratio is less than 2, the resulting polyurethane itself becomes too soft and is likely to be unsuitable as a paint; if the -NCO ratio exceeds 1O, the polyurethane itself becomes too hard and brittle, making it unsuitable for use as a paint. likely to be inappropriate.

Examples of low molecular weight diols include ethylene glycol, propylene glycol, butanediol-1°4, butanediol-1,3, butanediol-2,3, diethylene glycol, dipropylene glycol, triethylene glycol, bentanediol-1,5, One type or a mixture of two or more of hexanediol-1,6, neopentyl glycol, etc. is used.

This low molecular weight diol is added to the reaction product of the mixture of polyester diol and polyether diol and diisocyanate. When the usage ratio is high, the ratio of 10H becomes higher than the ratio of -NCO, producing polyurethane with terminal -0H, and when it is less, the ratio of -NCO becomes relatively higher.
The proportion of GO is greater than the proportion of -OH, and the terminal -NCO
Polyurethane is produced, but any one can be used, so it is set as appropriate depending on the purpose of use.

Isocyanate i or a polyurethane having a hydroxyl group can be obtained by first reacting a mixture of a polyester diol and a polyether diol with a diisocyanate, and then reacting the reaction product with the low molecular weight diol, as described above.

At this time, a solvent may be used if desired. Examples of the solvent include n-hexane, cyclohexane, benzene, toluene, xylene, ethylbenzene, athene, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, tetrahydrofuran, methyl acetate, ethyl acetate, isopropyl acetate, isobutyl acetate, methylene chloride, 1. 1.1-) Lichloroethane, dimethylsulfoxide, dimethylformamide (DMF), and the like.

As a halogenating agent, N-promsuccinimide (N
BSI), acid imide halogen compounds such as N-bromphthalimide, trichloroisocyanuric acid 71 (TCIA
), isocyanuric acid halides such as dichloroisocyanuric acid, halogenated hydantoins such as dichlorodimethylhydantoin, alkyl hypohalides, etc. are used.

The above-mentioned alkyl hypohalide is normal, secondary or tertiary alkyl hypohalide, particularly stable tertiary alkyl chloride or bromide, i.e. tertiary butyl hypochloride (t-BHC),
Tertiary butyl hypobromide, tertiary amyl hypobromide and the like are preferred, and further halogen-substituted alkyl hypochlorides such as dichloro, trichloro or fluoromethyl hypochloride can also be used.

The halogenating agent is blended in an amount of 0.002 to 20 parts by weight based on 100 parts by weight of the polyushituff.

If the blending ratio is less than 2 parts by weight of O, OO, the degree of chlorination is small, so there is little improvement in adhesion, and if it exceeds 20 parts by weight, the stability of the coating composition becomes poor.

[Function] By adopting the above structure, the rigidity etc. of a high molecular weight polyurethane having a specific structure obtained by reacting a low molecular weight diol with a reaction product of a mixture of a polyester diol and a polyether diol and a diisocyanate, etc. This property improves the abrasion resistance of the resulting coating, and in particular, the halogenating agent halogenates the adhesive composition and halogenates the adherend, thereby improving the mutual bonding strength of the coating. The adhesion between the material and the adherend is improved.

[Examples 1 to 6 and Comparative Examples 1 to 10] Examples in which the present invention was embodied in a coating composition will be described below.

First, the object to be coated is a vulcanized product as shown below.

That is, the vulcanizate contains 0 parts by weight of EPDMI O (hereinafter simply referred to as parts), 70 parts of carbon black, 35 parts of mineral oil, 7 parts of zinc oxide, 2 parts of stearic acid, 2 parts of vulcanization accelerator, and 1.5 parts of sulfur. The composition was vulcanized at 160°C for 30 minutes.

In addition, the wear resistance test was conducted by the following method, and the wear resistance was evaluated based on the amount of wear loss.

That is, worn wheel: H-22, load: 1 kg, worn rotation speed:
6Qrpm Sample size: 10,100 mm x 100 Number of wear: 1,000 times (Example 1) 120 parts of PPG (Molecular Standard 2000), 44 parts of polyethylene adipate (Molecular Standard 2000), MDI 100
A mixture of 1 part and 264 parts of trichlorethylene was heated at 80° C. for 3 hours in a stream of dry nitrogen.

Furthermore, 24.8 parts of 1,6-hexanediol, I)M
170 parts of F was added and heated for 80°C12O minutes in a stream of dry nitrogen. As a result, polyurethane was obtained.

For 100 parts of this polyurethane, 3 parts of carbon blank
0 parts, 100 parts of toluene, 40 parts of DMF, TCIAo,
002 parts were mixed to obtain a coating composition.

This coating composition was applied to the object to be coated and cured by heating at 100° C. for 2 minutes to prepare a test piece. This test piece was subjected to the abrasion resistance test described above. The results are shown in Table 1 below.

(Example 2) Polyurethane 100 prepared in the same manner as in Example 1 above
per part, 10 parts of carbon black, 80 parts of toluene,
A coating composition was obtained by blending 50 parts of DMF and 4 parts of NBSTo.

This coating composition was applied to the object to be coated and heated at 100° C. for 5 minutes to prepare a test piece. Regarding this test piece,
The abrasion resistance test was conducted. The results are shown in Table 1 below.

(Example 3) 140 parts of PPG (Molecular Standard 2000), 60 parts of polyethylene adipate (Molecular Standard 2000), MDI 100
After reacting 300 parts of trichlorethylene in the same manner as in Example 1, 1,6-hexanediol 24,2
and 246 parts of DMF were added and reacted in the same manner as in Example 1 to synthesize polyurethane.

For 100 parts of this polyurethane, 3 parts of carbon blank
0 parts, 100 parts of benzene, 50 parts of DMF, TCIAo,
A coating composition was prepared by blending 1 part.

This coating composition was applied to the object to be coated and heated at 100° C. for 5 minutes to prepare a test piece. Regarding this test piece,
The abrasion resistance test was conducted. The results are shown in Table 1 below.

(Example 4) 60 parts of PPG (molecular weight: 2000), 140 parts of PEBA (molecular weight: 2000), 100 parts of MDI, and 300 parts of trichlorethylene were mixed and reacted in the same manner as in Example 1 to obtain polyurethane.

A coating composition was prepared by blending 189 parts of 1,4-butanediol, 246 parts of DMF, and parts of TCIAIO with 100 parts of this polyurethane.

Using this coating composition, a test piece was prepared in the same manner as in Example 3 above. This test piece was subjected to the abrasion resistance test described above. The results are shown in Table 1 below.

(Example 5) 60 parts of PPG (2000 molecular weight), 140 parts of PBA (2000 molecular weight), 100 parts of MD I, and 300 parts of trichlorethylene were mixed and reacted in the same manner as in Example 1 to obtain polyurethane. Ta.

A coating composition was prepared by blending 12.2 parts of ethylene glycol, 300 parts of DMF, and 20 parts of TCIA with 100 parts of this polyurethane.

A test piece was prepared in the same manner as in Example 1 using this coating composition. This test piece was subjected to the abrasion resistance test described above. The results are shown in Table 1 below.

(Example 6) 140 copies of PPG (Molecular Compact 2000), P'E BA
(Molecular Approximately 2000), 100 parts of MDI, and 300 parts of trichlorethylene were mixed and reacted in the same manner as in Example 1 to obtain polyurethane.

A coating composition was prepared by blending 12.2 parts of ethylene glycol, 300 parts of DMF, and parts of TCIAIO with 100 parts of this polyurethane.

A test piece was prepared in the same manner as in Example 1 using this coating composition. This test piece was subjected to the abrasion resistance test described above. The results are shown in Table 1 below.

(Comparative Example 1) 100 parts of liquid polybutadiene (trade name: Idemitsu Seal AB-700W, manufactured by Idemitsu Petrochemical Industries, Ltd.) and parts of MDIIO were mixed to prepare a paint. This paint was applied to the object to be coated and cured at room temperature to prepare a test piece. This test piece was subjected to the abrasion resistance test described above. The results are shown in the table below.
Shown in 1.

(Comparative Example 2) 100 parts of liquid polybutadiene (trade name: Idemitsu Seal AB-100, manufactured by Idemitsu Petrochemical Industries Co., Ltd.), MD I 10
A paint was prepared by mixing the two parts. This paint was applied to the object to be coated and cured at room temperature to prepare a test piece. This test piece was subjected to the abrasion resistance test described above. The results are shown in Table 1 below.

(Comparative Example 3) A 70% solution of N-methoxymethylated nylon (trade name: Torezin M-20, manufactured by Teikoku Kagaku Sangyo Co., Ltd.) was applied to the coated object and cured at room temperature to prepare a test piece. This test piece was subjected to the abrasion resistance test described above. The results are shown in Table 1 below.

(Comparative Example 4) 100 parts of epoxy resin (trade name: Araldite PZ820, manufactured by Nippon Ciba Geigy Co., Ltd.), polyaminoamide (
Product name Hardener H2) 1 manufactured by Nippon Ciba Geigy Co., Ltd.
00 parts were mixed to prepare a paint. This paint was applied to the object to be coated and cured at room temperature to prepare a test piece. This test piece was subjected to the abrasion resistance test described above. The results are shown in Table 1 below.

(Comparative Example 5) 100 parts of epoxy resin (trade name: Araldite GY250, manufactured by Nippon Ciba Geigy Co., Ltd.), polyaminoamide (
Product name Hardener H2)3 manufactured by Nippon Ciba Geigy Co., Ltd.
0 parts were mixed to prepare a paint. This paint was applied to the object to be coated and cured at room temperature to prepare a test piece. This test piece was subjected to the abrasion resistance test described above. The results are shown in Table 1 below.

(Comparative Example 6) As a paint, a 74% toluene solution of chloroprene rubber (trade name: Bond G2, manufactured by Konishi Co., Ltd.) was applied to the object to be coated, and cured at room temperature to prepare a test piece. This test piece was subjected to the abrasion resistance test described above. The results are shown in Table 1 below.

(Comparative Example 7) SBR (trade name: Diabond 5010, manufactured by Nogawa Chemical Co., Ltd.) was applied to the coated object and cured at room temperature to prepare a test piece. This test piece was subjected to the abrasion resistance test described above. The results are shown in Table 1 below.

(Comparative Example 8) As a paint, an acrylic resin emulsion with a non-volatile content of 70% (trade name Diabond DA manufactured by Nogawa Chemical Co., Ltd.) was used.
-830A) was applied to the object to be coated and cured at room temperature to prepare a test piece. This test piece was subjected to the abrasion resistance test described above. The results are shown in Table 1 below.

(Comparative Example 9) As a paint, an acrylic-ethylene modified emulsion (manufactured by Sunstar Chemical Co., Ltd., trade name: Penguin Cemen 1-138) with a non-volatile content of 55% was applied to the object, cured at room temperature, and a test piece was prepared. Created.

This test piece was subjected to the abrasion resistance test described above.

The results are shown in Table 1 below.

(Comparative Example 10) As a paint, a polyurethane paint (trade name: Diabond DA700E, manufactured by Nogawa Chemical Co., Ltd.) was applied to the object to be coated and cured at room temperature to prepare a test piece. This test piece was subjected to the abrasion resistance test described above. The results are shown in Table 1 below.

Table 1 As can be seen from Table 1, the amount of wear of the test pieces coated with the paints of each comparative example was as large as 482 cm or more in 1000 wear tests using a wear wheel, whereas the amount of wear of the paints of the present invention was as large as 482 cm or more. The amount of abrasion of the test piece coated with the composition was very small, less than 28 cm, indicating excellent abrasion resistance. This is thought to be based on the properties such as rigidity of a high molecular weight polyurethane obtained by using a polyester diol and a polyether diol in combination and reacting a low molecular weight polyol as a chain extender.

In addition, the coating compositions of Examples 1 to 6 exhibited good adhesion to the object to be coated. This is thought to be because the halogenating agent halogenates the coating composition itself and also halogenates the object to be coated to improve mutual bonding strength.

[Examples 7 to 12 and Comparative Examples 11 and 12] Below,
An example in which the present invention is applied to a coating composition for use in automobile weather strips will be described.

The base material constituting the weather strip is usually polyolefin vulcanized rubber. Specific examples include EPDM, ethylene-propylene copolymer rubber (EPM), and the like.

Furthermore, it is also possible to use other rubber components blended in amounts that do not affect the properties of these copolymer rubbers, such as 1/2 part by weight or less of the polyolefin vulcanized rubber. Other rubber components include the above-mentioned NR, 5BRSNBR
1IR, CRXI IR, etc.

The above various vulcanized rubbers contain commonly used compounds such as vulcanizing agents, vulcanization accelerators, anti-aging agents, antioxidants, anti-ozonants, fillers, plasticizers, blowing agents, blowing aids, etc. is appropriately blended depending on the purpose.

Examples of the vulcanizing agent include sulfur, morpholine, disulfide, dicumyl peroxide, and the like.

Examples of the vulcanization accelerator include 2-mercaptobenzothiazole, zinc dimethyldithiocarbamate, and tetramethylthiuram disulfide.

As anti-aging agents, antioxidants, and ozone deterioration inhibitors,
Examples include phenyl-α-naphthylamine and 2,6-di-t-butyl-p-cresol.

Examples of the filler include carbon black, hydrated silicic acid, magnesium carbonate, and clay.

Examples of plasticizers include dioctyl sebacate and mineral oil.

As a blowing agent, N,N'-dinitrosopentamethylenetetramine, N,N'-dimethyl-N.

N'-dinitrosoterephthalamide, azodicarbonamide, azobisisobutyronitrile, benzenesulfonylhydrazide, p,p'-oxybis(benzenesulfonylhydrazide), toluenesulfonylhydrazide, and the like.

Examples of foaming aids include urea and salicylic acid.

Now, as a base material for a weather strip, an EPDM compound having the composition shown in Table 2 below was extruded and then vulcanized at 160 DEG C. for 30 minutes to produce a weather strip for an automobile. A test piece was prepared by coating the same weatherstrip with a coating composition according to each of the following examples.

Table-2 (Example 7) The coating composition of Example 1 above was used.

(Example 8) The coating composition of Example 2 above was used.

(Example 9) The coating composition of Example 3 above was used.

(Example 10) The coating composition of Example 4 above was used.

(Example 11) The coating composition of Example 5 above was used.

(Example 12) The coating composition of Example 6 above was used.

(Comparative Example 11) In Example 1, TCIA as the halogenating agent
Instead of using 0.002 parts of the same (2 parts of TCIA)
Five parts were used. A coating composition was otherwise prepared in the same manner as in Example 1.

(Comparative Example 12) In Example 2, NBSI as the halogenating agent
Instead of using 0.4 parts of the same <NBSt, 30 parts of the same <NBSt was used. A coating composition was otherwise prepared in the same manner as in Example 2.

Next, the test pieces obtained in Examples 7 to 12 and Comparative Examples 11 and 12 were subjected to an abrasion test using a Glass Edge abrasion tester, which is an improved version of the Gakushin II abrasion tester, under the following conditions. The results are shown in Table-3.

(Test conditions) Friction element Nigarasu (thickness 5 mm) Friction element cycle 260 times/min Friction element stroke near 0 mm (Test method) Normal wear: The base material is attached to the above testing machine, and the base material is rubbed against normal wear. Examine the abrasion properties of

○ in Table 3 indicates that the amount of wear is small and the wear resistance is good.

As can be seen from Table 3, in Comparative Examples 11 and 12, the coating composition itself gelled, whereas in Examples 7 to 1,
No. 2 can withstand abrasion of 50,000 times and has no problems with abrasion.

In addition, the weatherstrips treated with the coating compositions of Examples 7 to 12 were bent 180 degrees to examine their followability.

As a result, the flexibility and flexibility, which are the characteristics of the polyolefin vulcanized rubber used as the base material of the weatherstrip, were not impaired in any way and good followability was exhibited. It is believed that the above-mentioned good abrasion resistance and trackability are based on the characteristics of the high molecular weight polyurethane having the above-mentioned specific structure.

Therefore, the coating compositions of Examples 7 to 12 are weather-resistant.
Suitable as a coating composition for strips.

[Examples 13 to 18 and Comparative Examples 13 and 141 Next,
An example in which the present invention is embodied in an adhesive composition used for electrostatic flocking will be described.

On each of the following sides, electrostatic flocking was performed by applying the adhesive composition of each example below to the EPDM substrate (Examples 13 to 15), or the adhesive composition was glued onto the pile after electrostatic flocking. A test piece was prepared by applying the composition (Examples 16 to 18).

A wear resistance test was conducted on this test piece under the following conditions. The results are shown in Table 4 below.

(Test condition) Wear wheel: H-22, load: 5kg Wear rotation speed: 60 rpm Sample size: 10100mmX100 Wear count: 1000 times (Example 13) The composition described in Example 1 above was used.

(Example 14) The composition described in Example 2 above was used.

(Example 15) The composition described in Example 3 above was used.

(Example 16) The composition described in Example 4 above was used.

(Example 17) The composition described in Example 5 above was used.

(Example 18) The composition described in Example 6 above was used.

(Comparative Example 13) The composition described in Comparative Example 11 above was used.

(Comparative example 14) The composition described in Comparative Example 12 above was used.

Table 4 In Table 4, O in the column for number of wears indicates that the amount of wear was small and was good, and × indicates that there was a lot of wear and was poor.

As can be seen from Table 4, Comparative Examples 13 and 14 were all defective after 30,000 wear tests, whereas Examples 13 to 18 failed after 30,000 wear tests. Good durability and no wear problems.

This is believed to be based on the high molecular weight polyurethane having the specific structure described above.

Therefore, the adhesive compositions of Examples 13 to 18 are suitable as adhesive compositions for electrostatic flocking.

[Examples 19 to 24 and Comparative Examples 15 and 161 Next,
Examples of embodiments of adhesive compositions used in adhesive tapes will be described.

The following adhesive composition was used.

(Example 19) An adhesive composition was prepared by adding 0.002 parts of t-BHC as a halogenating agent to 100 parts of the polyurethane in Example 1.

(Example 20) 60 parts of PPG (molecule 9 about 1000), 22 parts of polyethylene butylene adipate (molecule 11000), MDI 1
A mixture of 0.00 parts and 264 parts of trichlorethylene was reacted at 80° C. for 3 hours in a stream of dry nitrogen.

Then, 24.8 parts of 1,6-hexanediol, DMF
170 parts were added thereto, and the reaction was carried out at 80° C. for 20 minutes in a stream of dry nitrogen to obtain polyurethane.

An adhesive composition was prepared by adding 0.4 parts of NBSI as a halogenating agent to 100 parts of this polyurethane.

(Example 21) 20 parts of TCIA as a halogenating agent was added to 100 parts of the polyurethane in Example 3 to prepare an adhesive composition.

(Example 22) An adhesive composition was prepared by adding 2 parts of t-BHC as a halogenating agent to 100 parts of the polyurethane in Example 4.

(Example 23) An adhesive composition was prepared by adding 0.4 parts of NBSI as a halogenating agent to 100 parts of the polyurethane in Example 5.

(Example 24) 20 parts of TCIA as a halogenating agent was added to 100 parts of the polyurethane in Example 6 to prepare an adhesive composition.

Next, using the adhesive compositions of the above Examples and Comparative Examples, the adhesive area and tensile shear strength were measured in the following manner.

8 times foamed polyethylene is used as the base material of the double-sided adhesive tape, and the above-mentioned double-sided adhesive tape is pasted on one side and adhered to the painted steel plate, and the other side is coated with an adhesive and the vinyl chloride is applied. A test piece was prepared by adhering it to a resin plate. The same test piece was immersed in gasoline or wax remover as a solvent for 1 hour. Then, the adhesive area and tensile shear strength were measured. The tensile shear strength was measured at a tensile speed of 30 mm/min. The results are shown in Table-5.

Table 5 In Table 5, in Comparative Examples 15 and 16, no adhesive composition was used. Further, G in the solvent (capital) represents gasoline, and W represents wax remover.

As seen from Table 5, in Comparative Examples 15 and 16, the adhesive area was 25% and the tensile shear strength was 1.5 kg/cn.
1, whereas in Examples 19 to 24, the adhesive area was 8
Sufficiently secured at 9-92%, and tensile shear strength is also 7.5-92%.
It shows a high strength of 8.0. This is thought to be because the halogenating agent halogenates the adhesive composition itself and polyethylene, which is the base material of the adhesive tape, to improve their mutual bonding strength.

Therefore, the adhesive compositions of Examples 19 to 24 are suitable for use as adhesive tapes for attaching moldings to the body of automobiles, or as adhesive tapes for use in chemical equipment where solvents may adhere. Ru.

[Effects of the Invention] The adhesive composition of the present invention has excellent effects in that the resulting film has excellent abrasion resistance and also has good adhesion to adherends.

Claims (1)

[Claims] 1. For 100 parts by weight of polyurethane having isocyanate groups or hydroxyl groups, which is obtained by reacting a low molecular weight diol with a reaction product of a mixture of polyester diol and polyether diol and diisocyanate,
An adhesive composition containing 0.002 to 20 parts by weight of a halogenating agent.