JPH02102285A - Self-adhesive tape - Google Patents

Abstract

PURPOSE:To prepare a self-adhesive tape through which a solvent such as a fuel does not penetrate to an adhesive surface and which retains a sufficient adhesive strength, by compounding an isocyanate-terminated polyurethane with a specific amt. of a halogenating agent and applying the resulting compsn. to a base. CONSTITUTION:A polyol (e.g., polyoxypropylene glycol) is reacted with a polyisocyanate (e.g., 2,4-tolylene diisocyanate) to produce an isocyanate- terminated polyurethane. 100 pts.wt. resulting polyurethane is compounded with 0.002-20 pts.wt. halogenating agent (e.g., t-butyl hypochloride) to give a compsn., which is applied to a base to give a self-adhesive tape. The resulting self-adhesive tape is suitable for bonding a side protective molding to an automotive body.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an adhesive tape, for example, an adhesive tape for attaching a molding to an automobile body.

[Prior Art] Conventionally, side protixilane moldings attached to the side surfaces of automobile bodies are fixed using 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 wax remover.

Furthermore, when refilling a fuel tank of a vehicle with fuel such as gasoline, the fuel may spill.

[Problem to be Solved by the Invention 1] As mentioned above, when a car is washed with wax remover or fuel is spilled, the wax remover or fuel gets on the side of the double-sided adhesive tape and adheres to the rubber or resin base material. Double-sided adhesive may cause the base material to swell, or wax remover or fuel may penetrate between the double-sided adhesive tape and the body or between the double-sided adhesive tape and the molding, reducing the adhesive area. There was a problem in that the tensile shear strength and peel strength between the tape and the body and molding were reduced.

For example, use gasoline or wax remover at room temperature (23℃).
) for 1 hour, the adhesive area will change from 100% to 25%.
% and the tensile shear strength decreases from 8°8+r/cd to 1.5 kg/c+a.

The purpose of the present invention is to prevent solvents such as wax remover and fuel from penetrating between the adhesive tape and the body or between the adhesive tape and the molding, and to improve the tensile shear strength and peel strength of the adhesive tape. An object of the present invention is to provide an adhesive tape that has sufficient adhesive strength.

[Means for Solving the Problems] In order to achieve the above object, the adhesive tape of the present invention is a polyurethane having an isocyanate group obtained by reacting a polyol and a polyisocyanate, and a halogenating agent added to 100 parts by weight of the polyurethane. 0.002-20 for
A method is adopted in which a mixture of parts by weight is applied to the side surface.

In addition, the above polyurethane having an isocyanate group,
It is also suitable to apply a composition containing 0.002 to 20 parts by weight of a halogenating agent per 100 parts by weight of the polyurethane and a polyol to the side surface.

[Detailed Description of Means] First, the polyurethane used in the present invention will be described.

Examples of polyols include polyoxypropylene glycol, polyoxyethylene glycol, polytetramethylene oxide glycol, propylene oxide adduct of glycerin, propylene oxide adduct of trimethylolpropane, propylene oxide adduct of pentaerystol, polyethylene adipate, and polybutylene. Adipate, polyethylene butylene adipate, polydiethylene adipate, and adipate esters of 1,6-hexanediol or diethylene glycol are used.

As the polyisocyanate, 2,4-tolylene diisocyanate, 65/35 (ratio of (2,4-)lylene diisocyanate and 2,6-)lylene diisocyanate, the same applies hereinafter) tolylene diisocyanate, 80
/20 tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, dianisidine diisocyanate, tridene diisocyanate, hexamethylene diisocyanate, metaxine diisocyanate, 1,5 naphthalene diisocyanate, hydrogenated 4,4' diphenylmethane diisocyanate, hydrogenated xylene Diisocyanate, hydrogenated 2,4-tolylene diisocyanate, hydrogenated 65/
351-lylene diisocyanate, hydrogenated 80/20)
Lylene diisocyanate, isophorone diisocyanate, 4.4'4'' triphenylmethane triisocyanate, tris(P-isocyanate phenyl) thiophosphate, etc. are used.

Solvents that may be used as desired include n-hexane, cyclohexane, benzene, toluene, xylene, ethylbenzene, acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, tetrahydrofuran, methyl acetate, ethyl acetate, isopropyl acetate, isobutyl acetate, methylene. Chloride, l 1,1
Examples include -1-lychloroethane, dimethylsulfoxide, dimethylformamide, and the like.

The polyurethane having isocyanate groups is prepared, for example, as follows. First, the polyol, polyisocyanate, and necessary solvent are appropriately selected and mixed, and the mixture is heated at 50 to 130°C in dry nitrogen gas at 60 to 36°C.
Obtained by reacting for 0 minutes.

Next, the following ingredients are blended into this polyurethane.

As the halogenating agent, normal, secondary or tertiary alkyl hypohalides, particularly stable tertiary alkyl chlorides and bromides, are used. Specifically, tertiary butyl hypochloride (t-BHC),
Tertiary butyl hypobromide, tertiary amyl hypochloride, tertiary amyl hypobromide, etc. are particularly preferred, and halogen-substituted alkyl hypochlorides such as dichloro, trichloro, or fluoromethyl hypochloride may also be used. can.

Also, 100NX-bond in the molecule (X is halogen in the formula)
Examples include acid imide halogen compounds such as N-promsuccinimide (NBSI), N-bromphthalimide, and isocyanuric acid halides such as trichloroisocyanuric acid (TCIA) and dichloroisocyanuric acid. , halogenated hydantoin such as dichlorodimethylhydantoin, etc. are used.

The halogenating agent is blended in an amount of 0.002 to 20 parts by weight per 100 parts by weight of the polyurethane.

When the blending ratio is less than 0.002 parts by weight, the degree of halogenation is small, so that there is little improvement in adhesion, and when it exceeds 20 parts by weight, the stability of the composition deteriorates.

Further, the polyol used as a curing agent for the polyurethane is a low molecular weight polyol, and examples thereof include ethylene glycol, propylene glycol, butanediol, 1,4-butanediol, bentanediol, hexanediol, and heptanediol. , octanediol, diethylene glycol, triethylene glycol, dithioglycol, dipropylene glycol, neopentyl glycol, 2-ethyl-2-n-butyl1.
3-propanediol, 2.2.4-)dimethyl-1,
Examples include 3-bentanediol, triethanolamine, glycerin, trimethylolpropane, and the like.

The amount of the curing agent used is determined between the isocyanate group (-NGO) in the polyurethane and the hydroxyl group (-O
An appropriate amount is such that the molar ratio (-NCO/-0H) of H) is around 1.

Moreover, the above-mentioned solvent can also be blended if desired. The blending ratio of this solvent is 10 to 90 parts by weight in 100 parts by weight of the composition.
A range of parts by weight is preferred. If the blending ratio is less than 10 parts by weight, the solid content will be relatively high and the viscosity of the composition will increase, which tends to lead to a decrease in adhesion, whereas if it exceeds 90 parts by weight, the solid content will be low. This is not preferable because the film thickness of the composition becomes thinner and the adhesion is lowered.

In addition, the base materials for adhesive tapes include rubber, resin, paper,
Fibers etc. are used.

[Function] The adhesive tape to which the above-mentioned means of the present invention has been applied has a property that the adhesive tape and the automobile are bonded together by the action of the halogenating agent in the composition applied to the adhesive tape and the action of the isocyanate group of the polyurethane. This greatly improves the adhesion between the adhesive tape and the car body, and between the adhesive tape and the molding. Since it does not penetrate between the adhesive tape and the molding, a sufficient adhesive area of the adhesive tape is ensured and adhesive strength is maintained, and the base material of the adhesive tape does not swell.

Furthermore, when a polyol is blended into the polyurethane as a curing agent, the polyol extends the chain of the polyurethane two-dimensionally or three-dimensionally to improve solvent resistance.
The above effect is further promoted.

[Example] Next, an example embodying the present invention will be described in comparison with a comparative example. In addition, in each of the following, parts by weight are abbreviated as parts.

(Example 1) Polyoxypropylene glycol (number average molecular weight 20
00), 50 parts of 4,4'-diphenylmethane diisocyanate, and 50 parts of trichloroethylene were mixed and reacted at 80° C. for 3 hours in a dry nitrogen gas atmosphere to synthesize polyurethane. Thereafter, 0.02 parts of t-BHCo was added to 100 parts of the solid content of this polyurethane to obtain a composition.

(Example 2) Polyoxypropylene glycol (number average molecular weight 10
00), 50 parts by weight of 4,4'-diphenylmethane diisocyanate, and 70 parts of trichlorethylene were mixed and reacted in the same manner as in Example 1 to synthesize polyurethane. Thereafter, 1 part of TCIAo was added to 100 parts of the solid content of this polyurethane to obtain a composition.

(Example 3) Polyethylene adipate (number average molecular weight 2000) 2
00 parts of 4.4'-diphenylmethane diisocyanate and 50 parts of dimethylformamide were mixed and reacted in the same manner as in Example 1 to synthesize polyurethane. After that, TC was added to 100 parts of the solid content of this polyurethane.
A composition was obtained by adding part IAIO.

(Example 4) Polyethylene butylene adipate (number average molecular weight 10
00), 100 parts of 4,4'-diphenylmethane diisocyanate, and 100 parts of dimethylformamide were mixed, and a polyurethane was synthesized in the same manner as in Example 1. Thereafter, 20 parts of TCIA was added to 100 parts of the solid content of this polyurethane to obtain a composition.

(Example 5) Polypropylene glycol (number average molecular weight 2000)
200 parts of propylene glycol adduct of pentaerystol (number average molecular weight: 400), 150 parts of 4,4'-diphenylmethane diisocyanate, and 70 parts of trichlorethylene were mixed and reacted in the same manner as in Example 1 to produce polyurethane. Synthesized. Thereafter, 5 parts of NB was added to 100 parts of the solid content of this polyurethane to obtain a composition.

(Example 6) Polyoxypropylene glycol (number average molecular weight 20
00), 1.8 parts of 1,4-butanediol, 120 parts of tolylene diisocyanate, and 80 parts of trichlorethylene were mixed, and a polyurethane was synthesized in the same manner as in Example 1. Thereafter, 510.4 parts of NB was added to 100 parts of the solid content of this polyurethane to obtain a composition.

(Example 7) Polyethylene azelate (number average molecular weight 1000) 1
00 parts of hydrogenated 4,4'-diphenylmethane diisocyanate, 2.9 parts of ethylene glycol, and 50 parts of trichloroethylene were mixed to synthesize polyurethane in the same manner as in Example 1.

After that, N per 100 parts of solid content of this polyurethane was added.
A composition was obtained by adding 0 part of B511.

(Example 8) Polyethylene adipate (number average molecular weight 1000) 1
9.2 parts and 52°1 part of xylene diisocyanate
The mixture was reacted for 3 hours in dry nitrogen gas at 0°C, and then 4.4 parts of ethylene glycol was further added and reacted for 30 minutes in dry nitrogen gas at 80°C to synthesize polyurethane.

After that, NB was added to 100 parts of the solid content of this polyurethane.
A composition was obtained by adding 20 parts of SI.

Next, the composition obtained as described above was applied to the side surface of a double-sided pressure-sensitive adhesive tape, and the tape was left at room temperature for -1 week for testing.

Measurement of adhesive area and tensile shear strength: 8 times foamed polyethylene was used as the base material of the double-sided adhesive tape, and the above-mentioned double-sided adhesive tape was pasted on one side and adhered to a painted steel plate, and the other side was A test piece was prepared by applying adhesive to the surface and adhering it to a vinyl chloride resin plate. The same test piece
It was immersed for 1 hour in gasoline or wax remover as a solvent at room temperature of 3°C. Then, the adhesive area and tensile shear strength were measured. Tensile shear strength is tensile speed 3
The test was carried out under the condition of 0 mm/min. The results are shown in Table-1 and Table-2.

Table 1 Table 2 As Comparative Example 1, the above test was conducted using a general double-sided adhesive tape whose side surface was not coated with the composition of the present invention. As a result, whether gasoline or wax remover was used as the solvent, the adhesive area was 25% and the tensile shear strength was 1.5 kg/CIA.

As can be seen from Tables 1 and 2 above, in Comparative Example 1, the adhesive area was 25% and the tensile shear strength was 1.5 k.
g/ca, whereas in Examples 1 to 8 of the present invention, the adhesive area was 90% or more and the tensile shear strength was 8.1 kg/ca.
It is high, more than cJ. Therefore, the double-sided pressure-sensitive adhesive tape of this example maintains a sufficiently high adhesive force against solvents such as gasoline and wax remover.

This is because halogenating agents such as t-BHCSTCI A halogenate the foamed polyethylene foam as an adherend and the composition itself to improve adhesive strength, and the isocyanate groups of polyurethane made of polyol and polyisocyanate increase adhesive strength. It is estimated that this is to improve the

Therefore, even if a solvent such as gasoline or wax remover spills onto the molding, there will be no damage between the base material of the double-sided adhesive tape that fixes the molding and the molding, and between the base material of the double-sided adhesive tape and the body. The molding will not peel off from the body because no solvent will penetrate between the parts.

Next, an example using a polyol as a curing agent will be described.

(Example 9) To 100 parts of the solid content of the polyurethane obtained in Example 1, 6.2 parts of ethylene glycol was added as a curing agent. Additionally, 002 parts of t-BHCo was added as a halogenating agent to obtain a composition.

(Example 10) 7.6 parts of 1.3-propylene glycol was added as a curing agent to 100 parts of the solid content of the polyurethane obtained in Example 2.
Added a section. In addition, as a halogenating agent, TCIAo, 1
Added a section.

(Example 11) To 100 parts of the solid content of the polyurethane obtained in Example 3, 9.0 parts of 1,4-butanediol was added as a curing agent. Additionally, TCIAIO moiety was added as a halogenating agent.

(Example 12) To 100 parts of the solid content of the polyurethane obtained in Example 4, 35.5 parts of 1.6-hexanediol was added as a curing agent. Additionally, 20 parts of TCIA was added as a halogenating agent.

(Example 13) To 100 parts of the solid content of the polyurethane obtained in Example 5, 499 parts of polypropylene glycol (weight average molecular weight: about 1000) was added as a curing agent. Additionally, 0.4 parts of NB5l was added as a halogenating agent.

(Example 14) To 100 parts of the solid content of the polyurethane obtained in Example 6, 456 parts of polypropylene glycol (weight average molecular weight: about 800) was added as a curing agent. Further, 5 parts of NB51 was added as a halogenating agent.

(Example 15) To 100 parts of the solid content of the polyurethane obtained in Example 7, 9.5 parts of ethylene glycol was added as a curing agent. Additionally, 110 parts of NB was added as a halogenating agent.

(Example 16) To 100 parts of the solid content of the polyurethane obtained in Example 8, 16.8 parts of 1,4-butanediol was added as a curing agent. Additionally, 20 parts of NB5I was added as a halogenating agent.

Next, the composition obtained as described above was applied to the side surface of a double-sided adhesive tape, and the tape was left at room temperature for -1 week to be tested. Then, the adhesive area and tensile shear strength were measured in the same manner as in Examples 1 to 8 above. The results are shown in Tables 3 and 4.

As can be seen from Tables 3 and 4 above, in the comparative example described above, the adhesive area was 25% and the tensile shear strength was 1.
In contrast, in Examples 9 to 16 of the present invention, the adhesive area was 94% or more and the tensile shear strength was 8 kg/cta.
．． High at over 4 kg/ca. Therefore, the double-sided adhesive tape of this example maintains a sufficiently high adhesive force against solvents such as gasoline and wax remover.

This is because a composition in which polyurethane having isocyanate groups is blended with a polyol as a curing agent is chain-extended two-dimensionally and three-dimensionally by the polyol, increasing the molecular weight and improving solvent resistance. This is thought to be because the adhesive strength of this composition to the double-sided adhesive tape is improved by the action of the agent.

Therefore, even if a solvent such as gasoline or wax remover spills onto the molding, there will be no damage between the base material of the double-sided adhesive tape that fixes the molding and the molding, and between the base material of the double-sided adhesive tape and the body. The molding will not peel off from the body because no solvent will penetrate between the parts.

Note that the present invention is not limited to the above embodiments,
The gist of the invention can be modified as appropriate without evading tax, and for example, the invention can be constructed as follows.

That is, the adhesive tape of the present invention, in addition to the adhesive tape used for attaching the molding of an automobile to the body in the above embodiment, is also suitable for chemical equipment and kerosene to which solvents such as toluene and xylene may adhere. It is also used as an adhesive tape for use on potentially dangerous parts.

[Effect of the invention] In the adhesive tape of the present invention, solvents such as wax remover and fuel do not penetrate into the adhesive surface of the adhesive tape, and adhesive strength such as tensile shear strength and peel strength is sufficiently maintained. It has this excellent effect.

In addition, an adhesive tape coated with a composition containing polyurethane and polyol exhibits the above-mentioned effects even more effectively.

Claims (1)

[Claims] 1. A halogenating agent is added to a polyurethane having isocyanate groups obtained by reacting a polyol and a polyisocyanate at 0.002 parts by weight per 100 parts by weight of the polyurethane.
An adhesive tape made by applying a composition containing ~20 parts by weight to the side surface. 2. 0.002 parts by weight of a halogenating agent per 100 parts by weight of the polyurethane is added to a polyurethane having isocyanate groups obtained by reacting a polyol and a polyisocyanate.
An adhesive tape made by applying a composition containing ~20 parts by weight and a polyol to the side surface.