JPH02269753A - Adhesive composition - Google Patents

Abstract

PURPOSE:To obtain an adhesive composition which can exhibit a strong adhesiveness even to a difficultly bondable polymer by mixing a halogenated polyolefin with an oxide/amine adduct and a halogenating agent. CONSTITUTION:This adhesive composition is obtained by mixing 100 pts.wt. halogenated polyolefin (e.g. chlorinated polyethylene or chlorinated polypropylene) of a degree of halogenation of 5-50% with 0.001-50 pts.wt. oxide/ amine adduct (e.g. propylamine/ethylene oxide adduct) and 0.002-20 pts.wt. halogenating agent (e.g. t-butyl hypochlorite or isocyanuric trichloride). This adhesive composition can exhibit a strong adhesiveness even to a polymer molding comprising a difficultly bondable polyolefin such as PE, PP or EPM.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is applicable to side broaches on adherends such as automobile bodies. The present invention relates to an adhesive composition used for adhering other adherends such as molds (hereinafter referred to as molds).

Prior Art and Problems to be Solved by the Invention] Conventionally, polyethylene (PE), polypropylene (PP), poly-α-olefin, ethylene-propylene copolymer (
BACKGROUND ART Polymer molded bodies made of polyolefins such as EPM) and ethylene-propylene-Sheet 7a original copolymer (EPDM) are effectively used in various fields.

However, since polyolefin does not have a digging group in its molecule, there is a problem in that even if an adhesive is applied to the polymer molded product, the adhesive strength is insufficient.

Furthermore, if a molding made of polymer molded material such as polyvinyl chloride (PVC) having a polar group is used to form a molding that is attached to the body of a car, for example, this molding will change during the day and night, summer and winter, etc. Temperature differences can cause dimensional changes due to repeated contraction and expansion, and additives such as plasticizers and stabilizers can decompose over time, become low molecular weight, and come out of the mold, causing the mold to deteriorate. There is a problem in that adhesive strength to the car body decreases due to shrinkage.

Therefore, various adhesives that exhibit adhesion to general polymer molded objects have been proposed, but there are still no adhesives that have excellent adhesive properties for polymer molded objects such as those mentioned above. Not discovered.

An object of the present invention is to provide an adhesive composition that exhibits strong adhesion to polymer molded articles that are difficult to adhere to.

[Means for Solving the Problems] Therefore, in order to achieve the above object, the present invention provides 0.001 to 50 parts by weight of oxide-added amine and 100 parts by weight of halogenated polyolefin having a degree of halogenation of 5 to 60%. Halogenating agent 0. The gist thereof is an adhesive composition containing 2 to 20 parts by weight of OO.

[Detailed description of means] (a) Examples of the halogenated polyolefin include chlorinated polyethylene, chlorinated polypropylene, chlorinated ethylene-propylene copolymer, chlorinated ethylene-propylene-Che 7a original copolymer, and chlorosulfonated polyethylene. etc. are used. As this halogenated polyolefin, 5
Those having a degree of halogenation of ~60% are used. If the degree of halogenation is less than 5%, not only will the solubility in the solvent described below decrease and a good adhesive composition will not be obtained, but also the adhesion to the polymer molded article will not improve, and the degree of halogenation will be 60%. If it exceeds this amount, the resulting adhesive composition will become hard and the adhesion will not improve.

(b) Oxide-added amines are those obtained by adding oxides such as ethylene oxide, propylene oxide, butylene oxide to -class amines.
It is a bifunctional adduct having a hydroxyl group at the terminal, for example, the structural formula is (R20)nH / R, -N \ (R20)nH (R1: alkyl group having 1 to 18 carbon atoms, R2: alkylene group). expressed. When R2 in the above structural formula is an ethylene group, n is preferably 1 to 3.

The blending ratio of the oxide-added amine is 0.001 to 50 parts by weight per 100 parts by weight of the halogenated polyolefin. The blending ratio of this oxide-added amine is O
If the amount is less than 0.001 parts by weight, for example, when the adhesive composition is used as a primer for a urethane adhesive, the reaction between the isocyanate groups in the adhesive and the hydroxyl groups in the oxide-added amine will be poor, and if the adhesive composition is less than 50 parts by weight. If the amount exceeds 50%, the oxide-added amine becomes an impurity and the performance deteriorates.

(c) As a halogenating agent, an alkylhypochloride, for example, t-butylhypochloride (t-BHC)
, hypohalites and N-bromosuccinimide (NB
The most preferred halogenating agent is a compound having a -CONX- bond in the molecule (X means a halogen atom) such as SI), trichloroisocyanuric acid (TCIA), etc., but other halogenating agents include antimony pentafluoride, Examples include a mixed solution of sulfur fluoride and bromine, a mixed solution of iodine and potassium iodide, a mixed solution of halogen oxyacid and concentrated hydrochloric acid, and a mixed solution of alkali bromide and beroxonisulfuric acid.

The blending ratio of this halogenating agent is 0.002 to 20 parts by weight per 100 parts by weight of the halogenated polyolefin. If the blending ratio of the halogenating agent is less than 0,002 parts by weight, the surface of the polymer molded article cannot be sufficiently activated by the halogenating agent, and if it exceeds 20 parts by weight, the adhesive composition may gel. The effect will not be achieved.

Further, a solvent is used if necessary. Examples of this solvent include aliphatic hydrocarbons such as n-hexane and cyclohexane, aromatic hydrocarbons such as benzene, ethylbenzene, toluene, and xylene, ketones such as acetone, methyl ethyl ketone, ethyl propyl ketone, and methyl butyl ketone;
Ethers such as tetrahydrofuran, acetate esters such as methyl acetate, ethyl acetate, isopropyl acetate, halogenated hydrocarbons such as methylene chloride, 1,1,1-trichloroethane, trichloroethylene, dimethyl sulfoxide (DMSO), dimethyl formamide Single solvents or mixed solvents such as black are used.

[Function] When the adhesive composition is applied to a polymer molded article, the surface of the polymer molded article is halogenated by the halogenating agent,
It is presumed that the intermolecular force between the surface and the halogen in the halogenated polyolefin increases, thereby increasing the adhesion between the two.

Further, when the adhesive composition is used as a primer for a polyurethane adhesive having an isocyanate group, for example, the hydroxyl group in the oxide-added amine reacts with the isocyanate group, and the adhesive and the adhesive composition adhere to each other. do.

[Examples 1 to 7 and Comparative Examples 1 to 3] Examples 1 to 7 embodying the present invention will be described below as Comparative Examples 1 to 3.
This will be explained in comparison with In addition, each part represents a part by weight.

(1) Production of adhesive Polytriethylene glycol with an average molecular weight of 3000 (trifunctional polypropylene glycol with an average molecular weight of 3000)
For 300 parts, 1.2 parts of ethylene glycol and 4,
125 parts of 4'-diphenylmethane diisocyanate was mixed, and toluene:dimethylformamide=1:
Add 426 parts of a mixed solvent of 1 (weight ratio) and heat at 80°C.
A time reaction was carried out to obtain a polyurethane adhesive having isocyanate groups at the ends. After this adhesive was left at room temperature for one week, it was subjected to a test.

(2) Production of adhesive composition 100 halogenated polyolefins with different degrees of halogenation
Ten types of adhesive compositions of Examples 1 to 7 and Comparative Examples 1 to 3 were prepared by blending predetermined amounts of oxide-added amine and halogenating agent with respect to parts by weight (see Table 1). It was used as a primer for the adhesive.

Table-1 The abbreviations in Table 1 above have the following meanings.

In the grasping of oxide-added amines, BtA is ethylamine, PA is propylamine, IAA is isoamylamine, IPA is isopropylamine, PO is propylene oxide, EO is ethylene oxide, BO is butylene oxide, and n is the above-mentioned oxide-added amine. The value of n in the structural formula is shown.

(3) Preparation of test piece and measurement of tensile shear strength PVC and PE foam expanded five times were used as adherends.

This PVC contains 120 parts of dioctyl phthalate and 3 parts of epoxidized soybean oil per 100 parts of PVC with a degree of polymerization of 1900.
1 part and 4.5 parts of a stabilizer.

The adhesive composition shown in Table 1 was applied on the PE foam to a film thickness of 10.
After coating to a thickness of ~15 μm, the adhesive was coated thereon to a thickness of 80 to 100 μm. continue,
On top of the PE foam coated with the adhesive composition and adhesive, the PVC was laminated with an adhesive area of 25 x 25 m, and a test piece was prepared by applying a load of 5 kg for 1 minute. After leaving each test piece at 80°C for 10 minutes,
Tensile shear strength was measured subcutaneously at the same temperature at a tensile speed of 301 m/min. The measurement results are shown in Table-2.

Table 2 As can be seen from Table 2 above, in Comparative Example 2, where the proportion of the halogenating agent was as high as 30 parts per 100 parts of halogenated polyolefin, the adhesive composition gelled.

In addition, the degree of halogenation of the halogenated polyolefin is 5 to
In Comparative Example 1, which is outside the range of 60%, and Comparative Example 3, where the blending ratio of the oxide-added amine is outside the range of 0.001 to 50 parts per 100 parts of halogenated polyolefin,
The tensile shear strength was as low as 1.7 to 1.9 kg/-. On the other hand, in Examples 1 to 7, the tensile shear strength was 6.
．． It showed a high value of 8 to 7.3 kg/-.

The reason why the adhesive composition of each example exhibits high adhesive strength is that the surface of the PE foam to which the adhesive composition is applied is halogenated with a halogenating agent, and the bond between the surface and the halogen in the halogenated polyolefin is In addition to increasing the intermolecular force between the two and increasing the adhesion between the two, the hydroxyl group in the oxide-added amine reacts with the isocyanate group in the adhesive, causing the adhesive and adhesive composition to adhere to each other. It is thought that these synergistic effects improve the adhesion force to PE foam, which is difficult to adhere to.

Therefore, the adhesive composition of each example can be suitably used for adhering, for example, double-sided tape used when attaching moldings to the body of an automobile, other resin products, rubber products, and the like.

[Effects of the Invention] As detailed above, the adhesive composition of the present invention has an excellent effect of being able to exhibit strong adhesiveness even to polymer molded articles that are difficult to adhere to.

Claims (1)

[Claims] 1. 0.0 parts of oxide-added amine per 100 parts by weight of halogenated polyolefin with a degree of halogenation of 5 to 60%
An adhesive composition comprising 0.01 to 50 parts by weight of a halogenating agent and 0.002 to 20 parts by weight of a halogenating agent.