JPH028633B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides at least one polyisocyanate and at least one active hydrogen compound having the general formula

[Formula] (wherein, R ₁ is an organic group having at least one -SH group in the molecule, and R ₂ is H or R ₁ or another organic group) (hereinafter referred to as P compound) ) A curable polyurethane adhesive composition. In general, polyurethane adhesives have poor adhesion to metals, so when using polyurethane adhesives to bond metals to each other or metals to other adherends, use a primer to adhere the metal to the metal before bonding. It is necessary to treat the surface. The use of a primer is useful as a means of improving adhesion to metals. However, on the other hand, the drawback is that the evaporation of the solvent in the primer solution causes environmental pollution, fire hazards, and health and safety issues for the human body. It is desired to improve the adhesion to. As a result of intensive research on this point, the inventor found that
The present inventors have discovered that by adding the P compound to the active hydrogen compound liquid of a polyurethane adhesive composition, the adhesion to metals can be easily and significantly improved, leading to the present invention. That is, according to the present invention, there is provided a curable polyurethane adhesive composition characterized in that the above-mentioned P compound is added to at least one polyisocyanate and at least one active hydrogen compound liquid. be done. Examples of the components used in the curable polyurethane adhesive composition of the present invention include: Examples of polyisocyanates include toluene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, hexamethylene diisocyanate, and derivatives thereof. Examples of active hydrogen compounds include (a) polyol;
For example, ethylene glycol, propylene glycol, glycerin, castor oil, and their derivatives such as polyether polyols and polyester polyols, (b) polyamines, such as aromatic polyamines such as ethylene diamine derivatives and methylene dianiline, and (c) polythiols. , for example 1,4
-butanediol, dimercaptoacetate, trimethylolpropane tris (mercaptoacetate), pentaerythritol tetrakis (mercaptoacetate), and the like. As an example of the P compound, for example, phosphoric acid and 2
- Reaction product with hydroxyethyl methacrylate (hereinafter referred to as PM) and thiol, for example, 1,4
-butanediol dimercaptoacetate (hereinafter
Examples include an adduct of PM and trimethylolpropane trismercaptopropionate (hereinafter referred to as TP) (hereinafter referred to as TP-PM), and the like. Examples of thiols used in the reaction include 1,4-
Butanediol dimercaptoacetate, trimethylolpropane tris (mercaptoacetate), dipentaerythritol hexa (mercaptoacetate), 1,4-butanediol mercaptopropionate, trimethylolpropane tris (mercaptopropionate), pentaerythritol tetrakis ( mercaptopropionate), dipentaerythritol hexa(mercaptopropionate), etc., but are not limited to these. The preferred content of the P compound in the curable polyurethane adhesive composition of the present invention is 0.1 to 20% by weight, particularly preferably 0.5 to 10% by weight. Further, a catalyst, a solvent, a plasticizer, a filler, a resin, etc. can be added to the polyurethane adhesive composition of the present invention, if necessary. According to the composition of the present invention, it is possible to bond metals to each other or to bond metals to other adherends, such as cloth, wood, plastic, etc., and a strong adhesive force can be obtained. Example 1 A polyurethane adhesive composition was prepared by stirring in a beaker at room temperature for 5 minutes at the blending ratios shown in Experiment Nos. 1 to 4 in Table 1 below (hereinafter referred to as preparation liquid). A portion of each prepared solution was taken and applied to two pieces of iron (JIS G314 SPCC-SB) with a thickness of 0.3 mm and adhered. After adhesion and curing for one week at room temperature, the T peel strength was measured at a temperature of 25°C, and the results are shown in Table 1.

【table】

[Table] Example 2 Polyurethane adhesive compositions were prepared using the formulations shown in Experiment Nos. 5 to 11 in Table 2 below (the content of the P compound was varied). A portion of each prepared solution was taken and bonded in the same manner as in Example 1, and the strength measurement results are shown in Table 2.

【table】

[Table] Example 3 A portion of the prepared liquids shown in Experiment Nos. 1 and 2 was taken and applied to various adhesives shown in Experiment Nos. 12 to 23 in Table 3 and adhered. After gluing and curing at room temperature for one week,
Bell peel strength was measured at a temperature of 25°C and the results are shown in Table 3.

[Table] From the above results, it can be seen that the curable polyurethane adhesive composition of the present invention is useful for bonding all kinds of metal materials.

Claims (1)

[Claims] 1 (A) at least one polyisocyanate,
and (B) in the at least one active hydrogen compound liquid, the following general formula [formula] (wherein R ₁ is an organic group having at least one -SH group in the molecule, R ₂
is H or R ₁ or other organic group. )
A curable polyurethane adhesive composition comprising a compound.