JPH0742404B2 - Adhesive liquid composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an adhesive liquid composition having adhesive force and useful as an adhesive, a paint, a waterproofing agent and the like.

[Prior Art] Conventionally, polyester polyol and polyoxyethylene-propylene polyol have been used as an adhesive useful for manufacturing a composite panel by bonding metal or metal or glass to a wood board or cloth such as plywood. There is known a composition in which a polyisocyanate compound and an organic silane compound are mixed in a mixture thereof with (Japanese Patent Laid-Open No. 59-113076).

However, these compositions have a drawback that they are inferior in peel adhesive strength, although they are almost satisfactory in tensile shear adhesive strength.

[Problems to be Solved by the Invention] It is an object of the present invention to provide an adhesive liquid composition which has excellent peel adhesion strength and is useful as an adhesive, a base material for paints and the like. is there.

[Means for Solving Problems] The present inventor has found that the combined use of zeolite is effective for improving the peel adhesion strength which is insufficient in an adhesive containing a hydroxyl group-containing liquid diene polymer and a polyisocyanate as an adhesive component. Based on this finding, the present invention has been completed.

That is, the present invention provides a liquid polymer composition comprising a hydroxyl group-containing liquid diene polymer, a polyisocyanate compound, an organic silane compound and zeolite.

As the hydroxyl group-containing liquid diene polymer used in the present invention, a liquid diene polymer having a hydroxyl group in the molecule or at the molecular end and having a number average molecular weight of 300 to 25,000, preferably 500 to 10,000 is used. Here, the hydroxyl group content is usually 0.1 to 1
It is 0 meq / g, preferably 0.3 to 7 meq / g.

Examples of these liquid diene-based polymers include diene polymers having 4 to 12 carbon atoms, diene copolymers, and copolymers of these diene monomers with α-olefin addition polymerizable monomers having 2 to 22 carbon atoms. There is. Specifically, butadiene homopolymer, isoprene homopolymer, butadiene-
Examples thereof include styrene copolymer, butadiene-isoprene copolymer, butadiene-acrylonitrile copolymer, butadiene-2-ethylhexyl acrylate copolymer, and butadiene-n-octadecyl acrylate copolymer. These liquid diene polymers can be produced, for example, by reacting a conjugated diene monomer in a liquid reaction medium in the presence of hydrogen peroxide with heating.

The polyisocyanate compound used in the present invention is 1
An organic compound having two or more isocyanate groups in the molecule, which has a reactive isocyanate group for the hydroxyl group of the hydroxyl group-containing liquid diene polymer.

Examples of such polyisocyanate compounds include ordinary aromatic, aliphatic and alicyclic compounds, for example, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate (MDI), liquid modified diphenylmethane diisocyanate. , Polymethylene polyphenyl isocyanate, xylylene diisocyanate, cyclohexyl diisocyanate, cyclohexane phenylene diisocyanate, naphthalene-1,5-diisocyanate, isopropylbenzene-2,4-diisocyanate, polypropylene glycol and tolylene diisocyanate addition reaction products, and the like,
Above all, MDI, liquid modified diphenylmethane diisocyanate, tolylene diisocyanate and the like can be preferably used.

The mixing ratio of the above-mentioned two components of the present invention is not particularly limited,
Usually, the molar ratio of the isocyanate group (NCO) of the polyisocyanate compound (NCO / OH) to the hydroxyl group (OH) of the hydroxyl group-containing liquid diene polymer is 0.2 to 25, preferably 0.5 to 15. If this molar ratio is out of the above range, curing becomes difficult, which is not preferable.

Examples of the organic silane compound used in the present invention include vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinyldimethylmethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxy. Silane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane and the like can be used.

In this case, the organic silane compound, relative to 100 parts by weight of the hydroxyl group-containing liquid diene polymer, 0.1 to 10 parts by weight, preferably
0.2 to 7 parts by weight can be used.

The organosilane compound is believed to function as an auxiliary agent for improving the adhesiveness.

Characteristic zeolites as additives to be added to the present invention include aluminosilicate, borosilicate, boroaluminosilicate, A-type zeolite, L-type, X-type, Y-type, and USY.
Type, ZSM type, etc. can be used. Either natural or synthetic zeolite can be preferably used.

In the present invention, the zeolite is 1 to 50 parts by weight, preferably 3 to 100 parts by weight of the hydroxyl group-containing liquid diene polymer.
~ 30 parts by weight can be used.

If desired, the composition of the present invention may contain a polyol compound, a polyamine compound, and other commonly used additives as a reinforcing agent.

As the polyol compound optionally added to the present invention, any type of primary polyol, secondary polyol, and tertiary polyol can be used. Specifically, for example, 1,2-propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-pentanediol, 2,3-pentane. Diol, 2,5-hexanediol,
2,4-hexanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, glycerin, N, N-
A low molecular weight polyol containing a hydroxyl group bonded to at least one secondary carbon, such as bis-2-hydroxypropylaniline, N, N'-bishydroxyisopropyl-2-methylpiperazine, and a propylene oxide adduct of bisphenyl A. Is mentioned.

Furthermore, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, etc., which do not have a hydroxyl group bonded to secondary carbon, may be used as the polyol. it can. A diol is usually used as the polyol,
Triol or tetraol may be used, and the molecular weight thereof is in the range of 50 to 500.

As the polyamine compound optionally added to the composition of the present invention, any of diamine, triamine and tetraamine can be used, and further, any of primary polyamine, secondary polyamine and tertiary polyamine can be used. You can As such a polyamine compound,
For example, aliphatic amines such as hexamethylenediamine, 3,
Aliphatic amines such as 3'-dimethyl-4,4'-diaminodicyclohexylmethane, aromatic amines such as 4,4'-diaminodiphenyl, 2,4,6-tri (dimethylaminomethyl)
Examples thereof include tetramine such as phenol.

When blending these polyol compounds and polyamine compounds, the blending ratio is not particularly limited, usually 1 to 10 polyol compound or polyamine compound to 100 parts by weight of the hydroxyl group-containing liquid diene polymer described above.
0 parts by weight, preferably 3 to 50 parts by weight can be added.

Other additives used in the composition of the present invention include fillers such as mica, graphite, flint, calcium carbonate, and slate powder.

In addition, a plasticizer such as dioctyl phthalate may be added as a viscosity modifier, or a softener such as aroma, naphthene, or paraffin oil may be added. Phenol resin, xylene formaldehyde resin,
It is also possible to add tackifying resins such as rosin, hydrogenated rosin, coumarone resins, aliphatic and aromatic petroleum resins.

Further, a curing accelerator such as dibutyltin dilaurate, stannous octoate, or polyethylenediamine may be added. Furthermore, an antiaging agent may be added to improve weather resistance, and a silicon compound or the like may be added as an antifoaming agent.

The composition of the present invention can be produced by blending and mixing the above raw materials. Usually, first of the above raw materials, preferably the raw materials excluding the polyisocyanate compound are blended, and the mixture is stirred and mixed at a temperature of 15 to 120 ° C, preferably 70 to 100 ° C for 5 to 240 minutes, preferably 30 to 180 minutes,
Then, a polyisocyanate compound is added to this mixture, and the mixture is stirred and mixed at 0 to 70 ° C., preferably 15 to 50 ° C. for 0.5 seconds to 180 minutes, preferably 1 second to 120 minutes to obtain a liquid composition.

In the compounding operation of the composition of the present invention, the order of adding the organic silane compound and the polyisocyanate compound is arbitrary.

The conditions for curing the composition of the present invention are not particularly limited, but the composition can be cured usually at a temperature of 0 to 120 ° C., preferably 15 to 70 ° C. for 1 to 72 hours.

[Advantages of the Invention] The adhesive liquid composition of the present invention has an advantage of exhibiting excellent 180 ° peel adhesive strength and tensile shear adhesive strength when it is used as an adhesive.

[Examples] The present invention will be described in more detail with reference to Examples.

The physical properties in each example were measured as follows.

(1) 180 ° peeling adhesive strength: Glass and cotton canvas were used as test bodies, and the samples were cured at 80 ° C. for 2 hours, and measured according to JIS-K-6854.

(2) Tensile shear adhesive strength: A steel sheet was used as a test body, and the one cured at 80 ° C. for 2 hours was measured according to JIS-K-6850.

Example 1, Comparative Example 1 Of the components shown in the table, other components except the polyisocyanate compound and the organic silane compound were blended in the amounts shown in the following table, and the mixture was stirred and mixed at a temperature of 80 ° C. for 1 hour. Add the polyisocyanate compound in the amount shown in the following table, and
The mixture was stirred and mixed at ℃ for 3 hours.

Next, add a predetermined amount of organosilane compound and add a temperature of 25 ° C.
The mixture was stirred and mixed for 30 minutes to prepare an adhesive liquid composition. The adhesive strength for this composition is shown in the following table.

Examples 2, 3, 4 and Comparative Example 2 Of the components shown in the table, the components excluding the polyisocyanate compound were stirred and mixed at a temperature of 80 ° C. for 1 hour, and then the polyisocyanate compound was added to the mixture at 1 ° C. at 25 ° C. An adhesive liquid composition was prepared by stirring and mixing for a minute.

The above results are shown in the following table.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09J 175/04 JFC JFE JFG C09K 3/10 DGZ

Claims (1)

[Claims] 1. An adhesive liquid composition comprising a hydroxyl group-containing liquid diene polymer, a polyisocyanate compound, an organic silane compound and zeolite.