JPH04149270A - One-pack type moisture-curing polyurethane composition and its production - Google Patents

Abstract

PURPOSE:To obtain a composition having excellent storing stability and curing property giving a cured material having excellent mechanical properties and durability, comprising an organic isocyanate compound, an organic polyhydroxyl compound and a halide of alkaline earth metal. CONSTITUTION:(A) An organic isocyanate compound is mixed with (B) an organic polyhydroxyl compound and (C) a halide of alkaline earth metal to obtain the objective moisture-curing composition of one-pack type. Otherwise, an adduct of the component B and the component C is mixed with the component A. The component B having primary hydroxyl group as the hydroxyl group is used in said composition. Calcium chloride is used as the component C. In mixing the three components, a filler is added. Furthermore, the component A is mixed with a previously dehydrated adduct of the components C and B. An amount of the component C is preferably >=1.0mol to the hydroxyl group of the component B.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a moisture-curable polyurethane composition having excellent mechanical properties, durability, etc. after curing. More specifically, the present invention relates to a liquid-type moisture-curable polyurethane composition that is useful for adhesives, waterproof materials, sealing materials, lining materials, etc. and has excellent mechanical properties and durability after curing.

(Prior Art) Conventionally, moisture-curing polyurethane made of organic isocyanate compounds can be used as a one-component type by reacting with moisture in the atmosphere, so there is no need to mix two components, and the moisture-curing polyurethane is Because of its excellent adhesion, it is used in many fields such as adhesives, waterproofing materials, sealing materials, and lining materials.

However, with conventional moisture-curable polyurethane resins made of organic isocyanates, compositions with an excellent balance between resin storage stability and curability during use have not been obtained.

In other words, if a resin with good storage stability is not subjected to many restrictions on the usage conditions during curing, foaming, cracking, poor curing, etc. may occur, and the desired performance of the cured product may not be achieved. . Furthermore, resins that have good curing conditions during use often have a short pot life due to increased viscosity and separation of components during storage.

Conventionally, moisture-curable resins with free isocyanate groups,
It is known to mix alkaline earth metal halides as fillers in two-component systems.

However, in this case, if a liquid type is used, even if many restrictions are placed on the usage conditions during curing, foaming, cracking, poor curing, etc. may occur, and the desired performance of the cured product may not be achieved. There are many problems especially when used for on-site construction.

A two-component method of adding an organic polyhydroxyl compound as a crosslinking agent to an organic polyisocyanate compound is also commonly used.

However, in this case - if it is made into a liquid type, the viscosity will increase,
There is a problem in that the composition cannot withstand long-term storage.

(Problems to be Solved by the Invention) An object of the present invention is to provide a one-component moisture-curable composition having free isocyanate groups that maintains good storage stability and curability.

(Means for Solving the Problems) The present inventors have conducted intensive research to solve the above problems, and as a result, have completed the present invention.

That is, the present invention is a moisture-curable polyurethane composition comprising an organic isocyanate compound (A), an organic polyhydroxyl compound (B), and an alkaline earth metal halide (C), and an organic polyhydrocyanate compound (B). and an alkaline earth metal halide (C), and an organic isocyanate compound (A), and an organic isocyanate (A).
This is a method for producing a moisture-curable polyurethane composition, characterized in that a filler is added when mixing an alkaline earth metal halide (C) with an organic polyhydroxyl compound (B).

The present invention is characterized by mixing an alkaline earth metal halide and an organic polyhydroxyl compound having two or more hydroxyl groups with an organic polyisocyanate compound having two or more free isocyanate groups, -i was prepared, and after storage over time, it exhibited good curability when applied in the air in the presence of moisture, and the molded sheet thereof had satisfactory performance.

The liquid-type moisture-curing composition of the present invention, which is a mixture of an organic polyisocyanate compound, an alkaline earth metal halide, and an organic polyhydroxyl compound, has no problems with curability or storage stability as described above, and can be used satisfactorily. It can withstand.

(Structure) The organic polyisocyanate compound (A>) of the present invention is a compound having two or more isocyanate groups, and is a prepolymer prepared by a conventional method using an organic polyisocyanate and an organic polyhydroxyl compound with an excess of isocyanate. and the organic polyisocyanate itself.

Specifically, the organic polyisocyanate (A) of the present invention includes 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, partially carbodiimidated diphenylmethane diisocyanate, polymethylene polyphenyl poly Isocyanate, toridine diisocyanate, naphthalene diisocyanate, phenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, aromatic diisocyanate such as cyclohexane diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate 1 Species or mixtures of two or more types may be mentioned.

The organic polyhydroxyl compound (B) of the present invention includes polyether polyols, polyester polyols, other polyols, and mixed polyols thereof. In this case, the hydroxyl group is preferably a -class hydroxyl group.

The polyether polyol includes one or more polyhydric alcohols such as ethylene glyfur, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, glucose, sorbitol, and sucrose, propylene oxide, ethylene oxide, Examples include polyols obtained by adding one or more types of butylene oxide, styrene oxide, etc., and polyoxytetramethylene polyols.

Polyester polyols include ethylene glyfur,
One or more of propylene glycol, butanediol, bentanediol, hexanediol, cyclohexane dimetatool, glycerin, trimethylolpropane or other low molecular weight polyols and glutaric acid,
Condensation polymers with one or more of adipic acid, pimelic acid, superric acid, sebacic acid, terephthalic acid, isophthalic acid, dimer acid, hydrogenated dimer acid, or other low-molecular-weight dicarboxylic acids or oligomer acids, and propionic acid. Examples include ring-opening polymers such as lactone, caprolactone, and valerolactone.

Other polyols include polycarbonate polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, acrylic polyols, and the like. Also, ethylene glycol, diethylene glycol,
Also included are low molecular weight polyols such as propylene glycol, dipropylene glycol, butanediol, bentanediol, hexanediol, cyclohexane dimetatool glycerin, trimethylolpropane, glucose, sorbitol, and sucrose.

Examples of the alkaline earth metal halide (C) of the present invention include calcium chloride, calcium bromide, magnesium chloride, and the like, with calcium chloride being particularly preferred.

Also, anhydrous substances are preferable, but 1°2, 4. Hexahydrates can also be used.

Next, a method for producing the moisture-curable polyurethane composition of the present invention will be explained.

The moisture-curable polyurethane composition of the present invention is obtained by mixing an organic isocyanate compound with an adduct of an alkaline earth metal halide and an organic polyhydroxyl compound that have been previously dehydrated.

An adduct of an alkaline earth metal halide and an organic polyhydroxyl compound can be made by mixing the two at room temperature. In this case, if the alkaline earth metal halide is anhydrous, there is no particular need for dehydration. It's better.

When the organic polyhydroxyl compound has a low molecular weight, the adduct will be solid, so the dehydration operation may be performed by mixing an inert solvent, plasticizer, process oil, etc. with the isocyanate group.

The amount of alkaline earth metal halide to be used in the organic polyhydrocysil compound is 0.25 mol or more based on the hydroxyl group of the organic polyhydroxyl compound, preferably 0.25 mol or more, but preferably 0.25 mol or more based on the hydroxyl group of the organic polyhydroxyl compound. The amount is most preferably 5 mol or more, more preferably 1.0 mol or more.

The upper limit for the use of alkaline earth metal halides is determined by the physical properties of the molded sheet depending on its intended use, but it is better not to exceed at least 50% of the polyurethane composition.

Adducts of alkaline earth metal halides and organic polyhydroxyl compounds can also be made in moisture-curable prepolymers having free isocyanate groups. That is, an anhydrous alkaline earth metal halide may be mixed in advance with the prepolymer, and a predetermined amount of the organic polyhydroxyl compound may be mixed therein. The amount of alkaline earth metal halide mixed into the organic polyisocyanate compound is 1.
If it is 0% or more, a predetermined amount of the organic polyhydroxyl compound may be mixed later, and a composition with no practical problems can be obtained.

Examples of the solvent of the present invention include toluene, xylene, turpentine, ethyl acetate, butyl acetate, methyl ethyl ketone, and cellosolve acetate.

Process oils are high-boiling point oils obtained through petroleum refining.

Examples of the plasticizer include dibutyl phthalate and dioctyl phthalate.

Examples of the thixotropic agent include polyvinyl chloride powder, finely powdered silica, and bentonite.

Examples of the filler include carbon black, calcium carbonate, talc, clay silica, and titanium oxide.

Examples of the stabilizer include antioxidants, ultraviolet absorbers, and the like.

Examples of the catalyst include tertiary amines and organometallic compounds.

(Examples) Next, examples will be shown, but the present invention is not limited only to these examples. "Parts" and "%" in the text are based on weight unless otherwise specified.

Comparative Example 1 Molecule fi320 was added to 120 parts of tolylene diisocyanate (a mixture of 2,4- and 2,6-isomers in a ratio of 80:20).
350 parts of polio bovine dipropylene glycol and molecules @
526 parts of 3000% polyoxypropylene triol were added and reacted at 85°C. Isocyanate content = 2.
At 65%, the product viscosity was 120 voids. This will be referred to as prepolymer A.

When this prepolymer A was stored at 50° C. for 10 hours, the viscosity was 130 voids.

Comparative Example 2 Add 10% anhydrous calcium chloride to Prepolymer A at room temperature
Mixed evenly. The viscosity was 160 boids. This will be referred to as prepolymer B.

When this prepolymer B was stored at 50° C. for 10 hours, the viscosity was 170 voids.

Comparative Example 3 10 parts of polyethylene glycol 400 (molecular weight = 400) was mixed with 100 parts of prepolymer A at room temperature. After one day at 20°C, it had become gelled.

Example 1 100 parts of prepolymer A were mixed with 20 parts of a solid obtained by reacting anhydrous calcium chloride and polyethylene glycol 400 in advance at room temperature in a ratio of 1=1.

The viscosity was 200 boids.

When this prepolymer was stored at 50° C. for 10 hours, the viscosity was 210 voids.

Example 2 110 parts of Prepolymer B were mixed with 10 parts of polyethylene glycol 400 at room temperature. The viscosity was 220 boids.

When this prepolymer was stored at 50°C for 10 hours, the viscosity was 240 voids.

Example 3 100 parts of prepolymer A were mixed with 20 parts of a solid material prepared by reacting anhydrous calcium bromide and polyethylene glycol 400 in a ratio of 1=1 at room temperature. The viscosity was 210 voices.

When this prepolymer was stored at 50° C. for 10 days, the viscosity was 230 voids.

Example 4 100 parts of prepolymer A were mixed with 20 parts of a solid obtained by reacting anhydrous magnesium chloride and polyethylene glycol 400 in a 1:1 ratio at room temperature.

The viscosity was 190 boids.

When this prepolymer was stored at 50° C. for 10 days, the viscosity was 230 voids.

Example 5 120 parts of the prepolymer of Example 1, 50 parts of dioctyl phthalate, and 100 m of calcium carbonate were mixed. The viscosity was 100 voids.

Example 6 The prepolymers of Comparative Examples 1 to 3 and Examples 1 to 5 were heated at 25°C.
Approximately 2m on a concrete board under conditions of 60% relative humidity.
Table 1 shows the results of coating with a thickness of m.

Table 1 *; Creation occurs **; Unmeasurable ***; Unmeasurable (Effect of the invention) The moisture-curable polyurethane composition of the present invention has excellent mechanical properties and durability after curing, so it can be used as an adhesive, waterproof, etc. It is useful for agents, sealants, lining materials, etc.

Claims (1)

[Scope of Claims] 1. A one-component moisture-curable polyurethane composition comprising an organic isocyanate compound (A), an organic polyhydroxyl compound (B), and an alkaline earth metal halide (C). 2. A one-component moisture-curable polyurethane composition comprising an adduct of an organic polyhydroxyl compound (B) and an alkaline earth metal halide (C), and an organic isocyanate compound (A). 3. Claim 1 or 2, characterized in that calcium chloride is used as the alkaline earth metal halide (C).
The one-component moisture-curable polyurethane composition described. 4. The moisture-curable polyurethane composition according to claim 1 or 2, wherein the hydroxyl group of the organic polyhydroxyl compound (B) is a primary hydroxyl group. 5. Organic isocyanate (A), organic polyhydroxyl compound (B), and alkaline earth metal halide (C)
A method for producing a one-component moisture-curable polyurethane composition, which comprises adding a filler when mixing the two components. 6. The method for producing a one-component moisture-curable polyurethane composition according to claim 5, characterized in that calcium chloride is used as the alkaline earth metal halide (C). 7. The method for producing a moisture-curable polyurethane composition according to claim 5, wherein the hydroxyl group of the organic polyhydroxyl compound (B) is a primary hydroxyl group.