JP2997511B2 - Polyurethane composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial application field> The present invention relates to a construction speed which does not use a thermoforming mold and which cures at room temperature for use in construction sites such as flooring materials, waterproof coating materials, and sealing materials. The present invention relates to a curable polyurethane composition.

<Conventional technology> Polyurethane has excellent elasticity.
Widely used as flooring materials, waterproof coating materials, casting materials, sealing materials, etc. In such applications, not only monomers but also prepolymerized isocyanate compounds (urethane prepolymers) are usually used in order to meet the conditions at the construction site and to maintain the quality of the polyurethane after curing. ) As the main component, and the formulation is designed so that it is further cured and polymerized.

Among such polyurethane compositions, two-pack type polyurethane compositions are often used in fields where quick curing is required, and the formulation contains a urethane prepolymer, a curing agent and a curing catalyst. is there. Generally, an amine compound is used as a curing agent, and an organic acid or an organic metal compound containing Sn ⁴⁺ or Pb ²⁺ is used as a curing catalyst.

Among such two-pack type polyurethane compositions, a two-pack type polyeletan composition having the characteristics of being fast-curing and having a small adhesiveness on the surface of a cured product is provided by tolylene diisocyanate (TDI) and a polyhydroxyl compound. Urethane prepolymer (base agent) synthesized from 3,3'-dichloro-4,4'-diaminodiphenylmethane (abbreviation: MOCA)
Known are those containing a (curing agent), an organic acid (curing catalyst) and an organometallic compound (curing catalyst) containing Sn ⁴⁺ or Pb ²⁺ . However, when the two-component polyurethane composition is formulated so as to obtain a cured product having sufficient hardness, the curing time is too fast, so that the working time (working time) cannot be sufficiently obtained.
When formulating a formulation with a sufficient pot life, the hardness of the cured product tends to be insufficient, and it is difficult to design a well-balanced formulation of the properties of the cured product, especially the hardness and the pot life. .

<Problems to be Solved by the Invention> The present invention is a curing method which is fast-curing but has a sufficient pot life, has sufficient hardness after curing, and has low surface tackiness. It is an object of the present invention to provide a two-component polyurethane composition which gives a product.

<Means for Solving the Problems> The present invention comprises a urethane prepolymer having an isocyanate group at a terminal, an organic polyamine compound, a polyhydroxyl compound, an organic acid and a bismuth carboxylate compound. It is an object of the present invention to provide a polyurethane composition for construction which does not use a thermoforming die and which is characterized by containing a specific amount of a rate compound and curing at room temperature.

 Hereinafter, the present invention will be described in detail.

In the present invention, the main agent is a urethane prepolymer having an isocyanate group at a terminal. This urethane prepolymer has an isocyanate group at a terminal among reaction products of a polyhydroxyl compound and a polyisocyanate compound.

The urethane prepolymer having an isocyanate group at the terminal used in the present invention may be any one as long as it is generally used in a two-pack type polyurethane composition, and is not particularly limited.

Examples of the polyhydroxyl compound which is one of the raw materials for producing the urethane prepolymer include various polyether polyols, polyester polyols and polymer polyols generally used for producing urethane compounds.

The polyether polyol, for example, ethylene oxide, propylene oxide, butylene oxide,
A product obtained by addition polymerization of one or more alkylene oxides such as tetrahydrofuran to a compound having two or more active hydrogens. Here, examples of the compound having two or more active hydrogens include polyhydric alcohols, amines, alkanolamines, and polyhydric phenols. Examples of the polyhydric alcohols include ethylene glycol and propylene glycol. , Butanediol, diethylene glycol, glycerin, hexanetriol, trimethylolpropane, pentaerythritol and the like; amines such as ethylenediamine and hexamethylenediamine; alkanolamines such as ethanolamine and propanolamine; Examples of polyhydric phenols include resorcinol and bisphenols.

The polyester polyol is a condensate of a polyhydric alcohol and a polybasic carboxylic acid, a condensate of a hydroxycarboxylic acid and a polyhydric alcohol, a polymer of lactone, and the like. , The compounds exemplified above in the section of the polyether polyol,
Examples of polybasic carboxylic acids include adipic acid, glutaric acid, azelaic acid, fumaric acid, maleic acid,
Examples include phthalic acid, terephthalic acid, dimer acid, and pyromellitic acid.

Further, as a condensate of a hydroxycarboxylic acid and a polyhydric alcohol, castor oil, a reaction product of castor oil and ethylene glycol, a reaction product of castor oil and propylene glycol, and the like are also useful.

The lactone polymer is ε-caprolactam,
α-methyl-ε-caprolactam, ε-methyl-ε-caprolactam, etc., obtained by ring-opening polymerization with a suitable polymerization initiator.

The polymer polyol is, for example, a polymer obtained by graft-polymerizing an ethylenically unsaturated compound such as acrylonitrile, styrene, methyl (meth) acrylate, or the like to the polyether polyol or polyester polyol,
It refers to 1,2- or 1,4-polybutadiene polyol or a hydrogenated product thereof.

The above-mentioned thing is illustrated as a polyhydroxyl compound which is a production raw material of a urethane prepolymer, and although 1 type may be used alone or 2 or more types may be used together, weight average molecular weight 100-1
It is preferably about 0000, more preferably about 500 to 5,000.

Examples of the polyisocyanate compound which is the other raw material for producing the urethane prepolymer include various compounds used in the production of ordinary polyurethane resins. Specifically, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, phenylene diisocyanate, xylene diisocyanate, diphenylmethane-4,4'-diisocyanate, naphthylene-1,5-diisocyanate,
And hydrogenated compounds thereof, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 1-methyl-2,4-diisocyanate cyclohexane, 1-methyl-2,6-diisocyanate cyclohexane, dicyclohexylmethane diisocyanate And triphenylmethane triisocyanate.

These polyisocyanate compounds may be used alone or in combination of two or more.

In the production of the polyurethane prepolymer having a terminal isocyanate group, the ratio between the polyhydroxyl compound and the polyisocyanate compound is such that the number of hydroxyl groups in the polyhydroxyl compound is one or less per isocyanate group in the polyisocyanate compound. The ratio is preferably 0.70 to 0.50.

The production conditions of the urethane prepolymer are not particularly limited, and may be ordinary production conditions of the urethane prepolymer. That is, in the presence or absence of a catalyst, the reaction temperature
The reaction may be performed at about 50 to 100 ° C. under normal pressure.

In the present invention, the curing agent (crosslinking agent) is an organic polyamine compound and a polyhydroxyl compound.

As organic polyvalent amine compounds, 3,3′-dichloro-
4,4'-diaminodiphenylmethane (abbreviation: MOCA), o-
Examples include an initial condensate of chloroaniline and formaldehyde, triethylenetetramine, hexamethylenediaminecarbamate, 4,4'-methylenebis-o-chloroaniline and the like.

Examples of the polyhydroxyl compound include the polyhydroxyl compounds described above as one raw material for producing the urethane prepolymer.

In the present invention, the curing catalyst is an organic acid and a bismuth carboxylate compound.

The organic acid is considered to mainly catalyze the reaction between the urethane prepolymer and the organic polyamine compound.

Examples of the organic acid include saturated fatty acids such as 2-ethylhexanoic acid, octylic acid, and stearic acid; unsaturated fatty acids such as oleic acid, linoleic acid, and arachidonic acid; and aromatic carboxylic acids such as benzoic acid and phthalic acid. Has 8 carbon atoms
Most preferred are saturated fatty acids of ~ 12.

It is believed that the bismuth carboxylate compound mainly catalyzes the reaction between the urethane prepolymer and the polyhydroxyl compound.

Bismuth carboxylate compounds are represented by the general formula Bi (RC
OO) ₂ (R is an alkyl group), and bismuth octylate, bismuth neodecanoate, bismuth naphthenate and the like are usually useful. As its properties, liquids and the like are known.

As commercial products, COSCAT83 (manufactured by Cosan Chemical Co.) and the like are known.

The polyurethane composition of the present invention contains the above five components, and each of them may be used alone or in combination of two or more.

Although the content ratio of the above five components in the polyurethane composition of the present invention is not limited, the curing agent (organic polyamine compound and polyhydroxyl compound) is such that all of the terminal isocyanate groups of the urethane prepolymer are curing agents (organic polyamine). (A hydroxyl group of a polyamine compound or an amino group of a polyamine compound), and is preferably used in such an amount that an isocyanate group does not remain excessively after the reaction. If the isocyanate group remains excessively after the reaction, foaming is caused, resulting in poor appearance, reduced physical properties, and the like. The ratio between the amount of the organic polyamine compound and the amount of the polyhydroxyl compound may be appropriately selected depending on the properties required for the cured product.

Although the content of the curing catalyst depends on the content of the curing agent, the organic acid is based on 100 parts by weight of the urethane prepolymer.
0.5 × 10 ^{−3 to} 2.0 × 10 ⁻³ mol is preferable, and the bismuth carboxylate compound is the urethane prepolymer 10
It is preferably about 0.1 to 0.5 part by weight based on 0 part by weight. If it is outside this range, there will be disadvantages such as a decrease in curability and an insufficient working time.

In addition, the polyurethane composition of the present invention may further contain a filler, a plasticizer, a tackifier and the like within a range not to impair the purpose of the present invention.

Fillers include calcium carbonate, carbon black, clay, talc, titanium oxide, quicklime, kaolin,
Zeolite, diatomaceous earth, vinyl chloride paste resin, glass balloons, vinylidene chloride resin balloons, etc., can be used alone or in combination.

As the plasticizer, for example, dioctyl phthalate (DO
P), dibutyl phthalate (DBP), dilauryl phthalate (DLP), butyl benzyl phthalate (BBP), dioctyl adipate (DOA), diisodecyl adipate (DID)
A), trioctyl phosphate (TOP), tris (chloroethyl) phosphate (TCEP), tris (dichloropropyl) phosphate (TDCPP), propylene glycol adipate polyester, butylene glycol adipate polyester, alkyl epoxystearate, epoxidized large And soybean oil and the like, and can be used alone or in combination.

Examples of the tackifier include various titanate-based or silane-based coupling agents, reaction products of coupling agents with isocyanate compounds, and reaction products of two or more coupling agents (for example, reaction products of various aminosilanes and epoxysilanes). And a condensation reaction product of an alkoxy group of two or more coupling agents) and the like, and these can be used alone or as a mixture.

Since the polyurethane composition of the present invention is a two-pack type,
It is composed of a main agent liquid containing a urethane prepolymer having an isocyanate group at a terminal, which is a main agent, and a curing agent liquid containing an organic polyamine compound and a polyhydroxyl compound, which are curing agents. The organic acid and the bismuth carboxylate compound as the curing catalyst are usually contained in the base liquid or the curing agent liquid, but may be separately stored as the curing catalyst liquid depending on the case.

The method for producing the two-component polyurethane composition of the present invention is not particularly limited, but for each of the base liquid and the curing agent liquid,
The components are preferably kneaded sufficiently under reduced pressure and uniformly dispersed to form a composition. At the time of use, the main agent liquid and the curing agent liquid are measured at a predetermined ratio, mixed and used.

<Example> Hereinafter, the present invention will be specifically described with reference to examples.

(Examples) Polyurethane compositions having the formulations shown in Table 1 were produced, and the pot life, hardness, and surface tack of the cured product were measured and evaluated by the following methods.

 The results are shown in Table 1.

(1) Measurement of pot life After mixing the main agent liquid, curing agent liquid and curing catalyst liquid,
At 20 ° C., the viscosity was measured with a BH type viscometer, and the time required to reach 1000 poise was measured.

(2) Hardness After mixing the base solution, the curing agent solution, and the curing catalyst solution, curing was performed at 20 ° C. for 24 hours to obtain a sample. The hardness was measured using a JIS A spring hardness meter. Table 1 shows the 5-second values of the measurement.

(3) Surface Adhesion A sample was obtained in the same manner as in (2), and the presence or absence of surface adhesion was sensory evaluated. Those having no tackiness were indicated by ○, and those having no stickiness were indicated by ×.

As is clear from Table 1, in the case of a conventional polyurethane composition containing an organic acid and an organometallic compound containing Pb ²⁺ as a curing catalyst, a formulation design (Comparative Example 1) that allows a sufficient pot life can be obtained. However, the curing of the cured product was insufficient. On the other hand, when the formulation was designed to give a cured product having sufficient hardness (Comparative Example 2), the pot life was insufficient.

On the other hand, in the polyurethane composition of the present invention containing an organic acid and a bismuth carboxylate compound as a curing catalyst, a sufficient pot life can be secured, and a formulation design (a cured product having sufficient hardness) can be obtained. Invention Example 1,
2) was possible.

<Effect of the Invention> According to the present invention, a quick-curing, but sufficient pot life can be obtained, and after curing, a cured product having sufficient hardness and low surface tackiness is provided. A two-part polyurethane composition is provided.

Therefore, the workability at the time of applying the floor material, the waterproof coating material and the sealing material using the polyurethane composition is improved, and a high-quality product having sufficient hardness is provided.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-2-269725 (JP, A) JP-A-2-269726 (JP, A) JP-A-2-269727 (JP, A) JP-A-2-26972 269728 (JP, A) U.S. Pat. No. 4,742,090 (US, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 18/00-18/87 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] An organic acid containing a urethane prepolymer having an isocyanate group at a terminal, an organic polyamine compound, a polyhydroxyl compound, an organic acid and a bismuth carboxylate compound, and based on 100 parts by weight of the urethane prepolymer. 0.5 × 10 ^{−3 to} 2.0 × 10 ⁻³ mol, 0.1 to 0.5 part by weight of the bismuth carboxylate compound, and is cured even at room temperature.