JPH11349656A - Construction and architecture polyurethane composition and polyurethane coated film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a construction and architecture polyurethane composition which uses a curing catalyst safe from the standpoint of preservation of the environment and, simultaneously, inexpensive and, in addition, whose cured products can exhibit the properties as construction materials in accordance with the site applied at least to the same extent as with the conventional properties, and a construction and architecture polyurethane coated film having environmentally friendly and, at the same time, excellent properties. SOLUTION: In the construction and architecture polyurethane composition comprising a urethane prepolymer having isocyanate groups as the main agent and a polyol compound and a polyamine compound as the curing agents, a zinc salt of a carboxylic acid is incorporated as the curing catalyst. The polyurethane coated film contain 0.15 to 2.5 mmol zinc per 100 pts.wt. polyurethane resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to construction of concrete, mortar, cushioning flooring materials, interior wall paneling materials, and the like laid in laboratories, factories, tennis courts, gymnasiums, elastic walking paths, rooftops, parking lots, and the like. The present invention relates to a polyurethane composition for civil engineering and construction used as a filler for a base material, a surface flattening material, a primer, a top coat, and the like, and a polyurethane coating film for civil engineering and construction formed using the composition.

[0002]

BACKGROUND OF THE INVENTION Floors in laboratories, factories, tennis courts, gymnasiums, poolsides, athletics stadiums, walkways, parking lots and the like generally have concrete, mortar or cushion layers. A polyurethane floor is laid on the surface of the base material to fill and flatten the base, and the floor is provided with abrasion resistance, cushioning property, waterproofness, weather resistance and the like.

[0003] Polyurethane flooring is superior in abrasion resistance and elasticity to other flooring and is suitable for floors (particularly tennis courts, gymnasiums, etc.) where it is necessary to reduce the impact of exercise on the floor. Yes, solvent resistance, waterproofness, weather resistance, aesthetics, and the like can be imparted by appropriately devising the raw materials of polyurethane, and therefore, it is excellent as a coated floor material.

However, when the polyurethane composition is used as a building material such as a flooring material, not only does the cured product have the properties required according to the intended use such as the flooring material, but also the physical properties of the polyurethane composition at the time of application. This is important from the viewpoint of workability.
In other words, the pot life can be ensured without excessively high viscosity, and the time during which the same paint can be applied is long (hereinafter, the pot life and the time during which the coating process is sufficient are collectively referred to as "good workability"). And dry quickly at normal temperature (rapid curing).

[0005] A polyurethane composition for civil and architectural use, which is capable of ensuring quick-curing properties and workability while securing the physical properties of a cured product, includes a prepolymerized urethane prepolymer, an organic polyamine compound as a curing agent, and a curing catalyst as a curing catalyst. A device using an organometallic compound containing tin or lead has been conventionally known.

However, these are the pot life or the time from the first application to the point at which the painted surface can be corrected and overpainted (hereinafter, this time is referred to as the "time available for coating").
Is not enough, and improvement is desired from the viewpoint of workability. In addition, from the viewpoint of environmental protection in recent years, environmentally friendly materials have been demanded, and it has been required not to use lead. For this reason, a polyurethane composition using an environment-friendly curing catalyst without impairing the rapid curing properties, workability, and properties (particularly, elasticity, abrasion resistance, etc.) of the conventional polyurethane composition, that is, lead, There is a need for a new curing catalyst as a substitute for the contained compounds.

As a polyurethane composition containing no lead, a polyurethane composition containing a urethane prepolymer, an organic polyamine compound, a polyhydroxyl compound, an organic acid, and bismuth carboxylate is proposed in JP-A-4-65417. . This has been proposed as an improvement in the workability of a polyurethane composition using lead carboxylate as a curing catalyst, but bismuth carboxylate secures the physical properties of the cured product and does not contain lead. Therefore, it can satisfy environmental requirements.

However, bismuth carboxylate is expensive, and has not been widely used in polyurethane compositions for civil engineering and construction used in large quantities. In addition, when bismuth carboxylate is used as the catalyst, the trade-off tendency that the pot life and / or the coating process possible time is shortened and the workability is inferior when trying to shorten the curing time is stronger than in the case of lead carboxylate. It is not easy to set the composition of the polyurethane and the specification conditions.

Furthermore, organometallic salts such as iron, sodium, and zirconium, which are less likely to cause environmental problems, have insufficient catalytic functions for the curing reaction, and generally require a long curing time, and the physical properties of the cured product use a lead salt catalyst. Inferior than if you had. For this reason, the fact is that the mainstream of the curing catalyst is a lead salt.

The present invention has been made in view of such circumstances, and it is an object of the present invention to use an inexpensive curing catalyst which is safe from the viewpoint of environmental protection, and in which a cured product is used as a building material. It is an object of the present invention to provide a civil engineering / architectural polyurethane composition capable of exhibiting characteristics according to the place where it is to be carried out to the same extent or more, and a civil engineering / architectural polyurethane coating film which is environmentally friendly and has excellent physical properties.

[0011]

Means for Solving the Problems As a result of intensive studies on the metal salts of various organic acids, the present inventors have confirmed that the physical properties of the cured product are at least as high as those of the prior art, and are excellent in workability and rapid curability. The present inventors have found a curing catalyst that can be used as a lead salt substitute and completed the present invention.

That is, the polyurethane composition for civil and architectural use of the present invention is a polyurethane composition for civil and architectural use mainly comprising a urethane prepolymer having an isocyanate group and a curing agent comprising a polyol compound and a polyamine compound. And a zinc salt of a carboxylic acid.

The zinc salt is preferably a zinc salt of a saturated aliphatic carboxylic acid or an alicyclic carboxylic acid, and the zinc salt has a total content of the urethane prepolymer, the polyol compound and the polyamine compound of 10%.
It is preferable that the content is 0.15 to 2.5 mmol relative to 0 parts by weight. Further, it is preferable to contain an organic acid of the same type as an organic acid that does not form a salt.

The polyurethane coating for civil and architectural use of the present invention contains 0.15 zinc per 100 parts by weight of the polyurethane resin.
２．５2.5 mmol.

[0015]

DETAILED DESCRIPTION OF THE INVENTION The polyurethane composition for civil and architectural use of the present invention contains a urethane prepolymer having an isocyanate group as a main component, a polyol compound and a polyamine compound as a curing agent, and a zinc carboxylate as a curing catalyst. Is what you do.

The urethane prepolymer used as the main component is synthesized by reacting a polyol with a polyisocyanate.

The polyisocyanate compound used for the synthesis may be any compound having at least two isocyanate groups, such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, tolidine diisocyanate, naphthalene diisocyanate, and hexamethylene diisocyanate. (HDI), xylylene diisocyanate (XD
I), hydrogenated xylylene diisocyanate (H ₆ XD
I), isophorone diisocyanate (IPDI), tetramethylxylylene diisocyanate (TMXDI),
Hydrogenated diphenylmethane diisocyanate (H ₁₂ MDI)
Such aliphatic, alicyclic, aromatic, araliphatic diisocyanate compounds can be used alone or in combination of two or more,
What is necessary is just to select suitably according to the physical property required as a hardened | cured material. For example, when weather resistance is required, it is preferable to use a non-yellowing isocyanate (aliphatic or alicyclic isocyanate).

The polyol used for synthesizing the urethane prepolymer may be a low molecular weight compound or a high molecular weight compound as long as it has a plurality of hydroxyl groups. Examples of low-molecular polyols include, for example, ethylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 1,3-butanediol,
1,4-butanediol, neopentyl glycol,
Diols such as 1,6-hexanediol; glycerin,
And triols such as trimethylolpropane and hexanetriol. As a high molecular polyol,
Polyether polyol; Polyester polyol; Acrylic polyol; Phenol resin polyol; Epoxy polyol; Butadiene polyol;
Polyether polyols; acrylic derivatives, vinyl group-added polymer polyols such as styrene, and urea-dispersed polyols.

The above-mentioned polyether polyol can be obtained by reacting an initiator having an active hydrogen atom with an alkylene oxide, such as polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, ethylene oxide / propylene oxide copolymer. And a tetrahydrofuran / ethylene oxide copolymer and a tetrahydrofuran / propylene oxide copolymer.

The above polyester polyols include condensed polyester polyols obtained by dehydration condensation of dibasic acids such as adipic acid, glutaric acid, fumaric acid, terephthalic acid and glycol or triol; ε-caprolactam, α-methyl-ε- A lactone-based polyester polyol obtained by ring-opening polymerization of a lactam such as caprolactam; and a polycarbonate diol synthesized using a cyclic diol may be used. Examples of the condensed polyester polyol include polyethylene adipate, polydiethylene adipate, polytetramethylene adipate, polyneopentyl adipate, polyhexamethylene adipate, polymethylpentane adipate, polyhexamethylene dodecandioate, and the like. Examples of the lactone-based polyester polyol include poly-ε-caprolactone, poly-β-methyl-δ-valerolactone, and the like.

The above-mentioned acrylic polyol refers to an acrylic copolymer into which a hydroxyl group is appropriately introduced, and specifically, a methacrylic acid ester or the like constituting a hard segment, an acrylic acid or the like constituting a soft segment, or a β for introducing a hydroxyl group. -Hydroxyethyl methacrylate and the like.

The above polybutadiene polyol includes:
Butadiene having a hydroxyl group at a terminal and a copolymer thereof (styrene, acrylonitrile and the like are appropriately copolymerized), and a hydrogenated product thereof.

Further, a block copolymer or a graft copolymer of the above polyol, or an acrylic derivative such as (meth) acrylic acid or (meth) acrylic ester or a vinyl group-containing monomer such as styrene in the above polyol may be appropriately used as a copolymer component. And the polyols used as the above.

The polyols described above may be used alone for the synthesis of urethane prepolymer, or may be used alone.
More than one species may be used in combination.

The urethane prepolymer used in the composition of the present invention has an isocyanate group at a terminal.
OH / NC with the above isocyanate compound and polyol
It is obtained by mixing and reacting at a value of O of 1 or more, preferably 0.7 to 0.5, and has a weight average molecular weight of 100
It is preferably about 10,000 to 10,000, more preferably 5
It is about 00 to 5000.

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

The curing agent used in the polyurethane composition of the present invention is a polyol compound and a polyamine compound. The reason for using both a polyol and a polyamine is that while the polyamine alone improves the strength of the cured product, the elasticity,
This is because the flexibility is reduced, and in particular, when used for an elastic flooring material, the cushioning property of the floor substrate may be impaired. In addition, the price of the polyamine is 3 to the price of the polyol.
This is because it is five times larger, which causes an increase in cost. On the other hand, if only the polyol is used, the strength of the cured product tends to be insufficient, so that the abrasion resistance and the scratch resistance are reduced, and the characteristics as a floor material are particularly unsatisfactory.

Here, as the polyol used for the curing agent, the polyol used for synthesizing the urethane prepolymer used as the main component can be used. That is,
Any low molecular weight compound or high molecular weight compound may be used as long as it has a plurality of hydroxyl groups. Examples of low-molecular polyols include, for example, ethylene glycol, diethylene glycol, triethylene glycol, butylene glycol,
Diols such as 1,3-butanediol, 1,4-butanediol, neopentyl glycol, and 1,6-hexanediol; and triols such as glycerin, trimethylolpropane, and hexanetriol. As the high molecular polyol, polyether polyol; polyester polyol; acrylic polyol; phenol resin polyol; epoxy polyol; butadiene polyol; polycarbonate polyol;
Polyether polyols; acrylic derivatives, vinyl-added polymer polyols such as styrene, urea-dispersed polyols, and the like, may be used alone or in combination of two or more.

The polyamine used as a curing agent in the polyurethane composition of the present invention is 3,3'-dichloro-4,
4'-diaminodiphenylmethane (abbreviation: MOCA),
3,5-dimethylthio-2,4-toluenediamine,
3,5-dimethyl-2,6-toluenediamine, an initial condensate of o-chloroaniline with formaldehyde, 4,
Aromatic diamines such as 4'-methylenebis-o-chloroaniline; and aliphatic amines such as triethylenetetramine and hexamethylenediaminecarbamate.

In the composition of the present invention, the isocyanate group of the urethane prepolymer as the main ingredient reacts with the polyamine compound and the polyol as the curing agent, respectively, to form polyurethane. Here, the polyurethane referred to in the present specification is NHCO obtained by the reaction between NCO groups and OH groups.
In addition to O bonds, allohanates; polymers containing urea bonds and burette bonds formed by reaction with amines.

Although the content ratio of the polyol and the organic polyamine compound in the curing agent is not particularly limited, the strength of the cured product (abrasion resistance,
As the ratio of the polyol increases, the elasticity and the flexibility of the cured product tend to be improved. Therefore, the content ratio may be appropriately selected according to the physical properties required for the cured product.
The ratio is preferably from 0:10 to 100: 200, more preferably from 100: 20 to 100: 100, and still more preferably from 100: 40 to 100: 80.

The ratio between the main agent and the curing agent is such that the isocyanate does not remain excessively after the reaction, specifically, the hydroxyl group (OH) of the polyol compound of the curing agent and the amino group (NH ₂ ) of the polyamine compound. NCO / (OH + NH ₂ ), which is the ratio of the number of moles of isocyanate groups of the urethane prepolymer of the main agent to the total number of moles of
It is preferably 1.5, especially about 1.1. If an excess of isocyanate remains, foaming occurs, resulting in poor appearance and reduced physical properties (particularly abrasion resistance and breaking strength).
This is because it causes the like.

The curing catalyst used in the polyurethane composition of the present invention is a zinc salt of a carboxylic acid. The zinc salt not only can secure the physical properties of the cured product to at least the same level as the conventional lead salt or bismuth salt, but also can secure a sufficient pot life and a possible coating process time without impairing the rapid curing property, and This is because the cost is about 1/3 of that of the bismuth salt and does not cause an increase in the cost of the composition. on the other hand,
This is because other metal salts of organic acids which do not cause a significant increase in cost tend to have insufficient catalytic function for the curing reaction, have poor rapid curability, and have poor strength of the cured product.

The zinc salt of a carboxylic acid used in the present invention includes zinc heptanoate, zinc octylate, zinc perargonate, zinc caprate, zinc laurate, zinc myristate, zinc palmitate, zinc stearate and the like. Zinc salt of linear saturated aliphatic carboxylic acid having about 6 to 17 carbon atoms; Zinc salt of unsaturated aliphatic carboxylic acid such as oleic acid, linoleic acid, linolenic acid; alicyclic carboxylic acid such as naphthenic acid And zinc salts of The naphthenic acid is
Not limited to a single ring represented by _{C n H 2n-2 O 2} , C n H 2n-4 O 2
And three rings represented by C _n H _2n-6 O ₂ and the like.

These zinc salts can be used alone or in combination of two or more. Among the above zinc salts, a zinc salt of a linear saturated fatty acid carboxylic acid and a zinc salt of an alicyclic carboxylic acid are preferable since the pot life and the balance between the coating process possible time and the curing time are particularly excellent, and the most preferable is Is
It is zinc octylate.

The amount of the zinc salt to be added is 0.15 to 2.5 mmol of zinc based on 100 parts by weight of the total components of the coating film forming components, that is, the urethane prepolymer, the polyol compound and the polyamine compound. preferable.
More preferably, it is from 0.3 to 2.0 mmol, even more preferably from 0.4 to 1.9 mmol. 2.5 mmol
If the content exceeds 0.15 g, the reaction rate tends to be too high and the workability tends to be reduced. If the content is less than 0.15 mmol, the reaction is insufficiently accelerated, the curing is slowed, and the breaking strength and the solvent resistance are reduced.

The above-mentioned zinc salt may be used alone as a catalyst, but organic acids which do not form a salt, ie, heptanoic acid, octylic acid, perargonic acid, capric acid, lauric acid, myristic acid, palmitic acid , Stearic acid, etc., linear saturated aliphatic carboxylic acids having 6 or more carbon atoms; oleic acid, linoleic acid, unsaturated aliphatic carboxylic acids, such as linolenic acid; naphthenic acid, etc., alicyclic carboxylic acids, benzoic acid, etc. Aromatic carboxylic acids; preferably used in combination with at least one kind among substituted carboxylic acids such as thiocarboxylic acid and dithiocarboxylic acid, and particularly the straight-chain saturated aliphatic carboxylic acid having 6 or more carbon atoms and unsaturated fatty acid. It is preferable to use in combination with at least one of aromatic carboxylic acids and alicyclic carboxylic acids. This is because by using a salt and an organic acid which does not form a salt in combination, the curing speed is increased and the strength of the cured product is increased.

The organic acid used in combination may be the same or different from the organic acid constituting the zinc salt used in the curing catalyst, but is preferably the same. When the organic acid is used in combination, the amount of the carboxylic acid is not particularly limited, but is 0.05 to 5.0 mmol, more preferably 1.0 to 4.0, per 100 parts by weight of the total amount of the main agent and the curing agent.
mmol, more preferably 2.0-4.0 mmol.
If the amount of the organic acid is too large, the effect of increasing the strength is reduced, and the possible coating time is reduced.

The polyurethane composition for civil and architectural use of the present invention may further comprise a filler, a plasticizer, a stabilizer,
It may contain additives that can be generally contained in civil engineering and architectural coatings, such as antifoaming agents and tackifiers. Here, as the filler, calcium carbonate, carbon black, clay,
Examples include inorganic substances such as talc, titanium oxide, quicklime, and kaolin. Examples of the plasticizer include dioctyl phthalate (DOP), dibutyl phthalate (DBP), dilauryl phthalate (DLP), butylbenzyl phthalate (BBP), dioctyl adipate (DOA), diisodecyl adipate (DIDA), and trioctyl phosphate (TOP). ), Tris (chloroethyl) phosphate (TCEP), tris (chloropropyl) phosphate (TDCPP) and the like.

The polyurethane composition of the present invention is of a two-pack type comprising a main agent and a curing agent. The curing catalyst and the fillers and the like added as necessary may be contained in the main component, may be contained in the curing agent, or may be stored separately. Therefore, the polyurethane composition of the present invention is used by mixing a separately prepared base agent and a curing agent (and further a curing catalyst when a curing catalyst is stored separately) so as to have a predetermined ratio before application. I just need.

The application location of the polyurethane composition for civil and architectural use of the present invention is not particularly limited as long as it can utilize the properties of polyurethane such as abrasion resistance and elasticity.
Various building materials, such as an inner wall material, are mentioned. Further, the building material according to the present invention is not limited to a house, but also includes a floor material of a parking lot without a roof, a paved road surface, a walking road surface, and the like. This is because the polyurethane flooring material has an appropriate cushioning property, so that the walking feeling is good and the abrasion resistance is excellent. The civil engineering / architectural polyurethane composition of the present invention is a precoat for filling or flattening the floor base material applied to such a wide variety of places, a precoat for smoothing, an intermediate coat for adjusting the thickness of the floor material, It is preferably used for a top coat for finishing and the like.

Particularly suitable flooring materials include natural rubber (NR), styrene-butadiene rubber (SBR), nitrile rubber (NBR), ethylene-propylene-diene terpolymer (EPDM), chloroprene rubber (CR ),
Rubbers such as butyl rubber (IIR) and isoprene rubber (IR); rubber-like elastic bodies obtained by curing these rubber chips (for example, rubber chips obtained by pulverizing waste tires) with a urethane-based binder or the like; For the purpose of filling the ground material, flattening the surface, slipperiness, and abrasion resistance,
The polyurethane composition of the present invention is particularly preferably used.

The polyurethane coating of the present invention is obtained by curing the polyurethane composition of the present invention.
0.15 to 2.5 mmol of zinc is contained in 00 parts by weight. Such a polyurethane coating film may be used as any of a filling layer, a precoat layer, an intermediate layer, and a topcoat layer of a floor material.

The flooring using the polyurethane coating film of the present invention as a filling layer, a precoat layer, and an intermediate layer is excellent in cushioning property and waterproofness. Also, in the case of the flooring material used for the top coat layer, the coating film can be more excellent in abrasion resistance, solvent resistance and elasticity, and can follow the deformation of the underlying flooring material. It does not occur, and is environmentally safe because it does not contain lead.

[0045]

Embodiment [Evaluation Method] First, the evaluation method used in the embodiment will be described.

Workability Evaluation was made based on pot life and possible coating process time. Here, the pot life refers to a time during which the main agent and the curing agent are mixed, and the fluidity is maintained without causing gelation or curing, and the viscosity measured using a B-type viscometer is 50,000c.
It is expressed in time (minutes) until it becomes ps. It can be said that the longer the pot life is, the better the workability is.

The possible coating time is defined as the time from the first application of a paint obtained by mixing a main agent and a curing agent, after which the applied coating can be modified or overcoated on the coated surface. It is an index indicating the time to a certain point in time. The longer the possible coating process time, the longer the time for correcting the applied surface and the time for repeated coating, indicating that the workability is excellent.
3 hours or more was judged as a pass.

The specific measuring method of the coating process possible time is as follows:
A paint immediately after mixing the main agent and the curing agent is applied on a glass plate, and the metal pin is moved at a constant speed while the tip of the metal pin is in contact with the portion where the coating film is formed. The coating formed by the movement of the metal pins will cause damage, but in the initial coating after coating, the fluidity of the coating will repair the damage caused by the pins and return to a flat surface without damage. it can. On the other hand, since the fluidity of the coating film decreases with time after application, the coating film remains damaged by pins. Measure the distance from the point where the metal pin starts to move to the point where the metal pin starts to remain, and divide that distance by the moving speed of the metal pin. The time until it began to be calculated. The time was defined as a possible coating process time (unit: hours).

Fast Curability (Time) After coating, the time until curing when kept at 5 ° C.
It was measured by a dry line recorder. The shorter the curing time, the better the quick-curing property.

When the polyurethane composition is applied to a cushioning flooring material, the polyurethane composition is required to be able to follow a deformation based on the cushioning property of the cushioning flooring material as the base material. If the film cannot be followed, the coating film will peel off or the coating film will crack.

The substrate followability was evaluated based on tensile strength at break and elongation at break. The tensile strength at break (Tb) and the elongation at break (Eb) were measured according to JIS K6301.

[0052] Tb is as acceptable 20kgf / cm ² or more, was considered good 39kgf / cm ² or more. Also, Eb
Was 400% or more.

Solvent resistance: Dipped in toluene at 40 ° C. for 24 hours, and the volume (V
₀ ) and the volume after immersion (V ₁ ), the swelling ratio (%) (ΔV
= (V ₁ −V ₀ ) / V ₀ × 100). The smaller the value of the swelling ratio (ΔV) is, the more excellent the solvent resistance is.
0% or less was regarded as a pass.

[Formulation composition of polyurethane composition] The composition was as shown in Table 1 except for the curing catalyst. Here, as a main agent, a urethane prepolymer (TDI) obtained by mixing and reacting tolylene diisocyanate and polypropylene glycol so that the ratio of NCO / OH becomes 2.
/ PPG prepolymer).

As the curing agent, 3,3'-dichloro-
4,4'-Diaminodiphenylmethane (MOCA) and polypropylene glycol were used.

[0056]

[Table 1]

[Types of Metal Salts for Curing Catalyst] Polyurethane composition No. 1 using various organic metal salts as shown in Table 2 as curing catalysts. The workability, quick-curing property, base followability, and solvent resistance of Nos. 1 to 8 were measured. Table 2 shows the measurement results together with the composition.

The catalyst used was a mineral spirit solution having the following concentrations. The amount was such that the metal amount was 0.90 to 1.0 mmol per 100 parts by weight of the resin component. The amount of the catalyst shown in Table 2 indicates the amount (parts by weight) of the solution actually used, and the amount of the catalyst is the amount of the film-forming component (TDI / P
The amount (mmol) of the metal is shown with respect to 100 parts by weight of the PG polymer, MOCA, and polypropylene glycol (total amount of the PG polymer, MOCA, and polypropylene glycol) (hereinafter, the same applies to the table of this example).

Zinc octylate: a mineral spirit solution with a zinc content of 8% Lead octylate: a mineral spirit solution with a lead content of 38% Iron octylate: a mineral spirit solution with an iron content of 8% Manganese octylate: Mineral spirit solution with 8% manganese content ・ Zirconium octylate: Mineral spirit solution with 6% zirconium content ・ Bismuth octylate: Mineral spirit solution with 13% bismuth content ・ Dibutyltin dilaurate: 45% tin content ・ o-phenyl Phenol sodium: a solution of sodium o-phenylphenol having a sodium content of 1% in xylene / methyl ethyl ketone

[0060]

[Table 2]

From Table 2, it was found that only the metal salt of octylic acid satisfied the quick-curing property. However, even with metal salts of octylic acid, lead salts have poor workability (pot life) and solvent resistance, iron salts have poor solvent resistance and poor substrate tracking, and manganese salts have poor solvent resistance. Bismuth salt was inferior in workability (pot life and pot life), substrate followability, and solvent resistance.

Therefore, workability, quick curing, substrate followability,
Only the zinc salt of octylic acid satisfied both the solvent resistance and the solvent resistance.

[Types of Organic Acids Constituting Zinc Salts] Polyurethane compositions (Nos. 9 to 12) using metal salts of various organic acids as curing catalysts, and polyurethane compositions with different amounts of zinc octylate With respect to the product (Nos. 13 to 17), workability, rapid curing property, substrate followability, and solvent resistance were measured. Table 3 shows the measurement results. No. for reference. The result of No. 1 is also shown.

As for the pot life, No. 1 having a large zinc octylate content was used. Except for 17, all of them were more than 60 minutes and were at the pass level.

[0065]

[Table 3]

From Table 3, it can be seen that the salts of dithiocarboxylic acid and benzoic acid were inferior in quick-curing properties, and that the salt of dithiocarboxylic acid had an acceptable level of breaking strength, but not a satisfactory level. Therefore, it is understood that saturated aliphatic carboxylic acids and alicyclic carboxylic acids are suitable as the zinc salt.

No. From 13 to 17, from the viewpoint of using zinc octylate as a catalyst, in order to satisfy the fast-curing property and the properties of the cured product, the amount of zinc per 100 parts by weight of the film-forming component is preferably 0.1 to 3.5 mmol. You can see that there is.

[Effect of Combined Use of Organic Acid] The amount of zinc is 0.96 m
mol of zinc octylate and octylic acid in the amount shown in Table 4 were used together. With regard to 18 to 20, the available time for the coating step, the rapid curing property, the base followability, and the solvent resistance were measured. Table 4 shows the measurement results. In addition, No. for reference. The result of No. 1 is also shown.

[0069]

[Table 4]

From Table 4, it can be seen that the use of octylic acid, which does not form a salt, slightly improves the quick-curing property and also improves the breaking strength of the cured product.

[0071]

EFFECT OF THE INVENTION The polyurethane composition for civil and architectural use of the present invention does not impair the physical properties of the cured product as compared with the conventional polyurethane composition for civil and architectural use, and also improves the workability during coating and the rapid curability. It is an environmentally friendly material that is excellent and does not use lead compounds without increasing costs. Therefore, the polyurethane composition of the present invention has the durability of a cured product,
For applications where workability during application and drying are important as well as strength, and applications where environmental safety is also important, for example, outdoors such as walking paths, rooftops, and parking lots; factories,
It is suitable as a paint in the field of civil engineering and construction, such as flooring indoors in laboratories and houses.

The polyurethane coating film of the present invention does not contain lead harmful to the human body and is excellent in the ability to follow the base material. Useful. It is also excellent in solvent resistance, so it is suitable for floor coatings in factories, laboratories and houses. Further, since the polyurethane coating film of the present invention is excellent in workability and workability in forming, it is convenient even when applied to a large area such as a floor of a factory or a laboratory.

Claims (5)

[Claims] 1. A polyurethane composition for civil engineering / architecture comprising a urethane prepolymer having an isocyanate group as a main component and a polyol compound and a polyamine compound as a curing agent, comprising a zinc salt of a carboxylic acid as a curing catalyst. And a polyurethane composition for civil engineering and construction. 2. The polyurethane composition for civil engineering and construction according to claim 1, wherein the zinc salt is a zinc salt of a saturated aliphatic carboxylic acid or an alicyclic carboxylic acid. 3. The zinc salt is added in an amount of 0.15 to 2.5 mmol per 100 parts by weight of the urethane prepolymer, the polyol compound and the polyamine compound in total.
The civil engineering / architectural polyurethane composition according to claim 1 or 2, wherein the polyurethane composition is contained in an amount of l. 4. The polyurethane composition for civil and architectural use according to claim 1, further comprising an organic acid which does not form a salt. 5. A polyurethane coating for civil and architectural use containing 0.15 to 2.5 mmol of zinc per 100 parts by weight of a polyurethane resin.