JP2006249274A - Two-liquid type polyurethane composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a two-liquid type polyurethane composition in which the reaction rate can be suppressed. <P>SOLUTION: The two liquid type polyurethane composition contains a main agent containing a urethane prepolymer, a curing agent and a retarder, which is contained in either one or both of the above main agent and the above curing agent. The above retarder for the two liquid type polyurethane composition contains at least one kind selected from the group consisting of N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazoridinone and dimethylsulfoxide, wherein the amount of at least one kind selected in the above is 0.5-10 pts.mass for 100 pts.mass of the component which is other than the one selected in the above. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a two-component polyurethane composition.

  In recent years, polyurethane coatings (urethane coatings) are excellent in adhesion, flexibility, weather resistance, etc., so in the field of civil engineering and construction, waterproof materials, coating materials, casting materials, sealing materials, adhesives Etc. are widely used. Of these polyurethane compositions for waterproofing, two-component polyurethane compositions are often used.

Examples of the two-component polyurethane waterproof material composition include a two-component room temperature curing waterproof material composition described in Patent Document 1. The two-component room temperature curable waterproof material composition described in Patent Document 1 is a main component mainly composed of an isocyanate-terminated urethane prepolymer obtained by a reaction between tolylene diisocyanate and a polyol, and a diamine compound having a toluenediamine structure. , A bifunctional polypropylene glycol having a molecular weight of 700 or less and a curing agent mainly composed of an acid catalyst, wherein the urethane prepolymer comprises tolylene diisocyanate and polyol in an equivalent ratio of NCO group / OH group = 1.5 to The urethane prepolymer has an NCO% of 1.5 to 6.0% by weight and a content of a diamine compound having a toluenediamine structure in the curing agent. to prepolymer in an equivalent ratio a NCO group / NH ₂ groups = 0.8 to 3.0, a molecular weight of 700 or less of 2 The content of the active polypropylene glycol is NCO group / OH group = 1.1 to 10.0 in an equivalent ratio with respect to the urethane prepolymer, and the content of the acid catalyst is 0.05 to 5% by weight of the curing agent. Is a two-component room temperature curable waterproofing material composition.

JP 2002-20727 A

  However, as a result of the study by the present inventors, when the two-component room temperature curable waterproof material composition described in Patent Document 1 is applied in a high temperature environment as in summer, the two-component room temperature curable waterproof material composition It has been found that there is a problem that the reaction rate of the product increases and the increase in viscosity cannot be suppressed. From this, the present inventor has found that there is room to improve the suppression of the reaction rate of the two-component room temperature curable waterproof material composition described in Patent Document 1.

  Examples of a method for suppressing the reaction rate of the conventional two-component polyurethane composition and delaying the reaction include a method using a blocked isocyanate compound in which an isocyanate group is blocked with a blocking agent. In this method, the reaction of the two-component polyurethane composition is suppressed until the blocking agent is dissociated from the blocked isocyanate compound. However, since the temperature at which the blocking agent dissociates from the blocked isocyanate compound is generally 100 ° C. or higher, and the two-component polyurethane composition needs to be heated to such a high temperature, the two-component type containing the blocked isocyanate compound Polyurethane compositions may not be practical.

  Accordingly, an object of the present invention is to provide a two-component polyurethane composition capable of suppressing the reaction rate.

As a result of intensive studies to achieve the above-mentioned problems, the present inventor has found that at least one selected from the group consisting of N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and dimethyl sulfoxide is 2 It has been found that the reaction rate of the liquid polyurethane composition can be suppressed, and the present invention has been completed.
That is, the present invention provides the following (1) to (3).

(1) A retarder for a two-component polyurethane composition containing at least one selected from the group consisting of N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and dimethyl sulfoxide.
(2) 2 containing a main agent containing a urethane prepolymer, a curing agent, and a retarder for a two-component polyurethane composition according to (1), which is contained in one or both of the main agent and the curing agent. A liquid polyurethane composition comprising:
The amount of at least one selected from the group consisting of the N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide is the N-methyl-2-pyrrolidone, 1,3-dimethyl. 2-component polyurethane composition which is 0.5-10 mass parts with respect to 100 mass parts of components other than the at least 1 sort (s) chosen from the group which consists of -2-imidazolidinone and a dimethylsulfoxide.
(3) A mixing step of adding a retarder for a two-component polyurethane composition as described in (1) above to a two-component polyurethane composition containing a main agent containing a urethane prepolymer and a curing agent to obtain a mixture When,
A construction method of a two-component polyurethane composition comprising a construction step of constructing the mixture.

  The two-component polyurethane composition of the present invention can suppress the reaction rate.

The present invention is described in detail below.
First, the retarder for a two-component polyurethane composition of the present invention will be described.
The retarder for a two-component polyurethane composition of the present invention contains two components containing at least one selected from the group consisting of N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and dimethyl sulfoxide. -Type polyurethane composition retarder.

  The retarder for a two-component polyurethane composition of the present invention suppresses the reaction rate of the two-component polyurethane composition and delays the reaction. Examples of the reaction of the two-component polyurethane composition include a reaction between an isocyanate group contained in the urethane prepolymer and a hydroxy group, an amino group, etc. contained in a curing agent (for example, a polyol compound or a polyamine compound). .

  N-methyl-2-pyrrolidone is a compound represented by the following formula (1).

  N-methyl-2-pyrrolidone is not particularly limited for its production. Moreover, a commercial item can be used. Examples of commercially available products include N-methyl-2-pyrrolidone manufactured by Mitsubishi Chemical Corporation.

  1,3-dimethyl-2-imidazolidinone is a compound represented by the following formula (2).

  1,3-dimethyl-2-imidazolidinone is not particularly limited for its production. Moreover, a commercial item can be used. Examples of commercially available products include dimethylimidazolidinone manufactured by Mitsui Chemicals, and 1,3-dimethyl-2-imidazolidinone manufactured by Kawaken Fine Chemicals.

Dimethyl sulfoxide is a compound represented by (CH ₃ ) ₂ S═O. Dimethyl sulfoxide is not particularly limited for its production. Moreover, a commercial item can be used.
N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and dimethyl sulfoxide can be used alone or in combination of two or more.

  The retarder for a two-component polyurethane composition of the present invention contains at least one selected from the group consisting of N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and dimethyl sulfoxide. If there is no particular limitation. If necessary, additives can be contained within a range that does not impair the object of the present invention.

  Examples of additives include fillers, curing catalysts (curing accelerators), latent curing agents, solvents, UV absorbers, dyes, pigments, flame retardants, reinforcing agents, adhesion-imparting agents, anti-aging agents, and antioxidants. Agents, thixotropic agents, surfactants (including leveling agents), dispersants, dehydrating agents, rust inhibitors, antistatic agents, and hollow spheres (balloons). An additive can be used individually or in combination of 2 types or more, respectively.

Examples of the solvent include mineral spirit, xylene, and methyl ethyl ketone. A solvent can be used individually or in combination of 2 types or more, respectively.
The amount of the solvent is preferably 1 to 99% by mass and more preferably 10 to 90% by mass in the retarder for the two-component polyurethane composition. In such a range, since the mixing property is excellent, the effect of making the two-component polyurethane composition uniform can be exhibited.

  When a solvent is used, at least one amount selected from the group consisting of N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and dimethyl sulfoxide is used for the two-component polyurethane composition. It is preferable that it is 1-99 mass% in a retarder, and it is more preferable that it is 10-90 mass%. In such a range, since the mixing property is excellent, the effect of making the two-component polyurethane composition uniform can be exhibited.

  The retarder for a two-component polyurethane composition of the present invention comprises at least one selected from the group consisting of N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and dimethyl sulfoxide, and an additive. When contained, the preparation is not particularly limited.

  The two-component polyurethane composition in which the retarder for the two-component polyurethane composition of the present invention is used is not particularly limited, and examples thereof include those containing a main agent containing a urethane prepolymer and a curing agent. Specific examples of the main agent and the curing agent will be described in the two-component polyurethane composition of the present invention.

  The method for using the retarder for a two-component polyurethane composition of the present invention is not particularly limited. For example, a method for containing the retardant for the two-component polyurethane composition of the present invention in the two-component polyurethane composition in advance, and the retardant for the two-component polyurethane composition of the present invention at the time of construction is a two-component polyurethane composition ( For example, a conventionally known method) is added to form a mixture, and the two-component polyurethane composition retarder of the present invention is previously contained in the two-component polyurethane composition, and the two-component type of the present invention is further added during construction. A method of adding a retarder for a polyurethane composition to a two-component polyurethane composition to form a mixture is exemplified.

  When the retarder for the two-component polyurethane composition of the present invention is previously contained in the two-component polyurethane composition, the retarder for the two-component polyurethane composition of the present invention is the main component and curing of the two-component polyurethane composition. It can be contained in one or both of the agents.

In addition, when the retarder for the two-component polyurethane composition of the present invention is previously contained in the two-component polyurethane composition, it is preferable to use a dehydrated retarder for the two-component polyurethane composition of the present invention. This is one aspect.
The method for dehydrating the retarder for the two-component polyurethane composition of the present invention is not particularly limited. For example, the retarder for the two-component polyurethane composition of the present invention is dehydrated using a desiccant such as a molecular sieve. A method is mentioned.

  It is mentioned as one of the preferred embodiments that the main agent contains a dehydrated two-component polyurethane composition retarder. In such a case, the amount of the dehydrated two-component polyurethane composition retarder is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the urethane prepolymer contained in the main agent. 5 mass parts is more preferable, and 1-3 mass parts is still more preferable. In such a range, the balance between suppression of reaction rate and curability is good and foaming is difficult.

  Moreover, it is mentioned as one of the preferable aspects that a dehydrating agent for a two-component polyurethane composition is contained in a curing agent from the viewpoint of storage stability.

  The amount of at least one selected from the group consisting of N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide is N-methyl-2-pyrrolidone, 1,3-dimethyl-2 -It is preferable that it is 0.5-10 mass parts with respect to 100 mass parts of components of 2 liquid type polyurethane compositions other than the at least 1 sort (s) chosen from the group which consists of imidazolidinone and dimethylsulfoxide, and 1-5 masses. Is more preferably 1 to 3 parts by mass. In such a range, the reaction rate of the two-component polyurethane composition can be more effectively suppressed, the curability is excellent, and foaming is difficult.

  The two-component polyurethane composition containing the retardant for the two-component polyurethane composition of the present invention and the mixture of the retardant for the two-component polyurethane composition of the present invention and the two-component polyurethane composition are usually the main component, By mixing the curing agent, the urethane prepolymer and the curing agent react and cure to form a cured product. At this time, the retarder for a two-component polyurethane composition of the present invention suppresses the reaction rate of the two-component polyurethane composition or mixture and delays the reaction. In particular, when the environment in which the two-component polyurethane composition or mixture is used is high or the temperature of the material used is high, the reaction rate can be effectively suppressed. Moreover, from such a thing, the pot life of a 2 liquid type polyurethane composition and a mixture can be ensured by using the retarder for 2 liquid type polyurethane compositions of this invention.

  In addition, the two-component polyurethane composition containing the retarder for the two-component polyurethane composition of the present invention and the mixture of the retarder for the two-component polyurethane composition of the present invention and the two-component polyurethane composition are conventionally used. It can be cured with a curing time equivalent to or shorter than the curing time of the two-component polyurethane composition. And the surface of the hardened | cured material obtained is excellent in curability without stickiness.

  Further, it is obtained from a two-component polyurethane composition containing the two-component polyurethane composition retarder of the present invention or a mixture of the two-component polyurethane composition retarder and two-component polyurethane composition of the present invention. The cured product has almost no foaming. Until now, when the reaction of the two-component polyurethane composition was delayed, there was a problem that the reaction was easily foamed due to the influence of water. In response to such a problem, the present inventor has found that the retarder for the two-component polyurethane composition of the present invention can delay the reaction of the two-component polyurethane composition and that there is almost no foaming. I found it.

Next, the two-component polyurethane composition of the present invention will be described.
The two-component polyurethane composition of the present invention is
A two-component polyurethane composition comprising a main agent containing a urethane prepolymer, a curing agent, and a retarder for the two-component polyurethane composition of the present invention contained in one or both of the main agent and the curing agent. And
The amount of at least one selected from the group consisting of the N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide is the N-methyl-2-pyrrolidone, 1,3-dimethyl. It is a two-component polyurethane composition that is 0.5 to 10 parts by mass with respect to 100 parts by mass of components other than at least one component selected from the group consisting of -2-imidazolidinone and dimethyl sulfoxide.

The urethane prepolymer will be described below.
A urethane prepolymer is a reaction product obtained by reacting a polyol compound with an excess of a polyisocyanate compound, and is a polymer containing an isocyanate group at a molecular end.

The polyisocyanate compound is not particularly limited. For example, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4′-diphenylmethane diisocyanate ( 4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 1,4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate (XDI), tetramethylxylidene diisocyanate ( Aromatic polyisocyanates such as TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI); hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHD) ), Lysine diisocyanate, aliphatic polyisocyanates such as norbornane diisocyanate methyl (NBDI); trans-cyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), H ₆ XDI (hydrogenated XDI), H ₁₂ MDI (water Alicyclic polyisocyanates such as MDI); carbodiimide-modified polyisocyanates of the above-mentioned polyisocyanates, or these isocyanurate-modified polyisocyanates. A polyisocyanate compound can be used individually or in combination of 2 types or more, respectively.

  The polyol compound is not particularly limited, and examples thereof include polyether polyols, polyester polyols, other polyols, and mixed polyols thereof.

  Examples of the polyether polyol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, 1,1,1-trimethylolpropane, 1,2,5-hexanetriol, 1,3-butanediol, 1, At least one selected from polyhydric alcohols such as 4-butanediol, 4,4'-dihydroxyphenylmethane, 4,4'-dihydroxyphenylpropane, pentaerythritol, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc. Polyols obtained by adding at least one selected from: polyoxytetramethylene oxide.

  Examples of the polyol obtained by adding at least one selected from ethylene oxide, propylene oxide, butylene oxide, styrene oxide and the like to at least one selected from the above polyhydric alcohols include, for example, polyethylene glycol, polypropylene glycol, polypropylene Examples include triol, polyglycerin, polytrimethylolpropane, polyhexanetriol, polybutanediol, polydihydroxyphenylmethane, and polydihydroxyphenylpropane.

  Examples of the polyester polyol include one or more of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol, glycerin, 1,1,1-trimethylolpropane, and other low molecular polyols. And a condensation polymer of glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, dimer acid, and other low molecular carboxylic acids and oligomeric acids; propionlactone , Ring-opening polymers such as valerolactone and caprolactone.

Other polyols include, for example, polymer polyols; polycarbonate polyols; polybutadiene polyols, hydrogenated polybutadiene polyols; acrylic polyols; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, and hexanediol. A low molecular polyol is mentioned.
These polyol compounds can be used alone or in combination of two or more.

  The combination of a polyol compound and an isocyanate compound is not particularly limited. Each of the polyol compounds and each of the isocyanate compounds can be used in any combination. Among them, a urethane prepolymer obtained from at least one selected from the group consisting of polyethylene glycol and polypropylene glycol and at least one selected from the group consisting of TDI and MDI is from the viewpoint of availability. preferable.

  The urethane prepolymer is not particularly limited for its production. For example, a method of obtaining a urethane prepolymer by reacting a polyol compound and a polyisocyanate compound under normal pressure at a reaction temperature of about 50 to 100 ° C. can be mentioned. Further, a urethanization catalyst such as an organic tin compound or an organic bismuth compound can be used.

  In the production of the urethane prepolymer, the equivalent ratio (NCO / OH) of the isocyanate group of the polyisocyanate compound to the hydroxy group of the polyol compound is preferably 1.4 to 3.0, and preferably 1.7 to 2.5. Is more preferable. When NCO / OH is in such a range, there is no foaming due to the remaining polyisocyanate compound, and there is no increase in the viscosity of the urethane prepolymer due to the extension of the molecular chain, and it can be obtained from the two-component polyurethane composition of the present invention. The physical properties of the cured product are improved.

  The urethane prepolymer can contain a blocked isocyanate group as long as the effects of the present invention are not impaired. Here, the “block isocyanate group” refers to a group in which an isocyanate group is blocked with a protective group, and the protective group can be removed by heat, moisture or the like to generate an isocyanate group. Examples of the blocked isocyanate group include groups obtained by blocking an isocyanate group with a blocking agent such as alcohols, phenols, oximes, pyrazoles, triazoles, and caprolactams.

  The blocking rate of the isocyanate group of the urethane prepolymer is not particularly limited. Depending on the application, physical properties after curing, etc., a part of the isocyanate group can be protected with a blocking agent.

  The urethane prepolymer is preferably liquid at room temperature from the viewpoint of handleability. In addition to the isocyanate group, the urethane prepolymer can have a group such as a hydroxy group, an acid anhydride group, an amino group, a latent amino group, a mercapto group, or a carboxy group in the molecule. When having such a group that can be cross-linked by reacting with an isocyanate group, the crosslink density of the cured product obtained from the two-component polyurethane composition of the present invention is improved, and the physical properties are excellent.

The curing agent will be described below.
The curing agent used in the two-component polyurethane composition of the present invention is not particularly limited as long as it is a compound having a functional group capable of reacting with an isocyanate group. For example, a polyamine compound having two or more amino groups in the molecule And a polyol compound having two or more hydroxy groups in the molecule.

Examples of the polyamine compound include amine compounds having two amino groups in the molecule (aliphatic diamine, aromatic diamine, etc.), and amine compounds having three or more amino groups in the molecule.
Examples of the aliphatic diamine include ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, and 1,7-heptane. Diamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine, hexamethylenediamine, trimethylhexamethylene Diamine, iminobispropylamine, methyliminobispropylamine, 1,5-diamino-2-methylpentane, isophoronediamine, 1,3-bisaminomethylcyclohexane, 1-cyclohexylamino-3-aminopropane, 3-aminomethyl -3,3,5-tri Chill - cyclohexylamine, dimethylene amines norbornane skeleton, meta-xylylenediamine (MXDA) and the like.

  Examples of the aromatic diamine include 3,3′-dichloro-4,4′-diaminodiphenylmethane (MOCA), 4,4′-diaminodiphenylmethane, 2,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,4-diaminophenol, 2,5-diaminophenol, o-phenylenediamine, m-phenylenediamine, p- Examples include phenylenediamine, 2,3-tolylenediamine, 2,4-tolylenediamine, 2,5-tolylenediamine, 2,6-tolylenediamine, and 3,4-tolylenediamine.

  Examples of the amine compound having three or more amino groups in the molecule include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.

  Examples of the polyol compound having two or more hydroxy groups in the molecule include those similar to the polyol compound used as a raw material for the urethane prepolymer.

Of these, MOCA and polypropylene glycol are preferable. A hardening | curing agent can be used individually or in combination of 2 or more types, respectively.
It is preferable that the quantity of a hardening | curing agent is 5-30 mass parts with respect to 100 mass parts of urethane prepolymers. When the amount of the curing agent is within such a range, the pot life can be sufficiently secured, and the amount of the filler, the plasticizer and the additive, the viscosity, and the curing time can be easily adjusted.

  The retarder for a two-component polyurethane composition will be described below.

  The retarder for two-component polyurethane compositions used in the two-component polyurethane composition of the present invention is the retarder for two-component polyurethane compositions of the present invention. The retarder for the two-component polyurethane composition used is a retarder containing at least one selected from the group consisting of N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and dimethyl sulfoxide. It is. The details of the retarder for the two-component polyurethane composition are the same as those of the retarder for the two-component polyurethane composition of the present invention. The retarder for a two-component polyurethane composition is contained in one or both of the main agent and the curing agent.

  The amount of at least one selected from the group consisting of N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide is N-methyl-2-pyrrolidone, 1,3-dimethyl-2 -It is 0.5-10 mass parts with respect to 100 mass parts of components other than the at least 1 sort (s) chosen from the group which consists of imidazolidinone and dimethylsulfoxide. In such a range, the reaction rate of the two-component polyurethane composition can be suppressed, the curability is excellent, and foaming is difficult. In addition, N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolide are more effective because the reaction rate of the two-component polyurethane composition is more effectively suppressed, the curability is superior, and foaming is more difficult. The amount of at least one selected from the group consisting of non-dimethylsulfoxide is preferably 1 to 5 parts by mass, and more preferably 1 to 3 parts by mass.

  Here, the “component other than at least one selected from the group consisting of N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and dimethyl sulfoxide” is included in the two-component polyurethane composition of the present invention. The component other than at least one selected from the group consisting of N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and dimethyl sulfoxide is included. The component other than at least one selected from the group consisting of N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and dimethyl sulfoxide is an essential component of the two-component polyurethane composition of the present invention. Certain urethane prepolymers and curing agents are included. In addition to at least one component selected from the group consisting of N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and dimethyl sulfoxide, in addition to the urethane prepolymer and the curing agent, for example, And additives.

  Examples of additives include fillers, curing catalysts (curing accelerators), latent curing agents, solvents, UV absorbers, dyes, pigments, flame retardants, reinforcing agents, adhesion-imparting agents, antioxidants, and antioxidants. , Thixotropic agents, surfactants (including leveling agents), dispersants, dehydrating agents, rust inhibitors, and antistatic agents. As the additive, those usually used in a two-component polyurethane composition can be used in a normal content. An additive can be used individually or in combination of 2 types or more, respectively. The additive is usually contained in the curing agent, but can also be contained in the main agent as needed or necessary.

  Examples of the filler include titanium dioxide, carbon black, silicic acid derivatives, talc, metal powder, calcium carbonate, and clay. A filler can be used individually or in combination of 2 types or more, respectively. The amount of the filler is preferably 50 to 90 parts by mass and more preferably 60 to 80 parts by mass with respect to 100 parts by mass of the urethane prepolymer. When the amount of the filler is within such a range, it becomes easy to adjust the viscosity and other physical properties of the two-component polyurethane composition.

Examples of the curing catalyst include organometallic catalysts and tertiary amines.
Examples of the organometallic catalyst include dibutyltin dilaurate, dioctyltin laurate, zinc octylate, and organic bismuth compounds.
Tertiary amines include trimethylamine, triethylamine, tributylamine, N, N-dimethylcyclohexylamine, N, N, N ′, N′-tetramethylethylenediamine, tetramethylguanidine, triethylenediamine, and N-methylmorpholine. .

  The curing catalysts can be used alone or in combination of two or more. The amount of the curing catalyst is preferably 0.5 to 5 parts by mass, and 1 to 3 parts by mass with respect to 100 parts by mass of the urethane prepolymer, from the viewpoints of curability and pot life (work life). Is more preferable.

  Examples of the plasticizer include dioctyl phthalate (DOP), dibutyl phthalate (DBP), dioctyl adipate, isodecyl succinate, diethylene glycol dibenzoate, pentaerythritol ester, butyl oleate, methyl acetylricinoleate, tricresyl phosphate, phosphoric acid Examples include trioctyl, trimellitic acid ester, propylene glycol adipate polyester, and butylene glycol polyester adipate. The plasticizers can be used alone or in combination of two or more. The amount of the plasticizer is preferably 5 to 200 parts by mass, more preferably 20 to 100 parts by mass with respect to 100 parts by mass of the urethane prepolymer, from the viewpoint of workability and curability. More preferably, it is 50 mass parts.

  Examples of latent curing agents include ketimines, enamines, which are reactants of polyamines and carbonyl compounds, aldimines, which are reactants of polyamines and aldehyde compounds, and oxazolidines, which are reactants of amino alcohols and carbonyl compounds. Kind.

  Pigments are roughly classified into inorganic pigments and organic pigments. Examples of the inorganic pigment include titanium oxide, zinc oxide, ultramarine, bengara, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, and sulfate. Examples of organic pigments include azo pigments and copper phthalocyanine pigments.

Examples of the antiaging agent include hindered phenol compounds and hindered amine compounds.
Examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).
Examples of the flame retardant include chloroalkyl phosphate, ammonium polyphosphate, neopentyl bromide polyether, and brominated polyether.

  Examples of the adhesion imparting agent include terpene resins, phenol resins, terpene-phenol resins, rosin resins, and xylene resins.

  In the two-component polyurethane composition of the present invention, the retarder for the two-component polyurethane composition is contained in one or both of the main agent and the curing agent including the urethane prepolymer.

One preferred embodiment of the retarder for a two-component polyurethane composition is to use a dehydrated one.
The method for dehydrating the retarder for the two-component polyurethane composition is not particularly limited, and examples thereof include a method for dehydrating the retarder for the two-component polyurethane composition of the present invention using a desiccant such as molecular sieve. It is done.

  It is mentioned as one of the preferred embodiments that the main agent contains a dehydrated two-component polyurethane composition retarder. In such a case, the amount of the dehydrated two-component polyurethane composition retarder is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the urethane prepolymer contained in the main agent. 5 mass parts is more preferable, and 1-3 mass parts is still more preferable. In such a range, the balance between suppression of reaction rate and curability is good and foaming is difficult.

  Moreover, it is mentioned as one of the preferable aspects that a dehydrating agent for a two-component polyurethane composition is contained in a curing agent from the viewpoint of storage stability.

  The two-component polyurethane composition of the present invention is obtained by separately preparing a main agent containing a urethane prepolymer and a curing agent, and then mixing them at the time of use. The method for preparing the main agent and the curing agent is not particularly limited. For example, the main ingredient containing a urethane prepolymer and the hardening | curing agent containing the retarder for 2 liquid-type polyurethane compositions of this invention are prepared, respectively, and after adding arbitrary components to these, the method of knead | mixing fully is mentioned. After kneading, the main agent and the curing agent can be stored in separate sealed containers, and the main agent and the curing agent can be sufficiently mixed and used at the time of use. The two-component polyurethane composition as described above is crosslinked and cured by reacting an isocyanate group in the main agent with a hydroxy group and / or an amino group in the curing agent to form a urethane bond and / or a urea bond.

  In addition, the two-component polyurethane composition of the present invention can be used as a mixture by further adding a retarder for the two-component polyurethane composition of the present invention. In such a case, at least one amount selected from the group consisting of N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and dimethyl sulfoxide is added to the two-component polyurethane composition of the present invention. Is preferably 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight, and more preferably 1 to 3 parts by weight with respect to 100 parts by weight of the two-component polyurethane composition of the present invention. In such a range, the reaction rate is suppressed, the curability is excellent, and foaming is difficult.

  The use of the two-component polyurethane composition of the present invention is not particularly limited. For example, a waterproofing material, a coating floor material, a casting material, a sealing material, an adhesive, and an injecting agent can be mentioned.

  When the two-component polyurethane composition of the present invention is used as a waterproofing material, for example, an outer wall of a building (for example, a roof surface, a wall surface, a veranda, an open corridor), a room (for example, a floor surface, a wall, a ceiling) Can be used for road paving surfaces.

  Moreover, when using the two-component polyurethane composition of the present invention as a waterproofing material, it is preferable that the curing agent contains a polyol compound and a polyamine compound from the viewpoints of pot life, curability, and physical properties. Specific polyol compounds and polyamine compounds are the same as described above.

  When the two-component polyurethane composition of the present invention is used as a waterproofing material, a preferable polyol compound includes, for example, polypropylene glycol. It is preferable that the quantity of a polyol compound is 5-30 mass parts with respect to 100 mass parts of urethane prepolymers. In such a range, it is excellent in workability (pot life), curability and physical properties.

  When the two-component polyurethane composition of the present invention is used as a waterproofing material, a preferred polyamine compound is, for example, 3,3′-dichloro-4,4′diaminodiphenylmethane (MOCA). The amount of the polyamine compound is preferably 2 to 15 parts by mass with respect to 100 parts by mass of the urethane prepolymer. In such a range, it is excellent in workability (pot life), curability and physical properties.

  Moreover, when using the two-pack type polyurethane composition of this invention as a sealing material, it is preferable from a viewpoint of pot life and sclerosis | hardenability that a hardening | curing agent contains a polyol compound. Specific polyol compounds are the same as described above.

  A preferable polyol compound when the two-component polyurethane composition of the present invention is used as a sealing material includes, for example, polypropylene glycol. The amount of the polyol compound is preferably 10 to 80 parts by mass with respect to 100 parts by mass of the urethane prepolymer. In such a range, it is excellent in workability (pot life), curability and physical properties.

  In the two-component polyurethane composition of the present invention, the retarder for the two-component polyurethane composition used can suppress the reaction rate of the two-component polyurethane composition of the present invention. In particular, when the environment in which the two-component polyurethane composition is used is a high temperature (for example, 25 to 40 ° C.) as in summer, or the temperature of the material used is high, the reaction rate can be effectively suppressed. . In addition, the two-component polyurethane composition of the present invention can suppress an increase in viscosity by containing the retarder for the two-component polyurethane composition of the present invention, and can sufficiently ensure the pot life. it can.

  Moreover, the two-component polyurethane composition of the present invention can be cured with a curing time that is equal to or shorter than the curing time of the conventional two-component polyurethane composition. Therefore, for example, when the two-component polyurethane composition of the present invention is applied, the cured product is sufficiently cured on the next day, and the next operation can be performed, so that the operation efficiency is excellent. Moreover, since there is no stickiness on the surface of the resulting cured product, the curability is excellent.

  Further, the cured product obtained from the two-component polyurethane composition has almost no foaming. Until now, when the reaction of the two-component polyurethane composition was delayed, there was a problem that the reaction was easily foamed due to the influence of water. In response to such a problem, the present inventor has found that the retarder for a two-component polyurethane composition of the present invention delays the reaction of the two-component polyurethane composition and has almost no foaming.

Next, the construction method of the two-component polyurethane composition of the present invention will be described.
The construction method of the two-component polyurethane composition of the present invention is the addition of the retarder for the two-component polyurethane composition of the present invention to the two-component polyurethane composition containing a main component containing a urethane prepolymer and a curing agent. Mixing step to obtain a mixture,
A construction method for a two-component polyurethane composition comprising a construction step of constructing the mixture.

  In the construction method of the two-component polyurethane composition of the present invention, the retarder for the two-component polyurethane composition used is the retarder for the two-component polyurethane composition of the present invention. The retarder for a two-component polyurethane composition used contains at least one selected from the group consisting of N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and dimethyl sulfoxide. The details of the retarder for the two-component polyurethane composition used are the same as the retarder for the two-component polyurethane composition of the present invention.

  The two-component polyurethane composition used in the construction method of the two-component polyurethane composition of the present invention is not particularly limited as long as it contains a main agent containing a urethane prepolymer and a curing agent. Examples of such a two-component polyurethane composition include the two-component polyurethane composition of the present invention and a conventionally known two-component polyurethane composition.

  The components contained in the two-component polyurethane composition can contain, for example, the same components as those contained in the two-component polyurethane composition of the present invention. Further, the two-component polyurethane composition used may or may not contain the retarder for the two-component polyurethane composition of the present invention.

The mixing process will be described below.
In the mixing step, the mixture is obtained by adding the retarder for the two-component polyurethane composition of the present invention to the two-component polyurethane composition containing the main agent containing the urethane prepolymer and the curing agent.

  In the mixing step, at least one amount selected from the group consisting of N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and dimethyl sulfoxide used is 100 masses of the two-component polyurethane composition. 0.5-10 mass parts is preferable with respect to part, 1-5 mass parts is more preferable, and 1-3 mass parts is more preferable. In such a range, the reaction rate of the mixture is suppressed, the curability is excellent, and foaming is difficult.

  The mixing method of the two-component polyurethane composition and the retarder for the two-component polyurethane composition of the present invention is not particularly limited. For example, the two-component polyurethane composition and the retarder for the two-component polyurethane composition of the present invention may be sufficiently stirred at a construction site using an electric stirrer and mixed uniformly. Thus, in the construction method of the two-component polyurethane composition of the present invention, the retarder for the two-component polyurethane composition of the present invention is added to the two-component polyurethane composition at the construction site, and the reaction rate of the mixture is adjusted. can do.

Next, the above mixture is applied in the construction process.
The construction method of the mixture is not particularly limited. Examples thereof include a method using a rubber spatula, plastering iron, brush, and roller.
The mixture can be applied to a substrate such as concrete, mortar, plastic, earthenware, metal, wood.
The number of times of applying the mixture to the base is not particularly limited. For example, it is one of the preferred embodiments that the number is two or more.

  When the mixture is applied to the base, the thickness of the obtained coating film is preferably 2 to 6 mm.

  In addition, before applying a mixture to a foundation | substrate, a primer process can be given to a foundation | substrate. The primer used is not particularly limited. Moreover, a protective finish layer can be applied after applying the mixture. The protective finish layer is not particularly limited.

  In the construction method of the two-component polyurethane composition of the present invention, N-methyl-2-pyrrolidone and / or 1,3-dimethyl-2-imidazolidinone is added to the two-component polyurethane composition as a retarder. The reaction rate of the mixture can be suppressed. The resulting mixture has a pot life, short curing time, good curability, and is difficult to foam. In particular, when the mixture is used in a high-temperature environment (for example, 25 to 40 ° C.) as in the summer or when the temperature of the mixture is high, the reaction rate is effectively suppressed and the increase in viscosity is suppressed. And fluidity is maintained. Therefore, the cured product obtained by applying such a mixture is flat and excellent in finish.

The application method of the two-component polyurethane composition of the present invention includes, for example, a waterproof material, a sealing material, a flooring material, and an adhesive.
As a waterproof material, for example, it is used for exterior walls of buildings (for example, floors, walls, verandas, open corridors on rooftops), indoors (for example, floors, walls, ceilings), and road paving surfaces. it can.
Examples of the sealing material include architectural sealing materials and civil engineering sealing materials. Examples of the building sealing material include a surface coating sealing material having a two-component polyurethane composition as a base layer and a finish paint layer on the surface.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely according to an Example, this invention is not limited to the following Example.

  With respect to the mixture (unit: part by mass) of the two-component polyurethane composition and each compound shown in Table 1, pot life, curability, and foamability were evaluated according to the following evaluation methods. The results are shown in Table 1.

(1) Pot life Time The two-component polyurethane composition shown in Table 1 and each compound were uniformly mixed at 35 ° C. and humidity 70% RH using an electric stirrer to obtain a mixture. The time from when the mixing was completed until the viscosity of the mixture reached 30 Pa · S was measured.

  Moreover, about the mixture obtained in Example 1 and Comparative Example 2, the viscosity after mixing completion, 60 minutes after mixing completion, and 120 minutes after was measured. The results are shown in Table 2. In Table 2, 0 minutes means when mixing is completed, 60 minutes means 60 minutes after completion of mixing, and 120 minutes means 120 minutes after completion of mixing. Moreover, the numerical value in [] in Table 2 is the value of the ratio of the viscosity 60 minutes or 120 minutes after the start of mixing to the viscosity at the completion of mixing in each of the examples and comparative examples.

(2) Curability After the two-component polyurethane composition shown in Table 1 and each compound were uniformly mixed to form a mixture, the resulting mixture was applied to a slate plate (coating amount: 2 by wet mass). .5 kg / m ² equivalent) to prepare a test piece. After this test piece was cured in a laboratory atmosphere (23 ° C., humidity 50% RH) for 15 hours, the degree of stickiness of the surface was evaluated by finger touch. The case where there was no stickiness was rated as ◯, the case where there was a slight stickiness as Δ, and the case where the stickiness was strong as x.

(3) Foamability Obtained after uniformly mixing the two-component polyurethane composition shown in Table 1 and each compound in an environmental test room atmosphere (35 ° C., humidity 70% RH) to obtain a mixture. The obtained mixture was applied to a slate plate (application amount: equivalent to 2.5 kg / m ² ) to prepare a test piece. This test piece was cured in an environmental test room atmosphere (35 ° C., humidity 70% RH) for 18 hours. Thereafter, the degree of foaming was visually evaluated. The case where foaming was not confirmed was marked with ◯, and the case where foaming was slightly observed was marked with △.

Details of each compound shown in Table 1 are as follows.
-Two-component polyurethane composition: containing 100 parts by weight of urethane prepolymer as agent A, 15 parts by weight of polypropylene glycol as agent B, 5 parts by weight of 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA), Two-component polyurethane composition containing 64.8 parts by mass of calcium carbonate, 10 parts by mass of phthalic acid plasticizer, 2 parts by mass of heat stabilizer, 3 parts by mass of light stabilizer, and 0.2 parts by mass of pigment. NMP: N- Methyl-2-pyrrolidone, manufactured by Mitsubishi Chemical Corporation, DMI: 1,3-dimethyl-2-imidazolidinone, manufactured by Kawaken Fine Chemicals, Inc., IPA: isopropyl alcohol (reagent)
・ MIBK: Methyl isobutyl ketone (reagent)
DMSO: dimethyl sulfoxide, manufactured by Toray Fine Chemical Co., Ltd. DMF: dimethylformamide, manufactured by DuPont, Inc. Octyl acid: manufactured by Kyowa Hakko Chemical Co., Ltd.

  As apparent from Table 1, the mixture (Examples 1 to 5) containing NMP, DMI or DMSO and the two-component polyurethane composition had a pot life longer than that of Comparative Examples 1 and 3 to 5. long. Further, as apparent from Table 2, the reaction rate of the mixture of Example 1 containing NMP is suppressed as compared with the mixture of Comparative Example 1 not containing NMP. Thus, the retarder for a two-component polyurethane composition of the present invention can suppress the reaction rate of the two-component polyurethane composition and has a long pot life.

  Further, as is clear from Table 1, the mixtures (Examples 1 to 5) containing the retarder for the two-component polyurethane composition of the present invention and the two-component polyurethane composition are shown in Comparative Examples 2 and 3. In comparison, the surface of the cured product is not sticky and has excellent curability.

  Furthermore, as is apparent from Table 1, foaming does not occur in the mixture (Examples 1 to 5) containing the retarder for the two-component polyurethane composition of the present invention and the two-component polyurethane composition. Conventionally, when the reaction of the two-component polyurethane composition is delayed, there is a problem that the reaction is easily foamed due to the influence of water (see Comparative Example 2). However, in the mixtures of Examples 1 to 5, the reaction rate is suppressed and foaming does not occur.

Claims (3)

  A retarder for a two-component polyurethane composition containing at least one selected from the group consisting of N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and dimethyl sulfoxide. A two-component polyurethane composition comprising a main agent comprising a urethane prepolymer, a curing agent, and a retarder for a two-component polyurethane composition according to claim 1 contained in one or both of the main agent and the curing agent. A thing,
The amount of at least one selected from the group consisting of the N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide is the N-methyl-2-pyrrolidone, 1,3-dimethyl. 2-component polyurethane composition which is 0.5-10 mass parts with respect to 100 mass parts of components other than the at least 1 sort (s) chosen from the group which consists of -2-imidazolidinone and a dimethylsulfoxide. A mixing step of adding a retarder for a two-component polyurethane composition according to claim 1 to a two-component polyurethane composition containing a main agent containing a urethane prepolymer and a curing agent, to obtain a mixture;
A construction method of a two-component polyurethane composition comprising a construction step of constructing the mixture.