JP2020147644A - Two-component curing type polyurethane resin composition - Google Patents

Abstract

To provide a two-component curing type polyurethane resin composition capable of obtaining a cured product which has an adequate pot life and excellent mechanical physical properties.SOLUTION: A two-component curing type polyurethane resin composition contains a polyisocyanate component, an active hydrogen group-containing component and a water-absorbing filler, in which an active hydrogen compound and a latent active hydrogen compound are contained in the active hydrogen group-containing component, the polyisocyanate component and the latent active hydrogen compound are contained in liquid A, the active hydrogen compound and a water-absorbing filler are contained in liquid B, an equivalent ratio of the isocyanate group in the polyisocyanate component to the active hydrogen group in the active hydrogen group-containing component is 0.8-1.2, a ratio of the active hydrogen group generated by reaction of the latent active hydrogen compound and water with respect to the total moles of the active hydrogen group in the active hydrogen group-containing component is 35-65 mol%, and a content ratio of the water-absorbing filler is 5-37.5 pts.mass with respect to 100 pts.mass of the total amount of the two-component curing type polyurethane resin composition.SELECTED DRAWING: None

Description

The present invention relates to a two-component curable polyurethane resin composition, and more particularly to a two-component curable polyurethane resin composition for forming a waterproof material used for floor materials, floor pavements, and the like.

Currently, waterproof materials made of polyurethane resin compositions and the like are used in waterproof pavements such as floors and corridors of various facilities, balconies, parking lots, and rooftops.

Examples of such a polyurethane resin composition include an isocyanate group-terminated urethane prepolymer (A) obtained by reacting an aliphatic and / or alicyclic polyisocyanate with a polyoxyalkylene polyol and a low molecular weight polyol, and a fat. A component (I) containing a urethane polyoxazolidine compound (B) obtained by reacting a group and / or alicyclic polyisocyanate with N-hydroxyalkyloxazolidine, and a component (II) containing water. A two-component urethane resin composition containing the same has been proposed (see, for example, Patent Document 1).

In such a two-component urethane resin composition, by mixing the component (I) and the component (II), the oxazolidine ring of the urethane polyoxazolidine compound (B) in the component (I) is contained in the component (II). It reacts with water to open the ring and generate hydroxyl groups and amino groups. Then, these hydroxyl groups and amino groups react with the isocyanate group of the isocyanate group-terminated urethane prepolymer (A) of the component (I) to produce a cured polyurethane resin product.

Japanese Unexamined Patent Publication No. 2008-222792

However, in the above-mentioned two-component urethane resin composition, when the component (I) and the component (II) are mixed, the oxazolidine ring and water react rapidly, so that the pot life is short and the workability at the time of construction is low. Not enough.

Further, in the above-mentioned two-component urethane resin composition, sufficient soft segments are not formed, so that the mechanical properties (particularly, elongation at break) of the cured polyurethane resin may not be sufficient.

Therefore, the two-component urethane resin composition is required to have both an appropriate pot life and mechanical properties (particularly, elongation at break) of the cured product.

The present invention is a two-component curable polyurethane resin composition capable of obtaining a cured product having an appropriate pot life and excellent mechanical properties.

The present invention [1] is a two-component curable polyurethane resin composition comprising a liquid A and a liquid B, which comprises a polyisocyanate component containing an isocyanate group, an active hydrogen group-containing component containing an active hydrogen group, and a water-absorbent filler. The active hydrogen group-containing component contains an active hydrogen compound having a free active hydrogen group and a latent active hydrogen compound that produces an active hydrogen group by reacting with water, and the liquid A is contained. However, the polyisocyanate component and the latent active hydrogen compound are contained, and the liquid B contains the active hydrogen compound and the water-absorbent filler, and the poly with respect to the active hydrogen group in the active hydrogen group-containing component. The equivalent ratio of isocyanate groups (isocyanate group / active hydrogen group) in the isocyanate component is 0.8 or more and 1.2 or less, and the latent ratio is relative to the total molar number of active hydrogen groups in the active hydrogen group-containing component. The ratio of active hydrogen groups generated by the reaction of the active hydrogen compound with water is 35 mol% or more and 65 mol% or less, and the content ratio of the water-absorbent filler is 100, which is the total amount of the two-component curable polyurethane resin composition. It contains a two-component curable polyurethane resin composition which is 5 parts by mass or more and 37.5 parts by mass or less with respect to parts by mass.

In the present invention [2], the polyisocyanate component contains an isocyanate group-terminated urethane prepolymer having an average isocyanate group number of 2 and a polyisocyanate derivative having an average isocyanate group number of 3 or more, and is contained in the isocyanate group-terminated urethane prepolymer. The ratio of the isocyanate group in the isocyanate group-terminated urethane prepolymer is 35 mol% or more and 65 mol% or less with respect to the total molar amount of the isocyanate group of the above and the isocyanate group in the polyisocyanate derivative, and the active hydrogen. The group-containing component contains an aromatic diamine compound, a monool compound, and a diol compound, and the active hydrogen group in the aromatic diamine compound, the active hydrogen group in the monool compound, and the diol compound. The ratio of the active hydrogen group in the aromatic diamine compound is 50 mol% or more and 90 mol% or less with respect to the total molar amount of the active hydrogen group in the monool compound, and the active hydrogen group in the monool compound and the diol. The two-component curable polyurethane according to the above [1], wherein the ratio of the active hydrogen group in the monool compound is 10 mol% or more and 75 mol% or less with respect to the total molar amount of the active hydrogen group in the compound. Contains a resin composition.

The present invention [3] is characterized in that the diol compound contains polyoxypropylene glycol having ethylene oxide added to the molecular end, and the monool compound contains one-ended sealed polyoxypropylene glycol. , The two-component curable polyurethane resin composition according to the above [2] is contained.

The two-component curable polyurethane resin composition of the present invention contains a polyisocyanate component containing an isocyanate group, an active hydrogen group-containing component containing an active hydrogen group, and a water-absorbent filler in a predetermined ratio, and is active. The hydrogen group-containing component contains an active hydrogen compound having a free active hydrogen group and a latent active hydrogen compound that produces an active hydrogen group by reacting with water in a predetermined ratio. Further, the two-component curable polyurethane resin composition includes a solution A containing a polyisocyanate component and a latent active hydrogen compound, and a solution B containing the active hydrogen compound and the water-absorbent filler.

In such a two-component curable polyurethane resin composition, when the liquid A and the liquid B are mixed, the polyisocyanate component and the active hydrogen group-containing component react with each other. More specifically, since the active hydrogen group of a part of the active hydrogen group-containing component (latent active hydrogen compound) is latent, the activity of the rest (active hydrogen compound) of the active hydrogen group-containing component at the beginning of mixing The hydrogen group reacts with the isocyanate group of the polyisocyanate component. After that, the reaction between the latent active hydrogen compound and water proceeds, and the generated active hydrogen group and isocyanate group gradually react. That is, in the mixture, the isocyanate group is excessive with respect to the active hydrogen group due to the latent part of the active hydrogen group, and the rate of the chain extension reaction (polymerization) becomes slow. There is.

Furthermore, since the water in the mixture of solutions A and B is absorbed by the water-absorbent filler, the reaction between the latent active hydrogen compound and water (liberation of active hydrogen groups) is delayed, and the polyisocyanate component and latent are latent. The reaction with the active hydrogen compound proceeds moderately.

Therefore, according to such a two-component curable polyurethane resin composition, an appropriate pot life can be obtained, and a cured product having excellent mechanical properties can be obtained.

The two-component curable polyurethane resin composition of the present invention is a resin composition of a two-component kit comprising separately prepared solutions A and B.

Liquids A and B are two-component kits for forming a cured polyurethane resin (hereinafter, simply referred to as a cured product), and are mixed (mixed) at the time of use and cured to produce a cured product. ..

Specifically, the liquid A contains a polyisocyanate component and is used as the main agent of the two-component curable polyurethane resin composition. Further, the liquid A contains a part of the active hydrogen group-containing component (specifically, a latent active hydrogen compound (described later)), as will be described in detail later.

Further, the liquid B contains the rest of the active hydrogen group-containing component (specifically, a non-latent active hydrogen compound (described later)) and is used as a curing agent for the two-component curable polyurethane resin composition. .. Further, the liquid B contains a water-absorbent filler (described later), as will be described in detail later.

More specifically, the two-component curable polyurethane resin composition contains a polyisocyanate component and an active hydrogen group-containing component.

The polyisocyanate component is a component containing a free isocyanate group.

Examples of the polyisocyanate component include a polyisocyanate monomer, a polyisocyanate derivative, and an isocyanate group-terminated urethane prepolymer.

Examples of the polyisocyanate monomer include aromatic polyisocyanates, aromatic aliphatic polyisocyanates, and aliphatic polyisocyanates.

Examples of the aromatic polyisocyanate include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof) (TDI), phenylenediisocyanate (m-, p-phenylenediocyanate or a mixture thereof), 4, 4'-diphenyldiisocyanate, 1,5-naphthalenediisocyanate (NDI), diphenylmethane diisocyanate (4,4'-, 2,4'-or 2,2'-diphenylmethane diisosinate or a mixture thereof) (MDI), Examples thereof include aromatic diisocyanates such as 4,4'-toluidine diisocyanate (TODI) and 4,4'-diphenyl ether diisocyanate.

Examples of the aromatic aliphatic polyisocyanate include xylylene diisocyanate (1,3- or 1,4-xylene diisocyanate or a mixture thereof) (XDI) and tetramethylxylene diisocyanate (1,3- or 1,4-tetra). Methylxylene diisocyanate or a mixture thereof) (TMXDI), aromatic aliphatic diisocyanates such as ω, ω'-diisocyanate-1,4-diethylbenzene and the like can be mentioned.

Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), 1 , 5-Pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl caproate, etc. Examples include aliphatic diisocyanate.

In addition, the aliphatic polyisocyanate includes an alicyclic polyisocyanate. Examples of the alicyclic polyisocyanate include 1,3-cyclopentanediisocyanate, 1,3-cyclopentenediisocyanate, cyclohexanediisocyanate (1,4-cyclohexanediisocyanate, 1,3-cyclohexanediisocyanate), and 3-isocyanatomethyl-3. , 5,5-trimethylcyclohexylisocyanate (isoholodiisocyanate) (IPDI), methylenebis (cyclohexylisocyanate) (4,4'-, 2,4'-or 2,2'-methylenebis (cyclohexylisocyanate, Trans, Transs thereof) -Form, Trans, Cis-form, Cis, Cis-form, or a mixture thereof)) (H ₁₂ MDI), methylcyclohexanediisocyanate (methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate), norbornan Oil rings such as diisocyanate (various isomers or mixtures thereof) (NBDI), bis (isocyanatomethyl) cyclohexane (1,3- or 1,4-bis (isocyanatomethyl) cyclohexane or a mixture thereof) (H ₆ XDI) Group diisocyanate can be mentioned.

These polyisocyanate monomers can be used alone or in combination of two or more.

Examples of the polyisocyanate derivative include multimers of the above-mentioned polyisocyanate monomers (for example, dimer and trimeric (for example, isocyanurate modified and iminooxadiazinedione modified), pentamer and 7). Quantities, etc.), allophanate modified products (for example, allophanate modified products produced by the reaction of the above-mentioned polyisocyanate monomer with low molecular weight polyol), polyol modified products (for example, polyisocyanate monomer and low molecular weight polyol) Polyisocyanate modified product (alcohol adduct) produced by reaction with, biuret modified product (for example, biuret modified product produced by reaction of the above-mentioned polyisocyanate monomer with water or amines), urea modification Body (for example, urea modified product produced by the reaction of the above-mentioned polyisocyanate monomer and diamine), oxadiazine trione modified product (for example, produced by the reaction of the above-mentioned polyisocyanate monomer with carbon dioxide gas) Examples thereof include oxadiazine trione), carbodiimide modified products (carbodiimide modified products produced by the above-mentioned decarbonate condensation reaction of polyisocyanate monomers, etc.), uretdione modified products, uretonimine modified products, and the like.

The low molecular weight polyol used as a modifier in the polyol modified product or allophanate modified product is a compound having two or more hydroxyl groups and having a number average molecular weight of less than 300, preferably less than 400, and is, for example, ethylene glycol or propylene glycol. , 1,3-Propanediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl -1,5-pentanediol, 2,2,2-trimethylpentanediol, 3,3-dimethylolheptan, alcoholic (C7-20) diol, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof , 1,3- or 1,4-cyclohexanediol and mixtures thereof, bisphenol hydride A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, bisphenol A , Dihydric alcohols such as diethylene glycol, triethylene glycol, dipropylene glycol, for example, trihydric alcohols such as glycerin, trimethylolpropane, triisopropanolamine, for example, tetrahydric alcohols such as tetramethylolmethane (pentaerythritol), diglycerin. , For example, pentahydric alcohols such as xylitol, eg, hexahydric alcohols such as sorbitol, mannitol, alitol, iditor, darsitol, altritor, inositol, dipentaerythritol, eg, heptavalent alcohols such as persetol, eg, sucrose, etc. The octavalent alcohol of the above can be mentioned.

These low molecular weight polyols can be used alone or in combination of two or more.

Further, examples of the polyisocyanate derivative include polymethylene polyphenyl polyisocyanate (crude MDI, polypeptide MDI, polynuclear compound-containing diphenylmethane diisocyanate) and the like.

These polyisocyanate derivatives can be used alone or in combination of two or more.

As the polyisocyanate derivative, from the viewpoint of mechanical properties (particularly, elongation at break), an aromatic polyisocyanate derivative is preferable, an aromatic diisocyanate derivative is more preferable, and a tolylene diisocyanate derivative is more preferable. And / or derivatives of diphenylmethane diisocyanate, with particular preference being derivatives of tolylene diisocyanate. Further, as the tolylene diisocyanate, preferably, a combination of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate can be mentioned. The combined ratio of these is appropriately set according to the purpose and application.

Further, as the polyisocyanate derivative, from the viewpoint of mechanical properties (particularly, elongation at break), a multimer and a modified polyol are preferably mentioned, and more preferably a trimeric or higher multimer and a trivalent or higher alcohol. Examples include a polyol modified product (alcohol adduct), more preferably a trimeric and a polyol modified product using a trihydric alcohol (alcohol adduct), and particularly preferably a polyol modified product using a trihydric alcohol (alcohol addition). Body).

The average number of isocyanate groups of the polyisocyanate derivative is, for example, 2 or more, preferably 2.5 or more, more preferably 3 or more, and for example, 6 or less, preferably 5 or less, more preferably 4 or less. , Particularly preferably 3.

Examples of the polyisocyanate derivative having an average number of isocyanate groups of 3 or more include a trimer or more multimer (for example, a trimer, a pentamer, a heptameric, etc.) and a polyol-modified product with a trihydric or higher alcohol. (Alcohol adduct) and the like. These can be used alone or in combination of two or more.

Examples of the polyisocyanate derivative having an average number of isocyanate groups of 3 or more include a polyisocyanate derivative having an average number of isocyanate groups of 3, and more preferably an aromatic diisocyanate trimerate and an aromatic diisocyanate trivalent alcohol adduct. More preferably, a trihydric alcohol adduct of an aromatic diisocyanate is mentioned, and particularly preferably, a trimethylolpropane adduct of an aromatic diisocyanate is mentioned.

The isocyanate group-terminated urethane prepolymer is a urethane prepolymer having at least two isocyanate groups at the molecular ends, and is a polyisocyanate (polyisocyanate selected from a polyisocyanate monomer and a polyisocyanate derivative) and a high molecular weight polyol (polyisocyanate). And if necessary, low molecular weight polyol), and the ratio of polyisocyanate equivalent ratio (NCO / OH) to hydroxyl group of high molecular weight polyol (and low molecular weight polyol if necessary) to be larger than 1, preferably 1.3 to 50. , More preferably, it can be obtained by subjecting it to a urethanization reaction at a ratio of 1.5 to 2.

The polyisocyanate preferably includes a polyisocyanate monomer, more preferably an aromatic polyisocyanate, still more preferably a tolylene diisocyanate and / or a diphenylmethane diisocyanate, and particularly from the viewpoint of elongation. Preferred is tolylene diisocyanate.

The high molecular weight polyol is a compound having a number average molecular weight of 300 or more, preferably 400 or more, for example, 10,000 or less, which has two or more hydroxyl groups, and is, for example, a polyether polyol, a polyester polyol, a polycarbonate polyol, a polyurethane polyol, or an epoxy polyol. , Vegetable oil polyols, polyolefin polyols, acrylic polyols, and vinyl monomer modified polyols.

Examples of the polyether polyol include a polyoxyalkylene polyol and a polytetramethylene ether polyol.

The polyoxyalkylene polyol is an addition polymerization of an alkylene oxide using, for example, the above-mentioned low molecular weight polyol or the polyamine compound described later as an initiator.

Examples of the alkylene oxide include propylene oxide, ethylene oxide, butylene oxide, styrene oxide and the like. In addition, these alkylene oxides can be used alone or in combination of two or more. Moreover, among these, propylene oxide and ethylene oxide are preferable. The polyoxyalkylene polyol includes, for example, a random and / or block copolymer of propylene oxide and an alkylene oxide such as ethylene oxide.

Examples of the polytetramethylene ether polyol include a ring-opening polymer obtained by cationic polymerization of tetrahydrofuran, and an amorphous (non-crystalline) polymer obtained by copolymerizing an alkyl-substituted tetrahydrofuran or the above-mentioned divalent alcohol with a polymerization unit such as tetrahydrofuran. Sex) Polytetrahydrofuran ether glycol and the like can be mentioned.

In addition, amorphous (amorphous) means that it is liquid at room temperature (25 ° C.).

The amorphous polytetramethylene ether glycol is, for example, a copolymer of tetrahydrofuran and alkyl-substituted tetrahydrofuran (eg, 3-methyltetrahydrofuran) (tetrahydrofuran / alkyl-substituted tetrahydrofuran (molar ratio) = 15/85-85 /. 15. A copolymer of tetrahydrofuran and branched glycol (eg, neopentyl glycol, etc.) (tetrahydrofuran / branched glycol (molar ratio)) or a number average molecular weight of 500 to 4000, preferably 800 to 2500) = It can be obtained as 15 / 85-85 / 15, number average molecular weight 500-4000, preferably 800-2500) and the like.

Examples of the polyester polyol include a polycondensate obtained by reacting the above-mentioned low molecular weight polyol with a polybasic acid under known conditions.

Examples of the polybasic acid include oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane, and 3-methyl-3-ethylglutaric acid. , Azelaic acid, sebacic acid, other saturated aliphatic dicarboxylic acids (C11-13), such as maleic acid, fumaric acid, itaconic acid, other unsaturated aliphatic dicarboxylic acids, such as orthophthalic acid, isophthalic acid, terephthalic acid. , Toluenedicarboxylic acid, naphthalenedicarboxylic acid, other aromatic dicarboxylic acids such as hexahydrophthalic acid, other alicyclic dicarboxylic acids such as dimeric acid, hydrogenated dimeric acid, hetic acid and other carboxylic acids. And acid anhydrides derived from these carboxylic acids, such as oxalic acid anhydride, succinic acid anhydride, maleic anhydride, phthalic acid anhydride, 2-alkyl anhydride (C12-C18) succinic acid, tetrahydrophthalic acid anhydride, trihydride. Merit acids and acid halides derived from these carboxylic acids and the like, such as oxalic acid dichloride, adipate dichloride, sebacic acid dichloride and the like can be mentioned.

Further, as the polyester polyol, for example, a plant-derived polyester polyol, specifically, the above-mentioned low molecular weight polyol as an initiator, a hydroxyl group-containing vegetable oil fatty acid (for example, lysinoleic acid-containing castor oil fatty acid, 12-hydroxystearic acid). Examples thereof include vegetable oil-based polyester polyols obtained by subjecting a hydroxycarboxylic acid such as (hydrogenated castor oil fatty acid, etc.) containing the above to a condensation reaction under known conditions.

Further, as the polyester polyol, for example, using the above-mentioned low molecular weight polyol (preferably dihydric alcohol) as an initiator, lactones such as ε-caprolactone and γ-valerolactone, and for example, L-lactide and D- Examples thereof include polycaprolactone polyols and polyvalerolactone polyols obtained by ring-opening polymerization of lactides such as lactide, and lactone-based polyester polyols obtained by copolymerizing them with the above-mentioned divalent alcohol.

Examples of the polycarbonate polyol include a ring-opening polymer of ethylene carbonate using the above-mentioned low molecular weight polyol (preferably a dihydric alcohol) as an initiator, and for example, 1,4-butanediol and 1,5-pentanediol. Examples thereof include an amorphous polycarbonate polyol obtained by copolymerizing a dihydric alcohol such as 3-methyl-1,5-pentanediol or 1,6-hexanediol with a ring-opening polymer.

Further, the polyurethane polyol is a polyester polyol, a polyether polyol and / or a polycarbonate polyol obtained as described above, at a ratio in which the equivalent ratio (OH / NCO) of the hydroxyl group (OH) to the isocyanate group (NCO) exceeds 1. By reacting with polyisocyanate, it can be obtained as a polyester polyurethane polyol, a polyether polyurethane polyol, a polycarbonate polyurethane polyol, a polyester polyether polyurethane polyol, or the like.

Examples of the epoxy polyol include an epoxy polyol obtained by reacting the above-mentioned low molecular weight polyol with a polyfunctional halohydrin such as epichlorohydrin and β-methylepichlorohydrin.

Examples of the vegetable oil polyol include hydroxyl group-containing vegetable oils such as castor oil and coconut oil. Examples thereof include castor oil polyol or ester-modified castor oil polyol obtained by reacting castor oil fatty acid with polypropylene polyol.

Examples of the polyolefin polyol include polybutadiene polyol and a partially Ken-valent ethylene-vinyl acetate copolymer.

Examples of the acrylic polyol include a copolymer obtained by copolymerizing a hydroxyl group-containing acrylate and a copolymerizable vinyl monomer copolymerizable with the hydroxyl group-containing acrylate.

Examples of the hydroxyl group-containing acrylate include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2,2-dihydroxymethylbutyl (meth) acrylate, and polyhydroxyalkylmalate. Examples thereof include polyhydroxyalkyl fumarate. Preferably, 2-hydroxyethyl (meth) acrylate and the like can be mentioned.

Examples of the copolymerizable vinyl monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and s-butyl ( Alkyl (meth) acrylates, t-butyl (meth) acrylates, pentyl (meth) acrylates, isopentyl (meth) acrylates, hexyl (meth) acrylates, isononyl (meth) acrylates, 2-ethylhexyl (meth) acrylates, cyclohexyl acrylates, etc. Meta) acrylates (1-12 carbon atoms), eg aromatic vinyls such as styrene, vinyltoluene, α-methylstyrene, eg vinyl cyanide such as (meth) acrylonitrile, eg (meth) acrylic acid, fumaric acid , Maleic acid, vinyl monomer containing carboxyl group such as itaconic acid, or alkyl ester thereof, for example, ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, oligoethylene glycol. Alcan polyol poly (meth) acrylates such as di (meth) acrylates, trimethylolpropandi (meth) acrylates, trimethylolpropane tri (meth) acrylates, for example 3- (2-isocyana-2-propyl) -α-methyl Examples thereof include vinyl monomers containing an isocyanate group such as styrene.

The acrylic polyol can be obtained by copolymerizing these hydroxyl group-containing acrylates and copolymerizable vinyl monomers in the presence of a suitable solvent and polymerization initiator.

Further, the acrylic polyol includes, for example, a silicone polyol and a fluorine polyol.

Examples of the silicone polyol include a modified polysiloxane polyol in which a hydroxyl group is introduced into a dialkylpolysiloxane, and, for example, in the above-mentioned copolymerization of an acrylic polyol, as a copolymerizable vinyl monomer, for example, γ-methacryloxypropyltrimethoxysilane and the like. Acrylic polyols containing a silicone compound containing a vinyl group of the above can be mentioned.

Examples of the fluorine polyol include an acrylic polyol in which a fluorine compound containing a vinyl group such as tetrafluoroethylene and chlorotrifluoroethylene is blended as the copolymerizable vinyl monomer in the above-mentioned copolymerization of the acrylic polyol. ..

The vinyl monomer-modified polyol can be obtained by reacting the above-mentioned high molecular weight polyol with a vinyl monomer.

These high molecular weight polyols can be used alone or in combination of two or more.

Examples of the high molecular weight polyol include a polyether polyol, a polyester polyol, and a polycarbonate polyol, and more preferably, a polyether polyol.

The average number of hydroxyl groups of the high molecular weight polyol is, for example, 1.8 or more, preferably 2 or more, and for example, 6 or less, preferably 4 or less.

The urethanization reaction can be based on a known method. The reaction temperature in the urethanization reaction is, for example, 50 ° C. or higher, for example, 120 ° C. or lower, preferably 100 ° C. or lower. The reaction time is, for example, 0.5 hours or more, preferably 1 hour or more, and for example, 15 hours or less, preferably 10 hours or less.

Further, in the urethanization reaction, if necessary, an organic solvent can be blended to prepare an isocyanate group-terminated urethane prepolymer in the presence thereof (solution polymerization).

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, nitriles such as acetonitrile, alkyl esters such as methyl acetate, ethyl acetate, butyl acetate and isobutyl acetate, for example, n-. Aliper hydrocarbons such as hexane, n-heptane, octane, eg, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, eg aromatic hydrocarbons such as toluene, xylene, ethylbenzene, eg, methyl cellosolve acetate. , Ethyl cellosolve acetate, methyl carbitol acetate, ethyl carbitol acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl-3-ethoxypropionate and other glycol ether esters. Such as ethers such as diethyl ether, tetrahydrofuran, dioxane, for example, halogenated aliphatic hydrocarbons such as methyl chloride, methylene chloride, chloroform, carbon tetrachloride, methyl bromide, methylene iodide, dichloroethane, for example. Polar aprotons such as N-methylpyrrolidone, dimethylformamide, N, N'-dimethylacetamide, dimethylsulfoxide, hexamethylphosphonylamide, and known non-flammable solvents can be mentioned.

These organic solvents can be used alone or in combination of two or more.

In solution polymerization, the blending ratio of the organic solvent is appropriately set depending on the purpose and application.

Further, in the urethanization reaction, for example, a known urethanization catalyst such as amines or an organometallic compound can be added at an appropriate ratio, if necessary.

Examples of amines include tertiary amines such as triethylamine, triethylenediamine, bis- (2-dimethylaminoethyl) ether and N-methylmorpholine, and quaternary ammonium salts such as tetraethylhydroxylammonium, for example, imidazole. Examples thereof include imidazoles such as 2-ethyl-4-methylimidazole.

Examples of the organometallic compound include tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, dibutyltin dilaurate, and dibutyltin. Organic tin compounds such as dineodecanoate, dioctyltin dimercaptide, dioctyltin dilaurylate, dibutyltin dichloride, eg, organolead compounds such as lead octanate, lead naphthenate, eg organic nickel compounds such as nickel naphthenate, eg , Organic cobalt compounds such as cobalt naphthenate, for example, organic copper compounds such as copper octene, for example, organic bismuth compounds such as bismuth octylate and bismuth neodecanoate.

Further, examples of the urethanization catalyst include potassium salts such as potassium carbonate, potassium acetate and potassium octylate.

These urethanization catalysts can be used alone or in combination of two or more.

Preferred examples of the urethanization catalyst include organometallic compounds.

Further, in the case of preparing an isocyanate group-terminated urethane prepolymer by solution polymerization, when an organic solvent is used, the organic solvent can be removed by a known removing means, if necessary.

Further, if necessary, the free (unreacted) polyisocyanate from the obtained isocyanate group-terminated urethane prepolymer may be removed by a known removing means such as distillation or extraction.

The average number of isocyanate groups of the isocyanate group-terminated urethane prepolymer (solid content) is, for example, 1.2 or more, preferably 1.5 or more, more preferably 2 or more, and for example, 4 or less, preferably 3 or less. , More preferably 2.5 or less, and particularly preferably 2.

The isocyanate group-terminated urethane prepolymer having an average number of isocyanate groups of 2 contains, for example, a diisocyanate monomer (for example, a diisocyanate such as an aromatic diisocyanate, an aromatic aliphatic diisocyanate, an aliphatic diisocyanate, or an alicyclic diisocyanate) and a hydroxyl group. It can be obtained by reacting two high molecular weight polyols (high molecular weight diols) as described above.

The isocyanate group-terminated urethane prepolymer (solid content) has an isocyanate group equivalent of, for example, 84 to 3500, preferably 150 to 2800, and more preferably 168 to 2335. The isocyanate group equivalent is synonymous with the amine equivalent, and can be determined by the method A or method B of JIS K 1603-1 (2007).

The isocyanate group content (isocyanate group content, NCO%) of such an isocyanate group-terminated urethane prepolymer (solid content) is, for example, 1.2% by mass or more, preferably 1.5% by mass or more. More preferably, it is 1.8% by mass or more, further preferably 2.0% by mass or more, particularly preferably 3.0% by mass or more, and for example, 50% by mass or less, preferably 28% by mass or less. It is more preferably 25% by mass or less, further preferably 10% by mass or less, and particularly preferably 6% by mass or less.

The isocyanate group-terminated urethane prepolymer can be used alone or in combination of two or more.

The isocyanate group-terminated urethane prepolymer preferably includes an isocyanate group-terminated urethane prepolymer which is a reaction product of an aromatic polyisocyanate and a polyether polyol, and more preferably a tolylene diisocyanate and / or a diphenylmethane diisocyanate and a poly. Examples thereof include isocyanate group-terminated urethane prepolymers which are reaction products with ether polyols, and more preferably, isocyanate group-terminated urethane prepolymers which are reaction products of tolylene diisocyanate and polyether polyols.

Further, in the isocyanate group-terminated urethane prepolymer, the tolylene diisocyanate used as a raw material is preferably a combination of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate. The combined ratio of these is appropriately set according to the purpose and application.

These polyisocyanate components can be used alone or in combination of two or more.

As the polyisocyanate component, from the viewpoint of adjusting the ratio of the cross-linking point, the soft segment and the hard segment to obtain a cured product having excellent mechanical properties, a combination of an isocyanate group-terminated urethane prepolymer and a polyisocyanate derivative is preferable. More preferably, a polyisocyanate derivative having an average number of isocyanate groups of 3 or more and an isocyanate group-terminated urethane prepolymer having an average number of isocyanate groups of 2 may be used in combination.

The combined ratio of the polyisocyanate derivative having an average number of isocyanate groups of 3 or more and the isocyanate group-terminated urethane prepolymer having an average number of isocyanate groups of 2 is the isocyanate group in the isocyanate group-terminated urethane prepolymer and the isocyanate group in the polyisocyanate derivative. From the viewpoint of mechanical properties (particularly, elongation at break), the ratio of isocyanate groups in the isocyanate group-terminated urethane prepolymer to the total mole of is, for example, 10 mol% or more, preferably 20 mol% or more, more preferably. Is 30 mol% or more, more preferably 35 mol% or more, particularly preferably 40 mol% or more, and from the viewpoint of mechanical properties (particularly hardness), for example, 90 mol% or less, preferably 90 mol% or more. It is 80 mol% or less, more preferably 70 mol% or less, still more preferably 65 mol% or less, and particularly preferably 50 mol% or less. Further, the isocyanate group in the polyisocyanate derivative is, for example, 10 mol% or more, preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 35 mol% or more, and particularly preferably 40 mol. % Or more, for example, 90 mol% or less, preferably 80 mol% or less, more preferably 70 mol% or less, still more preferably 65 mol% or less, and particularly preferably 50 mol% or less.

Further, from the viewpoint of environmental friendliness, the polyisocyanate component preferably has a reduced content of tolylene diisocyanate (monomer).

More specifically, for example, when the isocyanate group-terminated urethane prepolymer or polyisocyanate derivative is produced using tolylene diisocyanate (monomer) as a raw material, the obtained isocyanate group-terminated urethane prepolymer or polyisocyanate derivative is obtained. Is purified by a known purification means such as thin film distillation or extraction to reduce the content ratio of unreacted tolylene diisocyanate (monomer).

From the viewpoint of environmental friendliness, the content ratio of tolylene diisocyanate (monomer) is, for example, 5% by mass or less, preferably 1% by mass or less, more preferably 0.1, based on the total amount of the polyisocyanate component. It is mass% or less.

An active hydrogen group-containing component is a component containing a free or non-free active hydrogen group. Examples of the active hydrogen group include a hydroxyl group, an amino group, a mercapto group and the like, and preferably a hydroxyl group and an amino group.

More specifically, the active hydrogen group-containing component has a compound having a free active hydrogen group (hereinafter, referred to as an active hydrogen compound (or a non-latent active hydrogen compound)) and a non-free active hydrogen group. However, it contains a compound that produces an active hydrogen group by reacting with water (hereinafter referred to as a latent active hydrogen compound).

Examples of the active hydrogen compound include an amino group-containing compound and a hydroxyl group-containing compound.

The amino group-containing compound is a compound containing at least one amino group in the molecule, and is, for example, a polyamine compound such as an aromatic polyamine compound, an aromatic aliphatic polyamine compound, an alicyclic polyamine compound, or an aliphatic polyamine compound. Can be mentioned.

Examples of the aromatic polyamine compound include 4,4'-diphenylmethanediamine, 3,3'-dichloro-4,4'-diphenylmethanediamine, 2,4- and 2,6-diethyltoluenediamine (DETDA), and dimethylthio. Toluene diamine, 4,4'-methylenebis (3-chloro-2,6-diethylaniline), N, N'-di-secondary-butyl-para-phenylenediamine, 4,4'-bis (secondary-butylamino) Diphenylmethane, 4,4'-bis (methylamino) diphenylmethane, trimethylene-bis (4-aminobenzoate), polytetramethylene oxide-di-p-aminobenzoate, N-phenyl-N'-isopropyl-p-phenylenediamine, Examples thereof include aromatic diamine compounds such as N-phenyl-N'-(1,3-dimethylbutyl) -p-phenylenediamine and 4,4'-methylenebis (2-chloroaniline) (abbreviation: MOCA). Examples of the aromatic polyamine compound include commercially available products, and more specifically, for example, ETCURE 100 (DETDA, trade name: Albemarle Corporation), Etaxure 300 (trade name: Albemarle Corporation), Etaxure 534 (trade name: Albemarle Corporation). Examples thereof include aromatic diamine compounds such as product name: Albemarle Corporation) and TCDAM (trade name: Ihara Chemical Corporation).

Examples of the aromatic aliphatic polyamine compound include aromatic aliphatic diamine compounds such as 1,3- or 1,4-xylylenediamine or a mixture thereof.

Examples of the alicyclic polyamine compound include 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis- (4-aminocyclohexyl) methane, diaminocyclohexane, and 3,9-bis (3-amino). Propyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,3- and 1,4-bis (aminomethyl) cyclohexane and mixtures thereof, 1,3- and 1,4- Examples thereof include alicyclic diamine compounds such as bis (aminoethyl) cyclohexane and mixtures thereof.

Examples of the aliphatic polyamine compound include ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, hydrazine, 1,2-diaminoethane, 1,2-diaminopropane, and 1,3-diaminopentane. Examples include aliphatic diamine compounds. Further, examples of the aliphatic polyamine compound include polyoxyalkylene polyamines such as polyoxyethylene polyamine, polyoxypropylene polyamine, polyoxytetramethylene polyamine, and polyoxyethylene polyoxypropylene polyamine.

These amino group-containing compounds can be used alone or in combination of two or more.

As the amino group-containing compound, preferably, an aromatic polyamine compound is mentioned, and more preferably, an aromatic diamine compound is mentioned.

Further, as the amino group-containing compound, a commercially available product is preferable from the viewpoint of availability, and further preferably from the viewpoint of pot life and mechanical properties, EtaCure 100 (manufactured by Albemarle) and EtaCure 534 (Albemarle). ), And particularly preferably, the combined use of EtaCure 100 (manufactured by Albemarle) and EtaCure 534 (manufactured by Albemarle) can be mentioned.

The combined ratio of EtaCure 100 (manufactured by Albemarle) and EtaCure 534 (manufactured by Albemarle) is appropriately set according to the purpose and application, but EtaCure 100 (manufactured by Albemarle) per mass part of EtaCure 534 (manufactured by Albemarle Corporation) is, for example, 1 part by mass or more, preferably 5 parts by mass or more, and for example, 50 parts by mass or less, preferably 20 parts by mass or less.

Further, from the viewpoint of environmental friendliness, the amino group-containing compound preferably has a reduced content of 4,4'-methylenebis (2-chloroaniline) (MOCA). That is, the amino group-containing compound is preferably an aromatic diamine compound excluding 4,4'-methylenebis (2-chloroaniline) (MOCA).

The content ratio of 4,4'-methylenebis (2-chloroaniline) is, for example, 5% by mass or less, preferably 1% by mass or less, more preferably 0.% by mass, based on the total amount of the amino group-containing compounds. It is 1% by mass or less, particularly preferably 0% by mass.

The hydroxyl group-containing compound is a compound containing at least one hydroxyl group in the molecule, and examples thereof include monool compounds and polyol compounds.

The monool compound is a compound containing one hydroxyl group in the molecule, and examples thereof include a low molecular weight monool compound and a high molecular weight monool compound.

The low molecular weight monool compound is a compound having one hydroxyl group and having a number average molecular weight of less than 300, preferably less than 400, for example, methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, s-butanol, and the like. t-Butanol, 2-ethylhexyl alcohol, other alkanols (C5-38) and aliphatic unsaturated alcohols (C9-24), alkenyl alcohols, 2-propen-1-ol, alkazienol (C6-8), 3 , 7-Dimethyl-1,6-octadien-3-ol and other monohydric alcohols having 1 to 30 carbon atoms can be mentioned.

These low molecular weight monool compounds can be used alone or in combination of two or more.

The high molecular weight monool compound is a compound having a number average molecular weight of 300 or more, preferably 400 or more, for example, 10,000 or less, having one hydroxyl group, and examples thereof include one-ended blockade polyoxyalkylene glycol.

Examples of the one-ended blockade polyoxyalkylene glycol include monoalkoxypolyoxyalkylene glycol in which one end of the polyoxyalkylene glycol is sealed with an alkyl group or the like.

In the monoalkoxypolyoxyalkylene glycol, examples of the oxyalkylene group include an oxyalkylene group having 1 to 4 carbon atoms such as an oxyethylene group, an oxypropylene group, an oxytrimethylene group and an oxytetramethylene group, and preferably. , An oxyalkylene group having 2 to 3 carbon atoms is mentioned, more preferably an oxyethylene group and an oxypropylene group, and further preferably an oxypropylene group.

That is, examples of the one-ended closed polyoxyalkylene glycol include one-ended sealed polyoxyethylene glycol and one-ended sealed polyoxypropylene glycol.

The alkyl group for sealing one end is, for example, an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. , More preferably, an alkyl group having 1 to 4 carbon atoms, particularly preferably an alkyl group having 1 to 2 carbon atoms, and more specifically, a methyl group or an ethyl group.

As polyoxyalkylene glycol (that is, monoalkoxypolyoxyalkylene glycol) whose one end is sealed with such an alkyl group, specifically, methoxypolyoxyethylene glycol, ethoxypolyoxyethylene glycol, methoxypolyoxypropylene. Glycol, ethoxypolyoxypropylene glycol and the like can be mentioned, and methoxypolyoxypropylene glycol is preferable.

These high molecular weight monool compounds can be used alone or in combination of two or more.

These monool compounds can be used alone or in combination of two or more.

From the viewpoint of pot life and mechanical properties, the monool compound is preferably a high molecular weight monool compound, and more preferably one-ended sealed polyoxypropylene glycol or one-ended sealed polyoxyethylene glycol. From the viewpoint of mechanical properties, one-ended sealed polyoxypropylene glycol is more preferable, and methoxypolyoxypropylene glycol is particularly preferable.

The polyol compound is a compound containing two or more hydroxyl groups in the molecule, for example, a diol compound containing two hydroxyl groups in the molecule, a triol compound containing three hydroxyl groups in the molecule, and 4 in the molecule. Examples thereof include tetravalent or higher polyol compounds containing one or more hydroxyl groups.

These polyol compounds can be used alone or in combination of two or more.

As the polyol compound, a diol compound is preferable.

Examples of the diol compound include a low molecular weight diol compound and a high molecular weight diol compound.

The low molecular weight diol compound is a compound having two hydroxyl groups and having a number average molecular weight of less than 300, preferably less than 400, and examples thereof include the above-mentioned dihydric alcohols. More specifically, for example, ethylene glycol and propylene. Glycol, 1,3-propanediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3- Methyl-1,5-pentanediol, 2,2,2-trimethylpentanediol, 3,3-dimethylolheptan, alkane (C7-20) diol, 1,3- or 1,4-cyclohexanedimethanol and theirs. Mixtures, 1,3- or 1,4-cyclohexanediol and mixtures thereof, hydride bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, bisphenol Examples thereof include dihydric alcohols such as A, diethylene glycol, triethylene glycol, and dipropylene glycol.

These low molecular weight diol compounds can be used alone or in combination of two or more.

The high molecular weight diol compound is a compound having two hydroxyl groups and having a number average molecular weight of 300 or more, preferably 400 or more, and examples thereof include the above high molecular weight polyol having an average number of hydroxyl groups of 2. More specifically, examples thereof include a polyether polyol (polyether diol) having an average number of hydroxyl groups of 2, a polyester polyol (polyester diol) having an average number of hydroxyl groups of 2, and a polycarbonate polyol (polycarbonate diol) having an average number of hydroxyl groups of 2.

The high molecular weight diol compound can be used alone or in combination of two or more.

The high molecular weight diol compound is preferably a polyether diol.

Examples of the polyether diol include polyoxyalkylene glycol.

The polyoxyalkylene glycol can be obtained as an addition polymer of an alkylene oxide using the above-mentioned low molecular weight polyol or the like or a polyamine compound as an initiator.

Examples of the alkylene oxide include propylene oxide, ethylene oxide, butylene oxide, styrene oxide and the like. In addition, these alkylene oxides can be used alone or in combination of two or more. Further, among these, alkylene oxide having 2 to 3 carbon atoms is preferable, and ethylene oxide and propylene oxide are specifically mentioned.

In other words, as the polyoxyalkylene glycol, preferably, polyoxyalkylene glycol having 2 to 3 carbon atoms in the oxyalkylene group (hereinafter, polyoxy C2-3 alkylene glycol) can be mentioned, and more preferably polyoxyethylene. Examples thereof include glycols, polyoxypropylene glycols, and polyoxyethylene / oxypropylene (random / block) glycols.

As the polyoxyalkylene glycol, polyoxypropylene glycol is preferably used from the viewpoint of pot life and mechanical properties.

Further, in the polyoxypropylene glycol, an alkylene oxide other than propylene oxide (ethylene oxide, butylene oxide, etc.) can be added to the molecular end by a known method, if necessary. As the alkylene oxide added to the end of the molecule, ethylene oxide is preferable.

The addition ratio of the oxyethylene unit (preferably ethylene oxide) to the polyoxypropylene glycol is not particularly limited, but is, for example, 5% by mass or more, preferably 10% by mass, based on the total amount of the polyoxypropylene glycol. % Or more, for example, 30% by mass or less, preferably 20% by mass or less.

These polyether diols can be used alone or in combination of two or more.

As the polyether diol, preferably, polyoxypropylene glycol is mentioned, and from the viewpoint of mechanical properties (particularly, elongation at break and tensile strength), polyoxypropylene glycol (molecular terminal) in which ethylene oxide is added to the molecular end is more preferable. Polyoxypropylene glycol having an oxyethylene group).

These diol compounds can be used alone or in combination of two or more.

These hydroxyl group-containing compounds can be used alone or in combination of two or more.

The hydroxyl group-containing compound preferably includes a monool compound and a polyol compound in combination, and more preferably a monool compound and a diol compound in combination.

Further, in such a case, more preferably, the diol compound contains polyoxypropylene glycol having ethylene oxide added to the molecular end, and the monool compound contains one-ended sealed polyoxypropylene glycol. Can be mentioned.

If the diol compound contains polyoxypropylene glycol having ethylene oxide added to the molecular end, and the monool compound contains one-ended sealed polyoxypropylene glycol, the mechanical strength and elongation characteristics of the cured product It is possible to achieve both.

That is, when the solution A and the solution B are mixed, the polyisocyanate component is first reacted with a more reactive diol compound (polyoxypropylene glycol having ethylene oxide added to the molecular end) to form a network of polyurethane resins. , And excellent mechanical strength (tensile strength, hardness, etc.) can be obtained, and then a monool compound (single-ended sealed polyoxypropylene glycol), which has relatively low reactivity, is reacted to obtain excellent elongation. Characteristics (break elongation) can be measured. Therefore, in the cured product, both mechanical strength and elongation characteristics can be achieved at the same time.

Particularly preferably, the diol compound is composed of polyoxypropylene glycol having ethylene oxide added to the molecular end, and the monool compound is composed of one-ended sealed polyoxypropylene glycol.

These active hydrogen compounds (non-latent active hydrogen compounds) can be used alone or in combination of two or more.

As the active hydrogen compound, from the viewpoint of adjusting the ratio of the cross-linking point, the soft segment and the hard segment to obtain a cured product having excellent mechanical properties, a combination of an amino group-containing compound and a hydroxyl group-containing compound is preferable, and more preferably. Can be used in combination with an aromatic polyamine compound, a monool compound, and a polyol compound, and more preferably, a combination of an aromatic diamine compound, a monool compound, and a diol compound can be mentioned.

When an aromatic diamine compound, a monool compound, and a diol compound are used in combination, the combined ratio thereof adjusts the cross-linking point, urea bond (cohesiveness), etc., and is appropriate from the viewpoint of pot life and mechanical properties. Set.

More specifically, for example, with respect to the total moles of the active hydrogen group in the aromatic diamine compound, the active hydrogen group in the monool compound, and the active hydrogen group in the diol compound, in the aromatic diamine compound. From the viewpoint of mechanical properties (particularly hardness), the ratio of active hydrogen groups is, for example, 30 mol% or more, preferably 40 mol% or more, more preferably 50 mol% or more, still more preferably 60 mol% or more. From the viewpoint of pot life, for example, it is 99 mol% or less, preferably 95 mol% or less, more preferably 90 mol% or less, still more preferably 80 mol% or less.

Further, the ratio of the active hydrogen group in the monool compound to the total mole of the active hydrogen group in the aromatic diamine compound, the active hydrogen group in the monool compound, and the active hydrogen group in the diol compound is determined. From the viewpoint of pot life and mechanical properties, for example, 1 mol% or more, preferably 2 mol% or more, more preferably 3 mol% or more, still more preferably 5 mol% or more, for example, 40 mol% or less. It is preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less.

Further, the ratio of the active hydrogen group in the diol compound to the total mole of the active hydrogen group in the aromatic diamine compound, the active hydrogen group in the monool compound, and the active hydrogen group in the diol compound is a pot. From the viewpoint of life and mechanical properties, for example, 1 mol% or more, preferably 2 mol% or more, more preferably 3 mol% or more, still more preferably 5 mol% or more, for example, 40 mol% or less, It is preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less.

Further, the ratio of the active hydrogen group in the monool compound to the total mole of the active hydrogen group in the monool compound and the active hydrogen group in the diol compound is the mechanical property (particularly, elongation at break and tensile strength). From the viewpoint of, for example, 5 mol% or more, preferably 10 mol% or more, more preferably 30 mol% or more, still more preferably 40 mol% or more, particularly preferably 50 mol% or more, and also. From the viewpoint of mechanical properties (particularly, tensile strength), for example, 80 mol% or less, preferably 75 mol% or less, more preferably 70 mol% or less, still more preferably 65 mol% or less, particularly preferably 60. It is less than mol%. The proportion of active hydrogen groups in the diol compound is, for example, 20 mol% or more, preferably 25 mol% or more, more preferably 30 mol% or more, still more preferably 35 mol% or more, and particularly preferably. It is 40 mol% or more, for example, 95 mol% or less, preferably 90 mol% or less, more preferably 70 mol% or less, still more preferably 60 mol% or less, and particularly preferably 50 mol% or less. ..

The latent active hydrogen compound is a compound that produces an active hydrogen group by reacting with water, and examples thereof include urethane polyoxazolidine compounds, aldimine compounds, and ketimine compounds.

The urethane polyoxazolidine compound can be obtained, for example, as a reaction product of polyisocyanate and N-hydroxyalkyloxazolidine.

Examples of the polyisocyanate include the above-mentioned polyisocyanate monomer and the above-mentioned polyisocyanate derivative, and preferably the above-mentioned polyisocyanate monomer. More specifically, examples of the polyisocyanate monomer include the above-mentioned aromatic polyisocyanate, the above-mentioned aromatic aliphatic polyisocyanate, and the above-mentioned aliphatic polyisocyanate (including the above-mentioned alicyclic polyisocyanate). Can be mentioned. These polyisocyanate monomers can be used alone or in combination of two or more.

As the polyisocyanate, preferably, an aliphatic polyisocyanate (including the above-mentioned alicyclic polyisocyanate) can be mentioned, and more preferably, hexamethylene diisocyanate, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane can be mentioned, and further. Preferably, isophorone isocyanate is used.

N-Hydroxyalkyl oxazolidine is a compound in which a substituent having a hydroxyl group at the terminal is bonded to a nitrogen atom of the oxazolidine ring, and is represented by, for example, the following formula (1).

(In the formula, R1 represents a hydrogen atom or a monovalent organic group, and R2 represents a divalent organic group.)
In the above formula (1), R1 is a hydrogen atom or a monovalent organic group.

Examples of the monovalent organic group include a hydrocarbon group having 1 to 5 carbon atoms, and preferably an alkyl group having 1 to 5 carbon atoms. More specifically, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group and the like can be mentioned, preferably a propyl group and an isopropyl group, and more preferably an isopropyl group. Be done.

In the above formula (1), R2 is a divalent organic group.

Examples of the divalent organic group include an alkylene chain having 2 to 5 carbon atoms, and preferably an alkylene group having 2 to 4 carbon atoms. More specifically, for example, an ethylene group, a propylene group, a butylene group and the like can be mentioned, and an ethylene group is preferably mentioned.

As a combination of R1 and R2, R1 is an isopropyl group and R2 is an ethylene group, particularly preferably from the viewpoint of pot life.

The N-hydroxyalkyloxazolidine is not particularly limited and can be obtained by a known method. For example, N-hydroxyalkyloxazolidine can be a compound having two hydroxyl groups and one amino group in the molecule (eg, amino alcohols such as diethanolamine) and, for example, aldehydes (eg, propionaldehyde, isobutyraldehyde, etc.). It is obtained by reacting with n-hexanal, benzaldehyde, etc.). More specifically, in this method, for example, aminoalcohols and aldehydes are dehydrated in a known organic solvent (preferably benzene, toluene, xylene, etc.) at, for example, 70 to 150 ° C. Remove the generated water. This gives N-hydroxyalkyloxazolidine.

More specifically, as N-hydroxyalkyloxazolidine, for example, 2-isopropyl3- (2-hydroxyethyl) -1,3 oxazolidine, 2-pentyl-3-oxazolidine ethanol, 2- (1-methylbutyl) -3. -Oxazolidine ethanol and the like. These N-hydroxyalkyloxazolidines can be used alone or in combination of two or more.

As the N-hydroxyalkyloxazolidine, 2-isopropyl-3- (2-hydroxyethyl) -1,3-oxazolidine is preferable.

Then, in order to obtain a urethane polyoxazolidine compound, for example, the equivalent ratio (hydroxyl group / isocyanate group) of the hydroxyl group of N-hydroxyalkyloxazolidine to 1 mol of the isocyanate group of the polyisocyanate of polyisocyanate and N-hydroxyalkyloxazolidine is determined. For example, the reaction is carried out so as to be 0.5 to 2.0, preferably 0.9 to 1.1. The reaction conditions are not particularly limited, and the reaction temperature is, for example, 80 to 100 ° C. As a result, a urethane polyoxazolidine compound is obtained.

The formation of the urethane polyoxazolidine compound can be confirmed by the disappearance of the peak of 2250 cm ^{-1 in} the infrared spectroscopic measurement.

In the urethane polyoxazolidine compound thus obtained, the oxazolidine ring is opened by the reaction with water to generate a hydroxyl group and an amino group. That is, the urethane polyoxazolidine compound produces an active hydrogen group by reacting with water.

The aldimin compound can be obtained, for example, as a reaction product of a polyamine and an aldehyde.

Examples of the polyamine include the above-mentioned aromatic polyamine compound, for example, the above-mentioned aromatic aliphatic polyamine compound, for example, the above-mentioned alicyclic polyamine compound, for example, the above-mentioned aliphatic polyamine compound, and the like.

These polyamines can be used alone or in combination of two or more.

As the polyamine, an aliphatic polyamine compound is preferable, and tetramethylenediamine is more preferable.

Examples of the aldehyde include aromatic aldehydes and aliphatic aldehydes.

Examples of aromatic aldehydes include benzaldehyde, o-tolvaldehyde, m-tolualdehyde, p-tolvaldehyde, 4-ethylbenzaldehyde, 4-propylbenzaldehyde, 4-butylbenzaldehyde, 2,4-dimethylbenzaldehyde, 2,4. , 5-trimethylbenzaldehyde, p-anisaldehyde, p-ethoxybenzaldehyde and the like.

Examples of the aliphatic aldehyde include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, and allylaldehyde.

These aldehydes can be used alone or in combination of two or more.

As the aldehyde, preferably, aromatic aldehyde is mentioned, and more preferably, p-tolvaldehyde is mentioned.

Then, in order to obtain an argimine compound, for example, the equivalent ratio (carbonyl group / amino group) of the carbonyl group of the aldehyde to the amino group of the polyamine is 0.5 to 2, preferably 1 to 2. It is blended in a ratio of 2 and, if necessary, dehydrated in the presence of an acid catalyst and an organic solvent.

Examples of the acid catalyst include inorganic acids and organic acids. Examples of the inorganic acid include phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid and the like. Examples of the organic acid include sulfonic acid compounds such as methanesulfonic acid, p-toluenesulfonic acid and dodecylbenzenesulfonic acid, and phosphoric acid esters such as trimethyl phosphate, triethyl phosphate and monobutyl phosphate, for example, formic acid. , Acetic acid, oxalic acid and the like. These acid catalysts can be used alone or in combination of two or more. Examples of the acid catalyst include organic acids, and more preferably formic acid.

The amount of the acid catalyst added, the amount of the organic solvent added, and the reaction conditions in the dehydration reaction are not particularly limited, and are appropriately set according to the purpose and application.

As a result, an aldimine compound is obtained.

The formation of the aldimine compound can be confirmed by the peak of 1640 cm ^-1 in the infrared spectroscopic measurement.

The aldimine compound thus obtained is decomposed (hydrolyzed) by reaction with water to generate an amino group. That is, the aldimine compound is a latent active hydrogen compound that produces an active hydrogen group by reacting with water.

The ketimine compound can be obtained, for example, as a reaction product of a polyamine and a ketone.

Examples of the polyamine include the above-mentioned aromatic polyamine compound, for example, the above-mentioned aromatic aliphatic polyamine compound, for example, the above-mentioned alicyclic polyamine compound, for example, the above-mentioned aliphatic polyamine compound, and the like.

These polyamines can be used alone or in combination of two or more.

The polyamine preferably includes an aliphatic polyamine compound, more preferably a polyoxyalkylene polyamine, and further preferably a polyoxypropylene polyamine.

Examples of the ketone include aromatic ketones and aliphatic ketones.

Examples of the aromatic ketone include phenylmethyl ketone and diphenyl ketone.

Examples of the aliphatic ketone include acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diisopropyl ketone, methyl hexanone, methyl cyclohexanone, cyclopentanone, and cycloheptanone.

These ketones can be used alone or in combination of two or more.

Then, in order to obtain a ketimine compound, for example, a polyamine and a ketone have an equivalent ratio (carbonyl group / amino group) of the carbonyl group of the ketone to the amino group of the polyamine of 0.5 to 2, preferably 1 to 1. It is blended in a ratio of 2 and, if necessary, dehydrated in the presence of an acid catalyst and an organic solvent.

The amount of the acid catalyst added, the amount of the organic solvent added, and the reaction conditions in the dehydration reaction are not particularly limited, and are appropriately set according to the purpose and application.

The ketimine compound thus obtained is decomposed (hydrolyzed) by a reaction with water to generate an amino group. That is, the ketimine compound is a latent active hydrogen compound that produces an active hydrogen group by reacting with water.

These latent active hydrogen compounds can be used alone or in combination of two or more.

The latent active hydrogen compound is preferably a urethane polyoxazolidine compound from the viewpoint of pot life and mechanical properties (particularly, hardness and elongation at break).

From the viewpoint of particularly improving the pot life, a ketimine compound is preferable. However, when a ketimine compound is used, the storage stability may be lower than when a urethane polyoxazolidine compound is used.

Further, from the viewpoint of particularly improving the tensile strength, an aldimine compound is preferable. However, when an aldimin compound is used, the reaction between the aldimin compound and water may generate an odor, which may reduce the working environment.

In the active hydrogen group-containing component, the ratio of the latent active hydrogen compound is adjusted from the viewpoint of pot life and mechanical properties with reference to the active hydrogen group generated by the reaction between the latent active hydrogen compound and water.

More specifically, the total molar amount of active hydrogen groups in the active hydrogen group-containing component (that is, the active hydrogen groups derived from the non-latent active hydrogen compound and the activity generated by the reaction of the latent active hydrogen compound with water). From the viewpoint of pot life, the ratio of active hydrogen groups generated by the reaction of the latent active hydrogen compound with water is 35 mol% or more, preferably 40 mol% or more, more preferably with respect to the total of hydrogen groups). Is 45 mol% or more, and from the viewpoint of mechanical properties (particularly, elongation at break), it is 65 mol% or less, preferably 60 mol% or less, and more preferably 55 mol% or less. The proportion of active hydrogen groups (free) in the active hydrogen compound is 35 mol% or more, preferably 40 mol% or more, more preferably 45 mol% or more, 65 mol% or less, preferably 60 mol. % Or less, more preferably 55 mol% or less.

If the proportion of the latent active hydrogen compound is less than the above lower limit, the pot life derived from the latent active hydrogen compound is not sufficiently secured, and coating unevenness is likely to occur. Therefore, the appearance and mechanical properties of the cured product are also affected. Inferior. On the other hand, when the ratio of the latent active hydrogen compound exceeds the above upper limit, the pot life becomes excessively long, so that the curing efficiency (production efficiency) is inferior, and when the curing time is long, the mechanical properties of the cured product deteriorate. There is a problem.

Further, in the two-component curable polyurethane resin composition, the ratio of the polyisocyanate component to the active hydrogen group-containing component is based on the equivalent ratio of the active hydrogen group in the active hydrogen group-containing component to the isocyanate group in the polyisocyanate component. Is adjusted.

At this time, the active hydrogen group in the active hydrogen group-containing component is the total of the active hydrogen group derived from the non-latent active hydrogen compound and the active hydrogen group generated by the reaction of the latent active hydrogen compound with water. ..

More specifically, from the viewpoint of pot life and mechanical properties, active hydrogen groups in active hydrogen group-containing components (active hydrogen groups derived from non-latent active hydrogen compounds and latent active hydrogen compounds react with water). The equivalent ratio (isocyanate group / active hydrogen group) of the isocyanate group in the polyisocyanate component is 0.8 or more, preferably 0.9 or more, more preferably 0.9 or more, based on the total of the active hydrogen groups generated thereafter. , 0.95 or more, 1.2 or less, preferably 1.1 or less, and more preferably 1.05 or less.

The two-component curable polyurethane resin composition further contains a water-absorbent filler.

The water-absorbent filler is a filler having a property of absorbing (adsorbing) water.

That is, the water-absorbent filler reacts with water (hydration reaction, etc.) by contacting with water, or adsorbs water inside (pore adsorption, etc.) to isolate water from the outside (inert). It is a filler to be made into.

Examples of such a water-absorbent filler include hydraulic alumina, zeolite, magnesium oxide, calcium hydroxide, magnesium hydroxide, cement, and Zeolam (molecular sieve).

These water-absorbent fillers can be used alone or in combination of two or more.

Preferred examples of the water-absorbent filler include hydraulic alumina and zeolite.

In particular, from the viewpoint of pot life, zeolite is more preferable, and from the viewpoint of availability and mechanical properties, hydraulic alumina is more preferable.

Many forms such as α, β, γ, ∂, ε, and ζ are recognized from the crystal form of hydraulic alumina, and the properties differ depending on the degree of crystallinity. Preferably, hydraulic alumina containing ρ-alumina is mentioned, and examples of the trade names include BK-112 (hydraulic alumina) and BK-115 (hydraulic alumina) (all manufactured by Sumitomo Chemical Co., Ltd.). Can be mentioned.

By using hydraulic alumina, the pot life can be relatively long.

The water-absorbent filler is contained, for example, as a powder. The average particle size of the water-absorbent filler is, for example, 0.05 μm or more, preferably 0.2 μm or more, and for example, 500 μm or less, preferably 200 μm or less.

The water absorption rate of the water-absorbent filler is, for example, 5% or more, preferably 10% or more. The water absorption rate is measured by the curl fisher method equipped with a heating furnace. The water absorption rate can also be measured by a differential thermal analysis (DTA) method.

The content ratio of the water-absorbent filler is adjusted as a mass ratio to the total amount of the two-component curable polyurethane resin composition from the viewpoint of pot life and mechanical properties.

More specifically, the content ratio of the water-absorbent filler is 5 parts by mass or more from the viewpoint of pot life and mechanical properties (particularly, elongation at break) with respect to 100 parts by mass of the total amount of the two-component curable polyurethane resin composition. It is preferably 7 parts by mass or more, more preferably 9 parts by mass or more, further preferably 10 parts by mass or more, and from the viewpoint of mechanical properties (particularly, elongation at break), 37.5 parts by mass or less. It is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and further preferably 20 parts by mass or less.

When the content ratio of the water-absorbent filler is less than the above lower limit, there is a problem that foaming occurs due to water due to insufficient water absorption, and the mechanical properties of the obtained cured product are deteriorated. On the other hand, when the content ratio of the water-absorbent filler exceeds the above upper limit, the amount of the water-absorbent filler becomes excessively large, which causes a problem that the mechanical properties of the cured product are lowered and the elongation rate is lowered.

Further, such a two-component curable polyurethane resin composition can also contain a non-water-absorbent filler, if necessary.

The non-water-absorbent filler is a filler that does not absorb water.

That is, the non-water-absorbent filler is a filler that repels water even when it comes into contact with water, or that only surface-supports (surface-adsorbs) water and can easily release the surface-supported water, that is, water. It is a filler that does not isolate (inactivate) the outside from the outside.

Examples of such non-water-absorbent fillers include inorganic fillers such as calcium carbonate, calcium oxide, talc, clay, mica, barium sulfate, titanium oxide, kaolin, diatomaceous earth, glass balloons, and organic balloons.

These non-water-absorbent fillers can be used alone or in combination of two or more.

Calcium carbonate is preferably used as the non-water-absorbent filler.

The non-absorbent filler is contained, for example, as a powder. The average particle size of the water-absorbent filler is, for example, 0.05 μm or more, preferably 0.2 μm or more, and for example, 500 μm or less, preferably 200 μm or less.

The water absorption rate of the non-water-absorbent filler is, for example, less than 5%, preferably less than 0.5%, and more preferably less than 0.3%. The water absorption rate is measured by the curl fisher method equipped with a heating furnace. The water absorption rate can also be measured by a differential thermal analysis (DTA) method.

The content of the non-water-absorbent filler is adjusted as a mass ratio to the water-absorbent filler.

More specifically, the content of the non-water-absorbent filler is, for example, 5 parts by mass or more, preferably 10 parts by mass or more, based on 100 parts by mass of the total amount of the water-absorbent filler from the viewpoint of pot life and mechanical properties. , More preferably 20 parts by mass or more, still more preferably 30 parts by mass or more, particularly preferably 40 parts by mass or more, 200 parts by mass or less, preferably 150 parts by mass or less, more preferably 100 parts by mass. Hereinafter, it is more preferably 80 parts by mass or less, and particularly preferably 70 parts by mass or less.

The two-component curable polyurethane resin composition preferably contains a curing catalyst.

Examples of the curing catalyst include urethanization catalysts. The urethanization catalyst is a catalyst that promotes the reaction between an isocyanate group and an active hydrogen group, and examples thereof include the above-mentioned amines, the above-mentioned organometallic compound, and the above-mentioned potassium salt. These urethanization catalysts can be used alone or in combination of two or more.

Moreover, as a curing catalyst, for example, a catalyst which makes a latent active hydrogen group in a latent active hydrogen compound non-latent (explicit, liberating) can be mentioned. Examples of such a catalyst include a ring-opening catalyst for promoting ring-opening of the oxazolidine ring, and more specifically, for example, octylic acid, 2-ethylhexanoic acid, benzoyl chloride, adipic acid and the like. Can be mentioned. These ring-opening catalysts can be used alone or in combination of two or more.

The blending ratio of the curing catalyst is appropriately set according to the purpose and application.

For example, by using the ring-opening catalyst and the urethanization catalyst in an appropriate ratio, the reaction balance can be adjusted and the reaction rate can be adjusted according to the usage environment of the two-component curable polyurethane resin composition. .. For example, when the two-component curable polyurethane resin composition is used in a low temperature / low humidity environment (when used in winter, when a water-absorbent filler having a high water absorption rate is added, etc.), a curing reaction occurs. Slows down. Therefore, by adding a ring-opening catalyst, it is possible to promote the ring-opening reaction instead of the urethanization reaction, adjust the reaction rate, and obtain an appropriate pot life.

The two-component curable polyurethane resin composition preferably contains a plasticizer.

Examples of the plasticizer include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, din-octyl phthalate, diisooctyl phthalate, di2-ethylhexyl phthalate, dinonyl phthalate, and phthalate. Phthalate-based plasticizers such as diisononyl acid, diisodecyl phthalate, ditridecyl phthalate, dibutylpentyl phthalate, dicyclohexyl phthalate, for example, dioctyl adipate, diisononyl adipate, diisodecyl adipate, dioctyl azerate, dibutyl sebacate, Aliper dibasic acid ester-based plasticizers such as dioctyl sevacinate, eg, glycol ester-based plasticizers such as diethylene glycol benzoate and dipentaerythritol hexaester, for example, phthalate ester plasticizers such as tricresyl phosphate and trioctyl phosphate Agents include, for example, epoxidized soybean oil, butyl epoxidate stearate, octyl epoxidate and other epoxy-based plasticizers. These can be used alone or in combination of two or more. As the plasticizer, a phthalate ester-based plasticizer is preferable.

The blending ratio of the plasticizer is appropriately set according to the purpose and application.

Further, the two-component curable polyurethane resin composition is stable, for example, an antiaging agent, an antioxidant, an ultraviolet absorber, a heat-resistant stabilizer, a polymer light stabilizer, etc., as long as the excellent effects of the present invention are not impaired. Agents, organic solvents, pigments, dyes, defoamers, toners, dispersants, leveling materials, thixo-imparting agents, blocking inhibitors, mold release agents, lubricants and the like can be blended in appropriate proportions. Preferably, the two-component curable polyurethane resin composition contains an antiaging agent, an antifoaming agent, a toner, and a dispersant in an appropriate ratio.

Then, in this two-component curable polyurethane resin composition, the solution A is prepared so as to contain the polyisocyanate component and the latent active hydrogen compound, and the solution B is prepared so as to contain the active hydrogen compound and the water-absorbent filler. ..

That is, the two-component curable polyurethane resin composition includes a solution A containing a polyisocyanate component and a latent active hydrogen compound, and a solution B containing an active hydrogen compound and a water-absorbent filler.

The non-water-absorbent filler and the above-mentioned additive can be contained in either solution A or solution B, or can be contained in both solution A and solution B. Preferably, the non-absorbent filler and the above additives are contained in the liquid B.

Then, such a two-component curable polyurethane resin composition is a resin composition kit (two-component kit) for forming a cured product by blending (mixing) liquids A and B separately prepared at the time of use. Is. That is, a resin mixture (polyurethane mixture) is obtained by mixing the solutions A and B, and a cured product (polyurethane cured product) is obtained by the curing reaction of the resin mixture.

Since the solution A suppresses the reaction between the polyisocyanate component and water, it is preferably stored in a water-free environment. More specifically, the dew point is, for example, −30 degrees or less as the storage atmosphere of the liquid A. The storage atmosphere of the liquid B is, for example, a dry air atmosphere, a nitrogen substitution atmosphere, or the like.

In such a two-component curable polyurethane resin composition, a solution A containing a polyisocyanate component and a latent active hydrogen compound and a solution B containing an active hydrogen compound and a water-absorbent filler are provided. Since the ratio of the above is adjusted to the above range, an excellent pot life can be obtained, and a cured product having excellent mechanical properties can be obtained.

That is, in the two-component curable polyurethane resin composition, when the latent active hydrogen group-containing compound is not contained in either the liquid A (main agent) or the liquid B (curing agent), the active hydrogen group-containing compound is used. , Only non-latent active hydrogen group compounds (amino group-containing compounds, hydroxyl group-containing compounds, etc.) are used. This is a general two-component curable polyurethane resin composition.

In such a case, all the active hydrogen groups are in a free (non-latent) state in the active hydrogen group-containing component. Therefore, when the liquids A and B are mixed at the above equivalent ratio (isocyanate group / active hydrogen group), the free isocyanate group and the free active hydrogen group react rapidly, causing gelation and pot life. Causes a shorter period of time. In such a case, uneven construction may occur during the construction (coating) of the mixture, resulting in poor appearance, and the mechanical properties (particularly, elongation at break) of the obtained cured product may not be sufficient.

On the other hand, if a latent active hydrogen group-containing compound is used as the active hydrogen group-containing compound, some of the active hydrogen groups in the active hydrogen group-containing component are in a non-free (latent) state, so that they are free. The rapid reaction between the isocyanate group and the free active hydrogen group can be suppressed, and the occurrence of gelation and shortening of the pot life can be suppressed. Therefore, an appropriate pot life can be obtained, and the mechanical properties of the cured product can be improved.

However, even when a latent active hydrogen group-containing compound is used, the latent active hydrogen group-containing compound is contained in liquid B together with a non-latent active hydrogen group compound (amino group-containing compound, hydroxyl group-containing compound, etc.). When it is contained in (hardener), the above effect cannot be obtained.

That is, when the latent active hydrogen group-containing compound is contained in the liquid B, the water content in the latent active hydrogen group-containing compound and the liquid B (for example, the surface of the non-water-absorbing filler) before mixing the liquid A and the liquid B Reacts with the carried water, etc.). In this case, the active hydrogen group of the non-latent active hydrogen compound is delatented (liberated) in the liquid B.

In such a case, when the liquid A and the liquid B are mixed, the free isocyanate group and the free active hydrogen group rapidly react with each other and gelate as in the case where the latent active hydrogen group-containing compound is not used. And shortens the pot life.

In this respect, in the above-mentioned two-component curable polyurethane resin composition, the latent active hydrogen compound is contained in the liquid A together with the polyisocyanate component.

Such liquid A is usually stored in a water-free environment in order to prevent a reaction between the polyisocyanate component and water (moisture curing reaction). Therefore, if the latent active hydrogen compound is contained in the liquid A, the reaction between the latent active hydrogen compound and water can be suppressed.

As a result, in the above-mentioned two-component curable polyurethane resin composition, the active hydrogen group of the latent active hydrogen compound is non-latent in the A solution until the mixture of the A solution and the B solution (that is, during storage). Can be maintained in a free) state. Then, when the liquid A and the liquid B are mixed (that is, at the time of use), the latent active hydrogen compound is reacted with the water content in the liquid B, and the active hydrogen group of the latent active hydrogen compound is gradually removed. It can be latent (liberated).

As described above, in the above-mentioned two-component curable polyurethane resin composition, since the latent active hydrogen compound is contained in the A solution together with the polyisocyanate component, the active hydrogen group is contained in the mixture of the A solution and the B solution. Can be gradually increased, and an excellent pot life can be obtained.

Further, in the above-mentioned two-component curable polyurethane resin composition, from the viewpoint of pot life, the amount of the latent active hydrogen compound is higher than that of the active hydrogen group-containing component (and the non-latent active hydrogen compound). It is adjusted to an appropriate ratio of.

That is, when the amount of the latent active hydrogen compound is insufficient, when the solution A and the solution B are mixed at the above equivalent ratio, the number of free active hydrogen groups increases and the number of active hydrogen groups gradually increasing decreases. Therefore, the reaction between the isocyanate group and the active hydrogen group is fast, and the pot life is shortened.

On the other hand, when the amount of the latent active hydrogen compound is excessive, when the solution A and the solution B are mixed in the above equivalent ratio, the number of free active hydrogen groups decreases and the number of active hydrogen groups gradually increasing increases. As a result, the pot life becomes long, but the chain extension reaction becomes not smooth, so that the crystal structure of the polyurethane resin becomes inhomogeneous, and the mechanical properties of the cured product may deteriorate.

On the other hand, if the amount of the latent active hydrogen compound is appropriately adjusted with respect to the active hydrogen group-containing component (and the non-latent active hydrogen compound), an appropriate pot life can be obtained. At the same time, the chain extension reaction can be carried out smoothly to obtain a cured product having excellent mechanical properties.

However, even if the amount of the latent active hydrogen compound is adjusted appropriately, as described above, in order to gradually increase the active hydrogen group in the mixture of the solution A and the solution B, the latent active hydrogen compound is used. It is necessary to appropriately adjust not only the amount but also the amount of the water-absorbent filler in the liquid B to appropriately adjust the amount of water.

That is, when the amount of the water-absorbent filler in the liquid B is insufficient, or when the water-absorbent filler is not contained in the liquid B, the water in the liquid B is not sufficiently absorbed by the water-absorbent filler. The amount of water in the liquid becomes excessively large, and when such liquid B is mixed with liquid A, the amount of water in the mixture also becomes excessively large. Therefore, in the mixture of the liquid A and the liquid B, the latent active hydrogen compound reacts rapidly with water, and the rate of non-latent (liberation) of the active hydrogen group of the latent active hydrogen compound becomes excessively high. Pot life is shortened. Further, in such a case, an excess amount of water may react not only with the latent active hydrogen compound but also with the polyisocyanate component to generate carbon dioxide gas. As a result, the cured product may have an appearance defect such as expansion, and the mechanical properties may be deteriorated.

On the other hand, if the amount of the water-absorbent filler in the liquid B is excessive, the water-absorbent filler absorbs the water, so that the amount of water in the liquid B is reduced, so that the pot life is extended, but the pot life is obtained. An excessive amount of water-absorbent filler is contained in the cured product, which causes deterioration of mechanical properties.

On the other hand, in the above-mentioned two-component curable polyurethane resin composition, an appropriate amount of water-absorbent filler is contained in the B solution.

As described above, if an appropriate amount of the water-absorbent filler is contained in the liquid B, the water in the liquid B is appropriately absorbed by the water-absorbent filler and isolated (inactivated) from the outside. That is, the amount of water in the liquid B is adjusted to an appropriate amount.

Therefore, even when the liquid A and the liquid B are mixed, the amount of water in the mixture can be appropriately adjusted, and the active hydrogen group of the latent active hydrogen compound in the mixture can be gradually latentized, and further mixed. Even after that, it can act as a reaction delaying agent that delays the reaction between the latent active hydrogen compound and water, and an excellent pot life can be obtained.

Further, if the amount of water in the mixture can be adjusted appropriately, the reaction between water (excessive amount of water) and the polyisocyanate component can be suppressed, so that expansion of the cured product due to the generation of carbon dioxide gas can be suppressed, resulting in poor appearance and poor appearance. It is possible to suppress the deterioration of mechanical properties. Further, since the water-absorbent filler in the cured product is adjusted, excellent mechanical properties can be obtained.

Further, in the above-mentioned two-component curable polyurethane resin composition, not only a latent active hydrogen compound but also a non-latent active hydrogen compound is used from the viewpoint of mechanical properties of the cured product.

That is, from the viewpoint of pot life, as described above, the latent active hydrogen compound is blended in the liquid A and the water-absorbent filler is blended in the liquid B, but only the latent active hydrogen compound is mixed as the active hydrogen group-containing component. When used (for example, when liquid B is not used and only liquid A is used as a moisture-curable one-component polyurethane resin composition, or when liquid B contains only water and additives, for example). The amount of soft segments in the polyurethane resin is reduced, and the mechanical properties (particularly, elongation at break) are reduced. In addition, the pot life becomes excessively long, and dust or dirt may adhere to the uncured surface, resulting in poor appearance.

Therefore, in the above-mentioned two-component curable polyurethane resin composition, in order to improve the mechanical properties (particularly, elongation at break) of the cured product, the active hydrogen group-containing compound is not only a latent active hydrogen compound but also a non-latent one. The active hydrogen compound of is used.

Thereby, the amount of soft segments in the polyurethane resin can be adjusted to obtain a cured product of the polyurethane resin having excellent mechanical properties.

In particular, in the above-mentioned two-component curable polyurethane resin composition, the polyisocyanate component preferably contains an isocyanate group-terminated urethane prepolymer having an average isocyanate group number of 2 and a polyisocyanate derivative having an average isocyanate group number of 3 or more. In addition, the active hydrogen group-containing component preferably contains an aromatic diamine compound, a monool compound, and a diol compound in the above ratio. If the average number of isocyanate groups and their ratio and the average number of hydroxyl groups and their ratio are adjusted in this way, the mechanical properties of the cured product can be improved. More specifically, since the polyisocyanate component contains a polyisocyanate derivative having an average number of isocyanate groups of 3 or more, a network of polyurethane resins can be formed and excellent mechanical strength (tensile strength, hardness, etc.) can be obtained. Further, since the active hydrogen group-containing component contains a monool compound, excellent elongation characteristics (such as elongation at break) can be obtained. That is, it is possible to adjust the ratio of the cross-linking point, the soft segment and the hard segment to obtain a cured product having excellent mechanical properties (particularly, elongation at break, hardness, tensile strength, tear strength, etc.).

As described above, the above-mentioned two-component curable polyurethane resin composition contains a polyisocyanate component containing an isocyanate group, an active hydrogen group-containing component containing an active hydrogen group, and a water-absorbent filler in a predetermined ratio. Further, the active hydrogen group-containing component contains an active hydrogen compound having a free active hydrogen group and a latent active hydrogen compound that produces an active hydrogen group by reacting with water in a predetermined ratio. Further, the two-component curable polyurethane resin composition includes a solution A containing a polyisocyanate component and a latent active hydrogen compound, and a solution B containing the active hydrogen compound and the water-absorbent filler.

In such a two-component curable polyurethane resin composition, when the liquid A and the liquid B are mixed, the polyisocyanate component and the active hydrogen group-containing component react with each other. More specifically, since the active hydrogen group of a part of the active hydrogen group-containing component (latent active hydrogen compound) is latent, the activity of the rest (active hydrogen compound) of the active hydrogen group-containing component at the beginning of mixing The hydrogen group reacts with the isocyanate group of the polyisocyanate component. After that, the reaction between the latent active hydrogen compound and water proceeds, and the generated active hydrogen group and isocyanate group gradually react. That is, in the mixture, the isocyanate group is excessive with respect to the active hydrogen group due to the latent part of the active hydrogen group, and the rate of the chain extension reaction (polymerization) becomes slow. There is.

Furthermore, since the water in the mixture of solutions A and B is absorbed by the water-absorbent filler, the reaction between the latent active hydrogen compound and water (liberation of active hydrogen groups) is delayed, and the polyisocyanate component and latent are latent. The reaction with the active hydrogen compound proceeds moderately.

Therefore, according to such a two-component curable polyurethane resin composition, an appropriate pot life can be obtained, and a cured product having excellent mechanical properties can be obtained.

Since the above-mentioned two-component curable polyurethane resin composition and its cured product are excellent in pot life and mechanical properties, they are preferably used as a waterproof material on the floor surface, corridor lower surface, veranda, parking lot, rooftop roof of various facilities. It is used for waterproof pavement such as.

When the above-mentioned two-component curable polyurethane resin composition and the cured product thereof are used as a waterproof material, the above-mentioned two-component curable polyurethane resin composition can be used on the floor surface or corridor lower surface of various facilities by a known construction method. It will be installed on balconies, parking lots, rooftops, etc. Specifically, for example, after applying a primer to a substrate whose substrate has been adjusted, a two-component curable polyurethane resin composition is uniformly applied using a trowel, a roller, a rake, a spray gun, etc., depending on the construction conditions. , Cure.

As the curing conditions, the curing temperature is, for example, 0 ° C. or higher, preferably 5 ° C. or higher, for example, 50 ° C. or lower, preferably 40 ° C. or lower, and the curing time is, for example, 5 hours or longer, preferably. It is 8 hours or more, for example, 24 hours or less, preferably 18 hours or less.

Thereby, the two-component curable polyurethane resin composition can be cured to obtain a cured film (waterproof material).

Since such a waterproof material is formed from the above-mentioned two-component curable polyurethane resin composition, it can be obtained with good workability with an appropriate pot life, and is also excellent in mechanical properties.

Next, the present invention will be described based on Examples and Comparative Examples, but the present invention is not limited to the following Examples. In addition, "part" and "%" are based on mass unless otherwise specified. In addition, specific numerical values such as the compounding ratio (content ratio), physical property values, and parameters used in the following description are the compounding ratios corresponding to those described in the above-mentioned "Form for carrying out the invention". Substitute the upper limit value (value defined as "less than or equal to" or "less than") or the lower limit value (value defined as "greater than or equal to" or "excess") such as content ratio), physical property value, and parameters. be able to.

(Component a) Isocyanate group-terminated prepolymer Preparation example 1 (TDI-based prepolymer (a1))
Polyether polyol (Mitsui Kagaku SKC polyurethane, trade name: Actol Diol 3000, number average molecular weight 3000, average number of hydroxyl groups 2) 523 parts by mass and polyether polyol (Mitsui Kagaku SKC polyurethane, trade name: Actol Diol 1000, number) An average molecular weight of 1000, an average number of hydroxyl groups of 2) 261.5 parts by mass, 23.5 parts by mass of dipropylene glycol, and 192 parts by mass of toluene diisocyanate T-80 / 20 (manufactured by Mitsui Chemicals SKC Polyurethane) were placed in a flask. The mixture was heated and mixed at 95 ° C. for 4 hours under a nitrogen atmosphere.

As a result, a TDI-based prepolymer (a1) as an isocyanate group-terminated prepolymer was obtained.

The isocyanate group concentration (NCO%) of the TDI-based prepolymer (a1) was 3.9%, the viscosity (25 ° C.) was 17,000 mPa · s, and the TDI monomer concentration was 0.7% by mass.

Preparation Example 2 (MDI-based prepolymer (a2))
2 liters of 1500 parts by mass of polyether polyol (manufactured by Mitsui Kagaku SKC polyurethane, trade name: Actol Diol 3000, number average molecular weight 3000, average number of hydroxyl groups 2) and 500 parts by mass of diphenylmethane diisocyanate (manufactured by Mitsui Kagaku SKC polyurethane) In a nitrogen atmosphere, the mixture was heated and mixed at 80 ° C. for 4 hours.

As a result, an MDI-based prepolymer (a2) as an isocyanate group-terminated prepolymer was obtained.

The isocyanate group concentration (NCO%) of the MDI-based prepolymer (a2) was 6.1%, and the viscosity (25 ° C.) was 15,000 mPa · s.

(B component) Polyisocyanate derivative Preparation example 3 (TDI-TMP adduct)
A trimethylolpropane adduct of tolylene diisocyanate (manufactured by Mitsui Chemicals, trade name Takenate D-104, isocyanate group concentration 13%) was prepared.

Preparation Example 4 (TDI-isocyanurate derivative)
An isocyanurate derivative of tolylene diisocyanate (manufactured by Mitsui Chemicals, trade name Takenate D-204, isocyanate group concentration 7.5%) was prepared.

(C component) Latent active hydrogen compound Preparation example 5 (latent active hydrogen compound (1): urethane polyoxazolidine compound)
First, 32.90 parts by mass of diethanolamine and 40.00 parts by mass of toluene as an azeotropic solvent were placed in a reactor equipped with a reflux separator, and 27.10 parts by mass of isobutyraldehyde was added while stirring at 60 ° C. The mixture was added dropwise, and then the temperature was raised to about 130 ° C.

The temperature inside the system was raised by an exothermic reaction caused by dropping isobutyraldehyde, and a dehydration reaction was carried out with a reflux liquid separator to remove 5.6 parts by mass of water. The pressure was then reduced to remove excess isobutyraldehyde and toluene.

As a result, 2-isopropyl-3- (2-hydroxyethyl) -1,3-oxazolidine (hereinafter abbreviated as OZ) was obtained as N-hydroxyalkyloxazolidine.

Then, 582 parts by mass of the obtained 2-isopropyl-3- (2-hydroxyethyl) -1,3-oxazolidine (OZ) and 418 parts by mass of isophorone diisocyanate (IPDI) were placed in a flask (isocyanate group: OZ: 1.03 mol per 1 mol). Then, these were reacted at 90 ° C. for 2 hours in a nitrogen atmosphere. As a result, a urethane polyoxazolidine compound was obtained.

The formation of the urethane polyoxazolidine compound was confirmed by the disappearance of the peak of 2250 cm ^-1 (expansion and contraction vibration of NCO) by the infrared spectroscope.

Preparation Example 6 (latent active hydrogen compound (2): aldimine compound)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a water separator, 88 parts by mass (2.0 equivalents) of tetramethylenediamine, 0.1 parts by mass of formic acid and 500 parts by mass of toluene were placed and nitrogen was added. The mixture was mixed in an air stream at room temperature for 10 minutes.

Then, 300 parts by mass (2.5 eq) of p-tolvaldehyde was added dropwise to the reaction vessel over 30 minutes.

Then, reflux was started at 90 ° C., and after confirming the separation (distillation) of water by the water separator, the reaction was carried out for about 6 hours until the distillation of water stopped. The amount of distilled water was 36 parts.

Then, the outside temperature was set to 150 ° C., and the pressure was reduced to 1 mmHg with a vacuum pump to distill off toluene and unreacted p-tolualdehyde. As a result of measuring the infrared absorption spectrum of the obtained reaction product, a characteristic absorption spectrum of −N = CH− was confirmed at 1640 cm ^-1 . As a result, an aldimine compound was obtained. The amine equivalent of the aldimin compound was 147.

Preparation Example 7 (latent active hydrogen compound (3): ketimine compound)
230 parts by mass of polyoxypropylene diamine having a number average molecular weight of 230 and 400 parts by mass of methyl isobutyl ketone were charged in a flask and subjected to a reflux dehydration reaction at 140 to 150 ° C. When a predetermined amount of water (36 parts by mass) was obtained, the reaction was stopped and methyl isobutyl ketone was removed. As a result, a ketimine compound was obtained. The amine equivalent of the ketimine compound was 197.

(D component) Polyamine compound (aromatic diamine compound)
Preparation Example 8 (Polyamine Mixture)
7 parts by mass of EtaCure 100 (trade name, manufactured by Albemarle, aromatic diamine compound) and 73.5 parts by mass of EtaCure 534 (trade name, manufactured by Albemarle, aromatic diamine compound) were mixed to obtain a polyamine mixture. ..

Preparation example 9
4,4'-Methylenebis (2-chloroaniline) (MOCA, manufactured by Kumiai Chemical Industry Co., Ltd.) was prepared.

(E component) polyol compound (diol compound)
Preparation example 10
Polyoxypropylene glycol (manufactured by Mitsui Kagaku SKC Polyurethane, trade name Actol ED-37A, number average molecular weight 3000, average number of hydroxyl groups 2) with ethylene oxide added to the molecular end was prepared.

Preparation example 11
Polyoxypropylene glycol (manufactured by Mitsui Kagaku SKC Polyurethane, trade name Actol D-3000, number average molecular weight 3000, average number of hydroxyl groups 2) to which ethylene oxide was not added to the molecular end was prepared.

Preparation example 12
As a low molecular weight polyol, 1,4-butanediol (1,4-BG, manufactured by Mitsubishi Chemical Corporation) was prepared.

(F component) Monool compound Preparation example 13 (single-ended sealed polyoxypropylene glycol)
ACTCALL EH-56 (trade name, manufactured by Mitsui Kagaku SKC Polyurethane, number average molecular weight 1000, average number of hydroxyl groups 1) was prepared as a polyoxypropylene glycol having one end sealed with a methoxy group.

Preparation Example 14 (single-ended sealed polyoxyethylene glycol)
Uniox M-550 (trade name, manufactured by NOF Corporation, number average molecular weight 550, average number of hydroxyl groups 1) was prepared as a polyoxyethylene glycol having one end sealed with a methoxy group.

(G component) Water-absorbent filler Preparation example 15 (hydraulic alumina)
BK-115 (trade name, manufactured by Sumitomo Chemical Co., Ltd.) was prepared as hydraulic alumina.

Preparation example 16 (zeolite)
As a zeolite, Molecular Sieve 4A (trade name, manufactured by Union Showa) was prepared.

(H component) Other Preparation example 17 (Non-absorbent filler)
NS-200 (trade name, heavy calcium carbonate, manufactured by Nitto Flour Chemical Co., Ltd.) was prepared as a non-water-absorbent filler.

Example 1
-Liquid A Solution A was prepared so as to have the equivalent ratio shown in Table 1.

That is, 80.77 parts by mass of the TDI-based prepolymer (A1), 24.23 parts by mass of the trimethylolpropane adduct of TDI, and 12.67 parts by mass of the urethane polyoxazolidine compound are mixed to prepare a liquid A (main agent). Prepared.

-Liquid B Liquid B was prepared so as to have the equivalent ratio shown in Table 1.

That is, 9.15 parts by mass of diisononyl adipate (plasticizer, DINA, manufactured by J-PLUS), 3 parts by mass of toner (gray toner, manufactured by Mitsui Kagaku MC Kogyo), and antifoaming agent (Disparon P-450, Kusumoto Kasei). 1 part by mass of dispersant (Anti-Tera U-100, wet dispersant, manufactured by BYK), 0.5 parts by mass of anti-aging agent B-75 (manufactured by Ciba Specialty Chemicals) Was added.

There, 15.07 parts by mass of a polyol compound (polyoxypropylene glycol with ethylene oxide added to the end of the molecule, manufactured by Mitsui Kagaku SKC Polyurethane, Actol ED-37A, number average molecular weight 3000, average number of hydroxyl groups 2) and monool 12.59 parts by mass of a compound (polyoxypropylene glycol having one end sealed with a methoxy group, Actol EH-56, manufactured by Mitsui Kagaku SKC polyurethane, number average molecular weight 1000, average number of hydroxyl groups 2) and a polyamine mixture. 17 parts by mass (0.62 parts by mass of EtaCure 100, 6.55 parts by mass of EtaCure 534) and inorganic bismuth U-600 (urethaneization catalyst, diluted to 1% with phthalic acid diisononyl ester (manufactured by Jay Plus)). 2 parts by mass (manufactured by Nitto Kasei) was charged.

Next, a turbine blade having a diameter of 75 mm was attached to a Chemisterler B-200G type (manufactured by Tokyo Rika Kikai Co., Ltd.) so that the whole was uniform, and the mixture was stirred under a nitrogen stream at 1010 rpm for 5 minutes.

Next, 10.45 parts by mass of heavy calcium carbonate NS-200 (manufactured by Nitto Flour Chemical Co., Ltd.) as a non-water-absorbing filler and hydraulic alumina (manufactured by Sumitomo Chemical Co., Ltd., product name: BK-115) as a water-absorbing filler. 20.9 parts by mass was added, and the mixture was mixed and stirred at room temperature for 1 hour.

Then, the mixture was stirred under reduced pressure for 15 minutes to obtain a liquid B (hardener).

The obtained liquid B was a gray fluid liquid, and the viscosity at 25 ° C. measured by a BM type viscometer was 2700 mPa · s.

Examples 2-31 and Comparative Examples 1-9
Solutions A and B were prepared in the same manner as in Example 1 except that the formulations shown in Tables 1 to 9 were changed.

More specifically, in Example 2, an MDI-based prepolymer (a2) was used instead of the TDI-based prepolymer (a1) as the isocyanate group-terminated prepolymer (component a).

Further, in Example 3, as the polyisocyanate derivative (component b), an isocyanurate derivative of TDI was used instead of the trimethylolpropane adduct of TDI.

Further, in Examples 4 and 5, as the latent active hydrogen compound (component c), an aldimine compound or a ketimine compound was used instead of the urethane polyoxazolidine compound.

Further, in Example 6, MOCA was used as the polyamine compound (d component) instead of the polyamine mixture.

Further, in Example 7, zeolite was used as the water-absorbent filler (g component) instead of hydraulic alumina. Further, in Example 7, 1.6 parts by mass of a diluted solution of 2-ethylhexanoic acid (solvent DINA, concentration 10% by mass) was added as a ring-opening catalyst for promoting ring-opening of the oxazolidine ring. At the same time, the amount of the plasticizer added (9.15 parts by mass in Example 1) was adjusted to 6.82 parts by mass so that the total amount of DINA added was 9.15 parts by mass. ..

Further, in Examples 8 and 10, as the polyol compound (e component), instead of polyoxypropylene glycol having ethylene oxide added to the molecular end, polyoxypropylene glycol having no ethylene oxide added to the molecular end was used. Using.

Further, in Examples 9 and 10, as the monool compound (f component), one-ended sealed polyoxyethylene glycol was used instead of the one-ended sealed polyoxypropylene glycol.

Further, in Comparative Example 1, Examples 11 to 12 and Comparative Example 2, active hydrogen generated by the reaction of the latent active hydrogen compound (component c) with water with respect to the total moles of the active hydrogen groups in the active hydrogen group-containing component. The proportion of groups was changed.

Further, in Comparative Example 3, Examples 13 to 14 and Comparative Example 4, the mass ratio of the water-absorbent filler (g component) to the total amount of the two-component curable polyurethane resin composition was changed.

Further, in Examples 15 to 18, the isocyanate group-terminated urethane prepolymer (a) with respect to the total molars of the isocyanate groups in the isocyanate group-terminated urethane prepolymer (component a) and the isocyanate groups in the polyisocyanate derivative (component b). The ratio of isocyanate groups in the component) was changed.

Further, in Examples 19 to 22, the active hydrogen group in the polyamine compound (d component), the active hydrogen group in the monool compound (f component), and the active hydrogen group in the polyol compound (e component). The ratio of active hydrogen groups in the polyamine compound (component d) to the total mole of the compound was changed.

Further, in Examples 23 to 26, in the monool compound (f component) with respect to the total mole of the active hydrogen group in the monool compound (f component) and the active hydrogen group in the polyol compound (e component). The proportion of active hydrogen groups in was changed.

Further, in Examples 27 to 28, the polyamine compound (d component) was not used, but the polyol compound (e component) and the monool compound (f component) were used.

Further, in Example 29, the polyisocyanate derivative (component b) was not used.

Moreover, in Example 30, the polyol compound (e component) was not used.

Moreover, in Example 31, the monool compound (f component) was not used.

Further, in Comparative Example 5, the water-absorbent filler (g component) was not used.

Further, in Comparative Example 6, the latent active hydrogen compound (component c) was contained in the solution B instead of the solution A.

Further, in Comparative Example 7, the water-absorbent filler (g component) was contained in the solution A instead of the solution B.

Further, in Comparative Example 8, the latent active hydrogen compound (component c) was not used.

Further, in Comparative Example 9, solution B (polyamine compound, polyol compound and monool compound) was not used, and solution B reacted with 35.63 parts by mass of the latent active hydrogen compound (component c) in solution A. It contained 3.8 parts by mass of water for making it.

The equivalent ratio and mass ratio of each component are shown in Tables 1 to 9.

In Tables 1 to 9, the equivalent ratio (eq) indicates the ratio of isocyanate groups and active hydrogen groups. The equivalent ratio (eq) of the latent active hydrogen compound indicates the equivalent ratio of the active hydrogen group generated by the reaction of the latent active hydrogen compound with water.

<< Evaluation >>
(1) Measurement of Viscosity of Liquid B (Curing Agent) The day after the liquid B (curing agent) was prepared, the temperature was adjusted to 25 ° C., and No. 2 was used using a B-8M type rotational viscometer. It was measured under the condition of 3 rotors / 12 rpm.

(2) Pot life First, solution A (main agent) was weighed in a stirring container, then solution B (hardener) was added, and the mixture was stirred and mixed at room temperature for 3 minutes. Then, the obtained mixture was used for measuring the thickening behavior.

More specifically, 100 g of the obtained mixture was placed in a 100 cc polycup, and the viscosity was automatically measured using a B-8M type rotational viscometer in a constant temperature water bath at 25 ° C.

The measurement conditions are rotor No. The viscosity was measured every minute at 6 rpm at 4.

Then, the time until the viscosity reached 20,000 mPa · s / 25 ° C. after mixing and stirring was measured as the coating work possible time.

Further, the time until the viscosity reached 100,000 mPa · s / 25 ° C. after mixing and stirring was measured as the pot life.

(3) Appearance / Mechanical properties First, solution A (main agent) was weighed in a stirring container, then solution B (hardener) was added, and the mixture was stirred and mixed at room temperature for 3 minutes. Then, the obtained mixture was defoamed and cured to obtain a sheet made of a cured resin.

More specifically, the mixture was poured into a mold coated with Teflon (registered trademark) in accordance with the method described in JIS A6021 (2011) "Urethane rubber type of" roof coating waterproof material "". A sheet having a thickness of about 2 mm was produced.

The sheet was cured at 23 ° C. and 50% relative humidity for 7 days, then demolded, and cured for 2 days at 23 ° C. and 50% relative humidity with the back side facing up.

Then, the appearance of the obtained sheet was observed, and the presence or absence of expansion and the presence or absence of surface unevenness were confirmed.

In addition, the shore A hardness (HsA) and the shore D hardness (HsD) of the obtained sheet were measured according to JIS K 6253 (2012). In addition, tensile strength (TS), elongation at break (EL) and tear strength (TR) were measured in accordance with JIS A 6021 (2011), respectively.

The results are shown in Tables 1-9.

(4) Consideration In the use of waterproof material, pot life is required to be 30 minutes or more, and breaking elongation is required to be 250% or more. In this respect, the cured product obtained in each example had a long pot life of 30 minutes or more, a coating workable time of 20 minutes or more, and was excellent in mechanical properties of the cured product. In particular, an excellent elongation at break of 250% or more was obtained.

On the other hand, in Comparative Example 1, the pot life was short. It was speculated that this was because the amount of latent active hydrogen compounds was excessively small. That is, when the amount of the latent active hydrogen compound is insufficient, when the solution A and the solution B are mixed at the above equivalent ratio, the number of free active hydrogen groups increases and the number of active hydrogen groups gradually increasing decreases. Therefore, it was speculated that the reaction between the isocyanate group and the active hydrogen group was fast and the pot life was shortened.

Further, in Comparative Example 2, the mechanical properties (break elongation) of the cured product were not sufficient. It was speculated that this was due to the excessive amount of latent active hydrogen compounds. That is, when the amount of the latent active hydrogen compound is excessive, when the solution A and the solution B are mixed in the above equivalent ratio, the number of free active hydrogen groups decreases and the number of active hydrogen groups gradually increasing increases. As a result, although the pot life was lengthened, the chain extension reaction was not smooth, so it was presumed that the crystal structure of the polyurethane resin became inhomogeneous and the mechanical properties of the cured product deteriorated.

Further, in Comparative Example 3, the pot life was short, the cured product was expanded, and the mechanical properties were not sufficient. It was speculated that this was because the amount of water-absorbing filler was excessively small. That is, when the amount of the water-absorbent filler in the liquid B is insufficient, the water in the liquid B is not sufficiently absorbed by the water-absorbent filler, so that the amount of water in the liquid B becomes excessively large. When such solution B is mixed with solution A, the amount of water in the mixture also becomes excessively large. Therefore, in the mixture of the liquid A and the liquid B, the latent active hydrogen compound reacts rapidly with water, and the rate of non-latent (liberation) of the active hydrogen group of the latent active hydrogen compound becomes excessively high. It was speculated that the pot life was shortened. Furthermore, the excess amount of water reacts not only with the latent active hydrogen compound but also with the polyisocyanate component to generate carbon dioxide gas, and as a result, the cured product expands and the mechanical properties deteriorate. It was presumed that it was done.

Further, in Comparative Example 4, the mechanical properties (break elongation) of the cured product were not sufficient. It was speculated that this was due to the excessive amount of water-absorbing filler. That is, if the amount of the water-absorbent filler in the liquid B is excessive, the water-absorbent filler absorbs the water, so that the amount of water in the liquid B decreases, so that the pot life becomes long, but it can be obtained. It was presumed that an excessive amount of water-absorbent filler was contained in the cured product, causing deterioration of mechanical properties.

Further, in Comparative Example 5, the pot life was short, the cured product was expanded, and the mechanical properties were not sufficient. It was presumed that this was because the water-absorbent filler was not mixed. That is, when the water-absorbent filler is not contained in the liquid B, the water in the liquid B is not sufficiently absorbed by the water-absorbent filler as in Comparative Example 3, so that the amount of water in the liquid B becomes excessively large. When the liquid B is mixed with the liquid A, the amount of water in the mixture becomes excessively large. Therefore, in the mixture of the liquid A and the liquid B, the latent active hydrogen compound reacts rapidly with water, and the rate of non-latent (liberation) of the active hydrogen group of the latent active hydrogen compound becomes excessively high. It was speculated that the pot life was shortened. Furthermore, the excess amount of water reacts not only with the latent active hydrogen compound but also with the polyisocyanate component to generate carbon dioxide gas, and as a result, the cured product expands and the mechanical properties deteriorate. It was presumed that it was done.

Further, in Comparative Example 6, the mixture of the liquid A and the liquid B gelled, the pot life was short, and the appearance was poor (surface unevenness) on the coated surface. It was presumed that this was because the latent active hydrogen compound was contained in the liquid B. That is, when the latent active hydrogen group-containing compound is contained in the liquid B, the water content in the latent active hydrogen group-containing compound and the liquid B (for example, on the surface of the non-water-absorbent filler) before the liquids A and B are mixed. It was presumed that the active hydrogen group of the non-latent active hydrogen compound was delatented (liberated) in the liquid B by reacting with the carried water and the like. Then, when the solution A and the solution B were mixed, it was presumed that the free active hydrogen groups reacted rapidly, causing the occurrence of gelation and shortening of the pot life.

Further, in Comparative Example 7, the pot life was short, the cured product was expanded, and the mechanical properties were not sufficient. It was presumed that this was because the water-absorbent filler was contained in the liquid A and not in the liquid B. That is, when the water-absorbent filler is contained in the liquid A and not in the liquid B, the water in the liquid B is not sufficiently absorbed by the water-absorbent filler as in Comparative Example 3, so that the amount of water in the liquid B is not sufficiently absorbed. When such liquid B is mixed with liquid A, the amount of water in the mixture also becomes excessively large. Therefore, in the mixture of the liquid A and the liquid B, the latent active hydrogen compound reacts rapidly with water, and the rate of non-latent (liberation) of the active hydrogen group of the latent active hydrogen compound becomes excessively high. It was speculated that the pot life was shortened. Furthermore, the excess amount of water reacts not only with the latent active hydrogen compound but also with the polyisocyanate component to generate carbon dioxide gas, and as a result, the cured product expands and the mechanical properties deteriorate. It was presumed that it was done.

Further, in Comparative Example 8, the pot life was short, the appearance was poor (surface unevenness) on the coated surface, and the mechanical properties (break elongation) of the cured product were not sufficient. It was speculated that this was because the latent active hydrogen compound was not used. That is, only non-latent active hydrogen group compounds (amino group-containing compounds, hydroxyl group-containing compounds, etc.) are used as active hydrogen group-containing compounds, and all active hydrogen groups are free (non-latent) in the active hydrogen group-containing components. It is in a state of conversion. Therefore, it was presumed that when the liquid A and the liquid B were mixed at the above equivalent ratio (isocyanate group / active hydrogen group), the free isocyanate group and the free active hydrogen group reacted rapidly. As a result, the pot life is shortened, uneven construction occurs during the construction (coating) of the mixture, and the mechanical properties (particularly, elongation at break) of the obtained cured product are lowered. It was inferred.

Further, in Comparative Example 9, the pot life was short, and the mechanical properties (break elongation) of the cured product were remarkably low. It was presumed that this was because no water-absorbent filler was used and no active hydrogen compound (polyamine compound, polyol compound and monool compound) was used. That is, when the solutions A and B are mixed, the latent active hydrogen compound reacts rapidly with water, so that the pot life is not sufficient and the active hydrogen compounds (polyamine compound, polyol compound and monool compound) are present. Since it was not used, it was presumed that the amount of soft segments in the polyurethane resin was low and the mechanical properties (particularly, elongation at break) were reduced.

The details of the abbreviations in the table are shown below.
TDI-based prepolymer (a1): The TDI-based prepolymer (a1) obtained in Preparation Example 1.
MDI-based prepolymer (a2): The MDI-based prepolymer (a2) obtained in Preparation Example 2
D-104: Trade name Takenate D-104, trimethylolpropane adduct of tolylene diisocyanate D-204: Trade name Takenate D-204, isocyanurate derivative urethane polyoxazolidine compound of tolylene diisocyanate: obtained in Preparation Example 5. Urethane polyoxazolidine compound Ardimine compound: Aldimine compound obtained in Preparation Example 6 Ketimin compound: Ketimine compound obtained in Preparation Example 7 Polyamine mixture: Polyamine mixture obtained in Preparation Example 8, trade name EtaCure 100: trade name EtaCure 534 (Both manufactured by Albemar) = 1: 10.5 (mass ratio)
MOCA: 4,4'-Methylenebis (2-chloroaniline)
Actol ED-37A: Trade name, polyoxypropylene glycol with ethylene oxide added to the molecular end, manufactured by Mitsui Kagaku SKC polyurethane, number average molecular weight 3000, average number of hydroxyl groups 2
ACTCALL D-3000: Trade name, polyoxypropylene glycol without ethylene oxide added to the molecular end, manufactured by Mitsui Chemicals SKC polyurethane, number average molecular weight 3000
1,4-BG: 1,4-butanediol, average number of hydroxyl groups 2
ACTCALL EH-56: Trade name, polyoxypropylene glycol with one end sealed with a methoxy group, manufactured by Mitsui Kagaku SKC polyurethane, number average molecular weight 1000, average number of hydroxyl groups 1
Uniox M-550: Trade name, polyoxyethylene glycol with one end sealed with a methoxy group, manufactured by NOF Corporation, number average molecular weight 550, average number of hydroxyl groups 1
Hydraulic Alumina: Product Name BK-115, Sumitomo Chemical Zeolite: Product Name Molecular Sieve 4A, Union Showa Heavy Calcium Carbonate: Product Name NS-200, Nitto Powder Industry Co., Ltd.

Claims (3)

A two-component curable polyurethane resin composition comprising solutions A and B.
It contains a polyisocyanate component containing an isocyanate group, an active hydrogen group-containing component containing an active hydrogen group, and a water-absorbent filler.
The active hydrogen group-containing component contains an active hydrogen compound having a free active hydrogen group and a latent active hydrogen compound that produces an active hydrogen group by reacting with water.
The liquid A contains the polyisocyanate component and the latent active hydrogen compound.
The liquid B contains the active hydrogen compound and the water-absorbent filler.
The equivalent ratio (isocyanate group / active hydrogen group) of the isocyanate group in the polyisocyanate component to the active hydrogen group in the active hydrogen group-containing component is 0.8 or more and 1.2 or less.
The ratio of active hydrogen groups generated by the reaction of the latent active hydrogen compound with water is 35 mol% or more and 65 mol% or less with respect to the total moles of active hydrogen groups in the active hydrogen group-containing component.
The content ratio of the water-absorbent filler is 5 parts by mass or more and 37.5 parts by mass or less with respect to 100 parts by mass of the total amount of the two-component curable polyurethane resin composition. Resin composition. The polyisocyanate component contains an isocyanate group-terminated urethane prepolymer having an average number of isocyanate groups of 2 and a polyisocyanate derivative having an average number of isocyanate groups of 3 or more.
The ratio of the isocyanate group in the isocyanate group-terminated urethane prepolymer to the total molar number of the isocyanate group in the isocyanate group-terminated urethane prepolymer and the isocyanate group in the polyisocyanate derivative is 35 mol% or more and 65 mol. % Or less
The active hydrogen group-containing component contains an aromatic diamine compound, a monool compound, and a diol compound.
The active hydrogen group in the aromatic diamine compound is based on the total molar amount of the active hydrogen group in the aromatic diamine compound, the active hydrogen group in the monool compound, and the active hydrogen group in the diol compound. The ratio is 50 mol% or more and 90 mol% or less,
The ratio of the active hydrogen group in the monool compound to the total mol of the active hydrogen group in the monool compound and the active hydrogen group in the diol compound is 10 mol% or more and 75 mol% or less. The two-component curable polyurethane resin composition according to claim 1, wherein the composition is characterized by the above. The diol compound contains polyoxypropylene glycol having ethylene oxide added to the end of the molecule.
The two-component curable polyurethane resin composition according to claim 2, wherein the monool compound contains one-ended sealed polyoxypropylene glycol.