JP2019199541A - Resin composition, method for producing resin composition, cured product, civil engineering and construction structure, and coating method - Google Patents

Abstract

To provide a cured product having a sufficient tensile product and a civil engineering and construction structure having the cured product.SOLUTION: A resin composition has a prepolymer having an isocyanato group (a). The prepolymer (a) is a reaction product of: a component A that has a diol having an oxyalkylene group, with a total unsaturation degree of 0.07 meq/g or less; a component B that has a polyol having an oxyalkylene group and at least three functional groups excluding the oxyalkylene group, with a total unsaturation degree of 0.05 meq/g or more; and a component C that has a compound having an isocyanato group.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition, a method for producing a resin composition, a cured product, a civil engineering structure, and a coating method.

  Urethane paint waterproof materials are widely used for waterproofing various structures, and for example, roof paint waterproof materials for roofs and paint waterproof materials for outer walls are known. As for the waterproof coating material for roof and the waterproof coating material for outer wall, the types of high extension type and high strength type are defined in Japanese Industrial Standard JIS A 6021 “Coating waterproofing material for building”.

  The waterproof material is provided on a substrate that can be used outdoors. The waterproof material is excellent in conformity to the expansion and contraction of the base material in summer and winter. Among the waterproof materials, the highly stretchable urethane coating waterproof material is excellent in the followability to the expansion and contraction of the base material, but it is difficult to obtain sufficient strength, and it is used as a waterproof material applied to floor slabs where people and vehicles come and go It is necessary to provide a layer having further excellent strength.

  For this reason, improving the physical strength of a waterproof material is examined. For example, Patent Document 1 proposes a two-component curable composition comprising a main agent containing an isocyanate group-terminated prepolymer satisfying a predetermined relationship between the hydroxyl value and the total unsaturation, and a curing agent containing water. Has been.

JP 10-324732 A

  As described above, it is considered extremely useful if there is a material excellent in both tensile strength and followability. By the way, the tensile product is considered as an index reflecting both these characteristics. Tensile product is the product of tensile strength and elongation at break, and is a physical property value that represents the amount of energy required to break the material. For example, it is defined in JIS A 6021: 2011 waterproof coating material for buildings .

  An object of this invention is to provide the hardened | cured material which has sufficient tensile product, and a civil engineering building structure provided with the said hardened | cured material. Another object of the present invention is to provide a resin composition capable of forming a cured product as described above, a method for producing the resin composition, and a coating method.

  One aspect of the present invention is a resin composition containing a prepolymer having an isocyanato group, wherein the prepolymer contains a diol having an oxyalkylene group and has a total unsaturation of 0.07 meq / g or less. Ingredient containing component A, polyol having at least three functional groups other than oxyalkylene group and oxyalkylene group, component B having total unsaturation of 0.05 meq / g or more, and compound having isocyanato group A resin composition that is a reaction product of C and C is provided.

  The said resin composition contains the prepolymer (a) which uses the component A and the component B from which total unsaturation differs as a raw material. The total degree of unsaturation can be used mainly as an index of the content of a compound having an unsaturated group, which is by-produced when preparing a diol having an oxyalkylene group or a polyol having an oxyalkylene group. And in the compound which has an unsaturated group, the monohydric alcohol which has an unsaturated group is contained, The said monohydric alcohol moderately carries out the expansion | extension reaction and bridge | crosslinking formation reaction of a polymer | macromolecule when manufacturing a prepolymer. Can be suppressed. A prepolymer obtained by reacting a component A containing a diol having an oxyalkylene group and a component B containing a polyol having an oxyalkylene group with a component C containing a compound having an isocyanato group is obtained by reacting with a curing agent. , A cured product having an appropriate crosslinking density can be provided. Therefore, the resin composition containing such a prepolymer can form a cured product excellent in tensile product.

  The diol may be represented by the following general formula (1), and the polyol may be represented by the following general formula (2).

In the general formula (1), A represents an oxygen atom, or a divalent residue obtained by removing two active hydrogens from a dihydric alcohol, dihydric phenol, or divalent amine, and R ^{1 to} R ⁴ are: Each independently represents an alkylene group having 2 to 12 carbon atoms. p _{1 to} p ₄ each independently represents an integer of 0 to 1000, and p ₁ + p ₂ + p ₃ + p ₄ is an integer of 1 or more.

In the general formula (2), B represents an n-valent residue obtained by removing n active hydrogens from a polyhydric alcohol, a polyhydric phenol, or a polyvalent amine. R ^{5 to} R ⁸ each independently represents an alkylene group having 2 to 12 carbon atoms. n represents an integer of 2 to 6, m _{1 to} m ₄ each independently represents an integer of 0 to 1000, and m ₁ + m ₂ + m ₃ + m ₄ is an integer of 1 or more.

  The diol may contain a diol having a number average molecular weight of 2500 or more and a diol having a number average molecular weight of less than 2500. By using a combination of a plurality of diols having different number average molecular weights, the molecular weight distribution can be broadened, and the tensile strength and elongation at break of the obtained cured product can be made compatible at a higher level.

  The prepolymer (a) may have a structure derived from at least one isocyanate selected from the group consisting of tolylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate.

  The resin composition may further include a plasticizer (b), and the content of the plasticizer (b) may be 15% by mass or less. When the content of the plasticizer (b) is within the above range, the tensile elastic modulus of the obtained cured product can be further improved.

  The resin composition further includes a solvent (c), and the content of the solvent (c) may be 1% by mass or more. When the content of the solvent (c) is within the above range, the tensile product of the obtained cured product can be further improved.

The resin composition further includes a CO ₂ absorbent (d) containing at least one selected from the group consisting of magnesium hydroxide, magnesium oxide, calcium hydroxide and calcium oxide, and the CO ₂ absorbent (d). The specific surface area determined by the BET method may be 10 m ² / g or more. When the specific surface area determined by the BET method of the CO ₂ absorbent (d) is within the above range, the absorbability of CO ₂ and the dispersibility in the resin composition can be further improved.

  The above-mentioned resin composition may be a moisture curable type or a water curable type.

  The above-mentioned resin composition may be used for waterproofing a paint film of a building, flooring of a building floor, waterproofing of a concrete slab, prevention of tile peeling, protection of a concrete structure, or prevention of peeling of a concrete structure. .

  One aspect of the present invention is a method for producing a resin composition comprising a prepolymer (a) having an isocyanato group, comprising a diol having an oxyalkylene group, and having a total unsaturation of 0.07 meq / g or less. Including a component A, a polyol having at least three functional groups other than an oxyalkylene group and an oxyalkylene group, a component B having a total unsaturation of 0.05 meq / g or more, and a compound having an isocyanato group The manufacturing method of the resin composition containing the said prepolymer (a) which has the process of reacting component C and obtaining prepolymer (a) is provided.

  The manufacturing method of the said resin composition has obtained the prepolymer by using the specific component A, the specific component B, and the component C for reaction, and can manufacture the resin composition containing the said prepolymer. The resin composition manufactured by the manufacturing method of the said resin composition can give the hardened | cured material of moderate crosslinking density by reaction with a hardening | curing agent. Therefore, the resin composition containing such a prepolymer can form a cured product excellent in tensile product.

  One aspect of the present invention provides a cured product obtained by curing the above resin composition.

  Since the said hardened | cured material is obtained by hardening | curing the above-mentioned resin composition, it has sufficient tensile product.

The cured product may have a tensile strength at 23 ° C. of 6 N / mm ² or more.

  The tensile product at 23 ° C. of the cured product may be 600 N / mm or more.

  The tear strength of the cured product at 23 ° C. may be 30 N / mm or more.

  One aspect of the present invention provides a civil engineering building structure provided with a cured product of the resin composition described above.

  The civil engineering structure includes a cured product of the resin composition described above, and the cured product has a sufficient tensile product.

  One aspect of the present invention provides a coating method including a step of applying the above-described resin composition to a structure.

  Since the above coating method uses the above resin composition, a coating having a sufficient tensile product can be formed.

  The coating method may include a step of bringing the resin composition into contact with water.

  ADVANTAGE OF THE INVENTION According to this invention, the hardened | cured material which has sufficient tensile product and a civil engineering building structure provided with the said hardened | cured material can be provided. The present invention can also provide a resin composition capable of forming a cured product as described above, a method for producing the resin composition, and a coating method.

  Hereinafter, embodiments of the present invention will be described. However, the following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents.

<Resin composition>
One embodiment of the resin composition includes a prepolymer (a) having an isocyanato group. The prepolymer (a) contains a diol having an oxyalkylene group, a component A having a total unsaturation of 0.07 meq / g or less, and at least three functional groups other than the oxyalkylene group and the oxyalkylene group. It is a reaction product of component B containing a polyol having a total unsaturation of 0.05 meq / g or more and component C containing a compound having an isocyanato group. The prepolymer (a) has an isocyanato group, and can react with water to form, for example, a urea bond and a urethane bond. Therefore, a cured product having a sufficient tensile product can be obtained by using the resin composition according to this embodiment. Since the obtained cured product is excellent in tensile product, it is possible to achieve both tensile strength and elongation at break.

  The resin composition according to the present embodiment can be suitably used as a civil engineering resin composition. “For civil engineering and architecture” of the resin composition for civil engineering and construction means that the resin composition is, for example, civil engineering fields such as bridges, elevated roads, dams, tunnels, roads and land creation, and buildings, condominiums, and houses. It means to be used in the field. In the present specification, the “resin composition for civil engineering and construction” is used for, for example, coatings, paints (for example, top coats, intermediate coats, and undercoats), primers, top coats, paints, sprays, varnishes, and the like. Can do. Hereinafter, for example, a resin composition for civil engineering and architecture used for coating is referred to as a coating resin composition for civil engineering and architecture.

  The resin composition according to this embodiment may be used after being reacted with water. Here, the water supply method is not particularly limited. The resin composition according to the present embodiment may be reacted with, for example, water present as moisture in the air, or may be reacted by supplying liquid phase water. The civil engineering building coating resin composition according to the present embodiment can be used as a one-pack type (moisture curing type) coating resin composition, or as a water curing type coating resin composition used by mixing with water. You can also In the case of the moisture-curing type, it is not necessary to mix water as a curing agent when producing a cured product, so that the manufacturing process of the cured product can be further labor-saving. In the case of the water-curing type, since water can be supplied to the coating resin composition with high uniformity, it is possible to further suppress the curing failure in the cured product when manufacturing the cured product, and to further improve the properties of the cured product. it can.

  Since the resin composition according to the present embodiment can also use water as a curing agent, it includes general-purpose 3,3′-dichloro-4,4′-diaminodiphenylmethane (MOCA) and the like as a curing agent for urethane waterproof materials. A cured product can be obtained without using an aromatic diamine. MOCA is designated as the second class substance in the regulations on the prevention of specific chemical substances in the Occupational Safety and Health Act, and it is required to reduce its use as a curing agent.

  The prepolymer (a) has a structure derived from polyisocyanate contained in Component C. The prepolymer (a) may have a structure derived from at least one isocyanate selected from the group consisting of tolylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate, It may have a structure derived from at least one isocyanate selected from the group consisting of 6-tolylene diisocyanate and 4,4′-diphenylmethane diisocyanate, and 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate It may have a structure derived from at least one kind of isocyanate. When the prepolymer (a) has the above structure, the pot life and curing time of the resin composition when used as a water-curing type can be further improved.

  The prepolymer (a) may have a structure derived from at least one isocyanate of isophorone diisocyanate and dicyclohexylmethane 4,4′-diisocyanate. When the prepolymer (a) has the above structure, the reactivity of the resin composition with the latent curing agent when used as a moisture curing type can be further improved.

[Preparation Method of Prepolymer (a)]
The prepolymer (a) can be prepared, for example, by the following method. The prepolymer (a) contains a diol having an oxyalkylene group, has a component A having a total unsaturation of 0.07 meq / g or less, and at least three functional groups other than the oxyalkylene group and the oxyalkylene group. It can be produced by a method comprising a step of reacting a component B containing a polyol and having a total unsaturation of 0.05 meq / g or more and a component C containing a compound having an isocyanato group.

  The reaction of Component A, Component B, and Component C may be performed by, for example, heating and stirring at 50 to 130 ° C. In the production method of the prepolymer (a), for example, other active hydrogen compounds such as polyols and amines other than Component A and Component B may be used as necessary. Urethane catalysts such as organic bismuth and amines may be used.

  In the reaction of Component A, Component B, and Component C, the blending amount is preferably adjusted so that the polyols contained in Component A and Component B and the polyisocyanate contained in Component C have a predetermined relationship. The equivalent ratio of the isocyanate group possessed by the isocyanate and the hydroxyl group possessed by the polyol (equivalent of isocyanate group / equivalent hydroxyl group) is, for example, 1.5 to 3.0, 1.6 to 2.5, or 1.8 to It may be 2.2. When the equivalent ratio of the isocyanate group possessed by the polyisocyanate and the hydroxyl group possessed by the polyol is within the above range, the amount of unreacted polyisocyanate can be reduced and the safety can be further improved. High product.

  The blending of component A can be adjusted according to the use of the resin composition. The blending amount of component A may be, for example, 70 parts by mass or less, 80 parts by mass or less, or 90 parts by mass or less with respect to 100 parts by mass of the prepolymer (a). The amount of component A may be, for example, 30 parts by mass or more, or 40 parts by mass or more with respect to 100 parts by mass of the prepolymer (a). When the blending amount of Component A is within the above range, an appropriate crosslinking density is obtained, and a cured product having excellent tensile product can be obtained.

  The blending of component B can be adjusted according to the use of the resin composition. The blending amount of component B may be, for example, 60 parts by mass or less, 40 parts by mass or less, or 20 parts by mass or less with respect to 100 parts by mass of the prepolymer (a). The blending amount of Component B may be, for example, 5 parts by mass or more, or 10 parts by mass or more with respect to 100 parts by mass of the prepolymer (a). When the blending amount of Component B is within the above range, an appropriate crosslinking density is obtained, and a cured product having excellent tensile product can be obtained.

  The total degree of unsaturation of component A is 0.07 meq / g or less, preferably 0.03 meq / g or less, or 0.01 meq / g or less. When the total degree of unsaturation of component A is within the above range, the crosslink density in the cured product (for example, cured film) of the resin composition containing the prepolymer (a) to be obtained can be increased. The strength and tensile modulus can be further improved.

  The “total degree of unsaturation” in the present specification can be determined according to the method described in “Plastics—Polyurethane raw material polyol test method—Part 3: Determination of degree of unsaturation” of JIS K 1557-3: 2007. The total degree of unsaturation is mainly derived from an alcohol having an unsaturated group, which is by-produced when preparing a diol having an oxyalkylene group or a polyol having an oxyalkylene group. Alcohol produced as a by-product here (for example, a monohydric alcohol having an ethylenically unsaturated bond) can inhibit the elongation reaction and the cross-linking reaction of the polymer when the prepolymer (a) is produced.

  The diol having an oxyalkylene group contained in Component A may be represented by the following general formula (1).

In the general formula (1), A represents an oxygen atom or a divalent residue obtained by removing two active hydrogens from a dihydric alcohol, dihydric phenol, or divalent amine. In the general formula (1), R ^{1 to} R ⁴ each independently represents an alkylene group having 2 to 12 carbon atoms. The alkylene group may be linear, branched, or cyclic. In the general formula (1), p _{1 to} p ₄ each independently represents an integer of 0 to 1000, and p ₁ + p ₂ + p ₃ + p ₄ is an integer of 1 or more.

  The diol represented by the general formula (1) can be prepared, for example, by reacting alkylene oxide with at least one selected from the group consisting of water, dihydric alcohol, dihydric phenol and dihydric amine. .

  The alkylene oxide may be a compound having one or more epoxy rings in the molecule. Examples of the alkylene oxide include alkylene oxides having 2 to 12 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, and styrene oxide. An alkylene oxide may be used alone or in combination of two or more.

  Examples of the dihydric alcohol include propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, 1,6-hexanediol, tripropylene glycol, triethylene glycol, and polyoxyalkylene diol. Examples of the dihydric phenol include bisphenol A, bisphenol F, and bisphenol AD, and dihydroxybenzenes such as catechol, resorcin, and hydroquinone. Examples of the divalent amine include methylamine, ethylamine, propylamine, and butylamine.

  As the diol having an oxyalkylene group contained in Component A, a plurality of diols having different number average molecular weights may be used in combination. A diol having a relatively large number average molecular weight (high molecular weight diol component) and a number average molecular weight A relatively small diol (low molecular weight diol component) may be combined. By using a combination of a plurality of diols having different number average molecular weights, the molecular weight distribution can be broadened, and the tensile strength of the obtained cured product and the elongation at break can be made compatible at a higher level.

  The number average molecular weight of the high molecular weight diol component may be, for example, 2500 or more, 3000 or more, 4000 or more, or 5000 or more. The number average molecular weight of the high molecular weight diol component may be, for example, 15000 or less, 12000 or less, and 10000 or less. The number average molecular weight of the low molecular weight diol component may be, for example, less than 2500, 2000 or less, 1000 or less, or 500 or less. The difference in number average molecular weight between the high molecular weight diol component and the low molecular weight diol component may be, for example, 100 or more, 500 or more, 1000 or more, or 2000 or more. The number average molecular weight may be a number average molecular weight calculated stoichiometrically using the hydroxyl value obtained from the method for obtaining the hydroxyl value of JIS K1557-1: 2007. Moreover, when the number of functional groups is not known, it may be a number average molecular weight obtained from gel permeation chromatography (GPC: standard material polystyrene).

  Examples of the high molecular weight diol component that can be used include polypropylene glycol and an ethylene oxide adduct of polypropylene glycol. As the ethylene oxide adduct of polypropylene glycol, for example, Preminol 5001F, Preminol 5005, Preminol S 4004, Preminol S 4011, Preminol S 4013F, and Preminol S 4318 manufactured by Asahi Glass Co., Ltd. can be used. Examples of the low molecular weight diol component include dipropylene glycol, tripropylene glycol, polypropylene glycol (having a number average molecular weight of less than 2000), and ethylene oxide adducts thereof. As the low molecular weight diol component, a high-purity product or a product having a low total unsaturation can be used.

  The total unsaturation of component B is 0.050 meq / g or more, and may be 0.055 meq / g or more, 0.060 meq / g or more, 0.065 meq / g or more, or 0.070 meq / g or more. The total unsaturation of component B may be, for example, 0.100 meq / g or less, 0.090 meq / g or less, or 0.080 meq / g or less. When the total degree of unsaturation of component B is within the above range, the crosslink density in the cured product becomes more appropriate, and the elongation at break of the cured product and the flexibility at low temperatures can be further improved. When the total degree of unsaturation of component B is within the above range, the viscosity of the resin composition can be lowered, so that the workability of the resin composition can be further improved.

  In the polyol having at least three functional groups other than the oxyalkylene group and the oxyalkylene group contained in Component B, the number of functional groups other than the oxyalkylene group is, for example, 3, 4, 5, or 6. It may be one. Examples of the functional group include a hydroxyl group and an amino group. The number of functional groups other than oxyalkylene groups can be determined stoichiometrically by the number average molecular weight determined by gel permeation chromatography (GPC: standard material polystyrene) and the hydroxyl value.

  The polyol having at least three functional groups other than the oxyalkylene group and the oxyalkylene group may be represented by the following general formula (2).

In the general formula (2), B represents an n-valent residue obtained by removing n active hydrogens from a polyhydric alcohol, a polyhydric phenol, or a polyvalent amine. In said general formula (2), R < ⁵ > -R < ⁸ > shows a C2-C12 alkylene group each independently. The alkylene group may be linear, branched, or cyclic. In said general formula (2), n shows the integer of 2-6. In the general formula (2), m _{1 to} m ₄ each independently represents an integer of 0 to 1000, and m ₁ + m ₂ + m ₃ + m ₄ is an integer of 1 or more.

  The polyol represented by the general formula (2) is, for example, an alkylene oxide and at least one selected from the group consisting of a polyhydric alcohol, a polyhydric phenol and a polyhydric amine (a compound having at least three active hydrogens) , Can be prepared by reacting.

  The alkylene oxide may be a compound having one or more epoxy rings in the molecule. Examples of the alkylene oxide include alkylene oxides having 2 to 12 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, and styrene oxide. An alkylene oxide may be used alone or in combination of two or more.

  Examples of the polyhydric alcohol include glycerin, trimethylolpropane, 1,2,6-hexanetriol, and a low molecular weight polyol (for example, Sanix GP-250, GP-400, GP-600 manufactured by Sanyo Chemical Co., Ltd., GP-1000 and the like); pentaerythritol, and tetraglycol such as diglycerin; hexol, sorbitol, and sugar. Examples of the polyhydric phenol include pyrogallol, phloroglucinol, a phenol resin, and a resole resin. Examples of the polyvalent amine include amines such as ammonia, ethanolamine, diethanolamine, and triethanolamine.

  The number average molecular weight of the polyol having at least three functional groups other than the oxyalkylene group and the oxyalkylene group contained in Component B may be, for example, 3000 or more, 4000 or more, or 5000 or more. The number average molecular weight of the polyol having at least three functional groups other than the oxyalkylene group and the oxyalkylene group may be, for example, 15000 or less, 12000 or less, or 10,000 or less. When the number average molecular weight of the polyol having at least three functional groups other than the oxyalkylene group and the oxyalkylene group is within the above range, the tensile strength of the cured product and the elongation at break can be balanced at a higher level. .

  As the compound having an isocyanato group contained in Component C, for example, polyisocyanate can be used. Examples of the polyisocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate (polymeric MDI), 1 , 5-naphthalene diisocyanate, and aromatic polyisocyanates such as xylylene diisocyanate; dicyclohexylmethane 4,4′-diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, trimethylhexamethylene diisocyanate, decamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, hydrogen Added toluene diisocyanate and hydrogenated xylylene diisocyanate Aliphatic polyisocyanates; these isocyanate-containing prepolymer; and can be used modified products of these isocyanates. These polyisocyanates may be used alone or in combination of two or more.

  The polyisocyanate preferably contains at least one selected from the group consisting of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and 4,4′-diphenylmethane diisocyanate among the above exemplary compounds, More preferably, it contains at least one selected from the group consisting of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate. By using the said compound as polyisocyanate, the pot life and hardening time at the time of using the resin composition containing the prepolymer (a) obtained as a water curing type can be made more appropriate.

In addition to the prepolymer (a), the resin composition according to the present embodiment includes, for example, a plasticizer (b), a solvent (c), a CO ₂ absorbent (d), a filler (e), and a catalyst (f). , And other additives (g).

  The plasticizer (b) is a compound that imparts flexibility to the resin composition and improves processability. The viscosity at 25 ° C. of the plasticizer (b) may be, for example, 60 mPa · s or less, 30 mPa · s or less, or 20 mPa · s or less. When the viscosity at 25 ° C. of the plasticizer (b) is within the above range, the amount of the plasticizer used for reducing the viscosity of the resin composition can be further reduced.

  Content of a plasticizer (b) may be 15 mass% or less, 10 mass% or less, 7 mass% or less, 5 mass% or less, or 3 mass% or less with respect to the said resin composition whole quantity, for example. . When the content of the plasticizer (b) is within the above range, the tensile elastic modulus of the obtained cured product can be further improved. When using the resin composition as a waterproofing material for repairing asphalt waterproofing, it is possible to prevent the asphalt low fraction from being transferred to the waterproof layer by the content of the plasticizer (b) being within the above range. it can.

  When using a conventional urethane waterproof membrane as an asphalt repair, the compatibility between the asphalt and the plasticizer in the conventional urethane waterproof membrane is relatively high. It can move to a layer formed of urethane waterproof material. When the low distillate shifts, discoloration and deterioration of the urethane waterproof material can be promoted. In the case where a top coat is provided on a layer formed of a conventional urethane waterproof material, the same effect as described above can be caused to the top coat, and discoloration and deterioration of the top coat can be promoted. On the other hand, since the resin composition according to the present embodiment can reduce the content of the plasticizer (b), it is possible to further suppress deterioration as in a conventional urethane waterproof material.

  Examples of the plasticizer (b) include bis (2-ethylhexyl) phthalate (DOP, viscosity at 25 ° C .: 57 mPa · s), diisononyl phthalate (DINP, viscosity at 25 ° C .: 55 mPa · s), and phthalic acid Phthalate esters such as diundecyl (DUP, viscosity at 25 ° C .: 47 mPa · s); bis (2-ethylhexyl) adipate (DOA, viscosity at 25 ° C .: 11 mPa · s), diisononyl adipate (DINA, at 25 ° C. Viscosity: 16 mPa · s), di-n-alkyl adipate mixture (D610A, viscosity at 25 ° C .: 57 mPa · s), diisodecyl adipate (DIDA, viscosity at 25 ° C .: 23 mPa · s), and bis (2- Butoxyethyl) (D931, viscosity at 25 ° C .: 11 mP Adipate esters such as s); triethyl citrate (TEC, viscosity at 25 ° C .: 35 mPa · s), tributyl citrate (TBC, viscosity at 25 ° C .: 33 mPa · s), and acetyl tributyl citrate (ATBC, And citric acid esters such as viscosity at 25 ° C .: 34 mPa · s). These plasticizers may be used alone or in combination of two or more.

  The plasticizer (b) preferably contains an esterified product of an aliphatic polycarboxylic acid, and more preferably an esterified product of an aliphatic polycarboxylic acid and isononyl alcohol, because of its particularly low viscosity among the above exemplified compounds. Or an esterified product of an aliphatic polycarboxylic acid and 2-ethylhexanol, more preferably an esterified product of adipic acid and isononyl alcohol or an esterified product of adipic acid and 2-ethylhexanol. Since the plasticizer (b) has excellent compatibility with the prepolymer (a), it preferably contains bis (2-ethylhexyl) adipate or diisononyl adipate.

The solvent (c) is a low molecular compound that can dissolve the prepolymer (a) and can be removed later. When the resin composition further contains the solvent (c), the tensile product of the obtained cured product can be further improved. As the solvent (c), a compound having a high octanol / water partition coefficient ( _LogPow ) (compound that is hardly compatible with water) is preferable. Solvents octanol / water partition coefficient (c) (LogP _ow) is 0.5 or more, 1.0 or more, or may be 1.5 or more. When octanol / water partition coefficient of the solvent _(c) (LogP ow) is within the above range, it is possible to disperse water as a curing agent in the resin composition with higher uniformity.

Further, when the inorganic particles containing a later-described CO ₂ absorber (d) and the filler (e) including the resin composition, the octanol / water partition coefficient of the solvent (c) (LogP _ow) is within the above range Further, since the water as the curing agent can be dispersed in the resin composition as the water adhering to the inorganic particles, and the occurrence of defects in the cured product can be further suppressed, the tensile modulus can be further improved. If water cannot be uniformly dispersed in the resin composition and is present in the resin composition as droplets (aqueous phase), the curing reaction between the prepolymer (a) and water proceeds at the surface portion of the droplets. The resulting cured product can be defective. In such a case, it is preferable to use the inorganic particles and the solvent (c) having an octanol / water partition coefficient ( _LogPow ) within the above range in combination as described above.

Octanol / water partition coefficient (LogP _ow) is, JIS Z 7260-107: 2000 "Determination of the distribution coefficient (1-octanol / water) - shake-flask method", and JIS Z 7260-117: 2006 "partition coefficient (1 It can be determined according to the calculation method of the partition coefficient (P _ow ) described in the annex (normative) of “Measurement of octanol / water) -high performance liquid chromatography”.

  Content of a solvent (c) may be 1 mass% or more, 3 mass% or more, or 5 mass% or more with respect to the said resin composition whole quantity, for example. Content of a solvent (c) may be 20 mass% or less, 15 mass% or less, or 10 mass% or less with respect to the said resin composition whole quantity, for example. When the content of the solvent (c) is within the above range, water as a curing agent can be dispersed with higher uniformity in the resin composition, and moisture in the air can be more efficiently dispersed in the resin composition. Can be included. Moreover, the bubble which generate | occur | produced in the resin composition can be more defoamed as content of a solvent (c) is in the said range, and the defect of the hardened | cured material obtained can be suppressed more fully.

  As the solvent (c), for example, an aliphatic compound or the like can be used. Examples of the aliphatic compound include an aliphatic compound having a ring structure, an aliphatic compound having a branched structure, an aliphatic compound having an ester structure, an aliphatic compound having a ketone structure, and an aliphatic compound having an ether structure. Can be mentioned. These solvents may be used alone or in combination of two or more.

  Examples of the aliphatic compound having a ring structure include naphthenic hydrocarbons having 7 to 15 carbon atoms and mixtures thereof (for example, Suwaclean 150 manufactured by Maruzen Petrochemical Co., Ltd. and Daika Eco Thinner manufactured by Daisho Kasei Co., Ltd.). Etc.) can be used. Examples of the aliphatic compound having a branched structure include isoparaffin hydrocarbons having 7 to 15 carbon atoms and mixtures thereof (for example, IP solvent manufactured by Idemitsu Kosan Co., Ltd., NA solvent manufactured by NOF Corporation, etc.) Can be used. Examples of the aliphatic compound having an ester structure include ethyl acetate, methyl acetate, butyl acetate, sec-butyl acetate, methoxybutyl acetate, amyl acetate, normal propyl acetate, isopropyl acetate, ethyl lactate, methyl lactate, butyl lactate, and ethylene. Glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, butyl carbitol acetate, ethyl carbitol acetate, ethyl 3-ethoxypropionate, and the like can be used.

  As the aliphatic compound having a ketone structure, for example, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, diacetone alcohol and the like can be used. Examples of the aliphatic compound having an ether structure include isopropyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, diglyme, ethyl glyme, ethyl diglyme, triglyme, methyl carbitol, ethyl carbitol, butyl carbitol, methyl triglycol, Propylene glycol monomethyl ether, propylene glycol monobutyl ether, 3-methoxy-3-methyl-1-butanol, hexyl diglycol, dipropylene glycol methyl ether, and the like can be used.

  Among the above exemplary compounds, the solvent (c) is a water that is a curing agent as water adhering to the inorganic particles contained in the resin composition, and a viewpoint that disperses the water that is the curing agent in the resin composition with higher uniformity. From the viewpoint of more efficiently distributing the naphthenic hydrocarbon, a naphthene hydrocarbon having 7 to 15 carbon atoms and a mixture thereof, an isoparaffin hydrocarbon having 7 to 15 carbon atoms and a mixture thereof are preferably included. The solvent (c) is preferably an aliphatic compound having an ester structure or an aliphatic compound having a ketone structure from the viewpoint of further improving the compatibility with the resin composition and further improving the workability among the above exemplified compounds. including.

The CO ₂ absorbent (d) is a compound that absorbs CO ₂ that can be generated by the curing reaction of the prepolymer (a). Specific surface area determined by the BET method of CO ₂ absorbent (d) are, for example, ^{5 m} 2 / g or more, ^{10 m} 2 / g or more, or may be at ^35m 2 / g or more. Specific surface area determined by the BET method of CO ₂ absorbent (d) are, for example, 200 meters ² / g or less, 150 meters ² / g or less, or 100 m ² / g may be less. When the specific surface area determined by the BET method of the CO ₂ absorbent (d) is within the above range, the absorbability of CO ₂ and the dispersibility in the resin composition can be further improved.

CO ₂ absorbent content of (d) is the prepolymer (a) 100 parts by weight, for example, be 1 to 50 parts by weight, may be 10 to 40 parts by weight. When the content of the CO ₂ absorbent (d) is within the above range, CO ₂ generated by the curing reaction of the prepolymer (a) can be absorbed and the generation of bubbles can be suppressed. It can suppress more fully.

As the CO ₂ absorbent (d), for example, hydroxides, oxides, basic salts, complex salts, or double salts of metals of Group 2, 3, and 4 of the periodic table can be used. Examples of the CO ₂ absorbent (d) include metal hydroxides such as calcium hydroxide, barium hydroxide, and magnesium hydroxide; metal oxides such as magnesium oxide and barium oxide; and cements such as Portland cement. Can be mentioned. These compounds may be used alone or in combination of two or more. The CO ₂ absorbent (d) preferably contains at least one selected from the group consisting of magnesium hydroxide, magnesium oxide, calcium hydroxide, and calcium oxide.

  Examples of magnesium hydroxide include UD series (for example, UD-650-1, UD-653, UD-65, etc.) manufactured by Ube Materials Co., Ltd., and MAGSTAR series (for example, MAGSTAR manufactured by Tateho Chemical Industries, Ltd.). # 20, MAGSTAR # 5, MAGSTAR # 4, etc., MAGSTAR is a registered trademark), magnesium hydroxide manufactured by Kamishima Chemical Co., Ltd. (for example, # 200, # 300, 10A, etc.), light manufactured by Tomita Pharmaceutical Co., Ltd. Magnesium hydroxides such as series and heavy series, Kissuma series manufactured by Kyowa Chemical Industry Co., Ltd. can be used.

  Examples of magnesium oxide include UC95 series (for example, UC95S, UC95M, and UC95H) manufactured by Ube Materials Co., Ltd., and TATEHOMAG series (for example, TATEHOMAG # 500, TATEHOMAG # 700, and TATEHOMAG, manufactured by Tateho Chemical Industries, Ltd.). H-10, etc., TATEHOMAG is a registered trademark) Kamijima Chemical Industry Co., Ltd. Star Mag series (for example, Star Mag U, Star Mag U-2, Star Mag CX, Star Mag M, Star Mag L, Star Mag P, etc.), Kyowa Chemical Industry Co., Ltd. Magnesium oxides such as Kyowa Mug series (for example, Kyowa Mug 30) and Kyowa Mug MF series (for example, Kyowa Mug MF30) manufactured by the company can be used.

  The filler (e) is a compound added for the purpose of imparting high physical properties or high functionality (for example, improving tensile properties and weather resistance) or reducing costs. The average particle diameter of the filler (e) may be, for example, 0.1 to 20 μm, 0.5 to 10 μm, or 1 to 5 μm. The average particle size of the filler (e) is determined from a laser diffraction particle size distribution (JIS Z 8825: 2013 particle size analysis-laser diffraction / scattering method).

  Content of a filler (e) may be 1-200 mass parts with respect to 100 mass parts of prepolymers (a), and may be 10-100 mass parts, for example. When the content of the filler (e) is within the above range, tensile properties and weather resistance can be improved.

  Examples of the filler (e) include calcium carbonate, talc, clay, kaolin, aluminum hydroxide, barium hydroxide, barium sulfate, calcium sulfate, glass fiber, silica balloon, shirasu balloon, perlite, vermiculite, and powdered synthesis. Resin or the like can be used. The filler (e) preferably contains calcium carbonate. These compounds may be used alone or in combination of two or more.

  Examples of calcium carbonate include calcium carbonate (tancal) (for example, 100M and 325M) manufactured by Ube Materials Co., Ltd., NITREX series (for example, NITREX # 80, etc.) and NS series manufactured by Nitto Flour Chemical Co., Ltd. (For example, NS # 400, etc.), Shiraishi Kogyo Co., Ltd. white gloss flower series, Vigot series and Whiten series, Bihoku Powder Chemical Co., Ltd. Softon series, BF series and Lighton series, Sankyo Seiko Co., Ltd. Calcium carbonate such as Escalon series, EC series manufactured by Kamijima Chemical Co., Ltd., and light series can be used.

  The catalyst (f) is a compound that promotes the reaction between the active hydrogen-containing group and the isocyanato group. Content of a catalyst (f) may be 0.05-5 mass parts with respect to 100 mass parts of prepolymers (a), and may be 0.1-3 mass parts, for example. When the content of the catalyst (f) is in the above range, the tensile strength of the obtained cured product can be further improved by promoting the curing reaction of the prepolymer (a).

  As the catalyst (f), for example, a metal compound catalyst and an amine catalyst can be used. As the metal compound catalyst, for example, an organic tin compound such as tin dibutyl dilaurate can be used. Examples of the amine catalyst include trimethylamine, triethylamine, tributylamine, trioctylamine, diethylcyclohexylamine, N-methyl-morpholine, N-ethylmorpholine, N-octadecylmorpholine (N-cocomorpholine), N-methyl-diethanolamine, N, N-dimethylethanolamine, N, N′-bis (2-hydroxypropyl) piperazine, N, N, N ′, N′-tetramethylethylene-diamine, N, N, N ′, N ″, N '' -Pentamethyldiethylenetriamine, N, N, N ′, N′-tetramethyl-1,3-propanediamine, triethylenediamine (1,4-diazabicyclo [2.2.2] octane), 1,8-diazabicyclo [5.4.0] Undecene-7,1,4-bis (2-hydride) Xylpropyl) -2-methylpiperazine, N, N-dimethylbenzylamine, N, N-dimethylcyclohexylamine, benzyltriethylammonium bromide, bis (N, N-diethylaminoethyl) adipate, N, N-diethylbenzylamine, N- Ethylhexamethyleneamine, N-ethylpiperidine, α-methyl-benzyldimethylamine, dimethylhexadecylamine, dimethylcetylamine, and the like can be used. These compounds may be used alone or in combination of two or more.

  Other additives (g) include, for example, surfactants, antifoaming agents, latent curing agents, rheology control agents, wetting and dispersing agents, pigments, dyes, antioxidants, curability modifiers, metal deactivators, An ozone deterioration preventing agent, a lubricant, an anti-anticide, an antifungal agent and the like can be used.

  As the surfactant, for example, a nonionic active agent, an anionic active agent, a cationic active agent and the like can be used. The content of the surfactant may be, for example, 1 to 10 parts by mass or 1 to 5 parts by mass with respect to 100 parts by mass of the prepolymer (a). When the content of the surfactant is within the above range, water as a curing agent can be dispersed with higher uniformity in the resin composition, and thus the tensile strength of the obtained cured product is further improved. Can do.

  Examples of nonionic activators include polyoxyethylene alkyl ethers, polyoxyethylene (alkyl) phenols, polyoxyethylene alkylamines, polyoxyalkylene glycols, alkylolamides, and fatty acid esters. be able to. Examples of the anionic surfactant include α-olefin sulfonates and sulfonic acid surfactants such as alkylbenzene sulfonic acids and salts thereof; alkyl sulfate ester salts, alkyl (phenyl) ether sulfate ester salts, and sulfosuccinates. Sulfate ester surfactants such as acid salts; phosphate ester surfactants such as phosphate esters and salts thereof; carboxylate surfactants such as succinate and the like can be used. Examples of the cationic surfactant include surfactants such as quaternary ammonium salts, betaines, and alkylamine salts.

  Examples of antifoaming agents that can be used include silicone-based antifoaming agents, fluorine-modified silicone-based antifoaming agents, acrylic polymer-based antifoaming agents, and vinyl ether polymer-based antifoaming agents. The content of the antifoaming agent may be, for example, 0.05 to 5 parts by mass or 0.1 to 3 parts by mass with respect to 100 parts by mass of the prepolymer (a). When the content of the antifoaming agent is within the above range, foaming that may be caused by the reaction of the prepolymer (a) can be more sufficiently suppressed, and thus defects in the obtained cured product can be more sufficiently suppressed. Further, the appearance and tensile strength of the cured product can be further improved.

  The latent curing agent is a compound that reacts with water to generate active hydrogen that can react with the isocyanato group of the prepolymer (a). The content of the latent curing agent may be, for example, 1 to 20 parts by mass or 5 to 10 parts by mass with respect to 100 parts by mass of the prepolymer. When the content of the latent curing agent is within the above range, it can react with moisture in the air to generate a sufficient amount of active hydrogen, so that the tensile strength of the resulting cured product is further improved. Can do.

  As the latent curing agent, for example, a urethane compound having an oxazolidine group (reaction product using polyisocyanate and N-2-hydroxyalkyloxazolidine and, if necessary, a polyol), an organosilicon compound (hydrolyzed with moisture, Regenerating alcoholic hydroxyl group-containing compound or amino group-containing compound), polyol silicic acid ester (substitution of monohydric alcohol silicic acid ester with polyol and distilling off the produced monohydric alcohol, or silicic acid halogen compound And those obtained by dehydrohalogenation of polyol and polyol).

<Method for producing resin composition>
The above-mentioned resin composition contains, for example, a diol having an oxyalkylene group, a component A having a total unsaturation of 0.07 meq / g or less, and at least three functional groups other than the oxyalkylene group and the oxyalkylene group. A component B having a total unsaturation of 0.05 meq / g or more and a component C containing a compound having an isocyanato group to obtain a prepolymer (a). It can be manufactured by a manufacturing method.

More specifically, after the plasticizer (b) and the solvent (c) are charged into the kneader, the CO ₂ absorbent (d), the filler (e), the catalyst (f), and other additives (g ) And disperse until uniform. After dispersing, thoroughly dehydrate. In dehydration, if necessary, the pressure may be reduced or a dehydrating agent may be added. Thereafter, the prepolymer (a) is added, and the resin composition can be produced by stirring until the uniformity becomes high. Examples of the kneader include a disper, a ball mill, S.I. G. A mill, a roll mill, a planetary mixer, etc. can be used. As the CO ₂ absorbent (d), filler (e), catalyst (f), and other additives (g), those subjected to pretreatment such as dehydration may be used.

<Method for producing paint (mixture of curing agent and resin composition)>
The resin composition can also be used as a mixture (paint) of a curing agent (for example, water) and a resin composition. The paint can be produced, for example, by a production method having a step of bringing the resin composition into contact with water (for example, mixing).

  When adding and using water as a hardening | curing agent, the compounding quantity of water may be 1-40 mass parts with respect to 100 mass parts of prepolymers, and may be 10-30 mass parts, for example. When the amount of water is within the above range, the curability is excellent, and the tack-free time and the curing time can be shortened.

<Properties of resin composition>
The viscosity at 25 ° C. of the resin composition may be, for example, 0.5 Pa · s or more, 1 Pa · s or more, or 3 Pa · s or more, and 100 Pa · s or less, 50 Pa · s or less, or 20 Pa · s or less. It may be. When the viscosity at 25 ° C. of the resin composition is within the above range, the construction with a trowel and a spatula becomes easier and the workability can be improved. The viscosity of a resin composition can be calculated | required according to the evaluation method of the viscosity in the Example mentioned later.

  When water is used as a curing agent, the viscosity at 25 ° C. of the paint (the viscosity at 25 ° C. of the resin composition after blending water) is, for example, 0.5 Pa · s or more, 1 Pa · s or more, or It may be 3 Pa · s or more. When water is added and used as the curing agent, the viscosity of the coating at 25 ° C. (the viscosity of the resin composition after adding water at 25 ° C.) is, for example, 100 Pa · s or less, 50 Pa · s or less, or 20 Pa · It may be s or less. When the viscosity at 25 ° C. of the paint is within the above range, construction with a trowel, a spatula, or the like can be made easier, and the workability of the coating film can be further improved.

  The pot life of the resin composition and the paint may be, for example, 10 minutes or more, 30 minutes or more, or 60 minutes or more. If the pot life of the resin composition and the coating material is within the above range, it can be easily applied with a trowel, a spatula or the like even in a wide area. The pot life can be expressed as the time until the viscosity of the resin composition (after water mixing in the case of the water curing type and after opening in the case of the moisture curing type) reaches 100 Pa · s.

  The tack-free time of the resin composition and the paint may be, for example, 72 hours or less, 40 hours or less, or 16 hours or less. When the tack-free time of the resin composition and the paint is within the above range, a coating film and a cured product having an excellent appearance can be formed more easily. The tack-free time can be measured according to “5.19 Tack-free test” in JIS A1439 (2010) “Testing method for sealing material for building”.

  The curing time of the resin composition and the paint may be, for example, 72 hours or less, 40 hours or less, or 16 hours or less. When the curing time of the resin composition and the coating material is within the above range, the period until the top coating material such as the top coat is applied can be shortened, so that the work period can be shortened.

<Use of resin composition>
The above-mentioned resin composition can be used as, for example, a resin composition for waterproofing material, a resin composition for flooring material, a resin composition for peeling prevention, and a resin composition for protective film. Resin compositions include, for example, building waterproofing materials for buildings, painted floors for buildings, exterior wall coatings for buildings, floor slab waterproofing materials for concrete floor slabs, concrete structure peeling prevention materials, concrete structure protective films, and It can be used as an anti-peeling material for tiles.

  The resin composition for waterproofing material may use the above-mentioned resin composition for waterproofing a coating film of a building or the like, for example. Since the waterproof resin composition can be cured by reacting with water (including water absorbed from air), it is excellent in safety and workability during work. Since the obtained cured product can be excellent in tensile product, both excellent tensile strength and sufficient elongation can be achieved. In addition, since the obtained cured product can be excellent in tensile modulus, tear strength, etc., it can greatly improve durability and wear resistance compared to conventional urethane coating film waterproofing materials. it can. In addition, the obtained cured product can be excellent in appearance.

  The waterproof resin composition can be used for various waterproof applications. The composition for waterproofing material is, for example, a coating film waterproofing material for a veranda and a rooftop of a building, a waterproof sheet, a waterproof coating material for a vehicle, a flooring material for an apartment, a detached house, a hospital, a sports facility, etc. It can be used as an elastic pavement material and a rust preventive material such as metal. For example, when the waterproof resin composition is used for various waterproofing applications applied to the rooftop, the durability of the rooftop can be improved.

  When the waterproofing resin composition is used as a waterproof coating material for a building, a cured product (for example, urethane cured product) of a layer containing the above-described resin composition may be formed as a single layer or multiple layers, or The waterproof material may be formed by laminating other layers. As such a waterproof coating material, for example, a single-layer structure consisting only of a urethane cured product layer, a two-layer structure of a urethane cured product layer and a top coat layer, a three-layer structure of two urethane cured product layers and a top coat layer , Urethane cured material layer, reinforcing material layer, urethane cured material layer, and topcoat layer four-layer structure, and urethane cured material layer, breathable sheet, urethane cured material layer, topcoat layer four-layer structure, etc. .

  As the top coat layer, the reinforcing material layer, and the breathable sheet, those used for the waterproof coating material can be used similarly. The top coat layer is provided, for example, to protect the waterproof material from sunlight. As the top coat, for example, an acrylic urethane resin, an acrylic silicon resin, a fluorine resin, or the like can be used. These top coats may be, for example, a strong solvent type, a weak solvent type, and an aqueous type.

  For example, in the case of a water-curing type, a waterproof coating material for a building is prepared by mixing a resin composition and water with a mixer at a construction site to prepare a paint, and then a base material (for example, concrete as a base) ) Is applied and cured so as to have a thickness of about 1 to 4 mm. Here, the base material may have a surface subjected to primer treatment or the like. Moreover, in the construction method of the waterproofing | coated waterproofing material of a building, it is preferable to provide a topcoat layer further on the obtained hardened | cured material after coating and hardening. The coating method may be, for example, hand coating and spraying. When using the above-mentioned resin composition as a moisture curing type, it can be applied by applying the resin composition itself to the substrate instead of the above-mentioned paint.

  As a waterproof material, a portion requiring a high thickness can be applied again to a thickness of about 1 to 4 m on a cured product or a reinforcing material layer that has been cured to some extent, and can be cured.

  The resin composition for floor slab waterproofing may use, for example, the resin composition described above for the resin composition for floor slab waterproofing. The resin composition for floor slab waterproofing may be used for concrete floor slabs, for example, floor slab waterproof layer (NEXCO floor slab waterproof grade I), floor slab waterproof layer (NEXCO floor slab waterproof grade II), edge protection material Etc. may be used. The resin composition for floor slab waterproofing according to the present embodiment can be cured by reacting with water (including water absorbed by air), and thus has excellent safety and workability during work. Since the obtained cured product can be excellent in tensile product, both excellent tensile strength and sufficient elongation can be achieved.

  The above-mentioned floor slab waterproofing resin composition can form a cured resin having higher strength than conventional floor slab waterproofing. The obtained cured product is excellent in tensile elastic modulus, tear strength and the like, and can be excellent in appearance. Therefore, when used as a floor slab waterproof layer (NEXCO floor slab waterproof grade II), the floor slab waterproof material Can be used as an end protection material for floor slab waterproofing. By using the resin composition for waterproofing a floor slab, the floor slab waterproofing material and the end protection material have a seamless structure, and a structure that is more excellent in waterproofing reliability can be provided.

  The above-mentioned floor slab waterproofing composition has the performance described in the floor slab waterproofing of the structure construction management guidelines (July 2017, East Japan Expressway Co., Ltd., Central Japan Expressway Co., Ltd., West Japan Expressway Co., Ltd.). Can have

  For example, the resin composition for a flooring material may be one that uses the above-described resin composition as a flooring material for a building. Since the resin composition for a flooring material can be cured by reacting with water (including water absorbed from air), it is excellent in safety and workability during work. Since the obtained cured product can be excellent in tensile product, both excellent tensile strength and sufficient elongation can be achieved. Since the obtained cured product can be excellent in tensile elastic modulus, tear strength, and the like, durability and abrasion resistance can be improved as compared with conventional resin compositions for coating materials. In addition, the obtained cured product can be excellent in appearance.

  For example, the resin composition for preventing flaking may be one that uses the above-mentioned resin composition for preventing flaking of a concrete structure and preventing flaking of a tile. The resin composition for preventing flaking can be applied to, for example, the surface of a concrete structure or the surface of a tile, and can form a cured product capable of suppressing the flaking of concrete pieces or tiles due to deterioration of the structure. Since the resin composition for preventing flaking can be cured by reacting with water (including water absorbed by air), it is excellent in safety and workability during work. Since the obtained cured product can be excellent in tensile product, both excellent tensile strength and sufficient elongation can be achieved. Since the obtained cured product can be excellent in tensile modulus, tear strength, etc., compared to conventional concrete structure peeling prevention resin composition and conventional tile peeling prevention resin composition, Durability and wear resistance can be improved. In addition, the obtained cured product can be excellent in appearance.

  The resin composition for protective films may use the above-mentioned resin composition for protection of concrete structures, for example. Since the resin composition for a protective film can be cured by reacting with water (including water absorbed from air), it is excellent in safety and workability during work. Since the obtained cured product can be excellent in tensile product, both excellent tensile strength and sufficient elongation can be achieved. Since the obtained cured product can be excellent in tensile modulus, tear strength, etc., it can greatly improve durability, wear resistance, etc. compared to conventional resin compositions for protecting concrete structures. . In addition, the obtained cured product can be excellent in appearance. In particular, the protective film resin composition has a cured product appearance, adhesion to concrete, and deterioration factor blocking properties (for example, salt blocking properties, oxygen transmission blocking properties, water vapor transmission blocking properties, and neutralization blocking properties). Etc.) etc.

<Hardened product>
One embodiment of the cured product is a cured product obtained by curing the above resin composition. The form of the cured product may be a film, for example. The cured product includes, for example, a cured film and a coating.

  The thickness of the cured product may be, for example, 0.3 to 5 mm, 0.3 to 3 mm, or 0.5 to 2 mm. When the thickness of the cured product is within the above range, the waterproof performance can be more sufficient.

  The properties of the cured product (for example, tensile strength, elongation at break, elongation between grips at break, tensile product, tensile elastic modulus, tear strength, etc.) were adjusted to be 2 mm in thickness. The value measured using a cured film is shown.

Tensile strength at 23 ° C. of a cured product, for example, 6N / mm ² or more, 8.5 N / mm ² or more, 9.5 N / mm ² or more, or may be at 10 N / mm ² or more. Tensile strength at -20 ° C. of a cured product, for example, 6N / mm ² or more, 8.5 N / mm ² or more, 9.5 N / mm ² or more, or may be at 10 N / mm ² or more. The tensile strength at 60 ° C. of the cured product may be, for example, 2 N / mm ² or more, 4 N / mm ² or more, 5 N / mm ² or more, or 6 N / mm ² or more. When the tensile strength is within the above range, the cured product is excellent in durability and abrasion resistance, and thus can be suitably used as a civil engineering coating.

  The elongation at break of the cured product at 23 ° C. may be, for example, 500% or more, 550% or more, or 600% or more. When the elongation at break at 23 ° C. of the cured product is within the above range, the cured product is more excellent in base followability, and therefore can be suitably used as a civil engineering coating.

  The elongation percentage between the grips at the time of breaking at 23 ° C. of the cured product may be, for example, 300% or more, 350% or more, or 400% or more. The elongation percentage between the grips at the time of breaking at −20 ° C. of the cured product may be, for example, 250% or more, 300% or more, or 400% or more. The elongation percentage between the grips at break of the cured product at 60 ° C. may be, for example, 200% or more, 250% or more, or 350% or more. If the elongation at break is in the above range, the cured article can be used more favorably as a coating for civil engineering and construction because it is more excellent in base followability of the cured product.

  The tensile product at 23 ° C. of the cured product may be, for example, 600 N / mm or more, 800 N / mm or more, 900 N / mm or more, or 1000 N / mm or more. When the tensile product at 23 ° C. of the cured product is within the above range, the cured product is excellent in durability and abrasion resistance, and therefore can be suitably used as a civil engineering coating.

  The tensile elastic modulus at 23 ° C. of the cured product may be, for example, 10 MPa or more, 15 MPa or more, or 20 MPa or more. If the tensile elastic modulus at 23 ° C. of the cured product is within the above range, the cured product is excellent in wear resistance, and therefore can be suitably used as a civil engineering coating.

  The tear strength of the cured product may be, for example, 30 N / mm or more, 35 N / mm or more, or 40 N / mm or more. When the tear strength of the cured product is within the above range, the cured product is excellent in tear resistance, and thus can be suitably used as a civil engineering / coating coating.

<Civil engineering building structure>
One embodiment of the civil engineering structure includes a cured product of the above-described resin composition. In this specification, the “structure” refers to a structure to which a waterproof material is not applied and a structure before repair, and a structure including a cured product is referred to as a “civil engineering building structure”. In this specification, the civil engineering building structure means, for example, a structure in the civil engineering field such as a bridge, an elevated road, a dam, a tunnel, a road, and a land creation, and a structure in the building field such as a building, an apartment, and a house. Means. The civil engineering building structure according to the present embodiment forms a cured product using the above-described resin composition as, for example, a coating, top coating, intermediate coating, undercoating, primer, top coat, paint, spray, or varnish. It is a civil engineering building structure obtained by doing.

  The civil engineering and building structure includes, for example, a step of forming a resin composition layer by applying the above resin composition to a target structure and curing the resin composition layer to form a cured product (for example, coating). Obtained by the manufacturing method. The cured product may be referred to as a cured film depending on the shape. Since the said hardened | cured material in the civil engineering building structure which concerns on this embodiment is a hardened | cured material of the above-mentioned resin composition, it has the outstanding tensile product. Since the cured product of the above-described resin composition can be excellent in durability, it is possible to extend the life of the structure.

<Coating method (painting method)>
One embodiment of the coating method includes a step of applying the above-described resin composition to a structure. The said coating method may be a method which has the process of providing the resin composition layer which consists of the above-mentioned resin composition on the structure used as object, and hardening the said resin composition layer, for example. For example, before applying the above resin composition to a target structure (for example, concrete requiring repair), the surface of the structure is coated with a primer, a non-land surface adjusting material, a putty, and the like. May be applied. The coating method may include a step of bringing the resin composition into contact with water.

  Examples of a method of applying the above-described resin composition to a structure (for example, a method of providing a resin composition layer) include painting and coating. Since the above-mentioned resin composition can have a sufficiently long pot life, it can also be applied manually using a trowel, spatula, brush, roller, or the like. By coating the resin composition manually, a coating film having a desired film thickness can be formed outdoors.

  In the coating method, the thickness of the resin composition layer can be adjusted according to the thickness after curing (the thickness of the cured product), for example, 0.3 to 5 mm, 0.3 to 3 mm, Or 0.5-2 mm may be sufficient. When the thickness of the resin composition layer is within the above range, the waterproof performance can be more sufficient. The above-described resin composition may be applied in a plurality of times.

  In the description of the above-described resin composition, resin composition manufacturing method, civil engineering structure, and coating method, mutual explanations can be applied.

  As mentioned above, although embodiment of this invention was described, this invention is not limited to the said embodiment at all.

  Hereinafter, the contents of the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the following examples.

(Evaluation methods)
Evaluation in Examples and Comparative Examples was performed according to the following method.

<< Characteristic evaluation of resin composition >>
[Measurement of raw material content in resin composition]
After adding acetonitrile to a sample of the resin composition, a large excess of secondary amine relative to the amount of isocyanato groups in the sample (eg, diethylamine for aromatic isocyanates, 1-phenyl for aliphatic isocyanates). Piperazine) was added for derivatization at room temperature. Furthermore, it dilutes with acetonitrile, and it quantifies with a high performance liquid chromatography apparatus (The JASCO Corporation make, PU-2085 Plus type | mold, a detector: UV, a column: CAPCELL PAK C18 UG120, an eluent: A mixed solvent of acetonitrile and water). Analysis was carried out. For preparation of a calibration curve for quantitative analysis, a standard product synthesized from a pure compound by the same method as the above derivatization procedure was used. In addition, when blending the resin composition, it is a component to be blended, and when it is clear that the remaining amount is 1% by mass or more, it can be calculated from the blending ratio of the resin composition.

[Measurement of viscosity]
About a sample (prepolymer (a), resin composition, or resin composition (paint) containing water), an E-type viscometer TVE25H manufactured by Toki Sangyo Co., Ltd. was used, and JIS-Z8803: 2011 (liquid viscosity The viscosity was measured according to the measurement method. The cone rotor was 3 ° × R9.7, and the sample amount at this time was 0.2 ml. The measurement temperature was 23 ° C., and the rotation speed was 20 rpm or 100 rpm.
[Pot life]
After mixing the resin composition or paint (mixture of water and resin composition) until uniform, JIS K5600 2-6 (2016) "Paint General Test Method-Part 2: Properties and Stability of Paint" In accordance with “Section 6: Pot Life”, the pot life in a standard state at a temperature of 23 ° C. and a relative humidity of 50% was measured. More specifically, the time when the viscosity exceeded 100 Pa · s under the condition of 23 ° C. was determined and evaluated according to the following criteria. The viscosity was measured according to JIS-Z8803: 2011 (liquid viscosity measurement method) using an E-type viscometer TVE25H manufactured by Toki Sangyo Co., Ltd.
A: The pot life is 60 minutes or more B: The pot life is 30 minutes or more and less than 60 minutes C: The pot life is 10 minutes or more and less than 30 minutes D: The pot life is less than 10 minutes

<< Characteristic evaluation of cured film >>
[Preparation of cured film]
A resin composition or paint (mixture of water and resin composition) mixed until uniform is applied to a peeled substrate to a thickness of 2 mm, and then a standard at a temperature of 23 ° C. and a relative humidity of 50%. The cured film which is a sample for evaluation was produced by curing for 7 days in the state. If the properties of the cured film do not change, use an evaluation sample prepared by curing for 24 hours under conditions of a temperature of 23 ° C. and a relative humidity of 50%, and then for 24 hours under conditions of a temperature of 60 ° C. It was.

[Appearance of coating film]
The cured film obtained above was visually observed and evaluated according to the following criteria.
A: When there is no abnormality in the coating film and particularly excellent in flatness B: When there is no abnormality in the coating film C: When there are abnormalities such as swelling and pinholes in the coating film

[Evaluation of tensile performance (tensile strength at each temperature, elongation at break, elongation between grips at break, tensile product and tensile modulus)]
The cured film obtained above was measured based on the tensile performance test of JIS A 6021: 2011 “A waterproofing material for architectural coatings”.

[Evaluation of tear performance (tear strength)]
The cured film obtained above was measured in accordance with the tear performance test of JIS A 6021: 2011 “Waterproofing material for architectural coatings”.

(raw materials)
The raw materials used in the examples and comparative examples are as follows.

[Component A]
PPG P4000 (manufactured by Asahi Glass Co., Ltd., trade name: Preminol S4004): polypropylene glycol (bifunctional, hydroxyl value: 27.8 mg KOH / g, number average molecular weight: 4036, total unsaturation: 0.008 meq / g)
DPG: Dipropylene glycol (bifunctional, hydroxyl value: 836 mg KOH / g, number average molecular weight: 134, total unsaturation: less than 0.005 meq / g (below detection limit))
[Component B]
PPT E5000 (manufactured by Asahi Glass Co., Ltd., trade name: Exenol 5030): poly (oxypropylene) triol (trifunctional, hydroxyl value: 32.8 mgKOH / g, number average molecular weight: 5131, total unsaturation: 0.066 meq / g )
PPT P5000 (manufactured by Asahi Glass Co., Ltd., trade name: Preminol S3006): poly (oxypropylene) triol (trifunctional, hydroxyl value: 33.9 g KOH / g, number average molecular weight: 4965, total unsaturation: 0.008 meq / g )

[Component C]
TDI T100 (manufactured by Tosoh Corporation, trade name: Coronate T-100): 2,4-tolylene diisocyanate

[Plasticizer (b)]
DOA: Bis (2-ethylhexyl) adipate (viscosity at 25 ° C .: 11 mPa · s)
DINA: diisononyl adipate (viscosity at 25 ° C .: 16 mPa · s)
DINP: diisononyl phthalate (viscosity at 25 ° C .: 55 mPa · s)
Trinonyl trimellitic acid (viscosity at 25 ° C .: 88 mPa · s)

[Solvent (c)]
EEP: ethyl 3-ethoxypropionate ( _logPow : 1.35)
MEK: methyl amyl ketone (log _Pow : 1.98)
Swaclean 150 (trade name, manufactured by Maruzen Petrochemical Co., Ltd.): C9 alkylcyclohexane mixture ( _logPow : 3 or more)

[CO ₂ absorbent (d)]
Magnesium hydroxide # 200 (manufactured by Kamishima Chemical Co., Ltd., specific surface area: 50 m ² / g, average particle size: 4.2 μm)
[Filler (e)]
Calcium carbonate NS # 200 (manufactured by Nitto Flour Industry Co., Ltd., specific surface area: 12 m ² / g, average particle size: 1.8 μm)

[Catalyst (f)]
PMDETA: N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine [additive (g)]
Surfactant SLS: Sodium lauryl sulfate

<< Synthesis of Prepolymer (a) >>
(Synthesis Example 1)
A prepolymer having a terminal isocyanato group was synthesized as follows. While flowing nitrogen gas through a reaction vessel equipped with a stirrer, thermometer, nitrogen seal tube, and heating / cooling device, 54.8 parts by mass of PPG P4000 and 5.2 parts by mass of DPG as polyoxyalkylene diol and at least 3 As a polyoxyalkylene polyol having two hydroxyl groups, 16.9 parts by mass of PPT E5000 was charged, and 23.1 parts by mass of TDI T100 was further charged as a polyisocyanate while stirring. Then, it was made to react, stirring at 80 degreeC. The reaction was conducted when the content of isocyanate groups determined by neutralization titration according to the procedure of JIS K 1603-1: 2007 “How to Obtain the Isocyanate Group Content” became less than the theoretical value (about 3 hours). The prepolymer P1 of Synthesis Example 1 was synthesized by cooling and cooling. The isocyanato group content (isocyanate number) of the obtained prepolymer P1 was 6.3% by mass based on the total amount of the prepolymer P1. Moreover, the obtained prepolymer P1 was a transparent liquid at normal temperature, and the viscosity in 23 degreeC was 12.6 Pa.s. Table 1 summarizes the charge ratio (mass ratio), isocyanate value, and viscosity of each raw material.

(Synthesis Example 2)
Prepolymer P2 was synthesized in the same manner as in Synthesis Example 1 except that the raw materials and the charging ratio (mass ratio) were changed as shown in Table 1.

Example 1
<Manufacture of resin composition>
In a sealable container, 30 parts by weight of DOA as a plasticizer (b), 0.2 parts by weight of PMDETA as a catalyst (f), and 2 parts by weight of sodium lauryl sulfate as a surfactant were charged and stirred until uniform. did. Thereafter, 30 parts by mass of magnesium hydroxide previously dried as a CO ₂ absorbent (d) and 20 parts by mass of calcium carbonate as a filler (e) are further added to the container, and the mixture is stirred until uniform. It was dispersed using a machine. A resin composition was produced by adding 100 parts by mass of prepolymer P1 as a prepolymer (a) to this dispersion and stirring until uniform.

<Evaluation of resin composition>
About the obtained resin composition, it evaluated about the content rate of a viscosity, the content rate of a plasticizer, and a solvent. The results are shown in Table 2.

<Preparation of paint (mixture containing water and resin composition)>
To 172.2 parts by mass of the obtained resin composition, 20 parts by mass of water was added and stirred until uniform to obtain a paint (a mixture containing water and the resin composition).

<Evaluation of paint and cured film>
The obtained paint was evaluated for viscosity and pot life. The pot life was 60 minutes or more (evaluation: A). The cured film produced by the above-described method was evaluated for tensile strength, elongation at break, tensile product, tensile elastic modulus, tear strength, and appearance. The results are shown in Table 3. In Table 3, in the evaluation of the resin composition and the evaluation of the cured film, “−” indicates that it has not been measured.

[Examples 2 to 13 and Comparative Example 1]
A resin composition was produced in the same manner as in Example 1 except that the raw materials and the charging ratio (mass ratio) were changed as shown in Tables 2 and 4. Moreover, it carried out similarly to Example 1, and prepared the coating material (resin composition containing water), and produced the cured film. Further, in the same manner as in Example 1, the resin composition, the paint, and the cured film were evaluated. The results are shown in Tables 3 and 5. In Tables 3 and 5, in the evaluation of the resin composition and the evaluation of the cured film, “−” indicates that it has not been measured.

[Example 14]
A coating film was formed in the same manner as in Example 1 except that the thickness of the coating film was changed to 0.3 mm. Thereafter, the sample was cured for 7 days in a standard state at a temperature of 23 ° C. and a relative humidity of 50%, and the coating film was cured by moisture in the air to prepare a sample for evaluation. In the same manner as in Example 1, the resin composition, the paint, and the cured film were evaluated. The results are shown in Tables 3 and 5.

  From the results shown in Table 3 and Table 5, the resin composition containing the prepolymer P1 as in Examples 1 to 14 can form a cured film having a higher tensile product than the resin composition of Comparative Example 1. confirmed.

[Example 15]
A cured film was produced in the same manner as in Example 11 using the resin composition produced in Example 11. Except that the measurement temperature conditions were changed, the tensile performance and tear performance of the cured film were evaluated in the same manner as in Example 11. The tensile performance of the cured film is that the tensile strength at −20 ° C. is 18 N / mm ² , the elongation between grips at break is 300%, the tensile elastic modulus is 30 MPa, and the tensile strength at 23 ° C. Strength is 10 N / mm ² , elongation at break is 640%, elongation between grips at break is 420%, tensile modulus is 24 MPa, tensile strength at 60 ° C. Was 6 N / mm ² , the elongation between the grips at break was 370%, and the tensile modulus was 6 MPa.

Claims (17)

A resin composition comprising a prepolymer (a) having an isocyanato group,
The prepolymer (a) is
A component A containing a diol having an oxyalkylene group and having a total unsaturation of 0.07 meq / g or less;
A component B containing a polyol having at least three functional groups other than an oxyalkylene group and an oxyalkylene group, and having a total unsaturation of 0.05 meq / g or more;
A resin composition which is a reaction product of component C containing a compound having an isocyanato group. The resin composition according to claim 1, wherein the diol is represented by the following general formula (1), and the polyol is represented by the following general formula (2).

[In the general formula (1), A represents an oxygen atom or a divalent residue obtained by removing two active hydrogens from a dihydric alcohol, dihydric phenol or divalent amine, and R ^{1 to} R ⁴ are Each independently represents an alkylene group having 2 to 12 carbon atoms. p _{1 to} p ₄ each independently represents an integer of 0 to 1000, and p ₁ + p ₂ + p ₃ + p ₄ is an integer of 1 or more. ]

[In the general formula (2), B represents an n-valent residue obtained by removing n active hydrogens from a polyhydric alcohol, polyhydric phenol, or polyvalent amine, and R ^{5 to} R ⁸ are each independently Represents an alkylene group having 2 to 12 carbon atoms. n represents an integer of 2 to 6, m _{1 to} m ₄ each independently represents an integer of 0 to 1000, and m ₁ + m ₂ + m ₃ + m ₄ is an integer of 1 or more. ]   The resin composition according to claim 1 or 2, wherein the diol contains a diol having a number average molecular weight of 2500 or more and a diol having a number average molecular weight of less than 2500.   The resin according to any one of claims 1 to 3, wherein the prepolymer (a) has a structure derived from at least one isocyanate selected from the group consisting of tolylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate. Composition. Further comprising a plasticizer (b),
The resin composition as described in any one of Claims 1-4 whose content of the said plasticizer (b) is 15 mass% or less. Further comprising a solvent (c),
The resin composition as described in any one of Claims 1-5 whose content of the said solvent (c) is 1 mass% or more. A CO ₂ absorbent (d) containing at least one selected from the group consisting of magnesium hydroxide, magnesium oxide, calcium hydroxide and calcium oxide;
The CO specific surface area determined by the BET method of ₂ absorber (d) is at ^{10 m} 2 / g or more, the resin composition according to any one of claims 1 to 6.   The resin composition according to any one of claims 1 to 7, which is a moisture curable type or a water curable type.   The coating film according to any one of claims 1 to 8, which is used for waterproofing a coating film of a building, waterproofing a floor of a building, waterproofing a slab of a concrete slab, preventing flaking of a tile, protecting a concrete structure, or preventing a concrete structure from flaking. The resin composition according to item. A method for producing a resin composition comprising a prepolymer (a) having an isocyanato group,
A component A containing a diol having an oxyalkylene group and having a total unsaturation of 0.07 meq / g or less;
A component B containing a polyol having at least three functional groups other than an oxyalkylene group and an oxyalkylene group, and having a total unsaturation of 0.05 meq / g or more;
The manufacturing method of the resin composition which has the process of reacting the component C containing the compound which has an isocyanato group, and obtaining the prepolymer (a) which has an isocyanato group.   Hardened | cured material obtained by hardening | curing the resin composition as described in any one of Claims 1-9. The hardened | cured material of Claim 11 whose tensile strength in 23 degreeC is 6 N / mm < ² > or more.   The hardened | cured material of Claim 11 or 12 whose tensile product in 23 degreeC is 600 N / mm or more.   The hardened | cured material as described in any one of Claims 11-13 whose tear strength in 23 degreeC is 30 N / mm or more.   A civil engineering building structure comprising a cured product of the resin composition according to any one of claims 1 to 9.   The coating method which has the process of apply | coating the resin composition as described in any one of Claims 1-9 to a structure.   The coating method according to claim 16, further comprising a step of bringing the resin composition into contact with water.