JP5634745B2 - Curable composition - Google Patents

Description

  The present invention relates to a novel cured composition. The composition of the present invention is particularly suitable as a covering material for a floor surface.

  Conventionally, as a floor covering material, various materials such as urethane, epoxy, and acrylic are used. By using such a material, it is possible to protect the floor surface and to impart a desired color to the floor surface. However, when high performance is required in terms of heat resistance, chemical resistance, strength, etc., it is difficult for the above materials to sufficiently satisfy the requirements.

JP-A-8-169740 (Patent Document 1) includes a first component comprising an active hydrogen-containing compound, water, and a cement water reducing agent, a second component comprising hydraulic cement, and a third component comprising an isocyanate compound. A cement curable composition comprising at least three components is disclosed. According to such a curable composition, it is possible to ensure excellent physical properties in terms of heat resistance, chemical resistance, strength, and the like.
Japanese Unexamined Patent Application Publication No. 2004-292209 (Patent Document 2) discloses a resin cement composition in which an aggregate containing polyester polyol, polyphenyl polymethyl polyisocyanate, and hydraulic cement is blended. Specifically, it is described that an insulator of about 0.5 to 3 mm can be used as the aggregate. Such a composition can exhibit physical properties such as anti-slip properties in addition to heat resistance, chemical resistance, strength, and the like.

  However, in the above patent document, no consideration is given to coloring. Even if the composition of the above-mentioned patent document is mixed with a pigment and colored, the formed film is likely to have uneven color and the like, which is insufficient in terms of finish. In particular, when an aggregate having a large particle size is included in the composition, such a problem is likely to be caused.

JP-A-8-169740 JP 2004-292209 A

  The present invention has been made in view of the above-described problems, and can exhibit excellent performance in heat resistance, chemical resistance, strength, etc., and can be colored in a desired color tone. An object of the present invention is to obtain a curable composition having excellent finish in the formed film.

  In order to solve such problems, the present inventors have intensively studied, and as a result, a curable composition containing a polyol compound, a pigment, a dispersion containing water, an isocyanate compound, cement, fine aggregate, and coarse aggregate. In the product, the color tone of the coarse aggregate and the color tone of the film formed by the composition obtained by removing the coarse aggregate from the curable composition are approximated, and the present invention is completed. It was.

That is, the present invention has the following characteristics.
1. Dispersion liquid (L) containing polyol compound (a), pigment (b), and water (c), isocyanate compound (M) having two or more isocyanate groups in one molecule, cement (N), fine aggregate ( P), and a curable composition comprising coarse aggregate (Q),
As the polyol compound (a),
An acrylic polyol (a1) having a hydroxyl group and an acid group,
The color tone of the coarse aggregate (Q) is
The curable composition characterized by having a color difference of 20 or less with respect to the color tone of the film formed by the composition obtained by removing the coarse aggregate (Q) from the curable composition.
2. The acrylic polyol (a1) is contained in the polyol compound (a) in an amount of 0.5 to 20% by weight in terms of solid content. The curable composition as described.
3. As the acrylic polyol (a1) ,
1. An acrylic polyol having a hydroxyl value of 1 to 200 mgKOH / g and an acid value of 0.1 to 20 mgKOH / g is included. The curable composition as described.

  In the curable composition of this invention, while being able to color in a desired color tone, the stable effect can be exhibited also in finish etc., and the aesthetics of a formed film can be improved. The composition of the present invention can exhibit excellent performance in heat resistance, chemical resistance, strength, anti-slip property, and the like.

  Hereinafter, modes for carrying out the present invention will be described.

  The curable composition of the present invention comprises a dispersion (L), an isocyanate compound (M), a cement (N), a fine aggregate (P), and a coarse aggregate (Q). Among these, the dispersion liquid (L) is obtained by mixing the polyol compound (a), the pigment (b), and water (c).

  Among these, the polyol compound (a) (hereinafter referred to as “component (a)”) acts as a binder. As the component (a), various polyol compounds capable of reacting with the isocyanate (M) can be used. Specific examples include acrylic polyol, polyester polyol, polyether polyol, polydiene polyol, vegetable oil-based polyol, and cellulose compound. In the present invention, among these, acrylic polyol, vegetable oil-based polyol, and the like are preferable.

The acrylic polyol is a polyol whose resin skeleton is mainly formed by alkyl (meth) acrylate. Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. are mentioned, These 1 type (s) or 2 or more types can be used.
The acrylic polyol can be obtained by copolymerizing (meth) acrylic acid alkyl ester and a monomer copolymerizable therewith. Of all the monomer components constituting the acrylic polyol, the ratio of the (meth) acrylic acid alkyl ester is usually 30 parts by weight or more, preferably about 50 to 99.5 parts by weight.

In the present invention, it is desirable that the acrylic polyol contains at least an acrylic polyol (a1) having a hydroxyl group and an acid group (hereinafter referred to as “component (a1)”).
By including such a component (a1), it is possible to improve the color uniformity and color developability of the pigment, and thus improve the finish and aesthetics of the formed film. In addition, by including the component (a1), a composition having a high degree of freedom in coloring and capable of being colored in a desired color tone is obtained. Furthermore, the component (a1) contributes to the curing reaction of the formed film.

  The hydroxyl value of the component (a1) is preferably 1 to 200 KOHmg / g, more preferably 3 to 100 KOHmg / g, and further preferably 5 to 80 KOHmg / g. When the hydroxyl value of the component (a1) is within such a range, sufficient performance can be exhibited in terms of color uniformity, color development, finish, heat resistance, chemical resistance, strength, and the like. In addition, the hydroxyl value in this invention shows the value with respect to resin solid content.

The hydroxyl group of component (a1) can be introduced into the resin by, for example, a method using a hydroxyl group-containing monomer as a monomer component at the time of polymerization, a method of generating a hydroxyl group by an addition reaction after polymerization, or the like.
Of these, in the former method, the hydroxyl group-containing monomer may be copolymerized with another copolymerizable monomer. Specifically, examples of the hydroxyl group-containing monomer include hydroxyalkyl esters of (meth) acrylic acid such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate; polyethylene glycol , Monoesters of polyether polyols such as polypropylene glycol and polybutylene glycol and unsaturated carboxylic acids such as (meth) acrylic acid; acid anhydride group-containing monomers such as maleic anhydride, ethylene glycol, 1,6-hexanediol Monoesterified products or diesterified products with glycols such as hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether; primary hydroxyl group-containing monomers such as allyl alcohol, 2-hydroxypropyl (meth) Chryrate; Adduct of unsaturated carboxylic acid such as (meth) acrylic acid and monoepoxy compound such as α-olefin epoxide; Adduct of glycidyl (meth) acrylate and monobasic acid such as acetic acid, propionic acid and fatty acids Secondary hydroxyl group-containing monomers such as these can be used, and one or more of these can be used.

  Examples of the monomer copolymerizable with the hydroxyl group-containing monomer include, in addition to the aforementioned (meth) acrylic acid alkyl ester, acid group-containing monomer, amino group-containing monomer, amide group-containing monomer, styrene derivative, vinyl chloride, vinyl acetate, Maleic acid dialkyl ester, fluoroolefin, reactive silyl group-containing vinyl compound and the like can be used.

  Examples of a method for generating a hydroxyl group by an addition reaction after polymerization include, for example, a method of adding a monoepoxy compound such as an α-olefin epoxide to a carboxyl group in a resin, acetic acid, propionic acid, fatty acids to an epoxy group in a resin. And a method of adding a monobasic acid or the like.

The component (a1) has an acid group in addition to the hydroxyl group. This acid group acts to improve color uniformity, color developability, finish, etc., and also has an advantageous effect on curability during film formation, contributing to improvements in heat resistance, chemical resistance, strength, etc. It is.
(A1) The acid value of a component is 0.1-20 mgKOH / g normally, Preferably it is 0.3-10 KOHmg / g, More preferably, it is 0.5-5 KOHmg / g. If the acid value of the component (a1) is within such a range, sufficient performance in color uniformity, color developability, finish, etc. can be exerted, and heat resistance, chemical resistance, strength, etc. can be improved. You can also plan. In addition, the acid value in this invention shows the value with respect to resin solid content.

  In order to introduce an acid group into the component (a1), an acid group-containing monomer may be copolymerized together with the monomer. Examples of the acid group-containing monomer include unsaturated carboxylic acid, unsaturated sulfonic acid, unsaturated phosphonic acid and the like, and among these, unsaturated carboxylic acid is preferable. Examples of the unsaturated carboxylic acid include (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and salts thereof. As the acid group-containing monomer, one or more of these can be used.

  As the component (a1), those having an amino group can also be used. In order to introduce an amino group into the component (a1), an amino group-containing monomer may be copolymerized together with the above monomer. In this case, the amine value in the component (a1) may be about 0.05 to 10 KOHmg / g (preferably 0.1 to 3 KOHmg / g). In addition, an amine value shows the value with respect to resin solid content.

The weight average molecular weight of the component (a1) is 1000 to 100,000, preferably 10,000 to 50,000. With such a weight average molecular weight, it is possible to improve heat resistance, chemical resistance, strength and the like while improving coloring uniformity, color developability and the like.
The glass transition point (hereinafter also referred to as “Tg”) of the component (a1) is usually about −50 to 80 ° C., preferably about −20 to 60 ° C.

  The component (a1) is preferably one that can be dissolved and / or dispersed in the liquid organic compound described below. In particular, the component (a1) is preferably soluble in the solvent in the liquid organic compound. By using such (a1), the above effect can be sufficiently enhanced.

  When (a1) is used as the polyol compound (a), the component (a1) is contained in an amount of 0.5 to 30% by weight (more preferably 1 to 20% by weight) in the polyol compound (a) in terms of solid content. It is desirable that

  Among the components (a), examples of the vegetable oil-based polyol (a2) (hereinafter referred to as “component (a2)”) include soybean oil-based polyol and castor oil-based polyol. Of these, castor oil-based polyol is particularly preferable. As the castor oil-based polyol, for example, castor oil, alkylene oxide adduct of castor oil, epoxidized product of castor oil, halide of castor oil, transesterified product of castor oil and polyhydric alcohol, and hydride thereof can be used. .

  When the polyol compound (a) includes the component (a1) and the component (a2), the component (a1) is 0.5 to 30% by weight (more preferably) in the polyol compound (a) in terms of solid content. 1 to 20% by weight) is desirably contained, and the component (a2) is desirably contained by 70 to 99.5% by weight (more preferably 80 to 99% by weight). With such a ratio, the above-described effects can be sufficiently exhibited.

As the pigment (b) (hereinafter referred to as “component (b)”), various colored pigments can be used, and a colored pigment and an extender pigment can be used in combination.
Examples of coloring pigments include titanium oxide, zinc oxide, carbon black, black iron oxide, cobalt black, copper manganese iron black, red pepper, molybdate orange, permanent red, permanent carmine, anthraquinone red, perylene red, quinacridone red, yellow. Examples thereof include iron oxide, titanium yellow, first yellow, benzimidazolone yellow, chrome green, cobalt green, phthalocyanine green, ultramarine, bitumen, cobalt blue, phthalocyanine blue, quinacridone violet, and dioxazine violet. Examples of extender pigments include heavy calcium carbonate, light calcium carbonate, kaolin, clay, diatomaceous earth, talc, and barium sulfate. The particle size of the component (b) is usually less than 50 μm (preferably 0.1 to 30 μm).
It is possible to express various color tones by appropriately selecting and mixing one or more of these components (b).
The ratio of (b) component is 0.5-30 weight part normally with respect to 100 weight part of solid content of (a) component, Preferably it is 1-20 weight part.

Water (c) (hereinafter referred to as “component (c)”) contributes to a curing reaction or the like when the dispersion liquid (L), isocyanate compound (M), cement (N) and the like are mixed.
The ratio of the component (c) is preferably 20 to 200 parts by weight, more preferably 30 to 150 parts by weight with respect to 100 parts by weight of the solid content of the component (a).

  The dispersion (L) preferably contains a liquid organic compound (d) (hereinafter referred to as “component (d)”) in addition to the above components. By including the component (d) in the dispersion (L), the stability of the dispersion (L) is improved, and the effects of the present invention can be stably obtained. The component (d) is an organic compound that is liquid at room temperature, and specifically, a solvent (d1) and / or a plasticizer (d2) can be used.

As the solvent (d1), non-aqueous solvents such as aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, ester solvents and ketone solvents are suitable. Specific examples of the aliphatic hydrocarbon solvent include n-hexane, n-pentane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, terpin oil and mineral spirits. Etc. Examples of aromatic hydrocarbon solvents include toluene, xylene, solvent naphtha, etc .; Examples of ester solvents include ethyl acetate and butyl acetate; Examples of ketone solvents include methyl ethyl ketone and methyl isobutyl ketone. Is mentioned. As the solvent (d1), one or more of these can be used.
As such a non-aqueous solvent, a solvent in which 50% by weight or more (preferably 60% by weight or more, more preferably 70% by weight or more) is an aliphatic hydrocarbon, particularly does not contain toluene and xylene, and has a flash point. Those corresponding to the Fire Service Act Type 4 and Type 2 Petroleum at 21 ° C. or higher are suitable.

As a plasticizer (d2), a phthalic acid compound, an adipic acid compound, a sebacic acid compound, a phosphoric acid compound, an alkylsulfonic acid ester compound etc. can be used, for example. Specific examples of the phthalic acid compound include di (n-butyl) phthalate, bis (2-ethylhexyl) phthalate, diisononyl phthalate, and butyl benzyl phthalate. Examples of adipic acid compounds include, for example, di (n-butyl) adipate, bis (2-ethylhexyl) adipate; Dibutyl and the like; as the phosphoric acid compound, for example, tricresyl phosphate, cresyl diphenyl phosphate and the like; as the alkyl sulfonic acid ester compound, for example, decane sulfonic acid phenyl ester, undecane sulfonic acid phenyl ester, dodecane sulfonic acid phenyl ester, Tridecanesulfonic acid phenyl ester, tetradecanesulfonic acid phenyl ester, pentadecanesulfonic acid phenyl ester, pentadecanesulfonic acid cresyl ester, hexadecanesulfonic acid phenyl ester, heptadecanesulfonic acid Eniruesuteru, octadecanoic acid phenyl ester, nona decane sulfonic acid phenyl ester, equalizer San decyl phenyl sulfonate ester. As a plasticizer ( d2 ), these 1 type (s) or 2 or more types can be used.
In the present invention, those containing the solvent (d1) and the plasticizer (d2) are particularly suitable as the component (d).

The ratio of the component (d) is preferably about 20 to 200 parts by weight with respect to 100 parts by weight of the solid content of the component (a).
When the solvent (d1) and the plasticizer (d2) are included, the ratio of the solvent (d1) is 1 to 50 parts by weight (more preferably 2 to 20 parts by weight) with respect to 100 parts by weight of the solid content of the component (a). It is desirable to do. The ratio of the plasticizer (d2) is desirably 20 to 200 parts by weight (more preferably 30 to 150 parts by weight) with respect to 100 parts by weight of the solid content of the component (a).

As the isocyanate compound (M), a compound having two or more isocyanate groups in one molecule can be used. Specifically, for example, 4,4-diphenylmethane diisocyanate (pure-MDI), polymeric MDI, xylylene diisocyanate (XDI), tolylene diisocyanate, hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), hydrogenated XDI, Hydrogenated MDI or the like, or those derivatized by allophanatization, biuretization, dimerization (uretidioneization), trimerization (isocyanurate conversion), adduct formation, carbodiimidization reaction, etc. can be mentioned. Moreover, the isocyanate group terminal prepolymer obtained by reaction of isocyanate and a polyol can also be used. As an isocyanate compound, these 1 type (s) or 2 or more types can be used.
The mixing ratio of the isocyanate compound (M) is preferably 50 to 800 parts by weight, more preferably 100 to 500 parts by weight with respect to 100 parts by weight of the solid content of the component (a).

Cement (N) includes, for example, ordinary Portland cement, early-strength Portland cement, ultra-high-strength Portland cement, moderately hot Portland cement, sulfate-resistant Portland cement, white Portland cement, etc., as well as alumina cement, ultrafast cement Examples thereof include cement, expanded cement, acidic phosphate cement, silica cement, blast furnace cement, fly ash cement, and keens cement. These may be used alone or in combination of two or more. Among these, Portland cement is preferable.
The mixing ratio of the cement (N) is preferably 100 to 1000 parts by weight, more preferably 200 to 800 parts by weight with respect to 100 parts by weight of the solid content of the component (a).

The composition of the present invention further contains fine aggregate (P) in addition to the above components. By mixing such fine aggregate (P), it is possible to improve the strength of the coating, increase the thickness, and the like.
Examples of the fine aggregate (P) include natural stone pulverized material, ceramic powder, silica sand, ceramic powder, rubber particles, metal particles and the like, or those coated with a colored coating.
The particle diameter of the fine aggregate (P) is usually 50 μm to less than 1000 μm, preferably about 100 to 980 μm. As the fine aggregate (P), two or more kinds having different average particle diameters can be used.
The mixing ratio of the fine aggregate (P) is preferably 200 to 3000 parts by weight, more preferably 500 to 2500 parts by weight with respect to 100 parts by weight of the solid content of the component (a).

In the composition of the present invention, in addition to the above components, coarse aggregate (Q) is further included. Such coarse aggregate (Q) has a larger particle diameter than the fine aggregate (P). In the present invention, by mixing the coarse aggregate (Q), fine irregularities can be formed on the surface of the coating, and slip resistance can be imparted.
The particle diameter of the coarse aggregate (Q) is usually about 1 to 10 mm. As the base material of the coarse aggregate (Q), the same material as that exemplified for the fine aggregate (P) can be used.
The mixing ratio of the coarse aggregate (Q) is preferably 100 to 2000 parts by weight, more preferably 200 to 1000 parts by weight with respect to 100 parts by weight of the solid content of the component (a).

In the present invention, the color tone of the coarse aggregate (Q) is an approximate color of the color tone of the film formed by the composition obtained by removing the coarse aggregate (Q) from the curable composition. In the present invention, the finish can be improved by using the coarse aggregate (Q) having such a color tone.
Usually, the coarse aggregate appears on the surface of the coating and gives fine irregularities to the coating. However, the appearance of the coarse aggregate on the coating surface (density, uneven height, etc.) may slightly change depending on the state of the base, the atmosphere during curing, and the like. In this way, when the appearance of the coarse aggregate is changed, unevenness is likely to occur in the finished appearance of the coating, and the aesthetics are impaired.
On the other hand, in the present invention, by using the coarse aggregate (Q) having a specific color tone, the above-described problems can be solved, and the finish and aesthetics can be improved.

The color tone of the coarse aggregate (Q) is an approximate color of the color tone of a film formed by removing the coarse aggregate (Q) from the curable composition of the present invention (hereinafter referred to as “coarse aggregate-free coating”). And Specifically, the color tone of the coarse aggregate (Q) is desirably set so that the color difference from the color tone of the coarse aggregate-free coating is 20 or less (preferably 15 or less, more preferably 10 or less).
The color difference (ΔE) mentioned here is a value measured using a color difference meter, and can be calculated from the L ^* value, a ^* value, and b ^* value according to the following formula. L ^* , a ^* , b ^* of coarse aggregate (Q) is measured by filling the coarse aggregate (Q) into a rectangular container until the bottom of the container is concealed and flattening the surface. Can be calculated.
^{<Equation> △ E = {(L *} 1 -L * 2) 2 + (a * 1 -a * 2) 2 + (b * 1 -b * 2) 2} 0.5
(In the formula, L ^{* 1} , a ^{* 1} , b ^{* 1} are L ^* , a ^* , b ^{* of the} coarse aggregate (Q), respectively ^. L ^{* 2} , a ^{* 2} , b ^{* 2} are not coarse aggregates, respectively. L ^* , a ^* , b ^* ) of coating

  As the coarse aggregate (Q), those satisfying the above conditions can be used. Specifically, as the coarse aggregate (Q), a natural stone pulverized product, ceramic powder, silica sand, ceramic powder or the like is preferably applied with a colored coating. This color coating can be performed using a colorant including a color pigment and a binder. Among these, as the color pigment, the same pigment as the component (b) can be used. Examples of the binder include organic binders such as polyester resin, vinyl chloride resin, epoxy resin, acrylic resin, urethane resin, acrylic silicon resin, and fluorine resin, and inorganic binders such as water glass, alkoxysilane, and silicon resin. Can be mentioned.

  Various additives other than the said component can also be mixed with this invention composition. Examples of such additives include antifoaming agents, surfactants, reaction regulators, water reducing agents, fibers, antiseptics, algaeproofing agents, and antifungal agents.

  Among the above additives, examples of the reaction modifier include organic metal compounds, metal salts, and nitrogen-containing compounds. Specific examples of the organometallic compound include dibutyltin dilaurate, tetrabutyl titanate, zinc octoate, zinc naphthenate, tin octoate, lead octoate, potassium oleate, and cobalt 2-ethylhexanoate. Examples of the metal salt include stannic chloride and ferric chloride. Examples of nitrogen-containing compounds include N, N-dimethylcyclohexylamine, N, N, N ′, N′-tetramethylhexamethylenediamine, N, N-dimethylbenzylamine, N-ethylmorpholine, and 1,4-diazabicyclo-2. , 2,2-octane, 4-dimethylaminopyridine, oxypropylated triethanolamine, β-diethylaminoethanol and N, N, N ′, N′-tetrakis (2-hydroxy) ethylenediamine, polyamine compounds, hydrazides Compounds, piperidine compounds and the like. By mixing such a reaction regulator, curability and the like can be improved.

In the present invention, it is desirable to use a nitrogen-containing compound as the reaction modifier. In particular, an embodiment containing a piperidine compound as the nitrogen-containing compound is suitable. When a piperidine compound is used, an advantageous effect can be obtained in terms of resistance to discoloration as well as improvement in curability. As the piperidine compound, a compound having a piperidyl group can be used. Specifically, for example , bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6) -Tetramethyl-4-piperidyl) sebacate, 1- [2- {3- (3,5-di-tert-butyl-4-hydroxyfephenyl) propionyloxy} ethyl] -4- {3- (3,5 -Di-t-butyl-hydroxyphenyl) propionyloxy} 2,2,6,6′-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, poly [{6- (1 , 1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene { (2,2,6,6-tetramethyl-4-piperidyl) imino}] and the like.
Such a piperidine compound may be mixed within a range of preferably 0.01 to 20 parts by weight, more preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the solid content of the component (a).

  In the curable composition of the present invention, the dispersion (L), the isocyanate compound (M), and the cement (N) are stored in separate packages at the time of distribution, and these may be mixed at the time of use. . The fine aggregate (P) and the coarse aggregate (Q) are usually mixed in the same package as the component (N). Various additives may be usually mixed in the same package as the component (L).

  The curable composition of the present invention can form a film by mixing the above-mentioned components at the time of use and applying the mixture to a base such as mortar or concrete. The composition of the present invention can exhibit excellent physical properties in terms of heat resistance, chemical resistance, strength, and the like, and therefore is particularly preferable as a material applied to floor surfaces such as concrete.

At the time of application, various methods such as ironing, pouring, and spraying can be employed. The thickness after curing is usually about 2 to 10 mm. Within such a thickness range, it is also possible to divide and paint several times.
The coating and subsequent drying may be usually performed at room temperature (0 to 40 ° C.).

  Examples are given below to clarify the features of the present invention.

(Manufacture of curable composition)
According to the formulation shown in Tables 1 and 2, after each component was mixed uniformly to produce a dispersion, this dispersion, the isocyanate compound, cement, fine aggregate, and coarse aggregate were mixed uniformly. A curable composition was obtained. In each curable composition, the following raw materials were used. The color difference (ΔE) between the coarse aggregate and the coarse aggregate-free coating was measured using a color difference meter.

Resin 1: acrylic polyol (hydroxyl value 30 KOHmg / g, acid value 1.5 KOHmg / g, weight average molecular weight 15000, glass transition temperature 30 ° C., solid content 50% by weight, medium: mineral spirit)
Resin 2: Acrylic polyol (hydroxyl value 10 KOH mg / g, acid value 3 KOH mg / g, weight average molecular weight 20000, glass transition temperature 40 ° C., solid content 50% by weight, medium: mineral spirit)
Resin 3: Acrylic polyol (hydroxyl value 30 KOH mg / g, acid value 1.5 KOH mg / g, weight average molecular weight 120,000, glass transition temperature 30 ° C., solid content 50 wt%, medium: mineral spirit)
Resin 4: Acrylic resin (acid value 2 KOH mg / g, weight average molecular weight 18000, glass transition temperature 30 ° C., solid content 50 wt%, medium: mineral spirit)
Resin 5: Polyether polyol (hydroxyl value 35 KOHmg / g, solid content 50% by weight)
Resin 6: Castor oil-based polyol (hydroxyl value 160 KOH mg / g, acid value 1 KOH mg / g, solid content 100% by weight)
Pigment 1: Titanium oxide Pigment 2: Carbon black Pigment 3: Yellow iron oxide Pigment 4: Phthalocyanine blue Pigment 5: Yellow iron oxide aqueous dispersion (50% by weight)
Pigment 6: Phthalocyanine blue aqueous dispersion (28% by weight)
・ Liquid organic compound 1: Plasticizer (Bis (2-ethylhexyl) phthalate)
Liquid organic compound 2: Plasticizer (alkyl sulfonic acid phenyl ester)
Additive 1: Surfactant Additive 2: Antifoaming agent Isocyanate compound: Polymeric MDI
・ Cement: White Portland cement ・ Fine aggregate: Silica sand (particle size 0.2-0.8mm)
・ Coarse aggregate 1: Gray coarse aggregate (particle size 1-2mm, colored coating of ceramic powder)
-Coarse aggregate 2: Yellow coarse aggregate (particle diameter 1-2mm, colored coating of ceramic powder)
-Coarse aggregate 3: Pale yellow coarse aggregate (particle diameter 1-2mm, colored coating of ceramic powder)
・ Coarse aggregate 4: Green coarse aggregate (particle diameter 1-2mm, colored coating of ceramic powder)
・ Coarse aggregate 5: White coarse aggregate (particle diameter 1-2 mm, ceramic powder)

(Test I)
The following tests were conducted for each curable composition obtained by the above method.

(1) Finishing property Each cured composition was coated on a concrete base so that the thickness after curing was 6 mm, and after curing for 7 days, the finishing property of the coating was visually confirmed. The evaluation is made in three stages (A: A) when the coarse aggregate is uniform and the finish is “A”, and non-uniform finish due to the coarse aggregate is “C” (excellent: A>B> C: Inferior). In addition, both coating and curing were performed in a standard state (temperature 23 ° C., relative humidity 50%).

Test results are shown in Tables 1-2. Examples 1 to 7 and Reference Examples 1 to 3 had good finish.

(Test II)
The following tests were conducted for Examples 1 to 7 and Reference Examples 1 to 3 .

(2) Strength Each cured composition was coated on a flat concrete plate so that the thickness after curing was 6 mm, and cured for 7 days. In addition, both coating and curing were performed in a standard state.
A steel ball having a height of 1 m to 1 kg was dropped a plurality of times on the surface of the obtained coating. In this test, the steel balls were repeatedly dropped until an abnormality (cracking, peeling, etc.) occurred in the coating. Evaluation is “A” when no abnormality occurs even when the steel ball is dropped 20 times, “B” when abnormality is caused by dropping 11 to 20 times, and abnormality is caused by dropping 10 times or less. It was performed in three stages (excellent: A>B> C: inferior) with the thing as “C”.

(3) Chemical resistance Each cured composition was coated on a flat concrete plate so that the thickness after curing was 6 mm, and cured for 72 hours. In addition, both coating and curing were performed in a standard state.
2 ml of chemicals were placed in a spot shape on the surface of the obtained film, and allowed to stand for 24 hours in a standard state, and then the state of the film was visually confirmed. The evaluation was performed in three stages (excellent: A>B> C: inferior), with “A” indicating no abnormality and “C” indicating abnormality such as discoloration. For chemical resistance 1, a 30% by weight aqueous solution of sodium hydroxide was used, and for chemical resistance 2, ethyl acetate was used.

(4) Coloring uniformity Each cured composition was coated on a slate plate so that the thickness after curing was 6 mm, and after curing for 7 days, the coloring uniformity of the coating was visually confirmed. The evaluation was performed in three stages (excellent: A>B> C: inferior), in which “A” indicates that there was no color unevenness and a uniform film was formed, and “C” indicates that the color unevenness occurred. In addition, both coating and curing were performed in a standard state.

  The test results are shown in Table 3. In Examples 1 to 7, good results could be obtained in any test.

(Test III)
Example 11
As the curable composition of Example 11, a composition obtained by adding 0.5% by weight of the reaction modifier 1 to the dispersion of Example 3 was used. As the reaction modifier 1, an amine compound (N, N, N ′, N′-tetramethylhexamethylenediamine) was used.
Example 11 Each test similar to the above test I was performed on the curable composition, and the evaluation results were all A.

Example 12
As the curable composition of Example 12, a dispersion obtained by adding 0.5% by weight of the reaction modifier 2 to the dispersion of Example 3 was used. As the reaction regulator 2, a piperidine compound (bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate) was used.
When each test similar to the said test I was done about the curable composition of Example 12, all the evaluation results were A.

Next, the following tests were performed on the curable compositions of Example 3, Example 11 and Example 12.
(5) Curability Each cured composition was coated on a slate plate so that the thickness after curing was 6 mm, cured at 20 ° C. for 24 hours, and then the tackiness of the coating was confirmed by finger touch. As a result, in Example 3, a slight tackiness was observed, whereas in Examples 11 and 12, no tackiness was observed, indicating excellent curability.

(6) Discoloration resistance Each cured composition was coated on a slate plate so that the thickness after curing was 4 mm, followed by curing for 72 hours. In addition, both coating and curing were performed in a standard state.
The resulting coating was irradiated with an ultraviolet lamp from a distance of about 30 cm for 72 hours, and the color difference before and after irradiation was confirmed. As a result, the color difference was the smallest in Example 12, followed by Example 3 and Example 11.

Claims (3)

Dispersion liquid (L) containing polyol compound (a), pigment (b), and water (c), isocyanate compound (M) having two or more isocyanate groups in one molecule, cement (N), fine aggregate ( P), and a curable composition comprising coarse aggregate (Q),
As the polyol compound (a),
An acrylic polyol (a1) having a hydroxyl group and an acid group,
The color tone of the coarse aggregate (Q) is
The curable composition characterized by having a color difference of 20 or less with respect to the color tone of the film formed by the composition obtained by removing the coarse aggregate (Q) from the curable composition. The curable composition according to claim 1, wherein the acrylic polyol (a1) is contained in the polyol compound (a) in an amount of 0.5 to 20% by weight in terms of solid content. As the acrylic polyol (a1) ,
The curable composition according to claim 1, comprising an acrylic polyol having a hydroxyl value of 1 to 200 mgKOH / g and an acid value of 0.1 to 20 mgKOH / g.