JP5460461B2 - 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.

  British Patent No. 1192864 (Patent Document 1) discloses a cement composition containing cement, silica, water, an isocyanate compound, and a polyol as essential components. Japanese Patent No. 2898044 (Patent Document 2) discloses a curable composition containing cement, filler, isocyanate compound, castor oil rosin acid ester or castor oil, pine oil, and water as essential components. According to such a composition, it is possible to ensure good performance in physical properties such as heat resistance, chemical resistance and strength.

British Patent No. 1192864 Japanese Patent No. 2898044

  The composition described in the above-mentioned patent document is usually divided into at least three components: a first component containing an active hydrogen-containing compound such as a polyol and water, a second component containing cement, and a third component containing an isocyanate compound. However, these three components are mixed and used when constructed on the floor surface or the like. However, in the composition of the above-mentioned patent document, the stability of the first component tends to be lowered, and when such a first component is used, the curability, finish, etc. are insufficient, and desired film properties are expressed. There is a risk that it will not be.

  The present invention has been made in view of the above-described problems, and ensures the stability of the curable composition and exhibits excellent performance in the finish, heat resistance, chemical resistance, strength, etc. of the formed film. The purpose is to make it.

  In order to solve such problems, the present inventors have intensively studied and conceived a dispersion containing a polyol compound, a silver compound, and water, an isocyanate compound, and a curable composition containing cement, and the present invention. It came to complete.

That is, the present invention has the following characteristics.
1. Polyol compounds (a), supported silver oxide particles (b), water (c), and a dispersion containing a pigment (d) (L), isocyanate compound (M), as well as viewing containing cement (N),
As the polyol compound (a),
A curable composition comprising an acrylic polyol (a1) having a hydroxyl group and an acid group.
2. The acrylic polyol (a1) is
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 The curable composition according to 1.
3. The weight average molecular weight of the acrylic polyol (a1) is
It is 1000-100000. Or 2. The curable composition according to 1.
4). As the polyol compound (a),
Contains the acrylic polyol (a1) and vegetable oil-based polyol (a2)
It is characterized by 1. ~ 3. The curable composition according to any one of the above.

  According to the present invention, it is possible to ensure the stability of the curable composition and to exhibit excellent performance in the finish, heat resistance, chemical resistance, strength, and the like of the formed film.

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

  The curable composition of this invention contains a dispersion liquid (L), an isocyanate compound (M), and cement (N). Among these, the dispersion liquid (L) is obtained by mixing at least the polyol compound (a), the silver compound (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. The ratio of the (meth) acrylic acid alkyl ester in the total monomer components constituting the acrylic polyol is preferably 30 parts by weight or more, 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), the color uniformity and color developability can be improved, and as a result, the finish and aesthetics of the formed film can be improved. 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.
The acid value of the component (a1) is preferably 0.1 to 20 mg KOH / g, more preferably 0.3 to 10 KOH mg / g, and further preferably 0.5 to 5 KOH mg / 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 preferably about −50 to 80 ° C., more 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.

  The silver compound (b) (hereinafter referred to as “component (b)”) is a component that contributes to improving the stability of the dispersion liquid (L). In the present invention, by including the component (b), the dispersion stability in the dispersion liquid (L) is increased, and separation with time is suppressed. By using the dispersion liquid (L) thus stabilized, the cured composition of the present invention exhibits stable performance in terms of curability, finish, heat resistance, chemical resistance, strength, and the like. The reason why such an effect is achieved is not clear, but it is assumed that some kind of interaction is caused between the hydroxyl group in the polyol and silver.

  As the component (b), an organic or inorganic silver compound can be used. Examples of the silver compound include silver carbonate, silver oxide, silver phosphate, silver chloride, silver fluoride, silver iodide, silver bromide, silver nitrate, silver sulfate, silver acetate, and silver oxalate. These can be used alone or in combination of two or more.

The silver compound can also be used in a form supported on the base particles. Examples of such base particles include activated carbon, alumina, silica, zeolite, hydroxyapatite, zirconium phosphate, titanium phosphate, titanium oxide, potassium titanate, bismuth oxide, zirconium oxide, hydrotalcite, and the like.
As a method for supporting the silver compound on these substrate particles, a known method may be used. For example, a method of supporting by physical adsorption or chemical adsorption, a method of supporting by ion exchange reaction, a method of supporting by a binder, a silver compound Examples thereof include a method of supporting the substrate particles by implanting them, a method of forming a thin layer of a silver compound on the surface of the substrate particles by a thin film forming method such as vapor deposition, dissolution and precipitation, and sputtering.

  The ratio of component (b) is preferably 0.0001 to 2 parts by weight, more preferably 0.0005 to 1 part by weight, and still more preferably 0.001 to 100 parts by weight of component (a) in terms of solid content. 0.5 parts by weight. If it is such a ratio, the stability improvement effect by (b) component can be acquired.

Water (c) (hereinafter referred to as “component (c)”) contributes to the curing reaction when the dispersion (L), the isocyanate compound (M), and the cement (N) 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) in the present invention may contain a pigment (d) (hereinafter referred to as “component (d)”). In this invention, it becomes possible to prepare a curable composition in a desired color by including this (d) component. In the present invention, even when the dispersion liquid (L) contains the component (d), the stability of the dispersion liquid (L) can be sufficiently ensured, and it is also preferable in terms of color uniformity, color developability, and the like. is there.

  As the component (d), various color pigments can be used, and a color 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 (d) is preferably less than 50 μm (more preferably 0.1 to 30 μm).

By appropriately selecting and mixing one or more of these (d) components, various color tones can be expressed.
The ratio of the component (d) is preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight with respect to 100 parts by weight of the solid content of the component (a).

  The dispersion liquid (L) in the present invention can contain a liquid organic compound (e) (hereinafter referred to as “component (e)”). The component (e) is an organic compound that is liquid at room temperature, and specifically, a solvent (e1) and / or a plasticizer (e2) can be used. In the present invention, since the dispersion (L) contains the component (e), the stability of the dispersion (L) is further improved, and the effects of the present invention can be stably obtained.

As the solvent (e1), 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 (e1), 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 (e2), 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, etc .; examples of sebacic acid compounds, such as dibutyl sebacate; and examples of fumaric acid compounds include, for example, fumaric acid 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 the plasticizer (c2), one or more of these can be used.
In the present invention, those containing the solvent (e1) and the plasticizer (e2) are particularly suitable as the component (e).

The ratio of the component (e) 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 (e1) and the plasticizer (e2) are included, the ratio of the solvent (e1) is preferably 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). The ratio of the plasticizer (e2) 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 liquid (L) is produced by uniformly mixing the above components (a), (b), (c), and (d), (e) as required Can do. At this time, additives such as an antifoaming agent, a surfactant, a reaction adjusting agent, a water reducing agent, fibers, an antiseptic, an algaeproofing agent, and an antifungal agent can be mixed.

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 isocyanate compound (M) may be mixed within a range of 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).

Examples of the cement (N) include ordinary Portland cement, early strength Portland cement, super early strength Portland cement, moderately hot Portland cement, sulfate-resistant Portland cement, white Portland cement and the like, as well as alumina cement and ultrafast cement Examples thereof include cement, expanded cement, acidic phosphate cement, silica cement, blast furnace cement, fly ash cement, and keens cement. These can be used alone or in combination of two or more. Among these, Portland cement is preferable.
The cement (N) may be mixed within a range of 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).

In the composition of the present invention, in addition to the above components, fine aggregate can be further mixed. By mixing such fine aggregates, it is possible to improve the strength of the coating, increase the thickness, and the like.
Examples of the fine aggregate include natural stone pulverized material, ceramic powder, silica sand, ceramic powder, rubber particles, metal particles, etc., or those obtained by coloring these surfaces. The particle size of the fine aggregate is usually about 0.05 to 1 mm.
The fine aggregate may be mixed within a range of preferably 200 to 2000 parts by weight, more preferably 500 to 1500 parts by weight with respect to 100 parts by weight of the solid content of the component (a).
Further, in the present invention, by mixing coarse aggregate having a particle diameter larger than that of the fine aggregate, fine irregularities can be formed on the surface of the coating, and slip resistance can be imparted.

  In the curable composition of the present invention, the dispersion (L), the isocyanate compound (M), and the cement (N) may be stored in separate packages during distribution, and these may be mixed during use. Fine aggregates and coarse aggregates are usually mixed in the same package as the component (N).

  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 substrate. 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 possible to divide it into a plurality of 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 dispersion)
According to the formulation shown in Table 1, each component was uniformly mixed to produce a dispersion. In the dispersion, the following raw materials were used.

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)
Silver compound 1: 2% by weight dispersion of silver oxide-supported particles (base particles; titanium oxide, weight ratio of base particles to silver oxide = 20: 1)
Silver compound 2: 2% by weight dispersion of silver oxide-supported particles (substrate particles: silica-alumina composite, weight ratio of substrate particles to silver oxide = 20: 1)
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

The following tests were performed on each dispersion obtained by the above method. The test results are shown in Table 1.
(1) Stability After the dispersion was produced, it was immediately enclosed in a plastic container and stored in a 50 ° C. incubator for 7 days. After storage, the appearance of the dispersion was visually observed. In the evaluation, “◯” indicates that no abnormality such as separation was observed, and “X” indicates that abnormality was observed.

(Manufacture of curable composition)
The dispersion, the isocyanate compound, the cement and the fine aggregate were uniformly mixed to obtain a curable composition. The mixing ratio was 265 parts by weight of an isocyanate compound, 370 parts by weight of cement, and 860 parts by weight of fine aggregate with respect to 100 parts by weight of resin solids in the dispersion. As raw materials other than the dispersion, the following were used.
・ Isocyanate compounds: Polymeric MDI
・ Cement: White Portland cement ・ Fine aggregate: White quartz sand (particle size 0.2-0.8mm)

  The following tests were conducted for each curable composition obtained by the above method.

(2) Coloring uniformity Each cured composition was coated on a slate plate so that the thickness after curing was 4 mm, and after curing for 72 hours, 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 (temperature 23 ° C., relative humidity 50%).

(3) Finishing property Each cured composition was coated on a slate plate so that the thickness after curing was 4 mm, and after curing for 72 hours, the finishing property of the coating was visually confirmed. Evaluation is made in three stages (excellent: A>B> C: “A” when a smooth and uniform film is formed and “C” when the smoothness is impaired and / or when a hole is formed. Inferior). In addition, both coating and curing were performed in a standard state.

(4) Strength Each cured composition was coated on a slate plate so that the thickness after curing was 4 mm and cured for 72 hours. In addition, both coating and curing were performed in a standard state.
A jig was attached to the surface of the obtained coating with an adhesive, and the adhesion strength under standard conditions was measured using a tensile tester. Evaluation bond strength of 3N / mm ² or more of "A", those of less than 2.5 N / mm ² or more 3N / mm ² "B", "C" of less than 2.5 N / mm ² In three stages (excellent: A>B> C: inferior).

(5) Chemical resistance Each cured composition was coated on a slate plate so that the thickness after curing was 4 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. For chemical resistance 2, a 10% by weight aqueous solution of sodium hypochlorite was used. For chemical resistance 3, ethyl acetate was used.

The test results are shown in Table 2.
In Examples 1 to 9, good results could be obtained in any test.

Claims (4)

Polyol compounds (a), supported silver oxide particles (b), water (c), and a dispersion containing a pigment (d) (L), isocyanate compound (M), as well as viewing containing cement (N),
As the polyol compound (a),
A curable composition comprising an acrylic polyol (a1) having a hydroxyl group and an acid group. The acrylic polyol (a1) is
The curable composition according to claim 1, which is an acrylic polyol having a hydroxyl value of 1 to 200 mgKOH / g and an acid value of 0.1 to 20 mgKOH / g.   The weight average molecular weight of the acrylic polyol (a1) is
  It is 1000-100,000, The curable composition of Claim 1 or Claim 2 characterized by the above-mentioned.   As the polyol compound (a),
  Contains the acrylic polyol (a1) and vegetable oil-based polyol (a2)
The curable composition according to any one of claims 1 to 3.