JP5548558B2 - 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 an isocyanate compound, and a third component containing cement. 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, when a pigment is added and colored, unevenness or the like tends to occur partially in the formed film, and it may be difficult to obtain a uniform finished appearance.

  The present invention has been made in view of the problems as described above, and can form a colored film having a uniform finish appearance, and further exhibits excellent performance in film physical properties such as heat resistance, chemical resistance, and strength. It aims at obtaining the curable composition which can be used.

  In order to solve such problems, the present inventors have intensively studied, and have come up with a curable composition containing a polyol compound, a pigment, a fluorine-modified silicone, a dispersion containing water, an isocyanate compound, and cement. The present invention has been completed.

（Ｒ^１及びＲ^３が−ＣＨ_３、Ｒ^２が−Ｃ_２Ｈ_４−ＣＦ_３ 、ｍ、ｎは整数であって、ｍ＝０〜５００、ｎ＝１〜５００）
２．前記ポリオール化合物（ａ）として、水酸基及びアミノ基を有するポリオール化合物（ａ１）を含むことを特徴とする１．記載の硬化性組成物。
３．前記分散液（Ｌ）において、さらに界面活性剤（ｅ）を含むことを特徴とする１．または２．記載の硬化性組成物。

That is, the present invention has the following characteristics.
1. A dispersion (L) containing a polyol compound (a), a pigment (b), a fluorine-modified silicone (c) and water (d), an isocyanate compound (M), and a cement (N),
The curable composition, wherein the fluorine-modified silicone (c) is represented by the following formula (1).
[Chemical formula 1]

(R ¹ and R ³ are —CH ₃ , R ² is —C ₂ H ₄ —CF ₃ , m and n are integers, and m = 0 to 500, n = 1 to 500 )
2. The polyol compound (a) includes a polyol compound (a1) having a hydroxyl group and an amino group. The curable composition as described.
3. The dispersion (L) further contains a surfactant (e). Or 2. The curable composition as described.

  In the curable composition of this invention, the colored film which has a uniform finishing external appearance can be formed. Furthermore, excellent performance can be exhibited in film physical properties such as heat resistance, chemical resistance and strength.

  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 pigment (b), the fluorine-modified silicone (c), and water (d).

  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, the component (a) preferably contains a polyol compound (a1) having a hydroxyl group and an amino group (hereinafter also referred to as “component (a1)”). Such (a1) component contributes to the performance improvement in sclerosis | hardenability, finish, etc.

  As the component (a1), an amino group-containing polyether polyol obtained by addition polymerization of a cyclic ether using an amine compound as an initiator is particularly suitable. The hydroxyl value of the amino group-containing polyether polyol is preferably 250 to 900 mgKOH / g, more preferably 300 to 800 mgKOH / g. The pH of the amino group-containing polyether polyol is preferably 8 or higher, more preferably 9 or higher, and still more preferably 10-13. This pH is a value measured by a method defined in JIS K1557.

  Examples of the amine compound used as the initiator in the amino group-containing polyether polyol include an aliphatic amine compound, a saturated cyclic amine compound, and an aromatic amine compound. Among these, examples of the aliphatic amine compound include ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine. Examples of the saturated cyclic amine compound include N-aminomethylpiperazine, N- (2-aminoethyl) piperazine and the like. Examples of the aromatic amine compound include 2,4-toluenediamine, 2,6-toluenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, naphthalenediamine, and the like. It is done.

  Examples of the cyclic ether that is addition-polymerized to the amine compound include ethylene oxide, propylene oxide, isobutylene oxide, 1,2-epoxybutane, 2,3-epoxybutane, and the like. Among these, at least one selected from ethylene oxide and propylene oxide is preferable.

  Such component (a1) is 0.1 to 20% by weight (more preferably 0.2 to 10% by weight, still more preferably 0.3 to 3% by weight) in the polyol compound (a) in terms of solid content. It is desirable to be included.

  As the polyol compound (a), it is desirable to include a polyol compound other than the component (a1) together with the component (a1). As the polyol compound other than the component (a1), the above-described various polyol compounds can be used. In the present invention, however, the vegetable oil-based polyol (a2) is particularly suitable.

  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, castor oil and / or a polyol synthesized using castor oil as a starting material can be used. Among these, polyols synthesized using castor oil as a starting material include, for example, an alkylene oxide adduct of castor oil, an epoxidized product of castor oil, a halide of castor oil, a transesterified product of castor oil and polyhydric alcohol, and a hydride thereof. Etc.

  When the polyol compound (a) includes the component (a1) and the component (a2), the polyol compound (a) is 0.1 to 20% by weight (more preferably) in the polyol compound (a) in terms of solid content. 0.2 to 10% by weight, more preferably 0.3 to 3% by weight), and the component (a2) is 80 to 99.9% by weight (more preferably 90 to 99.8% by weight, The content is preferably 97 to 99.7% by weight). Such a ratio is preferable in terms of curability and finish.

  The dispersion (L) in the present invention contains the pigment (b) (hereinafter referred to as “component (b)”). In this invention, it becomes possible to prepare a curable composition in a desired color by including this (b) component. Further, in the present invention, even when the dispersion (L) contains the component (b), a colored film that hardly causes partial unevenness of the film and has a uniform finished appearance can be obtained.

  As the component (b), 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 diameter of the component (b) is preferably less than 50 μm (more preferably 0.1 to 30 μm).

In the present invention, it is possible to express various color tones by appropriately selecting and mixing one or more of the component (b).
The ratio of the component (b) is preferably 0.5 to 30 parts by weight and more preferably 1 to 20 parts by weight with respect to 100 parts by weight of the component (a) in terms of solid content.

  Fluorine-modified silicone (c) (hereinafter referred to as “component (c)”) is a component that acts on the formation of a colored film exhibiting a homogeneous finish appearance. In the present invention, by including the component (c) as an essential component, it is possible to suppress unevenness in both the color tone and the glossiness, and to form a uniform finished film. Although its mechanism of action is not clear, in the formation stage of the film formed by mixing and applying the dispersion liquid (L), the isocyanate compound (M), and the cement (N), the component (c) is applied to the surface of the film. It is presumed that proper orientation contributes.

The component (c) is a silicone compound containing a fluorine atom, and a fluorine atom is contained in a part of the compound having a polysiloxane unit as a main chain. Examples of such component (c) include a compound having a polysiloxane unit as a main chain and a perfluoroalkyl group bonded thereto. Such compounds are described, for example, in Japanese Patent Publication No. 41-9434, Japanese Patent Laid-Open No. 50-46800, Japanese Patent Laid-Open No. 2-97529, Japanese Patent Laid-Open No. 7-53719, and the like.
Specifically, examples of the component (c) include fluorine-modified silicone represented by the general formula (1). In the formula, R ¹ is the same or different alkyl group or aryl group having 1 to 20 carbon atoms, R ² is —R ⁴ —Rf (wherein R ⁴ is a divalent alkylene group having 2 to 6 carbon atoms). Rf represents a C 1-12 perfluoroalkyl group.), R ³ is either R ¹ or R ² , m and n are integers, and m = 0 to 500, n = 1 to 500. Moreover, the arrangement of each structural unit represented by the general formula (1) may be any of alternating, block, and random.

  The ratio of the component (c) is preferably 0.01 to 2 parts by weight, more preferably 0.05 to 1 part by weight with respect to 100 parts by weight of the solid content of the component (a). When the ratio of the component (c) is within such a range, it is possible to form a coating film having a sufficiently uniform finish.

Water (d) (hereinafter referred to as “component (d)”) in the dispersion (L) contributes to the curing reaction when the dispersion (L), the isocyanate compound (M), and the cement (N) are mixed. It is.
The ratio of the component (d) 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) in the present invention can contain a surfactant (e). Examples of the surfactant (e) include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. Among these, in the present invention, an embodiment including a nonionic surfactant (e1) (hereinafter also referred to as “component (e1)”) is preferable. In the present invention, by using the component (e1) and the component (a1) in combination, excellent effects in terms of pot life, curability and the like can be obtained. Moreover, by including (e1) component, the dispersion stability in a dispersion liquid (L) increases, and separation with time etc. are suppressed. By using the dispersion liquid (L) thus stabilized, finish, heat resistance, chemical resistance, strength, and the like can be improved in the present invention.

  The type of nonionic surfactant (e1) is not particularly limited. For example, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene distearate, polyoxyethylene lauryl ether, polyoxy Examples include ethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene higher alcohol ether, polyoxyethylene phenyl ether, and the like.

  As the nonionic surfactant (e1), those having an HLB of 9 or more are suitable. The HLB of the component (e1) is more preferably 15 or more, and further preferably 18-20. By using the (e1) component having such an HLB, the above-described effects can be further enhanced. HLB is an abbreviation for hydrophilic-lipophilic balance, and is a numerical representation of the hydrophilic / lipophilic strength ratio of an amphiphilic substance.

  The ratio of the component (e1) is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and still more preferably 0.3 to 100 parts by weight of the component (a) in terms of solid content. 3 parts by weight. If it is such a ratio, sufficient effects can be obtained in stability, pot life, curability and the like.

  The dispersion (L) in the present invention may contain a liquid organic compound (f) (hereinafter referred to as “component (f)”). The component (f) is an organic compound that is liquid at room temperature, and specifically, a solvent (f1) and / or a plasticizer (f2) can be used. In the present invention, since the dispersion (L) contains the component (f), the stability of the dispersion (L) is further improved, and the effects of the present invention can be stably obtained.

  As the solvent (f1), 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 (f1), one or more of these can be used.

As a plasticizer (f2), 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 (f2), one or more of these can be used.
In the present invention, those containing at least a plasticizer (f2) are particularly suitable as the component (f).

  The ratio of the component (f) is preferably about 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).

  In the dispersion liquid (L), the above components (a), (b), (c), (d), (e), (f) and the like are uniformly mixed by a conventional method. Can be manufactured. At this time, for example, additives such as an antifoaming agent, a reaction adjusting agent, a water reducing agent, fibers, an antiseptic, an algaeproofing agent, and an antifungal agent can be mixed in the dispersion liquid (L).

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 further mixing a 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 addition, a carbon dioxide absorbent or the like can be mixed.

  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, coarse aggregates, carbon dioxide absorbents, and the like 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. Since the composition of the present invention can exhibit excellent physical properties in terms of finish, heat resistance, chemical resistance, strength, etc., it 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 curable composition)
According to the formulation shown in Tables 1 to 3, after each component is uniformly mixed to produce a dispersion, the dispersion, isocyanate compound, cement and fine aggregate are uniformly mixed to obtain a curable composition. Manufactured. The following were used as raw materials.

Resin 1: Amino group-containing polyether polyol (hydroxyl value 450 KOHmg / g, pH 11.0, solid content 100% by weight)
Resin 2: Amino group-containing polyether polyol (hydroxyl value 500 KOHmg / g, pH 11.0, solid content 100% by weight)
Resin 3: Amino group-containing polyether polyol (hydroxyl value 760 KOHmg / g, pH 12.0, solid content 100% by weight)
Resin 4: Polyether polyol (hydroxyl value 385 KOH mg / g, pH 7.0, solid content 100% by weight)
Resin 5: castor oil-based polyol (hydroxyl value 160 KOHmg / g, solid content 100% by weight)
Pigment 1: Yellow iron oxide Pigment 2: Phthalocyanine blue Pigment 3: Titanium oxide Pigment 4: Carbon black Fluorine compound: Fluorine-modified silicone solution (R ¹ and R ³ in the above general formula (1) are —CH ₃ , a compound in which R ² is —C ₂ H ₄ —CF ₃ , a solid content of 2% by weight)
Surfactant 1: Nonionic surfactant (polyoxyethylene alkyl ether, HLB 9.7, solid content 100% by weight)
Surfactant 2: Nonionic surfactant (polyoxyethylene sorbitan trioleate, HLB 11.0, solid content 100% by weight)
Surfactant 3: Nonionic surfactant (polyoxyethylene alkyl ether, HLB 13.4, solid content 100% by weight)
Surfactant 4: Nonionic surfactant (polyoxyethylene alkyl ether, HLB 18.5, solid content 60% by weight)
Surfactant 5: Anionic surfactant (polyoxyethylene alkyl ether sodium acetate, solid content 24% by weight)
Surfactant 6: cationic surfactant (lauryltrimethylammonium chloride, solid content 27% by weight)
・ Liquid organic compound 1: Plasticizer (Bis (2-ethylhexyl) phthalate)
Liquid organic compound 2: Plasticizer (alkyl sulfonic acid phenyl ester)
Additive: Antifoaming agent (non-silicone defoaming agent, solid content 25% by weight)
・ 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.

(1) 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. The evaluation was made in three stages (excellent: A>B> C: inferior), with “A” indicating that a uniform film without uneven color and gloss was formed, and “C” indicating that uneven color or uneven gloss occurred. ) The coating and curing were both performed at a temperature of 23 ° C. and a relative humidity of 50% (hereinafter referred to as “standard state”).

(2) Pot life Time Each curable composition was produced and allowed to stand for 60 minutes, and then coated on a slate plate with a thickness of 4 mm. The pot life was evaluated based on the film-forming properties at this time. The evaluation was performed in three stages (excellent: A>B> C: inferior), where “A” indicates that there was no hindrance to the film-forming property and “C” indicates that the problem occurred. In addition, manufacture, leaving, and coating of the curable composition were all performed in a standard state.

(3) Curability Each cured composition was coated on a slate plate so that the thickness after curing was 4 mm, and after curing for 24 hours, the degree of tackiness of the coating was confirmed by finger touch. The evaluation was performed in three stages (excellent: A>B> C: inferior), where “A” indicates that no tackiness was observed and “C” indicates that tackiness was observed. 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 citric acid was used. For chemical resistance 3, ethyl acetate was used.

Test results are shown in Tables 4-6.
Examples 1 to 21 were better in finish than Comparative Examples 1 to 3. About Example, when tests other than finishing were conducted, in Examples 2 to 16, generally good results could be obtained.

Claims (3)

A dispersion (L) containing a polyol compound (a), a pigment (b), a fluorine-modified silicone (c) and water (d), an isocyanate compound (M), and a cement (N),
The curable composition, wherein the fluorine-modified silicone (c) is represented by the following formula (1).
[Chemical formula 1]

(R ¹ and R ³ are —CH ₃ , R ² is —C ₂ H ₄ —CF ₃ , m and n are integers, and m = 0 to 500, n = 1 to 500 )   The curable composition according to claim 1, wherein the polyol compound (a) includes a polyol compound (a1) having a hydroxyl group and an amino group. The curable composition according to claim 1, wherein the dispersion (L) further contains a surfactant (e).