JP6227368B2 - Curable composition - Google Patents

Description

  The present invention relates to a novel curable 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 compositions described in the above-mentioned patent documents are usually divided into at least three types: a first composition containing an active hydrogen-containing compound such as a polyol and water, a second composition containing an isocyanate compound, and a third composition containing cement. These three types are mixed and used when stored on the floor surface. However, since the composition of the above-mentioned patent document is cured by a plurality of reactions, it is difficult to control the curability and is easily influenced by environmental conditions and the like, and there is a possibility that the physical properties of the film such as finish may be affected.

  This invention is made | formed in view of the above problems, and it aims at improving the finishing property of the formation film in the curable composition containing the said 3 types of composition.

  In order to solve such a problem, as a result of intensive studies, the present inventors have determined that a first composition containing a polyol compound or the like, a second composition containing an isocyanate compound, and a third composition containing a cement are included. In the composition, the inventors came up with the idea of introducing a specific substance into the second composition and completed the present invention.

That is, the present invention has the following characteristics.
1. A curable composition comprising a first composition (L) containing a polyol compound, a surfactant, and water, a second composition (M) containing an isocyanate compound, and a third composition (N) containing a cement. And
The second composition (M), in addition to the isocyanate compound, seen containing a liquid material which is inert and low specific gravity to further isocyanate compound,
The liquid substance is one or more hydrocarbon compounds selected from nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, and liquid paraffin, and the weight ratio of the isocyanate compound to the liquid substance is 100: The curable composition characterized by being 0.1-100: 10 .

  According to the present invention, it is possible to improve the finish in the formed film of the curable composition.

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

  The curable composition of this invention contains a 1st composition (L), a 2nd composition (M), and a 3rd composition (N). Among these, the 1st composition (L) contains a polyol compound (a), surfactant (b), and water (c).

  The polyol compound (a) (hereinafter also referred to as “component (a)”) in the first composition (L) acts as a binder. As the component (a), various polyol compounds capable of reacting with an isocyanate compound can be used. Specific examples include acrylic polyols, polyester polyols, polyether polyols, polydiene polyols, vegetable oil-based polyols, and cellulose compounds, and these can be used alone or in combination of two or more. Such component (a) is usually a liquid compound at room temperature.

  In the present invention, the polyol compound (a) is preferably an embodiment containing a vegetable oil-based polyol (a1). Examples of the vegetable oil-based polyol (a1) (hereinafter also referred to as “component (a1)”) 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.

  The hydroxyl value of the component (a1) is preferably 50 to 500 mgKOH / g, more preferably 100 to 400 mgKOH / g, still more preferably 130 to 350 mgKOH / g. If the hydroxyl value of (a1) component is in such a range, it is suitable at points, such as sclerosis | hardenability and finish.

  Moreover, the number of functional groups of the hydroxyl group in one molecule of the component (a1) is preferably 2.0 to 5.0, more preferably 2.5 to 4.0. If the number of functional groups of the component (a1) is within such a range, it is preferable in terms of finish.

  The first composition (L) in the present invention contains a surfactant (b) (hereinafter also referred to as “component (b)”). In the present invention, by including such a component (b), the dispersion stability in the first composition (L) is increased, and also in terms of improving film properties such as finish, heat resistance, chemical resistance, and strength. Is preferred.

  Examples of the component (b) include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. Among these, in the present invention, an embodiment including a nonionic surfactant (b1) (hereinafter also referred to as “component (b1)”) is preferable. By such an aspect, in the present invention, it is possible to improve performance such as finish and curability.

  The type of the nonionic surfactant (b1) is not particularly limited. For example, polyoxyethylene alkylaryl ethers such as polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether; polyoxyethylene lauryl ether, polyoxyethylene lauryl ether Polyoxyethylene alkyl ethers such as oxyethylene cetyl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; other examples include polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, ethylene oxide-propylene oxide copolymer, etc. It is done. These can be used alone or in combination of two or more.

  The ratio of the component (b) 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 in terms of solid content. 3 parts by weight. With such a ratio, sufficient effects can be obtained in stability, finish, curability and the like.

  Water (c) in the first composition (L) (hereinafter also referred to as “component (c)”) is obtained by combining the first composition (L), the second composition (M), and the third composition (N). It contributes to the curing reaction when 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 1st composition (L) in this invention can contain the pigment (d) (henceforth "(d) component"). By including the component (d), the curable composition can be prepared in a desired color.

  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).

  In the present invention, it is possible to express various color tones by appropriately selecting and mixing one or more of such component (d). The ratio of the component (d) 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.

  The first composition (L) can be produced by uniformly mixing the above components (a) to (c) and, if necessary, the component (d) and the like by a conventional method. At this time, the first composition (L) includes, for example, an antifoaming agent, a reaction adjusting agent, a water reducing agent, fibers, an antiseptic, an algaeproofing agent, an antifungal agent, a dispersant, a solvent, a plasticizer, and a viscosity adjuster. It is also possible to mix additives such as an agent and a pH adjuster.

  The second composition in the present invention comprises an isocyanate compound (p) (hereinafter also referred to as “(p) component”), and a liquid substance (q) (hereinafter referred to as “( q) component ”.

  Among these, as the component (p), 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.

  (P) The specific gravity of a component becomes like this. Preferably it is 0.95 or more, More preferably, it is 1.00-1.50. The specific gravity is a measured value at 25 ° C.

  The component (p) 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).

  In this invention, in addition to the said (p) component, the 2nd composition contains the liquid substance (q) which is inactive and low specific gravity with respect to the said (p) component, In the formation film of a curable composition The finish can be improved. In particular, stable performance can be obtained in terms of uniformity of appearance on the surface of the coating. The reason why such an effect is achieved is not clear, but in the composition of the present invention, even if environmental conditions such as temperature and humidity change during the production or film formation, the isocyanate compound in the second composition It is presumed that the degree of activity is kept constant and that the curing reaction in the film forming stage after mixing the first to third compositions is stabilized.

  Such a (q) component needs to be inactive with respect to the (p) component. Here, “inactive with respect to component (p)” means having no reactivity with respect to component (p). That is, as the component (q), a substance having no active hydrogen is suitable, and specifically, a substance having no active hydrogen-containing group such as a hydroxyl group or an amino group is preferred.

  Furthermore, in the present invention, the component (q) needs to have a lower specific gravity than the component (p). That is, as the component (q), a component whose specific gravity is smaller than that of the component (p) is used. The specific gravity of the component (q) may be relatively smaller than the specific gravity of the component (p) used in combination with the component (q), but is preferably less than 1.00, more preferably 0.60 to 0.99. More preferably, it is 0.65-0.94. The specific gravity is a measured value at 25 ° C.

  As the component (q) in the present invention, a liquid material satisfying the above conditions can be used. Such a liquid substance should just be liquid at normal temperature (5-35 degreeC). Moreover, it is preferable that the boiling point of (q) component is 100 degreeC or more, More preferably, it is 150 degreeC or more, More preferably, it is 200 degreeC or more.

  Examples of the component (q) include hydrocarbon compounds, and specifically, nonane (specific gravity 0.72, boiling point 150 ° C.), decane (specific gravity 0.73, boiling point 174 ° C.), undecane (specific gravity 0. 74, boiling point 196 ° C.), dodecane (specific gravity 0.75, boiling point 216 ° C.), tridecane (specific gravity 0.76, boiling point 234 ° C.), tetradecane (specific gravity 0.76, boiling point 253 ° C.), pentadecane (specific gravity 0.77, Boiling point 268 ° C.), liquid paraffin (specific gravity 0.88, boiling point 300 ° C. or higher), and the like. These can be used alone or in combination of two or more.

  Such (q) component can take the state which floated on the upper part of (p) component in the 2nd composition. Such a state is preferable in terms of manifesting the effects of the present invention.

  The weight ratio {(p) :( q)} of the component (p) and the component (q) is preferably 100: 0.05 to 100: 20, more preferably 100: 0.1 to 100: 10. If it is such a weight ratio, the effect of the present invention can be exhibited stably.

  The third composition (N) in the present invention contains cement. Examples of cement include ordinary Portland cement, early-strength Portland cement, ultra-early strong Portland cement, moderately hot Portland cement, sulfate-resistant Portland cement, white Portland cement, etc., as well as alumina cement, ultrafast cement, expanded Cement, acid phosphate cement, silica cement, blast furnace cement, fly ash cement, keens cement and the like can be mentioned. These may be used alone or in combination of two or more. Among these, Portland cement is preferable. The cement 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. Examples of the carbon dioxide absorbent include calcium oxide, magnesium oxide, barium oxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide, magnesium hydroxide, calcium silicate, barium silicate, silica Sodium acid etc. are mentioned, These can be used by 1 type (s) or 2 or more types.

  When the curable composition of the present invention is distributed, the first composition (L), the second composition (M), and the third composition (N) are stored in separate packages. Can be mixed. Fine aggregate, coarse aggregate, carbon dioxide absorbent and the like may be mixed in the package of the third composition (N).

  The curable composition of this invention can form a film by mixing the said 1st-3rd composition at the time of use, and apply | coating the mixture to a base material. The composition of the present invention can exhibit excellent physical properties in terms of finish, heat resistance, chemical resistance, strength, and the like, and therefore is particularly preferable as a material to be applied to floor surfaces such as concrete.

  At the time of application, various methods such as ironing, pouring, and spraying can be employed. Moreover, aggregate etc. can also be spread | dispersed on the coating surface before drying. The thickness after curing is preferably about 0.5 to 12 mm, more preferably about 1 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 usually be performed at room temperature.

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

(Production of the first composition)
According to the formulation shown in Table 1, each component was uniformly mixed to produce a first composition. In the first composition, the following raw materials were used.

Resin 1: castor oil-based polyol (hydroxyl value 160 KOHmg / g, functional group number 2.7, solid content 100% by weight)
Resin 2: Castor oil-based polyol (hydroxyl value 320 KOHmg / g, functional group number 3, solid content 100% by weight)
Surfactant 1: Nonionic surfactant (polyoxyethylene alkyl ether, HLB 9.7, solid content 100% by weight)
Surfactant 2: Nonionic surfactant (polyoxyethylene alkyl ether, HLB 13.4, solid content 100% by weight)
Pigment 1: yellow iron oxide Pigment 2: phthalocyanine blue Plasticizer: bis (2-ethylhexyl) phthalate
Liquid material 1: Liquid paraffin (specific gravity 0.88, boiling point 300 ° C or higher)
・ Additive: Antifoaming agent

(Production of second composition)
According to the formulation shown in Table 2, each component was uniformly mixed to produce a second composition. In the second composition, the following raw materials were used.

Isocyanate compound: Polymeric MDI (specific gravity 1.23)
Liquid material 1: Liquid paraffin (specific gravity 0.88, boiling point 300 ° C or higher)
Liquid material 2: trimethyl orthoacetate (specific gravity 0.94, boiling point 108 ° C.)

(1) Finishability 1
According to the combinations shown in Table 3, the first composition, the second composition, and the third composition (a mixture of Portland cement and silica sand (weight ratio 1: 2), indicated as “3-1” in the table). The mixture was uniformly mixed at a weight ratio of 15:15:70 to obtain a curable composition.

  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 glossiness (60 °) of the coating was measured. The results are shown in Table 3. In the table, “A” indicates glossiness of less than 3, “B” indicates glossiness of 3 or more and less than 6, “C” indicates glossiness of 6 or more and less than 10, and “D” indicates glossiness of 10 or more. In addition, both coating and curing were performed in a standard state.

(2) Finishability 2
Each composition was stored for 3 days in an environment with an air temperature of 23 ° C. and a relative humidity of 90%, and then uniformly mixed according to the formulation shown in Table 3 to obtain a curable composition.

  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 glossiness (60 °) of the coating was measured. The results are shown in Table 3. The symbols in the table are as described above. In addition, both coating and curing were performed in a standard state.

  In Examples 1 to 6, there were no changes in the finishing properties 1 and 2, and good results were obtained.

Claims (1)

A curable composition comprising a first composition (L) containing a polyol compound, a surfactant, and water, a second composition (M) containing an isocyanate compound, and a third composition (N) containing a cement. And
The second composition (M), in addition to the isocyanate compound, seen containing a liquid material which is inert and low specific gravity to further isocyanate compound,
The liquid substance is one or more hydrocarbon compounds selected from nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, and liquid paraffin, and the weight ratio of the isocyanate compound to the liquid substance is 100: The curable composition characterized by being 0.1-100: 10 .