JP4952984B2 - Urethane flooring - Google Patents

Description

  The present invention relates to a urethane flooring composed of a urethane composition using a multi-branched polyether polyol as a polyol.

  Urethane hard flooring is a flooring material that has excellent extensibility and curability in winter, and does not have the disadvantages of brittleness of epoxy materials that are commonly used and harmfulness of amines. Attention has been paid.

  Therefore, conventionally, a mixture of a polyol having a structure in which a higher fatty acid is reacted with a bisphenol-type epoxy resin and castor oil fatty acid is used as the polyol, and diphenyl metadiisocyanate (abbreviated as MDI) and polymethylene polyphenyl polyisocyanate. (Hereinafter abbreviated as “polymeric MDI”) at a predetermined ratio, a composition using polyisocyanate as a polyisocyanate has a urethane-based flexibility, and is a hard and highly durable urethane flooring. It is known (see, for example, Patent Document 1).

However, although the urethane-based flooring is excellent in terms of durability and toughness, the abrasion resistance strongly required in parking lots and warehouses has not yet reached a level that satisfies the market. When the abrasion resistance is low, there is a drawback that the surface of the coating film is worn away due to traveling of the vehicle or the like and the floor repair period is shortened.
JP 2001-187863 A

  The subject of this invention is providing the urethane type flooring excellent in abrasion resistance in addition to the flexible and hard coating film.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a urethane composition using a specific multi-branched polyether polyol as a polyol as a flooring material. At the same time, the cohesive energy was increased due to the polyfunctionality, and it was found that a coating film excellent in abrasion resistance could be obtained, and the present invention was completed.

That is, the present invention is a multi-branched polyether polyol obtained by ring-opening reaction of a hydroxyalkyl oxetane (a1) and a monofunctional epoxy compound (a2), wherein the hydroxyalkyl oxetane (a1) is 3-hydroxy 1 or more types selected from the group consisting of methyl-3-ethyloxetane and 3-hydroxymethyl-3-methyloxetane, and the monofunctional epoxy compound (a2) is propylene oxide, 1-butene oxide, 1-pentene Oxide or 1-hexene oxide, which has a primary hydroxyl group (H1) and a secondary hydroxyl group (H2) in the molecular structure, and a number average molecular weight (Mn) of 1,000 to 2,500 And a multi-branched polyether polyol having a hydroxyl value of 200 to 300 mg · KOH / g There is provided a urethane-based flooring comprising a urethane composition containing the polyol (A) and the polyisocyanate (B) to. Further, the present invention is a floor structure composed of at least three layers of a base material layer, a first coating layer (lower layer) and a second coating layer (upper layer), wherein the second coating layer (upper layer) is claimed. The present invention provides a floor structure comprising the urethane floor material of any one of 1 to 5.

  The urethane flooring of the present invention is flexible, hard and excellent in wear resistance.

Hereinafter, the present invention will be described in more detail with reference to more preferable examples.
The multi-branched polyether polyol used as a main component of the polyol (A) used in the present invention is obtained by ring-opening reaction of a hydroxyalkyl oxetane (a1) and a monofunctional epoxy compound (a2).
Such a multi-branched polyether polyol is presumed to have a high cohesive energy between molecules because the functional groups are oriented on the surface of the molecule and have a nearly spherical structure.
Further, the “multi-branch” of the multi-branched polyether polyol means a molecular structure that further branches at the branch destination.

  Here, as a hydroxyalkyl oxetane (a1) used for this invention, what has a structure represented by following General formula (1) is mentioned as an example, for example.

ここで、一般式（１）中、Ｒ_１は、メチレン基、エチレン基、若しくはプロピレン基であり、一方、Ｒ_２は、水素原子、炭素原子数１〜８のアルキル基、炭素原子数１〜５のアルコキシアルキル基、又は炭素原子数１〜６のヒドロキシアルキル基を表す。また、炭素原子数１〜８のアルキル基の例としては、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、及び２−エチルヘキシル基が挙げられ、炭素原子数１〜５のアルコキシアルキル基の例としては、メトキシメチル基、エトキシメチル基、プロポキシメチル基、メトキシエチル基、エトキシエチル基、プロポキシエチル基が挙げられる。また、炭素原子数１〜３のヒドロキシアルキル基の例としては、ヒドロキシメチル基、ヒドロキシエチル基、及びヒドロキシプロピル基が挙げられる。

Here, in the general formula (1), R ₁ is a methylene group, ethylene group, or propylene group, while R ₂ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or 1 to 1 carbon atoms. 5 represents an alkoxyalkyl group or a hydroxyalkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and a 2-ethylhexyl group, and an alkoxyalkyl having 1 to 5 carbon atoms. Examples of the group include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a methoxyethyl group, an ethoxyethyl group, and a propoxyethyl group. Examples of the hydroxyalkyl group having 1 to 3 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.

Among such general formula (1) hydroxyalkyl oxetane represented (a1), the inertia radius is effective in reducing the smaller it becomes in thus viscosity, also from the viewpoint of hardness higher of the cured product, R ₁ Is a methylene group and R ₂ is an alkyl group having 1 to 7 carbon atoms, and 3-hydroxymethyl-3-ethyloxetane and 3-hydroxymethyl-3-methyloxetane are particularly preferable.

  Next, examples of the monofunctional epoxy compound (a2) that undergoes a ring-opening polymerization reaction with the hydroxyalkyl oxetane (a1) include olefin epoxides, glycidyl ether compounds, and glycidyl ester compounds.

  Here, olefin epoxides that can be used are, as specific examples, propylene oxide, 1-butene oxide, 1-pentene oxide, 1-hexene oxide, 1,2-epoxyoctane, 1,2-epoxide decane, cyclohexene oxide, cyclohexane. Examples include octene oxide, cyclododecene oxide, styrene oxide, and fluoroalkyl epoxide having 1 to 18 fluorine atoms.

  Specific examples of glycidyl ether compounds include methyl glycidyl ether, ethyl glycidyl ether, n-propyl glycidyl ether, i-propyl glycidyl ether, n-butyl glycidyl ether, i-butyl glycidyl ether, n-pentyl glycidyl ether, 2-ethylhexyl. -Glycidyl ether, undecyl glycidyl ether, hexadecyl glycidyl ether, aryl glycidyl ether, phenyl glycidyl ether, 2-methylphenyl glycidyl ether, 4-t-butylphenyl glycidyl ether, 4-nonylphenyl glycidyl ether, 4-methoxyphenyl glycidyl ether Examples thereof include ethers and fluoroalkyl glycidyl ethers having 1 to 18 fluorine atoms.

  Specific examples of the glycidyl ester compound include glycidyl acetate, glycidyl propionate, glycidyl butyrate, glycidyl methacrylate, and glycidyl benzoate.

  Among these, olefin epoxide is preferable from the viewpoint that high coating film hardness is obtained and the molecular weight is small, and propylene oxide, 1-butene oxide, 1-pentene oxide, or 1-hexene oxide is particularly preferable.

Examples of the method for subjecting the hydroxyalkyl oxetane (a1) and the monofunctional epoxy compound (a2) to the ring-opening polymerization reaction using the raw material components include the following methods.
That is, the hydroxyalkyl oxetane (a1) and the monofunctional epoxy compound (a2) are converted into (hydroxyalkyloxetane (a1) / 1 functional epoxy compound (a2) = 1/1 to 1/10 on a molar basis. Preferably, they are mixed at a ratio of 1/1 to 1/3, and these are mixed with a peroxide-free organic solvent such as diethyl ether, di-i-propyl ether, di-n-butyl ether, di-i-butyl ether, di- -T-butyl ether, t-aminomethyl ether, or dioxolane, dissolved at a ratio of the raw material component / organic solvent mass ratio of 1/1 to 1/5, preferably 1 / 1.5-1 to 2.5. To do.

  Next, the obtained solution is cooled with stirring to −10 ° C. to −15 ° C., and then the polymerization initiator alone or in the solution state is 0.1 to 1 hour, preferably 0.3 to 0.5. Dripping over time. Here, the polymerization initiator can be used at a ratio of 0.01 to 1% by mass, preferably 0.75 to 0.3% by mass, based on the total mass of the raw material monomers. Moreover, when using a polymerization initiator in a solution state, it is preferable that the density | concentration of the polymerization initiator in the said solution is 1-90 mass%, especially 25-50 mass%. Next, the polymerization solution is stirred until it reaches 25 ° C., then heated to a refluxing temperature, and the reaction is performed until all the raw material components are reacted over 0.5 to 3 hours. The conversion rate of the raw material monomer can be controlled by confirming with GC, NMR, or IR spectrum.

  After polymerization, the obtained multi-branched polyether polyol is agitated with an aqueous alkali hydroxide solution equivalent to the polymerization initiator, or neutralized by adding sodium alkoxide or potassium alkoxide equivalent to the polymerization initiator. To do. After neutralization, the mixture is filtered, and the target product is extracted with a solvent. Then, the solvent is distilled off under reduced pressure, whereby the target multi-branched polyether polyol can be obtained.

  The multibranched polyether polyol obtained by the above method has a primary hydroxyl group (H1) and a secondary hydroxyl group (H2) in its molecular structure, and the number average molecular weight of the multibranched polyether polyol. (Mn) is 1,000 to 2,500 and the hydroxyl value is 200 to 300 mg · KOH / g. When these are satisfied, a composition having good fluidity and workability is obtained, and a cured product having high hardness and high wear resistance can be obtained. The number average molecular weight (Mn) and the hydroxyl value can be preferably used as long as they are within the above range, but in order to obtain the maximum effect, the number average molecular weight is 1,000 to 2,000 and the hydroxyl value is 220 to 280. Further preferred.

  Furthermore, the multi-branched polyether polyol of the present invention has not only a primary hydroxyl group (H1) but also a secondary hydroxyl group (H2) in the molecular structure. In terms of the balance between pot life and cured product hardness, the ratio in which the number of secondary hydroxyl groups (H2) in one molecule is 30 to 60%, more preferably 35 to 55%, based on the total number of hydroxyl groups. It is preferable that The total number of hydroxyl groups of the polyol of the present invention is preferably 4 or more, more preferably 4-20.

The ratio of the number of secondary hydroxyl groups (H2) to the total number of hydroxyl groups in the multi-branched polyether polyol can be specified by measuring the multi-branched polyether polyol with ¹⁹ F-NMR after trifluoroacetic acid esterification. it can.

The urethane composition used for the urethane flooring of the present invention is a two-component curable composition with a polyol (A) and a polyisocyanate (B). Further, the multi-branched polyether polyol is used in the polyol (A).
In the present invention, it is preferable that a hydroxyl group-containing higher fatty acid alkyl ester is further included as a constituent component of the polyol (A) from the viewpoint of enhancing the hydrophobicity of the mixture in a two-component mixed state and suppressing foaming during curing.

Examples of such hydroxyl group-containing higher fatty acid alkyl esters include, for example, a hydroxyl group-containing ester compound obtained by reacting a higher fatty acid such as stearic acid and linoleic acid with a polyhydric alcohol such as glycol and glycerin so that the hydroxyl group remains, ricinoleic acid Examples include ester compounds obtained by reacting a hydroxyl group-containing higher fatty acid such as monoalcohol, glycol, glycerin, trimethylolpropane and the like, and other examples include hydroxyl group-containing natural fats and oils such as castor oil. These may be used alone or in combination of two or more.
In addition, even natural oils and fats such as coconut oil and soybean oil that do not contain an effective amount of hydroxyl groups can be used as hydroxyl-containing higher fatty acid alkyl esters by transesterifying them with polyhydric alcohols to introduce hydroxyl groups. Can do.

Furthermore, among the hydroxyl group-containing higher fatty acid alkyl esters described above, those having a double bond in the alkyl chain may be preferably used which are modified with dicyclopentadiene to further improve the hydrophobicity.
Among these examples of the hydroxyl group-containing higher fatty acid alkyl ester, a hydroxyl value of 100 to 300 mg · KOH / g is preferable for improving the coating strength, and an alkyl chain is used for improving the hydrophobicity of the coating. The number of carbon atoms in the portion is preferably 10-25.

  In the polyol (A), the use ratio of the multi-branched polyether polyol and the hydroxyl group-containing higher fatty acid alkyl ester can be selected as necessary, but the mass ratio of the former to the latter (the former / the latter) is 3/7 to 7 / 3 is preferable in terms of the effect of suppressing foaming. From the viewpoint of increasing hardness, the average number of functional groups when the former and the latter are mixed is preferably 4 or more. The upper limit can be selected as necessary.

  As said polyol (A), polyols other than the said multi-branched polyether polyol can also be used. Examples of such polyols include known and commonly used ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4 butanediol, 1,3 butanediol, 3-methylpentanediol, 3,3-dimethylolheptane, trimethylolpropane and the like. Single-chain polyols, polyalkylene ether polyols obtained by polymerizing these single-chain polyols and alkylene oxides (for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc.) or phthalic acid, maleic acid, adipic acid, and head Polyester polyols obtained by esterification reaction of dibasic acids such as acid, succinic acid, hydrogenated dimer acid and the above-mentioned single chain glycols, and epsilon caprolactone to polyols Pressurized polymerization was polyols and polytetramethylene ether glycol, polybutadiene polyols, mention may be made of polyol type xylene formaldehyde resin and the like. The above compounds may be used alone or in combination of two or more.

Next, the polyisocyanate (B) in the urethane composition used in the present invention will be described.
Examples of the polyisocyanate (B) include known aliphatic polyisocyanates and aromatic polyisocyanates. These can be used alone or in combination of two or more.

  Examples of aliphatic polyisocyanates include alkylene diisocyanates such as hexamethylene diisocyanate (hereinafter abbreviated as “HDI”), alicyclic hydrocarbon structure-containing diisocyanates, burette-modified HDI, and isocyanurate-modified HDI. And an addition reaction compound of HDI and trimethylolpropane.

  Next, as examples of aromatic polyisocyanates, diphenylmethane diisocyanate (hereinafter abbreviated as “MDI”), polymethylene polyphenyl polyisocyanate (hereinafter abbreviated as “polymeric MDI”), tolylene diisocyanate (hereinafter abbreviated as “MDI”). , Abbreviated as “TDI”), xylylene diisocyanate (hereinafter abbreviated as “XDI”), or diisocyanates of diisocyanates such as uretidione-modified TDI. These may be used alone or in combination of two or more as required.

Among these, aromatic polyisocyanate is preferable from the viewpoint that the hardness of the cured product can be particularly high, and polymeric MDI is particularly preferable from the viewpoint of remarkable hardness improvement effect. The polymeric MDI mentioned here is an isocyanate-modified high molecular weight product obtained by polycondensation of aniline and formalin, and has an MDI and a higher number of nuclei (ring number) (for example, Millionate MR). -200 (made by Nippon Polyurethane Co., Ltd.) etc.).
Usually, as the number of nuclei increases, the hardness of the cured product increases but the viscosity tends to increase. On the other hand, as the number of nuclei decreases, the compatibility with the polyol (A) is good and the viscosity is low, but it is easily crystallized and inferior in stability at low temperatures. Therefore, in the present invention, the proportion of the MDI in the polymeric MDI, that is, the proportion of the bifunctional component is preferably 50 to 80% by mass, and the adjustment to the rate of 55 to 75% by mass is preferable. This is particularly preferable from the viewpoint of performance balance. In particular, it is most preferably 60 to 70% by mass from the viewpoint that the balance of physical properties is excellent and the so-called finish properties such as prevention of color spots on the coating surface are improved.

  In addition, as polyisocyanate (B), MDI that can be used alone or MDI that can be used for adjusting the number of nuclei in polymeric MDI is (i) 2,2′-diphenylmethane diisocyanate (hereinafter referred to as “2”). , 2′-MDI ”), (ii) 2,4′-diphenylmethane diisocyanate (hereinafter abbreviated as“ 2,4′-MDI ”) and (iii) 4,4′-diphenylmethane diisocyanate ( Hereinafter, it is abbreviated as “4,4′-MDI”). These may be used alone or in combination of two or more. Here, when the total mass ((i) + (ii)) of (i) 2,2′-MDI and (ii) 2,4′-MDI in MDI is reduced, polyisocyanate (B) is crystallized at low temperature. On the contrary, if the total mass ((i) + (ii)) increases, the hardness of the cured product tends to be difficult to improve. Therefore, the mass ratio of (i) to (iii) is ((i) + (ii)) :( iii) = 5: 95-40: 60, especially ((i) + (ii)) :( iii ) = 10: 90 to 30:70 is preferable from the viewpoint of the low temperature stability of the polyisocyanate (B) and the hardness of the cured product.

  In the present invention, when the polyisocyanate (B) is an alicyclic hydrocarbon structure-containing diisocyanate alone or in combination with other isocyanates, the resulting cured film is hard, Expresses sufficient flexibility and exhibits sufficient followability to cracks. In addition, yellowing due to ultraviolet degradation that tends to occur when aromatic polyisocyanate is used can be reduced, and a coated surface with excellent design can be formed.

Examples of such alicyclic hydrocarbon structure-containing diisocyanates include isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, cyclohexane diisocyanate, norbornene diisocyanate, and dimethanonaphthalene diisocyanate, and these and a polyol. And polyisocyanates obtained. Among these, norbornene diisocyanate and dimethanonaphthalene diisocyanate are preferable because the balance between hardness and flexibility of the cured film is remarkably improved. These may be used alone or in combination of two or more.
Examples of polyols that can be used here include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tetramethylene glycol, 1,3-butanediol, 3-methylpentanediol, 3,3-dimethylolheptane, trimethylol. Examples include alkylene diols such as propane, or polyalkylene ether polyols obtained by polymerizing alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and styrene oxide on these alkylene diols. Further, polyester polyols obtained by esterification reaction with dibasic acids such as phthalic acid, maleic acid, adipic acid, het acid, succinic acid, and hydrogenated dimer acid are added to the alkylene diol, and epsilon caprolactone is added to the alkylene diol. Examples include polyols copolymerized.

  The urethane-based flooring of the present invention exhibits a specific effect by using the above-described alicyclic hydrocarbon structure-containing diisocyanate. For example, it is possible to obtain a coating with a hard coating hardness of Shore D75 or higher and a high elongation of 60% or higher, and sufficiently follow the cracks in the base material. High performance coating performance can be obtained. Moreover, since it has high weather resistance and has excellent yellowing prevention properties, it is possible to provide a floor surface that can maintain design properties for a long period of time.

  In addition, when the alicyclic hydrocarbon structure-containing diisocyanate is used as the polyisocyanate (B), the above-described hydroxyl group-containing higher fatty acid alkyl ester can be used as the polyol to increase the flexibility while maintaining the hardness. it can.

  The urethane composition used for the urethane-based flooring of the present invention improves the surface properties under high temperature and high humidity by adding activated alumina powder (C) in addition to the polyol (A) and the polyisocyanate (B). I can do it.

Such activated alumina powder (C) is represented by Al ₂ O ₃ and many crystal systems such as α, β, γ, δ, κ, θ, χ, η, and ρ are known. Ρ, χ, γ, and η alumina, which have high gas adsorbing ability, are preferred, and ρ alumina is particularly preferred. Those mainly composed of ρ-alumina are generally called hydraulic alumina and are most preferred. However, while the water adsorption capacity is high, the adsorption capacity is reduced by moisture absorption during storage, and as described in the section of the prior art, when a polyol is used as a main component of a resin skeleton having high hygroscopicity such as polyether. There is a tendency that a smooth coating film cannot be obtained.
The activated alumina powder (C) preferably has an average particle size of 150 μm or less, more preferably 50 μm or less. By using in this range, the compound obtained by kneading with the polyol (A) is less likely to cause sedimentation problems during storage.
The content of the activated alumina powder (C) is preferably 5 to 30% by weight, particularly preferably 10 to 25% by weight, based on the floor material. If it is used in the range of 5 to 30% by weight, good coating workability is ensured, a uniform coating film can be obtained without impairing the cured properties, and further effective in suppressing foaming of the coating film.

The urethane composition used in the present invention is further added to the polyol (A), the isocyanate (B), and the activated alumina powder (C) by further adding a filler and various other additives as required. Can be adjusted.
The urethane flooring of the present invention can be used for various coating methods and applications as long as there is no particular problem. For example, examples of the coating method include brush coating, roller coating, and spray coating. Of course, rake coating and other methods may be used. Moreover, as an example of a use application, a waterproof material, a pavement material, a coating etc. are mentioned besides a flooring.

  Examples of the filler include calcium carbonate, surface-treated calcium carbonate, aluminum hydroxide, precipitated barium sulfate, clay, silica, and talc.

Examples of other additives include synthetic zeolite, silica gel, diatomaceous earth, slaked lime, quicklime, magnesium hydroxide, anhydrous gypsum, calcium chloride, synthetic hydrotalcite, activated carbon, hygroscopic agents such as activated clay, azo, copper Organic or inorganic color pigments such as phthalocyanine, petal, yellow lead, titanium oxide, zinc white or carbon black, red lead, lead white, basic chromate, basic lead sulfate, zinc chromate, zinc Examples include rust preventive pigments such as powders and MIO, and various auxiliary agents such as thixotropic agents, leveling agents, hygroscopic agents, silane or titanate coupling agents.
In addition, if necessary, a curing catalyst such as an organometallic compound such as dibutyltin dilaurate or dibutyltin diacetate or various amines, a plasticizer such as dioctyl phthalate, asphalt or tar, and a petroleum oil such as heavy oil or aromatic hydrocarbon. You may use a system diluent etc. in the range which does not impair the effect of this invention.

  The above fillers, additives and the like can be preferably used alone or in combination as necessary. These fillers, additives and the like can be used by kneading them in advance with a conventional method mainly in the polyol (A).

The urethane-based flooring of the present invention is one that is generally used for construction such as concrete and mortar, civil engineering, etc., or is applied onto a base material such as metal or wood.
As the base material, synthetic polymer rugs, for example, PVC tiles, sheets or rubber tiles, sheets or similar tiles, and sheet-like ones that are attached to the base material with an adhesive are also available. Can be used.

The urethane flooring of the present invention can be applied after applying a primer to a substrate. In addition, depending on the situation of the base material and the application site, a primer is applied to the base material, and then a floor material (first floor material: lower layer) different from the urethane-based floor material of the present invention is applied thereon, The urethane floor material of the present invention (second floor material: upper layer) can be applied to have a multilayer coating structure, and in this case, the lower layer floor while utilizing the characteristics of the upper urethane floor material This is preferable because the characteristics of the material can be utilized.
Examples of the primer mainly include an epoxy-based, urethane-based, and polymerizable unsaturated primer. Specific examples of commercially available products include an epoxy-based chemicrete primer (manufactured by ABC Shokai Co., Ltd.), a urethane-based material based on PRIADEC T-150-35 (manufactured by Dainippon Ink & Chemicals, Inc.), and a polymerizable unsaturated system. Diover NS-19 (manufactured by Dainippon Ink & Chemicals, Inc.) and the like can be mentioned, but there is no problem even if other than these are used.
Examples of the flooring other than the urethane flooring include an epoxy flooring, a hard urethane flooring, a soft urethane flooring, and a polymerizable unsaturated flooring.

  Since the epoxy-based flooring material has high adhesion to the base material, when the base material such as concrete is wet, when it is applied as a lower layer of the urethane-based flooring material of the present invention, the effect is exhibited. This is preferable.

  Such an epoxy flooring is obtained by adding a polyamidoamine compound having an amide bond as a curing catalyst and an active hydrogen capable of reacting with an epoxy group to a compound having at least one epoxy group in the molecule. Obtainable. As a commercial product of such an epoxy-based flooring material, Chemicrete E (general-purpose epoxy resin: manufactured by ABC Shokai) is mentioned.

  Examples of typical compounds having an epoxy group are bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, (poly) ethylene diglycidyl ether, (poly) propylene diglycidyl ether, neopentyl glycol. And diglycidyl ether.

  Examples of typical polyamide amine compounds include ethylene diamine, diethylene triamine, triethylene tetramine, and tetraethylene pentamine.

  Since the hard urethane flooring has both flexibility and hardness, when it is applied as a lower layer of the urethane flooring of the present invention at a site such as a factory or warehouse where load resistance and impact resistance are required, Since the effect can be exhibited anyhow, it is preferable.

  Such a hard urethane flooring material preferably comprises polyisocyanate (e1), bisphenol-modified active hydrogen compound (e2), natural oil or derivative thereof (e3), and activated alumina powder (e4) as essential components.

  As the polyisocyanate (e1), aliphatic and aromatic polyisocyanates listed in the polyisocyanate (B) can be used.

  The said bisphenol modified | denatured active hydrogen compound (e2) means the thing obtained by reaction of the reaction material of a bisphenol type compound and alkylene oxide, and a bisphenol type | system | group epoxy compound and higher fatty acid.

  The reaction product of a bisphenol compound and an alkylene oxide here can be obtained by ring-opening polymerization of both. Examples of the bisphenol compound include bisphenol A, bisphenol B, bisphenol F, and bisphenol S. These may be used alone or in combination of two or more. On the other hand, examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and the like may be used alone or in combination of two or more.

  As for the addition mole number of alkylene oxide with respect to a bisphenol type compound, it is desirable to add 1 mol or more to the phenolic hydroxyl group of a bisphenol type compound, Preferably it is 2-10 mol.

  Examples of the bisphenol-type epoxy resin include compounds obtained by reacting various bisphenols such as bisphenol A and bisphenol F with epichlorohydrin. These may be used alone or in combination of two or more. Also good.

  On the other hand, as a higher fatty acid to be reacted with such a bisphenol-type epoxy resin, a higher fatty acid having 10 to 25 carbon atoms having an ethylenically unsaturated bond is preferable. Specific examples thereof include ricinoleic acid, oleic acid, and linoleic acid. And castor oil fatty acid and soybean oil fatty acid containing linolenic acid. Of these, castor oil fatty acid, which is a higher fatty acid having a hydroxyl group such as ricinoleic acid, is particularly preferable.

  If the higher fatty acid has 10 to 25 carbon atoms, the hydrophobicity of the polyol is not impaired, the effect on the foam improvement of the coating surface is not reduced, and the increase in the viscosity of the polyol can be prevented, Excellent workability.

  If the higher fatty acid has an ethylenically unsaturated bond, it is preferable in that the viscosity of the polyol is reduced and it can be easily used as a coating agent. As long as the effects of the present invention are not impaired, a higher fatty acid having an ethylenically unsaturated bond can be used in combination with a saturated higher fatty acid such as coconut oil fatty acid such as lauric acid, palmitic acid or decanoic acid.

  In this reaction, the reaction ratio between the epoxy group of the bisphenol type epoxy resin and the carboxylic acid group of the higher fatty acid is preferably in the range of 1/1 to 1 / 0.7, more preferably 1 / 0.95 to 1 /. It is in the range of 0.9. The end point of this reaction is preferably such that the acid value of the reaction mixture is 0.5 (KOHmg / g) or less.

  The natural oil or derivative thereof (e3) refers to natural oils such as castor oil, soybean oil, coconut oil and their derivatives, and has a hydroxyl group, among them, castor oil having a secondary hydroxyl group and its Derivatives are preferred.

  Examples of the natural oil derivative include transesterification products of natural oil and polyhydric alcohols (such as glycerol), natural oil polymers, and natural oil dicyclopentadiene adducts. Castor oil derivatives are preferred, and examples include transesterification products of castor oil and polyhydric alcohol, castor oil polymers, and dicyclopentadiene adducts of castor oil.

  As the activated alumina powder (e4), those mentioned in the activated alumina powder (C) can be used.

  Since the flexible urethane flooring has high flexibility and waterproofing performance, it will show its effect when applied as a lower layer of the urethane flooring of the present invention in applications requiring crack followability and waterproofing effect. This is preferable.

Such a flexible urethane flooring contains, as essential components, a urethane prepolymer (f1) having an isocyanate group at the terminal and a compound (f2) having active hydrogen.
The urethane prepolymer (f1) has two or more isocyanate groups at the terminal obtained by the reaction of a polyol having two or more primary or secondary hydroxyl groups in the molecule with an organic polyisocyanate. The reaction ratio between the hydroxyl group (OH) of the polyol and the isocyanate group (NCO) of the organic polyisocyanate is equivalent to NCO / OH, preferably 1.6 or more, particularly preferably 1.8 to 4.0. It is.
The amount of residual NCO is preferably 1 to 15% by weight. In addition, it is preferable that the urethane prepolymer has 2 to 3 terminal isocyanate groups in one molecule.

Examples of the polyol include ethylene glycol, diethylene glycol,
Single-chain polyols such as propylene glycol, dipropylene glycol, 1.4 butanediol, and trimethylolpropane, and these single-chain polyols and alkylene oxides (for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc.) are polymerized alone or in combination. Polyol ether polyol or polyester polyol obtained by esterification reaction of dibasic acid and single chain glycol, natural oil and derivatives thereof, polybutadiene polyol, polyol of xylene formaldehyde resin alone or a mixture thereof. Among these, polyether polyol is preferable, and polyether diol and / or polyether triol are particularly preferable. Other,
Polyols for urethane such as polycarbonate polyol and polybutadiene polyol can also be used. The molecular weight of this polyol is 500-1 in terms of number average molecular weight.
6,000 is preferred.

  As the organic polyisocyanate, aliphatic and aromatic polyisocyanates listed in the polyisocyanate (B) can be used.

Examples of the compound (f2) having active hydrogen include polyols and polyamines.
As this polyol, the polyol used for the said urethane prepolymer can be used. As polyamines, for example, 3,3′-dichloro-4,4′-diaminodiphenylmethane (hereinafter referred to as MBOCA), 4,4′-diaminodiphenylmethane, diethyltoluenediamine, and a condensate of orthochloroaniline and formaldehyde are known. Conventional aromatic polyamines are used. These alone or a mixture of two or more kinds can be used.

Such a urethane-based flooring can contain the urethane prepolymer (f1), the active hydrogen-containing compound (f2), a filler, and various other additives as required.
In addition, as a filler used for these, what was mentioned above can be used arbitrarily.

  When the polymerizable unsaturated flooring is applied as a lower layer of the urethane-based flooring of the present invention at a site where a short construction period is required because the curing speed is faster than that of a hard urethane-based flooring and an epoxy-based flooring, Since the effect can be exhibited anyhow, it is preferable.

  Such a polymerizable unsaturated flooring material is a polymerizable resin such as urethane (meth) acrylate resin, epoxy (meth) acrylate resin, polyester (meth) acrylate resin, α, β-unsaturated carboxylic acid or saturated carboxylic acid and polyvalent An unsaturated polyester resin obtained by a condensation reaction with alcohols, and a resin obtained by polymerizing radical polymerizable unsaturated group-containing monomers as essential components, such as Diover HTP-563 (polymerizable resin: large Nihon Ink Chemical Co., Ltd.) and Polylite FR-200 (unsaturated polyester resin: manufactured by Dainippon Ink & Chemicals, Inc.).

  Examples of the α, β-unsaturated carboxylic acid herein include fumaric acid, maleic acid, maleic anhydride, and dimethyl esters thereof. Examples of the saturated carboxylic acid include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, and the like. These carboxylic acids may be used alone or in combination of two or more.

  On the other hand, examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,3-pentanediol, Diols such as 1,6-hexanediol, triols such as trimethylolpropane, and tetraols such as pentaerythritol. These alcohols may be used alone or in combination of two or more.

  As the polymerizable resin, those produced by the reaction of an epoxy resin, a urethane resin or a polyester resin with acrylic acid or methacrylic acid are the most typical ones, and other examples include, for example, terminal carboxypolybutadiene and glycidyl methacrylate. It contains a polybutadiene type vinyl ester resin produced by a reaction and has excellent corrosion resistance and mechanical strength. Such a polymerizable resin is usually a solution with a liquid polymerizable monomer described later. The mixing ratio is preferably polymerizable resin: polymerizable monomer = 40 to 80% by weight: 60 to 20% by weight.

  The unsaturated polyester resin is a solution of an unsaturated polyester and a liquid polymerizable monomer described later. The mixing ratio is preferably unsaturated polyester: polymerizable monomer = 40-80 wt%: 60-20 wt%.

  The polymerizable monomer contained in the polymerizable resin or unsaturated polyester resin is a monomer having a polymerizable double bond that is liquid at room temperature. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, cyclohexyl (meth) acrylate And one or more (meth) acrylic acid esters selected from among (meth) acrylic acid esters. Furthermore, other polymerizable monomers, for example, (meth) acrylic acid ester having 1 to 12 carbon atoms, styrene, α-methylstyrene, (meth) acrylic acid amide, alkyl having 1 to 4 carbon atoms Examples thereof include maleic acid ester having a group and fumaric acid ester. Of these polymerizable monomers, styrene is preferred.

  The polymerizable monomer includes ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate. , Trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, hexanediol di (meth) acrylate, oligoethylenedi (meth) acrylate, and other polyfunctional polymerizable monomers can be used in combination.

As a method for applying the urethane flooring of the present invention to a substrate, various methods can be used as necessary. As an example, polyol (A), polyisocyanate (B), and, if necessary, fillers and other additives are mixed at a predetermined mixing ratio (room temperature) and applied to the substrate within the pot life. And curing it.
As an application method, it can be applied by a trowel, brush, roller, rake, spray or the like corresponding to the viscosity of each flooring. Moreover, it hardens | cures about 6 to 24 hours after application | coating.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples. In addition, “part” in the text indicates a part by mass.
In addition, the ratio of the secondary hydroxyl group (H2) to the total number of hydroxyl groups in the multi-branched polyether polyols in Reference Examples 1 and 2 was measured by ¹⁹ F-NMR after the multi-branched polyether polyol was trifluoroacetated. .

Synthesis example 1
<Synthesis of multi-branched polyether polyol (a-1)>
In a 2-liter three-necked flask equipped with a reflux condenser, a magnetic stirring bar, and a thermometer, 348 g (3 mol) of 3-hydroxymethyl-3-ethyloxetane and 348 g (6 mol) of propylene oxide were dried and filtered. It was dissolved in 1 liter of diethyl ether free of oxide and then the flask was cooled in a −14 ° C. ice bath.
Then, a 60% by mass aqueous solution of 5.5 g of HPF _{6 was} added dropwise for 10 minutes. The reaction mixture became slightly cloudy. The reaction was then allowed to react overnight at room temperature and the next morning the clear reaction mixture was refluxed for 3 hours. Next, the initiator was deactivated by adding a 30 mass% methanol solution of 9 g of NaOMe. After filtration, diethyl ether was removed under reduced pressure at a bath temperature of 75 ° C. After the diethyl ether was completely removed, 667 g of a multi-branched polyether polyol (a-1) was obtained. The yield was 89%.
This multi-branched polyether polyol (a-1) has Mn = 1,440, Mw = 3,350, OHV = 265 mg · KOH / g, and 3-hydroxymethyl-3-ethyl on a molar basis from proton NMR. It was found that oxetane: propylene oxide = 1: 1.9. Further, the ratio of the number of secondary hydroxyl groups (H2) to the total number of hydroxyl groups was 39.0%.

Synthesis example 2
<Synthesis of multi-branched polyether polyol (a-2)>
In a 500 ml three-necked flask equipped with a reflux condenser, a magnetic stirring bar and a thermometer, 69.6 g (0.6 mol) of 3-hydroxymethyl-3-ethyloxetane and 104.4 g of propylene oxide (1.8 mol) Mol) was dissolved in 250 ml of dry and peroxide-free diethyl ether, and the flask was then cooled in a −10 ° C. ice bath.
Then, a 60% by mass aqueous solution of 1.46 g of HPF _{6 was} added dropwise for 10 minutes. The reaction mixture became slightly cloudy. The reaction was then allowed to react overnight at room temperature and the next morning the clear reaction mixture was refluxed for 4 hours. Thereafter, 300 ml of diethyl ether was distilled off from the resin solution, and the product was washed with an aqueous solution consisting of 2.8 g of KOH and 400 ml of water.
The isolated organic layer was then washed twice with 400 ml of non-ionized water, and diethyl ether was removed again to obtain 163.2 g of a low viscosity transparent multi-branched polyether polyol. The yield was 94%.
This multi-branched polyether polyol has Mn = 1,750, Mw = 3,630, OHV = 188 mg · KOH / g, and 3-hydroxymethyl-3-ethyloxetane: propylene oxide on a molar basis from proton NMR It was found to be 1: 2.9. The ratio of the number of secondary hydroxyl groups (H2) to the total number of hydroxyl groups was 46.3%.

Reference example 1
<Preparation of polyol (A-1)>
491 parts of the multi-branched polyether polyol (a-1) obtained in Synthesis Example 1 and 509 parts of castor oil having a hydroxyl group equivalent of 350 were mixed to obtain a polyol (A-1) having an average hydroxyl group equivalent of 265.

Reference example 2
<Preparation of polyol (A-2)>
642 parts of the multi-branched polyether polyol (a-2) obtained in Synthesis Example 2 and 358 parts of castor oil having a hydroxyl equivalent weight of 350 were mixed to obtain a polyol (A-2) having an average hydroxyl equivalent weight of 315.

Reference example 3
<Preparation of polyol (A-3)>
Reaction of 40 parts by weight of bisphenol A type epoxy resin having an epoxy equivalent of 188 and 60 parts by weight of castor oil fatty acid in the presence of 0.2 parts by weight of triphenylphosphine at 110 ° C. for 15 hours while bubbling nitrogen. 340 parts by weight of an epoxy ester having an acid value of 0.1, a hydroxyl group equivalent of 265, and a molecular weight of 936, and 660 parts by weight of castor oil having a hydroxyl group equivalent of 350 are mixed to obtain a polyol (A-3) having an average hydroxyl group equivalent of 316 Got. The epoxy ester is different from the multi-branched polyether polyol of the present invention.

Reference example 4
<Preparation of polyisocyanate (B)>
Commercial Crude MDI (Millionate MR-200: Japan: MDI 40% by mass, polymeric MDI 60% by mass, 4,4′-MDI in MDI 97% by mass, 2,4′-MDI 3% by mass 100 parts by weight of Polyurethane Industry Co., Ltd.
26 parts by weight of MDI (Lupranate MI: BASF INOAC Polyurethane Co., Ltd.) containing 50% by mass of 4,4′-MDI and 50% by mass of 2,4′-MDI, and 4,4′-MDI ( 24 parts by weight of Millionate MT (manufactured by Nippon Polyurethane Industry Co., Ltd.) was added to obtain polyisocyanate (B).

Reference Example 5
<Preparation of urethane prepolymer (B-1)>
Cosmo is designed so that the isocyanate group / hydroxyl group (NCO group / OH group) of the resin design value is 2.0 in a 2 liter four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser. 149 parts of Nate T-80 (2,4 tolylene diisocyanate / 2,6 tolylene diisocyanate = 80/20 TDI: manufactured by Mitsui Takeda Chemical Co., Ltd.), 597 parts of Exenol 2020 (polypropylene glycol: manufactured by Asahi Glass Polyurethane Co., Ltd.) 254 parts of Exenol 3030 (polypropylene glycol: Asahi Glass Polyurethane Co., Ltd.) was added and reacted at 80 ° C. for 2 hours and at 100 ° C. for 3 hours to obtain a urethane prepolymer (B-1) having a free NCO% of 3.63. It was.

Reference Example 6
<Preparation of active hydrogen compound (A-4)>
Pandex M-3202 (MBOCA solution: manufactured by Dainippon Ink & Chemicals, Inc.) 128 parts, dioctyl phthalate (produced by Daihachi Chemical Co., Ltd.), 168 parts, NS-200 (calcium carbonate: manufactured by Nitto Powder Co., Ltd.) ) A total of 1000 parts of 674 parts and 30 parts of toner was charged in a planetary mixer and stirred and mixed while depressurizing at -600 mmHg or less to obtain an active hydrogen compound (A-4).

(Test method)
<Abrasion resistance test>
A specified weight is applied to a 30 cm x 30 cm slate plate with a specified weight of Priadec T-150-35 (urethane primer: manufactured by Dainippon Ink & Chemicals, Inc.) and 10 cm x 10 cm after curing. I was cut. The test specimen was evaluated for wear resistance in accordance with JISK7204 (wear wheel CS-17, load 1 kg, measuring weight loss after 1000 cycles).

<Fixing test>
A plyadec T-150-35, 1 layer or 2 layer flooring material was applied to a 30 cm × 30 cm concrete pavement plate and cured at room temperature for 2 weeks. After that, the stationary test was conducted with the stationary tester NKA-187 (manufactured by Nikken Co., Ltd.) under the installation pressure of 40 kg / cm ² until the abnormalities such as peeling occurred between the upper layer and the lower layer. The number of times was measured. If no abnormalities such as peeling occurred even after 300 times of setting, it was determined that there was no abnormality.

Example 1
Priadeck T-150-35 (manufactured by Dainippon Ink and Chemicals) was applied to a 30 cm × 30 cm slate plate and a concrete pavement plate at 150 g / m ² . As a lower layer flooring material, 500 parts of polyol (A-3) prepared in Reference Example 3, 250 parts of alumina oxide powder (BK-112: manufactured by Sumika Alchem Co., Ltd.), calcium carbonate (NN500: Nitto Powder Co., Ltd.) ) Made of 210 parts and 25 parts of pigment with vacuum mixing using a planetary mixer with uniform mixing and polyisocyanate (B) obtained in Reference Example 5 with a ratio of isocyanate equivalent to hydroxyl equivalent of 1.15 The mixture was stirred and mixed at a ratio of 1.5 kg / m ² . Then, as an upper-layer flooring material, 500 parts of polyol (A-1) prepared in Reference Example 1, 250 parts of alumina oxide (BK-112: manufactured by Sumika Alchem Co., Ltd.), calcium carbonate (NN500: Nitto Powder ( The ratio of the isocyanate equivalent to the hydroxyl equivalent of 210 parts and 25 parts of pigment, which were uniformly mixed while vacuum defoaming using a planetary mixer, and Cosmonate NBDI (Mitsui Chemical Polyurethane Co., Ltd.) The mixture was stirred and mixed at a ratio of 15 and coated with 1.0 kg / m ^2, and the above performance tests were performed. The results are shown in Table 1.

Example 2
Various performance tests were performed in the same manner as in Example 1 except that Chemicleet E (epoxy flooring: manufactured by ABC Shokai Co., Ltd.) was used for the lower layer flooring.

Example 3
As a lower layer flooring material, urethane prepolymer (B-1) and active hydrogen compound (A-4) are stirred and mixed at a ratio of 1.05 of isocyanate equivalent and hydroxyl equivalent, and coated at 2.0 kg / m ^2. Various performance tests were conducted in the same manner as in Example 1 except that. The results are shown in Table 1.

Example 4
Various performance tests were performed in the same manner as in Example 1 except that Diover HTP-563 (polymerizable unsaturated resin floor material: manufactured by Dainippon Ink & Chemicals, Inc.) was used as the lower floor material. The results are shown in Table 1.

Example 5
Various performance tests were performed in the same manner as in Example 1 except that the lower floor material was not applied. The results are shown in Table 1.

Comparative Example 1
Various performance tests were performed in the same manner as in Example 1 except that the polyol (A-2) of Reference Example 2 was used for the upper layer flooring. The results are shown in Table 1.

Comparative Example 2
Various performance tests were performed in the same manner as in Example 1 except that the same floor material as the lower layer floor material was used. The results are shown in Table 1.

Comparative Example 3
Various performance tests were performed in the same manner as in Example 2 except that Chemicleat E was used for the upper floor material. The results are shown in Table 1.

Comparative Example 4
Various performance tests were performed in the same manner as in Example 3 except that 0.2 kg / m ^{2 of} Dick Top 500 (acrylic urethane paint: manufactured by Dainippon Ink & Chemicals, Inc.) was applied to the upper layer flooring. The results are shown in Table 1.

Comparative Example 5
Various performance tests were performed in the same manner as in Example 4 except that 0.3 kg / m ^{2 of} Diover HTP-550 (polymerizable unsaturated resin floor material: manufactured by Dainippon Ink & Chemicals, Inc.) was applied to the upper layer flooring. Went. The results are shown in Table 1.
Comparative Example 6
Various performance tests were performed in the same manner as Comparative Example 1 except that the lower floor material was not applied. The results are shown in Table 1.

As shown in Table 1, it can be seen that the urethane flooring comprising the urethane resin composition containing the multi-branched polyether polyol of the present invention retains high wear resistance. In addition, since it has a good uprightness even when various resin systems are used as the lower layer, urethane flooring suitable for the condition of the groundwork and the construction period is provided at construction sites such as parking lots and warehouses. I can do it.

Claims (6)

A multi-branched polyether polyol obtained by ring-opening reaction of a hydroxyalkyl oxetane (a1) and a monofunctional epoxy compound (a2), wherein the hydroxyalkyl oxetane (a1) is 3-hydroxymethyl-3-ethyl Oxetane or 3-hydroxymethyl-3-methyloxetane, and the monofunctional epoxy compound (a2) is propylene oxide, 1-butene oxide, 1-pentene oxide, or 1-hexene oxide , Has a primary hydroxyl group (H1) and a secondary hydroxyl group (H2), a number average molecular weight (Mn) of 1,000 to 2,500, and a hydroxyl value of 200 to 300 mg · KOH / g. Polyol (A) and polyisocyanate (based on a multi-branched polyether polyol) ) Urethane flooring made of urethane composition containing. The multi-branched polyether polyol is obtained by reacting the monofunctional epoxy compound (a2) with a hydroxyalkyl oxetane (a1) [(a1) / (a2)] at a molar ratio of 1/1 to 1/3. The monofunctional epoxy compound (a2) is an olefin epoxide and the number of secondary hydroxyl groups (H2) in the molecular structure is 30 to 60% of the total number of hydroxyl groups. The urethane-based flooring as described. The urethane-based flooring according to claim 1 or 2, wherein the polyisocyanate (B) is an alicyclic hydrocarbon structure-containing diisocyanate. The polyol (A) contains a hydroxyl group-containing higher fatty acid alkyl ester, and a multi-branched polyether polyol (multi-branched polyether polyol / hydroxyl group-containing higher fatty acid alkyl ester) with respect to the hydroxyl group-containing higher fatty acid alkyl ester is 3/7 to The urethane-based flooring material according to any one of claims 1 to 3, wherein the polyol (A) has a total hydroxyl number of 4 or more. The urethane-based flooring according to any one of claims 1 to 4, wherein the urethane composition contains 5 to 30% by weight of activated alumina powder (C). A floor structure comprising at least three layers of a base material layer, a first coating layer (lower layer), and a second coating layer (upper layer), wherein the second coating layer (upper layer) is any one of claims 1 to 5. A floor structure comprising such a urethane flooring.