JP2017137441A - Aqueous polyurethane resin dispersion for glazing agent for floor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous polyurethane resin dispersion giving a glazing agent for floor having excellent glossiness retention.SOLUTION: There is provided an aqueous polyurethane resin dispersion for glazing agent for floor, where (A) a polyurethane resin containing at least (a) a polyol compound, (b) a polyisocyanate compound, (c) acidic group-containing polyol and (d) a chain extender as components is dispersed in an aqueous medium, (A) the polyurethane resin contains a carbonate group, and the total of concentrations of an urea group and an urethane group is 5 mass% or more and 18 mass% or less.SELECTED DRAWING: None

Description

  The present invention relates to an aqueous polyurethane resin dispersion for a floor polish used for floors of buildings and the like.

  The floor polish is applied to the floor material surface for the purpose of protecting the floor material and maintaining the beauty in buildings such as buildings and condominiums. By forming a film on the flooring material, it prevents the flooring material from wearing and adheres to the flooring material, and also plays a role of maintaining aesthetics and cleanliness by a glazing effect.

  Various performances are required for a floor polish. First, floor polishes are required to have slip resistance on the formed film in order to prevent accidents such as a person walking on the floor falling. Further, the formed film is also required to have high durability against external factors such as dirt. Further, the formed film is required not only to have a glossing performance but also to maintain a glossiness for maintaining the gloss in order to maintain the beauty and cleanliness of the flooring agent. In particular, convenience stores and mass retailers tend to lose luster due to wear because many people frequently walk on the floor. For this reason, it is very important that the floor polish is excellent in gloss maintenance.

  Floor polishes are mainly water-based, not oily, from the viewpoint of safety during work. Examples of floor polishes include homopolymers of acrylic acid, methacrylic acid or derivatives thereof, copolymers thereof, and copolymers of these with other vinyl monomers such as styrene (hereinafter referred to as acrylic resins). And the like, and those containing a crosslinking agent, polyethylene wax, alkali-soluble resin, plasticizer, film forming aid and the like.

  Further, from the viewpoint of slip resistance, a polyurethane resin is used, and is blended as an aqueous polyurethane resin dispersion in the above-described aqueous type floor polish. On the other hand, the aqueous polyurethane resin dispersion has a problem in durability as a floor polish. For this reason, adjusting the component of the polyurethane resin to mix | blend is examined. Patent Document 1 discloses an aqueous polishing composition (floor polish) having a polyurethane having a polycarbonate skeleton. Carbonate group-containing urethane greatly contributes to improving the performance of the aqueous polishing composition (floor polish).

  Further, Patent Document 2 discloses a floor polish (containing a urethane resin having an alicyclic part and a carbonate part, as a floor polish having an excellent balance between durability and removability such as peeling workability. Floor polishes) are disclosed.

JP-A-8-73814 Japanese Patent Laying-Open No. 2015-21104

  However, floor polishes are required to have various properties such as slip resistance and durability against external factors, and the degree to which these properties are satisfied is greatly influenced by each component to be blended. Among them, the gloss retention is an important characteristic in view of the purpose of the polish, but the conventional aqueous polyurethane resin dispersions described in Patent Documents 1 and 2 were used for the floor polish. Sometimes it was not satisfactory in terms of gloss maintenance, and there was room for improvement.

  Then, this invention makes it a subject to provide the water-based polyurethane resin dispersion for floor polishes excellent in gloss maintenance property.

  As a result of various studies to overcome the problems of the prior art, the present inventors have found that at least (a) a polyol compound, (b) a polyisocyanate compound, (c) an acidic group-containing polyol, and (d) (A) polyurethane resin having a chain extender as a constituent component is dispersed in an aqueous medium, (A) the polyurethane resin contains a carbonate group, and the total concentration of urea group and urethane group is 5% by mass. As described above, the present inventors have obtained the knowledge that the problem of the floor polish can be solved by using the aqueous polyurethane resin dispersion for floor polish that is 18% by mass or less, and have reached the present invention.

In the present invention (1), (A) a polyurethane resin comprising at least (a) a polyol compound, (b) a polyisocyanate compound, (c) an acidic group-containing polyol, and (d) a chain extender in an aqueous medium. Distributed over
(A) It is related with the aqueous | water-based polyurethane resin dispersion for polishes for floors in which a polyurethane resin contains a carbonate group and the sum total of the density | concentration of a urea group and a urethane group is 5 mass% or more and 18 mass% or less.
The present invention (2) relates to the aqueous polyurethane resin dispersion for a floor polish of the present invention (1), wherein the (A) polyurethane resin further contains an ether group.
In the present invention (3), the aqueous polyurethane for floor polish of the present invention (2), wherein the concentration of ether groups in the polyurethane resin (A) is 1.5% by mass or more and 3.7% by mass or less. It relates to a resin dispersion.
This invention (4) is for floors of this invention (1)-(3) whose content rate of the alicyclic structure in (A) polyurethane resin is 12.4 mass% or more and 26.0 mass% or less. The present invention relates to an aqueous polyurethane resin dispersion for a polish.

  ADVANTAGE OF THE INVENTION According to this invention, the aqueous polyurethane resin dispersion for floor polishes which gives the membrane | film | coat with high gloss maintenance property is provided.

  In one embodiment of the present invention, (A) a polyurethane resin comprising at least (a) a polyol compound, (b) a polyisocyanate compound, (c) an acidic group-containing polyol, and (d) a chain extender. And (A) an aqueous polyurethane resin dispersion in which the polyurethane resin contains carbonate groups and the total concentration of urea groups and urethane groups is 5.0% by mass or more and 18% by mass or less.

<(A) polyurethane resin>
The polyurethane resin (A) used in the present invention comprises at least (a) a polyol compound, (b) a polyisocyanate compound, (c) an acidic group-containing polyol, and (d) a chain extender, and contains a carbonate group. The total concentration of the urea group and the urethane group is not particularly limited as long as it is 5.0% by mass or more and 18% by mass or less.

<< (a) Polyol Compound >>
(A) A polyol compound is a compound which has a 2 or more hydroxyl group in 1 molecule, and will not be restrict | limited especially if it can become a structural component of the (A) polyurethane resin mentioned above. (A) As a polyol compound, a high molecular weight polyol or a low molecular weight polyol can be used, and there is no restriction | limiting in particular in the kind.

  Although it will not restrict | limit especially if it can become a structural component of (A) polyurethane resin mentioned above as a high molecular weight polyol, It is preferable that a number average molecular weight is 400-8,000. When the number average molecular weight is within this range, an appropriate viscosity and good handleability can be obtained. In addition, it is easy to ensure the performance as a soft segment, and when the resulting aqueous polyurethane resin dispersion containing the polyurethane resin is used as a floor polish, it is easy to suppress the occurrence of cracks in the resulting film. . Furthermore, the reactivity between the (a) polyol compound and the (b) polyisocyanate compound becomes sufficient, and the (A1) polyurethane prepolymer described later can be efficiently produced. The high molecular weight polyol more preferably has a number average molecular weight of 400 to 4,000.

  In this specification, the number average molecular weight is the number average molecular weight calculated based on the hydroxyl value measured according to JIS K1557. Specifically, the hydroxyl value is measured, and is calculated by (56.1 × 1,000 × valence) / hydroxyl value [mgKOH / g] by the terminal group determination method. In the above formula, the valence is the number of hydroxyl groups in one molecule.

  As the high molecular weight polyol, it is preferable to use a high molecular weight diol from the viewpoint of easy production of the aqueous polyurethane resin dispersion. Examples of the high molecular weight diol include polycarbonate diol, polyester diol, and polyether diol. (A) When an aqueous polyurethane resin dispersion containing a polyurethane resin is used as a floor polish, the resulting film has light resistance, weather resistance, heat resistance, hydrolysis resistance, oil resistance, and gloss maintenance. From the standpoint of further enhancing, it is preferable to use a polycarbonate diol, and from the viewpoint of further improving the gloss maintenance, it is more preferable to use a polycarbonate diol and a polyether polyol.

  Among the polycarbonate diols, the diol component is preferably an aliphatic diol and / or an alicyclic diol, has good dispersibility in an aqueous medium, and (A) an aqueous polyurethane resin dispersion containing a polyurethane resin. When used as a floor polish, the diol component may be an aliphatic diol that does not have an alicyclic structure because of the high gloss maintenance of the resulting film and the high drying properties when creating the film. More preferred.

Examples of the high molecular weight polyol include polycarbonate polyol, polyester polyol, and polyether polyol. (A) When a water-based polyurethane resin dispersion containing a polyurethane resin is used as a floor polish, the gloss retention of the resulting film is further improved, and various durability such as light resistance, weather resistance, heat resistance, etc. Polycarbonate polyol is preferable from the viewpoint of further improving hydrolysis resistance, oil resistance, stain resistance, and black heel mark resistance.
Here, the “black heel mark resistance” refers to resistance to black rubber stains on the shoe sole attached by walking. Particularly in convenience stores, mass retailers, etc., many people frequently walk on the floor, so the black heel mark due to walking tends to hit the floor. For this reason, black heel mark resistance is one of the important durability performances required for a floor polish.

The polycarbonate polyol is obtained by reacting one or more polyol monomers with a carbonate ester or phosgene. A polycarbonate polyol obtained by reacting one or more polyol monomers with a carbonate ester is preferred because it is easy to produce and has no by-product formation of terminal chlorinated products.
The polycarbonate polyol as referred to in the present invention may contain ether bonds or ester bonds in the molecule as many as or less than the average number of carbonate bonds in one molecule.

  The polyol monomer is not particularly limited, and examples thereof include an aliphatic polyol monomer, a polyol monomer having an alicyclic structure, an aromatic polyol monomer, a polyester polyol monomer, and a polyether polyol monomer.

  The aliphatic polyol monomer is not particularly limited, and examples thereof include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1 Linear aliphatic diols such as 1,8-octanediol and 1,9-nonanediol; 2-methyl-1,3-propanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5 -Branched aliphatic diols such as pentanediol and 2-methyl-1,9-nonanediol; polyfunctional alcohols having 3 or more functional groups such as trimethylolpropane and pentaerythritol.

  The polyol monomer having an alicyclic structure is not particularly limited, and examples thereof include 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclopentanediol, 1, Examples include diols having an alicyclic structure in the main chain, such as 4-cycloheptanediol, 2,7-norbornanediol, and 1,4-bis (hydroxyethoxy) cyclohexane.

  The aromatic polyol monomer is not particularly limited. For example, 1,4-benzenedimethanol, 1,3-benzenedimethanol, 1,2-benzenedimethanol, 4,4′-naphthalenediethanol, 3,4 '-Naphthalene diethanol is mentioned.

  Although it does not restrict | limit especially as a polyester polyol monomer, For example, dicarboxylic acid, such as polyester polyol of hydroxycarboxylic acid and diol, such as polyester polyol of 6-hydroxycaproic acid and hexanediol, polyester polyol of adipic acid and hexanediol And polyester polyol of diol.

  The polyether polyol monomer is not particularly limited, and examples thereof include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

  The carbonate is not particularly limited, and examples thereof include aliphatic carbonates such as dimethyl carbonate and diethyl carbonate, aromatic carbonates such as diphenyl carbonate, and cyclic carbonates such as ethylene carbonate. In addition, phosgene or the like capable of producing a polycarbonate polyol can be used. Among these, aliphatic carbonates are preferable and dimethyl carbonate is particularly preferable because of easy manufacture of polycarbonate polyols.

  As a method for producing a polycarbonate polyol from a polyol monomer and a carbonate ester, for example, a carbonate ester and a polyol monomer having an excess number of moles relative to the number of moles of the carbonate ester are added to a reactor, and a temperature of 160 to 200 ° C. A method of reacting at a pressure of about 50 mmHg for 5 to 6 hours and further reacting at 200 to 220 ° C. for several hours at a pressure of several mmHg or less. In the above reaction, it is preferable to carry out the reaction while extracting by-produced alcohol out of the system. At that time, if the carbonate ester escapes from the system by azeotroping with the by-produced alcohol, an excessive amount of carbonate ester may be added. In the above reaction, a catalyst such as titanium tetrabutoxide may be used.

  The polycarbonate diol is not particularly limited, but for example, a polycarbonate diol obtained by reacting 1,6-hexanediol with a carbonate ester, a mixture of 1,6-hexanediol and 1,5-pentanediol, and a carbonate ester. Polycarbonate diol, 1,4-cyclohexanedimethanol and carbonate obtained by reacting a mixture of polycarbonate diol, 1,6-hexanediol and 1,4-butanediol with carbonate And polycarbonate diol obtained by reacting a mixture of polycarbonate diol, 1,6-hexanediol and 1,4-cyclohexanedimethanol obtained by the reaction with carbonate.

  Polyester diol is not particularly limited, but for example, polyethylene adipate diol, polybutylene adipate diol, polyethylene butylene adipate diol, polyhexamethylene isophthalate adipate diol, polyethylene succinate diol, polybutylene succinate diol, polyethylene sebacate diol , Polybutylene sebacate diol, poly-ε-caprolactone diol, poly (3-methyl-1,5-pentylene adipate) diol, polycondensate of 1,6-hexanediol and dimer acid, and the like.

  The polyether diol is not particularly limited, and examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide and propylene oxide, and a random copolymer or block copolymer of ethylene oxide and butylene oxide. Further, a polyether polyester polyol having an ether bond and an ester bond may be used. (A) When using the aqueous polyurethane resin dispersion containing a polyurethane resin as a floor polish, polytetramethylene glycol is preferred because the resulting film has higher stain resistance.

Although low molecular weight polyol will not be restrict | limited especially if it can become a structural component of the above-mentioned (A) polyurethane resin, For example, a number average molecular weight 60 or more and less than 400 are mentioned.
Moreover, low molecular weight diol can use a low molecular weight diol suitably from the ease of manufacture of an aqueous polyurethane resin dispersion. Examples of the low molecular weight diol include ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, and 2-butyl-2-ethyl- 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 2-methyl- C2-C9 aliphatic diol such as 1,8-octanediol, diethylene glycol, triethylene glycol, tetraethylene glycol; 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol 1,4-bis (hydroxyethyl) cyclohexane, 2,7-norbornane Lumpur, tetrahydrofuran dimethanol, 2,5-bis can be mentioned diols having a cyclic structure having 6 to 12 carbon atoms such as (hydroxymethyl) -1,4-dioxane.
Moreover, low molecular weight polyols such as trimethylolpropane, pentaerythritol, and sorbitol can also be used as the low molecular weight polyol.

  (A) A polyol compound may be used independently and may use multiple types together.

<< (b) Polyisocyanate Compound >>
The (b) polyisocyanate compound is not particularly limited as long as it has two or more isocyanato groups in one molecule and can be a constituent component of the target polyurethane resin. (B) As a polyisocyanate compound, aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate etc. are mentioned, for example.

  Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate ( MDI), 2,4-diphenylmethane diisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-di Isocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m-isocyanatophenylsulfonyl isocyanate, p-isocyanatophenylsulfonyl isocyanate.

  Examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate. 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate It is done.

  Examples of alicyclic polyisocyanates include isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), and bis (2-isocyanato). Ethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate.

  Further, as the (b) polyisocyanate compound, one having two isocyanato groups per molecule can be used. In addition, (A1) a polyisocyanate compound having three or more isocyanate groups per molecule, such as triphenylmethane triisocyanate, can be used as long as the polyurethane prepolymer does not gel.

  (B) Among the polyisocyanate compounds, when an aqueous polyurethane resin dispersion is used as a floor polish, the gloss maintenance property and stain resistance of the resulting film are further improved. Preferably, isophorone diisocyanate (IPDI) and 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI) are more preferable, and 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI) is particularly preferable.

  (B) A polyisocyanate compound may be used independently and may use multiple types together.

<< (c) Acidic group-containing polyol >>
(C) The acidic group-containing polyol contains two or more hydroxyl groups (excluding phenolic hydroxyl groups) and one or more acidic groups in one molecule. Here, examples of the acidic group include a carboxy group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group. (C) As an acidic group containing polyol, what contains the compound which has two hydroxyl groups and one carboxy group in 1 molecule is preferable. (C) The acidic group-containing polyol may be used alone or in combination of two or more.

  (C) Although it does not restrict | limit especially as an acidic-group containing polyol, For example, dimethylol alkanoic acid, such as 2, 2- dimethylol propionic acid and 2, 2- dimethylol butanoic acid, N, N- bishydroxyethyl glycine, Examples thereof include N, N-bishydroxyethylalanine, 3,4-dihydroxybutanesulfonic acid, and 3,6-dihydroxy-2-toluenesulfonic acid. Among these, from the viewpoint of easy availability, a dimethylol alkanoic acid having 4 to 12 carbon atoms containing two methylol groups is preferable. Among dimethylolalkanoic acids, 2,2-dimethylolpropionic acid is more preferable.

  In the present invention, the total number of hydroxyl equivalents of (a) the polyol compound and (c) the acidic group-containing polyol is preferably 80 to 1,000. If the number of hydroxyl equivalents is within this range, (A) an aqueous polyurethane resin dispersion containing a polyurethane resin can be easily produced, and can be obtained when the aqueous polyurethane resin dispersion is used as a floor polish. The gloss maintenance property of the film tends to be higher, and a film excellent in hardness can be easily obtained. From the viewpoint of storage stability of the resulting aqueous polyurethane resin dispersion, drying properties when used as a floor polish, and hardness of the resulting film, the number of hydroxyl equivalents is preferably 100 to 700, more preferably 200. ˜500, particularly preferably 300˜400.

The number of hydroxyl equivalents can be calculated by the following formulas (1) and (2).
Number of hydroxyl equivalents of each polyol = molecular weight of each polyol / number of hydroxyl groups of each polyol (excluding phenolic hydroxyl groups) (1)
Total number of hydroxyl equivalents of polyol = M / total number of moles of polyol (2)
In the case of the polyurethane resin (A), in the formula (2), M is [[(a) number of hydroxyl equivalents of polyol compound × (a) number of moles of polyol compound] + [(c) hydroxyl equivalent of the acidic group-containing polyol. Number × (c) Number of moles of acidic group-containing polyol]].

<< (A1) polyurethane prepolymer >>
The (A1) polyurethane prepolymer is obtained by reacting at least (a) a polyol compound, (b) a polyisocyanate compound, and (c) an acidic group-containing polyol compound. (A1) The polyurethane prepolymer may contain a terminal stopper, but it is preferable that the polyurethane prepolymer does not contain a terminal stopper from the viewpoint of higher gloss maintenance.

(A1) In the case of obtaining a polyurethane prepolymer, the total amount of (a) polyol compound, (b) polyisocyanate compound, (c) acidic group-containing polyol compound, (d) chain extender described below, and in some cases, the terminal terminator. When it is 100 parts by mass, the proportion of (a) polyol compound is preferably 30 to 70 parts by mass, more preferably 40 to 60 parts by mass, and particularly preferably 45 to 55 parts by mass. (C) The ratio of the acidic group-containing polyol compound is preferably 0.5 to 10 parts by mass, more preferably 3 to 7 parts by mass. When the terminal terminator is contained, the ratio can be appropriately determined according to the molecular weight of the desired (A1) polyurethane prepolymer.
(A) By setting the ratio of the polyol compound to 30 parts by mass or more, when using a water-based polyurethane resin dispersion as a floor polish, the resulting film has stain resistance and black heel mark resistance. There exists a tendency which can be made higher, and there exists a tendency for the gloss maintenance property of the film | membrane obtained from the said polish for floors to increase more by setting it as 70 mass parts or less.
(C) By setting the ratio of the acidic group-containing polyol compound to 0.5 parts by mass or more, dispersibility of the obtained polyurethane resin in an aqueous medium tends to be good, and by setting it to 10 parts by mass or less. The drying property of the obtained aqueous polyurethane resin dispersion tends to be high. Moreover, when using as a floor polish using an aqueous polyurethane resin dispersion, the water resistance of the obtained film can be increased, and the gloss maintenance property of the obtained film tends to be further improved.

  In the case of obtaining (A1) polyurethane prepolymer, the ratio of the number of moles of isocyanate groups of (b) polyisocyanate compound to the number of moles of all hydroxyl groups of (a) polyol compound and (c) acidic group-containing polyol compound is 1 0.05 to 2.5 is preferable. The ratio of the number of moles of the isocyanate group of the polyisocyanate compound to the number of moles of all hydroxyl groups of the (a) polyol compound and (c) acidic group-containing polyol compound is 1.05 or more, so that the isocyanate is attached to the molecular terminal. (A1) The amount of the polyurethane prepolymer having no group is reduced, and (d) the number of molecules that do not react with the chain extender is reduced. Therefore, when an aqueous polyurethane resin dispersion is used as a floor polish, It becomes easy to form a film. In addition, the ratio of the number of moles of isocyanate groups in the polyisocyanate compound to the number of moles of all hydroxyl groups in the (a) polyol compound and (c) acidic group-containing polyol compound is set to 2.5 or less, whereby the reaction system The amount of unreacted (b) polyisocyanate compound remaining in the inside decreases, (b) the polyisocyanate compound and (d) the chain extender react efficiently, and it is difficult to cause undesired molecular elongation due to the reaction with water. Therefore, (A) polyurethane resin can be appropriately prepared, and the storage stability is further improved. Moreover, when using as a floor polish using an aqueous polyurethane resin dispersion, there also exists an advantage that the drying property becomes high. The ratio of the number of moles of isocyanate groups of (b) polyisocyanate compound to the number of moles of all hydroxyl groups of (a) polyol compound and (c) acidic group-containing polyol compound is preferably 1.1 to 2.0, particularly preferably. Is 1.3 to 1.8.

  (A1) In the case of obtaining a polyurethane prepolymer, (a) a polyol compound, (b) a polyisocyanate compound, (c) an acidic group-containing polyol compound, (d) a chain extender described later, and optionally a terminal terminator. When the total amount is 100 parts by mass, the amount of (b) polyisocyanate compound is within the range satisfying the above molar ratio, and is matched to the type or amount of (a) polyol compound and (c) acidic group-containing polyol compound. Can be set as appropriate.

  When (A1) polyurethane prepolymer is obtained from (a) polyol compound, (c) acidic group-containing polyol compound, and (b) polyisocyanate compound, (a) polyol compound, (c) acidic group-containing The polyol compounds may be reacted with the (b) polyisocyanate compound in any order. (A) Polyol compound and (c) acidic group-containing polyol compound may be reacted with (b) polyisocyanate compound at the same time.

  (A1) In the reaction for obtaining the polyurethane prepolymer, a catalyst may be used. The catalyst is not particularly limited. For example, a salt of a metal and an organic or inorganic acid such as a tin (tin) catalyst (trimethyltin laurylate, dibutyltin dilaurate, etc.) or a lead catalyst (lead octylate, etc.) And organic metal derivatives, amine-based catalysts (triethylamine, N-ethylmorpholine, triethylenediamine, etc.), and diazabicycloundecene-based catalysts. Among these, dibutyltin dilaurate is preferable from the viewpoint of reactivity.

  The reaction temperature for reacting the (a) polyol compound and the (c) acidic group-containing polyol compound with the (b) polyisocyanate compound is not particularly limited, and is preferably 40 to 150 ° C. By setting the reaction temperature to 40 ° C. or higher, the raw material is sufficiently dissolved or the raw material has sufficient fluidity, and the viscosity of the obtained (A1) polyurethane prepolymer is lowered to perform sufficient stirring. it can. By setting the reaction temperature to 150 ° C. or lower, the reaction can proceed without causing problems such as side reactions. The reaction temperature is more preferably 60 to 120 ° C.

The reaction of (a) a polyol compound, (c) an acidic group-containing polyol compound, and (b) a polyisocyanate compound may be performed without a solvent or by adding an organic solvent.
When the reaction is performed without a solvent, the mixture of (a) a polyol compound, (c) an acidic group-containing polyol compound, and (b) a polyisocyanate compound is preferably liquid.
When the reaction is carried out by adding an organic solvent, the organic solvent is not particularly limited as long as it does not react with each component such as (a) the polyol compound and the synthesis reaction of (A1) polyurethane prepolymer proceeds. Examples of the organic solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dioxane, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, N-ethylpyrrolidone, β-alkoxypropionamide (Examide (registered trademark) manufactured by Idemitsu Kosan); For example, Ecamide M-100, Ecamide B-100), and ethyl acetate can be used.
Among these, acetone, methyl ethyl ketone, and ethyl acetate are preferable because they can be removed by heating or reduced pressure after the polyurethane prepolymer is dispersed in water and subjected to a chain extension reaction. When N-methylpyrrolidone, N-ethylpyrrolidone, and β-alkoxypropionamide are used as a floor polish using the obtained aqueous polyurethane resin dispersion containing a polyurethane resin, a film is formed. This is preferable because it works as a film-forming aid.
The addition amount of the organic solvent is 0.1 to 2.0 times on a mass basis with respect to the total amount of (a) polyol compound, (c) acidic group-containing polyol compound, and (b) polyisocyanate compound. It is preferable that it is 0.15-0.8 times.

<< (d) Chain extender >>
(D) The chain extender is not particularly limited as long as it is a compound reactive with an isocyanato group. For example, ethylenediamine, 1,4-tetramethylenediamine, 2-methyl-1,5-pentanediamine, 1,4-butanediamine, 1,6-hexamethylenediamine, 1,4-hexamethylenediamine, 3-aminomethyl -Amines such as 3,5,5-trimethylcyclohexylamine, 1,3-bis (aminomethyl) cyclohexane, xylylenediamine, piperazine, adipoylhydrazide, hydrazine, 2,5-dimethylpiperazine, diethylenetriamine, triethylenetetramine Compounds, diol compounds such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, polyalkylene glycols typified by polyethylene glycol, and water. Among them, stain resistance is preferable. Perspective Amine compounds and the like, particularly preferably include primary diamine compound. These may be used alone or in combination of two or more.

  (D) The addition amount of the chain extender is preferably equal to or less than the equivalent of the isocyanate group serving as the chain extension origin in the obtained polyurethane prepolymer, and more preferably 0.7 to 0.99 equivalent of the isocyanate group. . The strength of the film obtained by applying the obtained aqueous polyurethane resin dispersion without lowering the molecular weight of the chain-extended urethane polymer by adding the chain extender in an amount equal to or less than the equivalent of the isocyanato group. Tend to be high. (D) The chain extender may be added after the dispersion of the polyurethane prepolymer in water, or may be added during the dispersion. Chain extension can also be carried out with water. In this case, water as a dispersion medium also serves as a chain extender.

<Aqueous medium>
In the present invention, the (A) polyurethane resin is dispersed in an aqueous medium. The aqueous medium is not particularly limited as long as it contains at least water. In the present invention, for example, clean water, ion exchange water, distilled water, ultrapure water, or the like can be used. Among them, it is preferable to use ion-exchanged water in consideration of the availability and the fact that the particles become unstable due to the influence of salt. The aqueous medium may contain an organic solvent.

In the present invention, the acid value (AV) of the polyurethane (A) is preferably 8 to 30 mgKOH / g, more preferably 10 to 22 mgKOH / g, and particularly preferably 14 to 19 mgKOH / g. By setting the acid value of the polyurethane prepolymer to 8 mgKOH / g or more, the storage stability of the aqueous polyurethane resin dispersion and the floor polish obtained using the aqueous polyurethane resin dispersion, and the floor polish There exists a tendency which can improve the damage resistance of the film obtained. Moreover, when the acid value of (A) polyurethane is 30 mgKOH / g or less, the water resistance of the resulting film tends to be improved when an aqueous polyurethane resin dispersion is used as a floor polish. Moreover, there exists a tendency which can further improve the gloss maintenance property of a film.
In the present invention, “(A) acid value of polyurethane resin” means (A) the solvent used in producing the polyurethane resin and the neutralizing agent for dispersing the polyurethane prepolymer (A1) in the aqueous medium. It is the acid value in the so-called solid content excluding.
Specifically, the acid value of (A) polyurethane resin can be derived from the following formula (3).
[(A) Acid value of polyurethane resin] = [(number of millimoles of acidic group-containing polyol compound (c)) × (number of acidic group-containing polyol compound (c) acidic groups in one molecule)] × 56.11 / [Total mass of polyol compound (a), acidic group-containing polyol compound (c), polyisocyanate compound (b), and (d) chain extender] (3)

The (A) polyurethane resin contained in the aqueous polyurethane resin dispersion of the present invention has a total concentration of urethane groups and urea groups in the (A) polyurethane resin of 5% by mass or more and 18% by mass or less based on the solid content. It will be. Moreover, it is more preferable that they are 11 mass% or more and 17.8 mass% or less, and it is especially preferable that they are 16 mass% or more and 17.5 mass% or less.
By setting the total concentration of the urethane group and the urea group within this range, when the aqueous polyurethane resin dispersion is used as a floor polish, the gloss retention of the resulting film is further enhanced. Also, the stain resistance of the film obtained from the floor polish is likely to be higher.

  The (A) polyurethane resin contained in the aqueous polyurethane resin dispersion of the present invention contains a carbonate group. (A) Although the density | concentration of the carbonate group in a polyurethane resin is not restrict | limited in particular, For example, it is preferable that they are 5 mass% or more and 30 mass% or less on a solid content basis, and they are 15 mass% or more and 25 mass% or less. Is more preferable, and it is particularly preferably 15% by mass or more and 20% by mass or less. (A) When the concentration of the carbonate group in the polyurethane resin is 5% by mass or more and 30% by mass or less, when the aqueous polyurethane resin dispersion is used as a floor polish, the resulting film has black heel resistance. The mark property and stain resistance tend to be higher.

  The (A) polyurethane resin contained in the aqueous polyurethane resin dispersion of the present invention preferably further contains an ether group. (A) It is because the gloss maintenance property of the film obtained tends to be higher when the polyurethane resin contains an ether group and is used as a floor polish using an aqueous polyurethane resin dispersion. (A) The concentration of the ether group in the polyurethane resin is not particularly limited. For example, it is preferably 1% by mass or more and 8% by mass or less, and 1.5% by mass or more and 3.7% by mass or less based on the solid content. It is more preferable that (A) By making the concentration of the ether group in the polyurethane resin in the above range, when the aqueous polyurethane resin dispersion is used as a floor polish, the gloss retention of the resulting film becomes higher, and This is because the black heel mark resistance tends to be high. The ether group may be derived from any component among the components constituting the (A) polyurethane resin. For example, the polyether polyol described above as the (a) polyol compound can be used.

  The polyurethane resin (A) contained in the aqueous polyurethane resin dispersion of the present invention may further have an alicyclic structure. In that case, the content of the alicyclic structure of the polyurethane resin (A) is not particularly limited, but it is preferably 5% by mass or more and 40% by mass or less, and 12.4% by mass or more and 26.0% by mass based on the solid content. % Or less is particularly preferable. By setting the content of the alicyclic structure in the above range, when the aqueous polyurethane resin dispersion is used as a floor polish, the gloss retention of the resulting film tends to be higher. The alicyclic structure may be derived from any of the components constituting the (A) polyurethane resin. For example, the polyol compound containing the polyol monomer which has the alicyclic structure demonstrated previously, and the polyisocyanate which has an alicyclic structure can be used.

<Method for producing aqueous polyurethane resin dispersion>
Next, a method for producing an aqueous polyurethane resin dispersion in which (A) polyurethane resin is dispersed in an aqueous medium will be described. The production method of the aqueous polyurethane resin dispersion is:
(A) a step (a) of obtaining a polyurethane prepolymer by reacting the (a) polyol compound and the (c) acidic group-containing polyol compound with (b) a polyisocyanate compound;
The step (β) of neutralizing acidic groups of the polyurethane prepolymer (A1),
(A1) a step of dispersing the polyurethane prepolymer in an aqueous medium (γ),
A step (δ) of reacting the (A1) polyurethane prepolymer with a (d) chain extender having reactivity with the isocyanate group of the (A1) polyurethane prepolymer.

  The step (α) of obtaining the (A1) polyurethane prepolymer may be performed in an inert gas atmosphere or in an air atmosphere. (A1) The method for preparing the polyurethane prepolymer is as described above.

  As the neutralizing agent that can be used in the step (β) of neutralizing the acidic group of the polyurethane prepolymer (A1), a base known to those skilled in the art can be used without particular limitation. Examples of the neutralizing agent include trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-phenyldiethanolamine, dimethylethanolamine, diethylethanolamine, N-methylmorpholine. And organic amines such as pyridine; inorganic alkali salts such as sodium hydroxide and potassium hydroxide; and ammonia. Among these, organic amines can be preferably used, and tertiary amines can be more preferably used. Triethylamine is more preferable in terms of improving dispersion stability. Here, the acidic group of the (A1) polyurethane prepolymer means a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, and the like.

  In the step (γ) of dispersing the polyurethane prepolymer in the aqueous medium (A1), the method for dispersing the polyurethane prepolymer in the aqueous medium is not particularly limited. For example, the polyurethane prepolymer is stirred by a homomixer or a homogenizer. And (A1) a method of adding a polyurethane prepolymer to the aqueous medium, and (A1) a method of adding an aqueous medium to the polyurethane prepolymer that is stirred by a homomixer or a homogenizer.

  In the step (δ) of reacting the (A1) polyurethane prepolymer with the (d) chain extender having reactivity with the isocyanate group of the (A1) polyurethane prepolymer, the step (δ) is slowly performed under cooling. In some cases, the reaction may be promoted under heating conditions of 60 ° C. or lower. The reaction time under cooling can be, for example, 0.5 to 24 hours, and the reaction time under heating conditions of 60 ° C. or less can be, for example, 0.1 to 6 hours.

In the production of the aqueous polyurethane resin dispersion, either the step (β) or the step (δ) may be performed first or at the same time. The step (β) and the step (δ) may be performed simultaneously.
Further, the step (β), the step (γ), and the step (δ) may be performed simultaneously.

Specific examples of the method for producing the aqueous polyurethane resin dispersion include the following methods:
(A) a polyol compound and (c) an acidic group-containing polyol compound are reacted with (b) a polyisocyanate compound to obtain (A1) a polyurethane prepolymer (step (α));
Next, the acidic group of the polyurethane prepolymer (A1) is neutralized (step (β)),
Dispersing the solution obtained in the step (β) in an aqueous medium (step (γ)),
By reacting the (A1) polyurethane prepolymer dispersed in the dispersion medium with the (D) chain extender having reactivity with the isocyanate group of the (A1) polyurethane prepolymer (step (δ)), aqueous A polyurethane resin dispersion is obtained.

  The proportion of the polyurethane resin in the aqueous polyurethane resin dispersion is preferably 5 to 60% by mass, more preferably 15 to 50% by mass.

  The weight average molecular weight of the (A) polyurethane resin contained in the aqueous polyurethane resin dispersion of the present invention is usually about 25,000 to 10,000,000. More preferably, it is 50,000-5,000,000, More preferably, it is 100,000-1,000,000. The weight average molecular weight is measured by gel permeation chromatography (GPC), and a conversion value determined from a standard polystyrene calibration curve prepared in advance can be used. When the weight average molecular weight is 25,000 or more, when blended with a floor polish, a good film tends to be obtained by drying. By setting the weight average molecular weight to 1,000,000 or less, there is a tendency that the drying property of the floor polish containing the aqueous polyurethane resin dispersion can be further increased.

  In addition, the (A) polyurethane resin in the present invention includes a thickener, a photosensitizer, a curing catalyst, an ultraviolet absorber, a light stabilizer, an antifoaming agent, a plasticizer, a surface conditioner, and a precipitation as necessary. Additives such as inhibitors can also be added. The said additive may be used individually by 1 type, and may use 2 or more types together. Moreover, the kind of these additives is well-known to those skilled in the art, and can be used in the amount of the range generally used.

<Glossing agent for floor>
The aqueous polyurethane resin dispersion of the present invention is used as a component of a floor polish. When using the aqueous polyurethane resin dispersion of the present invention as a floor polish, in addition to the aqueous polyurethane resin dispersion, acrylic resin, crosslinking agent, wax emulsion, alkali-soluble resin, colloidal silica, plasticizer, film forming agent , Wettability improvers and the like can be added as appropriate. The floor polish can be obtained by mixing the aqueous polyurethane dispersion of the present invention with the above-mentioned components and the like by a method known to those skilled in the art. Examples of the mixing means for various components include stirring means for mechanical stirring using a stirring bar, stirring means using a stirrer equipped with an impeller, stirring means using a magnetic stirrer, shaking means using a mechanical shaker, and the like. Can be used.

<acrylic resin>
An acrylic resin can be used when using the aqueous polyurethane resin dispersion of the present invention as a floor polish. As the acrylic resin, known water-soluble or water-dispersible acrylic resins that have been conventionally used can be used. Specific examples of the acrylic resin include, for example, styrene, methylstyrene, acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, 2-ethyl-hexyl acrylate, methacrylic acid, methacrylic acid. Methyl acid, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethyl-hexyl methacrylate, vinyl acetate, acrylonitrile, itaconic acid, maleic acid, and copolymers of these types alone or in mixture Etc. In addition, the acrylic resin preferably has a crosslinkable functional group such as a hydroxyl group, a carboxy group, or an epoxy group that can react with a crosslinking agent described later. Among these, a hydroxyl group-containing acrylic resin is more preferable.

<Crosslinking agent>
In the case of using the aqueous polyurethane resin dispersion of the present invention as a floor polish, a crosslinking agent can be used. A crosslinking agent bridge | crosslinks between the hydrophilic groups of an acrylic resin or (A) polyurethane resin. Examples of such cross-linking agents include existing water-based cross-linking agents such as isocyanate, aziridine, carbodiimide, oxazoline, and epoxy, silane coupling agents, and metal cross-linking agents for polyvalent metal compounds. In particular, a polyisocyanate compound dispersible in water is preferred. The polyisocyanate dispersible in water can be obtained by introducing a hydrophilic group such as a hydroxyl group or a carboxy group into the polyisocyanate, or a commercially available one. Specific examples include hexamethylene diisocyanate (HDI) or isophorone diisocyanate (IPDI) derivatives (Duranate (trademark) series manufactured by Asahi Kasei Chemical Co., Ltd.). A crosslinking agent can be applied individually or in combination of 2 or more types.

<Wax emulsion>
A wax emulsion can be used when using the aqueous polyurethane resin dispersion of the present invention as a floor polish. Such wax emulsions include natural waxes and synthetic waxes. Specifically, for example, carnauba wax, candelilla wax, montan wax, montan derived wax, ceresin wax, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, amide wax, polyethylene wax and its carboxyl-modified wax, oxidized polyethylene wax, Examples thereof include carboxyl-modified wax, polypropylene wax and carboxyl-modified wax, oxidized polypropylene wax and carboxy-modified wax, glycol-modified polyethylene oxide wax, glycol-modified oxide polypropylene wax, and ethylene-acrylic acid copolymer wax. Oxidized polyethylene wax and oxidized polypropylene wax are preferable.

<Alkali-soluble resin>
In the case of using the aqueous polyurethane resin dispersion of the present invention as a floor polish, an alkali-soluble resin can be used. Examples of such alkali-soluble resins include rosin-modified maleic acid, styrene-maleic anhydride copolymer, diisobutylene-maleic anhydride copolymer, styrene-acrylic acid copolymer, and styrene-methacrylic acid copolymer. Styrene-α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-methacrylic acid copolymer, styrene-acrylic acid ester-acrylic acid copolymer, styrene-methacrylic acid ester-acrylic acid copolymer Styrene-methacrylic acid ester-methacrylic acid copolymer, styrene-α-methylstyrene-acrylic acid ester-acrylic acid copolymer, styrene-α-methylstyrene-methacrylic acid ester-acrylic acid copolymer, styrene-α -Methylstyrene-methacrylic acid ester-methacrylic acid co A polymer, an acrylate-acrylic acid copolymer, a methacrylic acid ester-acrylic acid copolymer, a methacrylic acid ester-methacrylic acid copolymer, a shellac, etc. can be mentioned, and these can be used alone or in combination of two or more. Can be applied.

<Colloidal silica>
Colloidal silica can be used when using the aqueous polyurethane resin dispersion of the present invention as a floor polish. Such colloidal silica can be used without particular limitation as long as the transparency of the film is not impaired. Colloidal silica is composed of silicon dioxide (including its hydrates) as a main component and aluminates such as sodium aluminate and potassium aluminate, sodium hydroxide, potassium hydroxide and lithium hydroxide as minor components. Further, inorganic salts such as ammonium hydroxide and organic salts such as tetramethylammonium hydroxide may be contained. Moreover, colloidal silica may be manufactured by the method used normally, and a commercially available thing may be used. Examples of colloidal silica include silica sol in which fine particles of silicic acid anhydride are dispersed in water and having a particle size of 50 nm or less.

The average particle diameter of colloidal silica can be measured by a technique such as a light scattering method or a laser diffraction method, which is a general measurement of dispersed particles. Further, as a more direct method, there is a method of actually measuring the particle size of colloidal silica particles in a photograph taken by a TEM (transmission electron microscope) photographing method and calculating an average value thereof (for example, Japanese Patent Laid-Open No. 2015). (See the method described in Japanese Patent No. 078274).
Moreover, the shape of the colloidal silica which can be used is not specifically limited. For example, any of a spherical shape, a long shape, a needle shape, and a bead shape may be used.

<Plasticizer>
A plasticizer can be used when using the aqueous polyurethane resin dispersion of the present invention as a floor polish. Examples of such plasticizers include phosphate esters such as tributoxyethyl phosphate (TBEP), tributyl phosphate and triphenyl phosphate, phthalate esters such as dibutyl phthalate, and citrate esters such as tributyl alkyl citrate. And adipic acid esters such as dimethyl adipate and dibutyl adipate, polyoxyalkylene alkyl ether alkyl esters, and propanediol esters.

<Film forming agent>
A film forming agent can be used when using the aqueous polyurethane resin dispersion of the present invention as a floor polish. Examples of such a film forming agent component include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether (methyl carbitol), triethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether (ethyl carbitol), and triethylene. Examples include glycol ethers such as glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and tripropylene glycol monomethyl ether, and alcohols such as ethanol and isopropyl alcohol.

<Wettability improver>
When the aqueous polyurethane resin dispersion of the present invention is used as a floor polish, a wettability improver can be used. Examples of such wettability improvers include fluorine surfactants such as perfluoroalkylcarboxylates, silicone surfactants, nonionic surfactants such as polyoxyethylene alkyl ethers, and the like. .

<solvent>
When using the aqueous polyurethane resin dispersion of the present invention as a floor polish, a solvent may be added for the purpose of improving ease of handling and stability. Examples of such a solvent include water, carbitols such as ethyl carbitol and methyl carbitol, and alcohols such as ethanol. When the solvent is volatilized after being applied to the floor, the gaseous solvent is dispersed in the surroundings. Therefore, it is preferable to use water as the solvent from the viewpoint of the surrounding environment and the like. Moreover, when using a film forming agent, you may use a film forming agent as a solvent component. The aqueous medium of the aqueous polyurethane resin dispersion can also be used as a solvent. The amount of the solvent is not particularly limited as long as it can disperse the polishing agent uniformly, but the solid content of the polishing agent for floor is 10 to 30 because it is necessary to volatilize the solvent after applying to the floor. It is preferable to use in the range which becomes mass%.

<Combination of floor polish>
In the case of using the aqueous polyurethane resin dispersion of the present invention as a floor polish, the blending thereof is not particularly limited as long as the function as a floor polish can be expressed.
For example, when the floor polish includes an aqueous polyurethane resin dispersion, an acrylic resin, and a cross-linking agent, when the solid content excluding other additives is 100% by mass, (A) polyurethane It is preferable to mix | blend resin in the quantity of 45-90 mass%. More preferably, it is 50-80 mass%. (A) By making the quantity of a polyurethane resin into this range, the higher gloss maintenance property is brought about in the film | membrane obtained from the said polish for floors.

  The method of forming a coating film using the floor polishing agent of the present invention is not particularly limited as long as it is a method capable of forming a coating film. For example, a floor polishing agent is directly applied to a floor surface in the field. And a method of forming a coating film or a method of applying a floor polish to a base material in advance to form a coating film on the site. The base material is not particularly limited as long as it is a material usually used for flooring.

  EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention is not limited to these.

In addition, the measurement of the physical property of (A) polyurethane resin was performed as follows.
(1) Hydroxyl value: Measured according to JIS K 1557 method B.
(2) Urethane group and urea group concentration total (solid content basis): The molar concentration (mol / g) of urethane group and urea group is calculated from the charge ratio of each raw material of the aqueous polyurethane resin dispersion, and the mass fraction is calculated. The total value of the converted values is shown. The mass fraction is based on the solid content of the aqueous polyurethane resin dispersion. An aqueous polyurethane resin dispersion (0.3 g) was coated on a glass substrate with a thickness of 0.2 mm, and the mass remaining after heating and drying at 140 ° C. for 4 hours was measured, and a product obtained by dividing this by the mass before drying was solid. The partial concentration was used. The mass fraction was calculated using the product of the total mass of the aqueous polyurethane resin dispersion and the solid content concentration as the solid mass.
(3) Carbon group-based content ratio: The molar concentration (mol / g) of the carbonate group was calculated from the charge ratio of each raw material of the aqueous polyurethane resin dispersion and expressed as a mass fraction. The mass fraction was calculated by the same method as the total concentration of urethane groups and urea groups (solid content standard) based on the solid content of the aqueous polyurethane resin dispersion.
(4) Content ratio of ether group based on solid content: The molar concentration (mol / g) of the ether group was calculated from the charged ratio of each raw material of the aqueous polyurethane resin dispersion and expressed as a mass fraction. The mass fraction was calculated by the same method as the total concentration of urethane groups and urea groups (solid content standard) based on the solid content of the aqueous polyurethane resin dispersion.
(5) Solid content basis content of alicyclic structure: The mass fraction of the alicyclic structure calculated from the charged ratio of each raw material of the aqueous polyurethane resin dispersion was described. The mass fraction was calculated by the same method as the total concentration of urethane groups and urea groups (solid content standard) based on the solid content of the aqueous polyurethane resin dispersion.
(6) Acid value: The molar concentration (mol / g) of the carboxyl group is calculated from the charge ratio of each raw material of the aqueous polyurethane resin dispersion, and the mass of potassium hydroxide necessary to neutralize 1 g of the sample (mgKOH / The value converted into g) is shown. The sample mass was calculated by the same method as the total concentration of urethane groups and urea groups (solid content standard) based on the solid content of the aqueous polyurethane resin dispersion.

[Example 1]
ETERNACOLL (registered trademark) UH200 (manufactured by Ube Industries, Ltd .; number average molecular weight 2030; hydroxyl value 55.4 mgKOH / g; polyol component obtained by reacting 1,6-hexanediol and carbonate ester) and 2 , 2-dimethylolpropionic acid, isophorone diisocyanate, and 2-methyl-1,5-pentanediamine were reacted to obtain an aqueous polyurethane resin dispersion. The aqueous polyurethane resin dispersion had a solid content of 29.5%, a pH of 9.7, and a viscosity of 57 cP (20 ° C.). The urethane group concentration was 7.8% by mass, the urea group concentration was 3.1% by mass, the carbonate group concentration was 28.6% by mass, and the alicyclic content was 7.3% by mass.

[Example 2]
ETERNACOLL (registered trademark) UH200 (manufactured by Ube Industries, Ltd .; number average molecular weight 2030; hydroxyl value 55.4 mgKOH / g; polyol component obtained by reacting 1,6-hexanediol and carbonate ester) and 2 , 2-dimethylolpropionic acid, hydrogenated MDI, and 2-methyl-1,5-pentanediamine were reacted to obtain an aqueous polyurethane resin dispersion. The aqueous polyurethane resin dispersion had a solid content of 30.1%, a pH of 8.8, and a viscosity of 57 cP (20 ° C.). The urethane group concentration was 7.6% by mass, the urea group concentration was 4.6% by mass, the carbonate group concentration was 24.7% by mass, and the alicyclic content was 17.5% by mass.

[Example 3]
ETERNACOLL (registered trademark) UH100 (manufactured by Ube Industries; number average molecular weight 1000; hydroxyl value 112 mg KOH / g; polycarbonate component obtained by reacting a polyol component with 1,6-hexanediol and carbonate ester), 2,2 -Dimethylolpropionic acid, hydrogenated MDI, and 2-methyl-1,5-pentanediamine were reacted to obtain an aqueous polyurethane resin dispersion. The aqueous polyurethane resin dispersion had a solid content of 30.6%, a pH of 7.9, and a viscosity of 36 cP (20 ° C.). The urethane group concentration was 10.1% by mass, the urea group concentration was 6.1% by mass, the carbonate group concentration was 19.3% by mass, and the alicyclic content was 23.2% by mass.

[Example 4]
ETERNACOLL (registered trademark) UH100 (manufactured by Ube Industries; number average molecular weight 1000; hydroxyl value 112 mg KOH / g; polycarbonate component obtained by reacting a polyol component with 1,6-hexanediol and carbonate) and polytetramethylene Glycol (number average molecular weight 650, hydroxyl value 173 mgKOH / g), 2,2-dimethylolpropionic acid, hydrogenated MDI and 2-methyl-1,5-pentanediamine are reacted to form an aqueous polyurethane resin dispersion Got. The aqueous polyurethane resin dispersion had a solid content of 30.3%, a pH of 8.4, and a viscosity of 84 cP (20 ° C.). Urethane group concentration is 10.6% by mass, urea group concentration is 6.4% by mass, ether group concentration is 2.7% by mass, carbonate group concentration is 18.6% by mass, alicyclic content is It was 24.3 mass%.

[Example 5]
ETERNACOLL (registered trademark) UH100 (manufactured by Ube Industries; number average molecular weight 1000; hydroxyl value 112 mg KOH / g; polycarbonate component obtained by reacting a polyol component with 1,6-hexanediol and carbonate) and polytetramethylene Glycol (number average molecular weight 1000, hydroxyl value 112 mgKOH / g), 2,2-dimethylolpropionic acid, hydrogenated MDI and 2-methyl-1,5-pentanediamine are reacted to form an aqueous polyurethane resin dispersion Got. The aqueous polyurethane resin dispersion had a solid content of 30.9%, a pH of 8.2, and a viscosity of 940 cP (20 ° C.). The urethane group concentration is 10.1% by mass, the urea group concentration is 6.1% by mass, the ether group concentration is 4.6% by mass, the carbonate group concentration is 11.6% by mass, and the alicyclic content is It was 23.1 mass%.

[Example 6]
ETERNACOLL (registered trademark) UH100 (manufactured by Ube Industries; number average molecular weight 1000; hydroxyl value 112 mg KOH / g; polycarbonate component obtained by reacting a polyol component with 1,6-hexanediol and carbonate) and polytetramethylene Glycol (number average molecular weight 1000, hydroxyl value 112 mgKOH / g), 2,2-dimethylolpropionic acid, hydrogenated MDI and 2-methyl-1,5-pentanediamine are reacted to form an aqueous polyurethane resin dispersion Got. The aqueous polyurethane resin dispersion had a solid content of 30.7%, a pH of 8.2, and a viscosity of 290 cP (20 ° C.). The urethane group concentration is 10.1% by mass, the urea group concentration is 6.1% by mass, the ether group concentration is 5.8% by mass, the carbonate group concentration is 9.7% by mass, and the alicyclic content is It was 23.1 mass%.

[Example 7]
ETERNACOLL (registered trademark) UH100 (manufactured by Ube Industries; number average molecular weight 1000; hydroxyl value 112 mg KOH / g; polycarbonate component obtained by reacting a polyol component with 1,6-hexanediol and carbonate) and polytetramethylene Glycol (number average molecular weight 1000, hydroxyl value 112 mgKOH / g), 2,2-dimethylolpropionic acid, hydrogenated MDI and 2-methyl-1,5-pentanediamine are reacted to form an aqueous polyurethane resin dispersion Got. The aqueous polyurethane resin dispersion had a solid content of 30.3%, a pH of 8.1, and a viscosity of 96 cP (20 ° C.). Urethane group concentration is 9.7% by mass, urea group concentration is 7.3% by mass, ether group concentration is 4.4% by mass, carbonate group concentration is 10.9% by mass, alicyclic content is It was 24.3 mass%.

[Comparative Example 1]
ETERNACOLL (registered trademark) UM90 (1/3) (manufactured by Ube Industries; number average molecular weight 900; hydroxyl value 125 mgKOH / g; polyol component 1,6-hexanediol: 1,4-cyclohexanedimethanol (3: 1 mole) Ratio) and a polycarbonate diol obtained by reacting a carbonate ester), 2,2-dimethylolpropionic acid, hydrogenated MDI, and 2-methyl-1,5-pentanediamine, and an aqueous polyurethane. A resin dispersion was obtained. The aqueous polyurethane resin dispersion had a solid content of 29.9%, a pH of 8.0, and a viscosity of 48 cP (20 ° C.). The urethane group concentration was 11.6% by mass, the urea group concentration was 7.4% by mass, the carbonate group concentration was 15.9% by mass, and the alicyclic content was 32.1% by mass.

[Comparative Example 2]
ETERNACOLL (registered trademark) UH100 (manufactured by Ube Industries; number average molecular weight 1000; hydroxyl value 112 mg KOH / g; polycarbonate component obtained by reacting a polyol component with 1,6-hexanediol and carbonate ester), 2,2 -Dimethylolpropionic acid, hydrogenated MDI, and 2-methyl-1,5-pentanediamine were reacted to obtain an aqueous polyurethane resin dispersion. The aqueous polyurethane resin dispersion had a solid content of 30.5%, a pH of 8.8, and a viscosity of 130 cP (20 ° C.). The urethane group concentration was 10.5% by mass, the urea group concentration was 8.4% by mass, the carbonate group concentration was 15.4% by mass, and the alicyclic content was 27.1% by mass.

[Comparative Example 3]
ETERNACOLL (registered trademark) UH100 (manufactured by Ube Industries; number average molecular weight 1000; hydroxyl value 112 mg KOH / g; polycarbonate component obtained by reacting a polyol component with 1,6-hexanediol and carbonate ester), 2,2 -Dimethylolpropionic acid, hydrogenated MDI, and 2-methyl-1,5-pentanediamine were reacted to obtain an aqueous polyurethane resin dispersion. The aqueous polyurethane resin dispersion had a solid content of 31.1%, a pH of 8.5, and a viscosity of 86 cP (20 ° C.). The urethane group concentration was 11.6% by mass, the urea group concentration was 9.9% by mass, the carbonate group concentration was 14.0% by mass, and the alicyclic content was 28.6% by mass.

[Fabrication of floor polish]
50% by mass of the aqueous polyurethane resin obtained in Examples 1 to 7 and Comparative Examples 1 to 3 based on the total solid content, acrylic resin (Asahi Kasei Chemicals Polytron R5118 (trade name): solid content 38% ) 15 mass%, polyisocyanate (Duranate WB40-80D (trade name) manufactured by Asahi Kasei Chemicals Corporation: 80% solid content) 25 mass%, wettability improver (perfluoroalkylcarboxylate “Futer Gent 150CH (trade name) ") 0.02% by weight, polyethylene oxide wax (wax emulsion" Hi-Tech E6020 (trade name) "manufactured by Toho Chemical Industry Co., Ltd.) 10% by weight, defoaming agent (Toray Dow Corning Co., Ltd.) 0.03% by mass of company-made silicone-based “FS Antifoam 92 (trade name)”) The proportion of minute were produced by adjusting the moisture floor polishes such that 25% by weight.

(Gloss maintenance)
Polishing for floors obtained from aqueous polyurethane resin dispersions of Examples 1 to 7 and Comparative Examples 1 to 3 on a black homogeneous vinyl floor tile (15 cm × 10 cm: “MS Plane 5608 (trade name)” manufactured by Toli Co., Ltd.) Each agent was applied (20 ml per m ² ) and dried in a thermostatic bath (20 ° C. × 45 minutes). Next, coating and drying were repeated, and three layers were formed by repeated coating, and left to stand in a thermostatic bath for final drying (20 ° C. × 48 hours) to obtain a test piece.

  Each sample was laid in a pedestrian passage, and after a predetermined period (2 months), the gloss value was measured according to the polymer type defined in Japanese Industrial Standard “JIS-K3920”. Table 1 shows the value of 60 degree gloss. The larger the number, the higher the gloss retention. In order to equalize the conditions such as the ambient climate and walking frequency, tests on the floor polish obtained from the aqueous polyurethane resin dispersions of Examples 1 to 3 and Comparative Examples 1 to 3 were simultaneously performed. The results are shown in Table 1 as “Gloss maintenance property (Test condition 1)”.

  Comparison of Examples 1 to 3 and Comparative Examples 1 to 3 reveals that the gloss retention of the floor polish is enhanced by changing the total concentration of urethane groups and urea groups in (A) polyurethane resin. It was. When the total concentration of urethane groups and urea groups in the aqueous polyurethane resin dispersion is within a predetermined range (Examples 1 to 3), the total concentration of urethane groups and urea groups is higher than Comparative Examples 1 to 3. It can be seen that gloss maintenance is exhibited.

  Next, the same test was performed on the polishing agents of Examples 3 to 7 in a period different from the test of “Gloss maintenance property (Test condition 1)”. The results are shown in Table 2 as “Gloss maintenance property (Test condition 2)”. In Example 3, the gloss value was 70 in the test of “gloss maintenance property (test condition 1)”.

  At the gloss maintenance test period (test condition 2) shown in Table 2, the gloss value of the polishing agent of Example 3 was 59. From Table 2, it can be seen that even when the polishing agent has a total concentration of urethane groups and urea groups within a predetermined range, when the (A) polyurethane resin contains an ether group, it exhibits better gloss maintenance.

  Next, in order to clarify the durability performance of the floor polish of the present invention in more detail, tests for black heel mark resistance and stain resistance were performed.

(Black heel mark resistance)
The heel mark tester and method according to JISK-3920 were used for evaluation. A white homogeneous vinyl floor tile (225 mm × 225 mm: “MS Plane 5601 (trade name)” manufactured by Toli Co., Ltd.) was applied and dried in the same manner as in the gloss maintenance test, and a test piece was obtained. It was.

  The heel mark tester used a device called a snell capsule. The snell capsule has a hexagonal column shape, and an axis is passed through the center of the hexagon, and the snell capsule can rotate around the axis.

  The test piece was cut into a size of 225 mm × 225 mm, mounted on the inner wall surface of a snell capsule (tester), and six standard rubber blocks (JIS S 5050) 50 mm × 50 mm × 50 mm cubes (about 175 g) were put into the tester.

  The tester was rotated at 50 rpm for 5 minutes and then rotated in the reverse direction for 5 minutes. Since the standard rubber block collided with the test piece by rotation for 10 minutes, the heel mark resistance was evaluated by the contamination of the test piece due to the collision.

The evaluation was performed by visually determining the amount of black heel mark (stains such as black rubbing) adhering to the test piece. The evaluation criteria are shown below.
◎: Excellent black heel mark resistance ○: Good black heel mark resistance ×: Inferior to black heel mark resistance

  From Table 3, it was revealed that the film obtained by the floor polish composition of the present invention exhibits not only gloss maintenance but also high black heel mark resistance over a long period of time. Moreover, it became clear that when the (A) polyurethane resin contains an ether group in a predetermined range, the black heel mark resistance is further improved.

(Stain resistance)
Each of the compositions of Examples 1 to 4 was applied to white homogeneous vinyl floor tiles (15 cm × 10 cm: “MS Plane 5601 (trade name)” manufactured by Toli Co., Ltd.) (20 ml per 1 m ² ), and each in a thermostatic bath. Dry (20 ° C. × 45 minutes). Next, three layers were formed by repeating coating and drying, and then left to stand in a thermostatic bath for final drying (20 ° C. × 48 hours) to obtain a test piece.

Each sample was laid, and after a predetermined period (2 months), the appearance was observed to determine the stain resistance.
◎: There is almost no dirt ○: There is a little dirt △: There is some dirt ×: There is dirt

  From Table 4, among the polishes in which the total concentration of urethane groups and urea groups is within a predetermined range, in particular, (A) the polyurethane resin has a specific range of alicyclic content, or in an amount within a predetermined range. It can be seen that when the ether group is contained, better stain resistance is exhibited.

  The aqueous polyurethane resin dispersion for a floor polish of the present invention can exhibit high gloss maintenance when a floor polish is produced. Further, high durability performance (dirt resistance, black heel mark resistance) can be exhibited. Furthermore, the floor polish obtained by using the aqueous polyurethane resin dispersion of the present invention is also advantageous in terms of improving aesthetics. In these respects, it is effectively used in the building maintenance industry.

Claims (4)

(A) a polyurethane resin having at least (a) a polyol compound, (b) a polyisocyanate compound, (c) an acidic group-containing polyol, and (d) a chain extender as constituents is dispersed in an aqueous medium,
(A) An aqueous polyurethane resin dispersion for a floor polish, wherein the polyurethane resin contains carbonate groups, and the total concentration of urea groups and urethane groups is 5% by mass or more and 18% by mass or less.   (A) The aqueous polyurethane resin dispersion for floor polishes according to claim 1, wherein the polyurethane resin further contains an ether group.   (A) The aqueous polyurethane resin dispersion for floor polishes according to claim 2, wherein the concentration of ether groups in the polyurethane resin is 1.5% by mass or more and 3.7% by mass or less.   (A) The content rate of the alicyclic structure in a polyurethane resin is 12.4 mass% or more and 26.0 mass% or less, The aqueous | water-based for floor polishes as described in any one of Claims 1-3. Polyurethane resin dispersion.