JP2017137440A - Aqueous polyurethane resin dispersion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous polyurethane resin dispersion giving a glazing agent for floor having high glossiness retention, or the like.SOLUTION: There is provided an aqueous polyurethane resin dispersion, 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, the total of concentrations of an urea group and an urethane group is 14.5 mass% or more and 20 mass% or less, and an alicyclic structure content in the (A) polyurethane resin is 15 mass% or more and 30 mass% or less.SELECTED DRAWING: None

Description

  The present invention relates to a water-based polyurethane resin dispersion that can be used for a floor polish used for a floor of a building or 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. Furthermore, 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 aesthetics and cleanliness of the flooring material. 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 polish composition having a polyurethane having a polycarbonate skeleton. It is described that carbonate group-containing urethane greatly contributes to improving the performance of the aqueous polish composition.

  Further, Patent Document 2 discloses an aqueous resin for floor polishing that is excellent in balance of durability and removability such as peeling workability and includes a urethane resin having an alicyclic part and a carbonate part. .

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, gloss maintenance is an important characteristic in view of the purpose of the polish, but conventional aqueous polyurethane resin dispersions as described in Patent Documents 1 and 2 are satisfactory in terms of gloss maintenance. There was room for improvement. Further, the problem of maintaining gloss has been a demand for wide improvement in the fields of painting and printing.

  Then, this invention makes it a subject to provide the water-based polyurethane resin dispersion which can provide the polishing agent for floors etc. 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 groups and urethane groups is 14.5 masses. %, 20% by mass or less, and (A) The content of the alicyclic structure in the polyurethane resin is 15% by mass or more and 30% by mass or less. The knowledge that it can be obtained was obtained, and the present invention was achieved.

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) The polyurethane resin contains a carbonate group, and the total concentration of the urea group and the urethane group is 14.5% by mass or more and 20% by mass or less, and (A) the content of the alicyclic structure in the polyurethane resin However, it is related with the water-based polyurethane resin dispersion which is 15 to 30 mass%.
The present invention (2) relates to the aqueous polyurethane resin dispersion of the present invention (1), wherein the (A) polyurethane resin further contains an ether group.
The present invention (3) relates to the aqueous polyurethane resin dispersion 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.
The present invention (4) relates to a coating composition containing the aqueous polyurethane resin dispersion according to any one of the present inventions (1) to (3).
The present invention (5) relates to a coating agent composition containing the aqueous polyurethane resin dispersion according to any one of the present inventions (1) to (3).
The present invention (6) relates to an ink composition containing the aqueous polyurethane resin dispersion according to any one of the present inventions (1) to (3).

  According to the aqueous polyurethane resin dispersion of the present invention, it is possible to provide a floor polish that gives a film having high gloss maintenance. Furthermore, according to the aqueous polyurethane resin dispersion of the present invention, it is possible to provide a composition suitable for applications requiring gloss, such as a coating composition, a coating composition, and an ink composition.

  One embodiment of the present invention is that (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. Dispersed in an aqueous medium, (A) the polyurethane resin contains carbonate groups, and the total concentration of urea groups and urethane groups is 14.5% by mass or more and 20% by mass or less; (A) polyurethane It is an aqueous polyurethane resin dispersion whose alicyclic structure content rate in resin is 15 mass% or more and 30 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 14.5% by mass or more and 20% by mass or less, and the alicyclic structure content is 15% by mass or more and 30% by mass or less.

<< (a) Polyol Compound >>
(A) A high molecular weight polyol or a low molecular weight polyol can be used for the polyol compound. The polyol compound is not particularly limited as long as it has two or more hydroxyl groups in one molecule.

  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. Moreover, it is easy to ensure the performance as a soft segment, and it is easy to suppress the cracking of the coating film obtained from the aqueous polyurethane resin dispersion containing the obtained polyurethane resin. 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. From the viewpoint of further improving the light resistance, weather resistance, heat resistance, hydrolysis resistance, and oil resistance of the coating film obtained from the aqueous polyurethane resin dispersion containing the polyurethane resin, it is preferable to use polycarbonate diol. Moreover, when mix | blending an aqueous polyurethane resin dispersion with a floor polish, it also has the advantage that the gloss maintenance property of the film | membrane obtained from a floor polish is improved. Furthermore, it is more preferable to use polycarbonate diol and polyether polyol from the viewpoint of further improving the gloss maintenance property and black heel mark resistance of the film.

  Among the polycarbonate diols, the diol component is preferably an aliphatic diol and / or an alicyclic diol, and the diol component has an alicyclic structure from the viewpoint of good dispersibility in an aqueous medium and high drying properties. It is more preferable that the aliphatic diol is not present. In addition, when blending an aqueous polyurethane resin dispersion in a floor polish, there are also advantages such as high gloss maintenance of the film obtained from the floor polish and high drying characteristics when creating the film. .

  Examples of the high molecular weight polyol include polycarbonate polyol, polyester polyol, and polyether polyol. (A) From the viewpoint of enhancing light resistance, weather resistance, heat resistance, hydrolysis resistance, oil resistance, and the like of a coating film obtained from an aqueous polyurethane resin dispersion containing a polyurethane resin, a polycarbonate polyol is preferable. In addition, when blending an aqueous polyurethane resin dispersion with a floor polish, the gloss maintenance of the film obtained from the floor polish is further improved, and various durability performance 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) In the case where an aqueous polyurethane resin dispersion containing a polyurethane resin is blended in 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 polyhydric alcohols 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, and alicyclic polyisocyanate 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.

  (B) As the polyisocyanate compound, one having two isocyanato groups per molecule can be used, but (A1) as long as the polyurethane prepolymer does not gel, like triphenylmethane triisocyanate, Polyisocyanate compounds having 3 or more isocyanato groups per molecule can also be used.

  (B) Among polyisocyanate compounds, when a water-based polyurethane resin dispersion is blended to make a floor polish, the gloss retention and stain resistance of the resulting film are further improved. Is preferred, isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI) is more preferred, and 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI) is particularly preferred.

  (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. 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 property, etc., and from the viewpoint of drying property and the hardness of the film obtained by coating when blended in a floor polish, the number of hydroxyl equivalents is: Preferably it is 100-700, More preferably, it is 200-500, Most preferably, it is 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 the (a) polyol compound, the (b) polyisocyanate compound, and the (c) acidic group-containing polyol compound. The (A1) 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 retention.

In the case of obtaining the (A1) polyurethane prepolymer, the total amount of (a) polyol compound, (b) polyisocyanate compound, (c) acidic group-containing polyol compound, (d) chain extender described below and optionally a terminal stopper. Is 100 parts by mass, the proportion of the polyol compound (a) 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. The proportion of the (c) 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 proportion 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 coating is more resistant to dirt and black heel marks. There exists a tendency which can be made high and there exists a tendency for the gloss maintenance property of the film | membrane obtained from the 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, the dispersibility of the obtained aqueous polyurethane resin in an aqueous medium tends to be good, and the content is 10 parts by mass or less. Then, the drying property of the obtained aqueous polyurethane resin dispersion tends to be high. In addition, when a water-based polyurethane resin dispersion is used as a floor polish, the water resistance of the film obtained from the floor polish can be increased, and the gloss retention of the resulting film is also improved. There is a tendency to be able to.

  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, so that it becomes easier to form a film after drying the floor polish of the present invention. . 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 the (d) chain extender react efficiently, and cause undesired molecular elongation due to reaction with water. Since it becomes difficult, preparation of (A) polyurethane resin can be performed appropriately and the storage stability of an aqueous polyurethane resin dispersion improves more. Moreover, when using as a floor polish agent using an aqueous polyurethane resin dispersion, the drying property of the floor polish agent obtained 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) a polyurethane prepolymer is obtained from (a) a polyol compound, (c) an acidic group-containing polyol compound, and (b) a polyisocyanate compound, (a) and (c) are in any order (b ). (A) The polyol compound and (c) the acidic group-containing polyol compound may be simultaneously reacted with the (b) polyisocyanate compound.

  (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.), In addition, organic metal derivatives, amine catalysts (triethylamine, N-ethylmorpholine, triethylenediamine, etc.), diazabicycloundecene catalysts, and the like can be given. Among these, dibutyltin dilaurate is preferable from the viewpoint of reactivity.

  Although it does not restrict | limit especially as reaction temperature at the time of making a (a) polyol compound and (c) acidic group containing polyol compound and (b) polyisocyanate compound react, 40-150 degreeC is preferable. 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 between (a) a polyol compound, (c) an acidic group-containing polyol compound, and (b) a polyisocyanate compound may be carried out 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) ethyl acetate. 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. N-methylpyrrolidone, N-ethylpyrrolidone, and β-alkoxypropionamide are preferable because they function as a film-forming aid when a coating film is prepared from the aqueous polyurethane resin dispersion containing the obtained polyurethane resin. The addition amount of the organic solvent is preferably 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. More preferably, 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. The aqueous medium may contain an organic solvent. Examples of water contained in the aqueous medium include clean water, ion exchange water, distilled water, and ultrapure water. 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.

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 making the acid value of the polyurethane prepolymer 8 mgKOH / g or more, it is obtained from the aqueous polyurethane resin dispersion and the storage stability of the floor polish obtained using the aqueous polyurethane resin dispersion, from the floor polish. There is a tendency to improve the scratch resistance of the resulting film. Moreover, there exists a tendency for the water resistance of the coating film obtained from an aqueous polyurethane resin dispersion to improve by making the acid value of (A) polyurethane into 30 mgKOH / g or less. Moreover, when using as a floor polish using an aqueous polyurethane resin dispersion, there exists a tendency which can improve the water resistance of a film | membrane, and can further improve gloss maintenance property.
In the present invention, “(A) acid value of polyurethane” means (A) a solvent used for producing a polyurethane resin and a neutralizing agent for dispersing the polyurethane prepolymer (A1) in an 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 urea groups and urethane groups in the (A) polyurethane resin of 14.5% by mass or more and 20% by mass based on solid content. It is as follows. The total concentration of urea groups and urethane groups is more preferably 15% by mass or more and 17.8% by mass or less, and particularly preferably 16% by mass or more and 17.5% by mass or less. By setting the total concentration of the urea group and the urethane group within this range, when the aqueous polyurethane resin dispersion is used as a floor polish, the gloss retention of the resulting film becomes higher. 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 of 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 it is more preferable that they are 15 mass% or more and 25 mass% or less. It is particularly preferably 15% by mass or more and 20% by mass or less. When the concentration of the carbonate group 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 mark resistance and stain resistance. It tends to be higher.

  In the (A) polyurethane resin contained in the aqueous polyurethane resin dispersion of the present invention, the content of the alicyclic structure of the (A) polyurethane resin is 15 or less and 30% by mass based on the solid content. The content of the alicyclic structure is preferably 20% by mass or more and 26% by mass or less. 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.

  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. Furthermore, the concentration of the ether group in the polyurethane resin (A) is more preferably 1% by mass or more and 8% by mass or less, and more preferably 1.5% by mass or more and 3.7% by mass or less based on the solid content. More preferred. By making the concentration of the ether group in the above range, the gloss maintenance property of the film obtained from the floor polish is increased, and the black heel mark resistance tends to be increased. 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.

(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 polyurethane resin (A) 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. By setting the weight average molecular weight to 25,000 or more, there is a tendency that a good film can be obtained by drying the aqueous polyurethane resin dispersion. Further, when the aqueous polyurethane resin dispersion is 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 aqueous polyurethane resin dispersion can be further increased. In addition, when the aqueous polyurethane resin dispersion is blended in a floor polish, the drying property tends to be further increased.

  In addition, the (A) polyurethane resin of 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, a sedimentation 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.

  Since the aqueous polyurethane resin dispersion of the present invention can impart high gloss maintenance to the film, it can be used as a component of a polish for floors. In addition to the aqueous polyurethane resin dispersion, the floor polishing agent to be blended with the aqueous polyurethane resin dispersion of the present invention is an acrylic resin, a cross-linking agent, a wax emulsion, an alkali-soluble resin, colloidal silica, a plasticizer, a film forming agent, and a wetting agent. A property improver, a solvent and the like can be added as appropriate. 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.

<Coating composition, coating agent composition and ink composition>
Since the aqueous polyurethane resin dispersion of the present invention can provide high gloss maintenance, it can be preferably used in applications requiring glossiness in addition to a floor polish. For example, the gloss of the paint can be maintained, and the gloss of a printed matter such as a photograph can be maintained. Therefore, the present invention also relates to a coating composition, a coating agent composition and an ink composition containing the aqueous polyurethane resin dispersion.
In addition to the aqueous polyurethane resin dispersion, other resins may be added to the coating composition, coating agent composition, and ink composition of the present invention. Examples of other resins include polyester resins, acrylic resins, polyether resins, polycarbonate resins, polyurethane resins, epoxy resins, alkyd resins, polyolefin resins, and vinyl chloride resins. These may be used alone or in combination of two or more. The other resin preferably has one or more hydrophilic groups. Examples of the hydrophilic group include a hydroxyl group, a carboxy group, a sulfonic acid group, and a polyethylene glycol group.

  The other resin is preferably at least one selected from the group consisting of a polyester resin, an acrylic resin, and a polyolefin resin.

The polyester resin can be usually produced by an esterification reaction or an ester exchange reaction between an acid component and an alcohol component. As an acid component, the compound normally used as an acid component at the time of manufacture of a polyester resin can be used. As an acid component, an aliphatic polybasic acid, an alicyclic polybasic acid, an aromatic polybasic acid, etc. can be used, for example.
The hydroxyl value of the polyester resin is preferably about 10 to 300 mgKOH / g, more preferably about 50 to 250 mgKOH / g, and still more preferably about 80 to 180 mgKOH / g. The acid value of the polyester resin is preferably about 1 to 200 mgKOH / g, more preferably about 15 to 100 mgKOH / g, and still more preferably about 25 to 60 mgKOH / g.
The weight average molecular weight of the polyester resin is preferably 500 to 500,000, more preferably 1,000 to 300,000, and still more preferably 1,500 to 200,000.

As an acrylic resin when used in a coating composition, a coating agent composition, and an ink composition, a hydroxyl group-containing acrylic resin is preferable. Hydroxyl group-containing acrylic resin is a hydroxyl group-containing polymerizable unsaturated monomer and other polymerizable unsaturated monomer copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer, for example, in a solution polymerization method in an organic solvent, in water It can manufacture by making it copolymerize by known methods, such as an emulsion polymerization method.
The hydroxyl group-containing polymerizable unsaturated monomer is a compound having at least one hydroxyl group and one polymerizable unsaturated bond in one molecule. For example, (meth) acrylic acid such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like and 2 to 8 carbon atoms. Monoesterified products of dihydric alcohols with these compounds; ε-caprolactone modified products of these monoesterified products; N-hydroxymethyl (meth) acrylamide; allyl alcohol; (meth) acrylates having a polyoxyethylene chain whose molecular ends are hydroxyl groups Etc.

The hydroxyl group-containing acrylic resin preferably has an anionic functional group. For the hydroxyl group-containing acrylic resin having an anionic functional group, for example, a polymerizable unsaturated monomer having an anionic functional group such as a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group is used as one kind of the polymerizable unsaturated monomer. It can be manufactured by using.
The hydroxyl value of the hydroxyl group-containing acrylic resin is preferably about 1 to 200 mgKOH / g, more preferably about 2 to 100 mgKOH / g, and more preferably 3 to 60 mgKOH from the viewpoints of storage stability of the composition and water resistance of the resulting coating film. / G is more preferable.
When the hydroxyl group-containing acrylic resin has an acid group such as a carboxyl group, the acid value of the hydroxyl group-containing acrylic resin is preferably about 1 to 200 mgKOH / g from the viewpoint of water resistance of the resulting coating film, About 150 mgKOH / g is more preferable, and about 5 to 100 mgKOH / g is still more preferable.
The weight average molecular weight of the hydroxyl group-containing acrylic resin is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, and still more preferably in the range of 3,000 to 50,000. is there.

  Examples of the polyether resin include polymers or copolymers having an ether bond, and examples include aromatics such as polyoxyethylene-based polyether, polyoxypropylene-based polyether, polyoxybutylene-based polyether, bisphenol A or bisphenol F. And polyethers derived from group polyhydroxy compounds.

  Examples of the polycarbonate resin include a polymer produced from a bisphenol compound, such as bisphenol A / polycarbonate.

  Examples of the polyurethane resin include resins having a urethane bond obtained by reacting various polyol components such as acrylic, polyester, polyether, and polycarbonate with polyisocyanate.

  Examples of the epoxy resin include a resin obtained by a reaction between a bisphenol compound and epichlorohydrin. Examples of bisphenol include bisphenol A and bisphenol F.

  Alkyd resins include polybasic acids such as phthalic acid, terephthalic acid and succinic acid and polyhydric alcohols, as well as fats and oils and fatty acids (soybean oil, linseed oil, coconut oil, stearic acid, etc.) and natural resins (rosin, succinic acid). Alkyd resin obtained by reacting a modifier such as

As the polyolefin resin, a polyolefin resin obtained by polymerizing or copolymerizing an olefin monomer with another monomer in accordance with a normal polymerization method is dispersed in water using an emulsifier, or the olefin monomer is appropriately replaced with another monomer. And a resin obtained by emulsion polymerization. In some cases, a so-called chlorinated polyolefin-modified resin in which the polyolefin resin is chlorinated may be used.
Examples of the olefin monomer include ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-hexene, 1-hexene, Α-olefins such as decene and 1-dodecene; conjugated dienes and nonconjugated dienes such as butadiene, ethylidene norbornene, dicyclopentadiene, 1,5-hexadiene, styrenes and the like, and these monomers may be used alone It is also possible to use a plurality of types together.
Examples of other monomers copolymerizable with the olefinic monomer include vinyl acetate, vinyl alcohol, maleic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride, and itaconic anhydride. These may be used alone or in combination of two or more.

  The coating composition, coating agent composition and ink composition of the present invention may contain a curing agent, whereby a coating film or multilayer coating film, coating obtained using the coating composition or coating agent composition It is possible to improve the water resistance of the film or printed matter.

  As the curing agent, for example, amino resin, polyisocyanate, blocked polyisocyanate, melamine resin, carbodiimide and the like can be used. A hardening | curing agent may be individual and may use multiple types together.

  Examples of the amino resin include a partial or completely methylolated amino resin obtained by a reaction between an amino component and an aldehyde component. Examples of the amino component include melamine, urea, benzoguanamine, acetoguanamine, steroguanamine, spiroguanamine, dicyandiamide and the like. Examples of the aldehyde component include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, and the like.

  Examples of the polyisocyanate include compounds having two or more isocyanato groups in one molecule, such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate.

  Examples of the blocked polyisocyanate include those obtained by adding a blocking agent to the isocyanate group of the aforementioned polyisocyanate. Examples of the blocking agent include phenols such as phenol and cresol, aliphatics such as methanol and ethanol. Alcohols, active methylenes such as dimethyl malonate and acetylacetone, mercaptans such as butyl mercaptan and dodecyl mercaptan, acid amides such as acetanilide and acetate amide, lactams such as ε-caprolactam and δ-valerolactam, succinimide And blocking agents such as acid imides such as maleic imide, oximes such as acetoald oxime, acetone oxime and methyl ethyl ketoxime, and amines such as diphenylaniline, aniline and ethyleneimine.

  Examples of the melamine resin include methylol melamines such as dimethylol melamine and trimethylol melamine; alkyl etherified products or condensates of these methylol melamines; and condensates of alkyl etherified products of methylol melamine.

Coloring pigments, extender pigments, and glitter pigments can be added to the coating composition, coating agent composition, and ink composition of the present invention.
Examples of the color pigment include titanium oxide, zinc white, carbon black, molybdenum red, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinacridone pigment, isoindoline pigment, selenium pigment, and perylene pigment. These may be single and may use multiple types together. In particular, it is preferable to use titanium oxide and / or carbon black as the color pigment.
Examples of extender pigments include clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, and alumina white. These may be single and may use multiple types together. In particular, barium sulfate and / or talc are preferably used as extender pigments, and barium sulfate is more preferably used.
As the bright pigment, for example, aluminum, copper, zinc, brass, nickel, aluminum oxide, mica, aluminum oxide coated with titanium oxide or iron oxide, mica coated with titanium oxide or iron oxide can be used. .

  In the coating composition, coating agent composition and ink composition of the present invention, a thickener, a curing catalyst, an ultraviolet absorber, a light stabilizer, an antifoaming agent, a plasticizer, a surface conditioner, and a precipitation are added as necessary. Conventional additives such as an inhibitor can be contained. These may be used alone or in combination of two or more.

  Although the manufacturing method of the coating composition of this invention, a coating agent composition, and an ink composition is not specifically limited, A well-known manufacturing method can be used. In general, the coating composition and the coating composition are prepared by mixing the aqueous polyurethane resin dispersion and the various additives described above, adding an aqueous medium, and adjusting the viscosity according to the application method. Is done.

  Examples of the material to be coated of the coating composition, the material to be coated of the coating composition, or the material to be applied of the ink composition include metals, plastics, inorganic materials, and wood.

  Examples of the coating method of the coating composition or the coating method of the coating agent composition include bell coating, spray coating, roll coating, shower coating, and dip coating. Examples of the application method of the ink composition include an inkjet printing method, a flexographic printing method, a gravure printing method, a reverse offset printing method, a sheet-fed screen printing method, and a rotary screen printing method.

  Although the thickness of the coating film after hardening is not restrict | limited, The thickness of 1-100 micrometers is preferable. More preferably, it is preferable to form a coating film having a thickness of 3 to 50 μm.

<Polyurethane resin film>
The present invention further relates to a polyurethane resin film obtained from the aqueous polyurethane resin dispersion.

  A polyurethane resin film can also be obtained using an aqueous polyurethane resin dispersion. A polyurethane resin film is obtained by applying the aqueous polyurethane resin dispersion to a releasable substrate, drying and curing by means of heating or the like, and subsequently peeling the cured polyurethane resin from the releasable substrate. .

  Examples of the heating method include a heating method using its own reaction heat, a heating method using both the reaction heat and positive heating of the mold. Examples of the positive heating of the mold include a method of heating the mold in a hot air oven, an electric furnace, or an infrared induction heating furnace.

  The heating temperature is preferably 40 to 200 ° C, more preferably 60 to 160 ° C. By heating at such a temperature, drying can be performed more efficiently. The heating time is preferably 0.0001 to 20 hours, more preferably 1 to 10 hours. By setting it as such a heating time, a polyurethane resin film with higher hardness can be obtained. Preferable drying conditions for obtaining a polyurethane resin film include, for example, heating at 120 ° C. for 3 to 10 seconds.

  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) Concentration based on solid content of urethane group, Concentration based on solid content of urea group: The molar concentration (mol / g) of urethane group and urea group is calculated from the charged ratio of each raw material of the aqueous polyurethane resin dispersion, What was converted into a mass fraction was described. 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) 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 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) 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 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) 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 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 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 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 30.3%, 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) 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.

[Comparative Example 2]
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 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 30.5%, 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 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 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 5 and Comparative Examples 1 to 4 in terms of 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, antifoam (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 5 and Comparative Examples 1 to 4 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 make conditions such as ambient climate and walking frequency uniform, tests on the floor polish obtained from the aqueous polyurethane resin dispersions of Example 1 and Comparative Examples 1 to 4 were simultaneously performed. The results are shown in Table 1 as “Gloss maintenance property (Test condition 1)”.

  When Example 1 and Comparative Examples 1 to 4 were compared, it became clear that the gloss retention of the floor polish was increased by changing the total concentration of urethane groups and urea groups in (A) polyurethane resin. When the total concentration of urethane groups and urea groups and the alicyclic content in the aqueous polyurethane resin dispersion are within a predetermined range, at least one of the total concentration of urethane groups and urea groups and the alicyclic content is predetermined. It can be seen that the gloss maintainability is higher than those of Comparative Examples 1 to 4, which are larger or smaller than the above range.

Next, the same test was performed on the polishing agents of Examples 1 to 5 during 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 1, the gloss value was 70 in the test of “gloss maintenance property (test condition 1)”.
Further, in order to clarify the durability performance of the floor polish of the present invention in more detail, a black heel mark resistance property and a stain resistance test were conducted.

(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 black heel mark resistance

(Stain resistance)
The compositions of Examples 1 and 2 were applied to white homogeneous vinyl floor tiles (15 cm × 10 cm: “MS Plane 5601 (trade name)” manufactured by Toli Co., Ltd.) respectively (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

  The results of the gloss maintenance test for the floor polishes of Examples 1 to 5 (test condition 2) and the evaluation results of the black heel mark resistance were compared with the stain resistance of the floor polishes of Examples 1 and 2. The results are shown in Table 2.

In the gloss maintenance property test period (test condition 2) shown in Table 2, the gloss value of the polishing agent of Example 1 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.
Table 2 also revealed that the film obtained with the floor polish composition of the present invention exhibited high stain resistance and black heel mark properties over a long period of time. Moreover, it became clear that when the (A) polyurethane resin contains an ether group, the black heel mark resistance is further improved.
In this test, the gloss retention and other durability performances of the aqueous polyurethane resin dispersion of the present invention were shown by using a floor polish as a representative example, but these effects are limited to the floor polish. It is understood that the same effect will be obtained in other applications.

  The aqueous polyurethane resin dispersion of the present invention can be widely used as a raw material for paints, coating agents, primers, adhesives, inks, films and the like. In addition, the aqueous polyurethane resin dispersion of the present invention has high gloss maintenance when producing a floor polish. Furthermore, since it has high durability performance such as stain resistance and black heel mark resistance, it is suitable for improving aesthetics and is used effectively in the building maintenance industry.

Claims (6)

(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) The polyurethane resin contains a carbonate group, and the total concentration of the urea group and the urethane group is 14.5% by mass or more and 20% by mass or less,
(A) The aqueous polyurethane resin dispersion whose content rate of the alicyclic structure in a polyurethane resin is 15 to 30 mass%.   The aqueous polyurethane resin dispersion according to claim 1, wherein (A) the polyurethane resin further contains an ether group.   (A) The water-based polyurethane resin dispersion of Claim 2 whose density | concentration of the ether group in a polyurethane resin is 1.5 mass% or more and 3.7 mass% or less.   The coating composition containing the water-based polyurethane resin dispersion as described in any one of Claims 1-3.   The coating agent composition containing the water-based polyurethane resin dispersion as described in any one of Claims 1-3.   The ink composition containing the water-based polyurethane resin dispersion as described in any one of Claims 1-3.