JP6535827B2 - Polyurethane water dispersion, method of producing polyurethane water dispersion, water-based paint composition and coating film - Google Patents

Description

  The present invention relates to a polyurethane water dispersion, a method of producing a polyurethane water dispersion, a water-based paint composition, and a coating film. This application claims the priority based on Japanese Patent Application No. 2017-122609 filed on June 22, 2017, and incorporates all the contents described in the aforementioned Japanese application.

  For the purpose of surface protection of vehicle interior materials, audio equipment, personal computers, cellular phones, etc., a paint is applied to the surface to form a coating. As such a paint, methods using a solvent-based urethane resin composition or a urethane-modified acrylic resin composition have been proposed (for example, Patent Document 1 and Patent Document 2).

  In addition, there is a case where the surface of such a coating film is corroded by an ultraviolet absorber contained in cosmetics, sunscreen agents and the like. As a countermeasure, a method of using a polyurethane composition as the above-mentioned paint has been proposed (for example, Patent Document 3).

JP 2012-121984 A JP 2012-97127 A JP, 2016-169306, A

  In the urethane-based composition for protecting the surface of the substrate as described above, the flaws generated on the surface impair the design. Therefore, it is desirable to have a self-repairing property that naturally repairs the generated wound. In addition, it is desirable that the coating film on the surface of the substrate has resistance to an ultraviolet absorber (resistance to ultraviolet absorber). Furthermore, from the viewpoint of environmental protection in recent years, aqueous dispersions that do not contain an organic solvent as a main ingredient are required as the coating composition.

  Therefore, an environmentally-friendly water-based polyurethane dispersion capable of forming a coating film having self-healing properties and UV absorber resistance, a method of producing a polyurethane water dispersion, a water-based paint composition, and those are used One object is to provide a coating film.

  The polyurethane aqueous dispersion of the present application is a neutralized product of water, an OH group-containing polyurethane and a tertiary amine dispersed in water, wherein the OH group-containing polyurethane has an OH group at the molecular chain terminal, Contains an object. The OH group-containing polyurethane is derived from a structural unit (A1) derived from a polyol (A), a structural unit (B1) derived from a first diol (B), and a polyhydric alcohol (C) in a molecular chain Structural unit (C1), the structural unit (D1) derived from the second diol (D), and the structural unit (E1) derived from the diisocyanate component (E). The polyol (A) is at least one of a polycarbonate polyol and a polyester polyol, and is a polyol having a number average molecular weight of 500 or more and 5,000 or less. The first diol (B) is a diol having a number average molecular weight of 500 or less and having no carboxy group. The polyhydric alcohol (C) is a polyhydric alcohol having a number average molecular weight of 500 or less and a number of functional groups per molecule of more than 2 and 4 or less. The second diol (D) is a diol having a carboxy group. The diisocyanate component (E) contains xylylene diisocyanate (Ea). The structural unit (E1) also includes a structural unit (E1a) derived from xylylene diisocyanate (Ea). The weight average molecular weight of the OH group-containing polyurethane is 16000 or more and 140000 or less.

  According to the polyurethane water dispersion of the present invention, an environmentally-friendly water-based polyurethane dispersion capable of forming a coating film having self-healing properties and UV resistance resistance, a method of producing the polyurethane water dispersion, An aqueous coating composition and a coating film using them can be provided.

It is a flowchart which shows the typical process of the manufacturing method of the polyurethane water dispersion concerning one Embodiment of this invention.

Description of an embodiment of the present invention
First, embodiments of the present invention will be listed and described. The polyurethane water dispersion according to the present invention is a neutralized product of water, an OH group-containing polyurethane and a tertiary amine dispersed in water, and the OH group-containing polyurethane has an OH group at the molecular chain terminal, And a neutralized product. The OH group-containing polyurethane is derived from a structural unit (A1) derived from a polyol (A), a structural unit (B1) derived from a first diol (B), and a polyhydric alcohol (C) in a molecular chain Structural unit (C1), the structural unit (D1) derived from the second diol (D), and the structural unit (E1) derived from the diisocyanate component (E). The polyol (A) is at least one of a polycarbonate polyol and a polyester polyol, and is a polyol having a number average molecular weight of 500 or more and 5,000 or less. The first diol (B) is a diol having a number average molecular weight of 500 or less and having no carboxy group. The polyhydric alcohol (C) is a polyhydric alcohol having a number average molecular weight of 500 or less and a number of functional groups per molecule of more than 2 and 4 or less. The second diol (D) is a diol having a carboxy group. The diisocyanate component (E) contains xylylene diisocyanate (Ea). The structural unit (E1) also includes a structural unit (E1a) derived from xylylene diisocyanate (Ea). The weight average molecular weight of the OH group-containing polyurethane is 16000 or more and 140000 or less. With such a polyurethane water dispersion, it becomes possible to form a coating film having self-healing properties and UV absorber resistance. In addition, by adopting water as a solvent, it is possible to provide an environmentally friendly polyurethane water dispersion.

  In the polyurethane water dispersion, the proportion of the structural unit (A1) derived from the polyol (A) in the molecular chain of the OH group-containing polyurethane may be 10% to 60% by mass in mass conversion. Such a feature makes it possible to form a coating film which is more excellent in self-repairing property and in ultraviolet absorber resistance.

All OH groups contained in all polyols derived from the structural unit (A1), the structural unit (B1), the structural unit (C1), and the structural unit (D1) and the structural unit (E1) Assuming that all NCO groups contained in the diisocyanate react with each other, and assuming that the total number of OH groups contained in the hypothetical OH group-containing polyurethane molecule formed by the reaction is f value, the calculated molecular weight of the hypothetical OH group-containing polyurethane is 1000 The f ₁₀₀₀ value, which is the average value of the f values per, may be 2.1 or more and 2.9 or less. Such a feature makes it possible to form a coating film which is more excellent in self-repairing property and in ultraviolet absorber resistance.

  14 or more and 55 or less may be sufficient as the acid value of OH group containing polyurethane. Such a feature makes it possible to form a coating film which is more excellent in self-repairing property and in ultraviolet absorber resistance.

  The structural unit (E1) is a structural unit (E1 b) derived from at least one diisocyanate selected from the group consisting of aromatic diisocyanate compounds other than xylylene diisocyanate (Ea), alicyclic diisocyanate compounds and aliphatic diisocyanate compounds. ) May be further included. Such features make it possible to more reliably form a coating film having self-healing properties and resistance to ultraviolet light.

  The polyol (A) may be a polycarbonate polyol mainly composed of at least one of 1,6-hexanediol and 1,4-cyclohexanedimethanol. The polyol (A) may be mainly composed of lactone and polyester polyol. Such features make it possible to form an excellent coating film by the self-repairing property and the UV absorber resistance. In the present specification, "mainly" means that the ratio is 50% by mass or more, preferably 75% by mass or more. For example, the component X mainly comprises A means that 50% by mass or more of the substance constituting the component X is A. That is, 50% by mass or more of the polycarbonate polyol may be at least one of 1,6-hexanediol and 1,4-cyclohexanedimethanol. Further, 50% by mass or more of the polyester polyol may be lactone.

  The structural unit (C1) derived from a polyhydric alcohol may be mainly composed of a structural unit consisting of trimethylolpropane. By using such a polyurethane water dispersion, it becomes possible to form a coating film excellent in self-repairing property and ultraviolet absorber resistance.

  The structural unit (B1) derived from the first diol may be mainly composed of a structural unit consisting of 1,4-cyclohexanedimethanol. By using such a polyurethane water dispersion, it becomes possible to form a coating film excellent in self-repairing property and ultraviolet absorber resistance.

  The present invention also relates to a method of producing the above-mentioned polyurethane water dispersion. The production method of the present invention is a production method of a polyurethane water dispersion, comprising a polyol (A), a first diol (B), a polyhydric alcohol (C), and a second diol (D). A polyurethane synthesis step (1) of reacting an OH group-containing polyurethane having a weight average molecular weight of 16000 or more and 140000 or less by reacting with a diisocyanate component (E), and neutralization of the synthesized OH group-containing polyurethane from tertiary amine Preparation step of preparing a polyurethane water dispersion in which the neutralized product is dispersed in water by dispersing the neutralized product formed in the neutralization process (2) and the neutralized product formed by the neutralization process in water 3) and. According to this method, it is possible to provide a water-based polyurethane dispersion capable of forming a coating film having self-healing properties and UV absorber resistance.

  In the polyurethane synthesis step (1), the proportion of the structural unit (A1) derived from the polyol (A) in the entire OH group-containing polyurethane synthesized in the polyurethane synthesis step (1) is 10% by mass or more in mass ratio 60 It may be mass% or less. By adjusting the proportion of the structural unit (A1) as described above, it becomes possible to form a coating film which is more excellent in self-repairing property and ultraviolet absorber resistance.

In the polyurethane synthesis step (1), all OH groups contained in all polyols derived from the structural unit (A1), the structural unit (B1), the structural unit (C1), and the structural unit (D1), Assuming that all the NCO groups contained in the diisocyanate from which the structural unit (E1) is derived react, and assuming that the total number of OH groups contained in the hypothetical OH group-containing polyurethane molecule formed by the reaction is f value, The f ₁₀₀₀ value, which is an average value of f values per calculated molecular weight 1000 of the hypothetical OH group-containing polyurethane, may be 2.1 or more and 2.9 or less. By adjusting the f ₁₀₀₀ value to be in the above range and performing the reaction, it becomes possible to form a coating film having better self-healing properties and ultraviolet absorber resistance.

  In the polyurethane synthesis step (1), the reaction may be performed such that the acid value of the OH group-containing polyurethane is 14 or more and 55 or less. By adjusting the acid value in this manner, it is possible to form a coating film having better self-healing properties and UV absorber resistance.

  The diisocyanate component (E) is at least one selected from the group consisting of xylylene diisocyanate (Ea) and aromatic diisocyanate compounds other than xylylene diisocyanate (Ea), alicyclic diisocyanate compounds, and aliphatic diisocyanate compounds. And the diisocyanate (Eb) may be further included. By further including the diisocyanate (Eb), it is possible to more reliably provide a polyurethane water dispersion capable of reliably forming a coating film having self-healing properties and UV absorber resistance.

  The present invention further provides, as a first dispersion, the above-mentioned polyurethane water dispersion, and as a second dispersion, a carbodiimide crosslinking agent water dispersion containing 150 equivalents or more and 600 equivalents or less of carbodiimide groups as nonvolatile components, and nonvolatile components The present invention also relates to a water-based paint composition comprising at least one dispersion of a polyisocyanate crosslinking agent dispersion containing an isocyanate group in an amount of 5% by mass to 25% by mass in terms of mass. By employing such a water-based paint composition, it is possible to form a coating film having self-healing properties and UV absorber resistance.

  Multi-liquid type comprising a first liquid containing the above aqueous coating composition polyurethane water dispersion, and a second liquid containing a dispersion of at least one of a carbodiimide crosslinking agent water dispersion and a polyisocyanate crosslinking agent dispersion It may be a paint composition. By employing such a multi-component coating composition, coating can be carried out more easily and reliably.

  The above aqueous coating composition comprises a carbodiimide group (N = C = N group) in a carbodiimide crosslinking agent contained in a carbodiimide crosslinking agent water dispersion, and a carboxy group (COOH (COOH group) in an OH group-containing polyurethane contained in a polyurethane water dispersion. 0.30 or more and 1.7 or less may be sufficient as N = C = N / COOH ratio which is equivalent ratio with group. By employing such a water-based paint composition, it is possible to form a coating film which is more excellent in self-healing property and ultraviolet light absorber resistance.

  The above aqueous coating composition is an equivalent ratio of the isocyanate group (NCO) in the polyisocyanate crosslinking agent contained in the polyisocyanate crosslinking agent dispersion and the OH group in the OH group-containing polyurethane contained in the polyurethane water dispersion. The NCO / OH ratio may be 0.30 or more and 2.5 or less. By employing such a water-based paint composition, it is possible to form a coating film which is more excellent in self-healing property and ultraviolet light absorber resistance.

  The present invention also relates to a coating formed by applying the polyurethane water dispersion or the water-based paint composition on a substrate. Such coatings have self-healing properties and resistance to ultraviolet light.

[Details of the Embodiment of the Present Invention]
Next, details of the embodiment of the present invention will be described. The polyurethane water dispersion according to one embodiment of the present invention is a neutralized product of water, an OH group-containing polyurethane and a tertiary amine dispersed in water, wherein the OH group-containing polyurethane has OH at the molecular chain terminal. And a neutralized product having a group. The OH group-containing polyurethane is derived from a structural unit (A1) derived from a polyol (A), a structural unit (B1) derived from a first diol (B), and a polyhydric alcohol (C) in a molecular chain Structural unit (C1), the structural unit (D1) derived from the second diol (D), and the structural unit (E1) derived from the diisocyanate component (E). The polyol (A) is at least one of a polycarbonate polyol and a polyester polyol, and is a polyol having a number average molecular weight of 500 or more and 5,000 or less. The first diol (B) is a diol having a number average molecular weight of 500 or less and having no carboxy group. The polyhydric alcohol (C) is a polyhydric alcohol having a number average molecular weight of 500 or less and a number of functional groups per molecule of more than 2 and 4 or less. The second diol (D) is a diol having a carboxy group. The diisocyanate component (E) contains xylylene diisocyanate (Ea). The structural unit (E1) also includes a structural unit (E1a) derived from xylylene diisocyanate (Ea). The weight average molecular weight of the OH group-containing polyurethane is 16000 or more and 140000 or less.

  The polyurethane water dispersion is a dispersion or an emulsion in which a neutralized product obtained by neutralizing the above OH group-containing polyurethane is dispersed in water. By adopting such a configuration, it is possible to sufficiently perform the function as a surface protecting agent for a base material or a casing, having self-repairing property and ultraviolet ray absorbing agent property.

  The polyurethane water dispersion according to an embodiment of the present invention is a so-called water-based polyurethane dispersion. Therefore, the environmental load can be reduced as compared with the organic solvent polyurethane dispersion.

  Next, the configuration of the OH group-containing polyurethane will be described. The OH group-containing polyurethane is a neutralized product of an OH group-containing polyurethane and a tertiary amine. The OH group-containing polyurethane has a number average molecular weight of 500 and a structural unit (A1) derived from a polyol having at least one of a polycarbonate polyol and a polyester polyol and having a number average molecular weight of more than 500 and 5000 or less in the molecular chain. And a polyvalent compound having a number average molecular weight of 500 or less and a number of functional groups per molecule of more than 2 and 4 or less, which are derived from the first diol having no carboxy group and not having a carboxy group: It includes a structural unit (C1) derived from an alcohol, a structural unit (D1) derived from a second diol having a carboxy group, and a structural unit (E1) derived from a diisocyanate.

[About structural unit (A1)]
The OH group-containing polyurethane contains a structural unit (A1) derived from the polyol (A) in the molecular chain. Here, the polyol (A) is at least one of a polycarbonate polyol and a polyester polyol, and is a polyol having a number average molecular weight of more than 500 and not more than 5000.

  The structural unit (A1) is formed of a polyol (A) which is at least one of a polycarbonate polyol and a polyester polyol and has a number average molecular weight of more than 500 and 5,000 or less. The structural unit derived from the polycarbonate polyol and the structural unit derived from the polyester polyol are formed by using the polycarbonate polyol having the above-described number average molecular weight and the polyester polyol having the above-described number average molecular weight as raw materials, respectively.

  The polycarbonate polyol is obtained by, for example, dealcoholizing reaction or dephenoling reaction of a compound of polyols and a compound of carbonates.

  The compounds of the polyols which can be used for the synthesis of the polycarbonate polyol are not particularly limited, and examples thereof include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,1 3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,6-octanediol 9-nonanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, and diols such as sorbitol ring diol, and trimethylolpropane, glyol Phosphorus, and include polyhydric alcohols such as pentaerythritol. As compounds of polyols, one type may be used alone, or two or more types may be used in combination. Among them, it is preferable to use a polycarbonate polyol mainly composed of at least one of 1,6-hexanediol and 1,4-cyclohexanedimethanol. By using one of 1,4-cyclohexanedimethanol and 1,6-hexanediol alone or by using both in combination, a coating film having more excellent self-healing properties and UV absorber resistance can be obtained. Polyurethane water dispersions that can be formed can be formed.

  As a compound of carbonates used for the synthesis | combination of the said polycarbonate polyol, ethylene carbonate, a dimethyl carbonate, a diethyl carbonate, diphenyl carbonate etc. are mentioned, for example. As a compound of carbonates, one type may be used alone, or two or more types may be used in combination.

  The polyester polyol is obtained by co-condensation or polycondensation reaction between a carboxylic acid component and a diol and / or a polyhydric alcohol used in the synthesis of the polycarbonate polyol. The polyester polyol may be mainly composed of lactone. In particular, by using a polyester polyol mainly composed of lactone, it is possible to form a polyurethane water dispersion capable of forming a coating film having more excellent self-healing properties and UV absorber resistance.

  The structural unit (A1) can be formed, for example, by co-condensation of a polyester polyol. Polyester polyols are, for example, at least one of the diols and polyhydric alcohols mentioned above as usable in the synthesis of polycarbonate polyols, and at least one of succinic acid, adipic acid, azelaic acid, isophthalic acid, sebacic acid, terephthalic acid and isophthalic acid. Co-treatment with dicarboxylic acids such as acid, orthophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,4-cyclohexanedicarboxylic acid, etc. or oils such as castor oil It is possible to obtain by condensation reaction.

  The structural unit (A1) can also be formed, for example, by the polycondensation reaction of lactone polyol. For example, the structural unit (A1) can also be obtained by the polycondensation reaction of a diol and / or a lactone such as ε-caprolactone, δ-valerolactone, 3-methyl-δ-valerolactone and the like used in the synthesis of a polycarbonate polyol. Among these, it is particularly preferable to use ε-caprolactone.

  The structural unit (A1) constituting the OH group-containing polyurethane constitutes a molecular chain derived from a polyol (A) having at least one of a polycarbonate polyol and a polyester polyol and having a number average molecular weight of more than 500 and 5,000 or less. Unit to be By setting it as such a number average molecular weight, the coating film more excellent by self-healing property and an ultraviolet absorber resistance property can be formed more reliably.

[Structural unit (B1)]
The OH group-containing polyurethane contains a structural unit (B1) derived from the first diol (B) in the molecular chain. The first diol (B) is a diol having a number average molecular weight of 500 or less and having no carboxy group. That is, the structural unit (B1) is a structural unit that does not overlap with the structural unit (A1).

  Examples of the structural unit (B1) derived from the first diol are the diols described above as compounds of polyols which can be used for the synthesis of polycarbonate polyols, among which diol (B) having no carboxy group The structural unit derived from is mentioned. Among them, particularly, as the above-mentioned diol (B), 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol and the like can be mentioned. Among them, the structural unit (B1) derived from the first diol is preferably mainly composed of a structural unit consisting of 1,4-cyclohexanedimethanol.

  As the diol (B), one having a number average molecular weight of 500 or less is employed. Thereby, both self-repairing property and ultraviolet absorber resistance can form a more superior coating film. Moreover, it also becomes possible to give sufficient hardness to a coating film.

[Structural Unit (C1)]
The OH group-containing polyurethane contains a structural unit (C1) derived from a polyhydric alcohol (C) in a molecular chain. The polyhydric alcohol (C) is a polyhydric alcohol having a number average molecular weight of 500 or less and a number of functional groups per molecule of more than 2 and 4 or less. That is, the structural unit (C1) is a structural unit that does not overlap with the structural unit (A1) and the structural unit (B1).

  Examples of the polyhydric alcohol (C) include, but are not particularly limited to, trihydric alcohols such as glycerin and trimethylolpropane, tetrahydric alcohols such as tetramethylolmethane (pentaerythritol) and diglycerin, and the above-mentioned trihydric alcohols or These include PO or EO adducts of tetrahydric alcohols, castor oil and the like. Among them, the structural unit (C1) derived from a polyhydric alcohol is preferably mainly composed of a structural unit consisting of trimethylolpropane.

  The polyhydric alcohol compound (C) has a number average molecular weight of 500 or less, and the number of functional groups per molecule is more than 2 and 4 or less. By configuring in this manner, the crosslink density can be improved, and a coating film can be formed which is more excellent in self-repairing property and ultraviolet absorber resistance. In addition, the improvement of the solubility provides a highly transparent polyurethane water dispersion.

[Structural unit (D1)]
The OH group-containing polyurethane contains a structural unit (D1) derived from the second diol (D) having a carboxy group in the molecular chain. That is, the structural unit (D1) is a structural unit that does not overlap with the structural unit (B1) and the structural unit (C1).

  The second diol (D) having a carboxy group, which is the origin of the structural unit (D1), is not particularly limited, and di-methanes such as 2,2-dimethylol propionic acid and 2,2-dimethylol butanoic acid are not particularly limited. Methylolalkanoic acid, N, N-bishydroxyethyl glycine, N, N-bishydroxyethyl alanine, 3,4-dihydroxybutane sulfonic acid, 3,6-dihydroxy-2-toluene sulfonic acid, acidic group-containing polyether polyol, An acidic group containing polyester polyol etc. are mentioned. Among the above, dimethylolalkanoic acid is preferable, and 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid are more preferable. These may be used alone or in combination of two or more.

[Structural unit (E1)]
The OH group-containing polyurethane contains a structural unit (E1) derived from the diisocyanate component (E) in the molecular chain. The diisocyanate component (E) contains xylylene diisocyanate (Ea). The structural unit (E1) also includes a structural unit (E1a) derived from xylylene diisocyanate (Ea).

  The structural unit (E1a) derived from xylylene diisocyanate (Ea) is formed by using xylylene diisocyanate (Ea) as a raw material. Xylylene diisocyanate (Ea) is a type of aromatic diisocyanate. In the present invention, by having the structural unit (E1a) derived from xylene diisocyanate (Ea), it is possible to provide a polyurethane water dispersion capable of forming a coating film having further improved resistance to ultraviolet light.

  The structural unit (E1) derived from the diisocyanate is at least one diisocyanate selected from the group consisting of aromatic diisocyanate compounds other than xylylene diisocyanate (Ea), alicyclic diisocyanate compounds, and aliphatic diisocyanate compounds (Eb) The structural unit (E1 b) derived from may be further included. The structural unit (E1b) uses as raw material at least one diisocyanate (Eb) selected from the group consisting of aromatic diisocyanate compounds other than xylylene diisocyanate (Ea), alicyclic diisocyanate compounds and aliphatic diisocyanate compounds It is formed by

  The aromatic cyclic diisocyanate is not particularly limited, and examples thereof include diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylene-1,4-diisocyanate, and xylene-1,3-1, Diisocyanate, tetramethylxylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate and the like can be mentioned.

  The alicyclic diisocyanate is not particularly limited. For example, isophorone diisocyanate, 1,3-cyclopentadiisocyanate, 1,3-cyclohexanediisocyanate, 1,4-cyclohexanediisocyanate, cyclohexyl diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, Dicyclohexylmethane diisocyanate, bis (4-isocyanatocyclohexyl) methane, 1,3-bisisocyanatomethylcyclohexane, 1,4-bisisocyanatomethylcyclohexane, norbornane diisocyanate, hydrogenated diphenylmethane diisocyanate, norbornane diisocyanate, hydrogenated tolylene diisocyanate Hydrogenated xylene diisocyanate, and water Added tetramethyl xylene diisocyanate.

  The aliphatic diisocyanate is not particularly limited. For example, hexamethylene diisocyanate, tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, trimethylhexamethylene diisocyanate, 2-methyl-pentane-1,5-diisocyanate, 3-methyl-pentane 1,5-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, lysine isocyanate, trioxyethylene diisocyanate, norbornene diisocyanate and the like.

[About tertiary amine]
The polyurethane water dispersion according to the present embodiment contains a neutralized product of an OH group-containing polyurethane and a tertiary amine dispersed in water. The tertiary amine functions as a neutralizing agent for the OH group-containing polyurethane.

  The above-mentioned tertiary amine compound for neutralizing OH group-containing polyurethane is not particularly limited, but trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, dimethylethanol Amines, diethylethanolamine, N-methylmorpholine, pyridine and the like can be mentioned. Among them, dimethyl ethanolamine and triethylamine are preferred. These may be used alone or in combination of two or more.

[Polyurethane water dispersion]
The polyurethane water dispersion according to the present embodiment contains water, and a neutralized product of an OH group-containing polyurethane and a tertiary amine dispersed in water. The OH group-containing polyurethane has an OH group at the molecular chain terminal. The amount of the neutralized product, the amount of the dispersion medium, and the ratio thereof are not particularly limited, and the amount and the ratio necessary for sufficiently dispersing the OH group-containing polyurethane are appropriately selected.

[About OH group-containing polyurethane]
As described above, the OH group-containing polyurethane contained in the polyurethane water dispersion according to the present embodiment is the above-mentioned structural unit (A1), structural unit (B1), structural unit (C1), structural unit (D1), And the structural unit (E1).

  In the OH group-containing polyurethane, the proportion of the structural unit (A1) derived from the polyol in the molecular chain of the OH group-containing polyurethane is preferably 10% by mass to 60% by mass in mass conversion. Such a ratio is 10% by mass or more of the mass ratio of the polyol (A), which is at least one of the polycarbonate polyol and the polyester polyol from which the structural unit (A1) originates, to the entire OH group-containing polyurethane. This can be achieved by setting the content to less than mass%. By setting the ratio to 10% by mass or more and 60% by mass or less, it is possible to more reliably provide a polyurethane water dispersion that can form a coating film exhibiting self-healing properties and ultraviolet absorber resistance.

In addition, all OH groups contained in all the polyols derived from the structural unit (A1), the structural unit (B1), the structural unit (C1), and the structural unit (D1), and the structural unit (E1) Assuming that all NCO groups contained in a certain diisocyanate react with each other and assuming that the total number of OH groups contained in the hypothetical OH group-containing polyurethane molecule formed by the reaction is f value, the calculated molecular weight of the hypothetical OH group-containing polyurethane The f ₁₀₀₀ value, which is the average value of f values per 1000, is preferably 2.1 or more and 2.9 or less.

An example of how to determine the value of f ₁₀₀₀ (however, the method is not limited to this method) is shown below.

First, the calculated molecular weight is calculated.
Calculated total molecular weight = [(molecular weight of each raw material) x (mol number of each raw material)] x coefficient n

The coefficient n is determined as follows. For example, it is assumed that the OH raw material and the NCO raw material react to form an OH-terminated polyurethane. When the raw material is divalent or higher, the polyol is always synthesized as [(x mol) +1 mol] with respect to polyisocyanate (x mol). The coefficient n is determined from this.
Coefficient n = 1 / {(total number of moles of polyol)-(total number of moles of polyisocyanate)}

Next, f value is determined. The f value means all OH groups contained in all polyols derived from the structural unit (A1), the structural unit (B1), the structural unit (C1), and the structural unit (D1), and the structural unit (E1) And the total number of OH groups contained in the hypothetical OH group-containing polyurethane molecule formed by the reaction with all the NCO groups contained in the diisocyanate from which The f value is calculated as an average value per unit molecular weight calculated.
The above f value is
Mn (= calculated molecular weight) = 56.1 1 / OH group value x f x 1000
F value = (Mn × OH group valence) / (56.11 × 1,000)
(56.11 is potassium hydroxide molecular weight).

Next, an average value f ₁₀₀₀ per calculated molecular weight ₁₀₀₀ is calculated.
f ₁₀₀₀ = {(f−2) × (1000 / calculated molecular weight)} + 2
That is, assuming that both ends of the OH group-containing polyurethane molecule are OH groups, the f ₁₀₀₀ value is calculated by cutting out portions other than the both end OH groups from the OH group-containing polyurethane and connecting the cut out portion and both end OH groups It becomes a standard of the average value of the total OH group number which OH containing polyurethane has when the molecular model used as molecular weight 1000 is assumed.

An example of a method of calculating the average value f ₁₀₀₀ is shown below.
(A) ETERACOLL UC 100 (polycarbonate diol) (made by Ube Industries, Ltd.) as component (A) 0.46 (mol) × 1,000 (Mn) = 460, 1,4-CHD (1,4-cyclohexane as component (B) Dimethanol) (manufactured by Eastman Chemical Co., Ltd.) 2.3 (mol) × 144 (Mn) = 331.2, as component (C), TMP (trimethylolpropane) (manufactured by Evermore Japan) 0.4 (mol) ) .Times.134 (Mn) = 53.6, as component (D) DMPA (dimethylol propionic acid) (manufactured by Perstrop) 1.0 (mol) .times.134 (Mn) = 134, as component (Ea) Takenate 500 (xylylene diisocyanate) (manufactured by Mitsui Chemicals, Inc.) 2.0 (mol) x 188.2 (Mn) = 3 6.4, if it contains HDI (hexamethylene diisocyanate) (manufactured by Tosoh Corporation) 2.0 (mol) × 168.2 (Mn) = 336.4 as (Eb) component,
Total of [(molecular weight of each raw material) x (mol number of each raw material)] = 1691.6
Coefficient n = 1 / {(A) (mol) + (B) (mol) + (C) (mol) + (D) (mol)-(Ea) (mol)-(Eb) (mol)} = 1 /0.16=6.25
Calculated molecular weight = 1691.6 × 6.25 = 10572.5
OH group value = 56.11 × 0.72 × 1000 / 1691.6 = 23.88
f value = 4.50
Average value f _{1000 of} calculated molecular weight 1,000 per 1,000 f 2.24
It becomes.

  In the present embodiment, the acid value of the OH group-containing polyurethane is preferably 14 or more and 55 or less. By adjusting the above-mentioned acid value to the above-mentioned range, the synthesis of the OH group-containing polyurethane can be performed more reliably.

  The weight average molecular weight of the OH group-containing polyurethane is 16000 or more and 140000 or less. By setting it as such a specific range, excellent adhesiveness can be obtained by the improvement of the glossiness and the wettability to a substrate such as a plastic. It has excellent self-healing properties and is included in cosmetics, sunscreens and the like by forming a coating film with a polyurethane water dispersion comprising the OH group-containing polyurethane composition and an aqueous composition containing the polyurethane water dispersion. The coating film which can express durability with respect to a ultraviolet absorber can be obtained.

  Such a polyurethane water dispersion can reduce the environmental load, and can obtain a polyurethane water dispersion capable of forming a coating film having self-healing properties and UV absorber resistance. Further, according to the polyurethane water dispersion according to the present embodiment, it is possible to form a coating film further excellent in the appearance and the adhesion with the substrate.

[Water-based paint composition]
Next, the composition of the composition for water-based application concerning one embodiment of this invention is explained. The composition for water-based coating according to the present embodiment is a first dispersion comprising the above polyurethane water dispersion, and a second dispersion comprising carbodiimide groups containing 150 equivalents or more and 600 equivalents or less of carbodiimide groups as non-volatile components. And at least one dispersion of a polyisocyanate crosslinking agent dispersion containing an isocyanate group as a nonvolatile component in an amount of 5% by mass to 25% by mass in terms of mass. By using such a water-based coating composition, it is possible to provide a multi-component coating composition capable of forming a coating film having self-healing properties and UV absorber resistance.

  Moreover, the composition for water-based application | coating which concerns on this Embodiment contains the 1st liquid containing the said polyurethane water dispersion, a carbodiimide crosslinking agent water dispersion, and at least 1 type of dispersion among a polyisocyanate crosslinking agent dispersion. It is also possible to make a multi-liquid type paint composition containing the second liquid. Coating can be carried out more easily and reliably by using such a multi-component coating composition.

  The second liquid contains a carbodiimide dispersion-containing liquid, and the equivalent ratio of the content of carbodiimide group (N = C = N group) in the carbodiimide dispersion to the carboxy group (COOH group) of the polyurethane water dispersion A certain N = C = N / COOH ratio may be 0.30 or more and 1.7 or less. Such a water-based paint composition can form a coating film excellent in self-healing property and ultraviolet light absorber resistance.

  The second liquid contains a polyisocyanate dispersion-containing liquid and is an equivalent ratio of the content of isocyanate groups (NCO) in the polyisocyanate dispersion-containing liquid to the OH groups (OH groups) of the polyurethane water dispersion. The NCO / OH ratio may be 0.30 or more and 2.5 or less. Such a water-based paint composition can form a coating film excellent in self-healing property and ultraviolet light absorber resistance.

[Method of producing polyurethane water dispersion]
Next, a method of producing a polyurethane water dispersion according to an embodiment of the present invention will be described. The method for producing a polyurethane water dispersion according to the present embodiment includes a polyurethane synthesis step (1), a neutralization step (2), and a preparation step (3). FIG. 1 is a flowchart showing representative steps of a method of producing a polyurethane water dispersion according to one embodiment of the present invention.

  Referring to FIG. 1, first, the above-described first diol and the like are prepared as a preparation step (S11). That is, a polyol (A) which is at least one of polycarbonate polyol and polyester polyol and has a number average molecular weight of more than 500 and 5000 or less, and a number average molecular weight of 500 or less and does not have a carboxy group (B), a polyhydric alcohol (C) having a number average molecular weight of 500 or less and the number of functional groups per molecule being 2 or more and 4 or less, and a second diol (D) having a carboxy group And a diisocyanate component (E) containing xylylene diisocyanate (Ea).

  Next, a polyurethane synthesis step (1) for synthesizing an OH group-containing polyurethane is carried out (S12). In the polyurethane synthesis step (1), the polyol (A), the first diol (B), the polyhydric alcohol (C), the second diol (D), and the diisocyanate component (E) And react with) to synthesize an OH group-containing polyurethane having an OH group at the molecular chain terminal. In the polyurethane synthesis step (1), an OH group-containing polyurethane having a weight average molecular weight of 16000 or more and 140000 or less is synthesized. Further, the above reaction may be performed such that the proportion of the structural unit (A1) derived from the polyol (A) in the entire OH group-containing polyurethane synthesized is 10 mass% or more and 60 mass% or less in mass ratio The above reaction may be carried out so that the acid value of the OH group-containing polyurethane is 14 or more and 55 or less. In this step, the diisocyanate component (E) reacts with the other polyol components (A) to (D). Although the order of the reaction is not particularly limited, for example, the components (B), (C), and (D) are added stepwise, that is, after first reacting the component (A) with the component (E). By chain extension, the desired OH group-containing polyurethane can be synthesized.

  The synthesis of the OH group-containing polyurethane may be carried out in a solvent. The solvent is not particularly limited as long as it is a solvent substantially nonreactive with the isocyanate group and hydrophilic. For example, ketones such as acetone and ethyl methyl ketone, esters, ethers such as tetrahydrofuran and N-methylmorpholine, 3-methoxy-N, N-dimethylpropanamide, dimethylformamide, N-methylpyrrolidone and N-ethylpyrrolidone And the like. These may be used alone or in combination of two or more.

  Although the addition amount of the solvent is not particularly limited, it is preferably 10% to 150% by mass with respect to 100 parts by mass of the solid content of the OH group-containing polyurethane.

  Also, the reaction can be carried out in the presence of a catalyst. The type of the catalyst is not particularly limited. For example, metal catalysts such as tin-based catalysts (trimethyltin laurate, dibutyltin dilaurate etc.), Li-based catalysts, Bi-based catalysts, etc., amine-based catalysts (triethylamine, N-ethylmorpholine, triethylenediamine etc.) And diazabicycloundecene-based catalysts. Among them, from the viewpoints of reactivity and reduction of environmental load, Li-based / Bi-based combined metal catalyst is preferable.

  Next, a neutralization step (2) of neutralizing the synthesized OH group-containing polyurethane with a neutralizing agent consisting of a tertiary amine to form a neutralized product is performed (S13). More specifically, the OH group-containing polyurethane synthesized in the polyurethane synthesis step (1) is neutralized with a tertiary amine with a COOH group (carboxy group) contained in the OH group-containing polyurethane. The addition amount of the tertiary amine is appropriately determined in consideration of the amount of COOH group contained in the OH group-containing polyurethane before neutralization.

  Next, a polyurethane water dispersion in which the neutralized product neutralized in the neutralization step (2) is dispersed in water is prepared (S14). The method of preparing such a polyurethane water dispersion is not particularly limited. For example, using a stirrer, a homogenizer, or the like, the neutralized product obtained through steps S11 to S13 is dispersed in water charged in a container. The polyurethane water dispersion can be prepared by Further, the dispersion in water is not limited to the case after the neutralization product is obtained, and may be simultaneously dispersed while neutralizing the OH group-containing polyurethane. Therefore, steps S13 and S14 may not be completely separated, and at least a part of the steps may be common. For example, the polyurethane water dispersion can also be prepared by phase inversion emulsification or forced emulsification of an OH group-containing polyurethane using water to which a tertiary amine is added.

In the OH group-containing polyurethane synthesized in the polyurethane synthesis step (1), included in all polyols derived from the structural unit (A1), the structural unit (B1), the structural unit (C1), and the structural unit (D1) Assuming that all the OH groups to be reacted react with all the NCO groups contained in the diisocyanate from which the structural unit (E1) is derived, the total number of OH groups contained in the hypothetical OH group-containing polyurethane molecule formed by the reaction is When f value is used, f ₁₀₀₀ value which is an average value of f value per calculated molecular weight 1000 of the virtual OH group-containing polyurethane may be 2.1 or more and 2.9 or less.

  According to such a method of producing a polyurethane water dispersion, it is possible to easily produce a polyurethane water dispersion capable of reducing environmental impact and capable of forming a coating film having self-healing properties and UV absorber resistance. it can. Moreover, the coating film obtained from the polyurethane water dispersion formed by the manufacturing method of the polyurethane water dispersion in this Embodiment is excellent also in an external appearance and adhesiveness with a base material.

[Coating]
A coating can be formed from the above-mentioned polyurethane water dispersion or water-based paint composition. The coating film is formed by applying a polyurethane water dispersion or a water-based paint composition on a predetermined substrate and drying and curing it as required. Such a coating film has self-healing properties and UV absorber resistance.

[Use]
The above-mentioned polyurethane water dispersion or water-based paint composition can be used as a surface protection material for various substrates. For example, for the purpose of surface protection of vehicle interior materials, audio equipment, personal computers, mobile phones, etc., the above-mentioned polyurethane water dispersion or water-based paint composition is coated on a substrate to form a coating film, thereby achieving self-repairability It is possible to use as an ultraviolet absorber resistance and a surface protection material.

  The present invention will be specifically described below with reference to examples. The scope of the present invention is not construed as being limited by the description of these examples.

  In Examples 1 to 40 and Comparative Examples 1 to 7, polyurethane water dispersions were produced based on the compounding ratios shown in Tables 1 to 16 below. In the text below, "parts" means parts by mass. Moreover, the unit in the compounding ratio shown to Table 1-Table 16 is the mass% unless there is particular notice. In Tables 1 to 16, the description of Example 1 and the like is described multiple times from the viewpoint of easy understanding.

The weight average molecular weight of the OH group-containing polyurethane obtained in the polyurethane synthesis step (1) was measured as follows: GPC: manufactured by Showa Denko KK, Shodex GPC-101 column LF 804, styrene conversion sample concentration 0. 2 vol%, diluted with THF

Example 1
0.5 parts of JPP 100 (tetraphenyl dipropylene glycol diphosphite) (manufactured by Johoku Chemical Industry Co., Ltd.) as a phosphite-based antioxidant in a reactor, and ETERNACOLL UC 100 (polycarbonate diol) as a component (A) Dissolve 135.56 parts of Ube Industries, Ltd., in 55.56 parts of KJCMPA-100 (3 methoxy-NN-dimethylpropanamide) (KJ Chemicals, Inc.) as a solvent, and Borchi Kat 0243 (metal) as a catalyst Catalyst) (Borchers's product) 0.004 part is charged, stirred and dissolved sufficiently, 110.92 parts of Takenate 500 (xylylene diisocyanate) (made by Mitsui Chemicals, Inc.) as component (Ea), HDI as component (Eb) Hexamethylene diisocyanate) ( Added manufactured by Tosoh Corporation) 99.14 parts of reaction time of 2 hours at 85 ° C.. Next, after cooling to 60 ° C., 39.49 parts of DMPA (dimethylol propionic acid) (manufactured by Perstrop) as component (D), 1,4-CHD (1,4 cyclohexane as component (B) 97.6 parts of dimethanol) (manufactured by Eastman Chemical Co., Ltd.), 15.8 parts of TMP (trimethylolpropane) (manufactured by Evermore Japan) as component (C), MEK (methyl ethyl ketone) (manufactured by Idemitsu Kosan Co., Ltd.) 213.68 parts were added, sufficiently stirred and dissolved, 0.032 parts of Borchi Kat 0243 as a catalyst was added, and reaction was carried out at 80 ° C. for 5 hours. Here, the reaction was performed until the isocyanate value (mass content of the residual isocyanate group to the solid content) became 0.01% or less, and a polyurethane having an OH group at the end was obtained. In this polyurethane, 0.5 parts of TINUVIN 234 (Phenol, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) (manufactured by BASF), TINUVIN 770 (sebacic acid) 0.5 parts of bis (2,2,6,6-tetramethyl-4-piperidyl)) (manufactured by BASF Corp.) and 230.77 parts of MEK were added, sufficiently stirred to dissolve, and cooled to 50 ° C. Thereafter, 26.27 parts of DMEA (N, N-dimethylethanolamine) (manufactured by Nippon Emulsifier Co., Ltd.) were added for neutralization, and then 973.73 parts of water was added to carry out phase inversion emulsification. The aqueous dispersion of polyurethane according to Example 1 containing a terminal OH group-containing polyurethane having a nonvolatile content of 30%, an acid value of 33.17, a hydroxyl value of 23.88 and a pH of 8.6 by removing the solvent of the obtained emulsion. I got a body.

  Next, a water-based paint composition was produced using the obtained polyurethane water dispersion. An example of the formulation is as follows. TEGO FOAMEX 800 (polyoxyethylene stearyl ether, denoted as "TEG 800" in the table) as an antifoaming agent with respect to 100 parts of a polyurethane water dispersion having a nonvolatile content of 30% (indicated as "EM resin" in the table) (EVONIK) Co., Ltd.) 0.1 part, BYK-3455 (polyether modified polydimethylsiloxane) (made by Bick Chemie Co., Ltd.) as a leveling agent 0.15 part, as a crosslinking agent, Carbodilight V 02 (carbodiimide, non-volatile matter 40%, carbodiimide equivalent) 590) (Nisshinbo Chemical Co., Ltd.) is added in the specified amount shown in Table 1, and the viscosity is increased to about 1000 (mPa · s / ° C.) with Adecanol UH450 (urethane type) (made by ADEKA) as a thickener. It degased and produced the water-based paint composition concerning Example 1.

(Example 2)
A polyurethane water dispersion according to Example 2 was obtained in the same process as in Example 1 without containing HDI as the component (Eb) and using Takenate 500 etc. as the component (Ea) in the formulation shown in Table 1. Obtained. Moreover, the water-based paint composition which concerns on Example 2 by the mixing | blending shown in Table 1 similarly to Example 1 was produced from the obtained polyurethane water dispersion.

(Example 3)
By using lupranate MI (2,4 '/ 4,4'-diphenylmethane diisocyanate) (manufactured by BASF Corporation) as the component (Eb) instead of HDI, the composition shown in Table 1 such as Takenate 500 as the component (Ea) It was made to contain and the polyurethane water dispersion concerning Example 3 was obtained at the process similar to Example 1. Further, from the obtained polyurethane water dispersion, in the same manner as in Example 1, a water-based paint composition according to Example 3 was produced with the composition shown in Table 1.

(Example 4)
As the component (Eb), using Dismodule I (isophorone diisocyanate) (manufactured by Bayer) in place of HDI, and containing Takenate 500 etc. as the component (Ea) in the composition shown in Table 1, as in Example 1. The polyurethane water dispersion concerning Example 4 was obtained at the process of (1). Moreover, the water-based paint composition which concerns on Example 4 by the mixing | blending shown in Table 1 similarly to Example 1 from the obtained polyurethane water dispersion was produced.

(Comparative example 1)
A polyurethane water dispersion according to Comparative Example 1 is obtained in the same process as in Example 1 except that Takenate 500 as the component (Ea) is not contained, and lupranate MI etc. is included as the component (Eb) in Table 2 The Moreover, the water-based paint composition which concerns on the comparative example 1 by the mixing | blending shown in Table 2 similarly to Example 1 from the obtained polyurethane water dispersion was produced.

(Comparative example 2)
The polyurethane water dispersion according to Comparative Example 2 is obtained in the same process as in Example 1 except that Takenate 500 as the component (Ea) is not included, but Dismodul I etc. is included as the component (Eb) in Table 2 Obtained. Moreover, the water-based paint composition which concerns on the comparative example 2 by the mixing | blending shown in Table 2 similarly to Example 1 from the obtained polyurethane water dispersion was produced.

(Comparative example 3)
Implementation is carried out without containing Takenate 500 as the component (Ea) and Dismodulus W (4,4'-dicyclohexylmethane diisocyanate) (manufactured by Bayer) etc. as the component (Eb) in the formulation shown in Table 2. The same steps as in Example 1 were performed. However, in the polyurethane synthesis step (1), NCO did not disappear, and a stable polyurethane water dispersion was not obtained.

(Example 5)
(E) ETERNACOLL UM (3/1) (manufactured by Ube Industries, Ltd.) is used in place of ETERNACOLL UC100 as the component (A), is incorporated in the formulation shown in Table 3, and the same steps as in Example 1 are carried out in Example 5 The resulting polyurethane water dispersion was obtained. Moreover, the water-based paint composition which concerns on Example 5 by the mixing | blending shown in Table 3 similarly to Example 1 from the obtained polyurethane water dispersion was produced. ETERNACOLL UM (3/1) has a ratio of 1,4-CHD / 1,6-HD = 3/1 mol (1,6-HD: 1 relative to ETERNACOLL UC100, which is a polycarbonate diol of 1,4-CHD. It is set as the polycarbonate diol of 1, 6- hexanediol (made by Ube Industries, Ltd.).

(Example 6)
A polyurethane water dispersion according to Example 6 was obtained in the same manner as in Example 5. The water-based paint according to Example 6 in the composition shown in Table 3 in the same manner as in Example 1 except that Carbodilite V10 (carbodiimide, 40% non-volatile content, carbodiimide equivalent 410) (Nisshinbo Chemical Co., Ltd.) was used instead of Carbodilight V02. The composition was made.

(Example 7)
The same as Example 1, using ETERNACOLL UM (1/1) (manufactured by Ube Industries, Ltd.) instead of ETERNACOLL UC100 corresponding to the component (A) with respect to Example 1 and incorporating it in the composition shown in Table 4, A polyurethane water dispersion according to Example 7 was obtained in the steps of Further, from the obtained polyurethane water dispersion, a water-based paint composition according to Example 7 was produced using the composition shown in Table 4 in the same manner as Example 1 using Carbodilite V10 instead of Carbodilite V02. ETERNACOLL UM (1/1) is a polycarbonate diol of 1,4-CHD / 1,6-HD = 1/1 mol ratio to ETERNACOLL UC100 which is a polycarbonate diol of 1,4-CHD. is there.

(Example 8)
A polyurethane water dispersion according to Example 8 was obtained in the same manner as in Example 7. A water-based paint according to Example 8 in the composition shown in Table 4 in the same manner as in Example 1 except that Carbodilite SW12G (carbodiimide, 40% non-volatile content, carbodiimide equivalent 467) (Nisshinbo Chemical Co., Ltd.) was used instead of Carbodilight V10. The composition was made.

(Example 9)
(E) A polyurethane water dispersion according to Example 9 in the same manner as in Example 1 except that ETERNACOLL UH 100 (manufactured by Ube Industries, Ltd.) is used in place of ETERNACOLL UC 100 as the component (A) and contained in the formulation shown in Table 5 I got Further, from the obtained polyurethane water dispersion, a water-based paint composition according to Example 9 was produced using the composition shown in Table 5 in the same manner as Example 1 using Carbodilite V10 instead of Carbodilite V02. ETERNACOLL UH 100 is a 1,6-HD polycarbonate diol.

(Example 10)
A polyurethane water dispersion according to Example 10 was obtained in the same manner as in Example 9. A water-based paint according to Example 10 in the composition shown in Table 5 in the same manner as in Example 1 except that Carbodilite SW12G (carbodiimide, 40% non-volatile content, carbodiimide equivalent 467) (Nisshinbo Chemical Co., Ltd.) was used instead of Carbodilight V10. The composition was made.

(Example 11)
A polyurethane water dispersion according to Example 11 was obtained in the same manner as in Example 9. A water-based paint according to Example 11 in the composition shown in Table 5 in the same manner as in Example 1 except that Carbodilight E05 (carbodiimide, 40% non-volatile content, carbodiimide equivalent 304) (Nisshinbo Chemical Co., Ltd.) was used instead of Carbodilight V10. The composition was made.

(Example 12)
(A) Polyurethane water dispersion according to Example 12 in the same process as in Example 1 using Polylight ODX-2155 (manufactured by Daicel Co., Ltd.) instead of ETERNACOLL UC100 as the component (A) in the formulation shown in Table 6 I got a body. Moreover, the water-based paint composition which concerns on Example 12 by the mixing | blending shown in Table 6 similarly to Example 1 from the obtained polyurethane water dispersion was produced. In addition, Polylite ODX-2155 is a diol of polycaprolactone.

(Example 13)
A polyurethane water dispersion according to Example 13 was obtained in the same manner as in Example 12. A water-based paint according to Example 13 in the composition shown in Table 6 in the same manner as in Example 1 except that Carbodilite V10 (carbodiimide, 40% non-volatile content, carbodiimide equivalent 410) (Nisshinbo Chemical Co., Ltd.) was used instead of Carbodilight V02. The composition was made.

(Example 14)
The amount of ETERNACOLL UC100 as the component (A) is reduced relative to Example 1, and each component is contained in the formulation shown in Table 7, and the polyurethane water dispersion according to Example 14 is obtained in the same steps as Example 1. Obtained. Further, from the obtained polyurethane water dispersion, a water-based paint composition according to Example 14 was produced in the same manner as in Example 1 with the composition shown in Table 7.

(Example 15)
The amount of ETERNACOLL UC100 as the component (A) is increased relative to Example 2, each component is contained in the formulation shown in Table 7, and a polyurethane water dispersion according to Example 15 is obtained in the same steps as in Example 1. Obtained. Further, from the obtained polyurethane water dispersion, a water-based paint composition according to Example 15 was produced in the same manner as in Example 1 with the composition shown in Table 7.

(Example 16)
The amount of ETERNACOLL UC100 as the component (A) is larger than that in Example 15 relative to Example 2, and each component is contained in the formulation shown in Table 8, and Example 16 is carried out in the same step as Example 2. A polyurethane water dispersion according to Further, from the obtained polyurethane water dispersion, a water-based paint composition according to Example 16 was produced in the same manner as in Example 1 with the composition shown in Table 8.

(Example 17)
The amount of ETERNACOLL UC100 as the component (A) is larger than that in Example 16 with respect to Example 2, and each component is contained in the composition shown in Table 8, and Example 17 is carried out in the same step as Example 2. A polyurethane water dispersion according to Moreover, the water-based paint composition which concerns on Example 17 by the mixing | blending shown in Table 8 similarly to Example 1 from the obtained polyurethane water dispersion was produced.

(Example 18)
Each component was contained by the composition shown in Table 9, and in the same step as in Example 1, a polyurethane water dispersion according to Example 18 was obtained. Further, from the obtained polyurethane water dispersion, a water-based paint composition according to Example 18 was produced in the same manner as in Example 1 with the composition shown in Table 9.

(Example 19)
Each component was contained by the composition shown in Table 9, and a polyurethane water dispersion according to Example 19 was obtained in the same process as in Example 1. Moreover, the water-based paint composition which concerns on Example 19 by the mixing | blending shown in Table 9 similarly to Example 1 from the obtained polyurethane water dispersion was produced.

Example 20
Each component was contained by the composition shown in Table 9, and in the same step as in Example 1, a polyurethane water dispersion according to Example 20 was obtained. Moreover, the water-based paint composition which concerns on Example 20 by the mixing | blending shown in Table 9 similarly to Example 1 from the obtained polyurethane water dispersion was produced.

(Comparative example 4)
Each component was contained in the composition shown in Table 10, and the same steps as in Example 1 were performed, but gelation was observed in the polyurethane synthesis step (1). Therefore, the water-based paint composition could not be produced.

(Example 21)
The amount of TMP as the component (C) is smaller than in Example 1 as compared to Example 1, and each component is contained in the composition shown in Table 10, and Example 21 is applied in the same process as Example 1. A polyurethane water dispersion was obtained. Moreover, the water-based paint composition which concerns on Example 21 by the mixing | blending shown in Table 10 similarly to Example 1 from the obtained polyurethane water dispersion was produced.

(Comparative example 5)
The amount of TMP as the component (C) was larger than that in Example 21 relative to Example 14, and each component was contained in the composition shown in Table 10, and the same steps as in Example 1 were performed. However, gelation was observed in the polyurethane synthesis step (1). Therefore, the polyurethane water dispersion could not be prepared.

(Example 22)
The amount of DMPA as the component (D) is lower than in Example 1 as compared to Example 1, and each component is contained in the composition shown in Table 11, and Example 22 is applied in the same process as Example 1. A polyurethane water dispersion was obtained. Moreover, the water-based paint composition which concerns on Example 22 by the mixing | blending shown in Table 11 similarly to Example 1 from the obtained polyurethane water dispersion was produced.

(Example 23) (equivalent to Example 20)
The amount of DMPA as the component (D) relative to Example 1 is greater than in the case according to Example 1, each component is contained in the formulation shown in Table 11, and Example 23 relates to Example 23 in the same process as Example 1. A polyurethane water dispersion was obtained. Moreover, the water-based paint composition which concerns on Example 23 by the mixing | blending shown in Table 11 similarly to Example 1 from the obtained polyurethane water dispersion was produced.

(Example 24)
The amount of DMPA as the component (D) relative to Example 1 is greater than in the case according to Example 23, each component is contained in the formulation shown in Table 11, and Example 24 relates to Example 24 in the same process as Example 1. A polyurethane water dispersion was obtained. Moreover, the water-based paint composition which concerns on Example 24 by the mixing | blending shown in Table 11 similarly to Example 1 from the obtained polyurethane water dispersion was produced.

(Example 25)
The same steps as in Example 1 except that TEA (triethylamine) (manufactured by Mitsubishi Gas Chemical Co., Ltd.) is contained instead of DMEA as a neutralizing agent for Example 1 and each component is contained in the composition shown in Table 12 Thus, a polyurethane water dispersion according to Example 25 was obtained. Moreover, the water-based paint composition which concerns on Example 25 by the mixing | blending shown in Table 12 similarly to Example 1 from the obtained polyurethane water dispersion was produced.

(Example 26)
In Example 1, instead of DMPA as the component (D), DMBA (dimethylolbutanoic acid) (manufactured by Kosei Tiansu Kogyo Co., Ltd.) is contained, and each component is contained in the composition shown in Table 12, Example 1 A polyurethane water dispersion according to Example 26 was obtained in the same manner as in the above. Further, a water-based paint composition according to Example 26 was produced from the obtained polyurethane water dispersion in the same manner as in Example 1 under the composition shown in Table 12.

(Example 27)
For Example 2, instead of 1,4-CHD as the component (B), 1,6-HD (1,6-hexanediol) (manufactured by Ube Industries, Ltd.) is used and contained in the formulation shown in Table 13. Then, in the same steps as in Example 1, a polyurethane water dispersion according to Example 27 was obtained. Further, from the obtained polyurethane water dispersion, a water-based paint composition according to Example 27 was produced in the same manner as in Example 1 with the composition shown in Table 13.

(Example 28)
For Example 2, in addition to 1,4-CHD as the component (B), 1,6-HD is used and contained in the formulation shown in Table 14; The resulting polyurethane water dispersion was obtained. Moreover, the water-based paint composition which concerns on Example 28 by the mixing | blending shown in Table 14 similarly to Example 1 from the obtained polyurethane water dispersion was produced.

(Example 29)
For Example 1, in addition to 1,4-CHD as the component (B), 1,4-BG (1,4-butanediol) (manufactured by Mitsubishi Chemical Corporation) is used, and the contents shown in Table 14 are contained. Then, a polyurethane water dispersion according to Example 29 was obtained through the same steps as in Example 1. Moreover, the water-based paint composition which concerns on Example 29 by the mixing | blending shown in Table 14 similarly to Example 1 from the obtained polyurethane water dispersion was produced.

(Example 30)
For Example 1, in addition to 1,4-CHD as the component (B), 1,6-HD is used and contained in the formulation shown in Table 14, and Example 30 is prepared in the same process as Example 1. The resulting polyurethane water dispersion was obtained. Moreover, the water-based paint composition which concerns on Example 30 by the mixing | blending shown in Table 14 similarly to Example 1 from the obtained polyurethane water dispersion was produced.

(Example 31)
A polyurethane water dispersion according to Example 31 was obtained in the same manner as in Example 30. An aqueous paint composition according to Example 31 was produced using the composition shown in Table 14 in the same manner as in Example 1 except for using Carbodilite V10 instead of Carbodilite V02.

[Study of Crosslinking Agent in Water-Based Paint Composition (Comparative Examples 6 and 7 and Examples 32 to 40)]
Next, using the polyurethane water dispersion of Example 29, the crosslinking agent in the water-based paint composition was examined as shown in the following Comparative Examples 6 and 7 and Examples 32 to 40. The results are shown in Tables 15 and 16.

(Comparative example 6)
As shown in Table 15, using the polyurethane water dispersion of Example 29, 100 parts of polyurethane water dispersion having a nonvolatile content of 30%, 0.1 part of TEGO FOAMEX 800 as an antifoamer, and BYK as a leveling agent 0.15 parts of 3455 was added, and viscosity was increased to about 1000 (mPa · s / ° C.) with adequanol UH450 as a thickener, degassing, and a water-based paint composition according to Comparative Example 6 was prepared. In Comparative Example 6, no crosslinking agent was added.

(Comparative example 7)
As shown in Table 15, using the polyurethane water dispersion of Example 29, 100 parts of polyurethane water dispersion having a nonvolatile content of 30%, 0.1 part of TEGO FOAMEX 800 as an antifoamer, and BYK as a leveling agent 0.15 parts of 3455 and 6.80 parts of carbodilite V02 as a crosslinking agent were added, and the viscosity was increased to about 1000 (mPa · s / ° C.) with adanol UH 450 as a thickener, defoaming, and Comparative Example 7 The water-based paint composition was produced.

(Example 32)
As shown in Table 15, using the polyurethane water dispersion of Example 29, 100 parts of polyurethane water dispersion having a nonvolatile content of 30%, 0.1 part of TEGO FOAMEX 800 as an antifoamer, and BYK as a leveling agent 0.15 parts of 3455 and 13.54 parts of Carbodilite V02 as a cross-linking agent were added, and the viscosity was increased to about 1000 (mPa · s / ° C.) with adecanol UH450 as a thickener, defoaming, Example 32 The water-based paint composition was produced.

(Example 33)
As shown in Table 15, using the polyurethane water dispersion of Example 29, 100 parts of polyurethane water dispersion having a nonvolatile content of 30%, 0.1 part of TEGO FOAMEX 800 as an antifoamer, and BYK as a leveling agent Add 0.15 parts of 3455 and 20.30 parts of Carbodilite V02 as a crosslinker, thicken up to around viscosity 1000 (mPa · s / ° C) with Adecanol UH450 as a thickener and defoam, Example 33 The water-based paint composition was produced.

(Example 34) (corresponding to Example 29)
Example 34 corresponds to Example 29, and the water-based paint composition according to Example 34 was produced in the same manner as in Example 29. As shown in Table 15, using the polyurethane water dispersion of Example 29, 100 parts of polyurethane water dispersion having a nonvolatile content of 30%, 0.1 part of TEGO FOAMEX 800 as an antifoaming agent, as a leveling agent 0.15 parts of BYK-3455 and 25.72 parts of Carbodilite V02 as a crosslinking agent were added.

(Example 35)
As shown in Table 15, using the polyurethane water dispersion of Example 29, 100 parts of polyurethane water dispersion having a nonvolatile content of 30%, 0.1 part of TEGO FOAMEX 800 as an antifoamer, and BYK as a leveling agent Add 0.15 parts of 3455 and 27.10 parts of Carbodilite V02 as a crosslinker, thicken up to around viscosity 1000 (mPa · s / ° C) with Adecanol UH450 as a thickener, defoam, and give Example 35 The water-based paint composition was produced.

(Example 36)
As shown in Table 16, using the polyurethane water dispersion of Example 29, 100 parts of the polyurethane water dispersion having a nonvolatile content of 30%, 0.1 part of TEGO FOAMEX 800 as an antifoamer, and BYK as a leveling agent Add 0.15 parts of 3455 and 32.49 parts of Carbodilite V02 as a crosslinker, thicken up to around viscosity 1000 (mPa · s / ° C.) with Adecanol UH450 as a thickener, defoam, and give Example 36 The water-based paint composition was produced.

(Example 37)
As shown in Table 16, using the polyurethane water dispersion of Example 29, 100 parts of the polyurethane water dispersion having a nonvolatile content of 30%, 0.1 part of TEGO FOAMEX 800 as an antifoamer, and BYK as a leveling agent Add 0.15 part of 3455 and 40.60 parts of Carbodilite V02 as a crosslinker, thicken up to around viscosity 1000 (mPa · s / ° C) with Adecanol UH450 as a thickener, defoam, and give Example 37 The water-based paint composition was produced.

(Example 38)
As shown in Table 16, using the polyurethane water dispersion of Example 29, 100 parts of the polyurethane water dispersion having a nonvolatile content of 30%, 0.1 part of TEGO FOAMEX 800 as an antifoamer, and BYK as a leveling agent Add 0.154 parts of 3455 and 4.04 parts of Aquanate 210 (AQ210, HDI isocyanate, NCO% 16.5%) (made by Tosoh Corp.) as a cross-linking agent, and add viscosity to Adekanol UH450 as a thickener The viscosity was increased to about 1000 (mPa · s / ° C.) and degassing was performed to prepare a water-based paint composition according to Example 38.

(Example 39)
As shown in Table 16, using the polyurethane water dispersion of Example 29, 100 parts of the polyurethane water dispersion having a nonvolatile content of 30%, 0.1 part of TEGO FOAMEX 800 as an antifoamer, and BYK as a leveling agent 0.15 parts of 3455, 6.06 parts of aquanate 210 as a cross-linking agent is added, and viscosity is increased to about 1000 (mPa · s / ° C.) with adecanol UH450 as a thickener, defoaming, Example A water-based paint composition according to 39 was prepared.

(Example 40)
As shown in Table 16, using the polyurethane water dispersion of Example 29, 100 parts of the polyurethane water dispersion having a nonvolatile content of 30%, 0.1 part of TEGO FOAMEX 800 as an antifoamer, and BYK as a leveling agent 0.15 parts of 3455, 25.72 parts of carbodilite V02 as a crosslinking agent, and 1.68 parts of aquanate 210 are added, and adecanol UH450 as a thickener to a viscosity of around 1000 (mPa · s / ° C.) Thickening and degassing were carried out to prepare a coating composition according to Example 40.

[Preparation of coating film sample]
A coating film sample was formed from each water-based paint composition concerning the above-mentioned example and a comparative example, and evaluation was performed. In preparation of a coating film sample, an ABS test substrate (2 mm × 70 mm × 150 mm) (manufactured by Taiyo Kikai Co., Ltd.) was prepared as a test substrate. And it apply | coated so that it might become a film thickness of 30-35 micrometers by the bar-coat to the base material for a test. After that, curing was performed for 30 minutes in a hot-air dryer at 85 ° C., and then curing was performed at 50 ° C. for 4 hours to prepare a coating film sample.

[Evaluation of coating film sample]
As evaluation of a coating film, it carried out as follows. First, as the evaluation of the appearance, the appearance of the coating was evaluated visually. The case of clear was evaluated as “excellent”, the case of almost clear was evaluated as “good”, the case of turbidity but usable was rated as “OK”, and the case of turbidity and cloudiness not usable was rated as “impossible”.

  The pencil hardness test was conducted by the hand-drawing method in accordance with the pencil scratching test defined in the old JIS K5400. First, the tip of the pencil to be tested was applied at a right angle to the abrasive paper No. 400 placed on a hard flat surface and polished so that the tip was flat and the corners were sharp. Apply a sharpened core to the test surface at 45 °, and press it against the coated surface as strongly as possible without breaking the core, and extrude about 1 cm at a uniform speed in front of the tester to scratch the coated surface. The extrusion speed is about 1 cm / s. The tip of the pencil core was ground each time it was scratched, and the test was repeated five times with a pencil of the same density symbol. A mark of density one step below the hardness of the pencil was recorded, in which a break or a cut of the coating becomes two or more in five tests. As evaluation criteria, it evaluated with-2H, H, F, HB, B, 2B, 3B, 4B, 5B-from the hard one.

  A cross-cut test was conducted as an adhesion test of the coating. The cross-cut test was conducted in accordance with the cross-cut tape test specified in the old JIS K5400. Using a cutter knife on the test surface, 11 cuts were made to reach the substrate at 1 mm intervals to make 100 grids. Then, cellophane tape was strongly pressed to the grid portion, the end of the tape was pulled off at a 45 ° angle, and the grid status was evaluated as a standard drawing. "Good" for "100/100", "Good" for "90/100" or higher, "OK" for "70/100" or higher, "Not" for "69/100" or lower Evaluated as.

  The self-repairing test was performed as follows. A brass wire brush was vertically applied to the coating, and the surface of the coating was rubbed about 5 to 10 times to scratch about 40 of the coating surface. The number of flaws was recorded, the test piece was left at 20 ° C., and while counting the time, the number was counted and recorded visually until 24 hours had passed. As evaluation criteria, it evaluated by a percentage as (wire trace residual number / initial number) x 100 = self repair rate. If the self-repair rate is 100% within 24 hours is "good", if the self-repair rate is 70% or more is "good", if the self-repair rate is 10% or more "good" The case where the self-healing rate was less than 10% was evaluated as "not good". When the self-repair rate was 100% within 24 hours, the self-repair time was also described.

The UV absorber test was conducted as follows. 40 g / m ^{2 of a} commercially available Neutrogena (R) 100 + (manufactured by US company Neutrogena, official name Ultra Sheer (R) Dry-Touch Sunscreen Broad Spectrum SPF 100 +) was applied to the coating, and left at 50 ° C. for 4 hours. The temperature was returned to room temperature, and Neutrogena (R) 100+ was washed with detergent, washed away, and then water was wiped off. And the above-mentioned pencil hardness test was done like the above, and the state of degradation was evaluated. The case where there was no change in hardness was evaluated as "excellent", the case where hardness decreased by only one grade was evaluated as "good", and the case where hardness decreased by two or more grades or damage to a coating film was evaluated as "unacceptable".

In the above evaluation, the evaluation of “excellent” and the evaluation of “good” are considered to have practicability completely, and the evaluation of “acceptable” is considered to have practicability as necessary. The evaluation of "impossible" was regarded as having no practicability. The evaluation results are shown in Tables 1 to 16 below. In Tables 1 to 16, Example 1 and the like are redundantly described from the viewpoint of easy understanding. In the table, “f ₁₀₀₀ ” means “total number of OH groups contained in all polyols constituting“ structural unit (A1), structural unit (B1), structural unit (C1) and structural unit (D1) ” , An average value per 1000 molecular weight of the OH group-containing polyurethane. Moreover, "EM resin" in each table represents each polyurethane water dispersion.

  First, referring to Tables 1 and 2 comparing the polyisocyanate component, Example 2 containing xylylene diisocyanate as the component (Ea) is excellent in appearance evaluation and UV absorber resistance, and adhesion is And self-healing is at a practical level. Example 1 containing xylylene diisocyanate as the component (Ea) and HDI as the component (Eb) was excellent in all of the appearance evaluation, the adhesion, the self-repairing property, and the ultraviolet absorber resistance. Example 3 containing lupranate MI as the (Eb) component together with xylylene diisocyanate as the (Ea) component was excellent in appearance evaluation and UV absorber resistance, and adhesion and self-repairing properties were at practical levels . Moreover, Example 4 which contains Dismodule I as the (Eb) component together with xylylene diisocyanate as the (Ea) component is excellent in appearance evaluation, adhesion, and self-repairing property, and is excellent in ultraviolet absorber resistance. there were.

  On the other hand, in Comparative Examples 1 and 2 which contain poly (di) isocyanate as the component (Eb) but do not contain xylylene diisocyanate as the component (Ea), although the appearance evaluation was excellent, The self-repairing property was inferior or the ultraviolet absorber resistance was inferior. In Comparative Example 3 which contains poly (di) isocyanate as the component (Eb) but does not contain xylylene diisocyanate as the component (Ea), the disappearance of NCO is not performed, and the evaluation did not occur.

  Next, referring to Tables 3 to 6 in which the component (A) is compared, 1,4-CHD / 1, instead of ETERNACOLL UC100 which is a polycarbonate diol of 1,4-CHD as the component (A), About Example 5 using ETERNACOLL UM (3/1) which is a polycarbonate diol of 6-HD = 3/1 mol ratio, appearance evaluation, adhesion, self-repairing property, and ultraviolet ray absorption resistance as in Example 1. All of the formulation was excellent. In addition, in Example 6 in which Carbodilite V10 was used in place of Carbodilite V02 in Example 5, the appearance evaluation, the adhesion, and the ultraviolet light absorber resistance were excellent, and the self-repairing property was good.

  Corresponding to the component (A), instead of ETERNACOLL UC100, which is a polycarbonate diol of 1,4-CHD, ETERNACOLL UM (1/1/1, which is a polycarbonate diol of 1,4-CHD / 1,6-HD = 1/1 molar ratio) Also in Example 7 using 1), in the same manner as in Example 1, all in the appearance evaluation, the adhesion, the self-repairing property, and the ultraviolet absorber resistance were excellent. Further, in Example 8 in which Carbodilite SW12G was used instead of Carbodilite V10 in Example 7, the appearance evaluation, the adhesion, and the ultraviolet light absorber resistance were excellent, and the self-repairing property was good.

  In the same manner as in Example 1 with respect to Example 9 in which ETERNACOLL UH100, which is a polycarbonate diol of 1,6-HD, corresponding to the component (A) and used instead of ETERNACOLL UC100, which is a polycarbonate diol of 1,4-CHD. In addition, the appearance evaluation, the adhesion, the self-repairing property, and the UV absorber resistance were all excellent. Further, in Example 10 using Carbodilite SW12G instead of Carbodilite V10 in Example 9, as in Example 9, the appearance evaluation, adhesion, self-repairing property, and ultraviolet absorber resistance are all excellent. The In addition, in Example 11 in which Carbodilite E05 was used instead of Carbodilite V10 in Example 9, the appearance evaluation, the adhesion, and the ultraviolet light absorber resistance were excellent, and the self-repairing property was good.

  Appearance evaluation, adhesion and self-regarding example 12 using polylight ODX-2155 which is a diol of polycaprolactone instead of ETERNACOLL UC100 which is a polycarbonate diol of 1,4-CHD corresponding to the component (A) The reparability was excellent, and the UV absorber resistance was good. Further, in Example 13 in which Carbodilite V10 was used in place of Carbodilite V02 in Example 12, the appearance evaluation, the adhesion, and the ultraviolet light absorber resistance were excellent, and the self-repairing property was good.

  Next, referring to Tables 7 and 8 comparing the content of the component (A), 16.54% by mass of ETERNACOLL UC100, which is a polycarbonate diol of 1,4-CHD as the component (A), was contained. In Example 14, the appearance evaluation, the self-repairing property, and the ultraviolet absorber resistance were excellent. The adhesion was at a level having practicality. This content corresponds to 0.25 mol%. About Example 15 which contained 32.38 mass% of ETERNACOLL UC100 which is a polycarbonate diol of 1, 4-CHD as (A) component, it was excellent in an external appearance evaluation and an ultraviolet-ray absorber resistance. Self-healing properties and adhesion were each at good levels. This content corresponds to 0.6 mol%. About Example 16 which contained 44.11 mass% ETERNACOLL UC100 which is a polycarbonate diol of 1, 4-CHD as (A) ingredient, appearance evaluation, self-repairing property, adhesion nature like Example 1. And all of the UV absorber resistance were excellent. This content corresponds to 0.95 mol%. For Example 17 containing 46.83% by mass of ETERNACOLL UC100 which is a polycarbonate diol of 1,4-CHD as the component (A), appearance evaluation, self-repairing property, adhesion, as in Example 1. And all of the UV absorber resistance were excellent. This content corresponds to 1.05 mol%.

  Next, referring to Tables 9 and 10 comparing weight average molecular weights, the self-healing property and resistance to resistance of Example 18 in which the weight average molecular weight of the OH group-containing polyurethane is 26658 at the compounding ratio shown in Table 9 It was excellent in ultraviolet absorber properties. Moreover, it was favorable also about external appearance evaluation and adhesiveness. For Example 19 in which the weight average molecular weight of the OH group-containing polyurethane is 87980 at the compounding ratio shown in Table 9, all of the appearance evaluation, the self-repairing property, the adhesion, and the ultraviolet absorber resistance are the same as in Example 1. Were excellent. For Example 20 in which the weight average molecular weight of the OH group-containing polyurethane is 111072 at the compounding ratio shown in Table 9, all of the appearance evaluation, the self-repairing property, the adhesion, and the ultraviolet absorber resistance are the same as in Example 1. Were excellent.

  Next, referring to Table 10 in which the content of the component (C) is compared, gelation occurs at the time of synthesis for Comparative Example 4 in which the weight average molecular weight of the OH group-containing polyurethane is 145116 at the compounding ratio shown in Table 10. , Did not reach the evaluation. In Example 21 in which 1.99% by mass of TMP as the component (C) is contained, excellent in all of the appearance evaluation, self-repairing property, adhesion, and ultraviolet absorber resistance as in Example 1. there were. About the comparative example 5 made to contain 10.35 mass% of TMP as (C) component by the compounding ratio shown in Table 10, it gelatinized at the time of a synthesis | combination, and did not arrive at evaluation.

  Next, referring to Table 11 in which the content of the component (D) is compared, the appearance of Example 22 in which 5.54 mass% of DMPA as the component (D) is contained at the compounding ratio shown in Table 11 Self-healing property, adhesion and UV absorber resistance were excellent although the level was good in evaluation. About Example 23 which contained 9.55 mass% of DMPA as a component (D), all were excellent in external appearance evaluation, self-repairing property, adhesiveness, and an ultraviolet absorber resistance. This content corresponds to 1.2 mol%. In Example 24 in which 11.12% by mass of DMPA as the component (D) was contained, the appearance evaluation and the self-repairing property were excellent, and the adhesion and the UV absorber resistance were at a good level. This content corresponds to 1.4 mol%.

  Next, referring to Table 12 in which the neutralizing agent and the component (D) are compared, self-repairing property and ultraviolet light resistance for Example 25 using TEA (triethylamine) instead of DMEA as the neutralizing agent Absorbent property was excellent, and appearance evaluation and adhesion were at a good level. Example 26 using DMBA (dimethylol butanoic acid) instead of DMPA as the component (D) is excellent in appearance evaluation, adhesion, and self-repairing property, and the UV absorber resistance is at a good level. Met.

  Next, referring to Table 13 and Table 14 in which the component (B) is compared, the appearance evaluation of Example 27 using 1, 6-HD instead of 1,4-CHD as the component (B) And the level of practicality in adhesion. In addition, the self-repairing property was excellent, and the UV absorber resistance was at a good level. The appearance evaluation, the self-repairing property, and the ultraviolet light absorber resistance are excellent in Example 28 in which 1,6-HD is added to 1,4-CHD as the component (B), and the adhesion is good. Level. For Example 29 in which 1,4-BG is added to 1,4-CHD as the component (B), as in Example 1, appearance evaluation, self-repairing property, adhesion, and ultraviolet light resistant absorber It was excellent in all of the sex. Example 30 in which the content ratio of 1,4-CHD is increased as compared with Example 28 in addition to 1,4-CHD as the component (B) and 1,6-HD is added as in Example 28 and As in Example 1, all of the appearance evaluation, the self-repairing property, the adhesion, and the ultraviolet light absorber resistance were excellent in Example 31.

[Results of examination on crosslinking agent in water-based paint composition]
Next, referring to Tables 15 and 16 comparing the crosslinking agents, in Comparative Example 6 in which no crosslinking agent was added, and in Comparative Example 7 in which 6.80 parts of Carbodilite V02 was added as a crosslinking agent, the ultraviolet resistance was The film was broken in the evaluation of the absorbent property.

  On the other hand, in Example 32 in which 13.54 parts of carbodilite V02 was added as a crosslinking agent, the appearance evaluation, the adhesion, and the self-repairing property were excellent, and the ultraviolet absorber resistance was good. In Example 33 in which 20.30 parts of Carbodilite V02 were added as a crosslinking agent, Example 34 in which 25.72 parts were added, and Example 35 in which 27.10 parts were added, appearance evaluation, self-repairing property, adhesion, and All of the UV absorber resistances were excellent. In Example 36 in which 32.49 parts of Carbodilite V02 was added as a crosslinking agent, the appearance evaluation, the self-repairing property, and the ultraviolet absorber resistance were excellent, and the adhesion was good. In Example 37 in which 40.60 parts of carbodilite V02 was added as a crosslinking agent, the appearance evaluation, the self-repairing property, and the ultraviolet absorber resistance were excellent, and the adhesion was at a practical level.

  Referring to Table 16, for Example 38 in which 4.04 parts of aquanate 210 (AQ210: isocyanate crosslinking agent) was used instead of carbodilite V02 as the crosslinking agent, appearance evaluation, self-repairing property, and ultraviolet absorption resistance The agent properties were good and the adhesion was excellent. In Example 39 in which 6.06 parts of aquanate 210 was used as the crosslinking agent, the appearance evaluation and self-repairing property were at practical levels, and the adhesion and the ultraviolet absorber resistance were excellent. About Example 40 which used together carbodilite V02 and aquanate 210 as a crosslinking agent, all were excellent in external appearance evaluation, self-healing property, adhesiveness, and an ultraviolet absorber resistance.

  Thus, according to the polyurethane water dispersion of the present invention, it is possible to provide a water-based polyurethane dispersion capable of forming a coating film having self-healing properties and UV resistance.

  It should be understood that the embodiments and examples disclosed herein are illustrative in all respects and not restrictive in any respect. The scope of the present invention is not the above description, but is defined by the terms of the claims, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

  The polyurethane water dispersion according to the present invention, the method of producing the polyurethane water dispersion, the composition for water-based coating and the coating film are capable of reducing the environmental load and having excellent self-healing properties and ultraviolet absorber resistance. Particularly useful are polyurethane water dispersions that are capable of forming the following, and coating films that are required.

Claims (16)

water and,
A neutralized product of an OH group-containing polyurethane and a tertiary amine dispersed in the water, wherein the OH group-containing polyurethane has an OH group at a molecular chain terminal,
A polyurethane water dispersion containing
The OH group-containing polyurethane has a molecular chain,
A structural unit (A1) derived from a polyol (A), wherein the polyol (A) is at least one of a polycarbonate polyol and a polyester polyol, and is a polyol having a number average molecular weight of more than 500 and 5000 or less Unit (A1),
A structural unit (B1) derived from a first diol (B), wherein the first diol (B) is a diol having a number average molecular weight of 500 or less and having no carboxy group ( B1),
Structural unit (C1) derived from polyhydric alcohol (C), wherein the polyhydric alcohol (C) has a number average molecular weight of 500 or less and the number of functional groups per molecule is more than 2 and 4 or less Structural unit (C1), which is a polyhydric alcohol of
A structural unit (D1) derived from a second diol (D), wherein the second diol (D) has a carboxy group, and a structural unit (D1),
A structural unit (E1) derived from a diisocyanate component (E), wherein the diisocyanate component (E) contains xylylene diisocyanate (Ea), and the structural unit (E1) originates from xylylene diisocyanate (Ea) Structural unit (E1) containing structural unit (E1a),
Including
The weight average molecular weight of the OH group-containing polyurethane is 16000 or more and 140000 or less.
Polyurethane water dispersion. The proportion of the structural unit (A1) derived from the polyol (A) in the molecular chain of the OH group-containing polyurethane is 10% to 60% by mass in mass conversion,
The polyurethane water dispersion according to claim 1. All OH groups contained in all polyols derived from the structural unit (A1), the structural unit (B1), the structural unit (C1), and the structural unit (D1), and the structural unit (E1) Assuming that the reaction occurs with all NCO groups contained in the diisocyanate derived from), and the total number of OH groups contained in the virtual OH group-containing polyurethane formed by the reaction is the f value, the virtual OH group-containing polyurethane The f ₁₀₀₀ value which is the average value of the f value per 1000 molecular weight calculated is 2.1 or more and 2.9 or less,
The polyurethane water dispersion according to claim 1 or 2. The acid value of the OH group-containing polyurethane is 14 or more and 55 or less.
The polyurethane water dispersion according to any one of claims 1 to 3. The structural unit (E1) is a structural unit (E1 b) derived from at least one diisocyanate selected from the group consisting of aromatic diisocyanate compounds other than xylylene diisocyanate (Ea), alicyclic diisocyanate compounds and aliphatic diisocyanate compounds. Further include),
The polyurethane water dispersion according to any one of claims 1 to 4. The polycarbonate polyol is mainly composed of at least one of 1,6-hexanediol and 1,4-cyclohexanedimethanol,
The polyester polyol is mainly composed of lactone,
The polyurethane water dispersion according to any one of claims 1 to 5. The structural unit (C1) derived from a polyhydric alcohol is mainly composed of a structural unit consisting of trimethylolpropane,
The polyurethane water dispersion according to any one of claims 1 to 6. The structural unit (B1) derived from the first diol mainly comprises a structural unit consisting of 1,4-cyclohexanedimethanol,
The polyurethane water dispersion according to any one of claims 1 to 7. A method for producing a polyurethane water dispersion according to any one of claims 1 to 8, wherein
The weight average is obtained by reacting the polyol (A), the first diol (B), the polyhydric alcohol (C), the second diol (D), and the diisocyanate component (E). A polyurethane synthesis step (1) for synthesizing the OH group-containing polyurethane having a molecular weight of 16000 or more and 140000 or less;
A neutralization step (2) of neutralizing the synthesized OH group-containing polyurethane with a neutralizing agent comprising the tertiary amine;
Preparing a polyurethane water dispersion in which the neutralized product is dispersed in water by dispersing the neutralized product formed in the neutralization process in water;
including,
Method of producing polyurethane water dispersion. The proportion of the structural unit (A1) derived from the polyol (A) in the entire OH group-containing polyurethane synthesized in the polyurethane synthesis step (1) is 10% by mass or more and 60% by mass or less ,
The manufacturing method of the polyurethane water dispersion of Claim 9. In the OH group-containing polyurethane synthesized in the polyurethane synthesis step (1), the respective sources of the structural unit (A1), the structural unit (B1), the structural unit (C1), and the structural unit (D1) It is assumed that all OH groups contained in all the polyols which are all react with all NCO groups contained in the diisocyanate from which the structural unit (E1) is derived, to form a virtual OH group-containing polyurethane formed by the reaction. When the total number of OH groups included is f value, f ₁₀₀₀ value which is an average value of the f value per calculated molecular weight 1000 of the virtual OH group-containing polyurethane is 2.1 or more and 2.9 or less.
The manufacturing method of the polyurethane water dispersion of Claim 9 or Claim 10. In the polyurethane synthesis step (1), the reaction is performed such that the acid value of the OH group-containing polyurethane is 14 or more and 55 or less.
The manufacturing method of the polyurethane water dispersion of any one of Claims 9-11. The diisocyanate component (E) is at least one selected from the group consisting of xylylene diisocyanate (Ea) and aromatic diisocyanate compounds other than xylylene diisocyanate (Ea), alicyclic diisocyanate compounds, and aliphatic diisocyanate compounds. Further containing a diisocyanate (Eb) of
The manufacturing method of the polyurethane water dispersion of any one of Claims 9-12. The polyurethane water dispersion according to any one of claims 1 to 8 as a first dispersion.
As a second dispersion, a carbodiimide crosslinking agent water dispersion containing 150 equivalent or more and 600 equivalent or less of carbodiimide group as non volatile matter, and poly containing 5 mass% or more and 25 mass% or less of isocyanate group as non volatile matter And at least one dispersion of an isocyanate crosslinking agent dispersion ,
N = C = N / COOH ratio which is an equivalent ratio of the carbodiimide group in the carbodiimide crosslinking agent contained in the carbodiimide crosslinking agent water dispersion and the carboxy group in the OH group-containing polyurethane contained in the polyurethane water dispersion Is 0.30 or more and 1.7 or less,
The NCO / OH ratio which is an equivalent ratio of the isocyanate group in the polyisocyanate crosslinking agent contained in the polyisocyanate crosslinking agent dispersion to the OH group in the OH group-containing polyurethane contained in the polyurethane aqueous dispersion is 0 Water-based paint composition which is 30 or more and 2.5 or less . A first liquid containing the polyurethane water dispersion;
A second liquid containing at least one of the carbodiimide crosslinking agent water dispersion and the polyisocyanate crosslinking agent dispersion;
A multi-component coating composition comprising
The water-based paint composition according to claim 14. The coating film formed by apply | coating the polyurethane water dispersion of any one of Claims 1-8 , or the water-based coating composition of Claim 14 or 15 on a base material.

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