JP6231939B2 - Water-based coating composition - Google Patents

Description

  The present invention relates to an aqueous coating composition.

  In recent years, water-based coating agents have attracted attention from the viewpoint of the global environment, safety, hygiene, and the like. Among water-based coating agents, urethane-based coating agents that are cross-linked by isocyanate groups have very excellent abrasion resistance, chipping resistance, chemical resistance, and contamination resistance.

  For example, an aqueous coating agent containing an active hydrogen group-containing compound such as an acrylic resin and a block polyisocyanate composition is generally widely used because it is excellent in workability and the obtained coating film is highly durable. . However, depending on the intended use, the scratch resistance and water resistance may be insufficient.

  In order to overcome the drawbacks of scratch resistance and water resistance, water-based paint compositions containing a curing agent such as an acrylic resin or a polyester resin and a block polyisocyanate composition, and a polycarbonate component have been proposed as in Patent Documents 1 and 2. Yes.

International Publication No. 2011/010539 Japanese Patent Application Laid-Open No. 08-012925

  However, in Patent Document 1, although the scratch resistance is improved, the smoothness may be insufficient. Moreover, in patent document 2, since the hydrophilic group is not modified | denatured to the polycarbonate component, dispersibility may be insufficient depending on a mixing | blending.

  An object of the present invention is to provide an aqueous coating composition having excellent scratch resistance, water resistance, smoothness, and curability according to the present invention.

  As a result of intensive studies, the present inventors have achieved the above-described problems by using a polycarbonate composition having a specific structural unit and a water-based coating composition containing a block polyisocyanate composition, thereby reaching the present invention.

（式中、Ｒ²は、活性水素含有化合物の活性水素を除いた基を表す。）
〔８〕
前記ブロックポリイソシアネート組成物が、下記一般式（７）により表される少なくとも１種のブロックポリイソシアネートを含む、〔１〕〜〔６〕のいずれか一項に記載の水系コーティング組成物。

Ｒ¹−（Ｂ）_s（Ｃ）_t （７）

（式中、Ｒ¹は、脂肪族ポリイソシアネート、脂環族ポリイソシアネート、及び芳香族ポリイソシアネートからなる群より選ばれるいずれかからイソシアネート基を除いた基を表し、Ｂは、それぞれ独立して、下記一般式（６）により表される基を表し、Ｃは、それぞれ独立して、下記一般式（８）により表される基を表し、ｓ＋ｔ＝２〜２０であり、かつ、ｔは０ではない。）

（式中、Ｒ²は、活性水素含有化合物の活性水素を除いた基を表す。）

（式中、Ｒ³は、活性水素含有化合物の活性水素を除いた基を表す。）
〔９〕
前記ブロックポリイソシアネート組成物が、下記一般式（９）により表される少なくとも１種のブロックポリイソシアネートを含む、〔１〕〜〔６〕のいずれか一項に記載の水系コーティング組成物。

Ｒ¹−（Ａ）_x（Ｂ）_y（Ｃ）_z （９）

（式中、Ｒ¹は、脂肪族ポリイソシアネート、脂環族ポリイソシアネート、及び芳香族ポリイソシアネートからなる群より選ばれるいずれかからイソシアネート基を除いた基を表し、Ａは、それぞれ独立して、下記一般式（１０）により表される基、そのケト構造体、及びそのエノール構造体からなる群より選ばれるいずれかを表し、Ｂは、それぞれ独立して、下記一般式（６）により表される基を表し、Ｃは、それぞれ独立して、下記一般式（８）により表される基を表し、ｘ＋ｙ＋ｚ＝２〜２０であり、かつ、ｘとｚは０ではない。）

（式中、Ｒ⁴は、炭素数１〜８のアルキル基、フェニル基、又はベンジル基を表し、Ｒ⁵及びＲ⁶は、それぞれ独立して、炭素数１〜３０の炭化水素基を表す。なお、Ｒ⁵及びＲ⁶は、任意に、エーテル結合、エステル結合、水酸基、カルボニル基、及びチオール基からなる群より選ばれる少なくとも１種を含んでもよい。さらに、Ｒ⁵及びＲ⁶は、一緒になって３〜６員環の環状構造を形成してもよい。）

（式中、Ｒ²は、活性水素含有化合物の活性水素を除いた基を表す。）

（式中、Ｒ³は、活性水素含有化合物の活性水素を除いた基を表す。）
〔１０〕
活性水素含有化合物を更に含む、〔１〕〜〔９〕のいずれか一項に記載の水系コーティング組成物。 That is, the present invention is as follows.
[1]
A polycarbonate / polyoxyethylene block containing a polycarbonate structure represented by the following general formula (1) and a polyoxyethylene structure represented by the following general formula (2), wherein both ends are substantially hydroxyl groups A copolymer;
A polycarbonate diol represented by the following general formula (3);
A block polyisocyanate composition;
A water-based coating composition containing

-(R-O-CO-O) _m- (1)

(In the formula, each R independently represents a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, or a divalent aroma which may have a branch having 2 to 15 carbon atoms. Represents a group hydrocarbon group, and m represents a number.)

_{- (CH 2 -CH 2 -O)} n - (2)

(In the formula, n represents a number.)

HO- (RO-CO-O) _p- R-OH (3)

(In the formula, each R independently represents a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, or a divalent hydrocarbon group that may have 2 to 15 carbon atoms. Represents an aromatic hydrocarbon group, and p represents a number.)
[2]
The aqueous coating composition according to [1], wherein in the polycarbonate / polyoxyethylene block copolymer, the R is both a pentylene group and a hexylene group.
[3]
The polycarbonate / polyoxyethylene block copolymer and the polycarbonate diol are polycarbonate diol represented by the following general formula (3) as a raw material, and polyethylene glycol represented by the following general formula (4) as a raw material, The aqueous coating composition according to [1] or [2], which is obtained by transesterification.

HO- (RO-CO-O) _p- R-OH (3)

(In the formula, each R independently represents a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, or a divalent hydrocarbon group that may have 2 to 15 carbon atoms. Represents an aromatic hydrocarbon group, and p represents a number.)

HO— (CH ₂ —CH ₂ —O) _q —H (4)

(In the formula, q represents a number.)
[4]
In the polycarbonate diol represented by the general formula (3) as the raw material, the water-based coating composition according to [3], wherein R is at least a pentylene group and a hexylene group.
[5]
In the polycarbonate diol represented by the general formula (3) as the raw material, the ratio of the polycarbonate diol in which R is a pentylene group or a hexylene group is 50 mol% or more, and the aqueous coating composition according to [4] object.
[6]
The mass ratio of the polycarbonate diol represented by the general formula (3) as the raw material (polycarbonate diol / polyethylene glycol) to the polyethylene glycol represented by the general formula (4) as the raw material is 50/50 to The aqueous coating composition according to any one of [3] to [5], which is 95/5.
[7]
The aqueous coating composition according to any one of [1] to [6], wherein the block polyisocyanate composition contains at least one block polyisocyanate represented by the following general formula (5).

R ^1- (B) _l (5)

(In the formula, R ¹ represents a group obtained by removing an isocyanate group from any one selected from the group consisting of aliphatic polyisocyanate, alicyclic polyisocyanate, and aromatic polyisocyanate; Represents a group represented by the following general formula (6), and l = 2 to 20.)

(In the formula, R ² represents a group excluding active hydrogen of the active hydrogen-containing compound.)
[8]
The aqueous coating composition according to any one of [1] to [6], wherein the block polyisocyanate composition contains at least one block polyisocyanate represented by the following general formula (7).

R ^1- (B) _s (C) _t (7)

(In the formula, R ¹ represents a group obtained by removing an isocyanate group from any one selected from the group consisting of aliphatic polyisocyanate, alicyclic polyisocyanate, and aromatic polyisocyanate; Represents a group represented by the following general formula (6), each C independently represents a group represented by the following general formula (8), s + t = 2 to 20, and t is 0. Absent.)

(In the formula, R ² represents a group excluding active hydrogen of the active hydrogen-containing compound.)

(In the formula, R ³ represents a group excluding active hydrogen of the active hydrogen-containing compound.)
[9]
The aqueous coating composition according to any one of [1] to [6], wherein the block polyisocyanate composition contains at least one block polyisocyanate represented by the following general formula (9).

R ¹ − (A) _x (B) _y (C) _z (9)

(In the formula, R ¹ represents a group obtained by removing an isocyanate group from any one selected from the group consisting of aliphatic polyisocyanate, alicyclic polyisocyanate, and aromatic polyisocyanate; Represents one selected from the group consisting of the group represented by the following general formula (10), its keto structure, and its enol structure, and each B is independently represented by the following general formula (6). And each C independently represents a group represented by the following general formula (8), x + y + z = 2 to 20, and x and z are not 0.)

(In the formula, R ⁴ represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, or a benzyl group, and R ⁵ and R ⁶ each independently represents a hydrocarbon group having 1 to 30 carbon atoms. Incidentally, R ⁵ and R ^6, optionally, an ether bond, an ester bond, a hydroxyl group may include at least one selected from the group consisting of a carbonyl group and a thiol group. further, R ⁵ and R ^6, together To form a 3- to 6-membered ring structure.

(In the formula, R ² represents a group excluding active hydrogen of the active hydrogen-containing compound.)

(In the formula, R ³ represents a group excluding active hydrogen of the active hydrogen-containing compound.)
[10]
The aqueous coating composition according to any one of [1] to [9], further comprising an active hydrogen-containing compound.

  According to the present invention, it is possible to provide an aqueous coating composition having excellent scratch resistance, water resistance, smoothness, and curability.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as the present embodiment) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

The aqueous coating composition of this embodiment contains a polycarbonate structure represented by the following general formula (1) and a polyoxyethylene structure represented by the following general formula (2), and both ends are substantially A polycarbonate / polyoxyethylene block copolymer which is a hydroxyl group;
A polycarbonate diol represented by the following general formula (3);
A block polyisocyanate composition;
A water-based coating composition containing

-(R-O-CO-O) _m- (1)

(In the formula, each R independently represents a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, or a divalent aroma which may have a branch having 2 to 15 carbon atoms. Represents a group hydrocarbon group, and m represents a number.)

_{- (CH 2 -CH 2 -O)} n - (2)

(In the formula, n represents a number.)

HO- (RO-CO-O) _p- R-OH (3)

(In the formula, each R independently represents a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, or a divalent hydrocarbon group that may have 2 to 15 carbon atoms. Represents an aromatic hydrocarbon group, and p represents a number.)

  The polycarbonate / polyoxyethylene block copolymer (hereinafter referred to as block copolymer) is represented by the polycarbonate structure represented by the general formula (1) and the general formula (2) in the molecular chain. A polyoxyethylene structure. The block copolymer has (i) a terminal structure in which the terminal structure of the polyoxyethylene structure represented by the general formula (2) has one terminal bonded to a carbonate group and the other terminal bonded to a hydroxyl group. And / or a terminal structure in which both ends are bonded to a carbonate group, and (ii) both ends of the block copolymer are substantially hydroxyl groups.

  The block copolymer can be diluted with water. That is, when diluted in water, it can take a dissolved state or a dispersed state. And when a block copolymer is diluted in water, neither separation nor sedimentation occurs. Furthermore, this block copolymer is sufficiently stable under practical use conditions.

  The both ends of the block copolymer are substantially hydroxyl groups. However, due to impurities contained in each raw material used in the production of the polycarbonate diol represented by the general formula (3) to be described later, a terminal structure generated as a by-product during the production of the block copolymer, a part of the terminal May not be a hydroxyl group. Furthermore, in order to control the reactivity and reaction state with the crosslinking agent in the intended use of the block copolymer, a part of the hydroxyl group at the terminal of the block copolymer may be intentionally substituted with an alkyl group that does not react with the crosslinking agent. Or may be converted to an aryl group or the like.

  The phrase “substantially a hydroxyl group” in the present embodiment is not limited to the case where all of both ends (100 mol%) are strictly hydroxyl groups. From this viewpoint, the ratio of the hydroxyl group in the total amount of terminal groups of the block copolymer is preferably 90 mol% or more, and more preferably 95 mol% or more. The proportion of hydroxyl groups in the total amount of terminal groups of the block copolymer can be calculated, for example, according to the following method.

By heating the block copolymer under reduced pressure, a fraction corresponding to about 1 to 2% by mass of the block copolymer is obtained, and this is collected and measured using an alcohol such as ethanol as a solvent. Make a solution. The obtained measurement solution can be analyzed by gas chromatography (GC) and calculated from the peak area value of the resulting chromatogram. For example, it can be calculated based on the following formula.

Ratio of hydroxyl groups in the total amount of terminal groups (mol%) = (total sum of peak areas of diols having hydroxyl groups at both ends) / (total sum of peak areas of diol-containing alcohols (excluding ethanol)) × 100

  For example, in order to obtain sufficient water dilutability with respect to a composition obtained by transesterification of a polycarbonate polyol and a polyethylene glycol monoalkyl ether, as described in JP-A-2002-179787, for example, It is considered necessary to increase the proportion of polyethylene glycol monoalkyl ether. However, in that case, since the proportion of the alkyl ether is increased, the proportion of the molecular structure of the component contained in the resulting composition is reduced at the hydroxyl group. For this reason, the present inventors have paid attention to the fact that sufficient performance cannot be obtained when such a composition is allowed to react with a crosslinking agent or the like.

  When the proportion of the molecule having a hydroxyl group is low, even if a compound having reactivity with a hydroxyl group (for example, a melamine resin, an isocyanate compound, a blocked isocyanate compound, etc.) is added thereto, the reactivity with the compound (crosslinking) Properties) are not sufficient, the expected physical properties may not be exhibited. However, since the both ends of the block copolymer are substantially hydroxyl groups, the reactivity (crosslinkability) does not decrease even when reacted with a compound having reactivity with hydroxyl groups, etc. Excellent physical properties can be exhibited.

  R in the general formula (1) is a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, or a divalent aromatic hydrocarbon which may have a branch having 2 to 15 carbon atoms. Represents a group.

  Carbon number of a bivalent aliphatic hydrocarbon group becomes like this. Preferably it is 3-12, More preferably, it is 3-9. As a bivalent aliphatic hydrocarbon group which may have a C2-C15 branch, a C2-C15 linear or branched alkylene group etc. are mentioned, for example. Specific examples of the linear or branched alkylene group having 2 to 15 carbon atoms include, for example, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, tert-butylene group, pentylene group, isopentylene group, Examples include a hexylene group, an isohexylene group, a heptylene group, an isoheptylene group, an octylene group, and an isooctylene group. Among these, from the viewpoint of versatility, a butylene group, a pentylene group, an isopentylene group, a hexylene group, an isohexylene group, and the like are preferable.

  Carbon number of a bivalent alicyclic hydrocarbon group becomes like this. Preferably it is 6-15, More preferably, it is 6-8. Specific examples of the divalent alicyclic hydrocarbon group include a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, and the like. Among these, a cyclohexylene group and the like are preferable from the viewpoint of versatility.

Examples of the divalent aromatic hydrocarbon group include a divalent substituent represented by the following general formula (a).

  R in the general formula (1) may be the same or different. And among the specific examples mentioned above, you may use individually by 1 type and may use 2 or more types together. As the combination of two or more, for example, a combination of a pentylene group and a hexylene group, a butylene group and a hexylene group, a 2-methylpropylene group and a butylene group, a butylene group, a pentylene group, and a hexylene group is preferable.

  Among these, R is preferably a pentylene group or a hexylene group, because it is liable to be liquid at normal temperature, easily becomes low viscosity, and further improves water dilutability, and preferably includes at least a pentylene group and a hexylene group. More preferably both. In the present embodiment, the ratio of the polycarbonate structure in which R is a pentylene group or a hexylene group with respect to the total amount of the polycarbonate structure is 50 mol% or more from the viewpoint of the block copolymer being a liquid and water dilutability. Is more preferable, 80 mol% or more is more preferable, and 90 mol% or more is more preferable.

  In the past, there were few things which paid attention to improvement, such as water reducibility, in development of a polycarbonate diol system composition. However, as a result of diligent research to realize a polycarbonate diol-based composition excellent in water dilutability, the present inventors have changed the idea greatly, and as a result, polyoxyl having a specific structure is added to polycarbonate having a specific structure. Knowledge was obtained in using a block copolymer into which an ethylene block was introduced. As a result of further diligent examination based on this knowledge, by introducing a polycarbonate structure having both pentylene group and hexylene group, which has not been used in the past, to the block copolymer, water dilutability as a block copolymer, etc. And the physical properties of the water-based coating composition were further improved (however, the action of this embodiment is not limited to these).

  In the general formula (1), m represents a number. m is preferably 2 to 50, more preferably 3 to 30, and still more preferably 4 to 20.

  In the general formula (2), n represents a number. n is preferably 9 to 46, and more preferably 13 to 35. The value of n can be obtained by subjecting the block copolymer in the composition to alkali decomposition, taking out the diol component, and performing GC-MS measurement, LC-MS measurement, GPC measurement, and the like on this diol component. .

  The terminal structure of the polyoxyethylene structure represented by the general formula (2) is (i) a terminal structure in which one terminal is bonded to a carbonate group and the other terminal is bonded to a hydroxyl group, and / or ( ii) A terminal structure in which both ends are bonded to a carbonate group. That is, in the polycarbonate diol composition of this embodiment, the terminal of the polyoxyethylene structure is at least one of the terminal structures described above.

  The number average molecular weight of the block copolymer is preferably 300 to 10,000. When the number average molecular weight is 300 or more, the performance expected for the water-based coating composition is further exhibited. When the number average molecular weight is 10,000 or less, the increase in viscosity can be efficiently suppressed, so that the handleability is further improved and the water dilutability is further improved. The number average molecular weight of the block copolymer is more preferably 500 to 5000, and still more preferably 800 to 3000, from the viewpoint of water dilutability.

  Furthermore, the number average molecular weights of the block copolymer and the polycarbonate diol in the aqueous coating composition are preferably 300 to 10,000. When the number average molecular weight is 300 or more, the performance expected for the water-based coating composition is further exhibited. When the number average molecular weight is 10,000 or less, the increase in viscosity can be effectively suppressed, so that the handleability is further improved and the water dilutability is further improved. The number average molecular weight of the aqueous coating composition is more preferably 500 to 5000, and still more preferably 800 to 3000, from the viewpoint of water dilution. The number average molecular weight can be determined according to the method described in Examples.

  Examples of the method for controlling the number average molecular weight of the block copolymer and the polycarbonate diol in the aqueous coating composition include (a) a method using a polycarbonate diol or polyethylene glycol having an appropriate molecular weight as a raw material, and (b) a block copolymer. A block copolymer having a desired number average molecular weight can be obtained by using one or two or more diol compounds used when producing a polymer as a molecular weight regulator. In addition, the method illustrated here is an example, Comprising: It is not limited to these.

  The total amount of the hydroxyl value of the block copolymer and the polycarbonate diol in the aqueous coating composition is preferably 10 to 370 mgKOH, more preferably 20 to 200 mgKOH, from the viewpoints of blendability with other components and molecular weight control. More preferably, it is 40-140 mgKOH. The hydroxyl value can be determined according to the method described in the examples.

  The aqueous coating composition of the present embodiment contains a polycarbonate diol represented by the following general formula (3). As this polycarbonate diol, what was the raw material of a block copolymer etc. can also be used so that it may mention later. By containing the polycarbonate diol, the water dispersibility of the aqueous coating composition can be improved (however, the action of this embodiment is not limited to this).

<Method for producing polycarbonate / polyoxyethylene block copolymer and aqueous coating composition>
The block copolymer can be obtained by transesterifying a polycarbonate diol represented by the following general formula (3) and a polyethylene glycol represented by the following general formula (4). This transesterification reaction can be controlled as a so-called disproportionation reaction. According to this method, a composition containing not only the block copolymer but also the polycarbonate diol represented by the general formula (3) (hereinafter sometimes referred to as a polycarbonate diol composition) can be obtained. That is, the block copolymer and the polycarbonate diol in the aqueous coating composition of the present embodiment are a polycarbonate diol represented by the general formula (3) as a raw material and a polyethylene glycol represented by the general formula (4) as a raw material. Can be suitably obtained by transesterification.

HO- (RO-CO-O) _p- R-OH (3)

(In the formula, each R independently represents a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, or a divalent hydrocarbon group that may have 2 to 15 carbon atoms. Represents an aromatic hydrocarbon group, and p represents a number.)

HO— (CH ₂ —CH ₂ —O) _q —H (4)

(In the formula, q represents a number.)

  When an excessive amount of the polycarbonate diol represented by the general formula (3) is used when the polycarbonate diol represented by the general formula (3) is transesterified with the polyethylene glycol represented by the general formula (4). Or may exist in excess in the reaction system. In such a case, the polycarbonate diol represented by the general formula (3) may remain within a range in which the effects of the present embodiment can be obtained. As described above, when a polycarbonate diol composition containing a block copolymer and a polycarbonate diol is desired, the amount of the polycarbonate diol represented by the general formula (3) as a raw material is increased. Is possible. The content of the polycarbonate diol in the composition tends to increase by increasing the amount of the polycarbonate diol represented by the general formula (3) that is a raw material for the transesterification reaction. From this viewpoint, the mass ratio (polycarbonate diol / polyethylene glycol) of the polycarbonate diol represented by the general formula (3) as the raw material to the polyethylene glycol represented by the general formula (4) as the raw material is 50 / It is preferable that it is 50-95 / 5.

  Thus, when obtaining a polycarbonate diol composition, it is preferable that content of the polycarbonate diol in a composition is 0-90 mass%. The lower limit of the polycarbonate diol content is more preferably more than 0% by mass, still more preferably 40% by mass or more, and still more preferably 60% by mass or more. The upper limit of the content of the polycarbonate diol is more preferably 85% by mass or less, further preferably 80% by mass or less, and further preferably 75% by mass or less.

  On the other hand, it is preferable that the polyethylene glycol represented by the general formula (4) does not remain as much as possible in the block copolymer or the polycarbonate diol composition from the viewpoint of water resistance. Therefore, it is preferable that the polycarbonate diol composition and the aqueous coating composition do not substantially contain polyethylene glycol represented by the general formula (4).

  R in the general formula (3) has substantially the same meaning as R in the general formula (1). P in the general formula (3) has substantially the same meaning as m in the general formula (1). Q in the general formula (4) is substantially synonymous with n in the general formula (2). Hereinafter, the polycarbonate diol represented by the general formula (3) and the polyethylene glycol represented by the general formula (4) will be described.

  In the polycarbonate diol represented by the general formula (3) as a raw material, R in the general formula (3) is preferably at least a pentylene group and a hexylene group. Furthermore, in the polycarbonate diol represented by the general formula (3) as a raw material, the proportion of the polycarbonate diol in which R is a pentylene group or a hexylene group is preferably 50 mol% or more.

  The polycarbonate diol as the raw material is not particularly limited as long as it has a structure represented by the general formula (3). It does not specifically limit as a manufacturing method of polycarbonate diol, A well-known method is also employable. Examples of the method for producing polycarbonate diol include a method in which diol and alkylene carbonate are polycondensed by transesterification reaction; a method in which diol and dialkyl carbonate or diaryl carbonate are polycondensed by transesterification reaction, and the like.

  The diol is not particularly limited. For example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1 , 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, straight chain diol having no side chain such as 1,12-dodecanediol; 2-methyl-1, 3-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-ethyl- Branched diols having side chains such as 1,6-hexanediol and 2-methyl-1,8-octanediol; 1,3-cyclohexane Ol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2-bis (4-hydroxycyclohexyl) - cyclic diol such as propane.

  The alkylene carbonate is not particularly limited, and examples thereof include ethylene carbonate, trimethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, 1,2-pentylene carbonate, and the like. It is done.

  The dialkyl carbonate is not particularly limited, and examples thereof include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and dibutyl carbonate.

  The diaryl carbonate is not particularly limited, and examples thereof include diphenyl carbonate.

  In the production of polycarbonate diol, a transesterification reaction catalyst can be used. As a catalyst, what is normally used as a transesterification reaction catalyst can be used. Specific examples of the transesterification reaction catalyst are not particularly limited, and lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic Metals such as cerium, salts of these metals, alkoxides of these metals, and organic substances of these metals. Among these, titanium compounds such as titanium tetra n-butoxide, titanium tetra n-propoxide and titanium tetraisopropoxide (particularly titanium alkoxide); lead compounds such as tetraphenyl lead, lead acetate and lead stearate are preferable. . Although the usage-amount of a transesterification reaction catalyst is not specifically limited, Usually, it is 0.00001-0.1 mass% with respect to the total amount of a raw material.

  The polycarbonate diol may contain a catalyst poison such as an acidic phosphate ester compound in order to deactivate the transesterification catalyst used in the production thereof.

  The polycarbonate diol may be a so-called homo carbonate diol obtained from one kind of diol, or may be a so-called copolymerized polycarbonate diol obtained from two or more kinds of diols.

  Even if any of the polycarbonate diols exemplified above is used, a block copolymer can be obtained by a transesterification reaction with polyethylene glycol. The obtained block copolymer is preferably liquid at normal temperature from the viewpoint of handleability and the like, but in order to obtain such a block copolymer, polycarbonate diol which is usually liquid at normal temperature is used. Tends to be preferable. For example, a so-called C6 homopolycarbonate diol using only 1,6-hexanediol as a diol is versatile, but is solid at room temperature, and a block copolymer obtained therefrom tends to be solid at room temperature. is there.

  On the other hand, for example, as a diol, a polycarbonate diol (hereinafter, referred to as a diol having 5 carbon atoms (1,5-pentanediol, etc.) and a diol having 6 carbon atoms (1,6-hexanediol, etc.) “C56 copolymer polycarbonate diol” may be preferable because it is liquid at room temperature. Block copolymers obtained from such polycarbonate diols also tend to be liquid at room temperature. Therefore, from the viewpoint of handleability, the polycarbonate diol as the raw material is preferably liquid at room temperature. Among them, the C56 copolymer polycarbonate diol is particularly preferable because it has a low melting point and is widely available on the market.

  Although the number average molecular weight of polycarbonate diol is not specifically limited, Preferably it is 500-5000, More preferably, it is 1000-3000. When the number average molecular weight of the polycarbonate diol is 500 or more, the performance expected for the aqueous coating composition tends to be further improved. When the number average molecular weight of the polycarbonate diol is 5000 or less, the viscosity of the block copolymer can be suppressed, and the handleability tends to be further improved.

  The polycarbonate diol may contain a polyester component such as polybutylene adipate and a polyether component such as polytetramethylene glycol as necessary in order to adjust the viscosity and properties of the block copolymer. When the polycarbonate diol contains these components, the content of the polycarbonate diol is preferably 50% by mass or more, and more preferably 70% by mass or more.

  Polyethylene glycol has a structure represented by the general formula (4). As polyethylene glycol, products having a wide range of molecular weight are commercially available, and such commercially available products can be used. Examples of commercially available products include “polyethylene glycol” series manufactured by Wako Pure Chemical Industries, Ltd. Two or more polyethylene glycols having different molecular weights may be used in combination.

  The number average molecular weight of polyethylene glycol is not particularly limited, but is preferably 400 to 2000, more preferably 600 to 1500. When the number average molecular weight of polyethylene glycol is 400 or more, an increase in the dispersed particle size (and further the dispersed particle size of the aqueous coating composition) when the block copolymer is diluted with water can be suppressed, and the aqueous coating composition can be suppressed. This tends to further improve the dispersion stability. Furthermore, since the usage-amount of polyoxyethylene glycol as a raw material can be reduced as the number average molecular weight is 400 or more, it can also be expected that the water resistance and heat resistance of the aqueous coating composition are further improved. When the number average molecular weight of the polyethylene glycol is 2000 or less, the crystallinity of the block copolymer is lowered, so that it becomes easy to become a liquid block copolymer at room temperature, and the handleability is improved.

  Although the temperature of transesterification is not specifically limited, Preferably it is 120-200 degreeC, More preferably, it is 140-180 degreeC. By making reaction temperature more than the said lower limit, transesterification can be advanced in a shorter time, and it is excellent in production efficiency. By making reaction temperature below the said upper limit, coloring of the block copolymer obtained can be prevented.

  The pressure during the transesterification reaction is not particularly limited, but is preferably normal pressure to 1 MPa. Setting the pressure within the above range is preferable from the viewpoint that the reaction can be easily carried out, and when using a secondary raw material other than the polycarbonate diol and polyethylene glycol as raw materials, the pressure is increased to some extent in consideration of these vapor pressures and the like. It is also preferable from the viewpoint that the transesterification reaction can be promoted more efficiently.

  When a transesterification catalyst is used during the production of the polycarbonate diol, if the catalyst poison of this catalyst is contained in the polycarbonate diol, the transesterification reaction usually tends not to proceed in the positive direction. In such a case, a necessary amount of a transesterification reaction catalyst may be newly added in the production of the block copolymer.

  When the polycarbonate diol does not contain the catalyst poison of the transesterification reaction catalyst, the transesterification reaction tends to proceed in the positive direction. Even in such a case, when it is desired to lower the reaction temperature or to shorten the reaction time, a necessary amount of a transesterification reaction catalyst can be newly added.

  It does not specifically limit as a transesterification catalyst, A well-known transesterification catalyst can also be used. Specific examples of the transesterification reaction catalyst are not particularly limited, and lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic Metals such as cerium, salts of these metals, alkoxides of these metals, and organic substances of these metals. Among these, titanium compounds such as titanium tetra n-butoxide, titanium tetra n-propoxide and titanium tetraisopropoxide (particularly titanium alkoxide); lead compounds such as tetraphenyl lead, lead acetate and lead stearate, dioctyl tin Tin compounds such as dilaurate are preferred. Although the usage-amount of a transesterification reaction catalyst is not specifically limited, 0.001-0.1 mass% is preferable with respect to the total amount of the polycarbonate diol which is a raw material.

  The transesterification reaction can be controlled by measurement with GPC over time. For example, the progress of the transesterification reaction can be confirmed by extracting the reactant and measuring it by GPC. For example, with the progress of the transesterification reaction, the peak derived from the raw material polyethylene glycol becomes smaller over time, and the disappearance of the peak causes the end of the polycarbonate diol and the interior of the polymer chain to be converted into polyethylene glycol. It can be confirmed that substantially all of the derived structure has been introduced.

  In the production of the block copolymer, each raw material to be used may be dehydrated as a pretreatment before the transesterification reaction. Further, as a post-treatment of the transesterification reaction, a catalyst poison (for example, an acidic phosphate ester compound) for the transesterification reaction catalyst may be added.

  As described above, the block copolymer can be obtained by a method of transesterifying the polycarbonate diol represented by the general formula (3) and the polyethylene glycol represented by the general formula (4). As another method, it can also be obtained by the following method.

  For example, a diol that is a raw material of the polycarbonate diol represented by the general formula (3), a carbonate that is a raw material of the polycarbonate diol represented by the general formula (3), and a polyethylene glycol represented by the general formula (4) And the like. However, in order to advance such a polycondensation reaction, it is usually necessary to heat at a high temperature for a long time. Therefore, there is a possibility that an undesired side reaction is likely to occur or a work load in changing the production type is increased. From this point of view, it is preferable that the block copolymer production method is mainly transesterification rather than polycondensation reaction.

  The ratio of the polycarbonate structure represented by the general formula (1) and the polyoxyethylene structure represented by the general formula (2) in the aqueous coating composition is the polycarbonate represented by the general formula (3) used as a raw material. This substantially corresponds to the ratio between the diol and the polyethylene glycol represented by the general formula (4).

The polyethylene glycol content in the block copolymer or polycarbonate diol composition can be measured, for example, by the following method.
1. A block copolymer or a polymer bonate diol composition is alkali-decomposed in an ethanolic potassium hydroxide solution to regenerate the diol component.
2. Neutralize by adding hydrochloric acid with phenolphthalein as an indicator.
3. The precipitated salt is filtered off, and the filtrate is subjected to GPC measurement.
4). The concentration of polyethylene glycol in the filtrate is determined from a separately prepared calibration curve. The polyethylene glycol content is calculated by calculating the mass of polyethylene glycol from the concentration and dividing the mass by the mass of the block copolymer or polycarbonate diol composition used for alkali decomposition.

  The molecular weight of polyethylene glycol contained in the block copolymer and the polycarbonate diol composition is such that polyethylene glycol itself having a known molecular weight is obtained by subjecting the block copolymer to alkali decomposition to produce a diol component and performing GPC measurement on the decomposition product. It can obtain | require by comparing with the GPC measured value of.

（式中、Ｒ²は、活性水素含有化合物の活性水素を除いた基を表す。） <Block polyisocyanate composition>
Examples of the block polyisocyanate composition include those having at least a block derived from polyisocyanate. Specific examples include those containing at least one block polyisocyanate represented by the following general formula (5).

R ^1- (B) _l (5)

(In the formula, R ¹ represents a group obtained by removing an isocyanate group from any one selected from the group consisting of aliphatic polyisocyanate, alicyclic polyisocyanate, and aromatic polyisocyanate; Represents a group represented by the following general formula (6), and l = 2 to 20.)

(In the formula, R ² represents a group excluding active hydrogen of the active hydrogen-containing compound.)

  Examples of the aliphatic polyisocyanate include polyisocyanate derived from aliphatic diisocyanate, lysine triisocyanate (hereinafter sometimes referred to as “LTI”), 4-isocyanatomethyl-1,8-octamethylene diisocyanate (trimer triisocyanate). : Hereinafter referred to as “TTI”), bis (2-isocyanatoethyl) 2-isocyanatoglutarate (glutamate triisocyanate: hereinafter sometimes referred to as “GTI”), derived therefrom Polyisocyanate etc. are mentioned.

  As the aliphatic diisocyanate which is a raw material of the aliphatic polyisocyanate, an aliphatic diisocyanate having 4 to 30 carbon atoms is preferable. Examples thereof include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (hereinafter sometimes referred to as “HDI”), 2,2,4-trimethyl-1,6-diisocyanatohexane, and lysine diisocyanate. Among these, HDI is preferable from the viewpoint of availability. An aliphatic diisocyanate may be used individually by 1 type, and may use 2 or more types together.

  The alicyclic polyisocyanate can be derived from the alicyclic diisocyanate shown below. The alicyclic diisocyanate used as the raw material for the alicyclic polyisocyanate is preferably an alicyclic diisocyanate having 8 to 30 carbon atoms, such as isophorone diisocyanate (hereinafter sometimes referred to as “IPDI”), 1,3-bis. (Isocyanatomethyl) -cyclohexane, 4,4′-dicyclohexylmethane diisocyanate, norbornene diisocyanate, hydrogenated xylylene diisocyanate and the like. Among these, IPDI is preferable from the viewpoint of weather resistance and availability. An alicyclic diisocyanate may be used individually by 1 type, and may use 2 or more types together. In addition to the alicyclic diisocyanate, the alicyclic polyisocyanate can partially contain the above aliphatic diisocyanate and the following aromatic diisocyanate in the skeleton.

  The aromatic polyisocyanate can be derived from the aromatic diisocyanate shown below. Examples of aromatic diisocyanates used as raw materials for aromatic polyisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, and the like. Can be mentioned. Aromatic diisocyanate may be used individually by 1 type, and may use 2 or more types together. The aromatic polyisocyanate may contain the above aliphatic diisocyanate or alicyclic diisocyanate in the skeleton in addition to the aromatic diisocyanate.

  Among these, an aliphatic polyisocyanate and an alicyclic polyisocyanate are preferable from the viewpoint of weather resistance.

  The average number of isocyanate groups of the polyisocyanate that is a precursor of the block polyisocyanate composition is preferably 2.0 to 20. From the viewpoint of crosslinkability, the lower limit of the average number of isocyanate groups is more preferably 2.3 or more, still more preferably 2.5 or more, and even more preferably 3.0 or more. The upper limit of the average number of isocyanate groups is more preferably 15 or less, and even more preferably 10 or less, from the viewpoint of smoothness.

The average number of polyisocyanate groups is determined by the following formula (i).

Average number of isocyanate groups = {(Number average molecular weight of polyisocyanate groups) × Isocyanate group content (mass%)}} / {(Formula weight of isocyanate (42)) × 100} (i)

The number average molecular weight of the polyisocyanate can be measured as a number average molecular weight based on polystyrene by gel permeation chromatography (GPC). The isocyanate group content can be measured in accordance with the method described in JIS K7301-1995 (Testing Method for Tolylene Diisocyanate Prepolymer for Thermosetting Urethane Elastomer).

  Examples of polyisocyanates include triisocyanates such as LTI, TTI, and GTI, or derivatives thereof, biuret bonds, urea bonds, isocyanurate bonds, uretdione bonds, urethane bonds, allophanate bonds, oxadiazine trione bonds, and the like. It is an oligomer of 2 to 20 dimer of diisocyanate produced by forming.

  The polyisocyanate having a biuret bond includes, for example, a biuretizing agent (water, tert-butanol, urea, etc.) and a diisocyanate, and a (biuretizing agent) / (isocyanate group of diisocyanate) molar ratio of about 1/2 to about 1 After reacting at a ratio of / 100, unreacted diisocyanate can be removed and purified.

  The polyisocyanate having an isocyanurate bond, for example, undergoes a nucleation reaction of an isocyanate group with a catalyst or the like, and when the conversion rate becomes about 5 to about 80% by mass, the reaction is stopped to remove unreacted diisocyanate. It can also be obtained by purification. The nulation reaction here includes trimerization or higher. In addition, in the case of the nurating reaction, for example, a 1 to 6 valent alcohol compound may be used in combination.

As a reaction catalyst for the nurating reaction, a basic catalyst is generally preferable, and examples thereof include those shown below.
(1) Organic weak acid salts of tetraalkylammonium such as tetramethylammonium, tetraethylammonium and trimethylbenzylammonium, such as hydroxide, acetic acid and capric acid (2) trimethylhydroxypropylammonium, trimethylhydroxyethylammonium, triethylhydroxypropylammonium, Hydroxyalkylammonium such as triethylhydroxyethylammonium, weak organic acid salts such as hydroxide, acetic acid, capric acid, etc. (3) Alkylcarboxylic acid such as tin, zinc, lead and other alkyl metal salts (4) Metal such as sodium and potassium Alcoholates (5) aminosilyl group-containing compounds such as hexamethyldisilazane (6) Mannich bases (7) combined use of tertiary amines and epoxy compounds (8) Phosphorus compounds such as tributylphosphine

  When the reaction catalyst may adversely affect the physical properties of the paint or coating film, it is preferable to neutralize the catalyst with an acidic compound. Examples of acidic compounds in this case include inorganic acids such as hydrochloric acid, phosphorous acid, and phosphoric acid, and sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid methyl ester, and p-toluenesulfonic acid ethyl ester. Or derivatives thereof, ethyl phosphate, diethyl phosphate, isopropyl phosphate, diisopropyl phosphate, butyl phosphate, dibutyl phosphate, 2-ethylhexyl phosphate, di (2-ethylhexyl) phosphate, isodecyl phosphate, diisodecyl phosphate, oleyl acid phosphate, tetracosyl acid phosphate , Ethyl glycol acid phosphate, butyl pyrophosphate, butyl phosphite and the like. These may be used individually by 1 type and may use 2 or more types together.

  The polyisocyanate having a urethane bond is, for example, a divalent isocyanate compound having 2 to 6 valences such as trimethylolpropane and a molar ratio of (hydroxyl group of alcohol compound) / (isocyanate group of diisocyanate) of about 1/2 to about After reacting at a ratio of 1/100, unreacted diisocyanate can be removed and purified.

  Polyisocyanate compositions derived from triisocyanates such as LTI, TTI, GTI, etc. can be produced in the same manner as polyisocyanate compositions derived from diisocyanates, but when these triisocyanates are used, unreacted It is not always necessary to remove or purify the triisocyanate.

（式中、Ｒ²は、活性水素含有化合物の活性水素を除いた基を表す。） In the formula, each B independently represents a group represented by the general formula (6). That is, B in the block polyisocyanate composition may be the same or different.

(In the formula, R ² represents a group excluding active hydrogen of the active hydrogen-containing compound.)

  The active hydrogen-containing compound is not particularly limited as long as it is an active hydrogen-containing compound capable of reacting with an isocyanate group. As the active hydrogen-containing compound, those generally known as blocking agents are preferable. As the blocking agent, a compound having one active hydrogen in the molecule is preferable. For example, alcohol compounds, alkylphenol compounds, phenol compounds, active methylene compounds, mercaptan compounds, acid amide compounds, acid imide compounds Imidazole compounds, urea compounds, oxime compounds, amine compounds, imide compounds, pyrazole compounds, and the like.

Specific examples of the active hydrogen-containing compound described above are shown below.
(1) Aliphatic compounds such as methanol, ethanol, 2-propanol, n-butanol, sec-butanol, 2-ethyl-1-hexanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol as alcohol compounds Alcohols (2) Mono- and dialkylphenols having alkyl groups having 4 or more carbon atoms as substituents as alkylphenol compounds, such as n-propylphenol, i-propylphenol, n-butylphenol, sec- Monoalkylphenols such as butylphenol, tert-butylphenol, n-hexylphenol, 2-ethylhexylphenol, n-octylphenol, n-nonylphenol, di-n-propylphenol, diisopropylphenol Dialkylphenols such as benzene, isopropyl cresol, di-n-butylphenol, di-tert-butylphenol, di-sec-butylphenol, di-n-octylphenol, di-2-ethylhexylphenol, di-n-nonylphenol, etc. (3 ) Phenol compounds such as phenol, cresol, ethyl phenol, styrenated phenol, hydroxybenzoate, etc. (4) As active methylene compounds, dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, etc. ( 5) Examples of mercaptan compounds include butyl mercaptan, dodecyl mercaptan and the like (6) acid amides; acetanilide, acetic acid amide, ε-caprolactam, δ-valerolactam, γ-butyrolactam and the like (7 As acid imide compounds, succinimide, maleic acid imide, etc. (8) Imidazole compounds, imidazole, 2-methylimidazole, etc. (9) As urea compounds, urea, thiourea, ethylene urea, etc. (10) Oxime series (11) amine compounds such as diphenylamine, aniline, carbazole, di-n-propylamine, diisopropylamine, isopropylethylamine, diisobutylamine, formaldehyde oxime, acetaldoxime, acetoxime, methylethylketoxime, cyclohexanone oxime, etc. Di (2-butylamine), di (tert-butyl) amine, dicyclohexylamine, N-tert-butylcyclohexylamine, 2-methylpiperidine, 2,6-dimethylpiperidine, 2 2,12,6,6-tetramethylpiperidine etc. (12) As imine compounds, ethyleneimine, polyethyleneimine etc.
(13) Pyrazole compounds such as pyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole

  In the general formula (5), l is a value corresponding to the average number of isocyanate groups of the polyisocyanate that is the source of R, and is preferably 2.0 to 20. From the viewpoint of crosslinkability, the lower limit value of l is more preferably 2.3 or more, further preferably 2.5 or more, and still more preferably 3.0 or more. From the viewpoint of smoothness, the upper limit value of l is more preferably 15 or less, and still more preferably 10 or less.

（式中、Ｒ²は、活性水素含有化合物の活性水素を除いた基を表す。）

（式中、Ｒ³は、活性水素含有化合物の活性水素を除いた基を表す。） It is preferable that a block polyisocyanate composition contains the at least 1 sort (s) of block polyisocyanate represented by following General formula (7) from a dispersible viewpoint.

R ^1- (B) _s (C) _t (7)

(In the formula, R ¹ represents a group obtained by removing an isocyanate group from any one selected from the group consisting of aliphatic polyisocyanate, alicyclic polyisocyanate, and aromatic polyisocyanate; Represents a group represented by the following general formula (6), each C independently represents a group represented by the following general formula (8), s + t = 2 to 20, and t is 0. Absent.)

(In the formula, R ² represents a group excluding active hydrogen of the active hydrogen-containing compound.)

(In the formula, R ³ represents a group excluding active hydrogen of the active hydrogen-containing compound.)

In addition, about R < ¹ > and B in General formula (7), what was demonstrated in General formula (5) can be suitably employ | adopted unless there is particular notice.

  Examples of the active hydrogen-containing compound include nonionic compounds, anionic compounds, and cationic compounds. Among these, from the viewpoint of ease of production, nonionic compounds and anionic compounds are preferable, and nonionic compounds are more preferable. These may be used individually by 1 type and may use 2 or more types together.

  Examples of nonionic compounds include polyethylene glycol compounds having a structure in which three or more ethylene oxide groups are continuous. Furthermore, the number average molecular weight of the nonionic compound is preferably 200 to 2,000. The lower limit of the number average molecular weight is more preferably 300 or more, and still more preferably 400 or more. The upper limit of the number average molecular weight is more preferably 1500 or less, still more preferably 1200 or less, and still more preferably 1000 or less. When the lower limit of the number average molecular weight is not less than the above lower limit, the water dispersibility of the aqueous coating composition can be further improved. On the other hand, when the upper limit of the number average molecular weight is less than or equal to the above upper limit, it is possible to suppress deterioration of physical properties such as initial adhesion with a substrate or a laminated coating film and adhesion after a wet heat resistance test.

  In the polyethylene glycol compound, the repeating unit of the ethylene oxide group may further contain other oxyalkylene groups (for example, oxypropylene group, oxystyrene group, etc.). In this case, the molar ratio of the ethylene oxide group in the polyethylene glycol compound is preferably 60 mol% or more, more preferably 70 mol% or more, and further preferably 80 mol% or more. The higher the molar ratio of ethylene oxide groups, the better the compoundability in the aqueous coating adhesive composition, which is preferable.

  Examples of such polyethylene glycol compounds include so-called pluronic-type polypropylene glycols and polyoxypropylene polyoxyethylene copolymer diols obtained by addition polymerization of ethylene oxide at the ends of monoalkoxy polyethylene glycol, polyethylene glycol or triol, polypropylene glycol, and the like. Or a polyoxypropylene polyoxyethylene copolymer triol, a polyoxypropylene polyoxyethylene block polymer diol, a polyoxypropylene ethylene block polymer triol, etc. are mentioned.

  Among the above, monoalkoxy polyethylene glycol and polyethylene glycol are preferable, and monoalkoxy polyethylene glycol is more preferable. Monoalkoxy polyethylene glycol is obtained by adding an alcohol to one end of polyethylene glycol. The number of carbon atoms of the monoalcohol that can be used for the monoalkoxy polyethylene glycol is preferably 1 to 8, more preferably 1 to 6, and still more preferably 1 to 4. Preferable specific examples include methanol, ethanol and the like.

  As monoalkoxy polyethylene glycol, monomethoxy polyethylene glycol and monoethoxy polyethylene glycol are preferable, and monomethoxy polyethylene glycol is more preferable.

  The number average molecular weight of the polyethylene glycol compound is preferably 200 to 2000, more preferably 300 to 1500, and still more preferably 400 to 1000.

  A polyethylene glycol compound in which a monoalcohol having 1 to 4 carbon atoms is added to one end is also preferable.

  In addition, as a polyethylene glycol, a commercial item can also be used. Examples of such commercially available products include “PEG200”, “PEG300”, “PEG400”, “PEG600”, “PEG1000”, “PEG2000” manufactured by NOF Corporation. Examples of monomethoxypolyethylene glycol include “UNIOX M400”, “UNIOX M550”, “UNIOX M1000”, “UNIOX M2000” manufactured by NOF Corporation, and “MPG-081” manufactured by Nippon Emulsifier Co., Ltd. Can be mentioned.

  Examples of anionic compounds include carboxylic acid group-containing compounds and sulfonic acid group-containing compounds. Examples of the carboxylic acid group-containing compound include monohydroxycarboxylic acid, dihydroxycarboxylic acid, and derivatives thereof. Among the carboxylic acid group-containing compounds, monohydroxycarboxylic acid and dihydroxycarboxylic acid are preferable, and monohydroxycarboxylic acid is more preferable.

  Specific examples of the carboxylic acid-containing compound include hydroxypivalic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, or derivatives such as polycaprolactone diol and polyether polyol using these as initiators. Is mentioned.

  When using a carboxylic acid group containing compound, it is preferable to neutralize with a neutralizing agent after manufacture of a block polyisocyanate composition. Examples of the neutralizing agent include alkali metals, alkaline earth metals, tertiary amines such as ammonia, trimethylamine, triethylamine, and dimethylethanolamine.

  Examples of the sulfonic acid group-containing compound include aminoethylsulfonic acid, ethylenediamino-propyl-β-ethylsulfonic acid, 1,3-propylenediamine-β-ethylsulfonic acid, N, N-bis (2-hydroxyethyl) -2. -Aminoethanesulfonic acid etc. are mentioned. When a sulfonic acid group-containing compound is used, it is preferably neutralized with a neutralizing agent after the production of the block polyisocyanate composition as described above. Examples of the neutralizing agent include alkali metals, alkaline earth metals, tertiary amines such as ammonia, trimethylamine, triethylamine, and dimethylethanolamine.

  When the carboxylic acid group-containing compound and the sulfonic acid group-containing compound are compared, the carboxylic acid group-containing compound is preferable from the viewpoints of ease of production and blendability with other components in the composition.

  Examples of the cationic compound include a hydroxyl group-containing amino compound. Specific examples include dimethylethanolamine, diethylethanolamine, and hydroxypyridine. When using a hydroxyl-containing amino compound, it is preferable to neutralize with a neutralizing agent after manufacture of a block polyisocyanate composition like the above. Examples of the neutralizing agent include organic acids such as acetic acid, propionic acid, butanoic acid, and 2-ethylhexanoic acid.

  Examples of the active hydrogen of the active hydrogen-containing compound include hydrogen such as a hydroxyl group and an amino group. For example, in the case of hydroxypivalic acid which is an anionic compound, hydrogen of a hydroxyl group is exemplified, and in the case of aminoethylsulfonic acid, hydrogen of an amino group is exemplified. In the case of dimethylethanolamine which is a cationic compound, hydrogen of a hydroxyl group is exemplified. That is, the group obtained by removing active hydrogen from an active hydrogen-containing compound refers to a residue obtained by removing active hydrogen from a nonionic, anionic, or cationic active hydrogen-containing compound.

  The sum (s + t) of s and t in the general formula (7) is 2 to 20, and t is not 0. s + t is also a value corresponding to the average number of isocyanate groups of the polyisocyanate that is the source of R, and from the viewpoint of crosslinkability, the lower limit value is preferably 2.3 or more, more preferably 2.5 or more. More preferably, it is 3 or more. From the viewpoint of smoothness, the upper limit value of s + t is preferably 15 or less, more preferably 10 or less. From the viewpoint of dispersibility, t is not 0. In addition, s and t mean the statistical average number with respect to R of each of B and C.

（式中、Ｒ⁴は、炭素数１〜８のアルキル基、フェニル基、又はベンジル基を表し、Ｒ⁵及びＲ⁶は、それぞれ独立して、炭素数１〜３０の炭化水素基を表す。なお、Ｒ⁵及びＲ⁶は、任意に、エーテル結合、エステル結合、水酸基、カルボニル基、及びチオール基からなる群より選ばれる少なくとも１種を含んでもよい。さらに、Ｒ⁵及びＲ⁶は、一緒になって３〜６員環の環状構造を形成してもよい。）

（式中、Ｒ²は、活性水素含有化合物の活性水素を除いた基を表す。）

（式中、Ｒ³は、活性水素含有化合物の活性水素を除いた基を表す。） The block polyisocyanate composition preferably contains at least one block polyisocyanate represented by the following general formula (9) from the viewpoints of dispersibility and low-temperature curability.

R ¹ − (A) _x (B) _y (C) _z (9)

(In the formula, R ¹ represents a group obtained by removing an isocyanate group from any one selected from the group consisting of aliphatic polyisocyanate, alicyclic polyisocyanate, and aromatic polyisocyanate; Represents one selected from the group consisting of the group represented by the following general formula (10), its keto structure, and its enol structure, and each B is independently represented by the following general formula (6). And each C independently represents a group represented by the following general formula (8), x + y + z = 2 to 20, and x and z are not 0.)

(In the formula, R ⁴ represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, or a benzyl group, and R ⁵ and R ⁶ each independently represents a hydrocarbon group having 1 to 30 carbon atoms. Incidentally, R ⁵ and R ^6, optionally, an ether bond, an ester bond, a hydroxyl group may include at least one selected from the group consisting of a carbonyl group and a thiol group. further, R ⁵ and R ^6, together To form a 3- to 6-membered ring structure.

(In the formula, R ² represents a group excluding active hydrogen of the active hydrogen-containing compound.)

(In the formula, R ³ represents a group excluding active hydrogen of the active hydrogen-containing compound.)

In addition, about R < ¹ >, B, and C of General formula (9), it is synonymous with what was demonstrated in General formula (5) and General formula (7).

  The average number of isocyanate groups of the polyisocyanate that is the precursor of the block polyisocyanate composition is preferably 2.0 to 20. From the viewpoint of crosslinkability, the lower limit of the average number of isocyanate groups is more preferably 2.3 or more, still more preferably 2.5 or more, and still more preferably 3.0 or more. The upper limit of the average number of isocyanate groups is more preferably 15 or less, and even more preferably 10 or less, from the viewpoint of smoothness.

The average number of polyisocyanate groups is obtained by the following formula.

Average number of isocyanate groups = {(Number average molecular weight of polyisocyanate groups) × Isocyanate group content (mass%)}} / {(Formula weight of isocyanate (42)) × 100}

  The number average molecular weight of the polyisocyanate can be measured as a number average molecular weight based on polystyrene by gel permeation chromatography (hereinafter also referred to as “GPC”). The isocyanate group content can be measured according to the method described in JIS K 7301-1995 (Test Method for Tolylene Diisocyanate Prepolymer for Thermosetting Urethane Elastomer).

（式中、Ｒ⁴は、炭素数１〜８のアルキル基、フェニル基、又はベンジル基を表し、Ｒ⁵及びＲ⁶は、それぞれ独立して、炭素数１〜３０の炭化水素基を表す。なお、Ｒ⁵及びＲ⁶は、任意に、エーテル結合、エステル結合、水酸基、カルボニル基、及びチオール基からなる群より選ばれる少なくとも１種を含んでもよい。さらに、Ｒ⁵及びＲ⁶は、一緒になって３〜６員環の環状構造を形成してもよい。） The substituent A in the general formula (9) independently represents any one selected from the group consisting of a group represented by the following general formula (10), a keto structure thereof, and an enol structure thereof.

(In the formula, R ⁴ represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, or a benzyl group, and R ⁵ and R ⁶ each independently represents a hydrocarbon group having 1 to 30 carbon atoms. Incidentally, R ⁵ and R ^6, optionally, an ether bond, an ester bond, a hydroxyl group may include at least one selected from the group consisting of a carbonyl group and a thiol group. further, R ⁵ and R ^6, together To form a 3- to 6-membered ring structure.

The general formula (10) represents a keto structure, and the substituent A includes an enol structure and the like which are in a keto-enol tautomerism relationship with this. For example, an enol structure in which the proton of the methine group has moved to the amide group side, an enol structure in which the proton of the methine group has moved to the ester group side, and the like are included. The proportion of the keto structure and the enol structure in the entire keto structure is not particularly limited, but is preferably 50 mol% or more, more preferably 75 mol% or more, and still more preferably 90 mol% or more. It is. The ratio of the keto structure and the enol structure can be determined by ¹ H-NMR measurement of the blocked isocyanate composition.

R ^{4 in the} general formula (10) represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, or a benzyl group. From the viewpoint of compatibility with other components, R4 is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, still more preferably a methyl group or an ethyl group. More preferably an ethyl group.

R ⁵ and R ⁶ in the general formula (10) may be the same or different and each represents a hydrocarbon group having 1 to 30 carbon atoms. R ⁵ and R ⁶ may optionally contain at least one selected from the group consisting of an ether bond, an ester bond, a hydroxyl group, a carbonyl group, and a thiol group. Furthermore, R ⁵ and R ⁶ may together form a 3-6 membered ring structure. For example, R ⁵ and R ⁶ may be optionally combined to form a 5-membered or 6-membered cycloalkyl group, or together with a nitrogen atom between R ⁵ and R ^6. In addition, a 3-membered ring, a 4-membered ring, a 5-membered ring, or a 6-membered ring additionally containing a nitrogen atom, an oxygen atom, or the like may be formed as a bridging member.

Here, a structure in which R ⁵ and R ⁶ in the general formula (10) are each independently present (hereinafter referred to as an independent structure) to form a 3-6 membered ring together ( Hereinafter, each will be described.

First, the independent structure will be described. In the case of an independent structure, R ⁵ and R ⁶ are preferably alkyl having 1 to 8 carbon atoms, more preferably a branched alkyl group having 3 to 6 carbon atoms, still more preferably 3 to 3 carbon atoms. 4 branched alkyl groups, more preferably an isopropyl group. Preferable substituents that R ⁵ and R ⁶ may contain include an ether bond and an ester bond. When R ⁵ and R ⁶ are alkyl groups having 30 or less carbon atoms, a decrease in effective NCO% can be suppressed and compatibility with other components can be kept high.

Next, the connection structure will be described. In the case of a linked structure, examples of the structure of —NR ⁵ R ^{6 in} the general formula (10) include a group obtained by removing active hydrogen from a cyclic secondary amine containing a nitrogen atom. Examples of such cyclic secondary amines include azabicyclo compounds such as 2-azabicyclo [2.1.1] hexane and 7-azabicyclo [2.2.1] heptane; aziridine, azetidine, pyrrolidine, 2- Methylpyrrolidine, 3-pyrroldiol, 2-pyrrolidone, proline, 4-hydroxyproline, piperidine, 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine, 4-benzylpiperidine, 2,4-dimethylpiperidine, 3, 5-dimethylpiperidine, 2,6-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine, 3-piperidinemethanol, 2-piperidineethanol, 4-piperidineethanol, 4-piperidinol, 2-piperidone, 4-piperidone 4-piperidinecarboxylate methyl ester Ter, 4-piperidinecarboxylic acid ethyl ester, 2,2,6,6-tetramethyl-4-piperidone, 4-piperidinopiperidine, decahydroquinoline, piperazine, N-methylpiperazine, N-ethylpiperazine, N- Allylpiperazine, N-isobutylpiperazine, N-cyclohexylpiperazine, N-cyclopentylpiperazine, N-phenylpiperazine, 1- (2-pyridyl) piperazine, 1- (4-pyridyl) piperazine, 1- (2-pyrimidyl) piperazine, N-methylhomopiperazine, N-acetylhomopiperazine, N-butyrylhomopiperazine, oxazolidine, morpholine, imidazolidine, 2-imidazolidone, hydantoin, 1-methylhydantoin, 5-methylhydantoin, creatinine, paravanic acid, urazo Saturated cyclic secondary amines such as ru, thiazolidine and thiaridine; pyrrole, 2-methylpyrrole, 2,4-dimethylpyrrole, 3,4-dimethylpyrrole, 2-acetylpyrrole, 2-pyrrolecarboxylic acid, indole, 3H- Indole, 3-methylindole, 2-phenylindole, 3-hydroxylindole, 3-indoleacetic acid, indoline, 2-indolinone, isatin, α-cisatin oxime, isoindole, isoindoline, 1-isoindolinone, carbazole, 1, 2,3,4-tetrahydroquinoline, 1,2,3,4-tetrahydroisoquinoline, 9-acridone, pyrazole, 3,5-dimethylpyrazole, imidazole, benzimidazole, benzimidazolone, 1H-1,2,3- Triazole, 1H- , 2,4-triazole, benzotriazole, tetrazole, purine, xanthine, phenoxazine, isatoic anhydride, benzothiazoline, 2-benzothiazolone, phenothiazine, 5,10-dihydrophenazine, β-carboline, perimidine 2 Secondary amine; 2-pyrroline, 3-pyrroline, dihydropyridine, 2-pyrazoline, 5-pyrazolone, 2-imidazoline, 4H-1,4-oxazine, 4H-1,4-thiazine, 2H, 6H-1,5,2 -An unsaturated bond-containing cyclic secondary amine such as dithiazine and the like.

  Among these cyclic secondary amines, aziridine, azetidine, pyrrolidine, 2-methylpyrrolidine, 3-pyrroldiol, 2-pyrrolidone, proline, 4-hydroxyproline, piperidine, 2-methylpiperidine, 3-methylpiperidine, 4- Methylpiperidine, 4-benzylpiperidine, 2,4-dimethylpiperidine, 3,5-dimethylpiperidine, 2,6-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine, 3-piperidinemethanol, 2-piperidineethanol 4-piperidineethanol, 4-piperidinol, 2-piperidone, 4-piperidone, 4-piperidinecarboxylic acid methyl ester, 4-piperidinecarboxylic acid ethyl ester, 2,2,6,6-tetramethyl-4-piperidone, 4, -Piperidinopiperidine Decahydroquinoline, piperazine, N-methylpiperazine, N-ethylpiperazine, N-allylpiperazine, N-isobutylpiperazine, N-cyclohexylpiperazine, N-cyclopentylpiperazine, N-phenylpiperazine, 1- (2-pyridyl) piperazine, 1- (4-pyridyl) piperazine, 1- (2-pyrimidyl) piperazine, N-methylhomopiperazine, N-acetylhomopiperazine, N-butyrylhomopiperazine, oxazolidine, morpholine, imidazolidine, 2-imidazolidone, hydantoin, 1-methylhydantoin, 5-methylhydantoin, creatinine, parabanic acid, urazole, thiazolidine, and thiaridine are preferable.

  Among the above, more preferably, aziridine, azetidine, pyrrolidine, 2-methylpyrrolidine, piperidine, 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine, 4-benzylpiperidine, 2,4-dimethylpiperidine, 3, 5-dimethylpiperidine, 2,6-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine, 4-piperidinecarboxylic acid methyl ester, 4-piperidinecarboxylic acid ethyl ester, 2,2,6,6-tetramethyl -4-piperidone, 4-piperidinopiperidine, piperazine, N-methylpiperazine, N-ethylpiperazine, N-allylpiperazine, N-isobutylpiperazine, N-cyclohexylpiperazine, N-cyclopentylpiperazine, N-phenylpiperazine, 1 -(2-pi (Zyl) piperazine, 1- (4-pyridyl) piperazine, 1- (2-pyrimidyl) piperazine, N-methylhomopiperazine, N-acetylhomopiperazine, N-butyrylhomopiperazine; more preferably pyrrolidine, 2 -Methylpyrrolidine, piperidine, 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine, 2,4-dimethylpiperidine, 3,5-dimethylpiperidine, 2,6-dimethylpiperidine, 2,2,6,6- Tetramethylpiperidine; even more preferably 2-methylpiperidine, 2,6-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine.

  As shown in the above specific examples, examples of the cyclic secondary amine compound include saturated cyclic secondary amines, aromatic secondary amines, unsaturated bond-containing cyclic secondary amines, etc., among them, saturated cyclic secondary amines. Is preferred. Of the saturated cyclic secondary amines, secondary amines containing only one nitrogen atom are preferred, more preferably 5-membered or 6-membered rings, and still more preferably represented by the following general formula (11). Compounds and the like.

  Specific examples of these include 2-methylpiperidine, 2,6-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine and the like.

（式中、Ｒ⁷、Ｒ⁸、Ｒ⁹、及びＲ¹⁰は、それぞれ独立して、水素又はメチル基を表し、かつ、そのうち少なくとも１つはメチル基を表す。）

(In the formula, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent hydrogen or a methyl group, and at least one of them represents a methyl group.)

One or more of R ⁷ and R ⁸ are preferably a methyl group. Also, any one or more of R ⁹ and R ¹⁰ is preferably a methyl group.

  In the general formula (9), instead of the substituent A, the block poly having any one selected from the group consisting of the group A ′ represented by the following general formula (12), its keto structure, and its enol structure An isocyanate composition may further be included.

(In the formula, R ¹¹ and R ¹² each independently represent a hydrocarbon group having 1 to 30 carbon atoms. R ¹¹ and R ¹² are optionally an ether bond, an ester bond, a hydroxyl group, and a carbonyl group. , and it may include at least one selected from the group consisting of a thiol group. further, R ¹¹ and R ¹² together may form a ring structure having 3 to 6-membered ring .R ¹³ and R ¹⁴ each independently represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms, wherein R ¹³ and R ¹⁴ are optionally selected from an ether bond, an ester bond, a hydroxyl group, a carbonyl group, and a thiol group. And may contain at least one member selected from the group consisting of R ¹³ and R ¹⁴ together to form a 3- to 6-membered cyclic structure.)

R ¹¹ , R ¹² , R ¹³ and R ¹⁴ in the general formula (12) have the same meanings as R ⁵ and R ⁶ described in the general formula (10).

  The ratio of the substituent A ′ to the total amount of the substituents A and A ′ is preferably 50% by mass or less, more preferably 30% by mass or less from the viewpoint of suppressing crystallization while maintaining low temperature curability. More preferably, it is 20 mass% or less, More preferably, it is 10 mass% or less.

（式中、Ｒ²は、活性水素含有化合物の活性水素を除いた基を表す。） The substituent B in the general formula (5) independently represents a group represented by the following general formula (6).

(In the formula, R ² represents a group excluding active hydrogen of the active hydrogen-containing compound.)

（式中、Ｒ³は、活性水素含有化合物の活性水素を除いた基を表す。） The substituent C in the general formula (5) independently represents a group represented by the following general formula (8).

(In the formula, R ³ represents a group excluding active hydrogen of the active hydrogen-containing compound.)

  The sum (x + y + z) of x, y and z in the general formula (9) is a value corresponding to the average number of isocyanate groups of the polyisocyanate which is the source of R, and is preferably 2 to 20. From the viewpoint of crosslinkability, the lower limit of the total of x, y, and z is more preferably 2.3 or more, still more preferably 2.5 or more, and even more preferably 3.0 or more. preferable. From the viewpoint of smoothness, the upper limit of the total of x, y, and z is more preferably 15 or less, and further preferably 10 or less. In addition, x, y, and z mean the statistical average number with respect to R of each of the substituents A, B, and C. Further, x is preferably not 0 from the viewpoint of low temperature curability and storage stability, and z is preferably not 0 from the viewpoint of dispersibility in an aqueous system. Further, y may be 0, but is preferably not 0.

  Each method for producing the block polyisocyanate composition will be described.

(Production method of block polyisocyanate represented by the general formula (5))
It can be produced by reacting a polyisocyanate serving as a source of R ^{1 in} the general formula (5) with an active hydrogen-containing compound having a group represented by the general formula (6). Hereinafter, an example of the manufacturing method will be described in detail.

  When the isocyanate group of the polyisocyanate is reacted with the active hydrogen-containing compound, the ratio of (number of moles of active hydrogen-containing compound) / (number of moles of isocyanate group in the polyisocyanate composition) is 1.0 to 1.5. Preferably, it is 1.0 to 1.3, more preferably 1.0 to 1.2.

  Although the reaction temperature of polyisocyanate and an active hydrogen containing compound is not specifically limited, It is preferable that it is -20-150 degreeC, and it is more preferable that it is 0-100 degreeC from a viewpoint of reaction rate or side reaction suppression.

  The reaction between the polyisocyanate and the active hydrogen-containing compound can be performed with or without a solvent. When using a solvent, it is preferable to use a solvent inert to the isocyanate group. Although it does not specifically limit as an organic solvent, Specifically, Aliphatic hydrocarbon solvents, such as hexane, heptane, and octane; Alicyclic hydrocarbon solvents, such as cyclohexane and methylcyclohexane; Acetone, methyl ethyl ketone, methyl isobutyl ketone Ketone solvents such as cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate and isobutyl acetate; aromatic solvents such as toluene, xylene, diethylbenzene, mesitylene, anisole and chlorobenzene; ethylene glycol monoethyl ether acetate, Glycol solvents such as 3-methyl-3-methoxybutyl acetate and propylene glycol monomethyl ether acetate; ether solvents such as diethyl ether, tetrahydrofuran and dioxane; dichloromethane, -Halogenated hydrocarbon solvents such as dichloroethane and chloroform; Pyrrolidone solvents such as N-methyl-2-pyrrolidone; Amides solvents such as N, N-dimethylacetamide and N, N-dimethylformamide; Sulfoxides such as dimethyl sulfoxide Solvent solvents such as γ-butyrolactone; organic solvents that are not reactive with isocyanate groups such as amine solvents such as morpholine; and mixtures thereof.

  In the reaction, organometallic salts such as tin, zinc and lead; tertiary amine compounds; alkali metal alcoholates such as sodium may be used as catalysts. The reaction temperature in the case of using a catalyst is preferably −20 ° C. or higher from the viewpoint of increasing the reactivity. Moreover, 150 degrees C or less is preferable from a viewpoint of suppressing a side reaction. More preferably, it is 0-100 degreeC. When the isocyanate group remains after the reaction, it is preferable to further add a blocking agent or the like to completely disappear the isocyanate group.

(Method for producing composition containing block polyisocyanate represented by general formula (7))
Polyisocyanate which is a source of R ^{1 in} the general formula (7), an active hydrogen-containing compound having a group represented by the general formula (6), and an active hydrogen containing group represented by the general formula (8) It can be produced by reacting with a compound.

  In the above reaction, the reaction between the polyisocyanate and the active hydrogen-containing compound, the reaction between the polyisocyanate and the active hydrogen-containing compound can be performed simultaneously, or after performing any one of the reactions in advance, the second reaction is performed. You can also. Hereinafter, an example of the manufacturing method will be described in detail.

  The total ratio of the active hydrogen-containing compound to the isocyanate group of the polyisocyanate is preferably 75 to 150 mol%. From the viewpoint of curability, the lower limit value of this ratio is more preferably 90 mol% or more, further preferably 95 mol% or more, and still more preferably 100 mol% or more. The upper limit of this ratio is more preferably 130 mol% or less, further preferably 120 mol% or less, and still more preferably 110 mol% or less, from the viewpoint of water resistance.

  The addition amount of the active hydrogen-containing compound having the group represented by the general formula (6) is 2 to 50 mol based on the number of moles of active hydrogen with respect to the isocyanate group in the polyisocyanate which is a precursor of the block polyisocyanate. % Is preferred. The upper limit of the ratio is more preferably 40 mol% or less, and still more preferably 35 mol% or less. When the ratio is 2 mol% or more, sufficient water dispersibility of the composition can be obtained. Moreover, when the said ratio is 50 mol% or less, the fall of a crosslinking density can be suppressed and coating film physical properties, such as the water resistance of a coating film, can be improved further.

  The addition amount of the active hydrogen-containing compound having the group represented by the general formula (8) is preferably 50 to 98 mol% with respect to the isocyanate group in the polyisocyanate which is a precursor of the block polyisocyanate. As a lower limit of the said ratio, 60 mol% is more preferable, More preferably, it is 70 mol%. By the said ratio being 50 mol% or more, the fall of a crosslinking density can be prevented and desired physical properties, such as the water resistance of a coating film, can be obtained. When the ratio is 98 mol% or less, sufficient water dispersibility can be obtained.

  The reaction between the isocyanate group, the active hydrogen-containing compound, and the active hydrogen-containing compound can be performed regardless of the presence or absence of a solvent. When using a solvent, it is preferable to use a solvent inert to the isocyanate group.

  A reaction catalyst can be used in the reaction between the isocyanate group and the active hydrogen-containing compound. Specific examples of the reaction catalyst include organic metal salts such as tin, zinc and lead, metal alcoholates, and tertiary amines.

  In the case where the reaction catalyst used may adversely affect the properties of the aqueous coating composition or the coating film prepared therefrom, it is preferable to deactivate the catalyst with an acidic compound or the like. Examples of acidic compounds include inorganic acids such as hydrochloric acid, phosphorous acid, and phosphoric acid, sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid ethyl ester, and derivatives thereof. , Ethyl phosphate, diethyl phosphate, isopropyl phosphate, diisopropyl phosphate, butyl phosphate, dibutyl phosphate, 2-ethylhexyl phosphate, di (2-ethylhexyl) phosphate, isodecyl phosphate, diisodecyl phosphate, oleyl acid phosphate, tetracosyl acid phosphate, ethyl glycol Acid phosphate, butyl pyrophosphate, butyl phosphite and the like. Two or more of these acidic compounds may be used in combination.

  The reaction temperature between the isocyanate group and the active hydrogen-containing compound is usually preferably from -20 to 150 ° C, more preferably from 0 to 100 ° C, and further preferably from 40 to 80 ° C. By performing the reaction below the upper limit, side reactions can be efficiently suppressed, and by performing the reaction above the lower limit, the reaction rate can be maintained high.

(Method for producing composition containing polyblock isocyanate represented by general formula (9))
These block polyisocyanates can be broadly classified and synthesized by two production methods (hereinafter sometimes referred to as “production method 1” and “production method 2”).

  Production method 1 includes a polyisocyanate which is a source of R in the general formula (9), a malonic acid diester represented by the following general formula (VIII), and an active hydrogen containing group represented by the general formula (8) In this method, the compound is reacted with an organic amine compound represented by the following general formula (IX).

（式中、Ｒ¹⁵及びＲ¹⁶は、それぞれ独立して、炭素数１〜８のアルキル基、フェニル基、又はベンジル基を表す。）

(In the formula, R ¹⁵ and R ¹⁶ each independently represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, or a benzyl group.)

R ¹⁵ and R ¹⁶ in the general formula (VIII) may be the same as R ⁴ described in the general formula (10).

（式中、Ｒ¹⁷及びＲ¹⁸は、それぞれ独立して、炭素数１〜３０の炭化水素基を表す。Ｒ¹⁷及びＲ¹⁸は、任意にエーテル結合、エステル結合、水酸基、カルボニル基、及びチオール基から選ばれる少なくとも１種を含んでもよい。さらに、Ｒ¹⁷及びＲ¹⁸は、任意に一緒になって３〜６員環の環状構造を形成してもよい。）

(In the formula, R ¹⁷ and R ¹⁸ each independently represent a hydrocarbon group having 1 to 30 carbon atoms. R ¹⁷ and R ¹⁸ are optionally ether bonds, ester bonds, hydroxyl groups, carbonyl groups, and thiols. (At least one selected from the group may be included. Further, R ¹⁷ and R ¹⁸ may be optionally combined to form a 3- to 6-membered cyclic structure.)

（式中、Ｒ¹⁵は、炭素数１〜８のアルキル基、フェニル基、又はベンジル基を表し、Ｒ¹⁹及びＲ²⁰は、それぞれ独立して、炭素数１〜３０の炭化水素基を表す。Ｒ¹⁹及びＲ²⁰は、任意にエーテル結合、エステル結合、水酸基、カルボニル基、及びチオール基から選ばれる少なくとも１種を含んでもよい。Ｒ¹⁹及びＲ²⁰は、任意に一緒になって３〜６員環の環状構造を形成してもよい。） Production method 2 is a method in which the polyisocyanate serving as the source of R in general formula (9), the compound represented by general formula (X) below, and the above active hydrogen-containing compound are reacted.

(Wherein, R ¹⁵ represents an alkyl group, a phenyl group, or benzyl group having 1 to 8 carbon atoms, R ¹⁹ and R ²⁰ each independently represent a hydrocarbon group having 1 to 30 carbon atoms. R ¹⁹ and R ^20, optionally an ether bond, an ester bond, a hydroxyl group, a carbonyl group and optionally .R ¹⁹ and R ²⁰ include at least one selected from a thiol group, together optionally 3-6 (It may form a ring structure of member rings.)

R ¹⁵ in the general formula (X) may be the same as R ⁴ described in the general formula (10). R ^{19 in the} general formula (X) may be the same as R ⁵ described in the general formula (10). R ^{20 in the} general formula (X) may be the same as R ⁶ described in the general formula (10).

  The production method 1 is preferable from the viewpoint of simplicity of production and the like. Hereinafter, the production methods 1 and 2 will be described.

  The manufacturing method 1 is implemented by performing the following 1st processes and 2nd processes, for example. The first step is a step of reacting the isocyanate group of the polyisocyanate with the malonic acid diester represented by the formula (VIII) and the active hydrogen-containing compound. The second step is a step of reacting the product obtained in the first step with the organic amine compound represented by the formula (IX).

  In the first step, the reaction between the isocyanate group of the polyisocyanate and the active hydrogen-containing compound and the reaction between the isocyanate group of the polyisocyanate and the malonic acid diester can be performed simultaneously, or after any one of the reactions has been performed in advance. The remaining reaction may be performed. In that case, it is preferable to carry out the reaction between the isocyanate group and the active hydrogen-containing compound first, and then to carry out the reaction using a malonic acid diester.

  In the first step, the reaction is preferably performed in such a ratio that the ratio of the total amount of the active hydrogen-containing compound and the malonic acid diester represented by the formula (VIII) to the isocyanate group of the polyisocyanate is 75 to 150 mol%. The lower limit of the above ratio is more preferably 90 mol% or more, still more preferably 95 mol% or more, and still more preferably 100 mol% or more. The upper limit of the ratio is more preferably 130 mol% or less, still more preferably 120 mol% or less, and still more preferably 110 mol% or less. By the said ratio being 75 mol% or more, the fall of the low temperature curability of a composition can be prevented further. Moreover, when the said ratio is 150 mol% or less, the fall of coating-film physical properties, such as the water resistance of a baking coating film, can be suppressed further.

  The addition amount of the active hydrogen-containing compound is preferably 2 to 50 mol% with respect to the isocyanate group in the polyisocyanate which is a precursor of the block polyisocyanate, based on the number of moles of active hydrogen. As an upper limit of the said ratio, 40 mol% is more preferable, More preferably, it is 35 mol%. When the ratio is 2 mol% or more, sufficient water dispersibility of the composition can be obtained. Moreover, when the said ratio is 50 mol% or less, the fall of a crosslinking density can be suppressed and desired physical properties, such as the water resistance of a coating film, can be obtained.

  The active hydrogen-containing compound in the first step is selected from the aforementioned nonionic compounds, anionic compounds, and cationic compounds. Among these, nonionic compounds and anionic compounds are preferable from the viewpoint of ease of production, and nonionic compounds are more preferable. These active hydrogen-containing compounds may be used alone or in combination of two or more.

  The addition amount of the malonic acid diester is preferably 50 to 98 mol% with respect to the isocyanate group in the polyisocyanate which is a precursor of the block polyisocyanate. As a lower limit of the said ratio, 60 mol% is more preferable, More preferably, it is 70 mol%. By the said ratio being 50 mol% or more, the fall of a crosslinking density can be prevented and desired physical properties, such as the water resistance of a coating film, can be obtained. When the ratio is 98 mol% or less, sufficient water dispersibility can be obtained.

  Regarding the malonic acid diester represented by the general formula (VIII), R15 and R16 may be the same or different, but are preferably the same from the viewpoint of availability. When R15 and R16 are alkyl groups having 8 or less carbon atoms, a decrease in effective NCO% can be suppressed, and compatibility with other components in the aqueous coating composition of the present embodiment can be further improved. R15 and R16 are preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, still more preferably a methyl group or an ethyl group, and still more preferably ethyl. It is a group.

  Specific examples of the malonic acid diester include dimethyl malonate, diethyl malonate, di-n-propyl malonate, diisopropyl malonate, di-n-butyl malonate, diisobutyl malonate, di-tert-butyl malonate, methyl tert-malonate -Butyl ester, di-n-hexyl malonate, di-2-ethylhexyl malonate, diphenyl malonate, dibenzylisobutanoyl acetate malonate, n-propanoyl acetate, n-butanoyl acetate, n-pentanoyl acetate, Examples include n-hexanoyl acetate and 2-ethylheptanoyl acetate. Among these, dimethyl malonate, diethyl malonate, di-n-propyl malonate, diisopropyl malonate, di-n-butyl malonate, diisobutyl malonate, di-tert-butyl malonate, methyl tert-butyl malonate, malon Di-n-hexyl acid, di-2-ethylhexyl malonate isobutanoyl acetate, n-propanoyl acetate, and n-pentanoyl acetate are preferred. More preferably, dimethyl malonate, diethyl malonate, di-n-propyl malonate, diisopropyl malonate, di-n-butyl malonate, diisobutyl malonate, di-tert-butyl malonate, methyl tert-butyl malonate isobuta Noyl acetate. More preferred are dimethyl malonate and diethyl malonate, and most preferred is diethyl malonate. These malonic acid diesters may be used alone or in combination of two or more.

  The reaction of the isocyanate group, the active hydrogen-containing compound, and the malonic acid diester in the first step can be performed regardless of the presence or absence of a solvent. When using a solvent, it is preferable to use a solvent inert to the isocyanate group. A reaction catalyst can be used in the reaction between the isocyanate group and the malonic acid diester. Specific examples of the reaction catalyst include organic metal salts such as tin, zinc and lead, metal alcoholates, and tertiary amines.

  When the reaction catalyst used may adversely affect the physical properties of the coating film, it is preferable to deactivate the catalyst with an acidic compound or the like. Examples of acidic compounds include inorganic acids such as hydrochloric acid, phosphorous acid, and phosphoric acid, sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid ethyl ester, and derivatives thereof. , Ethyl phosphate, diethyl phosphate, isopropyl phosphate, diisopropyl phosphate, butyl phosphate, dibutyl phosphate, 2-ethylhexyl phosphate, di (2-ethylhexyl) phosphate, isodecyl phosphate, diisodecyl phosphate, oleyl acid phosphate, tetracosyl acid phosphate, ethyl glycol Acid phosphate, butyl pyrophosphate, butyl phosphite and the like. These acidic compounds may be used alone or in combination of two or more.

  Although reaction of the said 1st process can generally be performed at -20-150 degreeC, Preferably it is 0-100 degreeC, More preferably, it is 40-80 degreeC. By performing the reaction at 150 ° C. or lower, side reactions can be efficiently suppressed. Further, the reaction rate can be kept high by carrying out the reaction at −20 ° C. or higher.

  Next, the 2nd process of the manufacturing method 1 is demonstrated. The addition amount of the organic amine compound in the second step is 0.5 to 5.0 as a molar ratio of the organic amine compound to the malonic acid diester used in the first step (organic amine compound / malonic acid diester). It is preferable. The lower limit of this molar ratio is more preferably 0.7 or more, and still more preferably 0.9 or more. The upper limit of this molar ratio is more preferably 4.0 or less, still more preferably 3.0 or less, and even more preferably 2.0 or less. When the lower limit of the molar ratio is 0.5 or more, the storage stability of the aqueous coating composition can be further improved, and when it is 5.0 or less, the amount of free amine is reduced and baking is performed. Coloring of the coating film can be effectively prevented.

The organic amine compound used in the second step is an organic amine compound represented by the formula (IX). Specifically, in the organic amine compound represented by the formula (IX), R ¹⁷ and R ¹⁸ may be the same or different.

Examples of the organic amine compound include a chain amine compound and a cyclic amine compound. First, the chain amine compound will be described. For example, R17 and R18 in the chain amine compound represented by the formula (IX) may be the same or different. R17 and R18 are preferably hydrocarbons having 1 to 8 carbon atoms, more preferably a branched alkyl group having 3 to 6 carbon atoms, still more preferably a branched alkyl group having 3 to 4 carbon atoms, Even more preferred is an isopropyl group. When R ¹⁷ and R ¹⁸ are alkyl groups having 30 or less carbon atoms, a decrease in effective NCO% can be further suppressed, and compatibility with other components in the aqueous coating composition can be kept higher.

  Specific examples of the chain amine compound include linear secondary amines such as dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, dioctylamine, dilaurylamine, ditridecylamine, distearylamine; Branched secondary amines such as diisopropylamine, diisobutylamine, di (2-butylamine), di (tert-butyl) amine, di (2-ethylhexyl) amine, dicyclohexylamine, di (2-methylcyclohexyl) amine, diallylamine, etc. Secondary amines containing unsaturated double bonds of: methylethylamine, N-methylisopropylamine, methyl tert-butylamine, N-methylhexylamine, ethyl tert-butylamine, N-ethylhexylamine, N-ethyl-1 Asymmetric secondary amines such as 2-dimethylpropylamine, N-ethylisoamylamine, N-ethyllaurylamine, N-ethylstearylamine, N-methylcyclohexylamine, N-ethylcyclohexylamine, N-tert-butylcyclohexylamine; Aromatic substitution such as diphenylamine, dibenzylamine, methylbenzylamine, ethylbenzylamine, tert-butylbenzylamine, N-methylaniline, N-ethylaniline, N-cyclohexylaniline, 3- (benzylamino) propionic acid ethyl ester Secondary amine having a group; 2- (hydroxymethylamino) ethanol, diethanolamine, N-methylethanolamine, 4-methylaminobutanol, N-ethylethanolamine, N-propylethanol Triethanolamine, N- isopropyl ethanolamine, N- butyl ethanolamine, and the like.

  Among these chain amine compounds, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, dioctylamine, diisopropylamine, diisobutylamine, di (2-butylamine), di (tert-butyl) amine , Di (2-ethylhexyl) amine, dicyclohexylamine, di (2-methylcyclohexyl) amine, diallylamine, methylethylamine, N-methylisopropylamine, methyl tert-butylamine, N-methylhexylamine, ethyl tert-butylamine, N- Ethylhexylamine, N-ethyl-1,2-dimethylpropylamine, N-ethylisoamylamine, N-methylcyclohexylamine, N-ethylcyclohexylamine, N-te t-butylcyclohexylamine, diphenylamine, dibenzylamine, methylbenzylamine, ethylbenzylamine, tert-butylbenzylamine, N-methylaniline, N-ethylaniline, 2- (hydroxymethylamino) ethanol, diethanolamine, N-methyl Ethanolamine, 4-methylaminobutanol, N-ethylethanolamine, N-propylethanolamine, N-isopropylethanolamine, and N-butylethanolamine are preferred. Furthermore, diisopropylamine, diisobutylamine, di (2-butylamine), di (tert-butyl) amine, dicyclohexylamine, N-tert-butylcyclohexylamine are more preferable, diisopropylamine, diisobutylamine, di (2-butylamine), Di (tert-butyl) amine is more preferred, and diisopropylamine is even more preferred.

The cyclic amine compound will be described. As the cyclic amine compound, for example, in the formula (IX), R ¹⁷ and R ¹⁸ together form a 5- or 6-membered cycloalkyl group, or together with a nitrogen atom, Examples thereof optionally include a 3-membered ring, a 4-membered ring, a 5-membered ring, a 6-membered ring, or the like further containing an oxygen atom.

（式中、Ｒ⁷、Ｒ⁸、Ｒ⁹、及びＲ¹⁰は、それぞれ独立して、水素又はメチル基を表し、かつ、そのうち少なくとも１つはメチル基を表す。） Examples of the cyclic amine compound include saturated cyclic amines, aromatic amines, unsaturated bond-containing cyclic amines, and among these, saturated cyclic amines are preferable. Of the saturated cyclic amines, amines containing only one nitrogen atom are preferred, more preferred are 5-membered or 6-membered cyclic amines, and even more preferred are those represented by general formula (11). It is an amine compound.

(In the formula, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent hydrogen or a methyl group, and at least one of them represents a methyl group.)

  Specific examples of the cyclic amine compound include aziridine, azetidine, pyrrolidine, 2-methylpyrrolidine, 3-pyrroldiol, 2-pyrrolidone, proline, 4-hydroxyproline, piperidine, 2-methylpiperidine, 3-methylpiperidine, 4- Methylpiperidine, 4-benzylpiperidine, 2,4-dimethylpiperidine, 3,5-dimethylpiperidine, 2,6-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine, 3-piperidinemethanol, 2-piperidineethanol 4-piperidineethanol, 4-piperidinol, 2-piperidone, 4-piperidone, 4-piperidinecarboxylic acid methyl ester, 4-piperidinecarboxylic acid ethyl ester, 2,2,6,6-tetramethyl-4-piperidone, 4, -Piperidinopiperid , Decahydroquinoline, piperazine, N-methylpiperazine, N-ethylpiperazine, N-allylpiperazine, N-isobutylpiperazine, N-cyclohexylpiperazine, N-cyclopentylpiperazine, N-phenylpiperazine, 1- (2-pyridyl) piperazine 1- (4-pyridyl) piperazine, 1- (2-pyrimidyl) piperazine, N-methylhomopiperazine, N-acetylhomopiperazine, N-butyrylhomopiperazine, oxazolidine, morpholine, imidazolidine, 2-imidazolidone, hydantoin Saturated cyclic amines such as 1-methylhydantoin, 5-methylhydantoin, creatinine, paravanic acid, urazole, thiazolidine, thiaridine; pyrrole, 2-methylpyrrole, 2,4-dimethylpyrrole, 3,4-di Tilpyrrole, 2-acetylpyrrole, 2-pyrrolecarboxylic acid, indole, 3H-indole, 3-methylindole, 2-phenylindole, 3-hydroxylindole, 3-indoleacetic acid, indoline, 2-indolinone, isatin, α-cisatin oxime , Isoindole, isoindoline, 1-isoindolinone, carbazole, 1,2,3,4-tetrahydroquinoline, 1,2,3,4-tetrahydroisoquinoline, 9-acridone, pyrazole, 3,5-dimethylpyrazole, Imidazole, benzimidazole, benzimidazolone, 1H-1,2,3-triazole, 1H-1,2,4-triazole, benzotriazole, tetrazole, purine, xanthine, phenoxazine, isatoic anhydride, benzothiazoli , 2-benzothiazolone, phenothiazine, 5,10-dihydrophenazine, β-carboline, perimidine and other aromatic amines; 2-pyrroline, 3-pyrroline, dihydropyridine, 2-pyrazoline, 5-pyrazolone, 2-imidazoline, 4H-1 , 4-oxazine, 4H-1,4-thiazine, 2H, 6H-1,5,2-dithiazine, and the like, and the like, and the like.

  Among these cyclic amine compounds, aziridine, azetidine, pyrrolidine, 2-methylpyrrolidine, 3-pyrroldiol, 2-pyrrolidone, proline, 4-hydroxyproline, piperidine, 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine 4-benzylpiperidine, 2,4-dimethylpiperidine, 3,5-dimethylpiperidine, 2,6-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine, 3-piperidinemethanol, 2-piperidineethanol, 4 -Piperidine ethanol, 4-piperidinol, 2-piperidone, 4-piperidone, 4-piperidinecarboxylic acid methyl ester, 4-piperidinecarboxylic acid ethyl ester, 2,2,6,6-tetramethyl-4-piperidone, 4-pi Peridinopiperidine Decahydroquinoline, piperazine, N-methylpiperazine, N-ethylpiperazine, N-allylpiperazine, N-isobutylpiperazine, N-cyclohexylpiperazine, N-cyclopentylpiperazine, N-phenylpiperazine, 1- (2-pyridyl) piperazine, 1- (4-pyridyl) piperazine, 1- (2-pyrimidyl) piperazine, N-methylhomopiperazine, N-acetylhomopiperazine, N-butyrylhomopiperazine, oxazolidine, morpholine, imidazolidine, 2-imidazolidone, hydantoin, 1-methylhydantoin, 5-methylhydantoin, creatinine, parabanic acid, urazole, thiazolidine, and thiaridine are preferable.

  Among these, more preferably, aziridine, azetidine, pyrrolidine, 2-methylpyrrolidine, piperidine, 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine, 4-benzylpiperidine, 2,4-dimethylpiperidine, 3, 5-dimethylpiperidine, 2,6-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine, 4-piperidinecarboxylic acid methyl ester, 4-piperidinecarboxylic acid ethyl ester, 2,2,6,6-tetramethyl -4-piperidone, 4-piperidinopiperidine, piperazine, N-methylpiperazine, N-ethylpiperazine, N-allylpiperazine, N-isobutylpiperazine, N-cyclohexylpiperazine, N-cyclopentylpiperazine, N-phenylpiperazine, 1 -(2- Lysyl) piperazine, 1- (4-pyridyl) piperazine, 1- (2-pyrimidyl) piperazine, N-methylhomopiperazine, N-acetylhomopiperazine, N-butyrylhomopiperazine; more preferably pyrrolidine, 2 -Methylpyrrolidine, piperidine, 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine, 2,4-dimethylpiperidine, 3,5-dimethylpiperidine, 2,6-dimethylpiperidine, 2,2,6,6- Tetramethylpiperidine; even more preferably 2-methylpiperidine, 2,6-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine.

  In the second step of production method 1, the amine compounds described above may be used alone or in combination of two or more.

  Similarly to the reaction in the first step, the reaction in the second step can be performed regardless of the presence or absence of a solvent. When using a solvent, it is preferable to use a solvent inert to the isocyanate group. As the solvent, those described above can be used.

  In the reaction of the second step of production method 1, the catalyst exemplified in the first step can also be used. However, when used, the reaction solution may be colored, and it is desirable to reduce the amount used as much as possible. The reaction temperature in the second step is usually preferably from -20 to 150 ° C, more preferably from 0 to 100 ° C, still more preferably from 40 to 80 ° C. By setting the reaction temperature to 150 ° C. or lower, side reactions can be further suppressed. Further, by setting the reaction temperature to −20 ° C. or higher, the reaction rate can be kept higher.

  Moreover, you may manufacture collectively with one of said manufacturing methods, and you may mix the block polyisocyanate composition manufactured separately.

  Next, production method 2 is a method in which the polyisocyanate that is the source of R in the general formula (9), the compound represented by the general formula (X), and the above active hydrogen-containing compound are reacted.

  The reaction between the polyisocyanate and the active hydrogen-containing compound and the reaction between the polyisocyanate and the compound represented by the general formula (X) can be performed at the same time. A reaction may be performed. It is preferable to carry out the reaction between the polyisocyanate and the active hydrogen-containing compound first, and after that, the reaction using the compound represented by the general formula (X) is carried out.

  The total ratio of the active hydrogen-containing compound to the isocyanate group of the polyisocyanate is preferably 75 to 150 mol%. The lower limit of the above ratio is more preferably 90 mol% or more, still more preferably 95 mol% or more, and still more preferably 100 mol% or more. The upper limit of the ratio is more preferably 130 mol% or less, still more preferably 120 mol% or less, and still more preferably 110 mol% or less. By the said ratio being 75 mol% or more, the fall of the low temperature curability of a composition can be prevented further. Moreover, when the said ratio is 150 mol% or less, the fall of coating-film physical properties, such as the water resistance of a baking coating film, can be suppressed further.

  It is preferable that the addition amount of the active hydrogen containing compound used here is 2-50 mol% with respect to the isocyanate group in polyisocyanate which is a precursor of block polyisocyanate on the basis of the number of moles of active hydrogen. The upper limit of the ratio is more preferably 40 mol% or less, and still more preferably 35 mol% or less. When the ratio is 2 mol% or more, sufficient water dispersibility of the composition can be obtained. Moreover, when the said ratio is 50 mol% or less, the fall of a crosslinking density can be suppressed and coating film physical properties, such as the water resistance of a coating film, can be improved further.

  As the active hydrogen-containing compound, the above-mentioned nonionic compounds, anionic compounds, cationic compounds and the like can be used. Among these, from the viewpoint of ease of production, nonionic compounds and anionic compounds are preferable, and nonionic compounds are more preferable. These active hydrogen-containing compounds may be used alone or in combination of two or more.

  It is preferable that the usage-amount of the compound represented by general formula (X) is 50-98 mol% with respect to the isocyanate group in the polyisocyanate which is a precursor of block polyisocyanate. The lower limit of the ratio is more preferably 60 mol% or more, and even more preferably 70 mol% or more. By the said ratio being 50 mol% or more, the fall of a crosslinking density can be prevented and desired physical properties, such as the water resistance of a coating film, can be obtained. When the ratio is 98 mol% or less, sufficient water dispersibility can be obtained.

  The reaction between the isocyanate group, the active hydrogen-containing compound, and the compound represented by the general formula (X) can be performed regardless of the presence or absence of a solvent. When using a solvent, it is preferable to use a solvent inert to the isocyanate group. In the reaction between the isocyanate group and the compound represented by the general formula (X), a reaction catalyst can be used. Specific examples of the reaction catalyst include organic metal salts such as tin, zinc and lead, metal alcoholates, and tertiary amines.

  When the reaction catalyst may adversely affect the physical properties of the coating film, it is preferable to deactivate the catalyst with an acidic compound or the like. Examples of acidic compounds include inorganic acids such as hydrochloric acid, phosphorous acid, and phosphoric acid, sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid ethyl ester, and derivatives thereof. , Ethyl phosphate, diethyl phosphate, isopropyl phosphate, diisopropyl phosphate, butyl phosphate, dibutyl phosphate, 2-ethylhexyl phosphate, di (2-ethylhexyl) phosphate, isodecyl phosphate, diisodecyl phosphate, oleyl acid phosphate, tetracosyl acid phosphate, ethyl glycol Acid phosphate, butyl pyrophosphate, butyl phosphite and the like. These acidic compounds may be used alone or in combination of two or more.

  Although the reaction temperature of the manufacturing method 2 can generally be performed at -20-150 degreeC, Preferably it is 0-100 degreeC, More preferably, it is 40-80 degreeC. By performing the reaction at 150 ° C. or lower, side reactions can be efficiently suppressed. Further, the reaction rate can be kept high by carrying out the reaction at −20 ° C. or higher.

  In the water-based coating composition of the present embodiment, the mass ratio of the polycarbonate diol composition (= the composition containing the block copolymer and the polycartnate diol) to the blocked isocyanate composition (polycarbonate diol composition / block isocyanate composition) is It is preferable that it is 10 / 90-90 / 10. In the aqueous coating composition of this embodiment, it is preferable that content of a block copolymer is 5-90 mass% per resin part of an aqueous coating composition.

  The upper limit of the mass ratio of the block copolymer to the blocked isocyanate composition is more preferably 80/20 or less, still more preferably 70/30 or less, and still more preferably 60/40 or less. The lower limit of the mass ratio of the block copolymer to the block isocyanate composition is preferably 20/80 or more, more preferably 30/70 or more, and even more preferably 40/60 or more. By making the upper limit of the mass ratio of the block copolymer to the block polyisocyanate composition not more than the above value, the curability is further improved, and the lower limit of the mass ratio of the block copolymer to the block polyisocyanate composition is the above. By setting it to a value or more, the scratch resistance, appearance, and flexibility are further improved.

<Active hydrogen-containing compounds>
The aqueous coating composition of the present embodiment preferably further contains an active hydrogen-containing compound other than the polycarbonate composition. The active hydrogen compound here is a compound in which two or more active hydrogens are bonded in the molecule. Examples of the active hydrogen compound include polyols, polyamines, polythiols and the like, and polyols are preferably used from the viewpoint of workability and reactivity.

  The polyol is not particularly limited, and examples thereof include polyester polyol, acrylic polyol, polyether polyol, polyolefin polyol, fluorine polyol, polycarbonate polyol, and epoxy polyol.

  The polyester polyol is not particularly limited. For example, a polyester polyol obtained by a condensation reaction of a dibasic acid and a polyhydric alcohol, and polycaprolactones obtained by ring-opening polymerization of a polyhydric alcohol and ε-caprolactone. Etc. Although it does not specifically limit as a dibasic acid, For example, it is 1 type chosen from the group which consists of carboxylic acids, such as a succinic acid, adipic acid, a sebacic acid, a dimer acid, a maleic anhydride, a phthalic anhydride, an isophthalic acid, a terephthalic acid The above is mentioned. The polyhydric alcohol is not particularly limited, and examples thereof include one or more selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, trimethylolpropane, glycerin and the like.

  The acrylic polyol is not particularly limited. For example, a homopolymer of an ethylenically unsaturated bond-containing monomer having one or more kinds of hydroxyl groups, and an ethylenic group having one or more kinds of hydroxyl groups. Examples thereof include a copolymer of an unsaturated bond-containing monomer and one or more other ethylenically unsaturated bond-containing monomers copolymerizable therewith.

  The ethylenically unsaturated bond-containing monomer having a hydroxyl group is not particularly limited, and examples thereof include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and methacrylic acid. Hydroxybutyl etc. are mentioned. Among these, hydroxyethyl acrylate and hydroxyethyl methacrylate are preferable.

  Examples of other ethylenically unsaturated bond-containing monomers that can be copolymerized with an ethylenically unsaturated bond-containing monomer having a hydroxyl group include, but are not limited to, for example, methyl acrylate, ethyl acrylate, propyl acrylate Acrylates such as isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, benzyl acrylate, and phenyl acrylate Methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, methacrylic acid-n-butyl, methacrylate isobutyl, methacrylic acid-n-hexyl, methacrylic acid cyclohexyl, methacrylic acid-2-ethylhexyl, methacrylate Methacrylic acid esters such as lauryl acid, benzyl methacrylate, and phenyl methacrylate; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid; acrylamide, methacrylamide, N, N-methylenebisacrylamide, diacetone acrylamide , Unsaturated amides such as diacetone methacrylamide, maleic acid amide, maleimide; vinyl monomers such as glycidyl methacrylate, styrene, vinyl toluene, vinyl acetate, acrylonitrile, dibutyl fumarate; and vinyl trimethoxysilane, vinyl methyl And vinyl monomers having hydrolyzable silyl groups such as dimethoxysilane and γ- (meth) acryloxypropyltrimethoxysilane.

  The polyether polyols are not particularly limited. For example, polyether polyols obtained by adding an alkylene oxide to a polyvalent hydroxy compound using a hydroxide and / or a strong basic catalyst; ethylenediamines Polyether polyols obtained by reacting an alkylene oxide with a polyfunctional compound such as; and so-called polymer polyols obtained by polymerizing acrylamide or the like using these polyethers as a medium.

  Although it does not specifically limit as a polyvalent hydroxy compound, For example, diglycerin, ditrimethylol propane, pentaerythritol, dipentaerythritol, etc .; erythritol, D-threitol, L-arabinitol, ribitol, xylitol, sorbitol, mannitol, galactitol Sugar alcohol compounds such as rhamnitol; monosaccharides such as arabinose, ribose, xylose, glucose, mannose, galactose, fructose, sorbose, rhamnose, fucose, ribosese; trehalose, sucrose, maltose, cellobiose, gentiobiose, lactose, melibiose, etc. Disaccharides; trisaccharides such as raffinose, gentianose, and meletitose; tetrasaccharides such as stachyose.

  Examples of the alkylene oxide include one or more selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, styrene oxide, and the like. Although it does not specifically limit as a hydroxide, For example, hydroxides, such as lithium, sodium, potassium, etc. are mentioned. Further, the strong basic catalyst is not particularly limited, and examples thereof include alcoholate and alkylamine.

  The polyolefin polyol is not particularly limited, and examples thereof include polybutadiene having two or more hydroxyl groups, hydrogenated polybutadiene, polyisoprene, and hydrogenated polyisoprene.

  It is preferable that the number of statistical hydroxyl groups (hereinafter, also referred to as “hydroxyl average functional group number”) possessed by one molecule of polyol is 2 or more. When the number of hydroxyl group average functional groups is 2 or more, the crosslinking density of the obtained coating film tends to be further improved.

  A fluorine polyol is a polyol containing fluorine in its molecule. Although it does not specifically limit as a fluorine polyol, For example, fluoroolefin, cyclovinyl ether, hydroxyalkyl vinyl ether, monocarboxylic acid vinyl ester currently disclosed by Unexamined-Japanese-Patent No. 57-034107, Unexamined-Japanese-Patent No. 61-275111, etc. And the like.

  The polycarbonate polyol is not particularly limited. For example, a low molecular carbonate compound such as a dialkyl carbonate such as dimethyl carbonate, an alkylene carbonate such as ethylene carbonate, a diaryl carbonate such as diphenyl carbonate, and the low molecular polyol used in the polyester polyol described above. And the like obtained by condensation polymerization.

  Although it does not specifically limit as an epoxy polyol, For example, a novolak type, (beta) -methyl epichloro type, cyclic oxirane type, glycidyl ether type, glycol ether type, the epoxy type of an aliphatic unsaturated compound, epoxidized fatty acid ester type, polyvalent carboxylic Examples thereof include epoxy polyols such as acid ester type, aminoglycidyl type, halogenated type, and resorcin type.

  Among the above, acrylic polyol and polyester polyol are preferable, and acrylic polyol is more preferable.

  The mass ratio of the active hydrogen-containing compound to the block copolymer (active hydrogen-containing compound / block copolymer) is preferably 10/90 to 90/10. The upper limit of the mass ratio of the active hydrogen-containing compound to the block copolymer is more preferably 80/20 or less, still more preferably 70/30 or less, and still more preferably 60/40 or less. The lower limit of the mass ratio of the active hydrogen-containing compound to the block copolymer is more preferably 30/70 or less, still more preferably 40/60 or less, and still more preferably 50/50 or less. By setting the upper limit of the mass ratio of the active hydrogen-containing compound to the block copolymer to be the above value or less, the scratch resistance, appearance, and flexibility can be further improved, and by setting the lower limit to the above value or more, Curability and water resistance can be further improved.

  The aqueous coating composition of this embodiment can mix | blend the existing melamine resin, an epoxy resin, and a polyurethane resin. Moreover, when an active hydrogen containing compound has a carboxyl group, an oxazoline group containing compound and a carbodiimide group containing compound can be mix | blended. Moreover, when the polyol mentioned above has a carbonyl group, a hydrazide group containing compound and a semicarbazide group containing compound can be mix | blended. These compounds may be used alone or in combination of two or more.

  As a melamine resin, the part obtained by reaction of a melamine and an aldehyde, or a complete methylol-ized melamine resin etc. are mentioned, for example. Examples of aldehydes include formaldehyde and paraformaldehyde. Moreover, what methylated the methylol group of this methylolation melamine resin partially or completely with alcohol can also be used. Specific examples of the alcohol used for etherification include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-ethylbutanol, 2-ethylhexanol and the like.

  A commercial item can also be used as a melamine resin. Examples of such commercially available products include “Cymel 303”, “Cymel 323”, “Cymel 325”, “Cymel 327”, “Cymel 350”, “Cymel 370”, “Cymel 380”, “Cymel 385”, “Cymel 212”, “Cymel 251”, “Cymel 254”, “My Coat 776” (all trade names manufactured by Nippon Cytec Industries, Inc.), and the like.

  When melamine resin is used, sulfonic acids such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, and salts of these acids and amines are used as catalysts for baking and curing. be able to.

  The epoxy resin is not particularly limited as long as it is a resin having two or more epoxy groups per molecule, and a known one can also be used. Examples of the epoxy resin include a bisphenol type epoxy resin obtained by adding epoxychlorohydrin to bisphenol, a novolak type epoxy resin obtained by adding epichlorohydrin to a phenol novolac resin, and polyethylene glycol diglycidyl ether. The epoxy resin can be used after being dispersed in water as necessary.

  The polyurethane resin is not limited as long as it is generally used in paints, but a polyurethane resin that is chain-extended by reacting an isocyanate group with a polyol is preferable. The polyurethane resin includes those having a carboxyl group obtained by using a carboxyl group-containing polyol as part of the polyol, and those having a hydroxyl group at the terminal. The polyurethane resin having a carboxyl group is preferably neutralized with a basic substance. Commercially available products include “Superflex 110”, “Superflex 150”, “Superflex 460S” (all trade names manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), “Neolet's R9649”, “Neolet's R966” (all Avicia) Product name).

  Examples of the oxazoline group-containing compound include a polymer compound having at least two oxazoline groups in the side chain, and a monomer compound having at least two oxazoline groups in the molecule.

  The carbodiimide group-containing compound can be obtained, for example, by subjecting the isocyanate groups of the polyisocyanate compound to a carbon dioxide removal reaction. Examples of commercially available carbodiimide group-containing compounds include “carbodilite V-02”, “carbodilite V-02-L2”, “carbodilite V-04”, “carbodilite E-01”, “carbodilite E-02” (any And Nisshinbo Co., Ltd., trade names).

Examples of the hydrazide group-containing compound include compounds having at least 2, preferably 2 to 10, hydrazide groups represented by —CO—NH—NH ₂ in one molecule. Examples of the hydrazide group-containing compound include saturated dicarboxylic acid dihydrazides having 2 to 18 carbon atoms such as oxalic acid dihydrazide, malonic acid dihydrazide, glutaric acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide; maleic acid dihydrazide Monoolefinic unsaturated dicarboxylic acid dihydrazides such as fumaric acid dihydrazide and itaconic acid dihydrazide; polyhydrazides obtained by reacting a low polymer having a carboxylic acid lower alkyl ester group with hydrazine or hydrazine hydrate, etc. .

The semicarbazide group-containing compound includes a compound having at least 2, preferably 2 to 10, semicarbazide groups represented by —NH—CO—NH—NH ₂ in one molecule. As a semicarbazide group-containing compound, for example, bissemicarbazide; a diisocyanate such as hexamethylene diisocyanate or isophorone diisocyanate or a polyisocyanate compound derived therefrom is reacted with N, N-substituted hydrazine such as N, N-dimethylhydrazine or the hydrazine exemplified above. And polyfunctional semicarbazide obtained by the reaction.

  In preparing the aqueous coating composition, the polycarbonate diol composition and the block polyisocyanate composition can be directly added as they are, or those diluted in advance in an aqueous solvent can be blended. When diluting in advance with an aqueous solvent, a method of gradually dropping the aqueous solvent (so-called phase inversion emulsification method) or a method of adding and mixing the aqueous solvent in a lump can be employed.

  The aqueous solvent includes not only water but also other hydrophilic organic solvents. That is, water, a hydrophilic organic solvent, or both may be used. The usable organic solvent is preferably a hydrophilic solvent that can be mixed with water without phase separation. Specific examples include ethanol, butyl cellosolve, methyl ethyl ketone, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate and the like.

  If necessary, curing accelerators (for example, organometallic compounds such as tin, zinc, lead and other carboxylic acids), antioxidants (for example, hindered phenols), ultraviolet absorbers (for example, benzotriazole, benzophenone) Etc.), pigments (eg titanium oxide, carbon black, indigo, quinacridone, pearl mica etc.), metal powder pigments (eg aluminum), rheology control agents (eg hydroxyethyl cellulose, urea compounds etc.) Good.

  The water-based coating composition of this embodiment contains a block copolymer, a polycarbonate diol, and a blocked isocyanate composition, thereby improving elasticity, chipping resistance, adhesion, chemical resistance, abrasion resistance, and water resistance. And soft feel, crosslinkability, appearance improvement and the like can be imparted.

  The aqueous coating composition of the present embodiment is a curable composition such as a paint composition, an adhesive composition, an adhesive composition, a casting composition, or various surface treatment compositions such as a fiber treatment agent, It is used as a cross-linking agent, modifier, or additive for various elastomer compositions and foam compositions.

  When used as a coating composition, it is suitably used as a primer, intermediate coating, or top coating on various materials by roll coating, curtain flow coating, spray coating, electrostatic coating, bell coating, or the like. This coating composition is suitable for imparting cosmetic properties, weather resistance, acid resistance, rust resistance, chipping resistance, adhesion, etc. to pre-coated metal, automobile coating, plastic coating, etc., further containing a rust-proof steel plate. Used.

  In particular, the coating composition using the aqueous coating composition of the present embodiment has good surface smoothness and chemical resistance, and further has excellent adhesion to an organic coating film. It is useful as an aqueous top clear coat. The base coat and the top clear coat are preferably cured simultaneously.

  In addition, when the aqueous coating composition of the present embodiment is used as a pressure-sensitive adhesive composition or an adhesive composition, it is diluted with a solvent, for example, from the viewpoint of workability when applied to an adherend and ease of thinning It can be used as an applied coating solution.

  Fields of use when the pressure-sensitive adhesive composition and the adhesive composition are used include automobiles, building materials or home appliances, woodwork, solar cell laminates, and the like. Among them, optical members for liquid crystal displays of home appliances such as televisions, personal computers, digital cameras, and mobile phones exhibit various functions. Therefore, it is necessary to laminate films and plates of various adherends. Since sufficient tackiness or adhesiveness is required between films and plates of various adherends, it is preferable as an example of use of the pressure-sensitive adhesive composition and adhesive composition of the present invention.

  Examples of the adherend to which the water-based coating composition of this embodiment can be used (sometimes referred to as “substrate”) include various metals such as glass, aluminum, iron, galvanized steel, copper, and stainless steel. Porous materials such as wood, paper, mortar, stone, fluorine coated, urethane coated, acrylic urethane coated, silicone, modified silicone, urethane and other sealing materials, vinyl chloride, natural Rubbers such as rubber and synthetic rubber, leathers such as natural leather and artificial leather, plants, animals, fibers such as carbon fibers and glass fibers, non-woven fabrics, polyesters, acrylics, polycarbonates, triacetylcellulose, polyolefins, etc. Examples include films and plates of resins, UV curable acrylic resin layers, printing inks, inks such as UV inks, and the like.

  EXAMPLES Hereinafter, although this invention is demonstrated using an Example and a comparative example, this invention is not limited to a following example.

(Measurement of number average molecular weight)
The number average molecular weight is a polystyrene-based number average molecular weight by GPC measurement.
Equipment: “HLC-8120GPC (trade name)” manufactured by Tosoh Corporation
Column: manufactured by Tosoh Corporation, “TSKgelSuperH1000 (trade name)” × 1, “TSKgelSuperH2000 (trade name)” × 1, “TSKgelSuperH3000 (trade name)” × 1 Carrier: tetrahydrofuran Detection method: differential refractometer

(Measurement of hydroxyl value)
Measured according to JIS K1557-1: 2007.

[Evaluation of physical properties of coating film]
(Abrasion resistance)
On the surface of a glass plate (JIS R3202, 75 mm × 150 mm square, 1 mm thickness), the prepared paint is dropped onto the top of the plate so that the dry film thickness is 40 to 50 μm, and a glass rod having a diameter of 8 mm is used. Coated. Subsequently, the film was preliminarily dried for 30 minutes in an atmosphere of 23 ° C. and 50% RH on a horizontal table, and then dried at 140 ° C. for 30 minutes to form a coating film. Then, the surface of the coating film was rubbed 10 times with a certain force using a brass wire brush. The percent value of the value obtained by dividing the 60 degree gloss value after rubbing by the 60 degree gloss value before rubbing (initial 60 degree gloss value / 60 degree gloss value after rubbing) was evaluated as the gloss value. The case where the gloss value was 90% or more was evaluated as “◯”, the case where it was 80% or more and less than 90% was evaluated as “Δ”, and the case where it was less than 70% was evaluated as “X”. The gloss value was measured according to JIS Z8741.

(water resistant)
The prepared paint is dropped on the top of the glass plate (JIS R3202, 75 mm × 75 mm square, 1 mm thickness) so that the dry film thickness is 40 to 50 μm, and is applied using a glass rod with a diameter of 8 mm. Worked. Subsequently, the film was preliminarily dried for 30 minutes in an atmosphere of 23 ° C. and 50% RH on a horizontal table, and then dried at 140 ° C. for 30 minutes to form a coating film. And the coating film was immersed in 23 degreeC water for 24 hours, and the presence or absence of abnormality, such as whitening and a swelling, was evaluated visually. The case where there was a visual abnormality was evaluated as “×”, and the case where there was no abnormality was evaluated as “◯”.

(Smoothness)
The prepared paint is dropped onto the top of the ABS plate (acrylonitrile-butadiene-styrene resin; black, 150 mm × 75 mm) so that the dry film thickness is 50 μm, and coated using a glass rod with a diameter of 8 mm. did. Subsequently, the film was preliminarily dried for 30 minutes in an atmosphere of 23 ° C. and 50% RH on a horizontal table, and then dried at 140 ° C. for 30 minutes to form a coating film.
The appearance (sharpness and surface smoothness) of the obtained coating film should be measured using a digital oscilloscope “Wave Scan DOI” (BYK Gardner) along the long side direction of the ABS plate. Evaluated by. “Wave Scan DOI” is an arrangement in which a laser point light source emits a laser beam at an angle of 60 ° with respect to a normal to the film surface, and a detector receives reflected light of the same angle opposite to the normal. This apparatus moves the laser point light source over the film surface and scans it, thereby measuring the brightness of the reflected light point by point at a predetermined interval and detecting the optical profile of the film surface. The detected optical profile can be spectrally analyzed through a frequency filter to analyze the surface structure. In that, the value of the Wc area (wavelength 1.0-3.0 mm) of a coating film was used and evaluated. The measured value was an arithmetic average value of three measured values. Wc is an index of the smoothness of the coating film, and it was judged that the smaller the value, the better the smoothness. A measured value of 1.0 or less was evaluated as “◯”, and 1.0 or more was evaluated as “x”.

(Curable)
On the surface of the polypropylene plate, the prepared paint was dropped onto the top of the plate so as to have a dry film thickness of 40 to 50 μm, and coating was performed using a glass rod having a diameter of 8 mm. Subsequently, the film was preliminarily dried for 30 minutes in an atmosphere of 23 ° C. and 50% RH on a horizontal table, and then dried at 140 ° C. for 30 minutes to obtain a cured coating film. After immersing the cured coating film in acetone at 20 ° C. for 24 hours, the mass of undissolved components was measured, and the gel fraction was calculated based on the following formula. The case where the gel fraction was 80% by mass or more was evaluated as “◯”, and the case where it was less than 80% by mass was evaluated as “x”.

Gel fraction (mass%) = (mass of undissolved component) ÷ (total amount before dipping the sample) × 100

[Synthesis Example 1] (Production of Polycarbonate Diol Composition A-1 Containing Block Copolymer and Polycarbonate Diol)
The inside of the four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blowing tube was purged with nitrogen. “Duranol T5652 (trade name)” manufactured by Asahi Kasei Chemicals Co., Ltd. (a copolymer polycarbonate diol having a number average molecular weight of about 2000 using 1,5-pentanediol and 1,6-hexanediol as diols. Diol composition: 90 parts by mass of 1,5-pentanediol / 1.6-hexanediol = 50 mol% / 50 mol%, manufactured by Wako Pure Chemical Industries, Ltd., “polyethylene glycol 600 (trade name)” (number average molecular weight Is about 600 parts of polyoxyethylene diol), and dioctyl tin laurate (transesterification reaction catalyst) was charged so that the ratio was 140 ppm with respect to the copolymeric polycarbonate diol. And the temperature in a reactor was maintained at about 150 degreeC, and was stirred for 6 hours. Thereafter, the temperature in the reactor was cooled to room temperature to obtain a composition (polycarbonate diol composition) containing a block copolymer and a polycarbonate diol.
In the transesterification reaction, the reaction solution is subjected to GPC measurement over time, so that the disappearance of the peak derived from the polyethylene glycol as the raw material and the appearance of the peak derived from the product are confirmed over time. Confirmed progress. And about the polycarbonate diol composition finally obtained, based on the preparation amount of a raw material, reaction progressed substantially quantitatively, and the block copolymer may have the transesterified structure. confirmed.
Moreover, according to the method shown below, when the ratio of the hydroxyl group in the terminal structure of the block copolymer in a composition was confirmed, it confirmed that it was 95 mol% or more. First, the polycarbonate diol composition is heated under reduced pressure to obtain a fraction of an amount corresponding to about 1 to 2% by mass of the block copolymer, which is recovered using an alcohol such as ethanol as a solvent. A measurement solution was obtained. This measurement solution was subjected to gas chromatography (GC) analysis, and calculated from the peak area value of the obtained chromatogram based on the following formula.

Ratio of hydroxyl groups in the total amount of terminal groups (mol%) = (total sum of peak areas of diols having hydroxyl groups at both ends) / (total sum of peak areas of diol-containing alcohols (excluding ethanol)) × 100

Moreover, according to the method shown below, the kind of substituent R of general formula (1) of a block copolymer and the kind of substituent R of polycarbonate diol represented by general formula (3) in a composition were confirmed. As a result, the pentylene group was 46.5 mol% and the hexylene group was 51.6 mol%.
First, about 1 g of the composition and 0.5 g of 1,3-propanediol as an internal standard substance for GC analysis were added to a 100 mL eggplant flask. Then, 30 mL of ethanol and 3.95 g of potassium hydroxide were added to this, and a magnetic stirrer was further added, followed by stirring in an oil bath set at 105 ± 5 ° C. for 1 hour, thereby removing the carbonate bond portion in the composition. The alkali was decomposed. Thereafter, the mixture was cooled to room temperature, a few drops of phenolphthalein indicator were added to the reaction solution, and hydrochloric acid was added little by little until the color disappeared. After the color disappeared, the supernatant was transferred to a sample bottle, added with the same amount of ethanol, and allowed to stand overnight in a refrigerator with an internal temperature of 5 ° C. After standing, the supernatant was filtered using a membrane filter having a pore size of 0.45 μm to obtain a filtrate. The filtrate was subjected to GC analysis, and from the relationship between the peak area and the weight ratio, the factors of each component obtained in advance were converted, and the mol% was calculated based on the following formula (i).

Ratio (mol%) = {(molar amount of a structure in which R in the general formula (1) is a pentylene group or hexylene group) + (molar amount of a component in which R in the general formula (3) is a pentylene group or hexylene group) } / {(Total molar amount of the structure represented by the general formula (1)) + (total molar amount of the component represented by the general formula (3))} × 100 (i)

-GC analysis conditions Equipment: GC-14B manufactured by Shimadzu Corporation
Column: G-300 capillary column (20 m),
Detector: FID
Carrier gas: Helium Injection temperature: 250 ° C
Column temperature: 100 ° C to 210 ° C at a heating rate of 10 ° C / min

The appearance, hydroxyl value, number average molecular weight, water reducibility, and water-dispersed particle size of the polycarbonate diol composition containing the obtained polycarbonate diol were evaluated.

[Synthesis Example 2] (Production of Polycarbonate Diol Composition A-2 Containing Block Copolymer and Polycarbonate Diol)
The inside of the four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blowing tube was purged with nitrogen. “Duranol T5652 (trade name)” manufactured by Asahi Kasei Chemicals Co., Ltd. (a copolymer polycarbonate diol having a number average molecular weight of about 2000 using 1,5-pentanediol and 1,6-hexanediol as diols. Diol composition: 75 parts by mass of 1,5-pentanediol / 1,6-hexanediol = 50 mol% / 50 mol%, manufactured by Wako Pure Chemical Industries, Ltd., “polyethylene glycol 1000 (trade name)” (number average molecular weight Dioctyltin laurate (transesterification reaction catalyst) was charged so that 25 parts by mass of polyoxyethylene diol having a molecular weight of about 1000) was 140 ppm with respect to the copolymeric polycarbonate diol. And the temperature in a reactor was maintained at about 150 degreeC, and was stirred for 6 hours. Thereafter, the temperature in the reactor was cooled to room temperature to obtain a composition (polycarbonate diol composition) containing a block copolymer and a polycarbonate diol.
In the transesterification reaction, the reaction solution is subjected to GPC measurement over time, so that the disappearance of the peak derived from the polyethylene glycol as the raw material and the appearance of the peak derived from the product are confirmed over time. Confirmed progress. And about the polycarbonate diol composition finally obtained, based on the preparation amount of a raw material, reaction progressed substantially quantitatively, and the block copolymer may have the transesterified structure. confirmed.
Further, according to the method of Synthesis Example 1, the proportion of hydroxyl groups in the terminal structure of the block copolymer in the polycarbonate diol composition was confirmed, and it was confirmed that it was 95 mol% or more.
Further, according to the method of Synthesis Example 1, the type of substituent R of the general formula (1) of the block copolymer and the type of substituent R of the polycarbonate diol represented by the general formula (3) in the composition are changed. When confirmed, the pentylene group was 46.8 mol% and the hexylene group was 51.2 mol%.
The appearance, hydroxyl value, number average molecular weight, water reducibility, and water-dispersed particle size of the polycarbonate diol composition containing the obtained polycarbonate diol were evaluated.

[Synthesis Example 3] (Production of Polycarbonate Diol Composition A-3 Containing Block Copolymer and Polycarbonate Diol)
The inside of the four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blowing tube was purged with nitrogen. “Duranol T5652 (trade name)” manufactured by Asahi Kasei Chemicals Co., Ltd. (a copolymer polycarbonate diol having a number average molecular weight of about 2000 using 1,5-pentanediol and 1,6-hexanediol as diols. Diol composition: 1,5-pentanediol / 1,6-hexanediol = 50 mol% / 50 mol%) 85.5 parts by mass, manufactured by Wako Pure Chemical Industries, Ltd., “polyethylene glycol 600 (trade name)” (number 10 parts by mass of polyoxyethylene diol having an average molecular weight of about 600), 4.5 parts by mass of 1,5-pentanediol as a molecular weight regulator, and dioctyltin at a ratio of 140 ppm with respect to the copolymeric polycarbonate diol. Laurate (a transesterification catalyst) was charged. And the temperature in a reactor was maintained at about 150 degreeC, and was stirred for 6 hours. Thereafter, the temperature in the reactor was cooled to room temperature to obtain a composition (polycarbonate diol composition) containing a block copolymer and a polycarbonate diol.
In the transesterification reaction, the reaction solution is subjected to GPC measurement over time, so that the disappearance of the peak derived from the polyethylene glycol as the raw material and the appearance of the peak derived from the product are confirmed over time. Confirmed progress. And about the polycarbonate diol composition finally obtained, based on the preparation amount of a raw material, reaction progressed substantially quantitatively, and the block copolymer may have the transesterified structure. confirmed.
Further, according to the method of Synthesis Example 1, the proportion of hydroxyl groups in the terminal structure of the block copolymer in the polycarbonate diol composition was confirmed, and it was confirmed that it was 95 mol% or more.
Further, according to the method of Synthesis Example 1, the type of substituent R of the general formula (1) of the block copolymer and the type of substituent R of the polycarbonate diol represented by the general formula (3) in the composition are changed. When confirmed, the pentylene group was 47.3 mol% and the hexylene group was 50.7 mol%.
The appearance, hydroxyl value, number average molecular weight, water reducibility, and water-dispersed particle size of the polycarbonate diol composition containing the obtained polycarbonate diol were evaluated.

[Synthesis Example 4] (Production of polycarbonate diol composition A-4 containing block copolymer and polycarbonate diol)
The inside of the four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blowing tube was purged with nitrogen. “Duranol T5651 (trade name)” manufactured by Asahi Kasei Chemicals Co., Ltd. (a copolymer polycarbonate diol having a number average molecular weight of about 1000, using 1,5-pentanediol and 1,6-hexanediol as the diol. Diol composition: 90 parts by mass of 1,5-pentanediol / 1,6-hexanediol = 50 mol% / 50 mol%, manufactured by Wako Pure Chemical Industries, Ltd., “polyethylene glycol 600 (trade name)” (number average molecular weight 5 parts by mass of polyoxyethylene diol having a molecular weight of about 600, 5 parts by mass of “polyethylene glycol 1000 (trade name)” (polyoxyethylene diol having a number average molecular weight of about 1000) manufactured by Wako Pure Chemical Industries, Ltd. The amount was 140 ppm with respect to the polycarbonate diol. These were heated with stirring and maintained at about 150 ° C. for 6 hours as the reactor internal temperature. Then, it cooled to room temperature and obtained the composition (polycarbonate diol composition) containing a block copolymer and polycarbonate diol.
In the transesterification reaction, the reaction solution is subjected to GPC measurement over time, so that the disappearance of the peak derived from the polyethylene glycol as the raw material and the appearance of the peak derived from the product are confirmed over time. Confirmed progress. And about the polycarbonate diol composition finally obtained, based on the preparation amount of a raw material, reaction progressed substantially quantitatively, and the block copolymer may have the transesterified structure. confirmed.
Further, according to the method of Synthesis Example 1, the proportion of hydroxyl groups in the terminal structure of the block copolymer in the polycarbonate diol composition was confirmed, and it was confirmed that it was 95 mol% or more.
Further, according to the method of Synthesis Example 1, the type of substituent R of the general formula (1) of the block copolymer and the type of substituent R of the polycarbonate diol represented by the general formula (3) in the composition are changed. When confirmed, the pentylene group was 46.6 mol% and the hexylene group was 51.6 mol%.
The appearance, hydroxyl value, number average molecular weight, water reducibility, and water-dispersed particle size of the polycarbonate diol composition containing the obtained polycarbonate diol were evaluated.

[Synthesis Example 5] (Production of HDI-based isocyanurate type polyisocyanate)
The inside of a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen blowing tube was purged with nitrogen. Thereto was charged 1000 g of HDI, and 0.1 g of trimethylbenzylammonium hydroxide was added as a catalyst while stirring at 60 ° C. After 4 hours, when the conversion rate of the reaction solution reached 38%, 0.2 g of phosphoric acid was added to stop the reaction. Then, after filtering the reaction liquid, unreacted HDI monomer was removed by thin film distillation to obtain polyisocyanate.
The resulting polyisocyanate had a viscosity at 25 ° C. of 2700 mPa · s, an isocyanate group content of 22.2% by mass, a number average molecular weight of 650, and an average number of isocyanate groups of 3.4. Thereafter, the presence of an isocyanurate bond was confirmed by NMR measurement.

[Synthesis Example 6] (Production of Block Polyisocyanate Composition B-1)
A 4-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen blowing tube and dropping funnel was placed in a nitrogen atmosphere, and 100 parts by mass of the polyisocyanate obtained in Synthesis Example 5 (the isocyanate group of the polyisocyanate in this case) And 42.3 parts by mass of monomethoxypolyethylene glycol having a number average molecular weight of 400 (manufactured by NOF Corporation, trade name “Uniox M400”) (corresponding to 20 mol% of isocyanate group in polyisocyanate) Then, 131.3 parts by mass of diethylene glycol dimethyl ether was charged and held at 80 ° C. for 6 hours. Thereafter, the reaction solution temperature was cooled to 60 ° C., 72.0 parts by mass of diethyl malonate (corresponding to 85 mol% of the isocyanate group in polyisocyanate), 0.88 parts by mass of 28% methanol solution of sodium methylate, After holding for 4 hours, 0.86 parts by mass of 2-ethylhexyl acid phosphate was added. Thereafter, 45.5 parts by mass of diisopropylamine (corresponding to 85 mol% of the isocyanate group in the polyisocyanate) was added, and the temperature of the reaction solution was raised to 70 ° C. and held for 5 hours. This reaction solution was analyzed by gas chromatography to confirm that the reaction rate of diisopropylamine was 70%, and a block polyisocyanate composition having a solid content concentration of 60% by mass was obtained.

[Synthesis Example 7] (Production of Block Polyisocyanate Composition B-2)
A 4-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen blowing tube and dropping funnel was placed in a nitrogen atmosphere, and 100 parts by mass of the polyisocyanate obtained in Synthesis Example 5 (the isocyanate group of the polyisocyanate in this case) And 42.3 parts by mass of monomethoxypolyethylene glycol having a number average molecular weight of 400 (manufactured by NOF Corporation, trade name “Uniox M400”) (corresponding to 20 mol% of isocyanate group in polyisocyanate) , 116.9 parts by mass of diethylene glycol dimethyl ether were charged and held at 80 ° C. for 6 hours. Thereafter, the temperature of the reaction solution was cooled to 60 ° C., 39.0 parts by mass of methyl ethyl ketoxime (corresponding to 85 mol% of the isocyanate group in polyisocyanate) was maintained at 80 ° C. for 1 hour, and then 0.86 parts by mass of 2-ethylhexyl acid phosphate Was added. A block polyisocyanate composition having a solid content concentration of 60% by mass was obtained.

[Example 1]
12.3 parts by mass of “SETAQUA6510 (acryl polyol manufactured by Nuplex Resin, solid content 42%, hydroxyl group 4.2% by mass)”, 10.3 parts by mass of ion-exchanged water, and the polycarbonate diol composition produced in Synthesis Example 1 2.2 parts by mass of A-1 were weighed and mixed, and stirred for 20 minutes at 600 rpm using a stirrer to obtain a mixture free from insolubles and aggregates. To this, 5.3 parts by mass of the block polyisocyanate composition B-1 produced in Synthesis Example 6 was added and further stirred at 600 rpm for 10 minutes. Then, in order to remove air bubbles from the mixture, the mixture was allowed to stand for 10 minutes and then filtered through a filter cloth made of 110 mesh polyamide synthetic fiber to obtain a paint. The coating film properties of the obtained paint were evaluated.

[Example 2]
The same operation as in Example 1 was performed except that the polycarbonate diol composition A-1 in Example 1 was changed to the polycarbonate diol composition A-2 produced in Synthesis Example 2.

[Example 3]
The same operation as in Example 1 was performed except that the polycarbonate diol composition A-1 of Example 1 was changed to the polycarbonate diol composition A-3 produced in Synthesis Example 3.

[Example 4]
The same operation as in Example 1 was performed except that the polycarbonate diol composition A-1 of Example 1 was changed to the polycarbonate diol composition A-4 produced in Synthesis Example 4.

[Examples 5 to 8]
The same procedure as in Example 1 was performed except that the component composition shown in Table 2 was used.

[Example 9]
The same operation as in Example 1 was performed except that the blocked polyisocyanate composition B-1 of Example 1 was changed to the blocked polyisocyanate composition B-2 produced in Synthesis Example 7.

[Example 10]
8.9 parts by mass of neutralized dimethylaminoethanol of “SETAL 6306 (polyester polyol manufactured by Nuplex Resin, solid content 60%, hydroxyl group 89 mgKOH / resin g, acid value 42 mgKOH / resin g)” and 13.7 parts of ion-exchanged water 2.2 parts by mass of the polycarbonate diol composition A-1 produced in Synthesis Example 1 were weighed and mixed, and stirred for 20 minutes at 600 rpm using a stirrer to remove insolubles and aggregates. No mixture was obtained. To this, 5.3 parts by mass of the block polyisocyanate composition B-1 produced in Synthesis Example 6 was added and further stirred at 600 rpm for 10 minutes. Then, in order to remove air bubbles from the mixture, the mixture was allowed to stand for 10 minutes and then filtered through a filter cloth made of 110 mesh polyamide synthetic fiber to obtain a paint. The physical properties of the obtained paint were evaluated.

[Example 11]
7.4 parts by mass of the polycarbonate diol composition A-1 produced in Synthesis Example 1 and 17.5 parts by mass of ion-exchanged water were each weighed and mixed, and stirred at 600 rpm for 20 minutes using a stirrer. A mixture free of insolubles and aggregates was obtained. To this, 5.3 parts by mass of the block polyisocyanate composition B-1 produced in Synthesis Example 6 was added and further stirred at 600 rpm for 10 minutes. Then, in order to remove air bubbles from the mixture, the mixture was allowed to stand for 10 minutes and then filtered through a filter cloth made of 110 mesh polyamide synthetic fiber to obtain a paint. The physical properties of the obtained paint were evaluated.

[Comparative Example 1]
17.5 parts by mass of “SETAQUA6510” (acrylic polyol manufactured by Nuplex Resin, solid content 42%, hydroxyl group 4.2% by mass), 7.2 parts by mass of ion-exchanged water, block polyisocyanate composition produced in Synthesis Example 6 The product B-1 was added in an amount of 5.3 parts by mass, and further stirred at 600 rpm for 10 minutes. Then, in order to remove air bubbles from the mixture, the mixture was allowed to stand for 10 minutes and then filtered through a filter cloth made of 110 mesh polyamide synthetic fiber to obtain a paint. The physical properties of the obtained paint were evaluated.

[Comparative Example 2]
12.8 parts by mass of neutralized dimethylaminoethanol of “SETAL6306” (polyester polyol manufactured by Nuplex Resin, solid content 60%, hydroxyl group 89 mgKOH / resin g, acid value 42 mgKOH / resin g), and ion-exchanged water 12.0 parts 5.3 parts by mass of the block polyisocyanate composition B-1 synthesized in Synthesis Example 6 was added and further stirred at 600 rpm for 10 minutes. Then, in order to remove air bubbles from the mixture, the mixture was allowed to stand for 10 minutes and then filtered through a filter cloth made of 110 mesh polyamide synthetic fiber to obtain a paint. The physical properties of the obtained paint were evaluated.

  Hereinafter, the results of each of the synthesis examples, examples, and comparative examples are shown in each table. In addition, unless otherwise indicated, the following table | surface is based on a mass reference | standard.

単位：質量部

Unit: parts by mass

  From the above, it was confirmed that the aqueous coating composition of this example was excellent in scratch resistance, water resistance, smoothness and curability.

  The water-based coating composition of the present invention includes automobiles, buses, railway vehicles, construction machinery, agricultural machinery, floors and walls and roofs of buildings, metal products, mortar and concrete products, woodwork products, plastic products, calcium silicate plates and plaster. It can be suitably used in a wide range of fields such as water-based paints, water-based inks, water-based adhesives, etc. for ceramics and building materials such as boards.

Claims (10)

A polycarbonate / polyoxyethylene block containing a polycarbonate structure represented by the following general formula (1) and a polyoxyethylene structure represented by the following general formula (2), wherein both ends are substantially hydroxyl groups A copolymer;
A polycarbonate diol represented by the following general formula (3);
A block polyisocyanate composition;
A water-based coating composition containing

-(R-O-CO-O) _m- (1)

(In the formula, each R independently represents a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, or a divalent aroma which may have a branch having 2 to 15 carbon atoms. Represents a group hydrocarbon group, and m represents a number.)

_{- (CH 2 -CH 2 -O)} n - (2)

(In the formula, n represents a number.)

HO- (RO-CO-O) _p- R-OH (3)

(In the formula, each R independently represents a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, or a divalent hydrocarbon group that may have 2 to 15 carbon atoms. Represents an aromatic hydrocarbon group, and p represents a number.)   2. The aqueous coating composition according to claim 1, wherein in the polycarbonate / polyoxyethylene block copolymer, the R is both a pentylene group and a hexylene group. The polycarbonate / polyoxyethylene block copolymer and the polycarbonate diol are polycarbonate diol represented by the following general formula (3) as a raw material, and polyethylene glycol represented by the following general formula (4) as a raw material, The water-based coating composition according to claim 1 or 2, obtained by transesterification.

HO- (RO-CO-O) _p- R-OH (3)

(In the formula, each R independently represents a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, or a divalent hydrocarbon group that may have 2 to 15 carbon atoms. Represents an aromatic hydrocarbon group, and p represents a number.)

HO— (CH ₂ —CH ₂ —O) _q —H (4)

(In the formula, q represents a number.)   4. The aqueous coating composition according to claim 3, wherein in the polycarbonate diol represented by the general formula (3) as the raw material, the R is at least a pentylene group and a hexylene group.   5. The aqueous coating composition according to claim 4, wherein in the polycarbonate diol represented by the general formula (3) as the raw material, the ratio of the polycarbonate diol in which R is a pentylene group or a hexylene group is 50 mol% or more. object.   The mass ratio of the polycarbonate diol represented by the general formula (3) as the raw material (polycarbonate diol / polyethylene glycol) to the polyethylene glycol represented by the general formula (4) as the raw material is 50/50 to The aqueous coating composition according to any one of claims 3 to 5, which is 95/5. The water-based coating composition as described in any one of Claims 1-6 in which the said block polyisocyanate composition contains the at least 1 sort (s) of block polyisocyanate represented by following General formula (5).

R ^1- (B) _l (5)

(In the formula, R ¹ represents a group obtained by removing an isocyanate group from any one selected from the group consisting of aliphatic polyisocyanate, alicyclic polyisocyanate, and aromatic polyisocyanate; Represents a group represented by the following general formula (6), and l = 2 to 20.)

(In the formula, R ² represents a group excluding active hydrogen of the active hydrogen-containing compound.) The water-based coating composition as described in any one of Claims 1-6 in which the said block polyisocyanate composition contains the at least 1 sort (s) of block polyisocyanate represented by following General formula (7).

R ^1- (B) _s (C) _t (7)

(In the formula, R ¹ represents a group obtained by removing an isocyanate group from any one selected from the group consisting of aliphatic polyisocyanate, alicyclic polyisocyanate, and aromatic polyisocyanate; Represents a group represented by the following general formula (6), each C independently represents a group represented by the following general formula (8), s + t = 2 to 20, and t is 0. Absent.)

(In the formula, R ² represents a group excluding active hydrogen of the active hydrogen-containing compound.)

(In the formula, R ³ represents a group excluding active hydrogen of the active hydrogen-containing compound.) The water-based coating composition as described in any one of Claims 1-6 in which the said block polyisocyanate composition contains the at least 1 sort (s) of block polyisocyanate represented by following General formula (9).

R ¹ − (A) _x (B) _y (C) _z (9)

(In the formula, R ¹ represents a group obtained by removing an isocyanate group from any one selected from the group consisting of aliphatic polyisocyanate, alicyclic polyisocyanate, and aromatic polyisocyanate; Represents one selected from the group consisting of the group represented by the following general formula (10), its keto structure, and its enol structure, and each B is independently represented by the following general formula (6). And each C independently represents a group represented by the following general formula (8), x + y + z = 2 to 20, and x and z are not 0.)

(In the formula, R ⁴ represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, or a benzyl group, and R ⁵ and R ⁶ each independently represents a hydrocarbon group having 1 to 30 carbon atoms. Incidentally, R ⁵ and R ^6, optionally, an ether bond, an ester bond, a hydroxyl group may include at least one selected from the group consisting of a carbonyl group and a thiol group. further, R ⁵ and R ^6, together To form a 3- to 6-membered ring structure.

(In the formula, R ² represents a group excluding active hydrogen of the active hydrogen-containing compound.)

(In the formula, R ³ represents a group excluding active hydrogen of the active hydrogen-containing compound.)   The aqueous coating composition according to any one of claims 1 to 9, further comprising an active hydrogen-containing compound.