Polyol-containing composition, and polyurethane and aqueous polyurethane using same as starting material

Abstract

Provided is a novel polyol-containing composition or the like which is capable of forming a polyurethane or an aqueous polyurethane that not only has excellent durability, but also has improved functionality in accordance with introduction of functional groups. The present invention provides a polyol-containing composition comprising at least one hydroxyl compound, the polyol-containing composition having a number average molecular weight of 300 to 5,000, the number average molecular weight of the polyol-containing composition comprising at least one hydroxyl compound, the number average molecular weight of the polyol-containing composition comprising at least one hydroxyl compound; the at least one hydroxy compound has: at least one main skeleton structure selected from the group consisting of an isocyanurate skeleton, an iminooxadiazinedione skeleton, a biuret skeleton, an allophanate skeleton, an aromatic skeleton, and an alicyclic skeleton; at least one sub-skeleton structure connected to the main skeleton structure directly or via a linking group and selected from the group consisting of a carbonate bond, an ether bond, and an ester bond; at least two terminal hydroxyl groups connected to the sub-skeleton structure directly or via a linking group; and at least one functional group other than a hydroxyl group attached to the main skeleton structure directly or via a linking group.

Description

Technical Field

[0001] The present invention relates to a composition containing a polyol, and polyurethane and aqueous polyurethane using the composition as a raw material. Background Art

[0002] Polyurethane resins are used in a wide range of fields, including synthetic leather, artificial leather, adhesives, furniture coatings, and automotive coatings. Polyurethane resins are typically obtained as addition polymers of isocyanates and polyol components. Polyurethane resins are required to exhibit various durability properties, including heat resistance, water resistance, weather resistance, hydrolysis resistance, solvent resistance, sunscreen resistance, and scratch resistance. Therefore, polyol components having skeleton structures such as polyethers, polyesters, and polycarbonates have been studied as polyol components that react with isocyanates in polyurethane resin raw materials.

[0003] In recent years, research has been underway to develop polyurethanes with improved water dispersibility, antifouling properties, and abrasion resistance as high-performance polyurethane resins. Specifically, Patent Document 1 discloses a polyurethane resin (A) having an anionic group (a1) and a polyethylene oxide chain (a2) on a side chain, obtained by reacting an anionic group-containing polyol (b1), trimethylolpropane mono(polyethylene oxide methyl ether), and an aliphatic cyclic structure-containing polyol (b3) with a polyisocyanate (C). Furthermore, Patent Document 2 discloses a polyurethane-polysiloxane network with improved antifouling properties by combining a polysiloxane having two or more isocyanate functional groups as the isocyanate.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent No. 5316427

[0007] Patent Document 2: Japanese Patent No. 6235329 Summary of the Invention

[0008] Problems to be solved by the invention

[0009] To further enhance the functionality of polyurethanes, research is underway to introduce new functional groups while meeting the aforementioned durability requirements. However, the method of incorporating three or more polyol components, as in Patent Document 1, presents the following issues: Unexpected gelation, which can occur when mixed with isocyanates, reduces the reactivity with isocyanate groups, making it difficult to form the desired three-dimensional network. This, in turn, impairs the durability of the resulting polyurethane, creating the aforementioned trade-off. Furthermore, because Patent Document 1 incorporates a polyol component with a flexible alkyl group as its main skeleton and side chains, the resulting polyurethane suffers from weak intermolecular interactions and poor heat resistance.

[0010] Furthermore, when polysiloxane diisocyanate is used as in Patent Document 2, polysiloxane as a functional group is introduced into the main skeleton of the polyurethane. When functional groups are introduced into the main skeleton of the polyurethane in this manner, a relatively large amount of the component containing the functional group must be incorporated to achieve the desired functionality. Consequently, the proportion of other components used is inevitably limited, leading to trade-offs with other physical properties.

[0011] Therefore, an object of the present invention is to provide a novel polyol-containing composition, etc., which can form a polyurethane or water-based polyurethane having not only excellent durability but also various functionalities enhanced by the introduction of functional groups. Another object of the present invention is to provide high-quality polyurethane and water-based polyurethane, etc., obtained using the novel polyol-containing composition.

[0012] Solutions for solving problems

[0013] The present inventors conducted intensive research to address the above-mentioned issues and discovered that by using a hydroxy compound having a specific structure in which a functional group is introduced as a side chain with high mobility as a polyol component, the above-mentioned trade-off is less likely to occur. This discovery allows for the production of high-quality polyurethanes or water-based polyurethanes that not only exhibit excellent durability but also have various enhanced functionalities due to the introduction of the functional group. This has led to the completion of the present invention. Specifically, the present invention provides various specific embodiments as shown below. (1)

[0015] A polyol-containing composition comprising at least one hydroxyl compound,

[0016] The polyol-containing composition has a number average molecular weight of 300 to 5,000,

[0017] At least one of the hydroxyl compounds has: at least one main skeleton structure selected from the group consisting of an isocyanurate skeleton, an iminooxadiazinedione skeleton, a biuret skeleton, an allophanate skeleton, an aromatic skeleton and an alicyclic skeleton; at least one secondary skeleton structure connected to the main skeleton structure directly or via a connecting group and selected from the group consisting of a carbonate bond, an ether bond and an ester bond; at least two or more terminal hydroxyl groups connected to the secondary skeleton structure directly or via a connecting group; and at least one functional group other than a hydroxyl group connected to the main skeleton structure directly or via a connecting group. (2)

[0019] The polyol-containing composition according to (1), wherein the content ratio of the functional group is 0.1 to 60.0 parts by mass when the total amount of the polyol-containing composition is 100 parts by mass. (3)

[0021] The polyol-containing composition according to (1) or (2), wherein the content ratio of the functional group is 0.1 to 20.0 parts by mass when the total amount of the polyol-containing composition is 100 parts by mass. (4)

[0023] The polyol-containing composition according to any one of (1) to (3), wherein the functional group is at least one selected from the group consisting of a hydrophilic group, a hydrophobic group, an adsorptive group, and a crosslinkable group. (5)

[0025] The polyol-containing composition according to any one of (1) to (4), wherein the functional group is a hydrophilic group. (6)

[0027] The polyol-containing composition according to any one of (1) to (5), wherein the functional group is a hydrophobic group. (7)

[0029] The polyol-containing composition according to any one of (1) to (6), wherein the functional group is an adsorption group. (8)

[0031] The polyol-containing composition according to any one of (1) to (7), wherein the functional group is a cross-linking group. (9)

[0033] The polyol-containing composition according to any one of (1) to (8), wherein the functional group is at least two or more selected from the group consisting of a hydrophilic group, a hydrophobic group, an adsorptive group, and a crosslinkable group. (10)

[0035] The polyol-containing composition according to any one of (1) to (9), wherein at least one of the hydroxy compounds has a structure represented by the following formula (I).

[0036] Formula (I)

[0037]

[0038] (In formula (I), m is an integer greater than or equal to 1, n is an integer greater than or equal to 2, Z is at least one selected from the group consisting of an isocyanurate skeleton, an iminooxadiazinedione skeleton, a biuret skeleton, an allophanate skeleton, an aromatic skeleton, and an alicyclic skeleton, R 1 is a straight-chain or branched divalent hydrocarbon group, alicyclic structure or single bond, R 1 Each is optionally different, the divalent hydrocarbon group and the alicyclic structure optionally have a heteroatom, X 1 is a single bond or a divalent linking group, X 1 Each is optionally different, FG is the functional group, X 2 is a single bond or a divalent linking group, X 2 Each of them is optionally different, and P is represented by the following formula (II), and each of them is optionally different.

[0039] Formula (II)

[0040]

[0041] (In formula (II), n is an integer greater than or equal to 1, * is a connecting bond, and R 2 is a divalent straight-chain or branched hydrocarbon group, R 2 Each is optionally different and optionally has a heteroatom, and Y is at least one selected from the group consisting of a carbonate bond, an ether bond, and an ester bond. (11)

[0043] The polyol-containing composition according to (10), wherein the X in the formula (I) 1 、X 2 Contains at least one of carbamate, urea, and thiourea. (12)

[0045] The polyol-containing composition according to (10) or (11), wherein the Y in the formula (II) is a carbonate bond. (13)

[0047] A polyurethane obtained by using the polyol-containing composition according to any one of (1) to (12). (14)

[0049] A water-based polyurethane obtained by using the polyol-containing composition according to any one of (1) to (12). (15)

[0051] A polyurethane comprising an addition polymer of the polyol-containing composition according to any one of (1) to (12) and a polyfunctional isocyanate. (16)

[0053] A water-based polyurethane comprising an addition polymer of the polyol-containing composition according to any one of (1) to (12) and a polyfunctional isocyanate.

[0054] Effects of the Invention

[0055] According to the present invention, a novel polyol-containing composition can be achieved, which can form polyurethanes or water-based polyurethanes that not only exhibit excellent durability but also possess various enhanced functionalities through the introduction of functional groups. Furthermore, the use of such polyol-containing compositions can produce high-quality polyurethanes and water-based polyurethanes. Furthermore, according to the present invention, by introducing functional groups as highly mobile side chains, various functionalities can be exhibited with relatively small amounts of functional groups, thus minimizing the aforementioned trade-off. Consequently, design freedom can be increased when synthesizing polyurethanes and water-based polyurethanes with desired properties. DETAILED DESCRIPTION

[0056] Hereinafter, a method for implementing the present invention (hereinafter referred to as "this embodiment") is described in detail. It should be noted that the following embodiments are examples for illustrating the present invention, and the present invention is not limited thereto. That is, the present invention can be implemented by being arbitrarily changed within the scope of its main purpose. It should be noted that in this specification, for example, the marking of a numerical range of "1 to 100" includes both its lower limit "1" and its upper limit "100". In addition, the markings of other numerical ranges are also the same.

[0057] [Polyol-containing composition]

[0058] The polyol-containing composition of the present embodiment is characterized in that it contains at least one hydroxyl compound, the polyol-containing composition has a number average molecular weight of 300 to 5,000, and at least one of the hydroxyl compounds has: at least one main skeleton structure selected from the group consisting of an isocyanurate skeleton, an iminooxadiazinedione skeleton, a biuret skeleton, an allophanate skeleton, an aromatic skeleton and an alicyclic skeleton; at least one secondary skeleton structure directly or via a connecting group connected to the main skeleton structure and selected from the group consisting of a carbonate bond, an ether bond and an ester bond; at least two or more terminal hydroxyl groups connected to the secondary skeleton structure directly or via a connecting group; and at least one functional group other than a hydroxyl group connected to the main skeleton structure directly or via a connecting group.

[0059] The polyol-containing composition of the present embodiment has the above-mentioned characteristics, so that the above-mentioned trade-off is not likely to occur, thereby being able to form a high-quality polyurethane or water-based polyurethane that is not only excellent in durability but also has various functionalities improved with the introduction of functional groups (functional functional groups). It should be noted that the functional group refers to any functional group other than a hydroxyl group, which can form a high-quality polyurethane or water-based polyurethane by having a specific function. As a specific example of the functional group, there is no particular limitation, for example, a hydrophilic group, a hydrophobic group, an adsorptive group, a cross-linking group, etc. It should be noted that the functional group possessed by the specific hydroxy compound may be only one kind, or may be any two or more kinds. For example, the specific hydroxy compound may have only one functional group selected from the group consisting of a hydrophilic group, a hydrophobic group, an adsorptive group and a cross-linking group, or may have two or more or three or more functional groups.

[0060] The polyol-containing composition of the present embodiment contains at least one hydroxy compound. Here, in this specification, at least one hydroxy compound as an essential component is referred to as a "specific hydroxy compound," and hydroxy compounds as optional components other than the specific hydroxy compound are referred to as "other hydroxy compounds." Examples of other hydroxy compounds include polyol compounds other than specific hydroxy compounds, polycarbonate polyols other than specific hydroxy compounds, polyester polyols described in Japanese Patent Application Laid-Open No. 2018-012769, alkane diols, acrylic polyols, polyether polyols, polyester polyols, polyolefin polyols, and polyols such as fluoropolyols, but are not particularly limited thereto.

[0061] In addition, the polyol-containing composition of the present embodiment may be a single compound containing only the above-mentioned specific hydroxy compound, or may be a mixture of the above-mentioned specific hydroxy compound and other hydroxy compounds. Furthermore, the polyol-containing composition of the present embodiment may contain components other than the above-mentioned specific hydroxy compound and other hydroxy compounds (hereinafter sometimes referred to as "other components") within a range that does not excessively impair the effects of the present invention.

[0062] The polyol-containing composition of the present embodiment has a number average molecular weight (Mn) of 300 to 5,000. When the number average molecular weight is within the above range, a polyurethane coating film or a water-based polyurethane coating film having excellent water dispersibility and appearance when the coating film is formed can be formed. The number average molecular weight of the polyol-containing composition is preferably 500 or more, more preferably 800 or more, preferably 3,500 or less, more preferably 2,700 or less. The number average molecular weight of the polyol-containing composition can be calculated by GPC (gel permeation chromatography) measurement (THF) described in the examples described later. It should be noted that the method for controlling the number average molecular weight of the polyol-containing composition of the present embodiment within the above range is not particularly limited, and examples thereof include the following methods: a method of adjusting the ratio of raw materials so that the number average molecular weight is within the above range when manufacturing the polyol-containing composition; a method of controlling by adding and / or removing polyol compounds when manufacturing the polyol-containing composition.

[0063] The molecular weight distribution (mass average molecular weight (Mw) / number average molecular weight (Mn)) of the polyol-containing composition of the present embodiment is not particularly limited, but the lower limit is preferably 1.00 or greater, more preferably 1.20 or greater, even more preferably 1.50 or greater, even more preferably 1.80 or greater, particularly preferably 2.00 or greater, even more particularly preferably 2.10 or greater, and extremely preferably 2.20 or greater. The upper limit of the molecular weight distribution is not particularly limited, but is preferably 7.00 or less, more preferably 6.00 or less, even more preferably 5.00 or less, even more preferably 4.50 or less, particularly preferably 4.00 or less, even more particularly preferably 3.70 or less, extremely preferably 3.50 or less, and even more preferably 3.30 or less. The numerical range of the molecular weight distribution (Mw / Mn) of the polyol-containing composition can also be specified by appropriately combining the lower limit and upper limit values. For example, the numerical range of the molecular weight distribution can be set to 1.00-6.00, 1.20-5.00, 1.50-4.50, 1.80-4.00, 2.00-3.70, 2.10-3.50, 2.00-3.30, etc. By making the molecular weight distribution of the polyol-containing composition of the present embodiment be within the above range, for example, there is a tendency for the coating film of the obtained polyurethane to have an excellent appearance. It should be noted that the mass average molecular weight and number average molecular weight of the polyol-containing composition of the present embodiment can be calculated by GPC (gel permeation chromatography) measurement (THF) described in the examples described later. In addition, the molecular weight distribution (Mw / Mn) can be obtained by the following formula based on the calculated mass average molecular weight and number average molecular weight.

[0064] Molecular weight distribution (Mw / Mn) = mass average molecular weight (Mw) / number average molecular weight (Mn)

[0065] The number of functional groups calculated by the following formula in the polyol-containing composition of the present embodiment is preferably 1.20 to 10.00, more preferably 1.30 to 8.00, further preferably 1.40 to 6.00, further preferably 1.50 to 5.00, particularly preferably 1.60 to 4.00, even more preferably 1.70 to 3.50, and extremely preferably 1.80 to 3.00.

[0066] Number of functional groups = Mn × OHV / 56.11 / 1000

[0067] (In the above formula, Mn represents the number average molecular weight of the polyol-containing composition determined by GPC measurement (THF), and OHV represents the hydroxyl value of the polyol-containing composition.)

[0068] The content ratio of the functional group is not particularly limited, but is preferably 0.1 to 60 parts by mass, more preferably 0.1 to 40 parts by mass, further preferably 0.1 to 20 parts by mass, further preferably 0.2 to 20 parts by mass, further preferably 0.5 to 20 parts by mass, and extremely preferably 1 to 10 parts by mass, based on 100 parts by mass of the total amount of the polyol-containing composition.

[0069] <Specific Hydroxyl Compounds>

[0070] The specific hydroxy compound has: at least one main skeleton structure selected from the group consisting of an isocyanurate skeleton, an iminooxadiazinedione skeleton, a biuret skeleton, an allophanate skeleton, an aromatic skeleton and an alicyclic skeleton; at least one sub-skeleton structure selected from the group consisting of a carbonate bond (-O-(C=O)-O-), an ether bond (-O-) and an ester bond (-(C=O)-O-) connected to the main skeleton structure directly or via a connecting group; at least two or more terminal hydroxyl groups (-OH) connected to the sub-skeleton structure directly or via a connecting group; and at least one functional group other than a hydroxyl group connected to the main skeleton structure directly or via a connecting group.

[0071] The specific hydroxy compound is a polyol compound having the above-mentioned main skeleton structure and the above-mentioned sub-skeleton structure having two or more terminal hydroxyl groups. Due to such a structure, it exhibits excellent durability, such as heat resistance, water resistance, and chemical resistance. Furthermore, specific examples of functional groups that can be introduced into the main skeleton structure as highly mobile side chains, thereby exhibiting various functionalities with relatively small amounts of introduction, are not particularly limited, and examples thereof include hydrophilic groups, hydrophobic groups, adsorptive groups, and crosslinking groups.

[0072] A hydrophilic group refers to a functional group with high affinity for water. By introducing a hydrophilic group as a functional group, the water dispersibility of the polyurethane or water-based polyurethane obtained using the polyol-containing composition of the present embodiment can be improved. The hydrophilic group is not particularly limited, and nonionic hydrophilic groups, anionic hydrophilic groups, cationic hydrophilic groups, and amphoteric hydrophilic groups can be cited. Among them, from the viewpoints of versatility, nonionic hydrophilic groups and anionic hydrophilic groups are preferred. It should be noted that the hydrophilic groups herein do not contain hydroxyl groups.

[0073] The nonionic hydrophilic group is not particularly limited, and examples thereof include oxyalkylene groups, polyols and fatty acid-containing esters, and more specifically, oxyethylene alkyl ethers (such as polyethylene glycol monomethyl ether and polypropylene glycol monomethyl ether).

[0074] The anionic hydrophilic group is not particularly limited, and examples thereof include a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc. Among them, from the viewpoint of water resistance, etc., a carboxyl group and a sulfonic acid group are preferred, and a carboxylic acid group is more preferred.

[0075] The cationic hydrophilic group is not particularly limited, and examples thereof include tetraalkylammonium groups.

[0076] The amphoteric hydrophilic group is not particularly limited, and examples thereof include groups having anionic and cationic structures in the same molecule, and groups having a betaine structure such as a carboxybetaine group, a sulfobetaine group, and a phosphobetaine group.

[0077] The proportion of the hydrophilic group contained is not particularly limited. Based on 100 parts by mass of the total amount of the polyol-containing composition, the proportion is preferably 0.1 to 60 parts by mass, more preferably 0.2 to 40 parts by mass, further preferably 0.5 to 20 parts by mass, and extremely preferably 1 to 10 parts by mass. By setting the hydrophilic group content in the polyol-containing composition of this embodiment within the above range, the water dispersibility of the polyol-containing composition, the polyurethane obtained using the polyol-containing composition, or the water-based polyurethane tends to be improved, and the water resistance of the resulting polyurethane coating film is also improved.

[0078] The hydrophobic group is a functional group that can reduce the surface free energy of the resulting polyurethane or aqueous polyurethane. By introducing a hydrophobic group as a functional group, the water repellency of the polyurethane coating film obtained using the polyol-containing composition can be improved.

[0079] The hydrophobic group is not particularly limited, but examples thereof include a linear or branched hydrocarbon group having 3 or more carbon atoms, which may contain heteroatoms, and a group having a polydialkylsiloxane structure. The hydrocarbon group preferably has 5 or more carbon atoms, more preferably 6 or more carbon atoms, and most preferably 7 or more carbon atoms.

[0080] The proportion of the hydrophobic group contained is not particularly limited. When the total amount of the polyol-containing composition is 100 parts by mass, it is preferably 0.1 to 60 parts by mass, more preferably 0.2 to 30 parts by mass, further preferably 0.5 to 20 parts by mass, and extremely preferably 1 to 10 parts by mass. By setting the hydrophobic group content in the polyol-containing composition of this embodiment within the above range, there is a tendency to improve the water repellency and coating appearance of the polyurethane coating film or water-based polyurethane coating film obtained using the polyol-containing composition.

[0081] Adsorptive groups are functional groups capable of adsorbing to adjacent substrates through chemical bonds or physical interactions such as van der Waals forces, hydrogen bonds, and electrostatic interactions. By introducing adsorbent groups as functional groups, the adhesion of polyurethane coatings or water-based polyurethane coatings obtained using polyol-containing compositions to substrates can be improved.

[0082] Adsorptive groups that adsorb via chemical bonds are not particularly limited, and examples thereof include alkoxysilyl groups and phenolic hydroxyl groups. Adsorptive groups that adsorb via physical interactions are not particularly limited, and examples thereof include phenyl groups, amide groups, and urea groups. Introducing a structure identical to that of the substrate is also effective. For example, in the case of a PET substrate, introducing a polyester structure for the purpose of introducing an ester group can improve adsorption to the PET substrate.

[0083] The content of the adsorptive groups is not particularly limited, but is preferably 0.1 to 30 parts by mass, more preferably 0.2 to 15 parts by mass, and even more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the total amount of the polyol-containing composition. By setting the adsorbent group content in the polyol-containing composition of this embodiment within the above range, the adsorption of the polyurethane coating film and the aqueous polyurethane coating film obtained using the polyol-containing composition to a substrate tends to be improved, and the storage stability of the resulting polyurethane or aqueous polyurethane tends to be improved.

[0084] A crosslinking group refers to a functional group capable of undergoing a crosslinking reaction. By introducing an adsorptive group as a functional group, the durability of the resulting polyurethane coating or waterborne polyurethane coating can be improved. It should be noted that crosslinking based on the crosslinking group can be intramolecular or intermolecular. In the case of intermolecular crosslinking, a curing agent having a functional group reactive with the crosslinking group can be optionally used in combination with the polyurethane coating or waterborne polyurethane coating during production.

[0085] The crosslinkable group is not particularly limited, and examples thereof include epoxy groups, isocyanate groups, unsaturated carbon bonds, thiol groups, and carboxyl groups. Furthermore, the crosslinkable group may be protected by a protecting group for purposes such as improving the storage stability of the resulting polyurethane or water-based polyurethane. The protected crosslinkable group is not particularly limited, and examples thereof include isocyanate groups bonded to β-ketoester groups, oxazole groups, and secondary amino groups, and carboxyl groups bonded to tertiary carbon groups such as tert-butyl groups.

[0086] The content of the crosslinkable group is not particularly limited, but is preferably 0.1 to 50 parts by mass, more preferably 0.2 to 30 parts by mass, and even more preferably 0.5 to 20 parts by mass, based on 100 parts by mass of the total amount of the polyol-containing composition. By setting the crosslinkable group content in the polyol-containing composition of this embodiment within the above range, the durability of the polyurethane coating film or water-based polyurethane coating film obtained using the polyol-containing composition tends to be improved, and the storage stability of the resulting polyurethane and water-based polyurethane tends to be improved.

[0087] Specific examples of the specific hydroxy compound include those having a structure represented by the following formula (I).

[0088] Formula (I)

[0089]

[0090] (In formula (I), m is an integer greater than or equal to 1, n is an integer greater than or equal to 2, Z is at least one selected from the group consisting of an isocyanurate skeleton, an iminooxadiazinedione skeleton, a biuret skeleton, an allophanate skeleton, an aromatic skeleton, and an alicyclic skeleton, R 1 is a straight-chain or branched divalent hydrocarbon group, alicyclic structure or single bond, R 1 Each is optionally different, the divalent hydrocarbon group and the alicyclic structure optionally have a heteroatom, X 1 is a single bond or a divalent linking group, X 1 Each is optionally different, FG is the functional group, X 2 is a single bond or a divalent linking group, X 2 Each of them is optionally different, and P is represented by the following formula (II), and each of them is optionally different.

[0091] Formula (II)

[0092]

[0093] In formula (II), n is an integer greater than or equal to 1, * is a connecting bond, and R 2 is a divalent straight-chain or branched hydrocarbon group, R 2 Each is optionally different and optionally has a heteroatom, and Y is at least one selected from the group consisting of a carbonate bond, an ether bond, and an ester bond.

[0094] In above-mentioned formula (I), Z is at least one selected from the group consisting of isocyanurate skeleton, iminooxadiazinedione skeleton, biuret skeleton, allophanate skeleton, aromatic ring skeleton and alicyclic skeleton. Wherein, preferably isocyanurate skeleton, iminooxadiazinedione skeleton, biuret skeleton, allophanate skeleton, alicyclic skeleton, more preferably isocyanurate skeleton, iminooxadiazinedione skeleton, biuret skeleton. It should be noted that Z, as long as it includes the above-mentioned one, can also be used in combination with the main skeleton structure other than the skeleton mentioned herein.

[0095] In the above formula (I), X 1 is a single bond or a divalent linking group. Examples of divalent linking groups include ester bonds, amide bonds, urea bonds, carbamate bonds, thiourea bonds, and thioether bonds. 1 More preferred are single bonds, urea bonds, carbamate bonds, and thiourea bonds, and even more preferred are urea bonds and carbamate bonds. 1 It is sufficient to include one of the above-mentioned groups, and it may be used in combination with a linking group other than the groups listed here.

[0096] In the above formula (I), X 2 is a single bond or a divalent linking group. Examples of divalent linking groups include ester bonds, amide bonds, urea bonds, carbamate bonds, thiourea bonds, and thioether bonds. 2 More preferred are single bonds, urea bonds, carbamate bonds, and thiourea bonds, and even more preferred are urea bonds and carbamate bonds. 2 It is sufficient to include one of the above-mentioned groups, and it may be used in combination with a linking group other than the groups listed here.

[0097] In the above formula (I), X 1 、X 2 It is preferred to contain at least one of carbamate, urea, and thiourea. In this case, it is more preferred that X 1 Contains at least one of carbamate, urea, and thiourea, X 2 Contains at least one of carbamate, urea, and thiourea.

[0098] In the above formula (I), R 1 is a straight-chain or branched divalent hydrocarbon group, an alicyclic structure, or a single bond. 1 Each may be different, and the above-mentioned divalent hydrocarbon group may have a heteroatom. 1 The molecular weight is not particularly limited, but the lower limit is preferably 20 or more, more preferably 30 or more, and further preferably 40 or more, and the upper limit is preferably 3000 or less, more preferably 2500 or less, and further preferably 2200 or less.

[0099] In the above formula (I), R 1 Specific examples of are not particularly limited, and include: ethylene, propylene, butylene, 2-methylpropyl, pentylene, hexylene, heptylene, octylene, nonylene, decylene, oxyethylene, oxytetramethylene, polyoxyethylene, polyoxytetramethylene, fluoroalkyl, perfluoroalkyl, isopropylene, isobutylene, tert-butylene, isopentylene, 2,2-dimethyltrimethylene, isohexylene, isoheptylene, cyclopentylene, cyclohexylene, dihydroisophoronyl, isooctylene, oxy1-methylethylene, oxy2,2-dimethyltrimethylene, polyoxy1-methylethylene, and the like. Among them, from the viewpoint of versatility, etc., preferred are propylene, butylene, pentylene, hexylene, nonylene, decylene, oxyethylene, oxytetramethylene, polyoxyethylene, oxytetramethylene, isopropylene, isobutylene, isopentylene, 2,2-dimethyltrimethylene or isohexylene, oxy-1-methylethylene, and polyoxy-1-methylethylene.

[0100] In the above formula (I), m is an integer of 1 or greater, preferably 1-2, and more preferably 1. In the above formula (I), n is an integer of 2 or greater, preferably 2-5, and more preferably 2-4.

[0101] In above-mentioned formula (II), Y is at least one selected from the group consisting of carbonate bond, ether bond and ester bond. Wherein, from the viewpoints such as durability, carbonate bond and ester bond are preferred, and carbonate bond is further preferred. It should be noted that Y, as long as it comprises the above-mentioned one, can also be used in combination with the bond other than the bond enumerated herein.

[0102] In the above formula (II), R 2 is a linear or branched divalent hydrocarbon group, or a single bond. 2 Each may be different, and the above-mentioned divalent hydrocarbon group may have a heteroatom. 2 The molecular weight is not particularly limited, but the lower limit is preferably 20 or more, more preferably 30 or more, and further preferably 40 or more, and the upper limit is preferably 3000 or less, more preferably 2500 or less, and further preferably 2200 or less.

[0103] In the formula (I), R 2 Specific examples of are not particularly limited, and include: ethylene, propylene, butylene, 2-methylpropyl, pentylene, hexylene, heptylene, octylene, nonylene, decylene, oxyethylene, oxytetramethylene, polyoxyethylene, polyoxytetramethylene, fluoroalkyl, perfluoroalkyl, isopropylene, isobutylene, tert-butylene, isopentylene, 2,2-dimethyltrimethylene, isohexylene, isoheptylene, isooctylene, oxy1-methylethylene, oxy2,2-dimethyltrimethylene, polyoxy1-methylethylene, and the like. Among them, from the viewpoint of versatility, etc., preferred are propylene, butylene, pentylene, hexylene, nonylene, decylene, oxyethylene, oxytetramethylene, polyoxyethylene, polyoxytetramethylene, isopropylene, isobutylene, isopentylene, 2,2-dimethyltrimethylene or isohexylene, oxy-1-methylethylene, and polyoxy-1-methylethylene.

[0104] In the above formula (II), n is an integer of 1 or greater, preferably 1-50, and more preferably 3-30.

[0105] [Method for producing a polyol-containing composition]

[0106] The polyol-containing composition of this embodiment can be obtained by, for example, synthesizing a specific hydroxy compound by reacting an excess of a polyol compound with a polyisocyanate compound, reacting a polycarbonate polyol with an arbitrary polyol in the presence of an ester exchange catalyst, or the like, and the production method is not particularly limited. It should be noted that if the polyisocyanate used in the above method contains some terminals that are unreactive with the polyol, the unreactive terminals in the resulting polyol exist as side chains. Therefore, the polyol-containing composition of this embodiment can be a composition comprising a specific hydroxy compound alone or a mixture of the specific hydroxy compound and other hydroxy compounds.

[0107] The method for reacting the polyol compound and the polyisocyanate compound is not particularly limited. For example, the reaction can be carried out by mixing the raw materials and stirring while heating. The reaction temperature is not particularly limited. The lower limit is preferably 50°C or higher, more preferably 60°C or higher, even more preferably 70°C or higher, and even more preferably 80°C or higher. The upper limit is preferably 250°C or lower, more preferably 200°C or lower, even more preferably 180°C or lower, and even more preferably 160°C or lower. By setting the reaction temperature above the lower limit, the reaction can be carried out in a shorter time, resulting in excellent economic efficiency. By setting the reaction temperature below the upper limit, thermal degradation of the resulting polyol can be more effectively prevented.

[0108] The ratio of isocyanate groups to hydroxyl groups (NCO / OH) in the method of reacting a polyol compound with a polyisocyanate compound is not particularly limited, but is preferably 0.01 to 0.90, more preferably 0.03 to 0.40, further preferably 0.04 to 0.30, and particularly preferably 0.05 to 0.20.

[0109] Reaction pressure is not particularly limited, and is preferably more than normal pressure and below 1MPa. By making reaction pressure into above-mentioned scope, can more simply implement reaction. In addition, when using auxiliary raw material, consider these vapor pressure etc., by carrying out a certain degree of pressurization, can more efficiently promote reaction.

[0110] The progress and completion of the reaction can be confirmed, for example, by GPC (gel permeation chromatography) measurement and FT-IR (Fourier transform infrared spectrometer). As the reaction proceeds, the peak derived from the raw material becomes smaller over time by GPC measurement, and it can be confirmed by the disappearance of the peak. Alternatively, FT-IR can be used to determine the peak by the wave number 2273 cm-1 derived from the isocyanate group (-NCO group). -1It can be confirmed by the disappearance of the infrared absorption spectrum absorbance (Abs) peak nearby. When obtaining the polyol-containing composition of this embodiment, a step of dehydrating the raw materials used can be performed as a pretreatment before the above reaction.

[0111] [Method for Quantifying Functional Groups in Polyol-Containing Compositions]

[0112] The quantitative method of the functional group in the polyol-containing composition of the present embodiment is not particularly limited, and when the input amount and structure are clear, it can be calculated from the input amount. In addition, when the input amount and structure are unclear, it is preferred to first determine the structure of the functional group and then perform quantification using a method corresponding to the functional group. As a quantitative method for the functional group, for example, if it is a hydrophilic group used in the examples described later, the polyol-containing composition can be hydrolyzed in the presence of a base and then quantified using gas chromatography (Gas Chromatography: GC). If it is difficult to measure by GC, gel permeation chromatography (Gel Permeation Chromatography: GPC) can be used instead of GC. In addition, when the functional group itself is hydrolyzed, it is preferred to measure by 1 Quantitative method using H-NMR.

[0113] Hydrolysis method

[0114] Accurately weigh about 5g of a sample of a polyol-containing composition in a 100mL eggplant-shaped flask, and add 50g of ethanol and 4.0g of potassium hydroxide. Add a magnetic stirrer and stir in an oil bath set at 105±5°C for 1 hour to decompose the carbonate bond portion with alkali. Then, cool to room temperature, add a few drops of phenolphthalein indicator to the reaction solution, and gradually add hydrochloric acid until the color disappears. Take about 40mL of the supernatant, transfer it to a sample bottle, and let it stand overnight in a refrigerator with an internal temperature of 5°C. After standing, filter the supernatant using a membrane filter with a pore size of 0.45μm to obtain a filtrate. The obtained filtrate is subjected to GC analysis and GPC analysis. It should be noted that the functional group concentration in the sample is obtained by using a concentration standard curve prepared separately using the functional group components contained in the polyol-containing composition. The mass is calculated from the amount of solution and divided by the mass of the polyol-containing composition used for alkali decomposition to obtain the content of the functional groups in the polyol-containing composition.

[0115] ·pass 1 Quantitative method using H-NMR

[0116] A sample of a composition containing a polyol was dissolved in DMSO-d6 and 1H-NMR: The integrated value derived from the hydroxyl group of the polyol is defined as A, and the peak derived from the functional group is defined as B. The content of the functional group can be calculated from the ratio of A to B, the molar concentration of A determined from OHV, and the molecular weight of the functional group.

[0117] (Polycarbonate polyol)

[0118] The polycarbonate polyol used as a raw material for producing the polyol-containing composition of this embodiment is not particularly limited, and can be obtained, for example, by the polycarbonate polyol production method described in Comparative Example 1-1. Commercially available products can also be used. Examples of commercially available products include, but are not particularly limited to, T6002, T6001, T5652, T5651, T5650J, T5650E, G4672, T4672, T4671, G3452, T3451, G3450J, and AK011 manufactured by Asahi Kasei Corporation.

[0119] Alternatively, polycarbonate polyols having a diol structure incorporated into the main chain can be obtained by transesterifying a polycarbonate polyol with any diol, and these can also be used as raw materials. For example, a carbonate compound can be reacted with any diol compound in the presence of an ester exchange catalyst to obtain a polycarbonate polyol. Transesterification catalysts are not particularly limited, and examples thereof include alkali metals and alkaline earth metals, as well as their alkoxides, hydrides, oxides, amides, hydroxides, and salts thereof. The polycarbonate polyol synthesized by the above method has a diol structure incorporated into the main chain.

[0120] (Polyester polyol)

[0121] The polyester polyol used as a raw material for producing the polyol-containing composition of the present embodiment is not particularly limited, and can be obtained, for example, by the method for producing a polyester polyol described in Japanese Patent Application Laid-Open No. 2006-328372. Commercially available products can also be used. Examples of commercially available products include, but are not particularly limited to, the P-**10 and F-**10 series manufactured by Kuraray Co., Ltd. and the Polylite series manufactured by DIC Corporation.

[0122] (Polyether polyol)

[0123] The polyether polyol used as a raw material for producing the polyol-containing composition of this embodiment is not particularly limited, and can be obtained, for example, by the method for producing a polyether polyol described in Japanese Patent No. 3299803. Commercially available products can also be used. Examples of commercially available products include polyethylene glycol manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., and the like.

[0124] (Polyisocyanate compound)

[0125] The isocyanate compound as a raw material that can be used when producing the polyol-containing composition of the present embodiment is not particularly limited, and examples thereof include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate; toluene diisocyanate, 4,4'-diphenylmethane diisocyanate (hereinafter sometimes referred to as "MDI"), xylylene diisocyanate, and naphthalene diisocyanate; Aromatic diisocyanates; isocyanate compounds having three or more isocyanate groups such as triphenylmethane-4,4'-4"-triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene and 4,4'-dimethyldiphenylmethane-2,2',5,5'-tetraisocyanate; iminooxadiazinedione compounds; and isocyanurate-modified products and biuret-modified products of these isocyanates. The commercially available products are not particularly limited, and examples thereof include 24A-100, 22A-75P, TPA-100, TKA-100, P301-75E, D101, D201, 21S-75E, MFA-75B, MHG-80B, TUL-100, TLA-100, TSA-100, TSS-100, TSE-100, E402-80B, E405-80B, and AE700 manufactured by Asahi Kasei Corporation. -100, A201H, 17B-60P, TPA-B80E, MF-B60B, MF-K60B, SBB-70P, SBN-70D, E402-B80B, WB40-100, WT30-100, WT31-100, WB40-80D, WT20-100, WL70-100, WE50-100, WM44-L70G "Duranate (trade name)" series, etc.

[0126] In addition, the polyisocyanate compound used as a raw material in the manufacture of the polyol-containing composition of the present embodiment may also be a substance synthesized by a method other than the above. For example, the polyisocyanate having an allophanate structure obtained by reacting an alcohol with a diisocyanate and an allophanate catalyst as described in WO2003 / 027163, and the polyisocyanate having a biuret structure obtained by reacting an amine with a diisocyanate may also be used. In this case, if the above-mentioned alcohol and amine are monofunctional, a polyisocyanate having a side chain derived from the structure of the alcohol or amine may be obtained. It should be noted that there is no particular limitation on the identification of the structure of the polyisocyanate compound, and for example, the polyisocyanate based on the structure described in Japanese Patent No. 6647130 may be cited. 13 C-NMR method.

[0127] [Polyurethane, water-based polyurethane]

[0128] The polyurethane and water-based polyurethane of the present embodiment are obtained using the above-mentioned polyol-containing composition. The polyurethane and water-based polyurethane of the present embodiment are obtained by using the polyol-containing composition, so that the durability and other physical properties are not easily traded off, and high-quality polyurethane coating films and water-based polyurethane coating films can be formed. In addition, the polyurethane and water-based polyurethane mentioned here refer to those having a number average molecular weight of at least 10,000. It should be noted that the method for determining the number molecular weight of the polyurethane can be, for example, a method based on static light scattering (SLS) and a method using GPC (DMF) described later.

[0129] The polyurethane and water-based polyurethane of the present embodiment can be, for example, an addition polymer of the above-mentioned polyol-containing composition and a polyfunctional isocyanate (an isocyanate having two or more NCO groups, preferably having 2 to 4 NCO groups). The polyfunctional isocyanate is not particularly limited, and well-known polyfunctional isocyanates such as diisocyanates can be used without particular limitation. In addition, the polyurethane and water-based polyurethane of the present embodiment can be an addition polymer of the above-mentioned polyol-containing composition, a polyfunctional isocyanate, one or more well-known polyols, and one or more well-known polyfunctional isocyanates.

[0130] [Surface free energy of coating film]

[0131] As a method for measuring the surface free energy of a solid, the Owens-Wendt method, the Fowkes method, and the Zisman method are known. For example, in the Owens-Wendt method, if the surface free energy is γ and the dispersion component of the surface free energy is γ d , set the hydrogen term to γ H , then γ=γ d +γ H (*) holds. In addition, it is known that if the surface tension of a solid is γ S , set the surface tension of the liquid to γ L , then γ L (1+cosθ)=2(γ S d γ L d ) 1 / 2 +2(γ S h γ L h ) 1 / 2 (**) holds. Therefore, by adding γ L The contact angle θ of two known liquids is measured and substituted into the above equation (**) to solve the simultaneous equations, thereby calculating the dispersion component γ of the surface free energy. d, hydrogen-based term γ H , and calculate the surface free energy γ of the polyurethane coating film or the water-based polyurethane coating film according to the above formula (*).

[0132] Example

[0133] Hereinafter, specific examples and comparative examples are listed to further illustrate the present embodiment in detail, but the present embodiment is not limited to these examples and comparative examples as long as it does not exceed its purport. That is, the materials, usage amounts, ratios, processing contents, processing sequences, etc. shown below can be appropriately changed as long as they do not depart from the purport of the present invention. In addition, the values of the following various manufacturing conditions and evaluation results have the meaning of being the preferred upper limit or preferred lower limit in the embodiment of the present invention, and the preferred numerical range can be the range specified by the combination of the above-mentioned upper limit or lower limit and the value of the following embodiment or the values of the embodiments. The evaluation and physical properties in the examples and comparative examples described below are evaluated and measured by the following methods. In the present embodiment, unless otherwise specified, "parts" and "%" are based on mass reference.

[0134] [Determination of hydroxyl value (OHV)]

[0135] The hydroxyl values of the polyols and polyol-containing compositions obtained in the Examples and Comparative Examples described below were measured using the following method. An acetylating agent was prepared by adding pyridine to 12.5 g of acetic anhydride to make 50 mL using a volumetric flask. Samples of the polyols and polyol-containing compositions obtained in the Examples and Comparative Examples described below were accurately weighed and placed in 100 mL eggplant-shaped flasks. 5 mL of the acetylating agent and 10 mL of toluene were added to the eggplant-shaped flasks using a full pipette to obtain solutions. A condenser was then attached to the eggplant-shaped flask, and the solution was heated at 100°C with stirring for 1 hour. 2.5 mL of distilled water was added to the eggplant-shaped flask using a full pipette, and the resulting solution was further heated with stirring for 10 minutes. After cooling the solution for 2-3 minutes, 12.5 mL of ethanol was added to the eggplant-shaped flask, and 2-3 drops of phenolphthalein were added as an indicator. The solution was then titrated with 0.5 mol / L ethanolic potassium hydroxide. 5 mL of an acetylating agent, 10 mL of toluene, and 2.5 mL of distilled water were placed in a 100 mL eggplant flask, heated and stirred for 10 minutes, and the resulting solution was titrated in the same manner (blank test). Based on the results, the hydroxyl value of the polyol and the polyol-containing composition was calculated using the following formula (III).

[0136] Hydroxyl value (mg-KOH / g)={(ba)×28.05×f} / e…(III)

[0137] (In formula (III), a represents the titration amount of the sample (mL), b represents the titration amount of the blank test (mL), e represents the sample amount (g), and f represents the titrant factor.)

[0138] [GPC measurement (THF)]

[0139] The mass average molecular weight (Mw) and number average molecular weight (Mn) of the polyol and the polyol-containing composition were measured by GPC using the following method. The polyols and polyol-containing compositions obtained in the Examples and Comparative Examples described below were used as samples. The sample concentration was 0.5% by mass using tetrahydrofuran (hereinafter referred to as THF). The mass average molecular weight (Mw) and number average molecular weight (Mn) of the polyol and the polyol-containing composition were measured using the following GPC apparatus, calculated as standard polystyrene.

[0140] GPC equipment: HLC-8320 manufactured by Tosoh Corporation

[0141] Column: TSKgel G4000H 1 column

[0142] G3000H 1

[0143] G2000H 2

[0144] Eluent: tetrahydrofuran (THF)

[0145] Flow rate: 1.0 mL / min

[0146] Column temperature: 40°C

[0147] RI detector: RI (built-in device HLC-8320)

[0148] Standard curve type: cubic polynomial

[0149] Calibration curve: Standard polystyrene (manufactured by Tosoh Corporation)

[0150] F-40 (molecular weight: 4.27×10 5 )

[0151] ·F-20 (molecular weight: 1.90×10 5 )

[0152] F-10 (molecular weight: 9.64×10 4 )

[0153] F-4 (molecular weight: 3.79×10 4 )

[0154] F-2 (molecular weight: 1.81×10 4 )

[0155] F-1 (molecular weight: 1.02×10 4 )

[0156] A-5000 (molecular weight: 5.97×10 3 )

[0157] A-2500 (molecular weight: 2.63×10 3 )

[0158] A-500

[0159] A-1000

[0160] In addition, the molecular weight of dimer to decamer was calculated from A-500 and A-1000.

[0161] Dimer (molecular weight: 266)

[0162] Trimer (molecular weight: 370)

[0163] Tetramer (molecular weight: 474)

[0164] Pentamer (molecular weight: 578)

[0165] Hexamer (molecular weight: 682)

[0166] 7-mer (molecular weight: 786)

[0167] octamer (molecular weight: 890)

[0168] 9-mer (molecular weight: 994)

[0169] 10-mer (molecular weight: 1098)

[0170] [GPC measurement (DMF)]

[0171] The mass average molecular weight (Mw) and number average molecular weight (Mn) of the polyurethane were measured by GPC using the following method. The polyurethanes and water-based polyurethanes obtained in the Application Examples and Comparative Application Examples described below were used as samples. The polyurethanes were prepared using dimethylformamide (hereinafter referred to as DMF) to a concentration of 0.5% by mass, and the mass average molecular weight (Mw) and number average molecular weight (Mn) of the polyurethanes were measured in terms of standard polystyrene using the following GPC apparatus.

[0172] GPC equipment: HLC-8320 manufactured by Tosoh Corporation

[0173] Analytical columns: 3 TSKgel SuperHM-H

[0174] Guard column: TSKgel guardcolumn HH

[0175] Reference column: TSKgel SuperH-RC

[0176] Eluent: N,N-dimethylformamide (DMF)

[0177] Flow rate: 0.5 mL / min

[0178] Column temperature: 40°C

[0179] RI detector: RI (built-in device HLC-8320)

[0180] Standard curve type: cubic polynomial

[0181] Calibration curve: Standard polystyrene (manufactured by Tosoh Corporation)

[0182] F-40 (molecular weight: 4.27×10 5 )

[0183] ·F-20 (molecular weight: 1.90×10 5 )

[0184] F-10 (molecular weight: 9.64×10 4 )

[0185] F-4 (molecular weight: 3.79×10 4 )

[0186] F-2 (molecular weight: 1.81×10 4 )

[0187] F-1 (molecular weight: 1.02×10 4 )

[0188] A-5000 (molecular weight: 5.97×10 3 )

[0189] A-2500 (molecular weight: 2.63×10 3 )

[0190] A-1000 (molecular weight: 2.63×10 3 )

[0191] [FT-IR measurement]

[0192] The polyol-containing compositions obtained in the Examples and Comparative Examples described below were used as samples, and their infrared absorption spectra were measured using FT-IR (Fourier transform infrared spectroscopy) using the following method. The sample was thinly applied to a rock salt plate (NaCl plate, 35 × 35 × 5 mm), and the infrared absorption spectra of the sample were measured using FT-IR using the following apparatus and conditions.

[0193] FI-IR device: FT / IR-4600typeA (JASCO Corporation)

[0194] Light source: standard light source

[0195] Detector: TGS

[0196] Total number of times: 16

[0197] Decomposition: 4cm -1

[0198] Zero padding: On

[0199] Apodization: Cosine

[0200] Gain: Auto(2)

[0201] Aperture: Auto (7.1mm)

[0202] Scan speed: Auto (2mm / sec)

[0203] Filter: Auto (30000Hz)

[0204] Data type: Equally spaced data

[0205] Horizontal axis: Wave number (cm -1 )

[0206] Vertical axis: Abs

[0207] Start: 400cm -1

[0208] End: 40000cm -1

[0209] [Structural Analysis of Polyisocyanates]

[0210] For the structure of polyisocyanate, the 13 The analysis was performed by C-NMR method. 13 The molar ratios of isocyanurate groups, allophanate groups, and biuret groups were determined by C-NMR measurement. Specific measurement conditions are as follows.

[0211] 13 C-NMR apparatus: AVANCE600 (manufactured by Bruker)

[0212] Cryogenic probe (Bruker)

[0213] Cryo Probe

[0214] CPDUL

[0215] 600S3-C / HD-05Z

[0216] Resonant frequency: 150MHz

[0217] Concentration: 60wt / vol%

[0218] Displacement standard: CDCl3 (77ppm)

[0219] Cumulative times: 10,000 times

[0220] Pulse program: zgpg30

[0221] (Proton complete decoupling method, waiting time 2 seconds)

[0222] Then, the integrated value of the following signal was divided by the number of carbon atoms measured, and each molar ratio was determined from the resulting value.

[0223] Molar amount of isocyanurate groups (mol %, represented by "A"): around 148.6 ppm: integrated value divided by 3

[0224] Molar amount of allophanate groups (mol%, represented by "B"): around 154 ppm: integrated value divided by 1

[0225] Molar amount of biuret group (mol%, expressed as "C"): around 155.8 ppm: (integrated value - allophanate group integrated value) ÷ 2

[0226] [Isocyanate group concentration (mass %)]

[0227] The isocyanate group concentration (mass %) of the polyisocyanate compound is measured as follows. 1 to 3 g (Wg) of the polyisocyanate compound manufactured in the manufacturing example is accurately weighed in a conical flask, 20 mL of toluene is added, and the polyisocyanate (composition) is completely dissolved. Then, 10 mL of a toluene solution of 2 equivalents of di-n-butylamine is added, and after complete mixing, it is left at room temperature for 15 minutes. Furthermore, 70 mL of isopropanol is added to the solution and completely mixed. The solution is titrated with an indicator using a 1 normal concentration of hydrochloric acid solution (factor F) to obtain a titration value V2 mL. For the same titration operation, without using the polyisocyanate (composition), a titration value V1 mL is obtained. Based on the obtained titration value V2 mL and titration value V1 mL, the isocyanate group concentration (mass %) of the polyisocyanate is calculated based on the following formula.

[0228] Isocyanate group concentration = (V1-V2)×F×42 / (W×1000)×100

[0229] [Synthesis of polyisocyanate (PI)]

[0230] (Synthesis example 1)

[0231] Into a four-necked flask equipped with a stirrer, a thermometer and a condenser, 300 g of hexamethylene diisocyanate (hereinafter sometimes referred to as "HDI") and 200 g of polyethylene glycol monomethyl ether (mPEG) (manufactured by Nippon Emulsifier Co., Ltd., trade name "MPG-081") were placed, and the urethanization reaction was carried out at 90°C for 1 hour under stirring. Next, the temperature was raised to 130°C, and 0.26 g of a 20% solid content mineral spirit solution of 2-ethylhexanoyl zirconium as an allophanation catalyst (manufactured by Nippon Chemical Industry Co., Ltd., a solution obtained by diluting the trade name "Nikka Octhix Zirconium 12%" with mineral spirits) was added. After 1 hour, when the refractive index of the reaction solution rose to 0.008, 0.097 g (2.0 times the mol of the allophanation catalyst) of a 50% solid content isobutanol solution of pyrophosphoric acid (a reagent manufactured by Katayama Chemical Industry Co., Ltd.) was added to stop the reaction. The reaction solution was measured. 13 C-NMR results confirmed the presence of an allophanate group. Using a downflow thin film distillation apparatus, unreacted HDI was removed at 160°C (0.2 Torr) for the first time and 150°C (0.1 Torr) for the second time, yielding a polyisocyanate PI1-1 having a PEG side chain structure and an allophanate structure. The NCO% was 7.9%.

[0232] (Synthesis example 2)

[0233] 300 g of HDI and 20.1 g of sodium 2-aminoethanesulfonate (manufactured by Alfa Chemical Co., Ltd.) were placed in a four-necked flask equipped with a stirrer, a thermometer, and a condenser, and the mixture was stirred at 40°C for 1 hour. The mixture was then stirred at 160°C for 1 hour. 13 C-NMR confirmed that the polyisocyanate PI1-2 consisted solely of biuret groups, as determined by the molar ratio of biuret groups produced. Unreacted HDI was removed using a downflow thin-film distillation apparatus at 160°C (0.2 Torr) for the first distillation and 150°C (0.1 Torr) for the second distillation. This yielded polyisocyanate PI1-2 having a sulfonic acid side chain structure derived from 2-aminoethanesulfonic acid and a biuret structure. The NCO percentage was 17.9%.

[0234] (Synthesis example 3)

[0235] In a 300 ml separable flask, 100 g of 24A-100 (manufactured by Asahi Chemical Industry Co., Ltd.: NCO 24.0%) as a modified polyisocyanate, 14.8 g of DL-lactic acid (manufactured by Tokyo Chemical Industry Co., Ltd.: hereinafter referred to as LA) as a modifying raw material for the isocyanate, and 0.047 g of dibutyl phosphate (300 ppm relative to the solid content) as a catalyst were added, and the mixture was reacted at 50° C. for 4 hours while stirring under nitrogen. It should be noted that the ratio of the modifying raw material to NCO was set to 30 mol%. The reaction was terminated after confirming that the NCO% reached ±3% of the theoretical amount. This operation yielded a polyisocyanate PI1-3 having a biuret structure and a carboxyl side chain structure derived from LA. The NCO% was 14.0%.

[0236] (Synthesis Examples 4 to 8)

[0237] Polyisocyanates PI1-4 to PI1-8 were obtained by the same method except that the modification ratio of the polyisocyanate to be modified, the modification raw material, and the molar modification ratio relative to the charged NCO were changed as shown in Table 1.

[0238] (Synthesis Example 9)

[0239] Polyisocyanate PI2-1 having a fluorinated alkyl structure derived from HFBL in its side chain was obtained in the same manner as in Synthesis Example 2 except that 60.3 g of HFBL was used in place of sodium 2-aminoethanesulfonate.

[0240] (Synthesis Examples 10 to 13)

[0241] Polyisocyanates PI2-2 to PI2-5 were obtained by the same method except that the modification ratio of the polyisocyanate to be modified, the modification raw material, and the molar modification ratio relative to the charged NCO were changed as shown in Table 1.

[0242] (Synthesis Examples 14 to 22)

[0243] Polyisocyanates PI1-10 to 1-14 and PI2-6 to 2-9 were obtained by the same method except that the modification ratio of the polyisocyanate to be modified, the modification raw material, and the molar modification ratio relative to the charged NCO were changed as shown in Table 2.

[0244] Tables 1 and 2 show the synthesized polyisocyanates and their NCO %, the modified polyisocyanates used in the synthesis of the polyisocyanates, the modifying raw materials and their modification ratios (mol % relative to the molar number of NCO in the polyisocyanates), and the mass % of the modifying raw materials in the polyisocyanates.

[0245] In addition, the raw materials described in Table 1 and Table 2 are as follows.

[0246] Modified polyisocyanate

[0247] 24A-100: Polyisocyanate with a biuret structure, manufactured by Asahi Kasei Corporation, NCO 24.0%

[0248] TLA-100: Polyisocyanate with an isocyanurate structure, manufactured by Asahi Kasei Corporation, NCO 23.3%

[0249] CHTI: a polyisocyanate having an alicyclic structure, synthesized by the method described in Tetrahedron, 2007, vol. 63, #31, p7285-7301, NCO content 60.8%.

[0250]

[0251] Desmodul N3900: Polyisocyanate with an iminooxadiazinedione structure, manufactured by Covestro, NCO 2 3.5%

[0252] VESTANAT T1890: Isophorone diisocyanate-based isocyanurate, manufactured by Evonik, NCO 17.3%. Since it was diluted with butyl acetate to a solid content of 70%, butyl acetate was distilled off after modification.

[0253] Modified raw materials

[0254] mPEG: polyethylene glycol monomethyl ether (used to introduce a PEG structure into the side chain, manufactured by Nippon Emulsifier Co., Ltd., trade name "MPG-081." Monofunctional)

[0255] Sodium 2-aminoethanesulfonate (used to introduce sulfonic acid groups, manufactured by Alfa Chemistry)

[0256] LA: DL-lactic acid (used to introduce carboxyl groups, manufactured by Tokyo Chemical Industry Co., Ltd.)

[0257] m-dPEG4-thiol (used to introduce PEG structure into the side chain, manufactured by Sigma Aldrich)

[0258]

[0259] m-dPEG4-amine (used to introduce PEG structure into the side chain, manufactured by Sigma Aldrich)

[0260]

[0261] APTES: aminopropyltriethoxysilane (used to introduce trialkoxysilyl structure, manufactured by Tokyo Chemical Industry)

[0262] DMTAZ: 3,5-dimethylpyrazole (introduced as a protective group for the isocyanate group, manufactured by Tokyo Chemical Industry Co., Ltd.)

[0263] HFBL: 2,2,3,3,4,4,4-heptafluoro-1-butanol (used to introduce a fluorinated alkyl structure, manufactured by Tokyo Chemical Industry Co., Ltd.)

[0264] 1-Hexadecylmercaptan (used to introduce a hydrocarbon group with 16 carbon atoms, manufactured by Tokyo Chemical Industry Co., Ltd.)

[0265] Silaplane FM-0411 (for introducing polydimethylsiloxane structure, manufactured by JNC)

[0266] [Table 1]

[0267]

[0268] [Table 2]

[0269]

[0270] [Example 1-1]

[0271] 300 g of PI1-1 (NCO: 7.9%) and 6.4 g of PEG-1000 (manufactured by Wako Pure Chemical Industries, Ltd.) were added to a 500 ml separable flask. After nitrogen substitution, the mixture was reacted at 100°C for 1 hour to obtain POL1-1. The NCO / OH (molar ratio) was 0.02. FT-IR confirmed the disappearance of the NCO-derived peak. Furthermore, the mPEG content in PI1-1 was calculated by GPC quantification according to [Quantitative Method for Functional Groups in Polyol-Containing Compositions] and was found to be 1.36 wt %, relative to the 1.35 wt % calculated from the charge amount.

[0272] [Examples 1-2 to 1-12, Comparative Examples 1 to 4]

[0273] As shown in Table 3, POL1-2 to 1-12 and POL1-16 were synthesized using the same method as Example 1-1, except that the polyisocyanate used was changed to PI1-2 to PI1-8, and the alcohol used was changed to the NCO / OH (molar ratio) to the alcohol as shown in Table 3. The functional group content was also calculated according to the above-mentioned [Quantitative Determination of Functional Groups in Polyol-Containing Compositions].

[0274] [Comparative Example 1-1]

[0275] According to Example 2 of Japanese Patent No. 6276848, a 2L glass flask (hereinafter also referred to as the "reactor") equipped with a distillation column filled with structured packing and a stirring device was charged with 458g of 1,5-pentanediol, 500g of 1,6-hexanediol, and 760g of ethylene carbonate. Then, 0.086g of tetra-n-butoxytitanium was added as a catalyst. The reaction was conducted at a temperature of 160-175°C for 12 hours while a portion of the distillate was withdrawn. The reactor was then directly connected to a condenser, and the reaction temperature was raised to 175-190°C. The pressure was then gradually reduced, and appropriate samples were taken. The hydroxyl value of the produced polycarbonate polyol was measured while the diol component in the reactor was distilled off. This yielded 860g of a polycarbonate polyol with a hydroxyl value of 109.8mgKOH / g. To the obtained polycarbonate polyol (600 g) was added 200 g of PEG-1000 (manufactured by Wako Pure Chemical Industries, Ltd., "Polyethylene Glycol 1000" (trade name)), which is a raw material for forming a nonionic hydrophilic group. After stirring at 150° C. for 6 hours, the reaction temperature was lowered to 115° C., 0.056 g of 85% phosphoric acid was added, and the mixture was stirred at 115° C. for 3 hours to obtain POL1-13 having a hydroxyl value of 112.2 mgKOH / g.

[0276] [Comparative Examples 1-2, 1-3]

[0277] Except for the masses of PEG and OFHD described in Table 3, POL1-14 and 1-15 were synthesized by the same method as in Comparative Example 1-1.

[0278] [Comparative Examples 1-5]

[0279] As POL1-17, Ymer N120 (manufactured by Perstorp) was used.

[0280] [Examples 1-13 to 1-20]

[0281] As shown in Table 4, POL1-18 to 1-25 were synthesized using the same method as Example 1-1, except that the polyisocyanate and alcohol were modified and the NCO / OH (molar ratio) with the alcohol was changed to the values shown in Table y. The functional group content was also calculated according to the above-mentioned [Quantitative Determination of Functional Groups in Polyol-Containing Compositions].

[0282] Tables 3 and 4 show the raw materials and NCO / OH (molar ratio) and composition used in the synthesis of modified polyols. It should be noted that FG1 and FG2 described in the composition represent the functional groups (FG) contained in the modified polyol and their mass parts. Here, mass parts represent the mass of the structure described in FG. In addition, Z, R 1 、X 1 、X 2, P, R 2 , Y correspond to Z, R in the above formula (I) and formula (II) respectively. 1 、X 1 、X 2 , P, R 2 , Y. Furthermore, the masses described in FG1 and FG2 in Tables 3 and 4 represent the masses of the following partial structures. In addition, in each partial structure, * represents a connecting bond.

[0283]

[0284] In addition, the raw materials described in Table 3 and Table 4 are as follows.

[0285] PEG-1000: polyethylene glycol (reacts with polyisocyanate to introduce a PEG structure into the main chain of a polyol-containing composition, manufactured by Wako Pure Chemical Industries, Ltd., “Polyethylene glycol 1000” (trade name)).

[0286] ·NH2-PEG-OH

[0287]

[0288] SH-PEG-OH

[0289]

[0290] P-1010: Copolyester of 2-methylpropanediol and adipic acid (reacts with polyisocyanate to introduce a polyester structure into the main chain of a polyol-containing composition, manufactured by Kuraray Co., Ltd., “Kuraray Polyol P-1010” (trade name)).

[0291] PTMG2000: Used to introduce a polyether structure into the main chain of a composition containing a polyol. Manufactured by Mitsubishi Chemical Corporation

[0292] PPG: Polypropylene glycol, manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight 1000

[0293] The carbonate diol described below is used to react with polyisocyanate to introduce a carbonate structure into the main chain of the polyol-containing composition.

[0294] 4651: Polycarbonate diol obtained by copolymerizing 1,4-butanediol, 1,6-hexanediol, and a carbonate compound. Molecular weight: 1000.

[0295] 5001: Polycarbonate diol obtained by copolymerization of 1,5-heptanediol and a carbonate compound. Molecular weight: 1000.

[0296] T5650E: Manufactured by Asahi Kasei Corporation. Polycarbonate diol obtained by copolymerizing 1,5-heptanediol, 1,6-hexanediol, and a carbonate compound. Molecular weight: 500.

[0297] T5651: Manufactured by Asahi Kasei Corporation. Polycarbonate diol obtained by copolymerizing 1,5-heptanediol, 1,6-hexanediol, and a carbonate compound. Molecular weight: 1000.

[0298] T5652: Manufactured by Asahi Kasei Corporation. Polycarbonate diol obtained by copolymerizing 1,5-heptanediol, 1,6-hexanediol, and a carbonate compound. Molecular weight: 2000.

[0299] T6001: Manufactured by Asahi Kasei Corporation. Polycarbonate diol obtained by copolymerizing 1,6-hexanediol with a carbonate compound. Molecular weight: 1000.

[0300] 2,2,3,3,4,4,5,5-1,6-hexanediol (OFHD)

[0301] Ymer N120

[0302]

[0303] [Table 3]

[0304]

[0305] [Table 4]

[0306]

[0307] [Application Examples 1-1 to 1-12 and Application Comparative Examples 1-1 to 1-5]

[0308] <Method for producing a water-based polyurethane coating film (polyurethane dispersion (PUD))>

[0309] (Raw materials used)

[0310] Polyol-containing compositions obtained in Examples and / or Comparative Examples (hereinafter sometimes referred to as "Pol")

[0311] DMPA (2,2-dihydroxymethylpropionic acid)

[0312] Methyl ethyl ketone (MEK)

[0313] Dibutyltin dilaurate (DBTDL)

[0314] IPDI (isophorone diisocyanate)

[0315] Triethylamine (TEA)

[0316] Pure water

[0317] Ethylenediamine (EDA)

[0318] (Input amount)

[0319] Pol, IPDI, DMPA, TEA, and EDA were added at a molar ratio of Pol / IPDI / DMPA / TEA / EDA=1.0 / 3.0 / 1.0 / 1.0 / 0.5.

[0320] DBTDL is added so that the total amount of Pol, IPDI, and DMPA is 100 ppm. If necessary, DBTDL can be diluted with toluene before addition (e.g., 5% DBTDL-toluene solution).

[0321] MEK was added so that the solid content in the prepolymer step became 65%.

[0322] Pure water was added so that the final solid content after the MEK removal step would be 30%. If the viscosity increases during the chain extension step, pure water may be added as needed to adjust the solid content.

[0323] (Prepolymer process)

[0324] A 1L separable flask equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet tube and dropping funnel was set to a nitrogen atmosphere, and Pol, DMPA, DBTDL and MEK were added. The mixture was stirred at 200 rpm for 15 minutes while being refluxed at 80°C. Subsequently, IPDI was added with a syringe and stirred while being refluxed at 80°C until the NCO% reached 3.5±0.3% by mass, thereby obtaining a MEK solution of a urethane prepolymer containing terminal isocyanate groups. It should be noted that the above NCO% is the ratio of the mass of the isocyanate groups possessed by the polyisocyanate relative to the total mass of the raw materials used in the prepolymer step, and is determined by the method described in [Isocyanate Group Concentration (Mass %)].

[0325] (Neutralization process and emulsification process)

[0326] The obtained urethane prepolymer solution was cooled to 35° C. and TEA was added while stirring at 500 rpm. Then, pure water was added dropwise at a rate of 10 mL / min while the solution was maintained at 35° C. and continued stirring at 500 rpm to obtain an emulsion.

[0327] (Chain extension process)

[0328] The obtained emulsion was maintained at 35° C. and stirred at 500 rpm while EDA was added to carry out a chain extension reaction.

[0329] (MEK distillation removal step)

[0330] The solution after the chain extension reaction was heated and distilled under reduced pressure to remove methyl ethyl ketone, thereby obtaining aqueous polyurethane solutions of PUD-1 to PUD-17, respectively.

[0331] [Evaluation of water dispersion stability of PUD]

[0332] The particle size of dispersed particles in a PUD solution sealed in a glass container and heated in a thermostat at 50°C for four weeks was measured before and after. The volume average particle size of the water-based polyurethane was measured using the "Nanotrac UPA" manufactured by Nikkiso Co., Ltd. The evaluation criteria are as follows: smaller changes in particle size indicate better stability.

[0333] (Judgment Criteria)

[0334] A+: Particle size change ratio is less than 1%

[0335] A: The change in particle size is less than 2%

[0336] B: The change in particle size is 2% or more and less than 5%

[0337] C: The change in particle size is 5% or more

[0338] (PUD coating production process)

[0339] The resulting aqueous polyurethane solutions of PUD-1 to PUD-17 were applied to a polypropylene plate (JIS K6921) mounted on a mold frame to a dry film thickness of 300 μm. After standing at 23°C and 50% RH for one day, the solutions were baked at 80°C for three hours and cured at 23°C and 50% RH for one week to produce aqueous polyurethane coatings for Application Examples 1-1 to 1-12 and Comparative Examples 1-1 to 1-5. The resulting aqueous polyurethane coatings were evaluated for various physical properties using the methods described below. The evaluation results are shown in Table 5.

[0340] [Application Examples 1-13 to 1-20]

[0341] Aqueous polyurethane solutions of PUD-18 to PUD-25 were obtained by the same method as described in [Application Examples 1-1 to 1-12 and Application Comparative Examples 1-1 to 1-5], except that the polyol-containing compositions used were changed to PUD-1-18 to PUD-25. Subsequently, PUD coating films were prepared using the obtained aqueous polyurethane solutions of PUD-18 to PUD-25 in the same manner as described in Application Examples 1-13 to 1-20. Various physical properties of the obtained aqueous polyurethane coating films were evaluated. The evaluation results are shown in Table 6.

[0342] [Table 5]

[0343]

[0344] [Table 6]

[0345]

[0346] [Example 2-1]

[0347] In a 500 ml separable flask, 31.3 g of PI2-1 (NCO: 16.1%) and 300 g of PEG-1000 (manufactured by Wako Pure Chemical Industries, Ltd.) were placed. After nitrogen substitution, the mixture was reacted at 100°C for 1 hour to obtain POL2-1. The NCO / OH (molar ratio) was 0.02. FT-IR confirmed the disappearance of the NCO-derived peak. Furthermore, the mPEG content in PI1-1 was calculated by GPC quantification according to [Quantitative Method for Functional Groups in Polyol-Containing Compositions] and was found to be 1.30 wt %, relative to the 1.35 wt % calculated from the feed amount.

[0348] [Examples 2-2 to 2-9, Comparative Example 2-4]

[0349] As shown in Table 7, POL2-2 to 2-9 and POL2-13 were synthesized by the same method as in Example 2-1, except that the polyisocyanate used was changed to PI2-2 to 2-5, the alcohol used was changed, and the NCO / OH (molar ratio) with the alcohol was changed to the value described in Table 7.

[0350] [Comparative Examples 2-1 to 2-3]

[0351] Except for making changes as shown in Table 7, POL2-10 to 2-12 were synthesized in the same manner as in Comparative Example 1-1.

[0352] ·Silaplane FM-4421 (manufactured by JNC Corporation): A diol having polydimethylsiloxane in the main chain

[0353] Silaplane FM-DA-11 (manufactured by JNC Corporation): A diol having polydimethylsiloxane in its side chain

[0354] Table 7 shows the raw materials and NCO / OH (molar ratio) and composition used in the synthesis of modified polyols. It should be noted that FG1 and FG2 described in the composition represent the functional groups (FG) contained in the modified polyol and their mass parts. Here, mass parts represent the mass of the structure described in FG. In addition, Z, R 1 、X 1 、X 2 , P, R2 , Y correspond to Z, R in the above formula (I) and formula (II) respectively. 1 、X 1 、X 2 , P, R 2 , Y. Furthermore, the masses described in FG1 and FG2 in Table 7 represent the masses of the following partial structures. In addition, in each partial structure, * represents a connecting bond.

[0355] T4671: Manufactured by Asahi Kasei Corporation. Polycarbonate diol obtained by copolymerizing 1,4-butanediol, 1,6-hexanediol, and a carbonate compound. Molecular weight: 1000.

[0356] PEG-2000: Made by Sanyo Chemical Industries, Ltd. Polyethylene glycol with a molecular weight of 2000.

[0357]

[0358] Long chain alkyl: *-C 16 H 33

[0359] Trialkoxysilane: *-Si(OEt)3

[0360] Isopropyl alcohol (IPA): *-CH(CH3)2

[0361] Neopentyl alcohol: *-CH2C(CH3)3

[0362] [Examples 2-10 to 2-14]

[0363] As shown in Table 8, POL2-14 to 2-18 were synthesized using the same method as Example 2-1, except that the polyisocyanate and alcohol were modified and the NCO / OH (molar ratio) with the alcohol was changed to the values described in Table 8. The functional group content was also calculated according to the aforementioned [Method for Quantifying Functional Groups in Polyol-Containing Compositions].

[0364] [Table 7]

[0365]

[0366] [Table 8]

[0367]

[0368] [Application Examples 2-1 to 2-9 and Comparative Examples 2-1 to 2-4]

[0369] <Thermoplastic polyurethane (TPU) composition and method for producing polyurethane coating film (TPU)>

[0370] (Raw materials used)

[0371] Polyol-containing compositions obtained in Examples and / or Comparative Examples (hereinafter sometimes referred to as "Pol")

[0372] Methylene diphenyl diisocyanate (MDI)

[0373] Dimethylformamide (DMF)

[0374] Dibutyltin dilaurate (DBTDL)

[0375] 1,4-Butanediol (BDL)

[0376] (Input amount)

[0377] Pol, MDI, and BDL were added at a molar ratio of Pol / MDI / BDL=1.0 / 3.0 / 2.0.

[0378] DBTDL is added so that the total amount of Pol, IPDI, and DMPA is 100 ppm. If necessary, DBTDL can be diluted with toluene before addition (e.g., 5% DBTDL-toluene solution).

[0379] DMF was added so that the final solid content would be 20%.

[0380] Pol, DMF and DBTDL were added and mixed to prepare solution 1. It should be noted that DMF accounted for 80% of the total amount used. Next, a nitrogen atmosphere was set in a 1L detachable flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen blowing tube and a dropping funnel, MDI and DMF were added thereto, and stirred at 40°C until uniform. The remaining 20% of DMF was used. The previously prepared solution 1 was slowly added thereto while stirring for 30 minutes. After the addition was completed, the reaction was continued until NCO% became more than 90% calculated by the input molar ratio. NCO% was determined by the method described in [Isocyanate group concentration (mass %)]. Next, BDL was added and the temperature was raised to 80°C. The molecular weight was monitored by GPC. After confirming that the number average molecular weight was more than 50,000, 3 ml of ethanol was added to stop the reaction, thereby obtaining thermoplastic polyurethane (TPU) compositions of TPU-1 to TPU-13 respectively.

[0381] (TPU coating production process)

[0382] The resulting thermoplastic polyurethane compositions, TPU-1 to TPU-13, were applied to polycarbonate plates ("Takiron PC-1600" (trade name), 2 mm × 70 mm × 150 mm) to a dry film thickness of 40 μm. The coating compositions applied to the polycarbonate plates were baked at 60°C and dried until no finger marks remained on the surface. Polyurethane coating films of Application Examples 2-1 to 2-9 and Application Comparative Examples 2-1 to 2-4 were obtained. The resulting polyurethane coating films were evaluated for various physical properties using the methods described below. The evaluation results are shown in Table 9.

[0383] [Application Examples 2-10 to 2-14]

[0384] Thermoplastic polyurethane compositions TPU-14 to TPU-18 were obtained by the same method as described in [Application Examples 2-1 to 2-9 and Application Comparative Examples 2-1 to 2-4], except that the polyol-containing compositions used were changed to Pol2-14 to Pol2-18. TPU coating films were then prepared in the same manner using the obtained thermoplastic polyurethane compositions TPU-14 to Pol2-18, yielding polyurethane coating films of Application Examples 2-10 to 2-14. The resulting polyurethane coating films were evaluated for various physical properties using the methods described below. The evaluation results are shown in Tables 10 to 12.

[0385] [Table 9]

[0386]

[0387] [Table 10]

[0388]

[0389] [Table 11]

[0390]

[0391] [Table 12]

[0392]

[0393] [Tensile test]

[0394] A 1 cm x 10 cm strip sample was prepared from a polyurethane coating or a water-based polyurethane coating. A tensile test was performed using a tensile testing machine (manufactured by Orientec Co., Ltd., product name "Tensilon, Model RTE-1210") at a chuck distance of 20 mm and a tensile speed of 100 mm / min at a temperature of 23°C (relative humidity of 55%) to measure the breaking stress.

[0395] [Heat resistance test]

[0396] The coating films obtained by the above method and those subjected to an additional heating test in a 120°C oven for one week were tested for breaking stress during the tensile test. The stress retention before and after the heat resistance test was determined using the following formula. A stress retention of 50% or greater was considered acceptable. The breaking stress was measured using the method described for the tensile test above.

[0397] [(Breaking stress after heat resistance test) / (Breaking stress before heat resistance test)]×100

[0398] [Stress retention after water resistance test]

[0399] For the coating film obtained by the above method, and the coating film immersed in water and subjected to an additional water resistance test in a thermostat at 60°C for 1 week and then simply wiped with absorbent paper (Kim Towel), the breaking stress in the tensile test was measured, and the stress retention rate before and after heat resistance was measured according to the following formula. A stress retention rate of 50% or more was considered qualified. It should be noted that the breaking stress was measured by the method described in the above tensile test.

[0400] [(Breaking stress after water resistance test) / (Breaking stress before water resistance test)]×100

[0401] [Surface free energy]

[0402] The surface free energy of the polyurethane coating film was calculated using the surface free energy evaluation method based on the Owens-Wendt method. Specifically, water and diiodomethane, known liquids, were added dropwise to the polyurethane coating film, and the contact angle θ was measured to calculate the surface free energy γ of the polyurethane coating film. It should be noted that γ is used as a known value for water. L d =21.8(mN / m),γ L h =51.0 (mN / m), diiodomethane uses γ L d =50.8(mN / m),γ L h = 0 (mN / m). The lower the surface free energy, the better the water repellency of the film. A surface free energy of 25 mN / m or less was considered acceptable.

[0403] [Chemical resistance spot test]

[0404] As a chemical resistance test, solvent resistance was conducted using ethanol (EtOH) and xylene. A water-based polyurethane film was cut and attached to a glass plate (JIS R3202, 2 mm × 100 mm × 150 mm). A cotton ball soaked in solvent (ethanol, xylene) was placed on the coating surface at 23°C and 50% RH on a horizontal platform. The time until abnormalities such as scratches and whitening occurred was visually evaluated. For evaluation reproducibility, a time of less than 10 seconds was designated as "<10 seconds."

[0405] [Appearance of coating film]

[0406] The appearance of the obtained TPU coating film was visually checked. The method for judging the coating film appearance is as follows.

[0407] (Judgment method)

[0408] A: Smooth without cracks or particles

[0409] B: No cracks, but slightly granular

[0410] C: Cracks

[0411] [Metal adhesion]

[0412] A coating film was prepared on an aluminum plate (JIS H4000, A1050p; 1.0 × 70 × 150 mm) using the same method as above, and the adhesion was evaluated. Adhesion was evaluated using the cross-cut method of JIS K5600-5-6:1999. Using a cutter, cuts were made in the coating film, with 100 1 mm × 1 mm grids. Cellophane tape was then applied to the cut surface of the coating film, which was then peeled off and the number of remaining grids was measured. Adhesion was evaluated based on the number of grids measured, according to the following evaluation criteria.

[0413] (Evaluation Criteria)

[0414] A: The number of grids is more than 90

[0415] B: The number of grids is 80 or more and less than 90

[0416] C: The number of grids is less than 80 and cannot be evaluated

[0417] Industrial Application Possibilities

[0418] According to the present invention, a polyurethane or water-based polyurethane can be formed that not only has excellent durability but also has various functionalities enhanced by the introduction of functional groups. Various functionalities can be expressed with a relatively small amount of introduction, and the degree of design freedom is increased. Therefore, it can be widely and effectively utilized in the field of raw materials for polyurethane or water-based polyurethane.

Claims

1. A polyol-containing composition comprising at least one hydroxyl compound, The polyol-containing composition has a number average molecular weight of 300 to 5,000, At least one of the hydroxyl compounds has: at least one main skeleton structure selected from the group consisting of an isocyanurate skeleton, an iminooxadiazinedione skeleton, a biuret skeleton, an allophanate skeleton, an aromatic skeleton and an alicyclic skeleton; at least one secondary skeleton structure connected to the main skeleton structure directly or via a connecting group and selected from the group consisting of a carbonate bond, an ether bond and an ester bond; at least two or more terminal hydroxyl groups connected to the secondary skeleton structure directly or via a connecting group; and at least one functional group other than a hydroxyl group connected to the main skeleton structure directly or via a connecting group.

2. The polyol-containing composition according to claim 1, wherein The content ratio of the functional group is 0.1 to 60.0 parts by mass based on 100 parts by mass of the total amount of the polyol-containing composition.

3. The polyol-containing composition according to claim 1, wherein When the total amount of the polyol-containing composition is 100 parts by mass, the content ratio of the functional group is 0.1 to 20.0 parts by mass.

4. The polyol-containing composition according to claim 1, wherein The functional group is at least one selected from the group consisting of a hydrophilic group, a hydrophobic group, an adsorptive group, and a cross-linking group.

5. The polyol-containing composition according to claim 1, wherein The functional group is a hydrophilic group.

6. The polyol-containing composition according to claim 1, wherein The functional group is a hydrophobic group.

7. The polyol-containing composition according to claim 1, wherein The functional group is an adsorption group.

8. The polyol-containing composition according to claim 1, wherein The functional group is a cross-linking group.

9. The polyol-containing composition according to claim 1, wherein The functional groups are at least two or more selected from the group consisting of a hydrophilic group, a hydrophobic group, an adsorptive group, and a crosslinking group.

10. The polyol-containing composition according to claim 1, wherein At least one of the hydroxy compounds has a structure represented by the following formula (I); Formula (I) In formula (I), m is an integer greater than or equal to 1, n is an integer greater than or equal to 2, Z is at least one selected from the group consisting of an isocyanurate skeleton, an iminooxadiazinedione skeleton, a biuret skeleton, an allophanate skeleton, an aromatic skeleton, and an alicyclic skeleton, and R 1 is a straight-chain or branched divalent hydrocarbon group, alicyclic structure or single bond, R 1 Each is optionally different, the divalent hydrocarbon group and the alicyclic structure optionally have a heteroatom, X 1 is a single bond or a divalent linking group, X 1 Each is optionally different, FG is the functional group, X 2 is a single bond or a divalent linking group, X 2 Each is optionally different, P is represented by the following formula (II), each P is optionally different; Formula (II) In formula (II), n is an integer greater than or equal to 1, * is a connecting bond, and R 2 is a divalent straight-chain or branched hydrocarbon group, R 2 Each is optionally different and optionally has a heteroatom, and Y is at least one selected from the group consisting of a carbonate bond, an ether bond, and an ester bond.

11. The polyol-containing composition according to claim 10, wherein The X in the formula (I) 1 、X 2 Contains at least one of carbamate, urea, and thiourea.

12. The polyol-containing composition according to claim 10, wherein The Y in the formula (II) is a carbonate bond. 13 . A polyurethane obtained by using the polyol-containing composition according to claim 1 . 14 . Aqueous polyurethane obtained by using the polyol-containing composition according to claim 1 . 15 . A polyurethane comprising an addition polymer of the polyol-containing composition according to claim 1 and a polyfunctional isocyanate. 16 . A water-based polyurethane comprising an addition polymer of the polyol-containing composition according to claim 1 and a polyfunctional isocyanate.

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