Resin composition, method for producing same, coating agent, coating film, and article

Abstract

The resin composition contains a polyurethane resin (A) containing a polyol represented by formula (1) as a monomer unit and a resin (B) which is a resin different from the polyurethane resin (A) and has a glass transition temperature of 35°C or higher. [In formula (1), R1 represents a C40-10,000 hydrocarbon group.]

Description

Resin composition and method for producing the same, coating agent, coating film, and article

[0001] The present disclosure relates to a resin composition, a method for producing the same, a coating agent, a coating film, and an article.

[0002] A liquid-repellent (water- and / or oil-repellent) coating film may be formed on the surface of an article for the purpose of imparting functions such as antifouling properties, self-cleaning properties, releasability, etc. Known methods for forming a liquid-repellent coating film include, for example, a method in which a coating agent for forming the coating film contains a liquid-repellent compound such as a fluorine-based compound or a silicon-based compound (see, for example, Patent Documents 1 and 2).

[0003] JP 2019-189699 A JP 2018-2927 A

[0004]

[0003] From the viewpoint of reducing the environmental impact and preventing problems caused by residual liquid-repellent compounds in manufacturing equipment and products, there is a need for liquid-repellent compounds that can replace the conventionally used fluorine-based compounds and silicon-based compounds. In response to this need, the present inventors have discovered that polyurethane resins having specific structures contribute to the development of liquid repellency. However, the use of polyurethane resins can result in insufficient blocking resistance in coating films.

[0005] Therefore, one aspect of the present disclosure aims to form a liquid-repellent coating film with excellent blocking resistance using a coating agent containing a polyurethane resin. Other aspects of the present disclosure aim to provide an article having the coating film, a coating agent for forming the coating film, and a resin composition that can be used for the coating agent.

[0006] Some aspects of the present disclosure provide the following [1] to

[13] .

[0007] [1] A resin composition comprising: a polyurethane resin (A) containing, as a monomer unit, a polyol represented by the following formula (1); and a resin (B) different from the polyurethane resin (A) and having a glass transition temperature of 35°C or higher: [In formula (1), R １represents a hydrocarbon group having 40 to 10,000 carbon atoms.]

[0008] [2] The resin composition according to [1], wherein the amount of the polyol represented by the formula (1) contained as a monomer unit in the polyurethane resin (A) is 60 to 90 mass% based on the total mass of the polyurethane resin (A).

[0009] [3] The resin composition according to [1] or [2], wherein the polyol represented by the formula (1) comprises at least one polyol selected from the group consisting of polyolefin polyols and hydrogenated polyolefin polyols.

[0010] [4] The resin composition according to any one of [1] to [3], wherein the polyurethane resin (A) contains a diisocyanate as a monomer unit.

[0011] [5] The resin composition according to any one of [1] to [4], wherein the polyurethane resin (A) contains a polyol represented by the following formula (2) as a monomer unit: [In formula (2), R ２ represents a hydrocarbon group having 1 to 30 carbon atoms, X represents a single bond, an ether group, a carbonyl group, an ester group, an amino group, or an amide group, and Z represents a hydrocarbon group having 1 to 50 carbon atoms which may be substituted with a hetero atom or a functional group.

[0012] [6] The resin composition according to any one of [1] to [5], wherein the content of the polyurethane resin (A) is 0.50 to 80 mass% based on the total solid content of the resin composition.

[0013] [7] The resin composition according to any one of [1] to [6], wherein the resin (B) comprises at least one resin selected from the group consisting of polyester resins, (meth)acrylic resins, and imide resins.

[0014] [8] The resin composition according to any one of [1] to [7], wherein the content of the resin (B) is 20 to 99.5 mass% based on the total solid content of the resin composition.

[0015] [9] A method for producing the resin composition according to any one of [1] to [8], comprising a step of mixing the polyurethane resin (A) and the resin (B).

[0016]

[10] A coating agent comprising the resin composition according to any one of [1] to [8].

[0017]

[11] The coating agent according to

[10] , which is used to impart liquid repellency to an article.

[0018]

[12] A coating film formed using the coating agent according to

[10] or

[11] .

[0019]

[13] An article having a substrate and the coating film according to

[12] provided on the substrate.

[0020] According to one aspect of the present disclosure, a coating agent using a polyurethane resin can form a liquid-repellent coating film with excellent blocking resistance. In addition, according to other aspects of the present disclosure, it is possible to provide an article having the coating film, a coating agent for forming the coating film, a resin composition usable for the coating agent, and the like.

[0021] In this specification, a numerical range indicated using "to" indicates a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. Furthermore, unless otherwise specified, the units of the numerical values ​​before and after "to" are the same. In the numerical ranges described in stages in this specification, the upper or lower limit of a certain numerical range may be replaced with the upper or lower limit of a numerical range of another stage. Furthermore, in the numerical ranges described in this specification, the upper or lower limit of that numerical range may be replaced with a value shown in the Examples. Furthermore, the upper and lower limits individually described can be arbitrarily combined. Unless otherwise specified, the materials exemplified below may be used alone or in combination of two or more types. When multiple substances corresponding to each component are present in the composition, the content of each component in the composition refers to the total amount of the multiple substances present in the composition, unless otherwise specified. Furthermore, in this specification, room temperature refers to 20 to 30°C. Furthermore, in this specification, "and / or" means either one or both. For example, "A and / or B" means either A, B, or a combination of A and B.

[0022] Hereinafter, exemplary embodiments of the present disclosure will be described, but the present disclosure is not limited to the following embodiments.

[0023] <Resin Composition> One embodiment of the present disclosure is a resin composition containing a polyurethane resin (hereinafter referred to as "polyurethane resin (A)") containing a polyol represented by the following formula (1) as a monomer unit, and a resin (hereinafter referred to as "resin (B)") that is different from the polyurethane resin (A) and has a glass transition temperature of 35°C or higher. [In formula (1), R １ represents a hydrocarbon group having 40 to 10,000 carbon atoms.]

[0024] A coating agent containing the resin composition can form a liquid-repellent coating film with excellent blocking resistance. Therefore, the resin composition is suitable for coating agents, particularly for imparting liquid repellency to articles. The coating film formed by the coating agent containing the resin composition also tends to have excellent surface hardness.

[0025] (Polyurethane Resin (A)) The polyurethane resin (A) contains a polyol represented by the above formula (1) (hereinafter referred to as "first polyol") as a monomer unit. The monomer unit consisting of the first polyol is represented, for example, by the following formula (1a). Note that * in the following formula (1a) represents a bond.

[0026] R １ The number of carbon atoms in the hydrocarbon group represented by the formula (I) is 40 to 10,000, and from the viewpoint of blocking resistance, it may be 50 or more, 75 or more, or 100 or more, and from the viewpoint of obtaining better film-forming properties, it may be 5,000 or less, 1,000 or less, 500 or less, 400 or less, 375 or less, or 230 or less.

[0027] R １ The hydrocarbon group represented by R may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. １ The hydrocarbon group represented by R may be linear or branched, and may have a ring (for example, an aromatic ring). １ The hydrocarbon group represented by R may be branched from the viewpoint of obtaining better liquid repellency. １ The above effect is more easily obtained when the hydrocarbon group represented by R １ The above effect is more easily obtained when the hydrocarbon group represented by R １ The above effect is particularly easily obtained when the hydrocarbon group represented by the formula (I) has one or more branched chains having 1 to 13 carbon atoms. The branched chains of the hydrocarbon group may be linear or branched.

[0028] R １ The two oxygen atoms bonded to R １ may be bonded to different carbon atoms in R １ That is, the first polyol may have one hydroxyl group on each of two different carbon atoms in the molecule, or may have a hydroxyl group on a terminal carbon atom of the molecule.

[0029] The first polyol may consist of one type of compound or a plurality of types of compounds.

[0030] The first polyol may be a polyol having a structure derived from a polymer. Examples of such polyols include polyolefin polyols, hydrogenated polyolefin polyols, and polystyrene polyols. From the viewpoint of obtaining better liquid repellency, the first polyol may contain at least one polyol selected from the group consisting of polyolefin polyols and hydrogenated polyolefin polyols. In particular, when the first polyol contains a hydrogenated polyolefin polyol, the above-mentioned effect is more easily obtained. Here, "polyolefin" refers to a polymer of a hydrocarbon compound (olefin) having a carbon-carbon double bond (C=C), and polyolefin polyol refers to a polyol represented by the formula (1) R １ refers to a polyol in which the double bonds in the polyolefin polyol are all hydrogenated, or the double bonds in the polyolefin polyol are partially hydrogenated. The double bond content in the hydrogenated polyolefin polyol can be confirmed using the iodine value as an index.

[0031] Examples of polyolefin polyols include polyethylene polyols, polypropylene polyols, polybutene polyols, polyfarnesene polyols, polybutadiene polyols, and polyisoprene polyols. Examples of hydrogenated polyolefin polyols include hydrogenated farnesene polyols, hydrogenated polybutadiene polyols, and hydrogenated polyisoprene polyols. The first polyol may contain at least one polyol selected from the group consisting of hydrogenated polybutadiene polyols and hydrogenated polyfarnesene polyols, from the viewpoint of increasing the compatibility of the polyurethane resin (A) with the solvent. In particular, the above-mentioned effect is more easily achieved when the first polyol contains hydrogenated polybutadiene polyol.

[0032] The polyolefin polyol and the hydrogenated polyolefin polyol may contain structural isomers such as 1,2-adducts and 1,4-adducts, and may contain stereoisomers such as cis isomers and trans isomers. When the first polyol contains a polybutadiene polyol and / or a hydrogenated polybutadiene polyol, the molar ratio of the 1,2-adduct to the 1,4-adduct (number of moles of 1,2-adduct:number of moles of 1,4-adduct) may be 20:80 to 90:10, 65:35 to 90:10, 80:20 to 90:10, or 80:20 to 85:15, from the viewpoint of obtaining better liquid repellency.

[0033] From the viewpoint of obtaining better film-forming properties, the iodine value of the first polyol may be 50 g / 100 g or less, 25 g / 100 g or less, or 15 g / 100 g or less. The iodine value of the first polyol may be 10 g / 100 g or less. The lower limit of the iodine value of the first polyol is 0 g / 100 g. The iodine value of the first polyol may be 5 g / 100 g or more. That is, the iodine value of the first polyol may be 0 to 50 g / 100 g, 5 to 25 g / 100 g, 5 to 15 g / 100 g, or 5 to 10 g / 100 g. The iodine value can be measured in accordance with JIS K0070.

[0034] The hydroxyl group content of the first polyol may be 0.50 mol / kg or more, 0.83 mol / kg or more, or 1.10 mol / kg or more, from the viewpoint of reactivity with polyisocyanate. The hydroxyl group content of the first polyol may be 2.00 mol / kg or less, 1.50 mol / kg or less, or 1.30 mol / kg or less, from the viewpoint of obtaining better liquid repellency. From these viewpoints, the hydroxyl group content of the first polyol may be, for example, 0.50 to 2.00 mol / kg, 0.83 to 1.50 mol / kg, or 1.10 to 1.30 mol / kg. The hydroxyl group content can be measured in accordance with JIS K-1557-1.

[0035] The number average molecular weight of the first polyol may be 1,000 or more, 1,300 or more, or 1,500 or more, from the viewpoint of obtaining better liquid repellency. The number average molecular weight of the first polyol may be 4,000 or less, 2,400 or less, or 1,800 or less, from the viewpoint of reactivity with polyisocyanate. From these viewpoints, the number average molecular weight of the first polyol may be, for example, 1,000 to 4,000, 1,300 to 2,400, or 1,500 to 1,800. The number average molecular weight is a polystyrene-equivalent value measured using gel permeation chromatography (GPC).

[0036] The amount of the first polyol contained as a monomer unit in the polyurethane resin (A) may be 60% by mass or more, 65% by mass or more, or 70% by mass or more, based on the total mass of the polyurethane resin (A), from the viewpoint of obtaining better liquid repellency. The amount of the first polyol contained as a monomer unit in the polyurethane resin (A) may be 90% by mass or less, 85% by mass or less, or 80% by mass or less, based on the total mass of the polyurethane resin (A), from the viewpoint of obtaining better liquid repellency. From these viewpoints, the amount of the first polyol contained as a monomer unit in the polyurethane resin (A) may be 60 to 90% by mass, 65 to 85% by mass, or 70 to 80% by mass, based on the total mass of the polyurethane resin (A).

[0037] The amount of the first polyol contained as a monomer unit in the polyurethane resin (A) may be 60% by mass or more, 65% by mass or more, or 70% by mass or more, based on the total amount of all polyols contained as monomer units in the polyurethane resin (A), from the viewpoint of obtaining better blocking resistance. The amount of the first polyol contained as a monomer unit in the polyurethane resin (A) may be 100% by mass or less, 90% by mass or less, or 80% by mass or less, based on the total amount of all polyols contained as monomer units in the polyurethane resin (A), from the viewpoint of obtaining better liquid repellency. From these viewpoints, the amount of the first polyol contained as a monomer unit in the polyurethane resin (A) may be 60 to 100% by mass, 65 to 90% by mass, or 70 to 80% by mass, based on the total amount of all polyols contained as monomer units in the polyurethane resin (A).

[0038] From the viewpoint of improving blocking resistance, the polyurethane resin (A) may contain a polyol represented by the following formula (2) (hereinafter referred to as "second polyol") as a monomer unit. The monomer unit consisting of the second polyol is represented, for example, by the following formula (2a). In the following formula (2a), * represents a bond.

[0039] In formula (2) and formula (2a), R ２ represents a hydrocarbon group having 1 to 30 carbon atoms, X represents a single bond, an ether group, a carbonyl group, an ester group, an amino group or an amide group, and Z represents a hydrocarbon group having 1 to 50 carbon atoms which may be substituted with a hetero atom or a functional group.

[0040] R ２ The number of carbon atoms in the hydrocarbon group represented by R may be 2 or more from the viewpoint of the reactivity of the polyisocyanate, and may be 15 or less, 10 or less, or 5 or less from the viewpoint of obtaining better blocking resistance. ２ The hydrocarbon group represented by the formula (I) may have 2 to 15, 2 to 10, or 1 to 5 carbon atoms.

[0041] R２ The hydrocarbon group represented by R may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. ２ The hydrocarbon group represented by the formula (I) may be linear or branched, and may have a ring (for example, an aromatic ring).

[0042] R ２ The two oxygen atoms bonded to R ２ In other words, the second polyol may have one hydroxyl group on each of two different carbon atoms in the molecule.

[0043] From the viewpoint of bond stability, X may be a single bond, an ether bond, an ester group, or an amino group. In particular, when X is an ester group or an amino group, the above-mentioned effect is more easily obtained, and when X is an ester group, the above-mentioned effect is even more easily obtained.

[0044] The group represented by Z may be a hydrocarbon group having 1 to 50 carbon atoms, a group in which some of the carbon atoms in a hydrocarbon group having 1 to 50 carbon atoms have been substituted with heteroatoms, a group in which some or all of the hydrogen atoms in a hydrocarbon group having 1 to 50 carbon atoms have been substituted with heteroatoms and / or functional groups, or a group in which some of the carbon atoms in a hydrocarbon group having 1 to 50 carbon atoms have been substituted with heteroatoms and some or all of the hydrogen atoms in a hydrocarbon group having 1 to 50 carbon atoms have been substituted with heteroatoms and / or functional groups. The hydrocarbon group having 1 to 50 carbon atoms may be a saturated or unsaturated hydrocarbon group, may be linear or branched, and may have a ring (for example, an aromatic ring).

[0045] The number of carbon atoms in the group represented by Z may be 2 or more, 5 or more, or 10 or more from the viewpoint of obtaining better blocking resistance, and may be 28 or less, 25 or less, or 22 or less from the viewpoint of obtaining better film-forming properties. From these viewpoints, the number of carbon atoms in the group represented by Z may be 2 to 28, 5 to 25, or 10 to 22.

[0046] The heteroatom substituting the carbon atom of the group represented by Z may be an oxygen atom and / or a silicon atom from the viewpoint of obtaining better liquid repellency. The heteroatom substituting the hydrogen atom of the group represented by Z may be a fluorine atom from the viewpoint of obtaining better liquid repellency. Examples of functional groups substituting the hydrogen atom of the group represented by Z include a silyl group.

[0047] The second polyol may consist of one type of compound or a plurality of types of compounds.

[0048] The second polyol may contain a monoglyceride represented by the following formula (2-1), from the viewpoint of obtaining better blocking resistance and film-forming properties.

[0049] Z in formula (2-1) has the same meaning as Z in formula (2).

[0050] Examples of the monoglyceride represented by formula (2-1) include caprylic acid monoglyceride, capric acid monoglyceride, lauric acid monoglyceride, stearate monoglyceride, behenic acid monoglyceride, etc. From the viewpoint of obtaining better blocking resistance and film-forming properties, the second polyol may contain at least one monoglyceride selected from the group consisting of caprylic acid monoglyceride, capric acid monoglyceride, lauric acid monoglyceride, stearate monoglyceride, and behenic acid monoglyceride.

[0051] The amount of the second polyol contained as a monomer unit in the polyurethane resin (A) may be more than 0% by mass, or may be 10% by mass or more, or 20% by mass or more, based on the total mass of the polyurethane resin (A), from the viewpoint of obtaining better blocking resistance. The amount of the second polyol contained as a monomer unit in the polyurethane resin (A) may be 40% by mass or less, or 35% by mass or less, or may be 35% by mass or less, based on the total mass of the polyurethane resin (A), from the viewpoint of obtaining better film-forming properties. From these viewpoints, the amount of the second polyol contained as a monomer unit in the polyurethane resin (A) may be more than 0% by mass and 40% by mass or less, or may be 10 to 35% by mass, or 20 to 30% by mass, based on the total mass of the polyurethane resin (A). In the above description, the "second polyol" may be replaced with the "monoglyceride represented by formula (2-1)". For example, the amount of the monoglyceride represented by formula (2-1) contained as a monomer unit in the polyurethane resin (A) may be more than 0 mass% and not more than 40 mass%, or may be 10 to 35 mass%, or 20 to 30 mass%, based on the total mass of the polyurethane resin (A).

[0052] The ratio of the amount of the second polyol to the amount of the first polyol contained as monomer units in the polyurethane resin (A) (amount of second polyol / amount of first polyol) may be greater than 0, 0.1 or greater, or 0.2 or greater, from the viewpoint of obtaining better blocking resistance, and may be 0.5 or less, 0.4 or less, or 0.3 or less, from the viewpoint of obtaining better liquid repellency. From these viewpoints, the ratio may be greater than 0 and 0.5 or less, 0.1 to 0.4, or 0.2 to 0.3. In the above description, the "second polyol" may be replaced with the "monoglyceride represented by formula (2-1)."

[0053] The ratio of the hydroxyl equivalent of the second polyol to the hydroxyl equivalent of the first polyol (hydroxyl equivalent of the second polyol / hydroxyl equivalent of the first polyol) may be 0.010 to 99, 0.050 to 20, or 0.070 to 15, from the viewpoint of achieving an excellent balance between the physical properties derived from the first polyol (e.g., liquid repellency) and the physical properties derived from the second polyol (e.g., blocking resistance).

[0054] The polyurethane resin (A) may contain, as a monomer unit, a polyol other than the first polyol and the second polyol. Examples of the other polyol include glycols having a linear structure such as ethylene glycol, propylene glycol, and butylene glycol; glycols having a cyclic structure such as 1,4-cyclohexanedimethanol; and glycols having a polyether structure such as polyethylene glycol, polypropylene glycol, and polybutylene glycol. The amount of the other polyol contained as a monomer unit in the polyurethane resin (A) may be, for example, 0 to 10% by mass, 2 to 8% by mass, or 4 to 6% by mass, based on the total mass of the polyurethane resin (A).

[0055] The polyurethane resin (A) contains a polyisocyanate as a monomer unit. The polyisocyanate contained as a monomer unit in the polyurethane resin (A) is not particularly limited. The polyurethane resin (A) may contain a diisocyanate as a monomer unit from the viewpoint of obtaining better film-forming properties.

[0056] Specific examples of polyisocyanates include isocyanates having an aromatic skeleton, such as diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and 1,4-tetramethylxylylene diisocyanate. Examples of the isocyanates include isocyanates having an aliphatic skeleton, such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane-4,4'-diisocyanate, hydrogenated diphenylmethane-2,4'-diisocyanate, hydrogenated xylylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, and norbornene diisocyanate. These may be monomers or polymers, and may be allophanate-modified or biuret-modified. Among these, from the viewpoint of obtaining a coating film superior in surface hardness and mechanical strength, at least one diisocyanate selected from the group consisting of diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, 2,4-toluene diisocyanate, and 2,6-toluene diisocyanate may be used.

[0057] The polyisocyanate may be composed of one type of compound or a plurality of types of compounds.

[0058] The isocyanate group content in the polyisocyanate may be 1.7 mol / kg or more, 2.4 mol / kg or more, or 4.0 mol / kg or more, from the viewpoint of obtaining better film-forming properties. The isocyanate group content in the polyisocyanate may be 12.0 mol / kg or less, 11.0 mol / kg or less, or 8.0 mol / kg or less, from the viewpoint of obtaining better liquid repellency. From these viewpoints, the isocyanate group content in the polyisocyanate may be, for example, 1.7 to 12.0 mol / kg, 2.4 to 11.0 mol / kg, or 4.0 to 8.0 mol / kg. The isocyanate group content in the polyisocyanate can be measured in accordance with JIS K1603-1.

[0059] The amount of polyisocyanate contained as a monomer unit in the polyurethane resin (A) may be 10% by mass or more, 15% by mass or more, or 20% by mass or more, based on the total mass of the polyurethane resin (A), from the viewpoint of obtaining better blocking resistance. The amount of polyisocyanate contained as a monomer unit in the polyurethane resin (A) may be 40% by mass or less, 35% by mass or less, or 30% by mass or less, based on the total mass of the polyurethane resin (A), from the viewpoint of obtaining better liquid repellency. From these viewpoints, the amount of polyisocyanate contained as a monomer unit in the polyurethane resin (A) may be 10 to 40% by mass, 15 to 35% by mass, or 20 to 30% by mass, based on the total mass of the polyurethane resin (A).

[0060] The total hydroxyl group equivalent weight m of all polyols contained as monomer units in the polyurethane resin (A) ＯＨ The total isocyanate group equivalents m of all polyisocyanates contained as monomer units in the polyurethane resin (A) relative to ＮＣＯ Ratio (m ＮＣＯ / m ＯＨ) may be 0.70 to 1.3, 0.8 to 1.2, or 0.9 to 1.1. When the equivalent ratio is 0.70 or more, a sufficient molecular weight is easily obtained, and good drying properties are easily obtained. When the equivalent ratio is 1.3 or less, the molecular weight does not become too large, and good fluidity is easily obtained. In this embodiment, the ratio of the isocyanate group equivalent of the polyisocyanate to the sum of the hydroxyl group equivalent of the first polyol and the hydroxyl group equivalent of the second polyol may be within the above range. The hydroxyl group equivalent and isocyanate group equivalent are the hydroxyl group equivalent and isocyanate group equivalent in the monomer state.

[0061] The polyurethane resin (A) may contain a monomer unit other than the polyol and polyisocyanate (e.g., a monool or a monoisocyanate) as long as the object of the present disclosure is not impaired. From the viewpoint of reducing the environmental load and preventing problems caused by residues in the production equipment and in the product, the polyurethane resin (A) does not need to contain fluorine atoms or silicon atoms.

[0062] The polyurethane resin (A) may have an isocyanate group. When the polyurethane resin (A) has an isocyanate group and the resin (B) has a hydroxyl group, the isocyanate group in the polyurethane resin (A) may react with the hydroxyl group in the resin (B), resulting in a coating film with superior surface hardness and mechanical strength. The isocyanate group content of the polyurethane resin (A) may be 0.10 to 2.0 mol / kg, 0.50 to 1.5 mol / kg, or 0.70 to 1.0 mol / kg, from the viewpoint that a coating film with superior surface hardness and mechanical strength is more easily obtained by reaction with the resin (B) having a hydroxyl group. The isocyanate group content of the polyurethane resin (A) can be measured by the method described in the examples.

[0063] The urethane group concentration of the polyurethane resin (A) may be 0.50 mol / kg or more, 0.60 mol / kg or more, or 0.70 mol / kg or more, from the viewpoint of obtaining better blocking resistance. The urethane group concentration of the polyurethane resin (A) may be 2.0 mol / kg or less, 1.8 mol / kg or less, or 1.75 mol / kg or less, from the viewpoint of obtaining better liquid repellency. From these viewpoints, the urethane group concentration of the polyurethane resin (A) may be, for example, 0.50 to 2.0 mol / kg, 0.60 to 1.8 mol / kg, or 0.70 to 1.75 mol / kg. The urethane group concentration of the polyurethane resin (A) can be measured by the method described in the examples.

[0064] The weight average molecular weight of the polyurethane resin (A) may be 42,000 or less, 37,000 or less, or 25,000 or less, from the viewpoint of obtaining better film-forming properties. The weight average molecular weight of the polyurethane resin (A) may be 12,300 or more, 12,500 or more, or 13,000 or more, from the viewpoint of obtaining better blocking resistance. From these viewpoints, the weight average molecular weight of the polyurethane resin (A) may be, for example, 12,300 to 42,000, 12,500 to 37,000, or 13,000 to 25,000.

[0065] The number average molecular weight of the polyurethane resin (A) may be 3,000 to 500,000, 3,000 to 250,000, or 3,000 to 100,000, from the viewpoint of obtaining better blocking resistance.

[0066] The molecular weight distribution index (weight average molecular weight / number average molecular weight) of the polyurethane resin (A) may be 2.5 or more, 2.8 or more, or 3.0 or more, from the viewpoint of obtaining better liquid repellency. The molecular weight distribution index of the polyurethane resin (A) may be 6.0 or less, 5.5 or less, or 5.0 or less, from the viewpoint of obtaining better blocking resistance. From these viewpoints, the molecular weight distribution index of the polyurethane resin (A) may be, for example, 2.5 to 6.0, 2.8 to 5.5, or 3.0 to 5.0. The weight average molecular weight and number average molecular weight of the polyurethane resin (A) are polystyrene-equivalent values ​​measured using gel permeation chromatography (GPC) and may be measured by the method described in the examples.

[0067] From the viewpoint of obtaining better liquid repellency, the glass transition temperature of the polyurethane resin (A) may be −10° C. or lower, −20° C. or lower, or −28° C. or lower. The glass transition temperature of the polyurethane resin (A) may be, for example, −10 to −80° C., −20 to −70° C., or −28 to −65° C. The glass transition temperature of the polyurethane resin (A) can be measured in accordance with JIS K6240.

[0068] The polyurethane resin (A) may be a reaction product of the components contained as the above-described monomer units (hereinafter referred to as "polyurethane resin-forming raw materials"). The polyurethane resin (A) may be obtained, for example, by reacting the polyurethane resin-forming raw materials by heating them while mixing them in the presence of a catalyst (urethanization catalyst) and a solvent (reaction solvent). The reaction produces a composition containing the polyurethane resin (A) (hereinafter also referred to as a "polyurethane composition"). The polyurethane composition may contain, in addition to the polyurethane resin (A), components used in the reaction (unreacted polyol, unreacted polyisocyanate, catalyst, solvent, etc.).

[0069] Examples of the catalyst include organometallic compounds such as dibutyltin diacetate, dibutyltin dilaurate, and dioctyltin dilaurate; organic amines such as triethylenediamine and triethylamine, and salts thereof; etc. These may be used alone or in combination of two or more.

[0070] The amount of catalyst may be selected depending on the reactivity of the polyisocyanate used. The amount of catalyst may be, for example, 0.00010 parts by mass or more, 0.0010 parts by mass or more, or 0.010 parts by mass or more, per 1 part by mass of polyurethane resin-forming raw materials; 25 parts by mass or less, 6.0 parts by mass or less, or 1.0 part by mass or less, or 0.00010 to 25 parts by mass, 0.0010 to 6.0 parts by mass, or 0.010 to 1.0 part by mass, per 1 part by mass of polyurethane resin-forming raw materials. When the amount of catalyst is 0.00010 parts by mass or more per 1 part by mass of polyurethane resin-forming raw materials, a sufficient catalytic effect is more likely to be obtained. When the amount of catalyst is 25 parts by mass or less per 1 part by mass of polyurethane resin-forming raw materials, it is economically advantageous.

[0071] Examples of the solvent include aromatic hydrocarbon solvents such as toluene, ethylbenzene, trimethylbenzene, and xylene; aliphatic hydrocarbon solvents such as pentane, hexane, and cyclohexane; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohol solvents such as methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol, triethylene glycol, and propylene glycol; glycol ether solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl diglycol, ethyl diglycol, butyl diglycol, and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; amide solvents such as N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; ether solvents such as diethyl ether and tetrahydrofuran; and water. These may be used alone or in combination of two or more.

[0072] The amount of the solvent to be added is not particularly limited, and may be, for example, 1.0 part by mass or more and 10,000 parts by mass or less per 100 parts by mass of the polyurethane resin-forming raw materials.

[0073] The content of polyurethane resin (A) may be 0.50% by mass or more, 10% by mass or more, 20% by mass or more, or 30% by mass or more, based on the total solid content of the resin composition, from the viewpoint of obtaining a coating film with superior liquid repellency (particularly oil repellency). The content of polyurethane resin (A) may be 80% by mass or less, 60% by mass or less, 50% by mass or less, 40% by mass or less, or 10% by mass or less, based on the total solid content of the resin composition, from the viewpoint of obtaining a coating film with superior surface hardness and mechanical strength and further improving the blocking resistance of the coating film. From these viewpoints, the content of polyurethane resin (A) may be, for example, 0.50 to 80 mass%, 0.50 to 60 mass%, 0.50 to 50 mass%, 0.50 to 40 mass%, or 0.50 to 10 mass%, or may be 10 to 80 mass%, 20 to 80 mass%, 30 to 60 mass%, or 30 to 40 mass%, based on the total solid content of the resin composition. In this specification, solid content means components other than the solvent.

[0074] (Resin (B)) Resin (B) is a resin different from polyurethane resin (A) and has a glass transition temperature of 35° C. or higher.

[0075] Examples of the resin (B) include polyester resin, (meth)acrylic resin, polyurethane resin, acrylic silicone resin, fluororesin, and imide resin (e.g., polyimide resin). Here, "(meth)acrylic resin" refers to at least one of an acrylic resin and a methacrylic resin. As the resin (B), one of these resins may be used alone, or two or more may be used in combination.

[0076] From the viewpoint of achieving superior surface hardness of the coating film, the resin (B) may contain at least one resin selected from the group consisting of polyester resins, (meth)acrylic resins, and imide resins.

[0077] Resin (B) may have a hydroxyl group. When polyurethane resin (A) has an isocyanate group and resin (B) has a hydroxyl group, the isocyanate group in polyurethane resin (A) may react with the hydroxyl group in resin (B), resulting in a coating film with superior surface hardness and mechanical strength. The hydroxyl value of resin (B) may be 1 to 80 mgKOH / g, 3 to 70 mgKOH / g, or 5 to 60 mgKOH / g, from the viewpoint that a coating film with superior surface hardness and mechanical strength is more easily obtained by reaction with polyurethane resin (A) having an isocyanate group. The hydroxyl value of resin (B) is a value measured in accordance with JIS K1557-1.

[0078] The glass transition temperature of resin (B) is 35°C or higher, and from the viewpoint of obtaining a coating film having excellent surface hardness and mechanical strength, it may be 40°C or higher, 45°C or higher, 60°C or higher, 80°C or higher, 100°C or higher, 150°C or higher, 200°C or higher, or 250°C or higher. The glass transition temperature of the resin (B) may be 500 ° C. or less, 400 ° C. or less, 350 ° C. or less, 300 ° C. or less, 200 ° C. or less, 150 ° C. or less, 130 ° C. or less, 120 ° C. or less, 110 ° C. or less, 100 ° C. or less, 80 ° C. or less, or 60 ° C. or less, for example, 35 to 500 ° C., 35 to 400 ° C., 35 to 350 ° C., 35 to 300 ° C., 35 to 200 ° C., 35 to 150 ° C., 35 to 130 ° C., 40 to 120 ° C., 45 to 110 ° C., 45 to 100 ° C., 45 to 80 ° C., 45 to 60 ° C., 60 to 130 ° C., 80 to 130 ° C., 100 to 500 ° C., 150 to 500 ° C., 200 to 500 ° C., or 250 to 500 ° C. The glass transition temperature of the resin (B) can be measured in accordance with JIS K6240.

[0079] The content of resin (B) may be 20% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more, based on the total solid content of the resin composition, from the viewpoint of obtaining a coating film with superior surface hardness and mechanical strength and further improving the blocking resistance of the coating film. The content of resin (B) may be 99.5% by mass or less, 90% by mass or less, 80% by mass or less, or 70% by mass or less, based on the total solid content of the resin composition, from the viewpoint of obtaining a coating film with superior liquid repellency (particularly oil repellency). From these viewpoints, the content of resin (B) may be, for example, 20 to 99.5 mass%, 40 to 99.5 mass%, 50 to 99.5 mass%, 60 to 99.5 mass%, 70 to 99.5 mass%, 80 to 99.5 mass%, 90 to 99.5 mass%, 20 to 90 mass%, 20 to 80 mass%, 40 to 70 mass%, or 60 to 70 mass%, based on the total solid content of the resin composition.

[0080] The mass ratio of the content of resin (B) to the content of polyurethane resin (A) may be 0.1 or more, 1 or more, 10 or more, 20 or more, 40 or more, 60 or more, or 80 or more, from the viewpoint of obtaining a coating film having superior surface hardness and mechanical strength and further improving the blocking resistance of the coating film. The mass ratio of the content of resin (B) to the content of polyurethane resin (A) may be 99.5 or less, 90 or less, 70 or less, 50 or less, 30 or less, 10 or less, or 5 or less, from the viewpoint of obtaining a coating film having superior liquid repellency (particularly oil repellency). From these viewpoints, the mass ratio of the content of resin (B) to the content of polyurethane resin (A) may be 0.1 to 99.5, 1 to 99.5, 10 to 99.5, 20 to 99.5, 40 to 99.5, 60 to 99.5, or 80 to 99.5, or may be 0.1 to 99.5, 0.1 to 90, 0.1 to 70, 0.1 to 50, 0.1 to 30, 0.1 to 10, or 0.1 to 5.

[0081] Hydroxyl group equivalent M of resin (B) ＯＨ The total M of the isocyanate group equivalents of the polyurethane resin (A) ＮＣＯ The ratio (M ＮＣＯ / M ＯＨ) may be 0.070 to 2, or may be 0.40 to 1.5, or 0.65 to 1.0.

[0082] (Other Components) The resin composition may optionally contain other components (components other than the polyurethane resin (A) and the resin (B)) within the scope of the present disclosure. Examples of other components include solvents, catalysts used in the production of the polyurethane resin (A), antifoaming agents, leveling agents, organic thickeners, antioxidants, light stabilizers, adhesion improvers, release agents, reinforcing materials, softeners, colorants, flame retardants, antistatic agents, and wetting and dispersing agents.

[0083] Examples of the solvent include the same solvents as those used in the production of the polyurethane resin (A) described above. The content of the solvent may be selected depending on the coating method, the desired thickness of the coating film, etc. The content of the solvent may be, for example, 1 to 99% by mass based on the total mass of the resin composition.

[0084] The leveling agent is not particularly limited, but examples thereof include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, silicon surfactants, nonionic surfactants, fluorine-based surfactants, and acrylic surfactants. These may be used alone or in combination of two or more. The content of the leveling agent is not particularly limited, but may be, for example, 0.10 to 10 mass% based on the total mass of the resin composition.

[0085] The other components may be components used in the synthesis of the urethane resin (A), such as polyol, polyisocyanate, urethane catalyst, and reaction solvent.

[0086] The other component may be a polyurethane resin. When the resin composition contains a urethane resin other than the urethane resin (A), the content of the urethane resin (A) may be 80% by mass or more and less than 100% by mass, 85% by mass or more and less than 100% by mass, or 90% by mass or more and less than 100% by mass, based on the total mass of the urethane resins contained in the resin composition (the sum of the content of the urethane resin (A) and the content of the urethane resins other than the urethane resin (A)), from the viewpoint of making it easier to obtain the above-mentioned effects of the urethane resin (A). The content of the urethane resin (A) may be 100% by mass based on the total mass of the urethane resins contained in the resin composition (the sum of the content of the urethane resin (A) and the content of the urethane resins other than the urethane resin (A)).

[0087] The resin composition does not need to contain fluorine-based compounds (compounds having fluorine atoms in the molecule) and silicon-based compounds (compounds having silicon atoms in the molecule) from the viewpoint of reducing the environmental load and preventing problems caused by residues in the manufacturing equipment and in the product.

[0088] The resin composition described above can be produced, for example, by a method including a step of mixing polyurethane resin (A) and resin (B). In this step, in addition to polyurethane resin (A) and resin (B), the above-mentioned other components may be mixed. The timing of adding the other components may be simultaneous with the timing of mixing polyurethane resin (A) and resin (B), or may be before or after the timing of mixing polyurethane resin (A) and resin (B). For example, the other components may be premixed with polyurethane resin (A) and / or resin (B), or may be mixed with a mixture of polyurethane resin (A) and resin (B). Furthermore, for example, the polyurethane composition obtained by synthesizing polyurethane resin (A) may be mixed with resin (B). The mixing method is not particularly limited, and for example, mixing may be performed manually using a spatula or the like, or using a mechanical rotary mixer, static mixer, or the like.

[0089] <Coating Agent> Another embodiment of the present disclosure is a coating agent containing the resin composition of the above embodiment. The coating agent may consist solely of the resin composition of the above embodiment.

[0090] The coating agent may contain a solvent (such as the solvents exemplified above) from the viewpoint of viscosity adjustment. The viscosity of the coating agent is not particularly limited as long as it allows application to an article, but may be, for example, 5 to 1000 mPa·s at 25°C. The viscosity is measured in accordance with JIS K7117-1.

[0091] <Coating Film> Another embodiment of the present disclosure is a coating film formed using the coating agent of the above embodiment. The coating film is made of, for example, a dried product of the coating agent.

[0092] The coating film contains, for example, a polyurethane resin (A) and a resin (B). The coating film may contain a reaction product of the polyurethane resin (A) and the resin (B). As described above, when the polyurethane resin (A) has an isocyanate group and the resin (B) has a hydroxyl group, a reaction product of the polyurethane resin (A) and the resin (B) may be produced during coating film formation.

[0093] The thickness of the coating may be, for example, 1 to 100 μm.

[0094] The coating film can be formed, for example, by applying the coating agent to a substrate and drying it. Examples of methods for applying the coating agent include applicator method, bar coating method, spin coating method, spray coating method, dip coating method, nozzle coating method, gravure coating method, reverse roll coating method, die coating method, air doctor coating method, blade coating method, rod coating method, curtain coating method, knife coating method, transfer roll coating method, squeeze coating method, impregnation coating method, kiss coating method, calendar coating method, and extrusion coating method.

[0095] Examples of materials constituting the substrate include resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polycarbonate, acrylonitrile-butadiene-styrene copolymer synthetic resin (ABS resin), nylon 6, nylon 66, aramid, acrylic, polyethylene terephthalate, polybutylene terephthalate, etc., composite materials made of any of these resins and glass fiber, thermosetting resins such as epoxy resin, UV-curable resist resins such as acrylic resin, composite materials of thermoplastic resins such as polyphenylene sulfide and carbon fiber (CFRP, CFRTP), metals such as aluminum, aluminum alloy, magnesium, stainless steel, tinplate, electrogalvanized steel sheet, chrome-plated steel sheet, etc., glass, etc. The substrate may be made of one or more of these materials.

[0096] The coating film has high liquid repellency against water and / or oil. The liquid repellency is confirmed by the contact angle of various probe liquids on the surface of the coating film. When the contact angles of water and oil with a polyethylene substrate, which is conventionally known as a material exhibiting liquid repellency, are used as indicators, the contact angle of the coating film may be larger than the contact angles. The contact angle with water may be 90 degrees or more, and the contact angle with oil may be 15 degrees or more. Here, oil refers to normal hexadecane.

[0097] <Article> Another embodiment of the present disclosure is an article having a substrate and a coating film provided on the substrate. Examples of the substrate include the same substrates that can be used to form the coating film.

[0098] The above-mentioned articles can be suitably used for vehicle-related parts, electronic materials, structural materials, building materials, furniture, decorative sheets, sporting goods, stationery, and the like.

[0099] The contents of the present disclosure will be described in more detail below using examples and comparative examples, but the present disclosure is not limited to the following examples.

[0100] <Preparation of Materials> The following materials were prepared.[Polyols] Hydrogenated polybutadiene polyol: hydroxyl-terminated hydrogenated polybutadiene (trade name: GI-1000, manufactured by Nippon Soda Co., Ltd.), number average molecular weight = 1500, hydroxyl content = 1.22 mol / kg, iodine value = 9.2 g / 100 g, 1,2-adduct:1,4-adduct = 85:15 (molar ratio) Hydrogenated polyfarnesene polyol: hydroxyl-terminated hydrogenated polyfarnesene (trade name: KRASOL F3100, manufactured by Cray Valley), number average molecular weight = 2940, hydroxyl content = 0.68 mol / kg, iodine value = 9.7 g / 100 g Behenic acid monoglyceride: (trade name: Rikemal B-100, manufactured by Riken Vitamin Co., Ltd., "Rikemal" is a registered trademark) [Polyisocyanates] MDI: diphenylmethane-4,4'-diisocyanate (trade name: Millionate MT, manufactured by Tosoh Corporation, "Millionate" is a registered trademark), isocyanate group content = 7.99 mol / kg [Catalyst] Dioctyltin dilaurate: manufactured by Kishida Chemical Co., Ltd. [Solvent] Cyclohexanone: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Butyl acetate: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. [Polyester resin] Polyester resin 1: hydroxyl group-containing polyester resin (trade name: Byron 600, manufactured by Toyobo MC Co., Ltd., "Byron" is a registered trademark (the same applies below)), glass transition temperature = 47°C, hydroxyl value = 7 mgKOH / g, solid content (non-volatile content) = 100 mass% Polyester resin 2: hydroxyl group-containing polyester resin (trade name: Vylon 200, manufactured by Toyobo MC Co., Ltd.), glass transition temperature = 67°C, hydroxyl value = 6 mgKOH / g, solid content (non-volatile content) = 100% by mass [Acrylic resin] Acrylic resin 1: hydroxyl group-containing acrylic resin (trade name: Acrydic WFL-580, manufactured by DIC Corporation, "Acrydic" is a registered trademark (the same applies hereinafter)), glass transition temperature = 70°C, hydroxyl value = 54 mgKOH / g, solid content (non-volatile content) = 60% by mass Acrylic resin 2: hydroxyl group-containing acrylic resin (trade name: Acrydic WBU-1218, manufactured by DIC Corporation), glass transition temperature = 100°C, hydroxyl value = 10 mgKOH / g, solid content (non-volatile content) = 30% by mass [Imide resin] Imide resin 1: Polyimide varnish (product name: Neoprim S-100, manufactured by Mitsubishi Gas Chemical Company, Inc., "Neoprim" is a registered trademark), glass transition temperature = 300°C, solid content (non-volatile content) = 20 mass%.

[0101] Synthesis Example 1 (Preparation of Polyurethane Composition) 386.0 g of hydrogenated polybutadiene polyol, 155.8 g of MDI, 0.986 g of dioctyltin dilaurate, and 6072 g of cyclohexanone were charged into a 10 L four-neck separable flask equipped with a stirrer, thermometer, heater, and reflux condenser at room temperature. Nitrogen gas was then blown into the flask to replace the atmosphere inside the flask. The mixture in the flask was allowed to react for 2 hours with substantially uniform stirring at 80°C. Then, 177.3 g of behenic acid monoglyceride was added, and the reaction was continued for an additional 6 hours under the same conditions to obtain a polyurethane composition containing 10% by mass of polyurethane resin (A1). In this example, the amount of solids obtained by drying the polyurethane composition under reduced pressure and distilling off the solvent was considered to be the content of the polyurethane resin in the polyurethane composition.

[0102] (Analysis of Polyurethane Resin) The polyurethane composition obtained above was dried under reduced pressure to remove the solvent, and a polyurethane resin (A1) was extracted. The urethane group concentration, molecular weight, etc. of the polyurethane resin (A1) were measured by the methods described below. The results are shown in Table 1. Note that the polyurethane resin (A1) extracted by this method may contain residual catalyst used in the reaction. However, since the amount of residual catalyst was extremely small and below the detection limit of the measurement method, the following measurements were performed assuming that no catalyst remained.

[0103] [Measurement of Isocyanate Group Content and Urethane Group Concentration] First, the isocyanate group content (NCO content) remaining in the polyurethane resin (A1) after the synthesis reaction was measured in accordance with JIS K1603-1. Next, the nitrogen content in the polyurethane resin (A1) was measured by elemental analysis. The urethane group concentration in the polyurethane resin (A1) was calculated from the isocyanate group content obtained by the measurement and the results of the elemental analysis.

[0104] [Measurement of Molecular Weight] The weight average molecular weight (Mw) and number average molecular weight (Mn) were measured using gel permeation chromatography (GPC) under the following conditions, and the molecular weight distribution index (Mw / Mn) was calculated. The weight average molecular weight and number average molecular weight are molecular weights converted into polystyrene. -Conditions- Apparatus: High-speed GPC apparatus (HLC-8320GPC manufactured by Tosoh Corporation) Column: One TSKgel guard column α (6.0 mm I.D. x 4 cm) and two +α-M (67.8 mm I.D. x 30 cm) connected in series in this order (both manufactured by Tosoh Corporation). Mobile phase: Cyclohexanone Mobile phase rate: 1.0 mL / min Column temperature: 40°C Detector: RI detector (polarity (+)) Sample solution: Cyclohexanone solution (concentration: 1 mg / mL) Sample injection volume: 100 μL

[0105] [Measurement of Glass Transition Temperature] The glass transition temperature (Tg) of the polyurethane resin (A1) was measured using differential scanning calorimetry (DSC) in accordance with JIS K6240. The measurement was carried out in a nitrogen atmosphere in a temperature range of -80°C to 200°C, with a temperature rise rate of 10°C / min. The gas flow rate was 50 mL / min. The sample was used sealed in an Al pan.

[0106] Synthesis Example 2: 160.0 g of hydrogenated polyfarnesene polyol, 17.5 g of MDI, 0.0809 g of a catalyst (dioctyltin dilaurate), and 1598 g of a solvent (cyclohexanone) were placed in a 2 L four-neck separable flask equipped with a stirrer, thermometer, heater, and reflux condenser at room temperature. Nitrogen gas was then blown into the flask to replace the atmosphere inside the flask. The mixture in the flask was allowed to react for 6 hours with substantially uniform stirring at 80°C, yielding a polyurethane composition containing 10% by mass of polyurethane resin (A2). The polyurethane resin (A2) was then extracted from the resulting polyurethane composition in the same manner as in Synthesis Example 1, and the isocyanate group content, urethane group concentration, molecular weight, and glass transition temperature of the polyurethane resin (A2) were measured.

[0107]

[0108] Example 1 19.8 g of polyester resin 1 and 78.2 g of butyl acetate were placed in a 200 mL beaker at room temperature, and the mixture was stirred at a rotation speed of 150 rpm using a stirrer equipped with a stirring blade until the polyester resin 1 was dissolved. Next, 2.0 g of the polyurethane composition of Synthesis Example 1 (solid content (non-volatile content) = 10 mass%) was added, and the mixture was stirred under the same conditions for 5 minutes to obtain a resin composition containing polyurethane resin (A1) and polyester resin 1 (hereinafter referred to as "coating agent 1").

[0109] Next, Coating Agent 1 obtained above was applied to a polyethylene terephthalate film (PET film: Toyobo Ester Film E5100 manufactured by Toyobo Co., Ltd.) using a bar coater, and after leaving to stand at room temperature for 5 minutes, it was dried at 80° C. for 10 minutes using a hot air dryer. As a result, a coating film (film thickness 4 μm) consisting of the dried product of Coating Agent 1 was formed on the PET film.

[0110] (Evaluation of coating film physical properties) The physical properties (liquid repellency, surface hardness and blocking resistance) of the coating films prepared above were evaluated by the following methods.

[0111] [Evaluation of Liquid Repellency] The contact angles of various probe liquids on the surface of the coating film were measured by the sessile drop method in accordance with JIS R3257 to evaluate liquid repellency. 2.0 μL of the probe liquid was dropped, and the contact angle was measured 1 second after dropping using a contact angle measuring instrument (Kyowa Interface Science Co., Ltd., Automatic Contact Angle Meter DMo-601). Two types of probe liquid were used: pure water (72.8 mN / m, Fujifilm Wako Pure Chemical Industries, Ltd.) and normal hexadecane (27.6 mN / m, Fujifilm Wako Pure Chemical Industries, Ltd.). The contact angle was measured 10 times for each probe liquid, and the average value was used as the measured value. The results are shown in Table 2.

[0112] (Evaluation of Surface Hardness) The surface hardness of the coating film was evaluated by the pencil hardness of the coating film surface. The pencil hardness was measured in accordance with JIS K5600-5-4. The results are shown in Table 1.

[0113] (Evaluation of Blocking Resistance) An uncoated PET film was placed on top of the coating film made of the dried product of Coating Agent 1 used in the contact angle measurement, and the two films were then laminated together under a load of 1 kg for 24 hours to prepare a sample for evaluating blocking resistance. The PET film was peeled off from the resulting sample coating, and the presence or absence of tack when the PET film was peeled off and the appearance of the coating film after peeling off were confirmed, and the blocking resistance of the coating film was evaluated according to the following criteria. The smaller the evaluation value, the better the coating film's blocking resistance. The results are shown in Table 1. 1: No tack occurred between the coating film and the PET film, and there was no change in the appearance of the coating film. 2: Slight tack occurred between the coating film and the PET film, but there was no change in the appearance of the coating film. 3: Tack occurred between the coating film and the PET film, and there was a change in the appearance of the coating film.

[0114] Example 2 A resin composition of Example 2 (Coating Agent 2) was prepared in the same manner as Example 1, except that the blending amounts of each component were changed as shown in Table 2. Next, a coating film was produced in the same manner as Example 1, except that Coating Agent 2 was used instead of Coating Agent 1, and the coating film properties were evaluated. The results are shown in Table 2.

[0115] Examples 3 to 4 Resin compositions of Examples 3 to 4 (Coating Agents 3 to 4) were prepared in the same manner as in Example 1 or 2, except that the polyurethane composition of Synthesis Example 2 (solid content (non-volatile content) = 10 mass %) was used instead of the polyurethane composition of Synthesis Example 1. Then, coating films were produced in the same manner as in Example 1, except that Coating Agents 3 to 4 were used instead of Coating Agent 1, and the coating film physical properties were evaluated. The results are shown in Table 2.

[0116] Examples 5 to 12 Resin compositions (coating agents 5 to 12) of Examples 5 to 12 were prepared in the same manner as in Example 1 or 2, except that polyester resin 2, acrylic resin 1, acrylic resin 2, or imide resin 1 was used instead of polyester resin 1. Next, coating films were prepared in the same manner as in Example 1, except that coating agents 5 to 12 were used instead of coating agent 1, and the physical properties of the coating films were evaluated. The results are shown in Table 2. The blend amounts of acrylic resin 1, acrylic resin 2, and imide resin 1 are the amounts of solids (non-volatile content).

[0117] Comparative Examples 1 and 2 Coating films were prepared in the same manner as in Example 1, except that the polyurethane compositions of Synthesis Examples 1 and 2 were used instead of Coating Agent 1, and the coating film properties (contact angle, pencil hardness, and blocking resistance) were evaluated. The results are shown in Table 2.

[0118] Comparative Example 3: 20 g of polyester resin 1 and 80 g of butyl acetate were placed in a 200 mL beaker at room temperature, and the mixture was stirred at 150 rpm with a stirrer equipped with a stirring blade until the polyester resin was dissolved, yielding a high-Tg polymer composition. The high-Tg polymer composition was then applied to a polyethylene terephthalate film (PET film: Toyobo Ester Film E5100 manufactured by Toyobo) using a bar coater, allowed to stand at room temperature for 5 minutes, and then dried at 80°C for 10 minutes using a hot air dryer. This resulted in the formation of a coating film (high-Tg polymer coating film, film thickness 3.6 μm) made of the dried product of the high-Tg polymer composition on the PET film.

[0119] Next, the polyurethane composition of Synthesis Example 1 (solid content (non-volatile content)=10% by mass) was applied to the high Tg polymer coating film using a bar coater, and after leaving to stand at room temperature for 5 minutes, it was dried at 80° C. for 10 minutes using a hot air dryer. In this way, a film made of the dried product of the polyurethane composition (polyurethane coating film, film thickness 0.4 μm) was formed on the high Tg polymer coating film, and an article (coated film) comprising a PET film and a laminate film made of the high Tg polymer coating film and the polyurethane coating film was obtained.

[0120] The physical properties of the laminated film of the article prepared above were evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0121] Comparative Example 4 An article (coating film) comprising a PET film and a laminate film consisting of a high Tg polymer coating film and a polyurethane coating film was produced in the same manner as in Comparative Example 3, except that the type of bar coater was changed and the film thicknesses of the high Tg polymer coating film and the polyurethane coating film were adjusted to the values ​​shown in Table 3, and the physical properties of the laminate film were evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0122] Comparative Examples 5 and 6 Articles (coating films) comprising a PET film and a laminate film consisting of a high Tg polymer coating film and a polyurethane coating film were produced in the same manner as in Comparative Examples 3 or 4, except that acrylic resin 1 was used instead of polyester resin 1, and the physical properties of the laminate film were evaluated in the same manner as in Example 1. The results are shown in Table 3. The blend amount of acrylic resin 1 is the amount of solids (non-volatile content).

[0123]

[0124]

Claims

1. A resin composition comprising: a polyurethane resin (A) containing, as monomer units, a polyol represented by the following formula (1) and a polyol represented by the following formula (2); and a resin (B) different from the polyurethane resin (A) and having a glass transition temperature of 35°C or higher. [In formula (1), R １ represents a hydrocarbon group having 40 to 10,000 carbon atoms. [In formula (2), R ２ represents a hydrocarbon group having 1 to 30 carbon atoms, X represents a single bond, an ether group, a carbonyl group, an ester group, an amino group or an amide group, and Z represents a hydrocarbon group having 1 to 50 carbon atoms which may be substituted with a hetero atom or a functional group.

2. The resin composition according to claim 1, wherein the amount of the polyol represented by formula (1) contained as a monomer unit in the polyurethane resin (A) is 60 to 90 mass % based on the total mass of the polyurethane resin (A).

3. The resin composition according to claim 1, wherein the polyol represented by formula (1) comprises at least one polyol selected from the group consisting of polyolefin polyols and hydrogenated polyolefin polyols.

4. The resin composition according to claim 1, wherein the polyurethane resin (A) contains a diisocyanate as a monomer unit.

5. The resin composition according to claim 1, wherein the content of the polyurethane resin (A) is 0.50 to 80 mass % based on the total solid content of the resin composition.

6. The resin composition according to claim 1, wherein the resin (B) comprises at least one resin selected from the group consisting of polyester resins, (meth)acrylic resins and imide resins.

7. The resin composition according to claim 1, wherein the content of the resin (B) is 20 to 99.5 mass % based on the total solid content of the resin composition.

8. A resin composition comprising: a polyurethane resin (A) containing, as a monomer unit, a polyol represented by the following formula (1); and a resin (B) different from the polyurethane resin (A) and having a glass transition temperature of 35°C or higher. [In formula (1), R １ represents a hydrocarbon group having 40 to 10,000 carbon atoms.

9. A method for producing a resin composition according to any one of claims 1 to 8, comprising the step of mixing the polyurethane resin (A) and the resin (B).

10. A coating agent comprising the resin composition according to any one of claims 1 to 8.

11. The coating agent according to claim 10, which is used to impart liquid repellency to an article.

12. A coating film formed from the coating agent according to claim 10.

13. An article comprising a substrate and the coating film of claim 12 disposed on said substrate.

Images