Hydrocarbon end group-containing compound, curable composition for forming coating film, cured coating film, and article

Abstract

According to the present invention, by adding a hydrocarbon end group-containing compound which is represented by formula (1) and does not contain a fluorine atom in the structure to a thermosetting composition or a composition that is curable by an active energy ray such as an ultraviolet ray or an electron beam, excellent water repellency, antifouling properties and wear resistance can be imparted to a cured coating film produced from the composition. (X represents R1O- or R2R3N-, R1 represents a monovalent hydrocarbon group having 20 to 80 carbon atoms, R2 represents a monovalent hydrocarbon group having 10 to 40 carbon atoms, R3 represents H or R2, the total number of carbon atoms in R2 and R3 is 20 to 80, Y represents a single bond or the following group *-C(=O)-** *-C(=O)-O-** *-C(=O)-NR4-** *-C(=S)-NR4-** (wherein * denotes an atomic bond with X, ** denotes an atomic bond with Z, and R4 represents H or a monovalent hydrocarbon group), Z represents a single bond or a hydrocarbon group which has a valence of 2 to 4 and may contain O, S, N, and Si, V represents a polymerizable carbon-carbon double bond-containing monovalent hydrocarbon group which may contain O and N, and m represents a number of 1 to 3.)

Description

Compounds containing hydrocarbon end groups, curable compositions for film formation, cured films and articles

[0001] The present invention relates to a hydrocarbon terminal group-containing compound, and more particularly to a hydrocarbon terminal group-containing compound that does not contain fluorine atoms in its structure and that can be incorporated into an active energy ray-curable composition such as ultraviolet light or an electron beam, or a thermosetting composition to impart excellent water repellency, stain resistance, and abrasion resistance to the resulting cured coating; a curable composition for forming a coating that contains the hydrocarbon terminal group-containing compound; a cured coating obtained by curing the curable composition for forming a coating; and an article having the cured coating on the surface of a substrate.

[0002]

[0003] Conventionally, hard coating treatments have been widely used as a means for protecting the surfaces of resin molded articles and the like. This involves forming a hard cured resin layer (hard coating layer) on the surface of the molded article to make it scratch-resistant. Thermosetting compositions and active energy ray-curable compositions such as ultraviolet rays or electron beams are often used as materials for forming the hard coating layer.

[0003] As the range of applications for resin molded products expands and the trend toward higher added value continues, there is an increasing demand for higher functionality in cured resin layers (hard coat layers), and one such demand is the imparting of antifouling properties to hard coat layers. This is achieved by imparting properties such as water repellency and oil repellency to the surface of the hard coat layer, making it less susceptible to staining or making it easier to remove stains if any do occur.

[0004] Methods for imparting antifouling properties to a hard coat layer include a method of applying and / or fixing a fluorine-containing antifouling agent to the surface of a hard coat layer once formed, and a method of adding a fluorine-containing curable component to a curable resin composition before curing, applying and curing the composition, thereby simultaneously forming a hard coat layer and imparting antifouling properties. For example, JP-A-6-211945 (Patent Document 1) discloses the production of a hard coat layer imparted with antifouling properties by adding a fluoroalkyl acrylate to an acrylic curable resin composition and curing the composition.

[0005] The present inventors have been developing various fluorine-containing compounds that can impart antifouling properties to such curable resin compositions, and have proposed, for example, photocurable fluorine-containing compounds disclosed in JP-A-2010-53114 (Patent Document 2), JP-A-2010-138112 (Patent Document 3), and JP-A-2010-285501 (Patent Document 4).

[0006] On the other hand, fluorine-containing compounds, such as perfluorooctanoic acid (PFOA), tend to be highly persistent and highly accumulative in nature. Therefore, in recent years, a wide range of fluorine-containing compounds have been categorized as per / polyfluoroalkyl compounds (PFAS), and it is predicted that restrictions on the use, sale, and discharge of fluorine-containing compounds will be strengthened under the PFAS regulations. Therefore, in recent years, there has been a demand for the development of non-fluorine-based antifouling agents that do not contain fluorine atoms. However, when conventional non-fluorine-based compounds are used for the above-mentioned applications, the water repellency, antifouling properties, and abrasion resistance of the resulting cured coatings are still not at a level satisfactory for practical use.

[0007] Japanese Patent Laid-Open No. 6-211945 Japanese Patent Laid-Open No. 2010-53114 Japanese Patent Laid-Open No. 2010-138112 Japanese Patent Laid-Open No. 2010-285501

[0008] The present invention has been made in view of the above circumstances, and aims to provide a hydrocarbon terminal group-containing compound that does not contain fluorine atoms in its structure and that, when added to an active energy ray-curable composition such as ultraviolet light or an electron beam, or a thermosetting composition, can impart excellent water repellency, stain resistance, and abrasion resistance to the resulting cured coating; a curable composition for forming a coating that contains the hydrocarbon terminal group-containing compound; a cured coating obtained by curing the curable composition for forming a coating; and an article having the cured coating on the surface of a substrate.

[0009] As a result of intensive research conducted by the present inventors to achieve the above object, they have found that by incorporating a hydrocarbon terminal group-containing compound that does not contain a fluorine atom in the structure represented by general formula (1) described below as the non-fluorine-based antifouling agent into an active energy ray-curable composition such as ultraviolet light or an electron beam or a heat-curable composition, it is possible to impart excellent water repellency, antifouling properties, and abrasion resistance to the resulting cured coating, and have thus completed the present invention. [Wherein X is R 1 O- or R 2 R 3 N- and R 1 is a linear, branched or cyclic monovalent hydrocarbon group having 20 to 80 carbon atoms, and R 2 is a linear, branched or cyclic monovalent hydrocarbon group having 10 to 40 carbon atoms, and R 3 is a hydrogen atom or a linear, branched or cyclic monovalent hydrocarbon group having 10 to 40 carbon atoms, and R 2 and R 3 The total number of carbon atoms contained therein is 20 to 80, and Y is a single bond or a group represented by the following structural formula: * -C(=O)- ** * —C(═O)—O— ** * —C(═O)—NR 4 - ** * -C(=S)-NR 4 - ** (In the formula, * represents a bond bonded to X in general formula (1), ** represents a bond bonded to Z in general formula (1), and R 4 is a hydrogen atom or a linear, branched, or cyclic monovalent hydrocarbon group having 1 to 8 carbon atoms; Z is a single bond or a divalent to tetravalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more atoms selected from oxygen, sulfur, nitrogen, and silicon; V is independently a monovalent hydrocarbon group having 2 to 20 carbon atoms which contains a polymerizable carbon-carbon double bond which may contain an oxygen atom and / or a nitrogen atom; and m is an integer of 1 to 3.]

[0010] Accordingly, the present invention provides the following hydrocarbon terminal group-containing compound, a curable composition for forming a coating containing the hydrocarbon terminal group-containing compound, a cured coating obtained by curing the curable composition for forming a coating, and an article having the cured coating on its surface. [1] A compound represented by the following general formula (1): [Wherein X is R 1 O- or R 2 R 3 N- and R 1 is a linear, branched or cyclic monovalent hydrocarbon group having 20 to 80 carbon atoms, and R2 is a linear, branched or cyclic monovalent hydrocarbon group having 10 to 40 carbon atoms, and R 3 is a hydrogen atom or a linear, branched or cyclic monovalent hydrocarbon group having 10 to 40 carbon atoms, and R 2 and R 3 The total number of carbon atoms contained therein is 20 to 80, and Y is a single bond or a group represented by the following structural formula: * -C(=O)- ** * —C(═O)—O— ** * —C(═O)—NR 4 - ** * -C(=S)-NR 4 - ** (In the formula, * represents a bond bonded to X in general formula (1), ** represents a bond bonded to Z in general formula (1), and R 4 is a hydrogen atom or a linear, branched, or cyclic monovalent hydrocarbon group having 1 to 8 carbon atoms.) Z is a single bond or a divalent to tetravalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more atoms selected from oxygen, sulfur, nitrogen, and silicon atoms, V is a monovalent hydrocarbon group having 2 to 20 carbon atoms which contains a polymerizable carbon-carbon double bond which may contain an oxygen atom and / or a nitrogen atom, and m is an integer of 1 to 3.] A hydrocarbon terminal group-containing compound represented by the formula (I), which does not contain a fluorine atom in its structure. [2] The hydrocarbon terminal group-containing compound according to [1], wherein V in the above formula (1) is represented by the following formula: (wherein * represents a bond bonded to Z in general formula (1), and R' represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms.) [3] In the above formula (1), Y represents the following structural formula: * -C(=O)-NH- **(wherein * is a bond bonding to X in general formula (1), and ** is a bond bonding to Z in general formula (1)). [4] The hydrocarbon terminal group-containing compound according to any one of [1] to [3], wherein in formula (1), m is 1. [5] The hydrocarbon terminal group-containing compound according to any one of [1] to [4], wherein in formula (1), Z is a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms which may contain an oxygen atom and / or a nitrogen atom. [6] The hydrocarbon terminal group-containing compound according to any one of [1] to [5], which is a hydrocarbon terminal group-containing acrylic compound represented by the following general formula (2): (wherein X is the same as above, Z' is a divalent hydrocarbon group having 1 to 10 carbon atoms which may contain an oxygen atom and / or a nitrogen atom, and R" is a hydrogen atom or a methyl group.) [7] The hydrocarbon terminal group-containing compound according to any one of [1] to [5], which is a hydrocarbon terminal group-containing acrylic compound represented by the following general formula (3): (In the formula, R 2 , R 3 is the same as above, Z' is a divalent hydrocarbon group having 1 to 10 carbon atoms which may contain an oxygen atom and / or a nitrogen atom, and R" is a hydrogen atom or a methyl group.) [8] In the above formula (3), R 2 and R 3 is a linear monovalent hydrocarbon group having 10 to 40 carbon atoms, and R 2 and R 3The hydrocarbon terminal group-containing compound according to [7], wherein the number of carbon atoms in the hydrocarbon terminal group-containing compound is equal to the number of carbon atoms in the hydrocarbon terminal group-containing compound. [9] The hydrocarbon terminal group-containing compound according to any one of [1] to [8], which has a melting point of 20°C or higher.

[10] A curable composition for forming a film, comprising a non-fluorine-containing hydrocarbon terminal group-containing compound having one hydrocarbon terminal group having 20 to 80 carbon atoms or two hydrocarbon terminal groups having 10 to 40 carbon atoms and at least one polymerizable group in one molecule.

[11] The curable composition for forming a film according to

[10] , wherein the non-fluorine-containing hydrocarbon terminal group-containing compound is the hydrocarbon terminal group-containing compound according to any one of [1] to [9].

[12] The curable composition for forming a film according to

[10] , further comprising a polymerization initiator.

[13] The curable composition for forming a film according to

[12] , which is an active energy ray-curable type.

[14] The curable composition for forming a film according to any one of

[10] to

[13] , further comprising a solvent.

[15] The curable composition for forming a film according to any one of

[10] to

[14] , further comprising a non-fluorine-containing acrylic compound.

[16] The curable composition for forming a film according to any one of

[10] to

[15] , which does not contain fluorine atoms.

[17] A cured film obtained by curing the curable composition for forming a film according to any one of

[10] to

[16] .

[18] The cured film according to

[17] , which has a water contact angle of 90° or more and an oleic acid contact angle of 40° or more at a droplet size of 2 μL, at a temperature of 25°C, and a relative humidity of 40%.

[19] An article having the cured film according to

[17] or

[18] on its surface.

[0011] The cured coating obtained using the curable composition for forming a coating containing the hydrocarbon terminal group-containing compound of the present invention, which does not contain a fluorine atom in its structure, can be imparted with excellent water repellency, antifouling properties, and abrasion resistance. Therefore, the hydrocarbon terminal group-containing compound is useful as an antifouling additive for imparting water repellency, antifouling properties, and abrasion resistance to hard coating agents, paints, resins, antireflective coating compositions, etc. that are curable with active energy rays such as ultraviolet rays and electron beams, or that are heat-curable.

[0012] In the present invention, "acrylic compound" is a general term for compounds having an acryloyl (hereinafter also referred to as "acrylic") group or an α-substituted acryloyl (hereinafter also referred to as "α-substituted acrylic") group, and includes compounds in which two or more acrylic groups or α-substituted acrylic groups have been introduced into the side chains or ends of various polymers by any method. Furthermore, in the present invention, "(meth)acrylate" refers to either or both of acrylate and methacrylate, "(meth)acrylic group" refers to either or both of an acrylic group and a methacryloyl (hereinafter also referred to as "methacrylic") group, and "(meth)acrylic acid halide" refers to either or both of an acrylic acid halide and a methacrylic acid halide.

[0013] The hydrocarbon terminal group-containing compound of the present invention is represented by the following general formula (1), and the hydrocarbon terminal group-containing compound does not contain a fluorine atom in its structure. [Wherein X is R 1 O- or R 2 R 3 N- and R 1 is a linear, branched or cyclic monovalent hydrocarbon group having 20 to 80 carbon atoms, and R 2 is a linear, branched or cyclic monovalent hydrocarbon group having 10 to 40 carbon atoms, and R 3 is a hydrogen atom or a linear, branched or cyclic monovalent hydrocarbon group having 10 to 40 carbon atoms, and R 2 and R 3 The total number of carbon atoms contained therein is 20 to 80, and Y is a single bond or a group represented by the following structural formula: * -C(=O)- ** * —C(═O)—O— ** * —C(═O)—NR 4 - ** * -C(=S)-NR 4 - ** (In the formula, * represents a bond bonded to X in general formula (1), ** represents a bond bonded to Z in general formula (1), and R 4is a hydrogen atom or a linear, branched, or cyclic monovalent hydrocarbon group having 1 to 8 carbon atoms; Z is a single bond or a divalent to tetravalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more atoms selected from oxygen, sulfur, nitrogen, and silicon; V is independently a monovalent hydrocarbon group having 2 to 20 carbon atoms which contains a polymerizable carbon-carbon double bond which may contain an oxygen atom and / or a nitrogen atom; and m is an integer of 1 to 3.]

[0014] The hydrocarbon end group-containing compound of the present invention must have a hydrocarbon chain end group with a predetermined number of carbon atoms or more and a polymerizable carbon-carbon double bond in its structure. By having a hydrocarbon chain end group with a predetermined number of carbon atoms or more that exhibits high packing properties and a polymerizable carbon-carbon double bond as an active energy ray-curable group or a thermosetting group, when the compound is incorporated into a curable composition for forming a coating and cured, the compound segregates on the surface of the cured coating, forming a hard layer through the packing of the hydrocarbon chains and becoming fixed. This results in a cured coating that exhibits excellent water repellency, stain resistance, and abrasion resistance. Furthermore, by incorporating the compound in combination with other components, segregation to the outermost surface may not occur, but the effect of improving the water repellency of the cured coating itself can be fully expected. In the present invention, "packing properties" refers to the degree of tendency for multiple hydrocarbon chains to be densely oriented in one direction on the surface of the cured coating.

[0015] In the above formula (1), X is R 1 O- or R 2 R 3 N- and R 1 is a linear, branched or cyclic monovalent hydrocarbon group having 20 to 80 carbon atoms, and R 2 is a linear, branched or cyclic monovalent hydrocarbon group having 10 to 40 carbon atoms, and R 3 is a hydrogen atom or a linear, branched or cyclic monovalent hydrocarbon group having 10 to 40 carbon atoms, and R 2 and R 3 The total number of carbon atoms contained therein is 20 or more and 80 or less.

[0016] R 1When the number of carbon atoms is smaller than the above upper limit, the compatibility with the curable composition for forming a coating film is good, and when the number of carbon atoms is larger than the above lower limit, the packing property of the hydrocarbon chain is increased, and the characteristics as a group imparting water repellency and antifouling properties can be fully exhibited.

[0017] R 2 and R 3 When the total number of carbon atoms contained therein is smaller than the above upper limit, the compatibility with the curable composition for forming a coating film is good, and when it is larger than the above lower limit, the packing property of the hydrocarbon chain is enhanced, and the characteristics as a group imparting water repellency and antifouling properties can be fully exhibited.

[0018] R 1 is more preferably a linear or branched monovalent hydrocarbon group having 21 to 60 carbon atoms, and particularly preferably a linear or branched monovalent hydrocarbon group having 22 to 44 carbon atoms.

[0019] R 1 Examples of such a substance include the following: (In the formula, * represents a bond bonded to the oxygen atom in X, and y is independently an integer of 1 or greater, and is an integer such that the total number of carbon atoms in each structure is 20 or greater and 80 or less, more preferably 21 or greater and 60 or less, and particularly preferably 22 or greater and 44 or less.)

[0020] R 2 R is more preferably a linear or branched monovalent hydrocarbon group having 11 to 30 carbon atoms, and particularly preferably a linear or branched monovalent hydrocarbon group having 12 to 22 carbon atoms. 3 R is more preferably a hydrogen atom or a linear or branched monovalent hydrocarbon group having 11 to 30 carbon atoms, and particularly preferably a hydrogen atom or a linear or branched monovalent hydrocarbon group having 12 to 22 carbon atoms. 2 and R 3 The total number of carbon atoms contained therein is more preferably 21 or more and 60 or less, and particularly preferably 22 or more and 44 or less.

[0021] R 2 Examples of such a substance include the following: (In the formula, * represents a bond bonded to the nitrogen atom in X, and y' is independently an integer of 1 or greater, and is an integer such that the total number of carbon atoms in each structure is 10 or greater and 40 or less, more preferably 11 or greater and 30 or less, and particularly preferably 12 or greater and 22 or less.)

[0022] R 3 Examples of the aryl group include a hydrogen atom and the groups shown below. (In the formula, * represents a bond bonded to the nitrogen atom in X, and y' is independently an integer of 1 or greater, and is an integer such that the total number of carbon atoms in each structure is 10 or greater and 40 or less, more preferably 11 or greater and 30 or less, and particularly preferably 12 or greater and 22 or less.)

[0023] Examples of X include the following. (In the formula, * represents a bond bonded to Y in general formula (1), and each y is independently an integer of 1 or more, and is an integer such that the total number of carbon atoms in each structure is 20 or more and 80 or less, more preferably 21 or more and 60 or less, and particularly preferably 22 or more and 44 or less.)

[0024] It is particularly preferable for X to have two CH groups in its structure, as this can exhibit excellent antifouling properties. It is generally known that a solid surface having -CH groups has lower surface free energy and is therefore more excellent in antifouling properties than a solid surface having only -CH groups. The following groups are preferably used as such X: (In the formula, * represents a bond bonded to Y in general formula (1), and each y is independently an integer of 1 or more, and is an integer such that the total number of carbon atoms in each structure is 20 or more and 80 or less, more preferably 21 or more and 60 or less, and particularly preferably 22 or more and 44 or less.)

[0025] In the above formula (1), Y is a single bond or a divalent organic group represented by the following structural formula: * -C(=O)- ** * —C(═O)—O— ** * —C(═O)—NR 4 - ** * -C(=S)-NR 4 - **(In the formula, * represents a bond bonded to X in general formula (1), ** represents a bond bonded to Z in general formula (1), and R 4 is a hydrogen atom or a linear, branched, or cyclic monovalent hydrocarbon group having 1 to 8 carbon atoms.

[0026] Here, R 4 represents a hydrogen atom or a linear, branched, or cyclic monovalent hydrocarbon group having 1 to 8 carbon atoms. Examples of the linear, branched, or cyclic monovalent hydrocarbon group having 1 to 8 carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, and octyl groups; alkenyl groups such as vinyl, allyl, and propenyl groups; aryl groups such as phenyl, tolyl, xylyl, and naphthyl groups; and aralkyl groups such as benzyl, phenylethyl, and phenylpropyl groups. 4 is more preferably a hydrogen atom.

[0027] Y is represented by the following structural formula: * -C(=O)-NH- ** (wherein * is a bond bonding to X in general formula (1), and ** is a bond bonding to Z in general formula (1)) When Y has the above structure, compatibility with the curable composition for forming a coating film is particularly good.

[0028] In the above formula (1), Z is a single bond or a divalent to tetravalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more atoms selected from oxygen, sulfur, nitrogen, and silicon atoms. When Y is a single bond, Z is preferably a single bond. Specific examples of the di- to tetravalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more atoms selected from oxygen, sulfur, nitrogen, and silicon atoms include linear, branched, or cyclic di- to tetravalent hydrocarbon groups having 1 to 20 carbon atoms, and di- to tetravalent hydrocarbon groups having 1 to 20 carbon atoms which contain one or more atoms selected from the group consisting of ether groups, carbonyl (ketone) groups, ester groups, carbonate groups, —CH(OH)— groups, sulfinyl groups, sulfonyl groups, thioester groups, thiocarbonate groups, thiocarbamate groups, amino groups, amide groups, carbamate groups, urea groups, nitrogen-containing heterocyclic groups (such as oxazole groups, imidazole groups, and triazole groups), silalkylene groups, silarylene groups, and linear, branched, or cyclic organopolysiloxane groups.

[0029] Z is particularly preferably a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms which may contain an oxygen atom and / or a nitrogen atom. When Z is a divalent hydrocarbon group, the hydrocarbon terminal group-containing compound becomes a monoacrylic compound, which has good compatibility with the coating-forming curable composition.

[0030] As Z, the following groups are preferably used. (In the formula, * represents a bond bonded to Y in general formula (1), ** represents a bond bonded to V in general formula (1), q represents an integer of 1 to 10, r, s, and t each represent an integer of 1 to 8, the sum of r and s represents an integer of 2 to 10, and the sum of r, s, and t represents an integer of 3 to 10.)

[0031] In the above formula (1), each V is independently a monovalent hydrocarbon group having 2 to 20 carbon atoms and containing a polymerizable carbon-carbon double bond, which may contain an oxygen atom and / or a nitrogen atom. Specific examples of the group containing a polymerizable carbon-carbon double bond include an acrylic group, an α-substituted acrylic group, an acryloxy group, an α-substituted acryloxy group, an acrylamide group, an α-substituted acrylamide group, a vinyl ether group, a cinnamic acid group, and a sorbic acid group.

[0032] V is preferably an acrylic group, an α-substituted acrylic group, an acryloxy group, or an α-substituted acryloxy group represented by the following formula: (In the formula, * represents a bond bonded to Z in general formula (1), and R' represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms.)

[0033] Here, R' is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and examples of the monovalent hydrocarbon group having 1 to 8 carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, and octyl, alkenyl groups such as vinyl, allyl, and propenyl, aryl groups such as phenyl, tolyl, xylyl, and naphthyl, and aralkyl groups such as benzyl, phenylethyl, and phenylpropyl. R' is more preferably a hydrogen atom or a methyl group.

[0034] V is particularly preferably an acryloxy group or an α-substituted acryloxy group represented by the following formula: (In the formula, * represents a bond bonded to Z in general formula (1), and R' is the same as above.)

[0035] Specifically, the following are preferably used as such V: (In the formula, * represents a bond bonded to Z in general formula (1).)

[0036] In the above formula (1), m is an integer of 1 to 3, and preferably 1. If m is greater than the above upper limit, the proportion of hydrocarbon chain terminal groups as groups imparting water repellency and soil resistance becomes relatively small, resulting in a decrease in water repellency and soil resistance.

[0037] The hydrocarbon terminal group-containing compound represented by the formula (1) does not contain a fluorine atom in its structure, which makes it less likely to decompose and less likely to accumulate in nature than conventional fluorine-based compounds.

[0038] The hydrocarbon terminal group-containing compound represented by the formula (1) can be obtained in several different ways by changing the combination of X, Y, Z, and V in the formula.

[0039] As the hydrocarbon terminal group-containing compound represented by the above formula (1), a hydrocarbon terminal group-containing acrylic compound represented by the following general formula (2) is more preferred. (In the formula, X is the same as above, Z' is a divalent hydrocarbon group having 1 to 10 carbon atoms which may contain an oxygen atom and / or a nitrogen atom, and R" is a hydrogen atom or a methyl group.)

[0040] In the above formula (2), Z' is a divalent hydrocarbon group having 1 to 10 carbon atoms which may contain an oxygen atom and / or a nitrogen atom, and the following groups are preferably used. (In the formula, * represents a bond bonding to the nitrogen atom in general formula (2), ** represents a bond bonding to the oxygen atom in general formula (2), q represents an integer of 1 to 10, r and s each represent an integer of 1 to 8, and the sum of r and s represents an integer of 2 to 10.)

[0041] When the hydrocarbon terminal group-containing compound of the present invention is a hydrocarbon terminal group-containing acrylic compound represented by the above general formula (2), the addition of this compound to an active energy ray-curable composition such as ultraviolet light or electron beam or a heat-curable composition can provide a cured coating with even better water repellency, stain resistance, and abrasion resistance.

[0042] Particularly preferred examples of the hydrocarbon terminal group-containing acrylic compound represented by the above formula (2) include those represented by the following formula:

[0043] As the hydrocarbon terminal group-containing compound represented by the above formula (1), a hydrocarbon terminal group-containing acrylic compound represented by the following general formula (3) is particularly preferred. (In the formula, R 2 , R 3 , Z', and R" are the same as above.)

[0044] When the hydrocarbon terminal group-containing compound of the present invention is a hydrocarbon terminal group-containing acrylic compound represented by the above general formula (3), the addition of the compound to an active energy ray-curable composition such as ultraviolet light or electron beam, or to a heat-curable composition, results in a cured coating having particularly excellent water repellency, stain resistance, and abrasion resistance.

[0045] Particularly preferred examples of the hydrocarbon terminal group-containing acrylic compound represented by the above formula (3) include those represented by the following formula:

[0046] In the above formula (3), R 2 and R 3 is a linear monovalent hydrocarbon group having 10 to 40 carbon atoms, and R 2 and R 3 It is particularly preferred that the numbers of carbon atoms in R 2 and R 3 satisfies the above-mentioned condition, the distance between the hydrocarbon groups becomes closer, which further enhances the packing of the hydrocarbon groups in the hydrocarbon terminal group-containing compound, and in a cured coating film obtained by adding the compound to an active energy ray-curable composition such as ultraviolet light or an electron beam or a thermosetting composition, the compound forms a hard layer on the outermost surface, resulting in even better abrasion resistance.

[0047] Examples of the hydrocarbon terminal group-containing compound represented by formula (1) above other than the hydrocarbon terminal group-containing acrylic compound represented by formula (2) and the hydrocarbon terminal group-containing acrylic compound represented by formula (3) include compounds represented by the following formulas:

[0048] The hydrocarbon terminal group-containing compound represented by the general formula (1) above preferably has a melting point of 20° C. or higher, particularly preferably 20 to 100° C. When the melting point is 20° C. or higher, the compound forms a hard layer on the outermost surface of a cured coating obtained by adding the compound to an active energy ray-curable composition such as ultraviolet light or electron beam, or to a heat-curable composition, resulting in even better abrasion resistance.

[0049] In this specification, the melting point is a value measured under atmospheric pressure using a differential scanning calorimeter (DSC). The measurement method conforms to JIS K 7121. The measurement conditions are as follows: starting temperature: -150°C, ending temperature: 200°C, temperature increase / decrease rate: 10°C / min, atmospheric gas: nitrogen (flow rate: 50 mL / min).

[0050] When the hydrocarbon terminal group-containing compound of the present invention represented by the above general formula (1) is, in particular, a hydrocarbon terminal group-containing acrylic compound represented by the above general formula (2) or (3), the compound can be prepared, for example, by the following method.

[0051] An acrylic compound containing a hydrocarbon terminal group can be produced by mixing an alcohol compound or an amine compound containing a hydrocarbon terminal group with an isocyanate compound containing a (meth)acrylic group and subjecting the mixture to an addition reaction.

[0052] The alcohol compound containing a hydrocarbon terminal group is represented by the following formula (4), and the amine compound containing a hydrocarbon terminal group is represented by the following formula (5): 1 OH (4) R 2 R 3 NH (5) (wherein, R 1 , R 2 , R 3 is the same as above.)

[0053] Suitable examples of the alcohol compound represented by formula (4) include the compounds shown below.

[0054] Alcohol compounds containing hydrocarbon end groups can be prepared by hydride reduction of aldehyde or ketone compounds containing hydrocarbon end groups.

[0055] Examples of the aldehyde compound containing a hydrocarbon terminal group include the following.

[0056] Examples of ketone compounds containing a hydrocarbon terminal group include the following:

[0057] As the reducing agent for the hydride reduction, sodium borohydride and lithium aluminum hydride are preferred. It is preferable to charge an equimolar amount of these reducing agents to the aldehyde or ketone compound containing a hydrocarbon terminal group and react them to completely react the aldehyde or ketone. Specifically, it is desirable to use 1 to 5 equivalents of the reducing agent per equivalent of the aldehyde or ketone compound containing a hydrocarbon terminal group in the reaction system, and particularly preferably 1 to 3 equivalents.

[0058] These reactions may be carried out after dilution with an appropriate solvent, if necessary. Such a solvent can be used without particular limitation, as long as it does not react with the aldehyde compound or ketone compound containing a hydrocarbon terminal group and the reducing agent. Specific examples include hydrocarbon solvents (petroleum benzine, toluene, xylene, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, octane (n-octane, isooctane, etc.), nonane (n-nonane, isononane, etc.)), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc.), ether solvents (tetrahydrofuran (THF), dipropyl ether, dibutyl ether, methylcyclopentyl ether, methyl t-butyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, propylene glycol dimethyl ether, etc.), and alcohol solvents (propylene glycol monomethyl ether, butanol, isopropanol, methanol, etc.). The amount of solvent used is not particularly limited, but is preferably 20 times or less, and particularly preferably 15 times or less, the total mass of the reaction components. If the amount of solvent used is too large, the reaction rate may decrease significantly. When a solvent is used, the lower limit is preferably 0.5 times or more the total mass of the reaction components.

[0059] The reaction can be carried out at a temperature of −100 to 100° C., preferably −50 to 80° C., for 5 minutes to 70 hours, preferably 30 minutes to 48 hours. After the reaction is complete, the unreacted reducing agent and reaction solvent can be removed by distillation, adsorption, filtration, washing, or other methods to obtain an alcohol compound containing a hydrocarbon terminal group.

[0060] Suitable examples of the amine compound represented by formula (5) include the compounds shown below.

[0061] The isocyanate compound containing a (meth)acrylic group is represented by the following formula (6): O=C=N-Z'-OC(=O)CR"=CH2 (6) (wherein Z' and R" are the same as above).

[0062] Suitable examples of isocyanate compounds containing a (meth)acrylic group include the following: O=C=N-CH2CH2-O-C(=O)-CH=CH2 O=C=N-CH2CH2-O-C(=O)-C(CH3)=CH2 O=C=N-CH2CH2-O-CH2CH2-O-C(=O)-C(CH3)=CH2

[0063] It is preferable to charge and react these isocyanate compounds containing (meth)acrylic groups in an amount equal to or greater than the total amount of active hydrogen in the alcohol compound or amine compound containing a hydrocarbon terminal group, so that all of the active hydrogen is reacted. Specifically, it is desirable to use 1 to 2 equivalents of the isocyanate compound containing a (meth)acrylic group per equivalent of the alcohol compound or amine compound containing a hydrocarbon terminal group in the reaction system, and particularly preferably 1 to 1.4 equivalents. If the amount of the isocyanate compound containing a (meth)acrylic group is too large, it becomes difficult to remove the isocyanate compound containing a (meth)acrylic group that remains after the reaction.

[0064] These reactions may be carried out after dilution with an appropriate solvent, if necessary. Such a solvent can be used without any particular limitation, as long as it does not react with the hydroxyl group of an alcohol compound or amine compound containing a hydrocarbon terminal group, or the isocyanate group of an isocyanate compound containing a (meth)acrylic group. Specific examples of such a solvent include hydrocarbon-based solvents (petroleum benzine, toluene, xylene, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, octane (n-octane, isooctane, etc.), nonane (n-nonane, isononane, etc.), ketone-based solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone), and the like. Examples of suitable solvents include ether solvents (tetrahydrofuran (THF), dipropyl ether, dibutyl ether, methylcyclopentyl ether, methyl t-butyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, propylene glycol dimethyl ether, etc.), alcohol solvents (propylene glycol monomethyl ether, butanol, isopropanol, etc.), and ester solvents (ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, propylene glycol monomethyl ether acetate). This solvent may be removed by a known method such as distillation under reduced pressure after the reaction, or may be used as a diluted solution as is depending on the intended application. The amount of solvent used is not particularly limited, but is preferably 20 times or less, and particularly preferably 15 times or less, the total mass of the reaction components. If the amount of solvent used is too large, the reaction rate may be significantly reduced. When a solvent is used, the lower limit is preferably 1 time or more the total mass of the reaction components.

[0065] Furthermore, during the reaction, a polymerization inhibitor may be added as necessary. There are no particular limitations on the polymerization inhibitor, but those typically used as polymerization inhibitors for acrylic compounds can be used. Specific examples include hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, and dibutylhydroxytoluene. The amount of polymerization inhibitor used can be determined based on the reaction conditions, post-reaction purification conditions, and final use conditions, and is not particularly limited, but is preferably 0.01 to 5,000 ppm, and particularly preferably 0.1 to 500 ppm, based on the total mass of the reaction components.

[0066] Furthermore, during the reaction, an appropriate catalyst may be added, if necessary. Examples of the catalyst include alkyltin ester compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, and stannous dioctanoate, titanate esters or titanium chelate compounds such as tetraisopropoxytitanium, tetra-n-butoxytitanium, tetrakis(2-ethylhexoxy)titanium [also known as tetrakis(2-ethylhexyl) orthotitanate], dipropoxybis(acetylacetonate)titanium, and titanium isopropoxyoctylene glycol, zirconium tetraacetylacetonate, zirconium tributoxymonoacetylacetonate, zirconium monobutoxyacetylacetonate bis(ethylacetoacetate), zirconium dibutoxybis(ethylacetoacetate), zirconium tetraacetylacetonate, and zirconium chelate compounds. These catalysts are not limited to one type, and can be used as a mixture of two or more types. The reaction rate can be increased by adding these catalysts in an amount of preferably 0.01 to 2 mass %, more preferably 0.05 to 1 mass %, based on the total mass of the reaction components.

[0067] The reaction is carried out at a temperature of 0 to 120° C., preferably 10 to 70° C., for 1 minute to 500 hours, preferably 10 minutes to 48 hours. If the reaction temperature is too low, the reaction rate may become too slow, whereas if the reaction temperature is too high, polymerization of the (meth)acrylic group may occur as a side reaction.

[0068] After the reaction is completed, the unreacted isocyanate compound and the reaction solvent can be removed by distillation, adsorption, filtration, washing, or other methods to obtain the hydrocarbon terminal group-containing acrylic compound represented by the general formula (2) or (3).

[0069] Furthermore, when the reaction is terminated, an alcohol compound such as methanol or ethanol may be added to the system to form a urethane bond with the unreacted isocyanate compound. The urethane (meth)acrylates formed can be removed in the same manner as the unreacted isocyanate compound, but they can also be used as they are.

[0070] When the hydrocarbon terminal group-containing compound represented by the general formula (1) of the present invention is a compound other than the hydrocarbon terminal group-containing acrylic compound represented by the general formula (2) or (3), the following method can be mentioned as a method for preparing the compound.

[0071] For example, an alcohol compound or amine compound containing a hydrocarbon terminal group can be reacted with a (meth)acrylic acid halide to form an ester, thereby obtaining an acrylic compound containing a hydrocarbon terminal group. Here, examples of the alcohol compound or amine compound containing a hydrocarbon terminal group include those similar to those described above.

[0072] As the (meth)acrylic acid halide, acrylic acid chloride and methacrylic acid chloride are particularly preferred.

[0073] It is preferred that the (meth)acrylic acid halide is charged in an amount equal to or more than the molar amount of the alcohol compound or amine compound having a hydrocarbon terminal group, and the reaction is carried out so that all of the alcohol or amine is reacted. Specifically, it is desirable to use 1 to 2 equivalents of the (meth)acrylic acid halide, particularly preferably 1 to 1.8 equivalents, per equivalent of the alcohol compound or amine compound having a hydrocarbon terminal group in the reaction system.

[0074] These reactions may be carried out after dilution with an appropriate solvent, if necessary. Such a solvent may be used without particular limitation as long as it does not react with an alcohol compound or amine compound containing a hydrocarbon terminal group or with a halogen atom of the (meth)acrylic acid halide. Specific examples include hydrocarbon solvents such as toluene, xylene, and isooctane; ether solvents such as tetrahydrofuran (THF), diisopropyl ether, and dibutyl ether; and ketone solvents such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, and cyclohexanone. After the reaction, the solvent may be removed by a known method such as distillation under reduced pressure, or may be used as a diluted solution as is depending on the intended use.

[0075] The amount of solvent used is not particularly limited, but is preferably 20 times or less, and particularly preferably 15 times or less, the total mass of the reaction components. If the amount of solvent used is too large, the reaction rate may decrease significantly. When a solvent is used, the lower limit is preferably 1 time or more the total mass of the reaction components.

[0076] Furthermore, during the reaction, a polymerization inhibitor may be added as necessary. There are no particular limitations on the polymerization inhibitor, but those typically used as polymerization inhibitors for acrylic compounds can be used. Specific examples include hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, and dibutylhydroxytoluene. The amount of polymerization inhibitor used can be determined based on the reaction conditions, post-reaction purification conditions, and final use conditions, and is not particularly limited, but is typically 0.01 to 5,000 ppm, and particularly preferably 0.1 to 500 ppm, based on the total mass of the reaction components.

[0077] In the ester-producing reaction, an alcohol compound or amine compound containing a hydrocarbon terminal group, an acid acceptor, and optionally a solvent and a polymerization inhibitor are mixed and stirred at 0 to 100°C for 1 minute to 48 hours, and then a (meth)acrylic acid halide is added.

[0078] As the acid acceptor, triethylamine, pyridine, urea, etc. can be used. The amount of the acid acceptor used is preferably about 0.9 to 3 times the number of moles of the (meth)acrylic acid halide charged. If the amount is too small, a large amount of untrapped acid remains, and if the amount is too large, it becomes difficult to remove the excess acid acceptor.

[0079] After mixing the (meth)acrylic acid halide, the temperature of the reaction mixture is maintained at 0 to 100° C., and stirring is continued for 30 minutes to 10 hours. After completion of the reaction, the unreacted (meth)acrylic acid halide, the salt generated by the reaction, the reaction solvent, etc. are removed by a method such as distillation, adsorption, filtration, washing, etc., to obtain an acrylic compound having a hydrocarbon terminal group.

[0080] When the reaction is stopped, an alcohol compound such as methanol or ethanol may be added to the system to esterify the unreacted (meth)acrylic acid halide. The (meth)acrylic acid esters thus produced can be removed in the same manner as in the removal of the unreacted (meth)acrylic acid halide, but they may also be used as they are.

[0081] The hydrocarbon terminal group-containing compound represented by general formula (1) obtained by the reaction in the above example can be used as a single substance after purification and isolation procedures such as concentration, column purification, distillation, extraction, etc., or the reaction solution can be used as is as a mixture containing the hydrocarbon terminal group-containing compound represented by general formula (1), or it can be further diluted with an organic solvent or the like before use.

[0082] A further embodiment of the present invention is a curable composition for forming a coating, comprising a non-fluorine-containing hydrocarbon terminal group-containing compound having one hydrocarbon terminal group having 20 to 80 carbon atoms or two hydrocarbon terminal groups having 10 to 40 carbon atoms and at least one polymerizable group per molecule. The non-fluorine-containing hydrocarbon terminal group-containing compound is preferably one or more hydrocarbon terminal group-containing compounds that do not contain a fluorine atom in the structure represented by formula (1) above.

[0083] The amount of the non-fluorinated hydrocarbon terminal group-containing compound, particularly the hydrocarbon terminal group-containing compound represented by formula (1), is preferably from 0.005 to 99.9 mass% of all components of the curable composition for film formation, excluding the solvent. In particular, when used for thick films (e.g., cured films of 0.5 to 100 μm), the amount is preferably from 0.005 to 50 mass% of all components of the curable composition for film formation, excluding the solvent. When used for thin films (e.g., cured films of 1 to 500 nm), the amount is preferably from 50 to 99.9 mass% of all components of the curable composition for film formation, excluding the solvent.

[0084] The curable composition for forming a film of the present invention preferably contains a polymerization initiator. The polymerization initiator preferably contains a photopolymerization initiator, which allows the composition to be an active energy ray-curable curable composition for forming a film. The photopolymerization initiator is not particularly limited as long as it can cure the non-fluorine-containing hydrocarbon terminal group-containing compound (or the non-fluorine-containing acrylic compound described below when further blended) upon ultraviolet irradiation. Preferred examples of the photopolymerization initiator include acetophenone, benzophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone. 1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, and the like. These may be used alone or in combination of two or more.

[0085] The thermal polymerization initiator is not particularly limited as long as it can cure the non-fluorine-based hydrocarbon terminal group-containing compound (and, when further blended, a non-fluorine-based acrylic compound described below) by heating. Preferred examples include diacyl peroxides, ketone peroxides, hydroperoxides, dialkyl peroxides, peroxy esters, azo compounds, and persulfates, and these may be used alone or in combination of two or more.

[0086] The content of the polymerization initiator can be determined appropriately depending on the curing conditions and the desired physical properties of the cured product of the curable composition for forming a coating film, but it is desirable that the content be, for example, 0.001 to 15 parts by mass, and particularly 0.01 to 10 parts by mass, per 100 parts by mass of the total nonvolatile content excluding the solvent in the curable composition for forming a coating film. If the amount added is less than this, the curability may decrease, and if it is more than this, the physical properties after curing may be significantly affected.

[0087] The curable composition for forming a coating of the present invention preferably further contains a solvent. By containing a solvent, the viscosity of the curable composition is reduced, making it easier to handle. Such a solvent is preferably a non-fluorine-based solvent, and examples thereof include hydrocarbon solvents (petroleum benzine, toluene, xylene, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, octane (n-octane, isooctane, etc.), nonane (n-nonane, isononane, etc.)), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc.), ether solvents (tetrahydrofuran (THF), dipropyl ether, dibutyl ether, methylcyclopentyl ether, methyl t-butyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, propylene glycol dimethyl ether, etc.), alcohol solvents (propylene glycol monomethyl ether, butanol, isopropanol, etc.), and ester solvents (ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, propylene glycol monomethyl ether acetate). The amount of the solvent used is not particularly limited, but is preferably 1 to 1,000,000 parts by mass, and particularly preferably 10 to 500,000 parts by mass, per 100 parts by mass of the total of all components of the curable composition for forming a coating film excluding the solvent.

[0088] The curable composition for forming a film of the present invention is not particularly limited as an optional component as long as it gives a cured product upon irradiation with active energy rays such as ultraviolet rays or electron beams or upon heating, but when used as an active energy ray-curable curable composition for forming a film, it is particularly preferred that it contains a non-fluorine-containing acrylic compound (excluding the above-mentioned non-fluorine-containing hydrocarbon terminal group-containing compound). By containing a non-fluorine-containing acrylic compound, the cured film obtained by curing the curable composition for forming a film can exhibit excellent film properties such as high hardness in addition to liquid repellency, antifouling properties, and abrasion resistance.

[0089] The non-fluorine-based acrylic compound may be monofunctional or polyfunctional. It is particularly preferable to include an acrylic compound having two or more acrylic groups in one molecule. Such an acrylic compound may be any compound having two or more acrylic groups or α-substituted acrylic groups in one molecule, and examples thereof include 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, ethylene oxide isocyanurate-modified di(meth)acrylate, EO isocyanurate-modified tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerol tri(meth)acrylate, tris(meth)acryloyloxyethyl phosphate, hydrogen phthalate-(2,2,2-tri-(meth)acryloyloxymethyl)ethyl, glycerol tri(meth)acrylate, methyl ... Examples of the (meth)acrylic compound include di- to hexa-functional or polyfunctional (meth)acrylic compounds such as dipentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol polyacrylate, and sorbitol hexa(meth)acrylate; epoxy acrylates obtained by adding acrylic acid to these (meth)acrylic compounds with ethylene oxide, propylene oxide, epichlorohydrin, fatty acid, or alkyl-modified products; and copolymers in which a (meth)acrylic group is introduced into the side chain of an acrylic acid ester copolymer.

[0090] Also usable are urethane acrylates, those obtained by reacting a polyisocyanate with a (meth)acrylate having a hydroxyl group, those obtained by reacting a polyester of polyisocyanate and a terminal diol with a (meth)acrylate having a hydroxyl group, and those obtained by reacting a polyisocyanate obtained by reacting an excess of diisocyanate with a polyol with a (meth)acrylate having a hydroxyl group. Among these, urethane acrylates obtained by reacting a (meth)acrylate having a hydroxyl group selected from 2-hydroxyethyl (meth)acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and pentaerythritol triacrylate with a polyisocyanate selected from hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, methylenebis(4-cyclohexylisocyanate), 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane, and diphenylmethane diisocyanate are preferred.

[0091] Alternatively, the compound may be a mixture of at least two types of acrylic compounds, including a polyfunctional acrylic compound having two or more acrylic groups or α-substituted acrylic groups in one molecule and no urethane bond, or a polyfunctional urethane acrylate having three or more acrylic groups or α-substituted acrylic groups in one molecule obtained by reacting this polyfunctional acrylic compound with an aliphatic polyisocyanate and an acrylic compound having a hydroxyl group.

[0092] In this case, examples of polyfunctional acrylic compounds having two or more acrylic groups or α-substituted acrylic groups in one molecule and no urethane bond include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, and compounds obtained by modifying any of these with ethylene oxide or propylene oxide.

[0093] Further, examples of polyfunctional urethane acrylates having three or more acrylic groups or α-substituted acrylic groups in one molecule obtained by reacting an aliphatic polyisocyanate with an acrylic compound having a hydroxyl group include hexamethylene diisocyanate, norbornane diisocyanate, isophorone diisocyanate, and trimers thereof, and polyisocyanates having two or more functional groups obtained by reacting these difunctional and trifunctional isocyanates with an aliphatic diol, an aliphatic polyol, and polyacrylates having a hydroxyl group in the side chain, and polyisocyanates having two or more functional groups, such as trimethylolpropane di(meth)acrylate and glycerin di(meth)acrylate. Examples of the polymerizable monomer include those obtained by reacting bis(2-(meth)acryloyloxyethyl)hydroxyethyl isocyanurate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and ethylene oxide- or propylene oxide-modified versions of these, and those obtained by reacting an aliphatic polyol or a polyacrylate having a hydroxyl group in the side chain with an acrylic compound having an isocyanate group, such as 2-isocyanatoethyl (meth)acrylate or 1,1-(bisacryloyloxymethyl)ethyl isocyanate.

[0094] Furthermore, the non-fluorine-based acrylic compound may include, in addition to the above compounds, a fine particle of a high molecular weight substance or a fine particle of an inorganic filler whose surface has been modified with an acrylic group.

[0095] The above-mentioned non-fluorine-containing acrylic compounds may be used alone, but a plurality of corresponding compounds may also be blended and used in order to improve the coatability and properties of the cured coating film.

[0096] When a non-fluorine-containing acrylic compound is blended, the blending amount is preferably 20 to 1,000,000 parts by mass, and particularly preferably 100 to 100,000 parts by mass, per 100 parts by mass of the non-fluorine-containing hydrocarbon terminal group-containing compound.

[0097] The curable composition for forming a coating of the present invention may also contain other active energy ray-reactive compounds other than acrylic groups, such as thiol compounds and maleimide compounds, polymerization inhibitors, antistatic agents, antifoaming agents, viscosity modifiers, light resistance stabilizers, heat resistance stabilizers, antioxidants, surfactants, colorants, and polymer or inorganic fillers, etc. These are not particularly limited in structure, and known compounds can be used as long as they do not impair the object of the present invention.

[0098] Furthermore, the curable composition for forming a coating film of the present invention may contain unreacted raw materials and reaction intermediates before the reactive group of the hydrocarbon terminal group-containing compound represented by formula (1) is introduced.

[0099] Furthermore, as the curable composition for forming a coating film, existing compositions that are commercially available from various companies as active energy ray-curable compositions or thermosetting compositions containing various additives and classified as paints, inks, hard coating agents, etc. may be used as part or the entire curable composition for forming a coating film. Even when a commercially available hard coating agent is used in this way, polymerization inhibitors, antistatic agents, defoamers, viscosity modifiers, light resistance stabilizers, heat resistance stabilizers, antioxidants, surfactants, colorants, fillers, etc. can be added and blended depending on the purpose.

[0100] In recent years, it has been predicted that restrictions on the use, sale, discharge, etc. of fluorine-containing compounds will be strengthened due to PFAS regulations. Therefore, it is preferable that the curable composition for forming a coating of the present invention does not contain fluorine atoms (i.e., it does not contain any components containing fluorine atoms).

[0101] The curable composition for forming a coating of the present invention obtained as described above contains a hydrocarbon terminal group-containing compound of a specific structure having a hydrocarbon chain terminal group as a group that imparts water repellency and stain resistance and has high packing properties, and a polymerizable carbon-carbon double bond as an active energy ray-curable group or a thermosetting group, and therefore a cured coating having excellent water repellency, stain resistance, and abrasion resistance can be obtained.

[0102] Furthermore, the present invention provides a cured coating obtained by applying the above-described curable composition for film formation of the present invention to the surface of a substrate and curing the composition, and an article having the cured coating on its surface. As described above, the use of the curable composition for film formation of the present invention makes it possible to form a cured coating (cured resin layer) having excellent surface properties on the surface of a substrate. It is particularly useful for imparting water repellency, stain resistance, and abrasion resistance to the surface of an acrylic hard coat. This makes it difficult for stains such as fingerprints, sebum, sweat, and other human oils, cosmetics, etc. to adhere to the surface, and also provides a hard coat surface that is easy to wipe off. Therefore, the curable composition for film formation of the present invention is suitable for use as a coating film or protective film on the surface of a substrate (article) that may be soiled by human oils, cosmetics, etc. when touched by the human body.

[0103] Cured coatings (cured resin layers) formed using the curable composition for film formation of the present invention can be imparted with various properties to various articles by directly coating or vapor-depositing the curable composition for film formation of the present invention onto the surface of an article to which properties are to be imparted (for example, an article having a surface substrate such as paper, cloth, metal and its oxides, glass, plastic, ceramic, or quartz), followed by curing; or by coating or vapor-depositing the curable composition for film formation of the present invention onto various substrate films (for example, films of polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, vinyl chloride resin, polystyrene, acrylic resin, polycarbonate, polyphenylene sulfide, polyether ether ketone, polyether sulfone, aramid, polyimide, etc.), to produce a cured coating, and then attaching the film to the surface of the desired article.

[0104] The coating method for the curable composition for forming a coating film of the present invention is not particularly limited, and known coating methods such as roll coating, gravure coating, flow coating, dip coating, spray coating, spin coating, bar coating, and screen printing can be used. The vapor deposition method is not particularly limited, and may be either a resistance heating method or an electron beam heating method. After coating, the coating film is cured by irradiating it with active energy rays or by heating.

[0105] When the coating film is cured by irradiating it with active energy rays, any active energy rays such as electron beams or ultraviolet rays can be used, but ultraviolet rays are particularly preferred. Suitable sources of ultraviolet rays include mercury lamps, metal halide lamps, and LED lamps. The amount of ultraviolet irradiation should be 10 to 10,000 mJ / cm because too little will leave uncured components, and too much may cause deterioration of the coating film and substrate. 2 , especially 20 to 4,000 mJ / cm 2 It is desirable that the concentration of the fluorine-containing compound is in the range of 0.01 to 0.01. Furthermore, in order to prevent curing inhibition by oxygen, the irradiation atmosphere during ultraviolet irradiation may be replaced with an inert gas containing no oxygen molecules, such as nitrogen, carbon dioxide, or argon, or the coating surface may be covered with a protective layer that is releasable and ultraviolet-transmitting and then irradiated with ultraviolet light, or, if the substrate is ultraviolet-transmitting, the coating surface may be covered with a protective layer that has release properties and then ultraviolet light may be irradiated from the side opposite the coated surface of the substrate. Furthermore, in order to effectively level the coating film, the coating film and substrate may be heated by any method, such as a hot air drying oven, before and during ultraviolet light irradiation.

[0106] When curing is performed by heating, any heat source can be used, such as an oven, a hot plate, etc. Heating conditions are preferably 40 to 200°C, particularly 50 to 150°C, for 30 minutes to 36 hours, particularly 1 to 24 hours.

[0107] Furthermore, the appropriate thickness of the cured coating (cured resin layer) formed using the curable composition for film formation of the present invention varies greatly depending on the method of use, etc., and is therefore not limited by the thickness. For example, when a large amount of a non-fluorinated acrylic compound is blended into the curable composition for film formation, specifically when the proportion of the non-fluorinated hydrocarbon terminal group-containing compound in 100 parts by mass of all components of the curable composition for film formation of the present invention, excluding the solvent, is 0.005 parts by mass or more but less than 50 parts by mass, the preferred thickness of the cured coating is 0.5 to 100 μm. On the other hand, when a large amount of a non-fluorinated hydrocarbon terminal group-containing compound is blended into the curable composition for film formation, specifically when the proportion of the non-fluorinated hydrocarbon terminal group-containing compound in 100 parts by mass of all components of the curable composition for film formation of the present invention, excluding the solvent, is 50 parts by mass or more but less than 99.9 parts by mass, the preferred thickness of the cured coating is 1 to 500 nm. In the present invention, the film thickness can be measured by a thin film thickness measuring device based on optical interference (optical interference film thickness meter, reflection spectroscopic film thickness meter) or a thin film thickness measuring device based on spectroscopic ellipsometry (spectroscopic ellipsometer).

[0108] Furthermore, it is desirable that the cured coating (cured resin layer) formed using the curable composition for coating formation of the present invention has a water contact angle of 90° or more, preferably 95° or more, and an oleic acid contact angle of 40° or more, preferably 45° or more, at a temperature of 25°C and a relative humidity of 40%. In the present invention, the contact angle is a value measured using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) under conditions of a droplet size of 2 μL. In order to achieve the above contact angles, it is preferable that the curable composition for coating formation is mixed uniformly.

[0109] The article of the present invention has a cured coating formed on the surface of a substrate from the curable composition for forming a coating of the present invention, and the cured coating functions as a coating film and a surface protective film for the article. Examples of the material include housings for various devices carried by hand, such as tablet computers, mobile (communication) information terminals such as mobile phones and smartphones, notebook PCs, digital media players, watch-type and eyeglass-type wearable computers, digital cameras, digital video cameras, and e-book readers; surfaces of display and operation devices such as various flat panel displays and TV screens, such as liquid crystal displays, plasma displays, organic EL displays, rear projection displays, fluorescent display tubes (VFDs), field emission projection displays, CRTs, and toner-based displays; automobile exteriors; glossy surfaces of pianos and furniture; architectural stone surfaces such as marble; decorative building materials for wet areas such as toilets, baths, and washrooms; protective glass for displaying art works; show windows, showcases, photo frame covers; wristwatches; automobile window glass; window glass for trains and aircraft; transparent glass or transparent plastic (acrylic, polycarbonate, etc.) members such as automobile headlights and taillights; and various mirror members.

[0110] In particular, examples of the display input device include various devices having a display input device such as a touch panel display that allows operations on the screen with a person's fingers or palm, for example, tablet computers, notebook PCs, watch-type wearable computers, activity monitors, mobile (communication) information terminals such as mobile phones and smartphones, digital media players, e-book readers, digital photo frames, game consoles and game console controllers, digital cameras, digital video cameras, navigation devices for automobiles and the like, automatic cash withdrawal / deposit machines, automated teller machines, vending machines, digital signage (electronic billboards), security system terminals, POS terminals, various controllers such as remote controllers, and display input devices such as panel switches for in-vehicle devices.

[0111] Further examples of the article of the present invention include optical recording media such as magneto-optical disks and optical disks; eyeglass lenses, camera lenses, projector lens prisms, lens sheets, pellicle films, polarizing plates, optical filters, lenticular lenses, Fresnel lenses, anti-reflection films, optical parts and optical devices such as optical fibers and optical couplers, and various protective parts for these devices.

[0112] The present invention will be described in more detail below with reference to synthetic examples, comparative synthetic examples, working examples, and comparative examples, but the present invention is not limited to these examples. In the following examples, room temperature is 25°C, and normal pressure refers to atmospheric pressure. The melting point is a value measured at atmospheric pressure using a differential scanning calorimeter (DSC), and the measurement method conforms to JIS K 7121. The measurement conditions are as follows: starting temperature: -150°C, ending temperature: 200°C, temperature increase / decrease rate: 10°C / min, atmospheric gas: nitrogen (flow rate: 50 mL / min). The film thickness is a value measured using a reflection spectroscopic film thickness meter (measurement range: 400 nm to 800 nm).

[0113] Synthesis Example 1 Synthesis of Compound (b) A reaction vessel was charged with a compound represented by the following formula (a): 100.00 g (1.97 × 10 -1 mol) and 100.0 g of methanol were mixed and stirred at room temperature for 1 hour under a nitrogen atmosphere. -1 After mixing the above components (mol), the mixture was stirred at room temperature for 12 hours under a nitrogen atmosphere. After that, the mixture was washed with water and evaporated under reduced pressure to remove the solvent and unreacted materials, yielding 91.21 g of a product.

[0114] The resulting product is 1 H-NMR confirmed that the compound was the compound represented by the following formula (b):

[0115] Synthesis Example 2 Synthesis of hydrocarbon terminal group-containing compound (A) 10.00 g (1.96 × 10 -2 mol), 100.0 g of THF, 2.97 g of triethylamine (2.94 × 10 -2mol) were mixed and stirred at 40°C for 1 hour under a nitrogen atmosphere. -2 After mixing the above components (mol), the mixture was stirred for 6 hours at 40° C. under a nitrogen atmosphere. Thereafter, the solvent, by-products, and unreacted materials were removed by washing with water and distillation under reduced pressure, yielding 8.78 g of a product.

[0116] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (A): The melting point of the compound obtained at normal pressure was 28°C.

[0117] Synthesis Example 3 Synthesis of hydrocarbon terminal group-containing compound (B) 10.00 g (1.92 × 10 -2 mol), 100.0 g of THF, 2.91 g of triethylamine (2.88 × 10 -2 mol) were mixed and stirred at 40°C for 1 hour under a nitrogen atmosphere. -2 After mixing the components (mol), the mixture was stirred for 6 hours at 40° C. under a nitrogen atmosphere. Thereafter, the solvent, by-products, and unreacted materials were removed by washing with water and distillation under reduced pressure, yielding 8.62 g of a product.

[0118] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (B): The melting point of the compound obtained at atmospheric pressure was 32°C.

[0119] Synthesis Example 4 Synthesis of hydrocarbon terminal group-containing compound (C) 10.00 g (1.96 × 10 -2 mol), 2-isocyanatoethyl acrylate 3.04 g (2.15 × 10 -2 mol), 50.00 g of THF, and 0.03 g of tetrakis(2-ethylhexyl) orthotitanate were mixed and aged for 12 hours at 50° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 12.88 g of product.

[0120] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (C): The melting point of the compound obtained at normal pressure was 58°C.

[0121] Synthesis Example 5 Synthesis of hydrocarbon terminal group-containing compound (D) 10.00 g (3.06 × 10 -2 mol), 2-isocyanatoethyl acrylate 4.75 g (3.37 × 10 -2 mol), 50.00 g of THF, and 0.03 g of tetrakis(2-ethylhexyl) orthotitanate were mixed and aged for 12 hours at 50° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 14.40 g of a product.

[0122] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (D): The melting point of the compound obtained at normal pressure was 34°C.

[0123] Synthesis Example 6 Synthesis of hydrocarbon terminal group-containing compound (E) 10.00 g (1.96 × 10 -2 mol), 2-(2-methacryloyloxyethyloxy)ethyl isocyanate 4.29 g (2.15 × 10 -2 mol), 50.00 g of THF, and 0.03 g of tetrakis(2-ethylhexyl) orthotitanate were mixed and aged for 12 hours at 50° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 13.61 g of a product.

[0124] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (E): The melting point of the compound obtained at atmospheric pressure was 56°C.

[0125] Synthesis Example 7 Synthesis of hydrocarbon terminal group-containing compound (F) 10.00 g (1.92 × 10 -2mol), 2.98 g (2.11 × 10 mol) of 2-isocyanatoethyl acrylate -2 The resulting mixture was aged for 12 hours at 50° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 12.11 g of a product.

[0126] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (F): The melting point of the compound obtained at normal pressure was 38°C.

[0127] Synthesis Example 8 Synthesis of hydrocarbon terminal group-containing compound (G) A reaction vessel was charged with a compound represented by the following formula (e): 10.00 g (2.83 × 10 -2 mol), 2-isocyanatoethyl acrylate 4.39 g (3.11 × 10 -2 The resulting mixture was aged for 12 hours at 50° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 12.72 g of a product.

[0128] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (G): The melting point of the compound obtained at normal pressure was 21°C.

[0129] Synthesis Example 9 Synthesis of hydrocarbon terminal group-containing compound (H) A reaction vessel was charged with a compound represented by the following formula (f): 10.00 g (3.07 × 10 -2 mol), 2-isocyanatoethyl acrylate 4.77 g (3.38 × 10 -2 The resulting mixture was aged for 12 hours at 50° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 14.32 g of a product.

[0130] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (H): The melting point of the compound obtained at normal pressure was 48°C.

[0131] Synthesis Example 10 Synthesis of Hydrocarbon Terminal Group-Containing Compound (I) 10.00 g (1.92 × 10 -2 mol), 2-isocyanatoethyl methacrylate 3.28 g (2.11 × 10 -2 The resulting mixture was aged for 12 hours at 50° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 13.03 g of a product.

[0132] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (I): The melting point of the compound obtained at normal pressure was 47°C.

[0133] Synthesis Example 11 Synthesis of Hydrocarbon Terminal Group-Containing Compound (J) 10.00 g (1.92 × 10 -2 mol), 2-(2-methacryloyloxyethyloxy)ethyl isocyanate 4.21 g (2.11 × 10 -2 The resulting mixture was aged for 12 hours at 50° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 13.64 g of a product.

[0134] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (J): The melting point of the compound obtained at normal pressure was 39°C.

[0135] Synthesis Example 12 Synthesis of hydrocarbon terminal group-containing compound (K) 10.00 g (1.92 × 10 -2 mol), 1,1-(bisacryloyloxymethyl)ethyl isocyanate 5.05 g (2.11 × 10 -2 The resulting mixture was aged for 12 hours at 50° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 14.50 g of a product.

[0136] The resulting compound is 1H-NMR confirmed that the compound had a structure represented by the following formula (K): The melting point of the compound obtained at normal pressure was 20°C.

[0137] Comparative Synthesis Example 1 Synthesis of Hydrocarbon Terminal Group-Containing Compound (X) 10.00 g (3.70 × 10 -2 mol), 2-isocyanatoethyl acrylate 5.74 g (4.07 × 10 -2 mol), 50.00 g of THF, and 0.03 g of tetrakis(2-ethylhexyl) orthotitanate were mixed and aged for 12 hours at 50° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 13.28 g of a product.

[0138] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (X): The melting point of the compound obtained at normal pressure was 29°C.

[0139] Comparative Synthesis Example 2 Synthesis of Hydrocarbon Terminal Group-Containing Compound (Y) 10.00 g (3.71 × 10 -2 mol), 2-isocyanatoethyl acrylate 5.76 g (4.08 × 10 -2 The resulting mixture was aged for 12 hours at 50° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 15.01 g of a product.

[0140] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (Y): The melting point of the compound obtained at normal pressure was 42°C.

[0141] [Examples 1 to 22, Comparative Examples 1, 2, and 3] Preparation of curable compositions for forming active energy ray-curable coatings Compounds (A) to (K) synthesized in the above Synthesis Examples and compounds (X) and (Y) synthesized in the Comparative Synthesis Examples were blended in the proportions shown in Tables 1 and 2 below to prepare solutions (curable compositions for forming active energy ray-curable coatings).

[0142]

[0143]

[0144] A-9550: Dipentaerythritol polyacrylate (A-9550, manufactured by Shin-Nakamura Chemical Co., Ltd.) AcOBu: Butyl acetate I-184: 1-hydroxycyclohexyl phenyl ketone (Irgacure 184, manufactured by Ciba Japan Co., Ltd.)

[0145] Coating and Preparation of Cured Coating (1) Each of the solutions (curable compositions for forming active energy ray-curable coatings) prepared in Examples 1 to 11 and Comparative Examples 1 to 3 was applied to a polycarbonate substrate by spin coating. After coating, the coating was subjected to a nitrogen flow for 5 minutes in an inert box at room temperature to volatilize the solvent and level the coating. Then, the coating was applied to a conveyor-type metal halide UV irradiation device (manufactured by Panasonic Electric Works Co., Ltd.) in a nitrogen atmosphere at an accumulated irradiation dose of 1,600 mJ / cm. 2 The coated surface was irradiated with ultraviolet light of 1000 kJ / cm to cure the composition, yielding a cured coating having a thickness of 5 μm.

[0146] Coating and Preparation of Cured Coating (2) A solution prepared by mixing 100 parts by mass of dipentaerythritol polyacrylate (A-9550, manufactured by Shin-Nakamura Chemical Co., Ltd.), 142 parts by mass of butyl acetate, and 3 parts by mass of 1-hydroxycyclohexylphenyl ketone (Irgacure 184, manufactured by Ciba Japan Co., Ltd.) was applied by spin coating onto a polycarbonate substrate. After coating, the substrate was heated at 80°C for 1 minute to evaporate the solvent and level the substrate. After 5 minutes of nitrogen flow in an inert box at room temperature, the substrate was irradiated with a conveyor-type metal halide UV irradiation device (manufactured by Panasonic Electric Works Co., Ltd.) in air at an accumulated irradiation dose of 1,600 mJ / cm. 2 The coated surface was irradiated with ultraviolet light of 1000 kJ / cm to cure the coating, yielding a cured coating film of 5 μm in thickness. Each of the solutions (curable compositions for forming active energy ray-curable coatings) prepared in Examples 12 to 22 was then applied onto the resulting cured coating by spin coating. After application, the coating was heated at 80°C for 1 minute to evaporate the solvent and allow leveling. After this, the coating was placed in an inert box at room temperature under a nitrogen flow for 5 minutes, and then irradiated with ultraviolet light of 1,600 mJ / cm to obtain a cured coating film of 5 μm in thickness using a conveyor-type metal halide UV irradiation device (manufactured by Panasonic Electric Works Co., Ltd.) in a nitrogen atmosphere.2 The coated surface was irradiated with ultraviolet light of 1000 kJ / cm 2 to cure the composition, yielding a cured coating having a thickness of 5 nm.

[0147] The appearance (transparency) of the cured coating obtained above was visually evaluated, and the water contact angle, oleic acid contact angle, and marker wiping ability were measured to evaluate the antifouling properties, and the water contact angle after the abrasion test was measured to evaluate the abrasion resistance, all according to the methods described below. The results are shown in Tables 3 and 4. For the appearance (transparency), transparent films were marked with a circle, and non-transparent films were marked with an X.

[0148] Evaluation of Antifouling Properties [Water Contact Angle Measurement, Oleic Acid Contact Angle Measurement] The contact angles of the cured coatings prepared above with water and oleic acid were measured using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) (droplet: 2 μL, temperature: 25° C., relative humidity: 40%).

[0149] [Evaluation of Marker Ink Wiping Properties] A 3 cm straight line was drawn on each of the cured coatings prepared above using a marker pen (large marker pen, manufactured by Teranishi Chemical Industry Co., Ltd.), and after drying at room temperature for 3 minutes, the markings were wiped off with tissue paper. Those for which the markings were wiped off were evaluated as ○, and those for which they could not be wiped off were evaluated as ×.

[0150] Evaluation of abrasion resistance [Measurement of water contact angle after abrasion test] The cured coating surface was subjected to a reciprocating abrasion test using a friction and abrasion tester (manufactured by Shinto Scientific Co., Ltd.), and the water contact angle after the test was measured. The evaluation was based on the average number of tests conducted with N=4. The test conditions are as follows: Abrading material: Bonstar steel wool #0000 (manufactured by Bonstar Co., Ltd.) Travel distance (one way): 40 mm Travel speed: 4,800 mm / min Load: 300 gf / 1 x 1 cm 2 Number of wear times: 5,000

[0151]

[0152]

[0153] Cured coatings (Examples 1 to 22) of curable compositions for forming active energy ray-curable coatings using the hydrocarbon terminal group-containing compounds of the present invention (compounds (A) to (K)) exhibited excellent coating smoothness, water repellency, and antifouling properties, and abrasion tests confirmed high abrasion resistance without significant reduction in water contact angle. On the other hand, cured coatings (Comparative Examples 1 and 2) of curable compositions for forming active energy ray-curable coatings using hydrocarbon terminal group-containing compounds (compounds (X) and (Y)) that have structures different from the hydrocarbon terminal group-containing compounds of the present invention exhibited low water repellency, antifouling properties, and abrasion resistance. Furthermore, a cured coating (Comparative Example 3) of a curable composition for forming active energy ray-curable coatings that did not contain a hydrocarbon terminal group-containing compound exhibited no water repellency or antifouling properties at all.

Claims

1. The following general formula (1) [Wherein, X is R 1 O- or R 2 R 3 N- and R 1 is a linear, branched or cyclic monovalent hydrocarbon group having 20 to 80 carbon atoms; R 2 is a linear, branched or cyclic monovalent hydrocarbon group having 10 to 40 carbon atoms; R 3 is a hydrogen atom or a linear, branched or cyclic monovalent hydrocarbon group having 10 to 40 carbon atoms; R 2 and R 3 The total number of carbon atoms contained therein is 20 to 80, and Y is a single bond or a group represented by the following structural formula: * -C(=O)- ** * -C(=O)-O- ** * -C(=O)-NR 4 - ** * -C(=S)-NR 4 - ** (In the formula, * is a bond bonded to X in general formula (1), ** is a bond bonded to Z in general formula (1), and R 4 is a hydrogen atom, or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 8 carbon atoms.), Z is a single bond, or a divalent to tetravalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more atoms selected from oxygen atoms, sulfur atoms, nitrogen atoms and silicon atoms, V is a monovalent hydrocarbon group having 2 to 20 carbon atoms which contains a polymerizable carbon-carbon double bond which may independently contain an oxygen atom and / or a nitrogen atom, and m is an integer of 1 to 3.] A hydrocarbon end group-containing compound having no fluorine atom in its structure, represented by the following formula:

2. The compound according to claim 1, wherein in the above formula (1), V is represented by the following formula: (In the formula, * represents a bond bonded to Z in general formula (1), and R' represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms.) 3. In the above formula (1), Y is represented by the following structural formula: * -C(=O)-NH- ** 2. The hydrocarbon terminal group-containing compound according to claim 1, which is a group represented by the following formula: (in the formula, * is a bond bonded to X in general formula (1), and ** is a bond bonded to Z in general formula (1).

4. The compound containing a hydrocarbon terminal group according to claim 1, wherein m is 1 in the above formula (1).

5. The compound containing a hydrocarbon terminal group according to claim 1, wherein in the above formula (1), Z is a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms which may contain an oxygen atom and / or a nitrogen atom.

6. The compound according to claim 1, which is an acrylic compound having a hydrocarbon terminal group and is represented by the following general formula (2): (In the formula, X is the same as above, Z' is a divalent hydrocarbon group having 1 to 10 carbon atoms which may contain an oxygen atom and / or a nitrogen atom, and R" is a hydrogen atom or a methyl group.) 7. The hydrocarbon terminal group-containing compound according to claim 1, which is an acrylic compound having a hydrocarbon terminal group and is represented by the following general formula (3): (In the formula, R 2 , R 3 is the same as above, Z' is a divalent hydrocarbon group having 1 to 10 carbon atoms which may contain an oxygen atom and / or a nitrogen atom, and R" is a hydrogen atom or a methyl group.

8. In the above formula (3), R 2 and R 3 is a linear monovalent hydrocarbon group having 10 to 40 carbon atoms, R 2 and R 3 The hydrocarbon end group containing compound of claim 7, wherein the carbon numbers of 9. The hydrocarbon end group containing compound according to claim 1, having a melting point of 20°C or higher.

10. A curable composition for forming a coating, comprising a non-fluorine-containing hydrocarbon end group-containing compound having one hydrocarbon end group having 20 to 80 carbon atoms or two hydrocarbon end groups having 10 to 40 carbon atoms and at least one polymerizable group in one molecule.

11. The curable composition for forming a coating according to claim 10, wherein the non-fluorinated hydrocarbon terminal group-containing compound is the hydrocarbon terminal group-containing compound according to any one of claims 1 to 9.

12. The coating-forming curable composition according to claim 10, further comprising a polymerization initiator.

13. The curable composition for forming a coating according to claim 12, which is of an active energy ray curable type.

14. The coating-forming curable composition according to claim 10, further comprising a solvent.

15. The coating-forming curable composition according to claim 10, further comprising a non-fluorine-containing acrylic compound.

16. The coating-forming curable composition according to claim 10, which does not contain fluorine atoms.

17. A cured coating obtained by curing the coating-forming curable composition according to claim 10.

18. The cured coating according to claim 17, which has a water contact angle of 90° or more and an oleic acid contact angle of 40° or more when measured with a 2 μL droplet amount at a temperature of 25° C. and a relative humidity of 40%.

19. An article having the cured coating of claim 17 on its surface.