Hydrocarbon terminal group containing compound, curable composition for film formation, cured film and article

Abstract

By including a hydrocarbon terminal group containing a compound represented by the following formula (1) and not containing fluorine atoms in its structure in an active energy beam curable composition or a thermosetting composition such as ultraviolet rays or electron beams, excellent water repellency, antifouling properties, and wear resistance can be imparted to the resulting cured film. [X is R1O- or R2R3N-, R1 is a monovalent hydrocarbon group with 20–80 carbon atoms, R2 is a monovalent hydrocarbon group with 10–40 carbon atoms, R3 is H or R2, the sum of the carbon atoms in R2 and R3 is 20–80, Y is a single bond or the following group,*-C(=O)-***-C(=O)-O-***-C(=O)-NR4-***-C(=S)-NR4-** (* is a bonding hand bonding to X, ** is a bonding hand bonding to Z, R4 is H or a monovalent hydrocarbon group.) Z is a 2–4valent hydrocarbon group that may contain a single bond or O, S, N, or Si, V is a polymerizable carbon-carbon double-bond containing monovalent hydrocarbon group that may contain O or N, m is 1–3.]

Description

Technology Field

[0001] The present invention relates to a hydrocarbon terminal group-containing compound, and more specifically, to a hydrocarbon terminal group-containing compound that does not contain fluorine atoms in its structure, which can impart excellent water repellency, antifouling properties, and wear resistance to a cured film obtained by incorporating it into an active energy beam-curable composition or a thermosetting composition such as ultraviolet rays or electron beams; a curable composition for forming a film containing said hydrocarbon terminal group-containing compound; a cured film formed by curing said curable composition; and an article having said cured film on a substrate surface. Background Technology

[0002] Conventionally, hardcoat treatment has been widely used as a means to protect the surface of resin molded articles. This involves forming a hard, cured resin layer (hardcoat layer) on the surface of the molded article to make it resistant to scratching. Thermosetting compositions or active energy beam-curing compositions, such as ultraviolet rays or electron beams, are frequently used as materials to constitute the hardcoat layer.

[0003] With the expansion of application fields for resin molded products and the trend toward high value-added products, there is a growing demand for high functionality in cured resin layers (hardcoat layers). As one such requirement, there is a demand to impart antifouling properties to the hardcoat layer. This is achieved by imparting properties such as water repellency and oil repellency to the surface of the hardcoat layer, thereby making it difficult to contaminate or allowing for easy removal even if contaminated.

[0004] Methods for imparting antifouling properties to a hardcoat layer include a method of coating and / or fixing a fluorine-containing antifouling agent onto the surface of a hardcoat layer formed once, and a method of simultaneously forming a hardcoat layer and imparting antifouling properties by adding a fluorine-containing curable component to a curable resin composition before curing and applying and curing the same. For example, Japanese Patent Publication No. Hei 6-211945 (Patent Document 1) discloses the manufacture of a hardcoat layer imparting antifouling properties by adding a fluoroalkyl acrylate to an acrylic-based curable resin composition and curing it.

[0005] The inventors have developed various fluorine-containing compounds capable of imparting antifouling properties to such curable resin compositions, and have proposed photocurable fluorine-containing compounds disclosed in, for example, Japanese Patent Publication No. 2010-53114 (Patent Document 2), Japanese Patent Publication No. 2010-138112 (Patent Document 3), and Japanese Patent Publication No. 2010-285501 (Patent Document 4).

[0006] On the other hand, fluorine-containing compounds, such as perfluorooctanoic acid (PFOA), tend to be difficult to decompose and accumulate in nature. Consequently, a wide range of fluorine-containing compounds have recently been categorized as per / polyfluoroalkyl compounds (PFAS), and it is predicted that restrictions on the use, sale, and emission of fluorine-containing compounds will be strengthened under PFAS regulations. Therefore, there has recently been a demand for the development of non-fluorine antifouling agents that do not contain fluorine atoms. However, when conventional non-fluorine compounds are used for the aforementioned applications, the water repellency, antifouling properties, and wear resistance of the resulting cured film have not yet reached a level that is satisfactory for practical use. Prior art literature

[0007] Japanese Patent Publication No. Hei 6-211945, Japanese Patent Publication No. 2010-53114, Japanese Patent Publication No. 2010-138112, Japanese Patent Publication No. 2010-285501 The problem to be solved

[0008] The present invention has been made in consideration of the above circumstances and aims to provide a hydrocarbon terminal group containing a fluorine atom in its structure, which can impart excellent water repellency, antifouling properties, and wear resistance to a cured film obtained by adding to an active energy beam curable composition or a thermosetting composition such as ultraviolet rays or electron beams; a curable composition for forming a film containing said hydrocarbon terminal group containing said compound; a cured film formed by curing said curable composition; and an article having said cured film on a substrate surface. means of solving the problem

[0009] The inventors, after careful consideration to solve the above objective, discovered that by including a hydrocarbon terminal group containing a compound that does not contain a fluorine atom in a structure represented by the general formula (1) described below as a non-fluorine antifouling agent in a curable composition or thermosetting composition with active energy rays such as ultraviolet rays or electron beams, excellent water repellency, antifouling properties, and wear resistance can be imparted to the cured film obtained, and thus the present invention was made.

[0010]

[0011] [In the formula, X is R 1 O-, or R 2 R 3 N- and, R 1 is a monovalent hydrocarbon group having 20 to 80 carbon atoms in a straight, branched, or cyclic form, and R 2 is a monovalent hydrocarbon group having 10 to 40 carbon atoms in a straight, branched, or cyclic form, and R 3 It is a hydrogen atom, or a monovalent hydrocarbon group having 10 to 40 carbon atoms in a straight, branched, or cyclic form, and R 2 and R 3 The total number of carbon atoms contained therein is 20 or more and 80 or less, and Y is a single bond, or the following structural formula

[0012] *-C(=O)- **

[0013] * -C(=O)-O- **

[0014] * -C(=O)-NR 4 - **

[0015] * -C(=S)-NR 4 - **

[0016] (In the formula, * is a bonding hand that combines with X in general formula (1), ** is a bonding hand that combines with Z in general formula (1), and R 4 is a hydrogen atom, or a monovalent hydrocarbon group having 1 to 8 carbon atoms in a straight, branched, or cyclic form.

[0017] It is a divalent organic group represented by, where Z is a 2 to 4-valent hydrocarbon group having 1 to 20 carbon atoms that may include a single bond or one or more selected from oxygen, sulfur, nitrogen, and silicon atoms, V is a monovalent hydrocarbon group having 2 to 20 carbon atoms containing a polymerizable carbon-carbon double bond that may independently include an oxygen atom and / or a nitrogen atom, and m is an integer from 1 to 3.

[0018] Accordingly, the present invention provides the following hydrocarbon terminal group-containing compound, a curable composition for forming a film containing the hydrocarbon terminal group-containing compound, a cured film formed by curing the curable composition for forming a film, and an article having the cured film on its surface.

[0019] [1]

[0020] The following general formula (1)

[0021]

[0022] [In the formula, X is R 1 O-, or R 2 R 3 N- and, R 1is a monovalent hydrocarbon group having 20 to 80 carbon atoms in a straight, branched, or cyclic form, and R 2 is a monovalent hydrocarbon group having 10 to 40 carbon atoms in a straight, branched, or cyclic form, and R 3 It is a hydrogen atom, or a monovalent hydrocarbon group having 10 to 40 carbon atoms in a straight, branched, or cyclic form, and R 2 and R 3 The total number of carbon atoms contained therein is 20 or more and 80 or less, and Y is a single bond, or the following structural formula

[0023] * -C(=O)- **

[0024] * -C(=O)-O- **

[0025] * -C(=O)-NR 4 - **

[0026] * -C(=S)-NR 4 - **

[0027] (In the formula, * is a bonding hand that combines with X in general formula (1), ** is a bonding hand that combines with Z in general formula (1), and R 4 is a hydrogen atom, or a monovalent hydrocarbon group having 1 to 8 carbon atoms in a straight, branched, or cyclic form.

[0028] It is a divalent organic group represented by, where Z is a 2 to 4-valent hydrocarbon group having 1 to 20 carbon atoms that may include a single bond or one or more selected from oxygen, sulfur, nitrogen, and silicon atoms, V is a monovalent hydrocarbon group having 2 to 20 carbon atoms containing a polymerizable carbon-carbon double bond that may independently include an oxygen atom and / or a nitrogen atom, and m is an integer from 1 to 3.

[0029] A hydrocarbon terminal group-containing compound represented by and not containing a fluorine atom in its structure.

[0030] [2]

[0031] A hydrocarbon terminal group containing compound described in [1], wherein V is represented by the following formula in the above formula (1).

[0032]

[0033] (In the formula, * is a bonding hand that bonds with Z in general formula (1), and R' is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms.)

[0034] [3]

[0035] In the above equation (1), Y is the following structural formula

[0036] * -C(=O)-NH- **

[0037] (In the formula, * is a bonding hand that combines with X in general formula (1), and ** is a bonding hand that combines with Z in general formula (1).)

[0038] A hydrocarbon terminal group containing compound as indicated by [1] or [2].

[0039] [4]

[0040] A hydrocarbon terminal group containing compound described in any one of [1] to [3] in the above formula (1), where m is 1.

[0041] [5]

[0042] A hydrocarbon terminal group containing a compound described in any one of [1] to [4], wherein Z may be a single bond, or a divalent hydrocarbon group having 1 to 10 carbon atoms, and / or may include an oxygen atom and / or a nitrogen atom in the above formula (1).

[0043] [6]

[0044] A hydrocarbon terminal group containing acrylic compound represented by the following general formula (2), which is a hydrocarbon terminal group containing an acrylic compound [1] to [5].

[0045]

[0046] (In the formula, X is as above, Z' is a divalent hydrocarbon group having 1 to 10 carbon atoms that may include an oxygen atom and / or a nitrogen atom, and R" is a hydrogen atom or a methyl group.)

[0047] [7]

[0048] A hydrocarbon terminal group containing acrylic compound represented by the following general formula (3), which is a hydrocarbon terminal group containing an acrylic compound [1] to [5].

[0049]

[0050] (during food, R 2 , R 3 ...is as described above, Z' is a divalent hydrocarbon group having 1 to 10 carbon atoms that may include an oxygen atom and / or a nitrogen atom, and R" is a hydrogen atom or a methyl group.)

[0051] [8]

[0052] In the above equation (3), R 2 and R 3 This is a linear monovalent hydrocarbon group having 10 to 40 carbon atoms, and R 2 and R 3 A hydrocarbon terminal group-containing compound with the same number of carbon atoms as [7].

[0053] [9]

[0054] A hydrocarbon terminal group containing compound described in any one of [1] to [8], having a melting point of 20°C or higher.

[0055]

[10]

[0056] A curable composition for forming a film comprising a non-fluorinated hydrocarbon terminal group containing 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.

[0057]

[11]

[0058] A curable composition for forming a film as described in

[10] , wherein the non-fluorinated hydrocarbon terminal group containing compound is a hydrocarbon terminal group containing compound described in any one of [1] to [9].

[0059]

[12]

[0060] A curable composition for forming a film as described in

[10] , further containing a polymerization initiator.

[0061]

[13]

[0062] A curable composition for forming a film as described in

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

[0063]

[14]

[0064] A curable composition for forming a film, as described in any one of

[10] to

[13] , containing a solvent.

[0065]

[15]

[0066] A curable composition for forming a film as described in any one of

[10] to

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

[0067]

[16]

[0068] A curable composition for forming a film as described in any one of

[10] to

[15] , which is composed of not containing fluorine atoms.

[0069]

[17]

[0070]

[10] to

[16] A cured film formed by curing a curable composition for forming a film as described in any one of

[10] to

[16] .

[0071]

[18]

[0072] A cured film as described in

[17] , having a water contact angle of 90° or more and an oleic acid contact angle of 40° or more at a drop volume of 2 μL, a temperature of 25°, and a relative humidity of 40%.

[0073]

[19]

[0074] Article having a hardened film on the surface as described in

[17] or

[18] . Effects of the invention

[0075] A cured film obtained using a curable composition for forming a film comprising a hydrocarbon terminal group-containing compound that does not contain fluorine atoms in the structure of the present invention can impart excellent water repellency, antifouling properties, and wear resistance. Accordingly, this hydrocarbon terminal group-containing compound is useful as an antifouling additive for imparting water repellency, antifouling properties, and wear resistance to active energy beam-curable or thermosetting hardcoats, paints, resins, and compositions for anti-reflective coatings. Specific details for implementing the invention

[0076] (Form for carrying out the invention)

[0077] In the present invention, the term "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 also includes compounds in which two or more acrylic groups or α-substituted acrylic groups are introduced to the side chains or ends of various polymers by any method. Furthermore, in the present invention, the term "(meth)acrylate" refers to either or both of acrylate and methacrylate, the term "(meth)acrylic group" refers to either or both of an acrylic group and a methacryloyl (hereinafter also referred to as methacrylic) group, and the term "(meth)acrylic acid halide" refers to either or both of an acrylic acid halide and a methacrylic acid halide.

[0078] The hydrocarbon terminal group-containing compound of the present invention is represented by the following general formula (1), and this hydrocarbon terminal group-containing compound does not contain fluorine atoms in its structure.

[0079]

[0080] [In the formula, X is R 1 O-, or R 2 R 3 N- and, R 1 is a monovalent hydrocarbon group having 20 to 80 carbon atoms in a straight, branched, or cyclic form, and R 2is a monovalent hydrocarbon group having 10 to 40 carbon atoms in a straight, branched, or cyclic form, and R 3 It is a hydrogen atom, or a monovalent hydrocarbon group having 10 to 40 carbon atoms in a straight, branched, or cyclic form, and R 2 and R 3 The total number of carbon atoms contained therein is 20 or more and 80 or less, and Y is a single bond, or the following structural formula

[0081] * -C(=O)- **

[0082] * -C(=O)-O- **

[0083] * -C(=O)-NR 4 - **

[0084] * -C(=S)-NR 4 - **

[0085] (In the formula, * is a bonding hand that combines with X in general formula (1), ** is a bonding hand that combines with Z in general formula (1), and R 4 is a hydrogen atom, or a monovalent hydrocarbon group having 1 to 8 carbon atoms in a straight, branched, or cyclic form.

[0086] It is a divalent organic group represented by, where Z is a 2 to 4-valent hydrocarbon group having 1 to 20 carbon atoms that may include a single bond or one or more selected from oxygen, sulfur, nitrogen, and silicon atoms, V is a monovalent hydrocarbon group having 2 to 20 carbon atoms containing a polymerizable carbon-carbon double bond that may independently include an oxygen atom and / or a nitrogen atom, and m is an integer from 1 to 3.

[0087] The hydrocarbon terminal group-containing compound of the present invention is required to have hydrocarbon chain terminal groups with a predetermined number of carbon atoms or more and polymerizable carbon-carbon double bonds in its structure. By having hydrocarbon chain terminal groups with a predetermined number of carbon atoms or more that exhibit high packing properties and polymerizable carbon-carbon double bonds acting as active energy beam curable groups or thermosetting groups, when this compound is incorporated into a curable composition for film formation and cured, this compound segregates on the surface of the cured film and forms a hard layer through the packing of hydrocarbon chains, thereby becoming immobilized. The cured film obtained by this exhibits excellent water repellency, antifouling properties, and wear resistance. Furthermore, by combining it with other components, even if it does not segregate on the outermost surface, a sufficient effect of improving the water repellency of the cured film itself can be expected. In addition, in the present invention, packing properties refer to the degree of high or low tendency for multiple hydrocarbon chains to be oriented unidirectionally and densely on the surface of the cured film.

[0088] In the above equation (1), X is R 1 O-, or R 2 R 3 N- and, R 1 is a monovalent hydrocarbon group having 20 to 80 carbon atoms in a straight, branched, or cyclic form, and R 2 is a monovalent hydrocarbon group having 10 to 40 carbon atoms in a straight, branched, or cyclic form, and R 3 It is a hydrogen atom, or a monovalent hydrocarbon group having 10 to 40 carbon atoms in a straight, branched, or cyclic form, and R 2 and R 3 The total number of carbon atoms contained in it is 20 or more and 80 or less.

[0089] R 1 If the number of carbon atoms is smaller than the upper limit value, compatibility with the curable composition for film formation is good, and if it is larger than the lower limit value, the packing properties of the hydrocarbon chain are increased, allowing it to fully exhibit characteristics as a water-repellent and anti-fouling agent.

[0090] R2 and R 3 If the total number of carbon atoms contained therein is smaller than the upper limit value, compatibility with the curable composition for film formation is good, and if it is larger than the lower limit value, the packing properties of the hydrocarbon chains are increased, allowing it to fully exhibit characteristics as a water-repellent and anti-fouling agent.

[0091] R 1 It is more preferable that it be a monovalent hydrocarbon group with 21 to 60 carbon atoms in a straight or branched chain, and particularly preferable that it be a monovalent hydrocarbon group with 22 to 44 carbon atoms in a straight or branched chain.

[0092] R 1 Examples of what is represented as follows.

[0093]

[0094] (In the formula, * is a bonding hand bonding to an oxygen atom in X, and y is independently an integer greater than or equal to 1, and is also an integer such that the sum of the number of carbons 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.)

[0095] R 2 As for, it is more preferable that it be a straight-chain or branched monovalent hydrocarbon group having 11 to 30 carbon atoms, and particularly preferable that it be a straight-chain or branched monovalent hydrocarbon group having 12 to 22 carbon atoms. R 3 As for, it is more preferable that it be a hydrogen atom, a straight-chain or branched monovalent hydrocarbon group having 11 to 30 carbon atoms, and particularly preferable that it be a hydrogen atom, a straight-chain or branched monovalent hydrocarbon group having 12 to 22 carbon atoms. R 2 and R 3 It is more preferable that the total number of carbon atoms contained therein be 21 or more and 60 or less, and particularly preferable that it be 22 or more and 44 or less.

[0096] R 2 Examples of what is represented as follows.

[0097]

[0098] (In the formula, * is a bonding hand bonded to a nitrogen atom in X, and y' is independently an integer greater than or equal to 1, and is also an integer such that the sum of the number of carbons in each structure is 10 or more and 40 or less, more preferably 11 or more and 30 or less, and particularly preferably 12 or more and 22 or less.)

[0099] R 3 Examples include hydrogen atoms, and those shown below.

[0100]

[0101] (In the formula, * is a bonding hand bonded to a nitrogen atom in X, and y' is independently an integer greater than or equal to 1, and is also an integer such that the sum of the number of carbons in each structure is 10 or more and 40 or less, more preferably 11 or more and 30 or less, and particularly preferably 12 or more and 22 or less.)

[0102] As for X, the following can be cited.

[0103]

[0104] (In the formula, * is a bonding hand that bonds with Y in general formula (1), and y is an integer of 1 or more independently, and is also an integer such that the sum of the number of carbons 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.)

[0105] As for X, having two CH3 groups in the structure is particularly desirable in that it can exhibit excellent antifouling properties. Generally, it is known that solid surfaces having -CH3 have lower surface free energy compared to solid surfaces having only -CH2-, and thus exhibit superior antifouling properties. As such, the X described below is suitably used.

[0106]

[0107] (In the formula, * is a bonding hand that bonds with Y in general formula (1), and y is an integer of 1 or more independently, and is also an integer such that the sum of the number of carbons 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.)

[0108] In the above formula (1), Y is a single bond or a divalent organic group represented by the following structural formula.

[0109] * -C(=O)- **

[0110] * -C(=O)-O- **

[0111] * -C(=O)-NR 4 - **

[0112] * -C(=S)-NR 4 - **

[0113] (In the formula, * is a bonding hand that combines with X in general formula (1), ** is a bonding hand that combines with Z in general formula (1), and R 4 is a hydrogen atom, or a monovalent hydrocarbon group having 1 to 8 carbon atoms in a straight, branched, or cyclic form.

[0114] Here, R 4 is a hydrogen atom, or a linear, branched, or cyclic monovalent hydrocarbon group having 1 to 8 carbon atoms. Examples of linear, branched, or cyclic monovalent hydrocarbon groups 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. 4As for it, it is more desirable that it be a hydrogen atom.

[0115] As for Y, the following structural formula

[0116] * -C(=O)-NH- **

[0117] (In the formula, * is a bonding hand that combines with X in general formula (1), and ** is a bonding hand that combines with Z in general formula (1).)

[0118] It is particularly desirable that the cause be represented as such. When Y is the structure of the tactical method, compatibility with the curable composition for film formation becomes particularly good.

[0119] In the above formula (1), Z is a hydrocarbon group having 1 to 20 carbon atoms and having 2 to 4 valence, which may include a single bond or one or more selected from oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms. When Y is a single bond, it is preferable that Z is a single bond.

[0120] A 2- to 4-valent hydrocarbon group having 1 to 20 carbon atoms that may include one or more selected from oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms, specifically comprising one or more selected from the group consisting of a straight-chain, branched, or cyclic 2- to 4-valent hydrocarbon group having 1 to 20 carbon atoms, an ether group, a carbonyl (ketone) group, an ester group, a carbonate group, -CH(OH)- group, a sulfinyl group, a sulfonyl group, a thioester group, a thiocarbonate group, a thiocarbamate group, an amino group, an amide group, a carbamate group, a urea group, a nitrogen-containing heterocyclic group (oxazole group, imidazole group, triazole group, etc.), a silalkylene group, a silarylene group, and a straight-chain, branched, or cyclic organopolysiloxane group Hydrocarbon groups can be cited.

[0121] It is particularly preferable that Z be a divalent hydrocarbon group having 1 to 10 carbon atoms, which may include a single bond or an oxygen atom and / or a nitrogen atom. When Z is a divalent hydrocarbon group, the compound containing this hydrocarbon terminal group becomes a monoacrylic compound, and thus has good compatibility with a curable composition for film formation.

[0122] As for Z, it is appropriately used to represent it as follows.

[0123]

[0124]

[0125]

[0126]

[0127]

[0128] (In the formula, * is a connecting hand that combines with Y in general formula (1), ** is a connecting hand that combines with V in general formula (1), q is an integer from 1 to 10, r, s, and t are integers from 1 to 8 each, the sum of r and s is an integer from 2 to 10, and the sum of r, s, and t is an integer from 3 to 10.)

[0129] In the above formula (1), V is a monovalent hydrocarbon group having 2 to 20 carbon atoms containing a polymerizable carbon-carbon double bond that may independently contain an oxygen atom and / or a nitrogen atom. Specifically, groups 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.

[0130] As for V, it is preferable that it be an acrylic group, an α-substituted acrylic group, an acryloxy group, or an α-substituted acryloxy group represented by the following formula.

[0131]

[0132] (In the formula, * is a bonding hand that bonds with Z in general formula (1), and R' is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms.)

[0133] Here, R' is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and examples of monovalent hydrocarbon groups 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. It is more preferable that R' be a hydrogen atom or a methyl group.

[0134] As for V, an acryloxy group, an α-substituted acryloxy group represented by the following formula, is particularly preferred.

[0135]

[0136] (In the formula, * is a bonding hand that combines with Z in general formula (1), and R' is as above.)

[0137] As such a V, specifically, the following is appropriately used.

[0138]

[0139] (In the formula, * is a bonding hand that combines with Z in general formula (1).)

[0140] In the above formula (1), m is an integer from 1 to 3, preferably 1. If m is greater than the upper limit value, the proportion of hydrocarbon chain end groups as water-repellent and antifouling imparting groups becomes relatively small, and water-repellent and antifouling properties are reduced.

[0141] The hydrocarbon terminal group-containing compound represented by the above formula (1) does not contain fluorine atoms in its structure. Accordingly, compared to conventional fluorine-based compounds, it has low recalcitrant and accumulation properties in nature.

[0142] The hydrocarbon terminal group-containing compound represented by the above formula (1) can be varied by changing the combination of X, Y, Z, and V in the formula.

[0143] As for 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 preferable.

[0144]

[0145] (In the formula, X is as above, Z' is a divalent hydrocarbon group having 1 to 10 carbon atoms that may include an oxygen atom and / or a nitrogen atom, and R" is a hydrogen atom or a methyl group.)

[0146] In the above formula (2), Z' is a divalent hydrocarbon group having 1 to 10 carbon atoms that may include oxygen atoms and / or nitrogen atoms, and is suitably used as shown below.

[0147]

[0148] (In the formula, * is a bonding hand bonded to a nitrogen atom in general formula (2), ** is a bonding hand bonded to an oxygen atom in general formula (2), q is an integer from 1 to 10, r and s are integers from 1 to 8 each, and the sum of r and s is an integer from 2 to 10.)

[0149] 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 water repellency, antifouling properties, and wear resistance of the cured film obtained by adding this compound to an active energy beam-curable composition or a thermosetting composition, such as ultraviolet rays or electron beams, are further superior.

[0150] A particularly suitable example of an acrylic compound containing a hydrocarbon terminal group represented by the above formula (2) can be exemplified by the following formula.

[0151]

[0152]

[0153]

[0154]

[0155]

[0156]

[0157]

[0158]

[0159] As a 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.

[0160]

[0161] (during food, R 2 , R 3 , Z', R" are as above.)

[0162] 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 water repellency, antifouling properties, and wear resistance of the cured film obtained by adding this compound to an active energy beam-curable composition or a thermosetting composition, such as ultraviolet rays or electron beams, are particularly excellent.

[0163] A particularly suitable example of an acrylic compound containing a hydrocarbon terminal group represented by the above formula (3) can be exemplified by the following formula.

[0164]

[0165]

[0166]

[0167]

[0168] In the above equation (3), R 2 and R 3 This is a linear monovalent hydrocarbon group having 10 to 40 carbon atoms, and R 2 and R 3 It is particularly desirable that the number of carbon atoms of are the same. R 2 and R 3 When the conditions of this tactic are satisfied, the distance between hydrocarbon groups is brought closer, thereby increasing the packing ability of the hydrocarbon groups in the hydrocarbon terminal group-containing compound, and in the cured film obtained by adding this compound to an active energy beam-curable composition or a thermosetting composition such as ultraviolet rays or electron beams, the wear resistance becomes even better because this compound forms a hard layer on its outermost surface.

[0169] Examples of compounds containing hydrocarbon terminal groups represented by the above formula (1), other than the hydrocarbon terminal group-containing acrylic compound represented by the above formula (2) and the hydrocarbon terminal group-containing acrylic compound represented by the above formula (3), may be exemplified by the following formula.

[0170]

[0171]

[0172]

[0173] The hydrocarbon terminal group-containing compound represented by the above general formula (1) preferably has a melting point of 20°C or higher, and particularly preferably 20 to 100°C. When the melting point is 20°C or higher, in a cured film obtained by adding this compound to an active energy beam curable composition or a thermosetting composition such as ultraviolet rays or electron beams, the wear resistance is further improved because this compound forms a hard layer on its outermost surface.

[0174] In this specification, the melting point is a value measured under atmospheric pressure by differential scanning calorimetry (DSC). The measurement method conforms to JIS K 7121. The measurement conditions are described below. Starting temperature: -150℃, ending temperature: 200℃, rising / falling rate: 10℃ / min, atmosphere gas: nitrogen (flow rate: 50mL / min).

[0175] In the case where the hydrocarbon terminal group-containing compound represented by the general formula (1) of the present invention is, in particular, an acrylic compound represented by the general formula (2) or the general formula (3), a method for preparing this compound may be, for example, the following method.

[0176] An acrylic compound containing a hydrocarbon terminal group can be prepared by mixing an alcohol compound or an amine compound containing a hydrocarbon terminal group with an isocyanate compound containing a (meth)acrylic group and carrying out an addition reaction.

[0177] Alcohol compounds containing hydrocarbon terminal groups are represented by the following formula (4), and amine compounds containing hydrocarbon terminal groups are represented by the formula (5).

[0178] R 1 OH (4)

[0179] R 2 R 3 NH (5)

[0180] (during food, R 1 , R 2 , R 3 It is as stated above.)

[0181] Here, suitable examples of alcohol compounds represented by formula (4) include those shown below.

[0182]

[0183]

[0184]

[0185]

[0186] Alcohol compounds containing hydrocarbon terminal groups can be prepared by the hydride reduction of aldehyde compounds or ketone compounds containing hydrocarbon terminal groups.

[0187] Examples of aldehyde compounds containing hydrocarbon terminal groups include those shown below.

[0188]

[0189] Examples of ketone compounds containing hydrocarbon terminal groups include those shown below.

[0190]

[0191] Sodium borohydride and lithium aluminum hydride are preferred as reducing agents in hydride reduction.

[0192] It is preferable to charge and react these reducing agents in an equimolar or greater manner with respect to an aldehyde compound or ketone compound containing a hydrocarbon terminal group, thereby reacting both the aldehyde or ketone. Specifically, it is preferable to use 1 equivalent or more and 5 equivalents or less of the reducing agent for every 1 equivalent of the aldehyde compound or ketone compound containing a hydrocarbon terminal group in the reaction system, and particularly preferably 1 equivalent or more and 3 equivalents or less.

[0193] These reactions may be carried out by diluting with a suitable solvent as necessary. As such solvents, any solvent containing hydrocarbon terminal groups, such as aldehyde or ketone compounds, and any solvent that does not react with a reducing agent may be used without particular limitation; specifically, hydrocarbon-based solvents (petroleum benzine, toluene, xylene, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, octane (n-octane, isooctane, etc.), nonane (n-nonane, isononane, etc.), etc.), ketone-based solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc.), ether-based 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-based solvents Examples include solvents (propylene glycol monomethyl ether, butanol, isopropanol, methanol, etc.).

[0194] The amount of solvent used is not particularly limited, but it is preferably 20 times or less the total mass of the reaction components, and particularly preferably 15 times or less. If the amount of solvent used is excessive, the reaction rate may decrease significantly. As a lower limit for the use of solvent, it is preferable to have an amount of 0.5 times or more the total mass of the reaction components.

[0195] The above 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.

[0196] After the reaction is finished, unreacted reducing agents and reaction solvents, etc., can be removed by methods such as distillation, adsorption, filtration, and washing, thereby obtaining an alcohol compound containing hydrocarbon terminal groups.

[0197] Suitable examples of amine compounds represented by formula (5) include those shown below.

[0198]

[0199]

[0200]

[0201]

[0202] Also, isocyanate compounds containing (meth)acrylic groups are represented by the following formula (6).

[0203] O=C=N-Z'-OC(=O)CR"2 (6)

[0204] (In the formula, Z' and R" are as above.)

[0205] Suitable examples of isocyanate compounds containing (meth)acrylic groups include those shown below.

[0206] O=C=N-CH2CH2-OC(=O)-CH=CH2

[0207] O=C=N-CH2CH2-OC(=O)-C(CH3)=CH2

[0208] O=C=N-CH2CH2-O-CH2CH2-OC(=O)-C(CH3)=CH2

[0209] It is preferable to react these isocyanate compounds containing (meth)acrylic groups by adding an amount equal to or greater than the total amount of active hydrogen of alcohol compounds or amine compounds containing hydrocarbon terminal groups and reacting them to react all the active hydrogen. Specifically, it is preferable to have an amount of 1 equivalent or more and 2 equivalents or less of the isocyanate compound containing (meth)acrylic groups for every 1 equivalent of the alcohol compound or amine compound containing hydrocarbon terminal groups in the reaction system, and particularly preferably 1 equivalent or more and 1.4 equivalents or less. If the amount of isocyanate compound containing (meth)acrylic groups is excessive, it becomes difficult to remove the isocyanate compound containing (meth)acrylic groups remaining after the reaction.

[0210] These reactions may be carried out by diluting with a suitable solvent as necessary. As such solvents, any solvent that does not react with the hydroxyl groups of alcohol compounds or amine compounds containing hydrocarbon terminal groups, or the isocyanate groups of isocyanate compounds containing (meth)acrylic groups, may be used without particular limitation; specifically, hydrocarbon-based solvents (petroleum benzine, toluene, xylene, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, octane (n-octane, isooctane, etc.), nonane (n-nonane, isononane, etc.), hydrocarbon-based solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc.), ether-based 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, Examples include propylene glycol dimethyl ether, etc.), alcohol-based solvents (propylene glycol monomethyl ether, butanol, isopropanol, etc.), and ester-based solvents (ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, propylene glycol monomethyl ether acetate). These solvents may be removed after the reaction by known methods such as vacuum distillation, or they may be used as a diluted solution as is, depending on the intended use.

[0211] The amount of solvent used is not particularly limited, but it is preferably 20 times or less the total mass of the reaction components, and particularly preferably 15 times or less. If the amount of solvent used is excessive, the reaction rate may decrease significantly. As a lower limit for the use of solvent, it is preferable to have at least 1 time the total mass of the reaction components.

[0212] In addition, a polymerization inhibitor may be added during the reaction if necessary. There are no specific restrictions on the polymerization inhibitor, but those commonly used as polymerization inhibitors for acrylic compounds may be used. Specifically, examples include hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, dibutylhydroxytoluene, etc.

[0213] The amount of polymerization inhibitor used can be determined by the reaction conditions, purification conditions after the reaction, and final usage conditions, and is not particularly limited, but is preferably 0.01 to 5,000 ppm, particularly preferably 0.1 to 500 ppm with respect to the total mass of the reaction components.

[0214] In addition, during the reaction, a suitable catalyst may be added as needed. As catalysts, for example, alkyl tin ester compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, and stannous diocarbonate; titanium acid esters or titanium chelate compounds such as tetraisopropoxytitanium, tetran-butoxytitanium, tetrakis(2-ethylhexoxy)titanium [alias: tetrakis(2-ethylhexyl) orthotitanium], dipropoxybis(acetylacetonato)titanium, and titanium isopropoxyoctylene glycol; zirconium tetraacetylacetonate, zirconium tributoxymonoacetylacetonate, and zirconium monobutoxyacetylacetonatebis(ethylacetoacetate). Examples include zirconium dibutoxybis(ethyl acetoacetate), zirconium tetraacetylacetonate, and zirconium chelate compounds. These are not limited to just one type and may be used as a mixture of two or more types.

[0215] 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%, relative to the total mass of the reaction components.

[0216] The above 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 excessively low, the reaction rate may become excessively slow, and if the reaction temperature is excessively high, there is a possibility that polymerization of (meth)acrylic groups may occur as a side reaction.

[0217] After the reaction is finished, unreacted isocyanate compounds and reaction solvents, etc., can be removed by methods such as distillation, adsorption, filtration, and washing, thereby obtaining an acrylic compound containing hydrocarbon terminal groups represented by the above general formula (2) or the above general formula (3).

[0218] Additionally, when the reaction is stopped, 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 generated urethane (meth)acrylates can be removed in the same way as the unreacted isocyanate compound, but they may also be used while remaining in the system.

[0219] 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 the general formula (3), the method of preparing the compound may be, for example, the following method.

[0220] For example, an ester may be formed by reacting an alcohol compound or an amine compound containing a hydrocarbon terminal group with a (meth)acrylic acid halide, and an acrylic compound containing a hydrocarbon terminal group may be obtained.

[0221] Here, alcohol compounds or amine compounds containing hydrocarbon terminal groups may exemplify the same as those above.

[0222] As (meth)acrylic acid halides, acrylic acid chloride and methacrylic acid chloride are particularly preferred.

[0223] It is preferable to charge and react these (meth)acrylic acid halides in an amount equal to or greater than that of an alcohol compound or amine compound containing a hydrocarbon terminal group, thereby reacting both the alcohol or the amine. Specifically, it is preferable to use 1 equivalent or more and 2 equivalents or less of (meth)acrylic acid halide with respect to 1 equivalent of the alcohol compound or amine compound containing a hydrocarbon terminal group in the reaction system, and particularly preferably 1 equivalent or more and 1.8 equivalents or less.

[0224] These reactions may be carried out by diluting with a suitable solvent as needed. As such solvents, any alcohol or amine compound containing a hydrocarbon terminal group, or any solvent that does not react with the halogen atom of the (meth)acrylic acid halide, may be used without particular restriction. Specifically, 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. These solvents may be removed after the reaction by known methods such as vacuum distillation, or they may be used as a diluted solution as is, depending on the intended use.

[0225] The amount of solvent used is not particularly limited, but it is preferably 20 times or less the total mass of the reaction components, and particularly preferably 15 times or less. If the amount of solvent used is excessive, the reaction rate may decrease significantly. As a lower limit for the use of solvent, it is preferable to have at least 1 time the total mass of the reaction components.

[0226] In addition, a polymerization inhibitor may be added during the reaction if necessary. There are no specific restrictions on the polymerization inhibitor, but those commonly used as polymerization inhibitors for acrylic compounds may be used. Specifically, examples include hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, dibutylhydroxytoluene, etc.

[0227] The amount of polymerization inhibitor used can be determined by the reaction conditions, purification conditions after the reaction, and final usage conditions, and is not particularly limited, but typically it is 0.01 to 5,000 ppm, particularly preferably 0.1 to 500 ppm with respect to the total mass of the reaction components.

[0228] In this ester formation reaction, an alcohol compound or amine compound containing hydrocarbon terminal groups, a hydroxyl agent, 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 mixed.

[0229] Hydroxides such as triethylamine, pyridine, and urea can be used.

[0230] The amount of hydroxyl agent used is preferably about 0.9 to 3 times the amount of (meth)acrylic acid halide charged. If too little is used, a large amount of untrapped acid remains, and if too much is used, it becomes difficult to remove the excess hydroxyl agent.

[0231] 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 the reaction is finished, unreacted (meth)acrylic acid halide, salts generated by the reaction, and reaction solvents are removed by methods such as distillation, adsorption, filtration, and washing, thereby obtaining an acrylic compound containing hydrocarbon terminal groups.

[0232] Additionally, 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 generated (meth)acrylic acid esters can be removed in the same manner as the unreacted (meth)acrylic acid halide, but they may also be used while remaining.

[0233] The hydrocarbon terminal group-containing compound represented by general formula (1) obtained from a reaction such as the example above may be used as a single substance by performing purification and isolation operations such as concentration, column purification, distillation, and extraction, or the reaction solution may be used as a mixture containing the hydrocarbon terminal group-containing compound represented by general formula (1), or it may be used after further dilution with an organic solvent.

[0234] In addition, another embodiment of the present invention is a curable composition for forming a film comprising a non-fluorinated hydrocarbon terminal group containing a 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. As the non-fluorinated hydrocarbon terminal group containing compound, it is preferable to have one or more types of hydrocarbon terminal group containing compounds that do not contain fluorine atoms in the structure represented by the above formula (1).

[0235] The amount of a non-fluorinated hydrocarbon terminal group-containing compound, particularly a hydrocarbon terminal group-containing compound represented by Formula (1), is preferably 0.005 mass% or more and 99.9 mass% or less of the total components excluding the solvent of the curable composition for film formation. In particular, when used for a thick film (e.g., a cured film of 0.5 to 100 μm), it is preferably 0.005 mass% or more and less than 50 mass% of the total components excluding the solvent of the curable composition for film formation, and when used for a thin film (e.g., a cured film of 1 to 500 nm), it is preferably 50 mass% or more and 99.9 mass% or less of the total components excluding the solvent of the curable composition for film formation.

[0236] It is preferable that the curable composition for forming a film according to the present invention incorporates a polymerization initiator. As the polymerization initiator, it is particularly preferable to contain a photopolymerization initiator, thereby enabling the curable composition for forming an active energy beam curable film.

[0237] The photopolymerization initiator is not particularly limited as long as it is capable of curing the above-mentioned non-fluorinated hydrocarbon terminal group-containing compound (or the non-fluorinated acrylic compound described below when incorporated) by ultraviolet irradiation, but preferably, for example, acetophenone, benzophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenyl 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, Examples include 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-octanedion-1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyloxime), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, etc. Even if Type 1 is used alone, two or more types may be used in combination.

[0238] The thermal polymerization initiator is not particularly limited as long as it is capable of curing the above-mentioned non-fluorinated hydrocarbon terminal group-containing compound (or the non-fluorinated acrylic compound described later when combined) by heating, but preferably, examples include diacyl peroxides, ketone peroxides, hydroperoxides, dialkyl peroxides, peroxyesters, azo compounds, persulfates, etc., and may be used alone or in combination of two or more types.

[0239] The content of the polymerization initiator can be appropriately determined according to the curing conditions and the physical properties of the cured product produced by the curable composition for forming a film, but for example, it is preferable to have an amount of 0.001 to 15 parts by mass, particularly 0.01 to 10 parts by mass, per 100 parts by mass of the total non-volatile components excluding the solvent in the curable composition for forming a film. If the amount added is less than this, the curability may be reduced, and if it is more than this, there is a risk that the influence on the physical properties after curing will increase.

[0240] The curable composition for forming a film according to the present invention preferably also contains a solvent. By containing a solvent, the viscosity of the curable composition is reduced, making it easier to handle.

[0241] As such solvents, it is preferable that they be non-fluorinated solvents, including hydrocarbon solvents (petroleum benzene, 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, Examples include propyl acetate, butyl acetate, pentyl acetate, propylene glycol monomethyl ether acetate, etc.

[0242] The amount of 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 components excluding the solvent of the curable composition for film formation.

[0243] The curable composition for forming a film according to the present invention is not particularly limited as long as it forms a cured product by irradiation with active energy rays, such as ultraviolet rays or electron beams, or by heating, as an optional component; however, when used as a curable composition for forming a film that is curable by active energy rays, it is particularly preferable to include a non-fluorinated acrylic compound (excluding the above-mentioned non-fluorinated hydrocarbon terminal group containing compound). By including a non-fluorinated acrylic compound, the cured film formed by curing this curable composition for forming a film can exhibit excellent film properties such as liquid repellency, antifouling properties, wear resistance, and high hardness.

[0244] Non-fluorinated acrylic compounds can be used regardless of whether they are single-function or multi-function. In particular, it is preferable to include an acrylic compound having two or more acrylic groups in one molecule.

[0245] These acrylic compounds may be those having two or more acrylic groups or α-substituted acrylic groups in one molecule, for example, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, ethylene oxide-modified di(meth)acrylate of isocyanuric acid, EO-modified tri(meth)acrylate of isocyanuric acid, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerol tri(meth)acrylate, tris(meth)acryloyloxyethylphosphate, hydrogen phthalate-(2,2,2-tri-(meth)acryloyloxymethyl)ethyl, glycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate. Examples include (meth)acrylic compounds with 2 to 6 functions or multiple functions such as 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 ethylene oxide, propylene oxide, epichlorohydrin, fatty acids, alkyl modified products, or epoxy resins of these (meth)acrylic compounds; and copolymers in which (meth)acrylic groups are introduced into the side chains of acrylic acid ester copolymers.

[0246] In addition, urethane acrylates, those obtained by reacting a polyisocyanate with a (meth)acrylate having hydroxyl groups, those obtained by reacting a polyisocyanate with a (meth)acrylate having hydroxyl groups in a polyester of a terminal diol, and those obtained by reacting a polyisocyanate with an excess diisocyanate with a polyol with a (meth)acrylate having hydroxyl groups may also be used. Among these, urethane acrylates are preferred, such as those 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-cyclohexyl isocyanate), 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane, and diphenylmethane diisocyanate.

[0247] In addition, it may be a mixture of at least two types of acrylic compounds, comprising a polyfunctional acrylic compound having two or more acrylic groups or α-substituted acrylic groups in one molecule and not having urethane bonds, or a polyfunctional urethane acrylate having three or more acrylic groups or α-substituted acrylic groups in one molecule obtained by reacting the polyfunctional acrylic compound with an aliphatic polyisocyanate and an acrylic compound having hydroxyl groups.

[0248] In this case, polyfunctional acrylic compounds having two or more acrylic groups or α-substituted acrylic groups in one molecule and not having urethane bonds 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 modified from these with ethylene oxide or propylene oxide.

[0249] In addition, regarding 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, such as hexamethylene diisocyanate, norbornane diisocyanate, isophorone diisocyanate and their trimers, and their difunctional and trifunctional isocyanates, to which a polyisocyanate with two or more functions is obtained by reacting an aliphatic diol, an aliphatic polyol, and a polyacrylate having a hydroxyl group in a side chain, trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate, bis(2-(meth)acryloyloxyethyl)hydroxyethyl isocyanurate, pentaerythritol tri(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate, Dipentaerythritol penta(meth)acrylate and their ethylene oxide and propylene oxide modified forms may be reacted, or aliphatic polyols and polyacrylates having hydroxyl groups in their side chains may be reacted with acrylic compounds having isocyanate groups, such as 2-isocyanatoethyl(meth)acrylate or 1,1-(bisacryloyloxymethyl)ethylisocyanate.

[0250] In addition, as a non-fluorinated acrylic compound, in addition to the above compound, it may include a material in which the surface of a high molecular weight in the form of fine particles or the surface of an inorganic filler fine particle is modified with an acrylic group.

[0251] The above-mentioned non-fluorinated acrylic compounds can be used as a single type, but multiple corresponding compounds may also be used in combination to improve coating properties or the characteristics of the film after curing.

[0252] When incorporating a non-fluorinated acrylic compound, the amount of incorporation is preferably 20 to 1,000,000 parts by mass per 100 parts by mass of a non-fluorinated hydrocarbon terminal group-containing compound, and particularly preferably 100 to 100,000 parts by mass.

[0253] In addition to the above, the curable composition for forming a film according to the present invention may also incorporate active energy beam reactive compounds other than acrylic groups, such as thiol compounds or maleimide compounds, polymerization inhibitors, antistatic agents, defoaming agents, viscosity modifiers, light stabilizers, heat stabilizers, antioxidants, surfactants, coloring agents, and polymer or inorganic fillers. The structures of these are not particularly limited, and known materials may be used within a range that does not impair the purpose of the present invention.

[0254] In addition, the curable composition for forming a film of the present invention may include unreacted raw materials and reaction intermediates before introducing the reactive group of the hydrocarbon terminal group-containing compound represented by Formula (1).

[0255] In addition, as a curable composition for film formation, existing compositions commercially available by various companies under the classifications of paints, inks, hardcoats, etc., as active energy beam curable compositions or thermosetting compositions incorporating various additives, may be used as part or all of the curable composition for film formation. Even when using commercially available hardcoats in this manner, polymerization inhibitors, antistatic agents, defoaming agents, viscosity modifiers, light stabilizers, heat stabilizers, antioxidants, surfactants, colorants, and fillers may be added and incorporated depending on the purpose.

[0256] Recently, as it is predicted that restrictions on the use, sale, and emission of fluorine-containing compounds will be strengthened due to PFAS regulations, it is preferable that the curable composition for film formation of the present invention be made of a composition that does not contain fluorine atoms (i.e., does not incorporate a component containing fluorine atoms).

[0257] The curable composition for forming a film according to the present invention, obtained as described above, contains a hydrocarbon chain terminal group as a water-repellent and antifouling imparting group having high packing properties, and a hydrocarbon terminal group containing a specific structure having a polymerizable carbon-carbon double bond as an active energy beam curable group or a thermosetting group, thereby obtaining a curable film with excellent water repellency, antifouling properties, and wear resistance.

[0258] Furthermore, the present invention provides a cured film formed by applying the curable composition for forming a film of the present invention to a substrate surface and curing it, and an article having the cured film on its surface. As described above, by using the curable composition for forming a film of the present invention, it becomes possible to form a cured film (cured resin layer) having excellent surface characteristics on the surface of a substrate. In particular, it is useful for imparting water repellency, antifouling properties, and abrasion resistance to the surface of an acrylic hardcoat. As a result, it is difficult for fingerprints, sebum, sweat, and other contaminants, as well as cosmetics, to adhere to the surface of the substrate (article), and a hardcoat surface with excellent removable properties can be imparted to the substrate (article). For this reason, the curable composition for forming a film of the present invention can be suitably used as a coating film or protective film on the surface of a substrate (article) that may be contaminated by human contact, cosmetics, etc.

[0259] A cured film (cured resin layer) formed using the curable composition for forming a film of the present invention can be cured by directly coating or depositing the curable composition for forming a film of the present invention onto the surface of an article to be endowed with characteristics (e.g., an article having a surface substrate such as paper, cloth, metal and its oxide, glass, plastic, ceramic, quartz, etc.) and curing it, or by coating or depositing the curable composition for forming a film of the present invention onto various substrate films (e.g., films such as polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, vinyl chloride resin, polystyrene, acrylic resin, polycarbonate, polyphenylene sulfide, polyetheretherketone, polyethersulfone, aramid, polyimide, etc.) to produce a cured film, and attaching this film to the surface of the target article, thereby endowing various articles with characteristics.

[0260] Here, the coating method of the curable composition for forming a film according to the present invention is not particularly limited, but known coating methods such as roll coating, gravure coating, flow coating, dip coating, spray coating, spin coating, bar coating, and screen printing may be used. The deposition method may be either a resistance heating method or an electron beam heating method, and is not particularly limited. After coating, the coated film is cured by irradiating it with an active energy beam or by heating.

[0261] Here, when curing the coating film by irradiating it with active energy rays, any active energy ray, such as electron beams or ultraviolet rays, may be used, but ultraviolet rays are particularly preferred. Mercury lamps, metal halide lamps, and LED lamps are suitable as ultraviolet sources. Regarding the ultraviolet irradiation dose, if it is too low, uncured components may remain, and if it is too high, there is a possibility of degradation of the coating film and the substrate; therefore, 10 to 10,000 mJ / cm² is used. 2 , especially 20–4,000 mJ / cm² 2It is desirable that it be within the range. In addition, to prevent inhibition of curing by oxygen, the irradiation atmosphere during UV irradiation may be replaced with an inert gas that does not contain oxygen molecules, such as nitrogen, carbon dioxide, or argon, or the surface of the coating film may be covered with a UV-transmitting protective layer having release properties and UV irradiation may be performed over it, or if the substrate is UV-transmitting, UV irradiation may be performed from the opposite side of the coated surface of the substrate after covering the surface of the coating film with a release protective layer. In addition, to effectively level the coating film, the coating film and the substrate may be heated by any method, such as a hot air dryer, before and during UV irradiation.

[0262] In addition, when curing by heating, any heat source such as an oven or a hot plate may be used. As for the heating conditions, it is preferable to heat at 40 to 200°C, particularly 50 to 150°C for 30 minutes to 36 hours, particularly 1 to 24 hours.

[0263] In addition, since the appropriate thickness of the cured film (cured resin layer) formed using the curable composition for film formation of the present invention varies significantly depending on the method of use, etc., it is not limited to a specific thickness.

[0264] For example, when a large amount of a non-fluorinated acrylic compound is incorporated in a curable composition for forming a film, specifically, when the ratio of a compound containing a non-fluorinated hydrocarbon terminal group in 100 parts by weight of the total components excluding the solvent of the curable composition for forming a film of the present invention is 0.005 parts by weight or more and less than 50 parts by weight, the preferred film thickness of the cured film is 0.5 to 100 μm. On the other hand, when a large amount of a compound containing a non-fluorinated hydrocarbon terminal group is incorporated in a curable composition for forming a film, specifically, when the ratio of a compound containing a non-fluorinated hydrocarbon terminal group in 100 parts by weight of the total components excluding the solvent of the curable composition for forming a film of the present invention is 50 parts by weight or more and 99.9 parts by weight or less, the preferred film thickness of the cured film is 1 to 500 nm.

[0265] In addition, in the present invention, the film thickness can be measured by a thin film thickness measuring device based on optical interferometry (optical interferometry film thickness measuring device, reflection spectroscopic film thickness measuring device), or a thin film thickness measuring device based on spectroscopic ellipsometry (spectroscopic ellipsometer), etc.

[0266] In addition, the cured film (cured resin layer) formed using the curable composition for film formation of the present invention preferably has a water contact angle of 90° or more, preferably 95° or more, at a temperature of 25° and a relative humidity of 40%, and also preferably has an oleic acid contact angle of 40° or more, preferably 45° or more. Furthermore, in the present invention, the contact angle is a value measured under the condition of a droplet of 2μL using a contact angle meter Drop Master (manufactured by Kyowa Kaimen Kagaku Co., Ltd.). In addition, to achieve the above contact angle, it is preferable that the curable composition for film formation is uniformly mixed.

[0267] The article of the present invention has a cured film formed by the curable composition for forming a film of the present invention on the surface of a substrate, and the cured film functions as a coating film and a surface protection film of the article.

[0268] Examples include casings for various devices carried by people, such as tablet computers, portable (communication) information terminals such as mobile phones and smartphones, laptops, digital media players, watch-type and glasses-type wearable computers, digital cameras, digital video cameras, and electronic book readers; surfaces of display operation devices such as liquid crystal displays, plasma displays, organic EL displays, back-projection displays, fluorescent display tubes (VFDs), field emission projection displays, CRTs, toner-based displays, and TV screens; exteriors of automobiles; polished surfaces of pianos and furniture; architectural stone surfaces such as marble; decorative building materials around water, such as toilets, bathtubs, and washbasins; protective glass for art exhibitions; covers for shop windows, display cases, and photo frames; glass for wristwatches and automobile windows; glass for trains and aircraft windows; transparent glass or transparent plastic (acrylic, polycarbonate, etc.) components such as automobile headlights and taillights; and various mirror components.

[0269] In particular, various devices equipped with display input devices that perform operations on the screen using a person's finger or palm, such as touch panel displays, etc., can be cited as display input devices such as tablet computers, laptops, watch-type wearable computers, activity trackers, 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, automatic cash withdrawal and deposit devices, automatic cash payers, vending machines, digital signage (electronic signboards), security system terminals, POS terminals, various controllers such as remote controllers, and panel switches for vehicle-mounted devices.

[0270] In addition, articles of the present invention may include optical recording media such as magneto-optical discs and optical discs; optical components and optical devices such as eyeglass lenses, camera lenses, projector lens prisms, lens sheets, pellicle films, polarizers, optical filters, lenticular lenses, Fresnel lenses, anti-reflective films, optical fibers or optical couplers, or various protective components for these devices.

[0271] Examples

[0272] The present invention will be described in more detail below by presenting synthetic examples, comparative synthetic examples, and examples and comparative examples, but the present invention is not limited by the following examples. In addition, in the following examples, the room temperature is 25°C and the atmospheric pressure is under atmospheric pressure. Also, the melting point is a value measured under atmospheric pressure by differential scanning calorimetry (DSC), and the measurement method conforms to JIS K 7121. The measurement conditions are described below. Starting temperature: -150°C, ending temperature: 200°C, rising / falling rate: 10°C / min, atmosphere gas: nitrogen (flow rate: 50 mL / min). The film thickness is a value measured by a reflection spectroscopic film thickness meter (measurement range 400 nm to 800 nm).

[0273] [Synthesization Example 1] Synthesis of Compound (b)

[0274] In a reaction vessel, the following formula (a)

[0275]

[0276] 100.00g of the compound represented by (1.97×10⁻⁶ -1 100.0 g of methanol (mol), mixed with 100.0 mol of sodium borohydride, stirred at room temperature for 1 hour under a nitrogen atmosphere. Thereafter, 14.91 g of sodium borohydride (3.94 × 10⁻⁶ mol) was added to the system. -1 After mixing (mol), the mixture was stirred at room temperature for 12 hours under a nitrogen atmosphere. Subsequently, the solvent and unreacted materials were removed by washing with water and vacuum distillation, yielding 91.21 g of product.

[0277] The obtained product is 1It was confirmed by H-NMR that it is a compound represented by the following formula (b).

[0278]

[0279] [Synthesization Example 2] Synthesis of hydrocarbon terminal group containing compound (A)

[0280] In a reaction vessel, the following formula (b) obtained in Synthesis Example 1

[0281]

[0282] 10.00g of the compound represented by (1.96×10⁻⁶ -2 mol), THF 100.0 g, triethylamine 2.97 g (2.94 × 10⁻⁶ -2 (mol) was mixed and stirred at 40°C for 1 hour under a nitrogen atmosphere. Thereafter, 2.66 g (2.94 × 10⁻⁶ mol) of acrylic acid chloride was added to the system. -2 After mixing (mol), the mixture was stirred at 40°C for 6 hours under a nitrogen atmosphere. Subsequently, the solvent, by-products, and unreacted materials were removed by washing with water and vacuum distillation, yielding 8.78 g of product.

[0283] The obtained compound is 1 It was confirmed by H-NMR that the structure is represented by the following formula (A). In addition, the melting point of the obtained compound at atmospheric pressure was 28°C.

[0284]

[0285] [Synthesization Example 3] Synthesis of hydrocarbon terminal group containing compound (B)

[0286] In the reaction vessel, the following formula (c)

[0287]

[0288] 10.00g of compound represented by (1.92×10⁻⁶ -2 mol), THF 100.0 g, triethylamine 2.91 g (2.88 × 10⁻⁶ -2(mol) was mixed and stirred at 40°C for 1 hour under a nitrogen atmosphere. Thereafter, 2.61 g (2.88 × 10⁻⁶) of acrylic acid chloride was added to the system. -2 After mixing (mol), the mixture was stirred at 40°C for 6 hours under a nitrogen atmosphere. Subsequently, the solvent, by-products, and unreacted materials were removed by washing with water and vacuum distillation, yielding 8.62 g of product.

[0289] The obtained compound is 1 It was confirmed by H-NMR that the structure is represented by the following formula (B). In addition, the melting point of the obtained compound at atmospheric pressure was 32°C.

[0290]

[0291] [Synthesization Example 4] Synthesis of hydrocarbon terminal group containing compound (C)

[0292] In a reaction vessel, the following formula (b) obtained in Synthesis Example 1

[0293]

[0294] 10.00g of the compound represented by (1.96×10⁻⁶ -2 mol), 2-isocyanatoethyl acrylate 3.04 g (2.15 × 10⁻⁶ -2 50.00 g of THF (mol), 0.03 g of tetrakis(2-ethylhexyl) orthotitanium

[0295] The obtained compound is 1 It was confirmed by H-NMR that the structure is represented by the following formula (C). In addition, the melting point of the obtained compound at atmospheric pressure was 58°C.

[0296]

[0297] [Synthesization Example 5] Synthesis of hydrocarbon terminal group containing compound (D)

[0298] In the reaction vessel, the following formula (d)

[0299]

[0300] 10.00g of the compound represented by (3.06×10⁻⁶ -2 mol), 2-isocyanatoethyl acrylate 4.75 g (3.37 × 10⁻⁶ -2 50.00 g of THF (mol), 0.03 g of tetrakis(2-ethylhexyl) orthotitanium

[0301] The obtained compound is 1 It was confirmed by H-NMR that the structure is represented by the following formula (D). In addition, the melting point of the obtained compound at atmospheric pressure was 34°C.

[0302]

[0303] [Synthesization Example 6] Synthesis of a hydrocarbon terminal group-containing compound (E)

[0304] In a reaction vessel, the following formula (b) obtained in Synthesis Example 1

[0305]

[0306] 10.00g of the compound represented by (1.96×10⁻⁶ -2 mol), 2-(2-methacryloyloxyethyloxy)ethyl isocyanate 4.29 g (2.15 × 10⁻⁶ -2 50.00 g of THF (mol), 0.03 g of tetrakis(2-ethylhexyl) orthotitanium

[0307] The obtained compound is 1 It was confirmed by H-NMR that the structure is represented by the following formula (E). In addition, the melting point of the obtained compound at atmospheric pressure was 56°C.

[0308]

[0309] [Synthesization Example 7] Synthesis of hydrocarbon terminal group containing compound (F)

[0310] In the reaction vessel, the following formula (c)

[0311]

[0312] 10.00g of compound represented by (1.92×10⁻⁶ -2 mol), 2-isocyanatoethyl acrylate 2.98 g (2.11 × 10⁻⁶ -2 50.00 g of THF (mol) was mixed and aged at 50°C for 12 hours. Afterwards, the solvent and unreacted materials were removed by vacuum distillation to obtain 12.11 g of product.

[0313] The obtained compound is 1 It was confirmed by H-NMR that the structure is represented by the following formula (F). In addition, the melting point of the obtained compound at atmospheric pressure was 38°C.

[0314]

[0315] [Synthesization Example 8] Synthesis of hydrocarbon terminal group containing compound (G)

[0316] In the reaction vessel, the following formula (e)

[0317]

[0318] 10.00g of the compound represented by (2.83×10⁻⁶ -2 mol), 2-isocyanatoethyl acrylate 4.39 g (3.11 × 10⁻⁶ -2 50.00 g of THF (mol) was mixed and aged at 50°C for 12 hours. Afterwards, the solvent and unreacted materials were removed by vacuum distillation to obtain 12.72 g of product.

[0319] The obtained compound is 1 It was confirmed by H-NMR that the structure is represented by the following formula (G). In addition, the melting point of the obtained compound at atmospheric pressure was 21°C.

[0320]

[0321] [Synthesization Example 9] Synthesis of Hydrocarbon Terminal Group-Containing Compound (H)

[0322] In the reaction vessel, the following formula (f)

[0323]

[0324] 10.00g of the compound represented by (3.07×10⁻⁶ -2 mol), 2-isocyanatoethyl acrylate 4.77 g (3.38 × 10⁻⁶ -2 50.00 g of THF (mol) was mixed and aged at 50°C for 12 hours. Afterwards, the solvent and unreacted materials were removed by vacuum distillation to obtain 14.32 g of product.

[0325] The obtained compound is 1 It was confirmed by H-NMR that the structure is represented by the following formula (H). In addition, the melting point of the obtained compound at atmospheric pressure was 48°C.

[0326]

[0327] [Synthesization Example 10] Synthesis of Hydrocarbon Terminal Group-Containing Compound (I)

[0328] In the reaction vessel, the following formula (c)

[0329]

[0330] 10.00g of compound represented by (1.92×10⁻⁶ -2 mol), 2-isocyanatoethyl methacrylate 3.28 g (2.11 × 10⁻⁶ -2 50.00 g of THF (mol) was mixed and aged at 50°C for 12 hours. Afterwards, the solvent and unreacted materials were removed by vacuum distillation to obtain 13.03 g of product.

[0331] The obtained compound is 1 It was confirmed by H-NMR that the structure is represented by the following formula (I). In addition, the melting point of the obtained compound at atmospheric pressure was 47°C.

[0332]

[0333] [Synthesization Example 11] Synthesis of a hydrocarbon terminal group-containing compound (J)

[0334] In the reaction vessel, the following formula (c)

[0335]

[0336] 10.00g of compound represented by (1.92×10⁻⁶ -2 mol), 2-(2-methacryloyloxyethyloxy)ethyl isocyanate 4.21g (2.11×10⁻⁶ -2 50.00 g of THF (mol) was mixed and aged at 50°C for 12 hours. Afterwards, the solvent and unreacted materials were removed by vacuum distillation to obtain 13.64 g of product.

[0337] The obtained compound is 1 It was confirmed by H-NMR that the structure is represented by the following formula (J). In addition, the melting point of the obtained compound at atmospheric pressure was 39°C.

[0338]

[0339] [Synthesization Example 12] Synthesis of Hydrocarbon Terminal Group-Containing Compound (K)

[0340] In the reaction vessel, the following formula (c)

[0341]

[0342] 10.00g of compound represented by (1.92×10⁻⁶ -2 mol), 1,1-(bisacryloyloxymethyl)ethyl isocyanate 5.05g (2.11×10⁻⁶ -2 50.00 g of THF (mol) was mixed and aged at 50°C for 12 hours. Afterwards, the solvent and unreacted materials were removed by vacuum distillation to obtain 14.50 g of product.

[0343] The obtained compound is 1 It was confirmed by H-NMR that the structure is represented by the following formula (K). In addition, the melting point of the obtained compound at atmospheric pressure was 20°C.

[0344]

[0345] [Comparative Synthesis Example 1] Synthesis of hydrocarbon terminal group containing compound (X)

[0346] In a reaction vessel, the following formula (g)

[0347]

[0348] 10.00g of compound represented by (3.70×10⁻⁶ -2 mol), 2-isocyanatoethyl acrylate 5.74 g (4.07 × 10⁻⁶ -2 50.00 g of THF (mol), 0.03 g of tetrakis(2-ethylhexyl) orthotitanium

[0349] The obtained compound is 1 It was confirmed by H-NMR that the structure is represented by the following formula (X). In addition, the melting point of the obtained compound at atmospheric pressure was 29°C.

[0350]

[0351] [Comparative Synthesis Example 2] Synthesis of Hydrocarbon Terminal Group-Containing Compound (Y)

[0352] In the reaction vessel, the following formula (h)

[0353]

[0354] 10.00g of the compound represented by (3.71×10⁻⁶ -2 mol), 2-isocyanatoethyl acrylate 5.76 g (4.08 × 10⁻⁶ -2 50.00 g of THF (mol) was mixed and aged at 50°C for 12 hours. Afterwards, the solvent and unreacted material were removed by vacuum distillation to obtain 15.01 g of product.

[0355] The obtained compound is 1 It was confirmed by H-NMR that the structure is represented by the following formula (Y). In addition, the melting point of the obtained compound at atmospheric pressure was 42°C.

[0356]

[0357] [Examples 1–22, Comparative Examples 1, 2, 3]

[0358] active energy line Preparation of a curable composition for forming a curable film

[0359] A solution (curable composition for forming active energy beam curable films) was prepared by mixing compounds (A) to (K) synthesized in the above synthesis examples and compounds (X) and (Y) synthesized in comparative synthesis examples in the ratios shown in Tables 1 and 2 below.

[0360]

[0361]

[0362] A-9550: Dipentaerythritol polyacrylate (A-9550, manufactured by Shinnakamura Kagaku Kogyo Co., Ltd.)

[0363] AcOBu: Butyl acetate

[0364] I-184: 1-Hydroxycyclohexylphenylketone (Irgacure 184, manufactured by Chiba Japan Co., Ltd.)

[0365] Production of coating and hardened film (1)

[0366] Each solution (curable composition for forming an active energy beam curable film) prepared in Examples 1 to 11 and Comparative Examples 1 to 3 was spin-coated onto a polycarbonate substrate. After coating, the solvent was evaporated and leveled by nitrogen flow in an inert box for 5 minutes under room temperature conditions. Then, using a conveyor-type metal halide UV irradiation device (manufactured by Panasonic Denko, Inc.), an integrated irradiation dose of 1,600 mJ / cm² was applied in a nitrogen atmosphere. 2 The composition was cured by irradiating the coated surface with ultraviolet rays, and a cured film with a thickness of 5 μm was obtained.

[0367] Production of coating and hardened film (2)

[0368] A solution prepared by mixing 100 parts by mass of dipentaerythritol polyacrylate (A-9550, manufactured by Shinnakamura Kagaku Kogyo Co., Ltd.), 142 parts by mass of butyl acetate, and 3 parts by mass of 1-hydroxycyclohexylphenyl ketone (Irgacure 184, manufactured by Chiba Japan Co., Ltd.) was spin-coated onto a polycarbonate substrate. After coating, the substrate was heated at 80°C for 1 minute to allow for solvent evaporation and leveling. Subsequently, under room temperature conditions, nitrogen flow was applied in an inert box for 5 minutes. Finally, using a conveyor-type metal halide UV irradiation device (manufactured by Panasonic Denko Co., Ltd.), an integrated irradiation dose of 1,600 mJ / cm² was applied in air. 2 A cured film with a thickness of 5㎛ was obtained by irradiating the coated surface with ultraviolet rays to cure it.

[0369] Each solution prepared in Examples 12 to 22 (curable composition for forming active energy beam curable films) was applied by spin coating onto the obtained cured film. After coating, the mixture was heated to 80°C for 1 minute to allow for solvent evaporation and leveling. Subsequently, nitrogen flow was applied for 5 minutes in an inert box under room temperature conditions. Finally, using a conveyor-type metal halide UV irradiation device (manufactured by Panasonic Denko, Inc.), an integrated irradiation dose of 1,600 mJ / cm² was applied in a nitrogen atmosphere. 2 The composition was cured by irradiating the coated surface with ultraviolet rays, and a cured film with a thickness of 5 nm was obtained.

[0370] In addition to visually measuring the appearance (transparency) of the cured film obtained above, water contact angle measurement, oleic acid contact angle measurement, magic ink removal ability evaluation, and water contact angle measurement after a wear test were performed as evaluations of antifouling properties and wear resistance, respectively, using the methods described below. The results of these are shown in Tables 3 and 4. Furthermore, regarding appearance (transparency), transparent was marked with ○ and non-transparent was marked with ×.

[0371] Evaluation of antifouling properties

[0372] [Water contact angle measurement, Oleic acid contact angle measurement]

[0373] For the cured film prepared above, the contact angle of the cured film with respect to water and oleic acid was measured using a contact angle meter Drop Master (manufactured by Kyowa Kaimen Kagaku Co., Ltd.) (droplet: 2 μL, temperature: 25℃, relative humidity: 40%).

[0374] [Evaluation of Magic Ink Removability]

[0375] Regarding the cured film prepared above, a straight line of 3 cm was drawn with a magic pen (Magic Ink Large, manufactured by Teranishi Kagaku Kogyo Co., Ltd.), and after drying at room temperature for 3 minutes, the magic ink was wiped off with a tissue. ○ was marked where the magic ink mark was wiped off, and × was marked where it was not wiped off.

[0376] Evaluation of wear resistance

[0377] [Measurement of water contact angle after wear test]

[0378] The surface of the hardened film was subjected to a reciprocating abrasion test using a friction abrasion tester (manufactured by Shinto Kagaku Co., Ltd.), and the number contact angle was measured after the test. The evaluation was based on the average number of cycles performed with N=4.

[0379] The test conditions are shown below.

[0380] Friction material: Bonstar Steel Wool #0000 (Made by Bonstar Co., Ltd.)

[0381] Distance traveled (one way): 40mm

[0382] Movement speed: 4,800 mm / min

[0383] Load: 300gf / 1×1cm 2

[0384] Wear count: 5,000 times

[0385]

[0386]

[0387] The cured films (Examples 1–22) of the curable composition for forming active energy beam curable films using the hydrocarbon terminal group-containing compounds (Compounds (A)–(K)) of the present invention exhibited excellent film smoothness, water repellency, and antifouling properties. Furthermore, high abrasion resistance was confirmed as the water contact angle did not significantly decrease in the abrasion test. On the other hand, the cured films (Comparative Examples 1 and 2) of the curable composition for forming active energy beam curable films using hydrocarbon terminal group-containing compounds (Compounds (X), (Y)) having a structure different from that of the hydrocarbon terminal group-containing compounds of the present invention exhibited low water repellency, antifouling properties, and abrasion resistance. Additionally, the cured film (Comparative Example 3) of the curable composition for forming active energy beam curable films without incorporating hydrocarbon terminal group-containing compounds showed no water repellency or antifouling properties at all.

Claims

Claim 1 The following general formula (1) [In the formula, X is R 1 O-, or R 2 R 3 N- and, R 1 is a monovalent hydrocarbon group having 20 to 80 carbon atoms in a straight, branched, or cyclic form, and R 2 is a monovalent hydrocarbon group having 10 to 40 carbon atoms in a straight, branched, or cyclic form, and R 3 It is a hydrogen atom, or a monovalent hydrocarbon group having 10 to 40 carbon atoms in a straight, branched, or cyclic form, and R 2 and R 3 The total number of carbon atoms contained therein is 20 or more and 80 or less, and Y is a single bond, or the following structural formula * -C(=O)- ** * -C(=O)-O- ** * -C(=O)-NR 4 - ** * -C(=S)-NR 4 - ** (In the formula, * is a bonding hand that combines with X in general formula (1), ** is a bonding hand that combines with Z in general formula (1), and R 4 A hydrocarbon terminal group-containing compound that does not contain fluorine atoms in its structure, represented by [a divalent organic group represented by a hydrogen atom, or a linear, branched, or cyclic monovalent hydrocarbon group having 1 to 8 carbon atoms, Z is a 2 to 4-valent hydrocarbon group having 1 to 20 carbon atoms that may include a single bond, or one or more selected from oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms, V is a monovalent hydrocarbon group having 2 to 20 carbon atoms containing a polymerizable carbon-carbon double bond that may independently include oxygen atoms and / or nitrogen atoms, and m is an integer from 1 to 3.] Claim 2 A hydrocarbon terminal group containing compound in which, in the above formula (1), V is represented by the following formula. (In the formula, * is a bonding hand that bonds with Z in general formula (1), and R' is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms.) Claim 3 In claim 1, in the above formula (1), Y is the following structural formula * -C(=O)-NH- ** A hydrocarbon terminal group containing compound represented by (where * is a bonding hand that bonds with X in general formula (1), and ** is a bonding hand that bonds with Z in general formula (1).) Claim 4 In claim 1, a hydrocarbon terminal group containing compound in which m is 1 in the above formula (1). Claim 5 A hydrocarbon terminal group containing a divalent hydrocarbon group having 1 to 10 carbon atoms, wherein Z in formula (1) may include a single bond, or an oxygen atom and / or a nitrogen atom. Claim 6 In claim 1, a hydrocarbon terminal group containing acrylic compound represented by the following general formula (2). (In the formula, X is as above, Z' is a divalent hydrocarbon group having 1 to 10 carbon atoms that may include an oxygen atom and / or a nitrogen atom, and R" is a hydrogen atom or a methyl group.) Claim 7 A hydrocarbon terminal group containing acrylic compound represented by the following general formula (3) in claim 1. (during food, R 2 , R 3 ...is as described above, Z' is a divalent hydrocarbon group having 1 to 10 carbon atoms that may include an oxygen atom and / or a nitrogen atom, and R" is a hydrogen atom or a methyl group.) Claim 8 In paragraph 7, in the above formula (3), R 2 and R 3 This is a linear monovalent hydrocarbon group having 10 to 40 carbon atoms, and R 2 and R 3 A hydrocarbon terminal group-containing compound with the same number of carbon atoms. Claim 9 In claim 1, a hydrocarbon terminal group-containing compound having a melting point of 20°C or higher. Claim 10 A curable composition for forming a film comprising a non-fluorinated hydrocarbon terminal group containing 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. Claim 11 A curable composition for forming a film, wherein, in claim 10, the non-fluorinated hydrocarbon terminal group-containing compound is a hydrocarbon terminal group-containing compound described in any one of claims 1 to 9. Claim 12 A curable composition for forming a film, further comprising a polymerization initiator in claim 10. Claim 13 In Clause 12, a curable composition for forming a film that is an active energy beam curable type. Claim 14 A curable composition for forming a film as described in claim 10, further containing a solvent in claim 10. Claim 15 A curable composition for forming a film, further comprising a non-fluorinated acrylic compound, according to claim 10. Claim 16 A curable composition for forming a film according to claim 10, comprising not containing fluorine atoms. Claim 17 A cured film formed by curing the curable composition for forming a film described in paragraph 10. Claim 18 In claim 17, a cured film having a water contact angle of 90° or more and an oleic acid contact angle of 40° or more at a drop volume of 2 μL, a temperature of 25°, and a relative humidity of 40%. Claim 19 Article having a hardened film on its surface as described in paragraph 17.

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