Compound containing a hydrocarbon terminal group, curable composition for coating film formation, cured coating film, and article

Abstract

By including a compound represented by formula (1) and containing a hydrocarbon-terminated group that does not contain fluorine atoms in the structure of a curable composition cured by active energy rays such as ultraviolet light or electron beams, or a thermosetting composition, it is possible to impart excellent water repellency, stain resistance, and abrasion resistance to the resulting cured film. [X is R] 1 O- or R 2 R 3 N-, R 1 R is a monovalent hydrocarbon group with 20 to 80 carbon atoms. 2 R is a monovalent hydrocarbon group with 10 to 40 carbon atoms. 3 For H or R 2 R 2 and R 3 The total number of carbon atoms in the sample is 20–80, and Y is a single bond or one of the following groups: -C(=O)-C(=O)-O-C(=O)-NR 4 -C (=S) -NR 4 (* represents the binding terminal with X, ** represents the binding terminal with Z, R) 4 Z is a single bond or a divalent to tetravalent hydrocarbon group that may contain O, S, N, or Si; V is a monovalent hydrocarbon group containing a polymerizable carbon-carbon double bond that may contain O or N; and m is 1 to 3.

Description

Technical Field

[0001] This invention relates to compounds containing hydrocarbon terminal groups, and more specifically, to compounds containing hydrocarbon terminal groups that do not contain fluorine atoms in their structure, which can impart excellent water repellency, stain resistance, and abrasion resistance to the resulting cured film by compounding with an active energy ray curable composition or a thermosetting composition containing the hydrocarbon terminal group, a cured film formed by curing the cured film forming composition, and an article having the cured film on the surface of a substrate. Background Technology

[0002] Currently, hard coating is widely used as a means of protecting the surface of resin molded articles. This involves forming a hard, cured resin layer (hard coating) on ​​the surface of the molded article, making it less susceptible to damage. The materials constituting the hard coating are often thermosetting compositions or compositions cured by active energy rays such as ultraviolet light or electron beams.

[0003] With the expansion of the application fields of resin molded products and the trend towards high added value, the demand for high functionality of cured resin layers (hard coatings) is surging. One such demand is to endow hard coatings with stain resistance. This is achieved by giving the surface of the hard coating properties such as water repellency and oil repellency, making it less prone to getting dirty or easy to remove even if it does get dirty.

[0004] As methods for imparting antifouling properties to hard coatings, there are methods of applying and / or fixing a fluorinated antifouling agent to the surface of a temporarily formed hard coating, and methods of adding a fluorinated curing component to a curable resin composition before curing, thereby simultaneously forming a hard coating and imparting antifouling properties. For example, Japanese Patent Application Publication No. 6-211945 (Patent Document 1) discloses the manufacture of a hard coating that imparts antifouling properties by adding a fluoroalkyl acrylate to an acrylic curable resin composition and then curing it.

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

[0006] On the other hand, fluorinated compounds, such as perfluorooctanoic acid (PFOA), tend to be difficult to decompose in nature and have a high accumulation rate. Therefore, in recent years, a wide range of fluorinated compounds have been classified as per- / polyfluoroalkyl compounds (PFAS), and it is predicted that the regulation of fluorinated compounds as PFAS will lead to stricter restrictions on their use, sale, and emissions. Consequently, there has been a need in recent years to develop non-fluorinated antifouling agents that do not contain fluorine atoms. However, when using conventional non-fluorinated compounds for the aforementioned applications, the resulting cured films have not yet reached levels of water repellency, antifouling properties, and abrasion resistance that are practically satisfactory.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 6-211945

[0010] Patent Document 2: Japanese Patent Application Publication No. 2010-53114

[0011] Patent Document 3: Japanese Patent Application Publication No. 2010-138112

[0012] Patent Document 4: Japanese Patent Application Publication No. 2010-285501 Summary of the Invention

[0013] The problem that the invention aims to solve

[0014] The present invention was made in view of the above-mentioned actual situation, and its object is to provide a compound containing hydrocarbon terminal groups that does not contain fluorine atoms in its structure, which can impart excellent water repellency, stain resistance and wear resistance to the obtained cured film by adding it to an active energy ray curable composition or a thermosetting composition such as ultraviolet light or electron beam; a film-forming curable composition containing the compound containing hydrocarbon terminal groups; a cured film formed by curing the film-forming curable composition; and an article having the cured film on the surface of a substrate.

[0015] Methods for solving problems

[0016] In order to solve the above objectives, the inventors conducted in-depth research and found that: as the above-mentioned non-fluorine antifouling agent, the compound containing a hydrocarbon terminal group represented by the general formula (1) described below, which does not contain fluorine atoms in the structure, is contained in the active energy ray curable composition or thermosetting composition, which is cured by ultraviolet light, electron beam or other active energy rays. This can impart excellent water repellency, antifouling and wear resistance to the obtained cured film, thus completing the present invention.

[0017] [Chemistry 1]

[0018]

[0019] [In the formula, X is R] 1 O- or R 2 R 3 N-, R 1 It is a monovalent hydrocarbon group with 20 to 80 carbon atoms, in the form of straight chains, branches, or rings. 2 It is a monovalent hydrocarbon group with 10 to 40 carbon atoms, in the form of straight chains, branches, or rings, R. 3 R is a monovalent hydrocarbon group consisting of 10 to 40 carbon atoms, either a hydrogen atom or in a straight-chain, branched, or cyclic form. 2 and R 3 The total number of carbon atoms contained in it is 20 or more and less than 80, and Y is a single bond or a divalent organic group represented by the following structural formula.

[0020] -C (=O)

[0021] -C (=O) -O

[0022] -C (=O) -NR 4

[0023] -C (=S) -NR 4

[0024] (In the formula, * is the junction end that combines with X in general formula (1), ** is the junction end that combines with Z in general formula (1), R 4 Z is a hydrocarbon group with 1 to 8 carbon atoms in a monovalent state, consisting of a hydrogen atom, or in a straight-chain, branched, or cyclic form. Z is a single bond, or may contain one or more types of carbon atoms selected from oxygen, sulfur, nitrogen, and silicon, with 1 to 20 carbon atoms in a divalent to tetravalent state. V is independently a hydrocarbon group with 2 to 20 carbon atoms containing a polymeric carbon-carbon double bond, which may contain oxygen and / or nitrogen atoms. m is an integer from 1 to 3.

[0025] Therefore, the present invention provides a compound containing a hydrocarbon terminal group, a curable composition for forming a film containing the compound containing the hydrocarbon terminal group, a cured film formed by curing the cured composition for forming the film, and an article having the cured film on its surface.

[0026] [1] A compound containing a hydrocarbon terminal group that does not contain a fluorine atom in its structure, represented by the following general formula (1).

[0027] [Chemistry 2]

[0028]

[0029] [In the formula, X is R] 1 O- or R 2 R 3 N-, R 1 It is a monovalent hydrocarbon group with 20 to 80 carbon atoms, in the form of straight chains, branches, or rings. 2 It is a monovalent hydrocarbon group with 10 to 40 carbon atoms, in the form of straight chains, branches, or rings, R. 3 R is a monovalent hydrocarbon group consisting of 10 to 40 carbon atoms, either a hydrogen atom or in a straight-chain, branched, or cyclic form. 2 and R 3 The total number of carbon atoms contained in it is 20 or more and less than 80, and Y is a single bond or a divalent organic group represented by the following structural formula.

[0030] -C (=O)

[0031] -C (=O) -O

[0032] -C (=O) -NR 4

[0033] -C (=S) -NR 4

[0034] (In the formula, * is the junction end that combines with X in general formula (1), ** is the junction end that combines with Z in general formula (1), R 4 A hydrocarbon group with 1 to 8 carbon atoms, consisting of hydrogen atoms, or in a straight-chain, branched, or cyclic form.

[0035] Z is a single bond, or a hydrocarbon group with 1 to 20 carbon atoms and a valent charge of 2 to 4, selected from oxygen, sulfur, nitrogen, and silicon atoms; V is independently a hydrocarbon group with 2 to 20 carbon atoms and a valent charge of 2 to 20 containing a polymerizable carbon-carbon double bond, which may contain oxygen and / or nitrogen atoms; m is an integer from 1 to 3.

[0036] [2] The compound containing a hydrocarbon terminal group according to [1], wherein V in the above formula (1) is represented by the following formula.

[0037] [Chemistry 3]

[0038]

[0039] (In the formula, * is the bonding end that bonds with Z in general formula (1), and R' is a monovalent hydrocarbon group with 1 to 8 carbon atoms.)

[0040] [3] The compound containing a hydrocarbon terminal group according to [1] or [2], wherein, in the above formula (1), Y is a group represented by the following structural formula.

[0041] -C (=O)-NH

[0042] (In the formula, * is the junction end that combines with X in general formula (1), and ** is the junction end that combines with Z in general formula (1).)

[0043] [4] The compound containing a hydrocarbon terminal group according to any one of [1] to [3], wherein m is 1 in the above formula (1).

[0044] [5] A compound containing a hydrocarbon terminal group according to any one of [1] to [4], wherein, in the above formula (1), Z is a single bond or a divalent hydrocarbon group containing 1 to 10 carbon atoms that may contain oxygen atoms and / or nitrogen atoms.

[0045] [6] The compound containing a hydrocarbon terminal group according to any one of [1] to [5] is an acrylic compound containing a hydrocarbon terminal group represented by the following general formula (2).

[0046] [Chemistry 4]

[0047]

[0048] (In the formula, X is the same as above, Z' is a divalent hydrocarbon group with 1 to 10 carbon atoms that may contain oxygen atoms and / or nitrogen atoms, and R” is a hydrogen atom or a methyl group.)

[0049] [7] The compound containing a hydrocarbon terminal group according to any one of [1] to [5] is an acrylic compound containing a hydrocarbon terminal group represented by the following general formula (3).

[0050] [Chemistry 5]

[0051]

[0052] (where R) 2 R 3 As above, Z' is a divalent hydrocarbon group with 1 to 10 carbon atoms that may contain oxygen and / or nitrogen atoms, and R” is a hydrogen atom or a methyl group.

[0053] [8] According to [7], the compound containing a hydrocarbon terminal group, wherein, in the above formula (3), R 2 and R3 It is a linear hydrocarbon group with 10 to 40 carbon atoms and a monovalent valence, R 2 and R 3 They have the same number of carbon atoms.

[0054] [9] The compound containing a hydrocarbon terminal group according to any one of [1] to [8] has a melting point of 20°C or higher.

[0055]

[10] A curable composition for film formation, comprising a non-fluorinated compound containing a hydrocarbon terminal group 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.

[0056]

[11] The curable composition for film formation according to

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

[0057]

[12] The curable composition for film formation according to

[10] further contains a polymerization initiator.

[0058]

[13] The curable composition for film formation according to

[12] is of the active energy ray curable type.

[0059]

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

[10] to

[13] further contains a solvent.

[0060]

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

[10] to

[14] further contains a non-fluorinated acrylic compound.

[0061]

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

[10] to

[15] comprises a compound that does not contain fluorine atoms.

[0062]

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

[10] to

[16] .

[0063]

[18] The cured film according to

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

[0064]

[19] An article having a cured film on its surface as described in

[17] or

[18] .

[0065] The effects of the invention

[0066] Cured films obtained using curable compositions for film formation containing hydrocarbon-terminated groups and free of fluorine atoms in the structure of this invention can exhibit excellent water repellency, stain resistance, and abrasion resistance. Therefore, these hydrocarbon-terminated compounds can be used as antifouling additives to impart water repellency, stain resistance, and abrasion resistance, and are applicable to hard coatings, paints, resins, antireflective coating compositions, etc., that are cured by active energy rays such as ultraviolet light and electron beams, or thermosetting. Detailed Implementation

[0067] In this invention, the term "acrylic compounds" is a general term for compounds having an acryloyl group (hereinafter also referred to as acryloyl) or an α-substituted acryloyl group (hereinafter also referred to as α-substituted acryloyl), and also includes compounds in which two or more acryloyl groups or α-substituted acryloyl groups are optionally introduced into the side chains or ends of various polymers. Furthermore, in this invention, the term "(meth)acrylate" refers to one or both of acrylate and methacrylate; the term "(meth)acryloyl" refers to one or both of acryloyl and methacryloyl (hereinafter also referred to as methylpropionyl); and the term "(meth)acryloyl halide" refers to one or both of acryloyl halide and methacryloyl halide.

[0068] The compounds containing hydrocarbon terminal groups of the present invention are represented by the following general formula (1), wherein the compounds containing hydrocarbon terminal groups do not contain fluorine atoms in their structure.

[0069] [Chemistry 6]

[0070]

[0071] [In the formula, X is R] 1 O- or R 2 R 3 N-, R 1 It is a monovalent hydrocarbon group with 20 to 80 carbon atoms, in the form of straight chains, branches, or rings. 2 It is a monovalent hydrocarbon group with 10 to 40 carbon atoms, in the form of straight chains, branches, or rings, R. 3 R is a monovalent hydrocarbon group consisting of 10 to 40 carbon atoms, either a hydrogen atom or in a straight-chain, branched, or cyclic form. 2 and R 3 The total number of carbon atoms contained in it is 20 or more and less than 80, and Y is a single bond or a divalent organic group represented by the following structural formula.

[0072] -C (=O)

[0073] -C (=O) -O

[0074] -C (=O) -NR 4

[0075] -C (=S) -NR 4

[0076] (In the formula, * is the junction end that combines with X in general formula (1), ** is the junction end that combines with Z in general formula (1), R 4 A hydrocarbon group with 1 to 8 carbon atoms, consisting of hydrogen atoms, or in a straight-chain, branched, or cyclic form.

[0077] Z is a single bond, or a hydrocarbon group with 1 to 20 carbon atoms and a valent charge of 2 to 4, selected from oxygen, sulfur, nitrogen, and silicon atoms; V is independently a hydrocarbon group with 2 to 20 carbon atoms and a valent charge of 2 to 20 containing a polymerizable carbon-carbon double bond, which may contain oxygen and / or nitrogen atoms; m is an integer from 1 to 3.

[0078] The compounds containing hydrocarbon terminal groups of the present invention must have hydrocarbon chain terminal groups with a specified number of carbon atoms or more and polymerizable carbon-carbon double bonds in their structure. By having hydrocarbon chain terminal groups with a specified number of carbon atoms or more that exhibit high packing capacity and polymerizable carbon-carbon double bonds that are active energy-curable groups or thermosetting groups, when the compound is compounded and cured in a curable composition for film formation, the compound segregates on the surface of the cured film, forming a hard layer through the packing of hydrocarbon chains, thus immobilizing it. The resulting cured film exhibits excellent water repellency, stain resistance, and abrasion resistance. Furthermore, by combining and compounding with other components, sometimes there is no segregation even on the outermost surface, but the effect of significantly improving the water repellency of the cured film itself can be expected. Moreover, in the present invention, the term "packing" refers to the degree to which multiple hydrocarbon chains are oriented in one direction and closely on the surface of the cured film.

[0079] In the above equation (1), X is R 1 O- or R 2 R 3 N-, R 1 It is a monovalent hydrocarbon group with 20 to 80 carbon atoms, in the form of straight chains, branches, or rings. 2 It is a monovalent hydrocarbon group with 10 to 40 carbon atoms, in the form of straight chains, branches, or rings, R. 3 R is a monovalent hydrocarbon group consisting of 10 to 40 carbon atoms, either a hydrogen atom or in a straight-chain, branched, or cyclic form. 2 and R 3 The total number of carbon atoms contained in it is more than 20 and less than 80.

[0080] If R1 If the number of carbon atoms is less than the upper limit mentioned above, the compatibility with the curable composition for film formation is good; if it is greater than the lower limit mentioned above, the filling capacity of the hydrocarbon chain is improved, and the characteristics of the group that imparts water repellency and antifouling properties can be fully exerted.

[0081] If R 2 and R 3 If the total number of carbon atoms contained in the composition is less than the upper limit mentioned above, the composition has good compatibility with the curable composition for film formation. If it is greater than the lower limit mentioned above, the filling capacity of the hydrocarbon chain is improved, and the characteristics of the group that imparts water repellency and antifouling properties can be fully utilized.

[0082] As R 1 More preferably, it is a monovalent hydrocarbon group with 21 to 60 carbon atoms in a straight-chain or branched form, and particularly preferably a monovalent hydrocarbon group with 22 to 44 carbon atoms in a straight-chain or branched form.

[0083] As R 1 The following groups can be listed as examples.

[0084] [Chemistry 7]

[0085]

[0086] (In the formula, * represents the bonding end that bonds with the oxygen atom in X, y is an integer of 1 or more independently, and the total number of carbon atoms in each structure is an integer of 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.)

[0087] As R 2 More preferably, it is a monovalent hydrocarbon group with 11 to 30 carbon atoms, either linear or branched; particularly preferably, it is a monovalent hydrocarbon group with 12 to 22 carbon atoms, either linear or branched. As R 3 More preferably, it is a monovalent hydrocarbon group with 11 to 30 carbon atoms in a straight-chain or branched form, and particularly preferably a monovalent hydrocarbon group with 12 to 22 carbon atoms in a straight-chain or branched form. As R 2 and R 3 The total number of carbon atoms contained therein is more preferably 21 or more and 60 or less, and particularly preferably 22 or more and 44 or less.

[0088] As R 2 The following groups can be listed as examples.

[0089] [Chemistry 8]

[0090]

[0091] (In the formula, * is the bonding end that bonds with the nitrogen atom in X, y' is an integer of 1 or more independently, and the total number of carbon atoms in each structure is an integer of 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.)

[0092] As R 3 Examples include hydrogen atoms and the groups shown below.

[0093] [Chemistry 9]

[0094]

[0095] (In the formula, * represents the bonding end that bonds with the nitrogen atom in X, y' is an integer of 1 or more independently, and the total number of carbon atoms in each structure is an integer of 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.)

[0096] As X, the following groups can be listed.

[0097] [Chemistry 10]

[0098]

[0099] (In the formula, * is the bonding end that bonds with Y in general formula (1), y is an integer of 1 or more independently, and the total number of carbon atoms in each structure is an integer of 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.)

[0100] From the perspective of exhibiting excellent antifouling properties, it is particularly preferred that X has two CN3 groups in its structure. Generally, solid surfaces having -CN3 are known to have lower surface free energy and superior antifouling properties compared to solid surfaces having only -CN2-. As such X, the groups shown below are preferred.

[0101] [Chemistry 11]

[0102]

[0103] (In the formula, * is the bonding end that bonds with Y in general formula (1), y is an integer of 1 or more independently, and the total number of carbon atoms in each structure is an integer of 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.)

[0104] In the above formula (1), Y is a single bond or a divalent organic group represented by the following structural formula.

[0105] -C (=O)

[0106] -C (=O) -O

[0107] -C (=O) -NR 4

[0108] -C (=S) -NR 4

[0109] (In the formula, * is the junction end that combines with X in general formula (1), ** is the junction end that combines with Z in general formula (1), R 4 A hydrocarbon group with 1 to 8 carbon atoms, consisting of hydrogen atoms, or in a straight-chain, branched, or cyclic form.

[0110] Among them, R 4 A hydrocarbon group consisting of 1 to 8 monovalent carbon atoms, which is a hydrogen atom, or a straight-chain, branched, or cyclic group. Examples of monovalent hydrocarbon groups consisting of 1 to 8 monovalent carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, and octyl alkyl groups; vinyl, allyl, and propenyl alkenyl groups; phenyl, tolyl, xylyl, and naphthyl aryl groups; and benzyl, phenylethyl, and phenylpropyl aralkyl groups. As R 4 More preferably, it is a hydrogen atom.

[0111] As Y, a group represented by the following structural formula is particularly preferred.

[0112] -C (=O)-NH

[0113] (In the formula, * is the junction end that combines with X in general formula (1), and ** is the junction end that combines with Z in general formula (1).)

[0114] When Y has the structure described above, the compatibility with the curable composition for film formation becomes particularly good.

[0115] In formula (1) above, Z is a single bond, or may contain one or more hydrocarbon groups with 1 to 20 carbon atoms selected from oxygen, sulfur, nitrogen and silicon atoms, and with a 2 to 4 valence. When Y is a single bond, Z is preferably a single bond.

[0116] The hydrocarbon group may contain one or more of one to two carbon atoms with a valence of 1 to 20, selected from oxygen, sulfur, nitrogen and silicon atoms. Specifically, examples include hydrocarbon groups with a valence of 1 to 20 carbon atoms that are linear, branched or cyclic, and hydrocarbon groups with a valence of 1 to 20 carbon atoms that are linear, branched or cyclic, as well as hydrocarbon groups containing one or more of one to two carbon atoms with a valence of 1 to 20, selected from ether, carbonyl (ketone), ester, carbonate, -CN(ON)-, sulfinyl, sulfonyl, thioester, thiocarbonate, thiocarbamate, amino, amide, carbamate, urea, nitrogen-containing heterocyclic groups (oxazolyl, imidazolyl, triazolyl, etc.), silanediol, silanearyl, and linear, branched or cyclic organopolysiloxane groups that are linear, branched or cyclic, and hydrocarbon groups with a valence of 1 to 20 carbon atoms that are linear, branched or cyclic.

[0117] Z is particularly preferred as a single bond, or a divalent hydrocarbon group with 1 to 10 carbon atoms that may contain oxygen and / or nitrogen atoms. When Z is a divalent hydrocarbon group, the compound containing the hydrocarbon terminal group becomes a monoacrylate compound, which exhibits good compatibility with curable compositions for film formation.

[0118] As Z, the group shown below is preferred.

[0119] [Chemistry 12]

[0120]

[0121] [Chemistry 13]

[0122]

[0123] [Chemistry 14]

[0124]

[0125] [Chemistry 15]

[0126]

[0127] [Chemistry 16]

[0128]

[0129] (In the formula, * is the junction end that combines with Y in general formula (1), ** is the junction end that combines with V in general formula (1), q is an integer from 1 to 10, r, s, and t are each integers from 1 to 8, 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.)

[0130] In formula (1) above, V is independently a monovalent hydrocarbon group with 2 to 20 carbon atoms that may contain an oxygen atom and / or a nitrogen atom and has a polymerizable carbon-carbon double bond. Specifically, examples of groups containing a polymerizable carbon-carbon double bond include acryloyl, α-substituted acryloyl, acryloyloxy, α-substituted acryloyloxy, acrylamino, α-substituted acrylamino, vinyl ether, cinnamic acid, and sorbic acid.

[0131] V is preferably represented by the following formula: acryloyl group, α-substituted acryloyl group, acryloyloxy group, or α-substituted acryloyloxy group.

[0132] [Chemistry 17]

[0133]

[0134] (In the formula, * is the bonding end that bonds with Z in general formula (1), and R' is a 1-valent hydrocarbon group with 1 to 8 carbon atoms.)

[0135] Wherein, R' is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms. 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; alkenyl groups such as vinyl, allyl, and propenyl; aryl groups such as phenyl, tolyl, xylyl, and naphthyl; and aralkyl groups such as benzyl, phenylethyl, and phenylpropyl. More preferably, R' is a hydrogen atom or a methyl group.

[0136] As V, acryloyloxy or α-substituted acryloyloxy, represented by the following formula, is particularly preferred.

[0137] [Chemistry 18]

[0138]

[0139] (In the formula, * is the junction end that connects with Z in general formula (1), and R' is the same as above.)

[0140] Specifically, the group shown below is preferred as such a V.

[0141] [Chemistry 19]

[0142]

[0143] (In the formula, * represents the junction end that connects with Z in general formula (1).)

[0144] In the above formula (1), m is an integer from 1 to 3, preferably 1. When m is larger than the above upper limit, the proportion of hydrocarbon chain terminal groups that impart water repellency and antifouling properties decreases relatively, and the water repellency and antifouling properties decrease.

[0145] The compound represented by formula (1) above, containing a hydrocarbon terminal group, does not contain fluorine atoms in its structure. As a result, its recalcitrantness and accumulation in nature are reduced compared to conventional fluorine compounds.

[0146] By changing the combination of X, Y, Z, and V in the formula (1) above, several compounds containing hydrocarbon terminal groups can be obtained.

[0147] As a compound containing a hydrocarbon terminal group represented by the above formula (1), an acrylic compound containing a hydrocarbon terminal group represented by the following general formula (2) is more preferred.

[0148] [Chemistry 20]

[0149]

[0150] (In the formula, X is the same as above, Z' is a divalent hydrocarbon group with 1 to 10 carbon atoms that may contain oxygen atoms and / or nitrogen atoms, and R” is a hydrogen atom or a methyl group.)

[0151] In the above formula (2), Z' is a divalent hydrocarbon group with 1 to 10 carbon atoms that may contain oxygen atoms and / or nitrogen atoms, preferably the group shown below.

[0152] [Chemistry 21]

[0153]

[0154] (In the formula, * is the bonding end that bonds with the nitrogen atom in general formula (2), ** is the bonding end that bonds with the oxygen atom in general formula (2), q is an integer from 1 to 10, r and s are each integers from 1 to 8, and the sum of r and s is an integer from 2 to 10.)

[0155] When the compound containing a hydrocarbon terminal group of the present invention is an acrylic compound containing a hydrocarbon terminal group represented by the above general formula (2), the cured film obtained by adding the compound to an active energy ray curable composition such as ultraviolet light or electron beam or a thermosetting composition has better water repellency, stain resistance and wear resistance.

[0156] As a particularly preferred example of an acrylic compound containing a hydrocarbon terminal group represented by the above formula (2), an example represented by the following formula can be illustrated.

[0157] [Chemistry 22]

[0158]

[0159] [Chemistry 23]

[0160]

[0161] [Chemistry 24]

[0162]

[0163] [Chemistry 25]

[0164]

[0165] [Chemistry 26]

[0166]

[0167] [Chemistry 27]

[0168]

[0169] [Chemistry 28]

[0170]

[0171] [Chemistry 29]

[0172]

[0173] As a compound containing a hydrocarbon terminal group represented by the above formula (1), an acrylic compound containing a hydrocarbon terminal group represented by the following general formula (3) is particularly preferred.

[0174] [Chemistry 30]

[0175]

[0176] (where R) 2 R 3 (Z' and R are the same as above.)

[0177] When the compound containing a hydrocarbon terminal group of the present invention is an acrylic compound containing a hydrocarbon terminal group represented by the above general formula (3), the cured film obtained by adding the compound to an active energy ray curable composition such as ultraviolet light or electron beam or a thermosetting composition has particularly excellent water repellency, stain resistance and wear resistance.

[0178] As a particularly preferred example of an acrylic compound containing a hydrocarbon terminal group represented by the above formula (3), an example represented by the following formula can be illustrated.

[0179] [Chemistry 31]

[0180]

[0181] [Chemistry 32]

[0182]

[0183] [Chemistry 33]

[0184]

[0185] [Chemistry 34]

[0186]

[0187] In the above formula (3), R 2 and R 3 It is a linear hydrocarbon group with 10 to 40 carbon atoms and a monovalent valence, with R being particularly preferred. 2 and R 3 The number of carbon atoms is equal. In R 2 and R 3 When the above conditions are met, the distance between hydrocarbon groups is close, thereby further improving the filling capacity of hydrocarbon groups in compounds containing hydrocarbon terminal groups. By adding the compound to a curable film obtained by adding it to a composition that can be cured by active energy rays such as ultraviolet light or electron beams, or a thermosetting composition, the compound forms a hard layer on its outermost surface, thus exhibiting superior wear resistance.

[0188] As examples of compounds containing hydrocarbon terminal groups represented by the above formula (1), in addition to examples of acrylic compounds containing hydrocarbon terminal groups represented by formula (2) and acrylic compounds containing hydrocarbon terminal groups represented by formula (3), examples represented by the following formulas can also be exemplified.

[0189] [Chemistry 35]

[0190]

[0191] [Chemistry 36]

[0192]

[0193] [Chemistry 37]

[0194]

[0195] The compound containing a hydrocarbon terminal group 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, the compound forms a hard layer on its outermost surface when it is added to a curable film obtained by adding the compound to a composition that can be cured by active energy rays such as ultraviolet light or electron beams or a thermosetting composition, thus exhibiting superior wear resistance.

[0196] In this specification, the melting point is the value measured using a differential scanning calorimeter (DSC) at atmospheric pressure. The measurement method follows JIS K 7121. The measurement conditions are described below: Starting temperature: -150℃, Ending temperature: 200℃, Heating / cooling rate: 10℃ / min, Atmosphere gas: Nitrogen (flow rate: 50 mL / min).

[0197] In the case of the compound containing a hydrocarbon terminal group represented by the above general formula (1), especially the acrylic compound containing a hydrocarbon terminal group represented by the above general formula (2) or the above general formula (3), the following methods can be listed as a method for preparing the compound.

[0198] Acrylic compounds containing hydrocarbon terminal groups can be produced by mixing alcohol or amine compounds containing hydrocarbon terminal groups with isocyanate compounds containing (meth)acryloyl groups and carrying out an addition reaction.

[0199] Alcohols containing hydrocarbon terminal groups are represented by the following formula (4), and amines containing hydrocarbon terminal groups are represented by formula (5).

[0200] R 1 OH (4)

[0201] R 2 R 3 NH (5)

[0202] (where R) 1 R 2 R 3 Same as above.

[0203] Among them, the following examples can be cited as preferred examples of alcohol compounds represented by formula (4).

[0204] [Chemistry 38]

[0205]

[0206] [Chemistry 39]

[0207]

[0208] [Chemistry 40]

[0209]

[0210] [Chemistry 41]

[0211]

[0212] Alcohols containing hydrocarbon terminal groups can be produced by reducing hydrides of aldehydes or ketones containing hydrocarbon terminal groups.

[0213] Examples of aldehyde compounds containing hydrocarbon terminal groups include the compounds shown below.

[0214] [Chemistry 42]

[0215]

[0216] Examples of ketone compounds containing hydrocarbon terminal groups include the compounds shown below.

[0217] [Chemistry 43]

[0218]

[0219] Sodium borohydride and lithium aluminum hydride are preferred reducing agents in hydride reduction.

[0220] These reducing agents are added in equimolar amounts to the reaction relative to the aldehyde or ketone compound containing a hydrocarbon terminal group, preferably to react completely with the aldehyde or ketone. Specifically, the reducing agent is preferably 1 equivalent or more and 5 equivalents or less relative to 1 equivalent of the aldehyde or ketone compound containing a hydrocarbon terminal group in the reaction system, and particularly preferably 1 equivalent or more and 3 equivalents or less.

[0221] For these reactions, the reaction can be carried out by diluting with an appropriate solvent as needed. Such a solvent can be used without particular restriction, as long as it does not react with aldehydes or ketones containing hydrocarbon terminal groups and reducing agents. Specifically, examples include hydrocarbon solvents (petroleum ether, 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 tert-butyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, propylene glycol dimethyl ether, etc.), and alcohol solvents (propylene glycol monomethyl ether, butanol, isopropanol, methanol, etc.).

[0222] There is no particular limitation on the amount of solvent used, but it is preferably 20 times or less, and particularly preferably 15 times or less, relative to the total mass of the reactants. If too much solvent is used, the reaction rate may decrease significantly. As a lower limit for the amount of solvent used, it is preferably 0.5 times or more relative to the total mass of the reactants.

[0223] 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.

[0224] After the reaction is complete, unreacted reducing agents and reaction solvents are removed by methods such as distillation, adsorption, filtration, and washing, thereby obtaining alcohol compounds containing hydrocarbon terminal groups.

[0225] As preferred examples of amine compounds represented by formula (5), the examples shown below can be cited.

[0226] [Chemistry 44]

[0227]

[0228] [Chemistry 45]

[0229]

[0230] [Chemistry 46]

[0231]

[0232] [Chemistry 47]

[0233]

[0234] In addition, isocyanate compounds containing (meth)acryloyl groups are represented by the following formula (6).

[0235]

[0236] (In the formula, Z' and R” are the same as above.)

[0237] Among them, the following examples are preferred examples of isocyanate compounds containing (meth)acryloyl groups.

[0238] O=C=N-CH2CH2-OC(=O)-CH=CH2

[0239] O=C=N-CH2CH2-OC(=O)-C(CH3)=CH2

[0240] O=C=N-CH2CH2-O-CH2CH2-OC(=O)-C(CH3)=CH2

[0241] These isocyanate compounds containing (meth)acrylyl groups are preferably added in an equimolar or greater quantity relative to the total amount of active hydrogen in the alcohol or amine compounds containing hydrocarbon terminal groups, and reacted to allow all active hydrogen to react. Specifically, the amount of isocyanate compounds containing (meth)acrylyl groups is preferably 1 equivalent or more and 2 equivalents or less relative to 1 equivalent of the alcohol or amine compounds containing hydrocarbon terminal groups in the reaction system, and particularly preferably 1 equivalent or more and 1.4 equivalents or less. If there is an excessive amount of isocyanate compounds containing (meth)acrylyl groups, it becomes difficult to remove the residual isocyanate compounds containing (meth)acrylyl groups after the reaction.

[0242] These reactions can be carried out by diluting with a suitable solvent as needed. As such a solvent, any solvent that does not react with the hydroxyl groups of alcohols or amines containing hydrocarbon terminal groups, or the isocyanate groups of isocyanate compounds containing (meth)acryloyl groups, can be used without particular restriction. Specifically, examples include hydrocarbon solvents (petroleum ether, toluene, xylene, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, octane (n-octane, isooctane, etc.), nonane (n-nonane, isononane, etc.)), ketone solvents (acetone... The solvents used include ketones (methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc.), ether solvents (tetrahydrofuran (THF), dipropyl ether, dibutyl ether, methyl cyclopentanyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, propylene glycol dimethyl ether, etc.), alcohol solvents (propylene glycol monomethyl ether, butanol, isopropanol, etc.), and ester solvents (ethyl acetate, propyl acetate, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, etc.). These solvents can be removed after the reaction using known methods such as vacuum distillation, or, depending on the intended use, can be used directly as a diluent.

[0243] There is no particular limitation on the amount of solvent used, but it is preferably 20 times or less, and particularly preferably 15 times or less, relative to the total mass of the reactants. If too much solvent is used, the reaction rate may decrease significantly. As a lower limit for the amount of solvent used, it is preferably more than 1 times the total mass of the reactants.

[0244] Additionally, polymerization inhibitors can be added as needed during the reaction. There are no particular restrictions on the type of polymerization inhibitor, but inhibitors that are also used for acrylic compounds can generally be used. Specifically, examples include hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, and butylated hydroxytoluene.

[0245] The amount of polymerization inhibitor used is determined by the reaction conditions, the purification conditions after the reaction, and the final use conditions, and there are no particular restrictions. Relative to the total mass of the reaction components, it is preferably 0.01 to 5000 ppm, and particularly preferably 0.1 to 500 ppm.

[0246] In addition, a suitable catalyst may be added as needed during the reaction. Examples of catalysts include alkyl tin esters such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctanoate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dioctanoate, and stannous dioctanoate; titanate esters or titanium chelates such as tetraisopropoxytitanium, tetra-n-butoxytitanium, tetra(2-ethylhexyloxy)titanium [alias: tetra(2-ethylhexyl) titanate], dipropoxybis(acetylacetone)titanium, and isopropoxyoctanedioltitanium; zirconium tetraacetylacetone, zirconium tributoxymonoacetylacetone, zirconium monobutoxyacetylacetone bis(ethyl acetoacetate) zirconia, dibutoxybis(ethyl acetoacetate) zirconium, zirconium tetraacetylacetone, and zirconium chelates. These are not limited to one type and can be used as a mixture of two or more types.

[0247] The reaction rate is increased by adding preferably 0.01 to 2% by mass, more preferably 0.05 to 1% by mass, of these catalysts relative to the total mass of the reaction components.

[0248] The above reaction is carried out at a temperature of 0–120°C, preferably 10–70°C, for 1 minute to 500 hours, preferably 10 minutes to 48 hours. If the reaction temperature is too low, the reaction rate may be excessively slowed down; if the reaction temperature is too high, polymerization of (meth)acryloyl groups may occur as a side reaction.

[0249] After the reaction is completed, the unreacted isocyanate compounds and reaction solvents are removed by distillation, adsorption, filtration, washing and other methods, so as to obtain an acrylic compound containing a hydrocarbon terminal group represented by the above general formula (2) or the above general formula (3).

[0250] Alternatively, when the reaction stops, alcohols such as methanol and ethanol can be added to the system to form urethane bonds with unreacted isocyanate compounds. The resulting urethane (meth)acrylates can be removed using the same method as the unreacted isocyanate compounds, but they can also be used residually.

[0251] When the compound containing a hydrocarbon terminal group represented by the above general formula (1) of the present invention is a compound other than an acrylic compound containing a hydrocarbon terminal group represented by the above general formula (2) or the above general formula (3), the following methods can be listed as preparation methods for the compound.

[0252] For example, it is also possible to react alcohols or amines containing hydrocarbon terminal groups with (meth)acryloyl halides to form esters, thereby obtaining acrylic compounds containing hydrocarbon terminal groups.

[0253] Among them, for alcohols or amines containing hydrocarbon terminal groups, the same compounds as described above can be exemplified.

[0254] Acryloyl chloride and methacryloyl chloride are particularly preferred as (meth)acryloyl halides.

[0255] With respect to these (meth)acryloyl halides, it is preferable to add at least an equimolar amount relative to the alcohol or amine compound containing a hydrocarbon terminal group, allowing it to react completely. Specifically, relative to 1 equivalent of the alcohol or amine compound containing a hydrocarbon terminal group in the reaction system, it is preferable to have 1 equivalent or more and 2 equivalents or less, and particularly preferably 1 equivalent or more and 1.8 equivalents or less.

[0256] These reactions can be carried out by diluting with a suitable solvent as needed. Such a solvent can be used without particular restriction, as long as it does not react with alcohols or amines containing hydrocarbon terminal groups, or with the halogen atom of (meth)acryloyl halides. 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. The solvent can be removed after the reaction by known methods such as vacuum distillation, or it can be used directly as a diluent depending on the intended use.

[0257] There is no particular limitation on the amount of solvent used, but it is preferably 20 times or less, and particularly preferably 15 times or less, relative to the total mass of the reactants. If too much solvent is used, the reaction rate may decrease significantly. As a lower limit for the amount of solvent used, it is preferably more than 1 times the total mass of the reactants.

[0258] Additionally, polymerization inhibitors can be added as needed during the reaction. There are no particular restrictions on the type of polymerization inhibitor, but inhibitors that are also used for acrylic compounds can generally be used. Specifically, examples include hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, and butylated hydroxytoluene.

[0259] The amount of polymerization inhibitor used is determined by the reaction conditions, the purification conditions after the reaction, and the final use conditions, and there are no particular restrictions. Generally, it is preferred to be 0.01 to 5000 ppm relative to the total mass of the reaction components, and particularly preferred to be 0.1 to 500 ppm.

[0260] For this ester formation reaction, an alcohol or amine compound containing a hydrocarbon terminal group, an acid acceptor, and a solvent and polymerization inhibitor, as needed, are mixed and stirred at 0–100°C for 1 minute to 48 hours, and then (meth)acryloyl halide is mixed in.

[0261] As for acid-receiving agents, triethylamine, pyridine, urea, etc. can be used.

[0262] Regarding the amount of acid acceptor used, it is preferably about 0.9 to 3 times the molar amount of (meth)acryloyl halide. If it is too little, a large amount of uncaptured acid will remain; if it is too much, the removal of the remaining acid acceptor becomes difficult.

[0263] After mixing (meth)acrylyl halides, the temperature of the reaction mixture is maintained at 0–100°C, and stirring is continued for 30 minutes to 10 hours. After the reaction is complete, unreacted (meth)acrylyl halides, salts produced in the reaction, and reaction solvents are removed by methods such as distillation, adsorption, filtration, and washing, thereby obtaining an acrylic compound containing a hydrocarbon terminal group.

[0264] Alternatively, when the reaction stops, alcohols such as methanol and ethanol can be added to the system to esterify the unreacted (meth)acryloyl halide. The resulting (meth)acrylates can be removed using the same methods as the removal of unreacted (meth)acryloyl halides, or they can be used residually.

[0265] The compound containing a hydrocarbon terminal group, represented by the general formula (1), obtained by the reaction in the above example can also be purified and separated by concentration, column purification, distillation, extraction and other purification operations, and used as a single substance. In addition, the reaction solution can be used directly as a mixture containing the compound containing a hydrocarbon terminal group represented by the general formula (1), or it can be further diluted with organic solvents and used.

[0266] Furthermore, a further embodiment of the present invention comprises a curable composition for film formation of a non-fluorinated compound containing a hydrocarbon terminal group 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. Preferably, this non-fluorinated compound containing a hydrocarbon terminal group is one or more compounds containing hydrocarbon terminal groups that do not contain fluorine atoms in their structure, as represented by the above formula (1).

[0267] The amount of non-fluorinated compounds containing hydrocarbon terminal groups, particularly those represented by formula (1), in the curing composition for film formation is preferably 0.005% by mass or more and 99.9% by mass or less, excluding the solvent. Specifically, when used for thick films (e.g., cured films of 0.5–100 μm), the amount is preferably 0.005% by mass or more and less than 50% by mass, excluding the solvent. When used for thin films (e.g., cured films of 1–500 nm), the amount is preferably 50% by mass or more and 99.9% by mass or less, excluding the solvent.

[0268] The curable composition for film formation of the present invention preferably contains a polymerization initiator. As a polymerization initiator, a photopolymerization initiator is particularly preferred, thereby enabling the preparation of a curable composition for film formation that can be cured by active energy rays.

[0269] The photopolymerization initiator is not particularly limited as long as it can cure the aforementioned non-fluorinated compounds containing hydrocarbon terminal groups (and, in the case of compounding, the non-fluorinated acrylic compounds described later) by ultraviolet irradiation. However, preferably, examples include acetophenone, benzophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane. Ketones such as 1-, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyl oxime)], acetone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime), and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropane-1-one, etc., can be used alone or in combination with two or more.

[0270] The thermal polymerization initiator is not particularly limited to any thermal polymerization initiator that can cure the above-mentioned non-fluorinated compounds containing hydrocarbon terminal groups (and, in the case of compounding, the non-fluorinated acrylic compounds described later) by heating. However, it is preferable to include, for example, peroxydiacyl compounds, peroxyketides, hydroperoxides, dialkyl peroxides, peroxyesters, azo compounds, persulfates, etc. One type can be used alone, or two or more types can be used together.

[0271] The content of the polymerization initiator can be appropriately determined based on the physical properties of the cured product produced by the curable composition for film formation with the purpose of curing conditions. For example, it is preferably 0.001 to 15 parts by mass, particularly 0.01 to 10 parts by mass, relative to 100 parts by mass of the total non-volatile components excluding solvents in the curable composition for film formation. If the amount added is less than this, the curability may decrease; if it is more than this, the effect on the physical properties after curing may increase.

[0272] The curable composition for film formation of the present invention preferably further contains a solvent. By containing a solvent, the viscosity of the curable composition is reduced, making it easier to handle.

[0273] As such solvents, non-fluorinated solvents are preferred, and examples include hydrocarbon solvents (petroleum ether, 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 tert-butyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, propylene glycol dimethyl ether, etc.), alcohol solvents (propylene glycol monomethyl ether, butanol, isopropanol, etc.), and ester solvents (ethyl acetate, propyl acetate, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, etc.).

[0274] There is no particular limitation on the amount of solvent used, but it is preferably 1 to 1,000,000 parts by weight, and particularly preferably 10 to 500,000 parts by weight, relative to 100 parts by weight of all components of the curable composition for film formation excluding solvent.

[0275] The curable composition for coating formation of the present invention is not particularly limited to any other optional component, as long as it is cured by irradiation or heating with active energy rays such as ultraviolet light or electron beams. When used as an active energy ray curable coating composition, it is particularly preferred to include a non-fluorinated acrylic compound (excluding the aforementioned non-fluorinated compounds containing hydrocarbon terminal groups). By containing a non-fluorinated acrylic compound, the cured coating formed by curing the coating composition exhibits excellent film physical properties such as high hardness, in addition to liquid repellency, antifouling properties, and abrasion resistance.

[0276] As a non-fluorinated acrylic compound, it can be used whether it is monofunctional or polyfunctional. Acrylic compounds containing two or more acryloyl groups in one molecule are particularly preferred.

[0277] As such acrylic compounds, any compound having two or more acryloyl groups and / or α-substituted acryloyl groups in one molecule is acceptable. Examples include 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, ethylene oxide-modified di(meth)acrylate of isocyanurate, EO-modified tri(meth)acrylate of isocyanurate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerol tri(meth)acrylate, tri(meth)acryloyloxyethyl phosphate, and hydrogen phthalate (2,2,2-tri-(meth)acryloyloxymethyl) Ethyl ester, glycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di(trimethylolpropane) tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol polyacrylate, sorbitol hexa(meth)acrylate, and other 2- to 6-functional or multifunctional (meth)acrylate compounds; epoxy acrylates obtained by adding these (meth)acrylate compounds to acrylic acid with ethylene oxide, propylene oxide, epichlorohydrin, fatty acids, alkyl modifiers, or epoxy resins; and substances including copolymers in which (meth)acryloyl groups are introduced into the side chains of acrylate copolymers.

[0278] In addition, compounds obtained by reacting polyisocyanates with hydroxyl-containing (meth)acrylates can also be used, compounds obtained by reacting polyisocyanates and terminal diols with hydroxyl-containing (meth)acrylates, and compounds obtained by reacting polyisocyanates obtained by reacting polyols with excess diisocyanates with hydroxyl-containing (meth)acrylates. Preferably, urethane acrylates are prepared by reacting hydroxyl-containing (meth)acrylates selected from 2-hydroxyethyl methacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and pentaerythritol triacrylate with polyisocyanates selected from hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, lysine diisocyanate, norbornene diisocyanate, 1,3-bis(methyl isocyanate)cyclohexane, methylene bis(4-cyclohexyl isocyanate), 2-methyl-1,3-diisocyanate-cyclohexane, 2-methyl-1,5-diisocyanate-cyclohexane, and diphenylmethane diisocyanate.

[0279] Alternatively, it can be a mixture of at least two acrylic compounds comprising a polyfunctional acrylic compound having two or more acryloyl groups or α-substituted acryloyl groups in one molecule and not having a urethane bond, or a product comprising the polyfunctional acrylic compound and a polyfunctional carbamate acrylate having three or more acryloyl groups or α-substituted acryloyl groups in one molecule obtained by reacting an aliphatic polyisocyanate and an acrylic compound having hydroxyl groups.

[0280] In this case, examples of polyfunctional acrylic compounds having two or more acryloyl groups or α-substituted acryloyl groups in one molecule and without urethane bonds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di(trimethylolpropane) tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, and compounds modified with ethylene oxide or propylene oxide.

[0281] Furthermore, as polyfunctional carbamate acrylates having three or more acryloyl groups or α-substituted acryloyl groups in one molecule, obtained by reacting aliphatic polyisocyanates with acrylic compounds having hydroxyl groups, examples include polyisocyanates with more than two functions obtained by reacting hexamethylene diisocyanate, norbornene diisocyanate, isophorone diisocyanate and their trimers, and their difunctional and trifunctional isocyanates with aliphatic diols, aliphatic polyols and polyacrylates having hydroxyl groups in the side chain, and trimethylolpropane di(meth)acrylate. Products formed by reacting glycerol di(meth)acrylate, bis(2-(meth)acryloyloxyethyl)hydroxyethyl isocyanurate, pentaerythritol tri(meth)acrylate, di(trimethylolpropane)tri(meth)acrylate, dipentaerythritol penta(meth)acrylate and their ethylene oxide and propylene oxide modified forms, aliphatic polyols and polyacrylates with hydroxyl groups on the side chain and acrylic compounds with isocyanate groups such as 2-isocyanate-based ethyl(meth)acrylate and 1,1-(bisacryloyloxymethyl)ethyl isocyanate.

[0282] Furthermore, as a non-fluorinated acrylic compound, in addition to the compounds mentioned above, it may include products in which the surface of particulate high molecular weight particles or the surface of inorganic filler particles is modified with acryloyl groups.

[0283] The above non-fluorinated acrylic compounds can be used individually, or multiple compatible compounds can be mixed to improve coatability and the properties of the cured film.

[0284] When blending non-fluorinated acrylic compounds, the blending amount is preferably 20 to 1,000,000 parts by mass relative to 100 parts by mass of the non-fluorinated compound containing hydrocarbon terminal groups, and particularly preferably 100 to 100,000 parts by mass.

[0285] In addition to the above, the curable composition for film formation of the present invention can also be mixed with thiols, maleimide compounds, reactive energy radiation-reactive compounds other than acrylics, polymerization inhibitors, antistatic agents, defoamers, viscosity modifiers, light stabilizers, heat stabilizers, antioxidants, surfactants, colorants, and polymeric or inorganic fillers. There are no particular limitations on the structure of these components, and known substances can be used without prejudice to the purpose of the present invention.

[0286] Furthermore, the curable composition for film formation of the present invention may include unreacted raw materials and reaction intermediates before introducing the reactive groups of the compound containing hydrocarbon terminal groups represented by the above formula (1).

[0287] Furthermore, as a curable composition for film formation, an active energy ray curable composition or a thermosetting composition formulated with various additives can be made from conventional compositions sold by various companies in categories such as coatings, inks, and hard coatings, as part or all of the curable composition for film formation. Even when using commercially available hard coatings, polymerization inhibitors, antistatic agents, defoamers, viscosity modifiers, light stabilizers, heat stabilizers, antioxidants, surfactants, colorants, and fillers can be added and formulated according to the purpose.

[0288] In recent years, from the perspective of strengthening restrictions on the use, sale, and emission of fluorinated compounds as predicted by PFAS regulations, it is preferable that the curable composition for film formation of the present invention is composed of a substance that does not contain fluorine atoms (i.e., no components containing fluorine atoms are mixed in).

[0289] The curable composition for film formation of the present invention obtained as described above contains hydrocarbon chain terminal groups that have high filling capacity as groups that impart water repellency and antifouling properties, and compounds containing hydrocarbon terminal groups that have a specific structure of polymeric carbon-carbon double bonds that are active energy ray curable groups or thermosetting groups. Therefore, a cured film with excellent water repellency, antifouling properties and wear resistance is obtained.

[0290] Furthermore, this invention provides a cured film formed by coating a substrate surface with the aforementioned curable composition for film formation, curing the cured film thereon, and an article having the cured film on its surface. As described above, using the curable composition for film formation of this invention allows the formation of a cured film (cured resin layer) with excellent surface properties on the surface of the substrate. In particular, it can be used to impart water repellency, stain resistance, and abrasion resistance to the surface of acrylic hard coatings. As a result, dirt generated by fingerprints, sebum, sweat, human fat, cosmetics, etc., is difficult to adhere to, and a hard coating surface with excellent wipeability can be imparted to the substrate (article). Therefore, the curable composition for film formation of this invention is suitable for use as a coating film or protective film on the surface of a substrate (article) that comes into contact with the human body and may be soiled by human fat, cosmetics, etc.

[0291] Regarding the cured film (cured resin layer) formed using the curable composition for film formation of the present invention, the curable composition for film formation of the present invention is directly coated or vapor-deposited onto the surface of an article for which properties are imparted (e.g., an article with paper, cloth, metal and its oxides, glass, plastic, ceramic, quartz as a surface substrate) to cure it, or the curable composition for film formation of the present invention is coated or vapor-deposited onto various substrate films (e.g., films of polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, vinyl chloride resin, polystyrene, acrylic resin, polycarbonate, polyphenylene sulfide, polyetheretherketone, polyethersulfone, aromatic polyamide, polyimide, etc.) to produce a cured film, and the film is then adhered to the surface of the target article, thereby enabling the imparting of properties to various articles.

[0292] The coating method for the curable composition for film formation according to the present invention is not particularly limited, and known coating methods such as roller coating, gravure coating, flow coating, dip coating, spray coating, spin coating, rod coating, and screen printing can be used. The vapor deposition method can be either resistance heating or electron beam heating, and is not particularly limited. After coating, the coating is cured by irradiating it with active energy rays or by heating.

[0293] In the case of curing the coating by irradiating it with active energy rays, any active energy ray, such as an electron beam or ultraviolet light, can be used, with ultraviolet light being particularly preferred. As the ultraviolet light source, mercury lamps, metal halide lamps, and LED lamps are preferred. Regarding the ultraviolet irradiation amount, if it is too low, uncured components will remain; if it is too high, the coating and substrate may deteriorate. A range of 10–10000 mJ / cm² is preferred. 2 Especially 20–4000 mJ / cm 2The range is limited. Additionally, to prevent oxygen-induced curing obstacles, the irradiation atmosphere can be replaced with inactive gases such as nitrogen, carbon dioxide, or argon that do not contain oxygen molecules during UV irradiation. Alternatively, the coating surface can be covered with a release-type, UV-transparent protective layer, and then irradiated with UV light. If the substrate is UV-transparent, the coating surface can be covered with a release-type protective layer, and then irradiated with UV light from the opposite side of the coated surface of the substrate. Furthermore, to effectively achieve coating leveling, the coating and substrate can be heated using any method, such as a hot air drying oven, before and during UV irradiation.

[0294] Furthermore, when curing by heating, any heating source such as an oven or hot plate can be used as the heating source. 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.

[0295] Furthermore, the appropriate thickness of the cured film (cured resin layer) formed using the curable composition for film formation of the present invention varies depending on the method of use, etc., and is therefore not limited by thickness.

[0296] For example, when a large amount of a non-fluorinated acrylic compound is incorporated into the curable composition for film formation, specifically, when the proportion of a non-fluorinated compound containing a hydrocarbon terminal group in 100 parts by mass of all components excluding solvent in the curable composition for film formation of the present invention is 0.005 parts by mass or more and less than 50 parts by mass, the preferred thickness of the cured film is 0.5 to 100 μm. On the other hand, when a large amount of a non-fluorinated compound containing a hydrocarbon terminal group is incorporated into the curable composition for film formation, specifically, when the proportion of a non-fluorinated compound containing a hydrocarbon terminal group in 100 parts by mass of all components excluding solvent in the curable composition for film formation of the present invention is 50 parts by mass or more and less than 99.9 parts by mass, the preferred thickness of the cured film is 1 to 500 nm.

[0297] Furthermore, in this invention, the film thickness can be measured using thin film thickness measuring devices based on optical interferometry (optical interferometer, reflective spectrophotometer), thin film thickness measuring devices based on spectroscopic ellipsometer (spectral ellipsometer), etc.

[0298] Furthermore, preferably, the cured film (cured resin layer) formed using the curable composition for film formation of the present invention has a water contact angle of 90° or more, preferably 95° or more, and an oleic acid contact angle of 40° or more, preferably 45° or more, at a temperature of 25°C and a relative humidity of 40%. In the present invention, the contact angle is a value measured using a Drop Master contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) under conditions of 2 μL droplets. Additionally, to achieve the aforementioned contact angle, it is preferable that the curable composition for film formation is uniformly mixed.

[0299] The article of the present invention has a cured film formed using the curable composition for film formation of the present invention on the surface of a substrate, which functions as a coating film and a surface protective film of the article.

[0300] Examples include the casings of various portable (communication) information terminals such as tablet computers, mobile phones, and smartphones; laptop PCs; digital media players; wearable computers in watch or glasses styles; digital cameras; digital camcorders; and e-book readers. Also included are the display surfaces of various flat panel displays and TV screens, such as LCDs, plasma displays, organic EL displays, rear-projection displays, fluorescent tubes (VFDs), field emission projection displays, CRTs, and toner displays; the exterior of automobiles; the glossy surfaces of pianos and furniture; the surfaces of building stone such as marble; decorative building materials around water, such as toilets, bathtubs, and washrooms; protective glass for art displays; shop windows, display cabinets, picture frame covers; watch glass; automotive window glass; train and aircraft window glass; transparent glass or transparent plastic (acrylic, polycarbonate, etc.) components such as car headlights and taillights; and various reflector components.

[0301] Specifically, various devices that allow operation on the screen using fingers or palms, such as touch panel displays, can be listed. Examples include tablet computers, laptop PCs, wearable computers, activity meters, mobile phones, smartphones and other portable (communication) information terminals, digital media players, e-book readers, digital photo frames, game consoles and game console controllers, digital cameras, digital camcorders, navigation devices for automobiles, automatic cash withdrawal and deposit devices, automatic cash payment machines, vending machines, digital signage (electronic signage), security system terminals, POS terminals, remote controls and other controllers, and display input / output devices such as panel switches for vehicle-mounted devices.

[0302] Furthermore, examples of items in this invention include optical recording media such as optical disks and optical discs; optical components, optical devices, or various protective components of these devices such as spectacle lenses, camera lenses, projector lenses, prisms, lenses, semi-permeable films, polarizers, filters, biconvex lenses, Fresnel lenses, anti-reflective films, optical fibers, and optical couplers.

[0303] Example

[0304] The following examples, comparative examples, and exemplary and comparative examples illustrate the invention in more detail, but the invention is not limited to the examples described below. It should be noted that in the examples below, room temperature is 25°C, and atmospheric pressure refers to atmospheric pressure. Furthermore, the melting point is the value measured using a differential scanning calorimeter (DSC) at atmospheric pressure, according to JIS K 7121. The measurement conditions are described below: Starting temperature: -150°C, Ending temperature: 200°C, Heating / cooling rate: 10°C / min, Atmosphere gas: Nitrogen (flow rate: 50 mL / min). Film thickness is the value measured using a reflectance spectrophotometer (measurement range 400 nm to 800 nm).

[0305] [Synthesis Example 1] Synthesis of compound (b)

[0306] In the reaction vessel, it will be produced by the following formula (a)

[0307] [Chemistry 48]

[0308]

[0309] The compound represented is 100.00 g (1.97 × 10⁻⁶ g). -1 14.91 g (3.94 × 10⁻⁶ mol) of sodium borohydride and 100.0 g of methanol were mixed and stirred at room temperature under a nitrogen atmosphere for 1 hour. Then, 14.91 g (3.94 × 10⁻⁶ mol) of sodium borohydride was added to the system. -1 After mixing (mol), the mixture was stirred for 12 hours under a nitrogen atmosphere at room temperature. Then, it was washed with water, and the solvent and unreacted products were removed by vacuum distillation to obtain 91.21 g of the product.

[0310] pass 1 H-NMR confirmed that the product obtained was a compound represented by the following formula (b).

[0311] [Chemistry 49]

[0312]

[0313] [Synthetic Example 2] Synthesis of compound (A) containing a hydrocarbon terminal group

[0314] The product obtained in Synthesis Example 1 above, expressed as shown in equation (b), is placed in a reaction vessel.

[0315] [Transformation 50]

[0316]

[0317] The compound represented is 10.00 g (1.96 × 10⁻⁶ g). -2 mol), THF 100.0g, triethylamine 2.97g (2.94×10 -2 The mixture (mol) was stirred for 1 hour at 40°C under a nitrogen atmosphere. Then, 2.66 g (2.94 × 10⁻⁶ mol) of acryloyl chloride was added to the system. -2 After mixing (mol), the mixture was stirred at 40°C for 6 hours under a nitrogen atmosphere. Then, it was washed with water and the solvent, byproducts, and unreacted substances were removed by vacuum distillation, yielding 8.78 g of the product.

[0318] pass 1 H-NMR confirmed that the obtained compound had the structure represented by the following formula (A). In addition, the melting point of the obtained compound at normal pressure was 28°C.

[0319] [Chemistry 51]

[0320]

[0321] [Synthetic Example 3] Synthesis of compound (B) containing a hydrocarbon terminal group

[0322] In the reaction vessel, it will be produced by the following formula (c)

[0323] [Chemistry 52]

[0324]

[0325] The compound represented is 10.00 g (1.92 × 10⁻⁶). -2 mol), THF 100.0g, triethylamine 2.91g (2.88×10 -2 The mixture (mol) was stirred for 1 hour at 40°C under a nitrogen atmosphere. Then, 2.61 g (2.88 × 10⁻⁶ mol) of acryloyl chloride was added to the system. -2 After mixing (mol), the mixture was stirred at 40°C for 6 hours under a nitrogen atmosphere. Then, it was washed with water and the solvent, byproducts, and unreacted substances were removed by vacuum distillation, yielding 8.62 g of the product.

[0326] pass 1 H-NMR confirmed that the obtained compound had the structure represented by the following formula (B). In addition, the melting point of the obtained compound at normal pressure was 32°C.

[0327] [Chemistry 53]

[0328]

[0329] [Synthetic Example 4] Synthesis of a compound (C) containing a hydrocarbon terminal group

[0330] The product obtained in Synthesis Example 1 above, expressed as shown in equation (b), is placed in a reaction vessel.

[0331] [Chemistry 54]

[0332]

[0333] The compound represented is 10.00 g (1.96 × 10⁻⁶ g). -2 mol), 3.04 g (2.15 × 10⁻⁶) of 2-isocyanate ethyl acrylate. -2 50.00 g of THF and 0.03 g of tetra(2-ethylhexyl) titanate were mixed and aged at 50 °C for 12 hours. Then, the solvent and unreacted substances were removed by vacuum distillation to obtain 12.88 g of product.

[0334] pass 1 H-NMR confirmed that the obtained compound has the structure represented by the following formula (C). In addition, the melting point of the obtained compound at normal pressure is 58°C.

[0335] [Chemistry 55]

[0336]

[0337] [Synthetic Example 5] Synthesis of compound (D) containing a hydrocarbon terminal group

[0338] In the reaction vessel, it will be produced by the following formula (d)

[0339] [Chemistry 56]

[0340]

[0341] The compound represented is 10.00 g (3.06 × 10⁻⁶ g). -2 mol), 4.75 g (3.37 × 10⁻⁶) of 2-isocyanate ethyl acrylate. -2 50.00 g of THF and 0.03 g of tetra(2-ethylhexyl) titanate were mixed and aged at 50 °C for 12 hours. Then, the solvent and unreacted substances were removed by vacuum distillation to obtain 14.40 g of product.

[0342] pass 1 H-NMR confirmed that the obtained compound had the structure represented by the following formula (D). In addition, the melting point of the obtained compound at normal pressure was 34 °C.

[0343] [Chemistry 57]

[0344]

[0345] [Synthetic Example 6] Synthesis of a compound (E) containing a hydrocarbon terminal group

[0346] The following formula (b) obtained in the above synthesis example 1 is placed in a reaction vessel.

[0347] [Chem.58]

[0348]

[0349] The compound represented is 10.00 g (1.96 × 10⁻⁶ g). -2 4.29 g (2.15 × 10⁻⁶ mol) of 2-(2-methacryloyloxyethoxy)ethyl isocyanate. -2 50.00 g of THF and 0.03 g of tetra(2-ethylhexyl) titanate were mixed and aged at 50 °C for 12 hours. Then, the solvent and unreacted substances were removed by vacuum distillation to obtain 13.61 g of product.

[0350] pass 1 H-NMR confirmed that the obtained compound had the structure represented by the following formula (E). In addition, the melting point of the obtained compound at normal pressure was 56 °C.

[0351] [Chemistry 59]

[0352]

[0353] [Synthetic Example 7] Synthesis of a compound (F) containing a hydrocarbon terminal group

[0354] In the reaction vessel, it will be produced by the following formula (c)

[0355] [Transformation 60]

[0356]

[0357] The compound represented is 10.00 g (1.92 × 10⁻⁶). -2 mol), 2.98 g (2.11 × 10⁻⁶) of 2-isocyanate ethyl acrylate. -2 The solvent and unreacted product were mixed with 50.00 g of THF and aged at 50 °C for 12 hours. Then, the solvent and unreacted product were removed by vacuum distillation to obtain 12.11 g of product.

[0358] pass 1 H-NMR confirmed that the obtained compound has the structure represented by the following formula (F). In addition, the melting point of the obtained compound at normal pressure is 38°C.

[0359] [Chemistry 61]

[0360]

[0361] [Synthetic Example 8] Synthesis of a compound (G) containing a hydrocarbon terminal group

[0362] In the reaction vessel, it will be produced by the following formula (e)

[0363] [Chemistry 62]

[0364]

[0365] The compound represented is 10.00 g (2.83 × 10⁻⁶). -2 mol), 4.39 g (3.11 × 10⁻⁶) of 2-isocyanate ethyl acrylate. -2 The solvent and unreacted product were mixed with 50.00 g of THF and aged at 50 °C for 12 hours. Then, the solvent and unreacted product were removed by vacuum distillation to obtain 12.72 g of product.

[0366] pass 1 H-NMR confirmed that the obtained compound had the structure represented by the following formula (G). In addition, the melting point of the obtained compound at normal pressure was 21 °C.

[0367] [Chemistry 63]

[0368]

[0369] [Synthetic Example 9] Synthesis of a compound (H) containing a hydrocarbon terminal group

[0370] In the reaction vessel, it will be produced by the following formula (f)

[0371] [Chemistry 64]

[0372]

[0373] The compound represented is 10.00 g (3.07 × 10⁻⁶). -2 mol), 4.77 g (3.38 × 10⁻⁶) of 2-isocyanate ethyl acrylate. -2 The solvent and unreacted product were mixed with 50.00 g of THF and aged at 50 °C for 12 hours. Then, the solvent and unreacted product were removed by vacuum distillation to obtain 14.32 g of product.

[0374] pass 1 H-NMR confirmed that the obtained compound has the structure represented by the following formula (H). In addition, the melting point of the obtained compound at normal pressure is 48°C.

[0375] [Chemistry 65]

[0376]

[0377] [Synthetic Example 10] Synthesis of Compound (I) Containing Hydrocarbon Terminal Group

[0378] In the reaction vessel, it will be produced by the following formula (c)

[0379] [Chemistry 66]

[0380]

[0381] The compound represented is 10.00 g (1.92 × 10⁻⁶). -2 mol), 3.28 g (2.11 × 10⁻⁶) of ethyl 2-isocyanate methacrylate. -2 The solvent and unreacted product were mixed with 50.00 g of THF and aged at 50 °C for 12 hours. Then, the solvent and unreacted product were removed by vacuum distillation to obtain 13.03 g of product.

[0382] pass 1 H-NMR confirmed that the obtained compound had the structure represented by the following formula (I). In addition, the melting point of the obtained compound at normal pressure was 47 °C.

[0383] [Chemistry 67]

[0384]

[0385] [Synthetic Example 11] Synthesis of a compound (J) containing a hydrocarbon terminal group

[0386] In the reaction vessel, it will be produced by the following formula (c)

[0387] [Chemistry 68]

[0388]

[0389] The compound represented is 10.00 g (1.92 × 10⁻⁶). -2 4.21 g (2.11 × 10⁻⁶ mol) of 2-(2-methacryloyloxyethoxy)ethyl isocyanate. -2 The solvent and unreacted product were mixed with 50.00 g of THF and aged at 50 °C for 12 hours. Then, the solvent and unreacted product were removed by vacuum distillation to obtain 13.64 g of product.

[0390] pass 1 H-NMR confirmed that the obtained compound had the structure represented by the following formula (J). In addition, the melting point of the obtained compound at normal pressure was 39°C.

[0391] [Chemistry 69]

[0392]

[0393] [Synthetic Example 12] Synthesis of a compound (K) containing a hydrocarbon terminal group

[0394] In the reaction vessel, it will be produced by the following formula (c)

[0395] [Chemistry 70]

[0396]

[0397] The compound represented is 10.00 g (1.92 × 10⁻⁶). -2 5.05 g (2.11 × 10⁻⁶ mol) of 1,1-(bisacryloyloxymethyl)ethyl isocyanate -2 The solvent and unreacted product were mixed with 50.00 g of THF and aged at 50 °C for 12 hours. Then, the solvent and unreacted product were removed by vacuum distillation to obtain 14.50 g of product.

[0398] pass 1 H-NMR confirmed that the obtained compound has the structure represented by the following formula (K). In addition, the melting point of the obtained compound at normal pressure is 20°C.

[0399] [Chemistry 71]

[0400]

[0401] [Comparative Synthesis Example 1] Synthesis of Compound (X) Containing Hydrocarbon Terminal Groups

[0402] In the reaction vessel, the following formula (g) will be used.

[0403] [Chemistry 72]

[0404]

[0405] The compound represented is 10.00 g (3.70 × 10⁻⁶). -2 5.74 g (4.07 × 10⁻⁶ mol) of 2-isocyanate ethyl acrylate. -2 50.00 g of THF and 0.03 g of tetra(2-ethylhexyl) titanate were mixed and aged at 50 °C for 12 hours. Then, the solvent and unreacted substances were removed by vacuum distillation to obtain 13.28 g of product.

[0406] pass 1 H-NMR confirmed that the obtained compound had the structure represented by the following formula (X). In addition, the melting point of the obtained compound at normal pressure was 29°C.

[0407] [Chemistry 73]

[0408]

[0409] [Comparative Synthesis Example 2] Synthesis of Compound (Y) Containing Hydrocarbon Terminal Groups

[0410] In the reaction vessel, the following formula (h) will be used.

[0411] [Chemistry 74]

[0412]

[0413] The compound represented is 10.00 g (3.71 × 10⁻⁶). -2 5.76 g (4.08 × 10⁻⁶ mol) of 2-isocyanate ethyl acrylate. -2 The solvent and unreacted product were mixed with 50.00 g of THF and aged at 50 °C for 12 hours. Then, the solvent and unreacted product were removed by vacuum distillation to obtain 15.01 g of product.

[0414] pass 1 H-NMR confirmed that the obtained compound had the structure represented by the following formula (Y). In addition, the melting point of the obtained compound at normal pressure was 42°C.

[0415] [Chemistry 75]

[0416]

[0417] [Examples 1-22, Comparative Examples 1, 2, 3]

[0418] Preparation of curable compositions for forming active energy ray-curable films

[0419] Solutions were prepared by mixing compounds (A) to (K) synthesized in the above synthesis examples and compounds (X) and (Y) synthesized in the comparative synthesis examples in the proportions shown in Tables 1 and 2 below (curing compositions for forming films by active energy ray curing).

[0420] [Table 1]

[0421]

[0422] [Table 2]

[0423]

[0424] A-9550: Dipentaerythritol polyacrylate (A-9550, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0425] AcOBu: Butyl acetate

[0426] I-184: 1-Hydroxycyclohexylphenyl ketone (Irgacure 184, manufactured by Ciba Japan Co., Ltd.)

[0427] Preparation of coating and curing film (1)

[0428] The solutions (curable compositions for forming films using active energy ray curing) prepared in Examples 1-11 and Comparative Examples 1-3 were spin-coated onto a polycarbonate substrate. After coating, the substrate was evaporated and leveled by blowing nitrogen in an inert chamber at room temperature for 5 minutes. Then, a conveyor belt-type metal halide UV irradiation device (manufactured by Panasonic Electric Works Co., Ltd.) was used to irradiate the substrate in a nitrogen atmosphere with a cumulative irradiation dose of 1600 mJ / cm². 2 The coating surface was irradiated with ultraviolet light, which cured the composition and obtained a cured film with a thickness of 5 μm.

[0429] Preparation of coating and curing film (2)

[0430] A solution prepared by spin-coating a polycarbonate substrate with 100 parts by weight of dipentaerythritol polyacrylate (A-9550, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 142 parts by weight of butyl acetate, and 3 parts by weight of 1-hydroxycyclohexylphenyl ketone (Irgacure 184, manufactured by Ciba Japan Co., Ltd.) was spin-coated. After coating, the substrate was heated at 80°C for 1 minute to allow solvent evaporation and leveling. Then, it was irradiated with nitrogen in an inert chamber at room temperature for 5 minutes. Finally, it was irradiated with a cumulative dose of 1600 mJ / cm² in air using a conveyor belt-type metal halide UV irradiation device (manufactured by Panasonic Electric Works Co., Ltd.). 2 The coating surface was irradiated with ultraviolet light to cure it, resulting in a cured film with a thickness of 5μm.

[0431] The solutions (curing compositions for forming films using active energy ray curing) prepared in Examples 12-22 were spin-coated onto the obtained cured film. After coating, the film was heated at 80°C for 1 minute to allow solvent evaporation and leveling. Then, the film was purged with nitrogen in an inert chamber at room temperature for 5 minutes. Finally, a conveyor belt-type metal halide UV irradiation device (manufactured by Panasonic Electric Works Co., Ltd.) was used to irradiate the film in a nitrogen atmosphere with a cumulative irradiation dose of 1600 mJ / cm². 2 The coating surface was irradiated with ultraviolet light, which cured the composition and obtained a cured film with a thickness of 5 nm.

[0432] The appearance (transparency) of the cured film obtained above was visually determined. Simultaneously, the following methods were used to evaluate its antifouling properties: water contact angle, oleic acid contact angle, and marker ink wiping resistance were measured. For abrasion resistance, the water contact angle was measured after an abrasion test. These results are shown in Tables 3 and 4. Furthermore, cases where the appearance (transparency) is transparent are marked with ○, and cases where it is opaque are marked with ×.

[0433] Evaluation of stain resistance

[0434] [Water contact angle measurement, oleic acid contact angle measurement]

[0435] For the cured film prepared above, the contact angles of the cured film with water and oleic acid were measured using a Drop Master contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) (droplet: 2 μL, temperature: 25°C, relative humidity: 40%).

[0436] [Evaluation of the erasability of the marker ink]

[0437] For the cured film prepared above, draw a 3cm straight line with a marker (large Magic Ink manufactured by Teranishi Chemical Industry Co., Ltd.), let it dry at room temperature for 3 minutes, and then wipe off the marker ink with a paper towel. Mark the cases where the marker ink was wiped off as ○, and the cases where it was not wiped off as ×.

[0438] Evaluation of wear resistance

[0439] [Water contact angle measurement after wear test]

[0440] The surface of the cured film was subjected to a reciprocating wear test using a tribological testing machine (manufactured by Shin-Tung Science Co., Ltd.), and the water contact angle after the test was measured. The evaluation was set as the average number of tests conducted with N=4.

[0441] The test conditions are shown below.

[0442] Friction material: Bonstar steel wool #0000 (manufactured by Bonstar Co., Ltd.)

[0443] Travel distance (one way) 40mm

[0444] Movement speed: 4800 mm / min

[0445] Load: 300gf / 1×1cm 2

[0446] Wear cycles: 5000 times

[0447] [Table 3]

[0448]

[0449] [Table 4]

[0450]

[0451] Cured films (Examples 1-22) using the active energy ray-curable coating composition for forming a film using compounds containing hydrocarbon terminal groups (compounds (A) to (K)) of the present invention exhibit excellent smoothness, water repellency, and antifouling properties. Furthermore, abrasion tests confirmed high abrasion resistance as the water contact angle did not decrease significantly. On the other hand, cured films (Comparative Examples 1 and 2) using the active energy ray-curable coating composition for forming a film using compounds containing hydrocarbon terminal groups (compounds (X) and (Y)) with structures different from those of the compounds containing hydrocarbon terminal groups of the present invention exhibited low water repellency, antifouling properties, and abrasion resistance. Additionally, the cured film (Comparative Example 3) without the active energy ray-curable coating composition for forming a film using a film containing hydrocarbon terminal groups (without compounding) showed no water repellency or antifouling properties whatsoever.

Claims

1. A compound represented by the following general formula (1), which contains a hydrocarbon terminal group and does not contain a fluorine atom in its structure. [Chemistry 1] In the formula, X is R 1 O- or R 2 R 3 N-, R 1 It is a monovalent hydrocarbon group with 20 to 80 carbon atoms, in the form of straight chains, branches, or rings. 2 It is a monovalent hydrocarbon group with 10 to 40 carbon atoms, in the form of straight chains, branches, or rings, R. 3 R is a monovalent hydrocarbon group consisting of 10 to 40 carbon atoms, either a hydrogen atom or in a straight-chain, branched, or cyclic form. 2 and R 3 The total number of carbon atoms contained in it is 20 or more and less than 80, and Y is a single bond or a divalent organic group represented by the following structural formula. -C(=O) -C(=O)-O -C(=O)-NR 4 -C(=S)-NR 4 In the formula, * is the junction end that combines with X in general formula (1), ** is the junction end that combines with Z in general formula (1), and R 4 It consists of a hydrogen atom, or a monovalent hydrocarbon group with 1 to 8 carbon atoms in a straight chain, branched or cyclic form. Z is a single bond, or a hydrocarbon group with 1 to 20 carbon atoms in a 2 to 4 valence, which may contain one or more types of carbon atoms selected from oxygen, sulfur, nitrogen, and silicon. V is independently a hydrocarbon group with 2 to 20 carbon atoms in a 1 valence, which may contain oxygen and / or nitrogen atoms and has a polymerizable carbon-carbon double bond. m is an integer from 1 to 3.

2. The compound containing a hydrocarbon terminal group according to claim 1, wherein, In equation (1) above, V is represented by the following equation: [Chemistry 2] In the formula, * is the bonding end that bonds with Z in general formula (1), and R' is a 1-valent hydrocarbon group with 1 to 8 hydrogen atoms.

3. The compound containing a hydrocarbon terminal group according to claim 1, wherein, In the above formula (1), Y is a group represented by the following structural formula, -C(=O)-NH In the formula, * is the junction end that combines with X in general formula (1), and ** is the junction end that combines with Z in general formula (1).

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

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

6. The compound containing a hydrocarbon terminal group according to claim 1, wherein it is an acrylic compound containing a hydrocarbon terminal group represented by the following general formula (2), [Chemistry 3] In the formula, X is the same as above, Z' is a divalent hydrocarbon group with 1 to 10 carbon atoms that may contain oxygen atoms and / or nitrogen atoms, and R” is a hydrogen atom or a methyl group.

7. The compound containing a hydrocarbon terminal group according to claim 1, wherein it is an acrylic compound containing a hydrocarbon terminal group represented by the following general formula (3), [Chemistry 4] In the formula, R 2 R 3 As above, Z' is a divalent hydrocarbon group with 1 to 10 carbon atoms that may contain oxygen and / or nitrogen atoms, and R” is a hydrogen atom or a methyl group.

8. The compound containing a hydrocarbon terminal group according to claim 7, wherein, In the above equation (3), R 2 and R 3 It is a linear hydrocarbon group with 10 to 40 carbon atoms and a monovalent valence, R 2 and R 3 They have the same number of carbon atoms.

9. The compound containing a hydrocarbon terminal group according to claim 1, wherein the melting point is above 20°C.

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

11. The curable composition for film formation according to claim 10, wherein, The non-fluorinated compounds containing hydrocarbon terminal groups are the compounds containing hydrocarbon terminal groups according to any one of claims 1 to 9.

12. The curable composition for film formation according to claim 10, further comprising a polymerization initiator.

13. The curable composition for film formation according to claim 12, wherein it is an active energy ray curable type.

14. The curable composition for film formation according to claim 10, further comprising a solvent.

15. The curable composition for film formation according to claim 10, further comprising a non-fluorinated acrylic compound.

16. The curable composition for film formation according to claim 10, comprising a compound that does not contain fluorine atoms.

17. A cured film formed by curing the curable composition for film formation according to claim 10.

18. The cured film according to claim 17, wherein the water contact angle is greater than 90° and the oleic acid contact angle is greater than 40° at a droplet volume of 2 μL, a temperature of 25°C and a relative humidity of 40%.

19. An article having a cured film according to claim 17 on its surface.

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