Surface conditioner, leveling agent, resin composition and coating film

Abstract

To provide a surface conditioner which has high surface tension reduction capability, and has good bubble-breaking property.SOLUTION: A surface conditioner contains a compound represented by formula (1), wherein R1 and R2 are CH3 groups, a to c are each independently integers of 0 to 10, the total of a to c is 4 or more and 14 or less, R3 is each independently a linear or branched allylene group having 1 to 6 carbon atoms, m and n each independently represent numbers of 0 to 50, the total of m and n is 3 to 50, m and n represent an addition mole number of (R3O) in a (poly)alkylene glycol group, when m and / or n are 2 or more, the kind of R3 constituting each of the polyalkylene glycol groups may be different, and R4 is each independently a hydrogen or a linear or branched alkyl group having 1 to 8 carbon atoms.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a surface conditioner, a leveling agent, a resin composition, and a coating film. [Background technology]

[0002] Leveling agents are added to smooth the coating film when a composition such as a paint is applied. Leveling agents orient themselves on the coating film surface during the drying process, thereby reducing the surface tension of the coating film and smoothing the coating film. Therefore, leveling agents are required to have a high ability to reduce surface tension.

[0003] If the leveling agent exhibits foaming properties, a defoaming operation is required when preparing the composition, which deteriorates workability. Furthermore, if bubbles remain in the coating film, the coating film will have a condition known as orange peel, orange peel, rough skin, etc., and the smoothness of the coating film will deteriorate. Therefore, in addition to the surface tension reducing ability, low foaming properties and high foam breaking properties (defoaming properties) are also important physical properties of the leveling agent.

[0004] Acrylic and silicone leveling agents have been proposed as polymer leveling agents (for example, Patent Documents 1 and 2). Additionally, surfactant leveling agents such as acetylene compounds and fluorine compounds have been proposed as low molecular weight leveling agents (Patent Documents 3 and 4). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent Publication No. 2021-515815 [Patent Document 2] Patent Publication No. 2021-92961 [Patent Document 3] Japanese Patent Application Publication No. 2018-83938 [Patent Document 4] Japanese Patent Application Publication No. 2018-106172 Summary of the Invention [Problem to be solved by the invention]

[0006] However, conventional polymeric leveling agents have a low surface tension reducing ability, and there is still room for improvement in terms of leveling properties. Furthermore, polymeric leveling agents have problems such as compatibility during composition preparation and residues after baking in baked coating. Meanwhile, low molecular weight leveling agents have a high foaming property and a low foam breaking property, so they also have the problem of poor leveling properties.

[0007] Therefore, an object of the present invention is to provide a surface conditioner that has a high surface tension reducing ability and a good foam breaking (defoaming) property. [Means for solving the problem]

[0008] As a result of extensive research, the present inventors have discovered the following formula (1):

[0009] [ka]

[0010] In formula (1), R1 and R2 are CH3 groups, a to c are each independently an integer of 0 to 10, and the sum of a to c is 4 or more and 14 or less; R3 is independently a linear or branched alkylene group having 1 to 6 carbon atoms, m and n each independently represent a number from 0 to 50, and the sum of m and n is from 3 to 50; Here, m and n represent the number of moles of (RO) added in the (poly)alkylene glycol group, and when m and / or n is 2 or more, the types of R constituting each polyalkylene glycol group may be different from each other. R4 is independently hydrogen or a linear or branched alkyl group having 1 to 8 carbon atoms; The present invention has been completed based on the discovery that the above problems can be solved by a surface conditioner containing a compound represented by the following formula: [Effects of the Invention]

[0011] According to the present invention, a surface conditioner having a high surface tension reducing ability and a good bubble breaking property is provided. DETAILED DESCRIPTION OF THE INVENTION

[0012] Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to only the following embodiments. In this specification, unless otherwise specified, "%" and "parts" mean "% by mass" and "parts by mass", respectively, and "boiling point" means the boiling point at normal pressure. In the following examples, unless otherwise specified, operations were carried out under conditions of room temperature (25°C) and relative humidity of 40 to 50% RH.

[0013] <Surface conditioner> The surface conditioner of the present invention contains a compound represented by the following formula (1):

[0014] [ka]

[0015] In formula (1), R1 and R2 are CH3 groups, a to c are each independently an integer of 0 to 10, and the sum of a to c is 4 or more and 14 or less; R3 is independently a linear or branched alkylene group having 1 to 6 carbon atoms, m and n each independently represent a number from 0 to 50, and the sum of m and n is from 3 to 50; Here, m and n represent the number of moles of (RO) added in the (poly)alkylene glycol group, and when m and / or n is 2 or more, the types of R constituting each polyalkylene glycol group may be different from each other. Each R4 is independently hydrogen or a linear or branched alkyl group having 1 to 8 carbon atoms.

[0016] Furthermore, a surface conditioner according to a preferred embodiment of the present invention contains a compound in which the sum of a to c in the above formula (1) is 8 or more and 10 or less.

[0017] The surface conditioner according to a preferred embodiment of the present invention is a leveling agent.

[0018] A resin composition having surface conditioning ability can be obtained by mixing the surface conditioner with a resin or a monomer and dispersion medium constituting the resin, as needed. When the resin composition is applied to an object to be coated and cured as needed, a coating film is formed on the object to be coated. Because the surface conditioner of the present invention has high surface tension reducing ability and high bubble breaking ability, a resin composition containing the surface conditioner of the present invention can form a coating film with good smoothness on the object to be coated. The mechanism by which the surface conditioner of the present invention exhibits the effects of high surface tension reducing ability and high bubble breaking ability is unknown, but is presumed to be as follows.

[0019] As described above, the surface conditioner of the present invention contains a compound represented by formula (1). This compound has a hydrocarbon main chain containing 8 to 18 carbon atoms and one or two polyalkylene glycol chains as side chains. Generally, when a surface conditioner containing a surfactant compound is used, its high foaming tendency tends to result in bubbles remaining in the coating film, which can lead to a deterioration in the smoothness of the coating film. In contrast, the compound represented by formula (1) contains a polyalkylene glycol chain that imparts hydrophilicity and a hydrocarbon main chain that imparts hydrophobicity in an appropriate balance. Furthermore, the polyalkylene glycol chain is present as a side chain of a secondary carbon. This allows for a well-balanced combination of surface tension reducing ability and high foam breaking properties. In particular, since the hydrocarbon main chain of the compound represented by formula (1) is a hydrocarbon having 12 to 14 carbon atoms, the surface conditioner containing the compound represented by formula (1) can efficiently exhibit surface tension reducing ability. As a result, the wettability of a resin composition containing the surface conditioner of the present invention to a substrate is improved. Therefore, a resin composition containing the surface conditioner of the present invention has good coatability onto an object to be coated, and can also impart good smoothness to the object to be coated.

[0020] It should be noted that the present invention is not limited to the above mechanism.

[0021] The surface conditioner may contain only one compound represented by the following formula (1), or two or more compounds. Hereinafter, the compound represented by the following formula (1) will also be referred to as "compound (1)."

[0022] [ka]

[0023] In the above formula (1), R1 and R2 are CH3 groups (methyl groups).

[0024] In the above formula (1), a to c are each independently an integer of 0 to 10, preferably an integer of 0 to 8, and more preferably an integer of 1 to 6. The sum of a to c is 4 or more and 14 or less, preferably 6 or more and 12 or less, and further preferably 8 or more and 10 or less.

[0025] In the above formula (1), R3 is each independently a linear or branched alkylene group having 1 to 6 carbon atoms. In formula (1), R3 is preferably a linear or branched alkylene group having 1 to 5 carbon atoms, and more preferably a linear or branched alkylene group having 2 to 4 carbon atoms. Examples of the linear or branched alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, and an isobutylene group. In formula (1), "R3O" represents an oxyalkylene group; for example, when R3 is an ethylene group, it represents an oxyethylene group (-(CH2CH2-O)-); when R3 is an isopropylene group, it represents an oxypropylene group (-(CH2-CH(CH3)-O)-); and when R3 is a butylene group, it represents an oxybutylene group (-(CH2-CH(CH2CH3)-O)-). In formula (1), multiple R3s may be the same or different.

[0026] In the above formula (1), "-(RO) m -" and "-(RO) n"-" represents a polyoxyalkylene chain. m and n represent the average number of moles of (poly)alkylene glycol groups (-(RO)-) added. m and n each independently represent a number from 0 to 50, and in this case, the total of m and n is 3 to 50. From the viewpoint of the surface conditioner further exhibiting the surface tension reducing ability, m and n each independently represent a number from 0 to 30, more preferably a number from 0 to 20, even more preferably a number from 0 to 18, still more preferably a number from 0 to 15, particularly preferably a number from 0 to 14, and most particularly preferably a number from 1 to 12. Furthermore, the total of m and n is preferably 3 to 50, more preferably 3 to 25, even more preferably 3 to 22, even more preferably 3 to 18, particularly preferably 3 to 15, and most preferably 3 to 12. When n and / or m is 2 or more, the types of R3 constituting each polyalkylene glycol group may be different from each other. It is a number between 2 and 4.

[0027] In formula (1), multiple R3 may be the same or different and may form a single polyoxyalkylene chain ("-(R3O) m -", "-(RO) n In one polyoxyalkylene chain ("-(R3O)"), R3 may be the same or different. m -", "-(RO) n When "-") is an oxyalkylene group composed of two or more types of R3, the arrangement may be either random or block.

[0028] Examples of the compound represented by the formula (1) include ethylene oxide (EO) adducts of linear or branched dodecanediol, linear or branched tridecanediol, linear or branched tetradecanediol, etc. These may be used alone or in combination of two or more.

[0029] In the above formula (1), each R4 is independently hydrogen or a linear or branched alkyl group having 1 to 8 carbon atoms. In formula (1), R4 is hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms, more preferably hydrogen or a linear or branched alkyl group having 1 to 2 carbon atoms. Examples of linear or branched alkyl groups having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-heptyl, and n-octyl. Of these, R4 is preferably hydrogen, methyl, or ethyl, more preferably hydrogen or methyl. In formula (1), two R4s may be the same or different.

[0030] The method for producing the compound represented by the formula (1) is not particularly limited. For example, a diol compound (R1-(CH2)) can be produced by the method described in JP-A-50-159595. a -CH2(OH)-(CH2) b -CH2(OH)-(CH2) c -R2; R1, R2, and a to c are the same as R1, R2, and a to c in the above formula (1), respectively. Specifically, a polyalkylene glycol chain can be introduced into the diol compound (R1-(CH2) a -CH2(OH)-(CH2) b -CH2(OH)-(CH2) c -R2; R1, R2, and a to c are defined as R1, R2, and a to c in the above formula (1), respectively, and are obtained by an addition reaction of an alkylene oxide. The resulting reaction mixture is further treated with at least one calcium compound selected from calcium hydroxide and calcium oxide, and water (in an amount equimolar to the calcium compound), to obtain a compound represented by formula (1) suitable for the present invention.

[0031] The static surface tension of the surface conditioner of the present invention at 0.1% by mass as measured by the Wilhelmy method (plate method) is preferably 20 to 45 mN / m, more preferably 25 to 40 mN / m, even more preferably 30 to 35 mN / m, and particularly preferably 30 to 33 mN / m. The static surface tension is the value measured by the Wilhelmy method (plate method) using a surface tensiometer (K100, manufactured by KRUSS) at 25°C for a 0.1% by mass aqueous solution.

[0032] The dynamic surface tension of the surface conditioner of the present invention at 15 Hz according to the maximum bubble pressure method is preferably 25 to 55 mN / m, more preferably 30 to 50 mN / m, even more preferably 30 to 45 mN / m, and particularly preferably 30 to 40 mN / m. The dynamic surface tension is the value measured at 15 Hz of a 1% by mass aqueous solution according to the maximum bubble pressure method using a bubble pressure dynamic surface tensiometer (BP100, manufactured by KRUSS).

[0033] In a foaming test conducted by the Ross-Miles method (JIS K 3362; 2008), the surface conditioner of the present invention preferably produces foam height immediately after application of less than 20 cm, more preferably less than 15 cm, even more preferably less than 10 cm, and particularly preferably less than 5 cm, and the foam height after 5 minutes is preferably less than 5 cm, more preferably less than 3 cm, even more preferably less than 2 cm, and particularly preferably less than 1 cm. In other words, the surface conditioner of the present invention has low foaming properties and high foam-breaking properties. Therefore, a resin composition containing the surface conditioner of the present invention has good applicability to substrates and can also impart good smoothness to the substrates.

[0034] The surface conditioner of the present invention may be used alone as compound (1) or in combination with other surface conditioners, and may also contain other components such as a resin or a dispersion medium.

[0035] In a preferred embodiment, the surface conditioner of the present invention is a leveling agent. The surface conditioner of the present invention has a high surface tension reducing ability and a high bubble breaking ability, and therefore, by applying a composition containing the surface conditioner of the present invention to an object to be coated, a coating film with excellent smoothness can be formed.

[0036] <Resin composition> The surface conditioner of the present invention may be used together with other components such as a resin and a dispersion medium to form a resin composition. That is, the present invention also provides a resin composition containing the surface conditioner, a resin or a monomer constituting the resin, and a dispersion medium. The resin composition has a sufficiently high surface tension reducing ability and exhibits high bubble breaking properties, allowing the formation of a coating film with good smoothness.

[0037] In the resin composition of the present invention, the content of the surface conditioner is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and even more preferably 0.1 parts by mass or more, per 100 parts by mass of the resin. When the content of the surface conditioner is equal to or greater than the above-mentioned lower limit, the surface tension reducing effect on the substrate is sufficiently obtained, and the wettability of the resin composition is sufficiently high. Furthermore, in the resin composition of the present invention, the content of the surface conditioner is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, even more preferably 15 parts by mass or less, even more preferably 10 parts by mass or less, particularly preferably 7 parts by mass or less, and most preferably 5 parts by mass or less, per 100 parts by mass of the resin. When the content of the surface conditioner is equal to or less than the above-mentioned upper limit, the surface tension reducing effect on the substrate is sufficiently obtained, and the formed coating film also has good smoothness.

[0038] [resin] The resin composition contains a resin or a monomer constituting the resin. Specifically, the resin composition according to the present invention is obtained by dispersing or dissolving a surface conditioner and a resin or a monomer constituting the resin in a dispersion medium. Such a resin composition can be produced, for example, by dispersing or dissolving a surface conditioner and a resin or a monomer constituting the resin in a dispersion medium. In particular, the resin composition preferably contains a monomer constituting the resin together with the surface conditioner and the dispersion medium.

[0039] Examples of resins include (meth)acrylic resin, melamine resin, phenolic resin, urea resin, epoxy resin, polyester resin, silicone resin, polyamide resin, polycarbonate resin, polyurethane resin, polystyrene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl acetate resin, polyvinylidene fluoride resin, acrylonitrile-butadiene-styrene resin (ABS resin), acrylonitrile-styrene resin (AS resin), polyolefin resins such as polyethylene and polypropylene, hydroxyethyl cellulose resin, polyvinyl alcohol resin, polyethylene glycol (PEG) resin, polyethylene oxide resin, polypropylene oxide resin, polysaccharide resins, other photopolymerizable resins, and combinations thereof.

[0040] Among these, the resin is preferably at least one selected from the group consisting of (meth)acrylic resin, polystyrene resin, polyolefin resin, polyurethane resin, polyester resin, epoxy resin, melamine resin and silicone resin.

[0041] In one embodiment of the present invention, the resin is preferably a (meth)acrylic resin obtained by homopolymerizing or copolymerizing various (meth)acrylic acid ester monomers.

[0042] Examples of monomers constituting the resin include (meth)acrylic monomers, other monomers, unsaturated ethylenic monomers having an amide group, unsaturated ethylenic monomers having a urea group, unsaturated ethylenic monomers having an isocyanate group, and unsaturated ethylenic monomers having a urethane group.

[0043] Specific examples of monofunctional (meth)acrylic monomers include (meth)acrylic acid, (meth)acrylic acid alkyl esters having 1 to 18 carbon atoms such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate, hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, and (meth)acrylonitrile.

[0044] Specific examples of polyfunctional (meth)acrylic monomers include polyethylene glycol diacrylate, decanediol diacrylate, nonanediol diacrylate, hexanediol diacrylate, tricyclodecane dimethanol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.

[0045] Specific examples of other monomers include (meth)acrylic acid esters such as glycidyl (meth)acrylate, monoesters of (meth)acrylic acid and polyethylene glycol, 2-aminoethyl (meth)acrylate and its salts, caprolactone-modified (meth)acrylic acid, 2,2,6,6-tetramethylpiperidine (meth)acrylate, and 1,2,2,6,6-pentamethylpiperidine (meth)acrylate; (meth)acrylic acid salts such as sodium (meth)acrylate, potassium (meth)acrylate, and ammonium (meth)acrylate; acrylonitrile, meth ... Examples of such an unsaturated nitrile include unsaturated amides such as (meth)acrylamide, N-methylol (meth)acrylamide, and N-(2-hydroxyethyl) (meth)acrylamide; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; α-olefins such as ethylene and propylene; halogen-containing α,β-unsaturated aliphatic hydrocarbons such as vinyl chloride, vinylidene chloride, and vinyl fluoride; and α,β-unsaturated aromatic hydrocarbons such as styrene, divinylbenzene, α-methylstyrene, and sodium styrenesulfonate. These may be used alone or in combination of two or more, but it is preferable to use two or more.

[0046] Specific examples of unsaturated ethylenic monomers having an amide group include (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, Nn-butyl(meth)acrylamide, N-tert-butyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-methylol(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-methyl-N-ethyl(meth)acrylamide, N-hydroxyethyl-N-methyl(meth)acrylamide, (meth)acryloylmorpholine, and vinylacetamide.

[0047] Examples of unsaturated ethylenic monomers having a urea group include (meth)acryloyloxyethyl ethylene urea and (meth)acryloyloxypropyl ethylene urea. Examples of unsaturated ethylenic monomers having an isocyanate group include 2-(meth)acryloyloxyethyl isocyanate. Examples of unsaturated ethylenic monomers having a urethane group include (meth)acryloyloxyethyl methyl carbamate and urethane acrylate. These monomers can be used in appropriate combinations depending on the properties required for the resin composition and the coating film formed therefrom.

[0048] The surface conditioner according to the present invention, when incorporated into a resin or a resin composition containing a monomer constituting the resin, can improve the smoothness of a coating film obtained by applying the resin composition to an object to be coated. From this perspective, for example, it is preferable to combine the surface conditioner according to the present invention with one or more monomers selected from (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and other C1-18 (meth)acrylic acid alkyl esters, hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylonitrile, and urethane acrylates, or with a resin composed of such monomers to form a resin composition.

[0049] The content of the resin or the monomer constituting the resin in the resin composition of the present invention is not particularly limited, but is, for example, preferably 10 to 90 mass %, more preferably 20 to 80 mass %, and even more preferably 30 to 70 mass %. Only one type of resin may be used alone, or two or more types may be used in combination. When two or more types of resins (or monomers) are used, the content of the resins (or monomers) is the total amount.

[0050] [Dispersion medium] In this specification, the resin composition contains a dispersion medium (solvent). The dispersion medium (solvent) adjusts the viscosity of the resin composition and improves the applicability of the resin composition when it is applied to an object to be coated. The coating film obtained after the resin composition is applied to an object to be coated and, if necessary, undergoes a curing step may contain the dispersion medium (solvent), or the dispersion medium (solvent) may have been removed by evaporation or the like.

[0051] The type of dispersion medium (solvent) is not particularly limited, but preferably includes a protic polar solvent, an aprotic polar solvent, or a nonpolar solvent. Examples of protic polar solvents include water; alcoholic solvents such as ethyl alcohol, methyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol (1-butanol), 2-butyl alcohol (2-butanol), isobutyl alcohol, ethylene glycol, and propylene glycol; and acetic acid. Examples of aprotic polar solvents include ketone solvents such as dimethyl sulfoxide, N-methylpyrrolidone, N-ethylpyrrolidone, N,N-dimethylformamide, acetonitrile, tetrahydrofuran, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, acetone, methyl ethyl ketone, and methyl isobutyl ketone; monoalkylene glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, and dipropylene glycol monomethyl ether; and dialkylene glycol ether solvents such as diethylene glycol diethyl ether and triethylene glycol diethyl ether. Examples of nonpolar solvents include hexane, heptane, octane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, decalin, tetralin, methylene chloride, chloroform, and dichloroethane, as well as derivatives thereof. The water used is not particularly limited and may be any type of water, such as industrial water, purified water, ion-exchanged water, or ultrapure water. The solvents may be used alone or in combination of two or more, and may also be used as a mixed solvent with water.

[0052] Among these, from the viewpoint of dispersibility of compound (1), ethyl alcohol, methyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, 2-butyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol, toluene, and xylene are preferred, and 2-butyl alcohol, propylene glycol monomethyl ether, toluene, and xylene are more preferred.

[0053] The dispersion medium (solvent) can be appropriately selected depending on the components contained in the resin composition, but for example, when the resin is composed of a (meth)acrylic resin, the solvent is preferably toluene.

[0054] [Polymerization initiator] When the resin composition contains a monomer, it is preferable to use a polymerization initiator such as a thermal polymerization initiator or a photopolymerization initiator for polymerizing the monomer, and these may be used alone or in combination of two or more. The amount of the polymerization initiator added is preferably 0.1 to 5 parts by mass per 100 parts by mass of the total amount of all monomers.

[0055] Examples of the thermal polymerization initiator include methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methylacetoacetate peroxide, acetylacetate peroxide, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)-cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)-2-methylcyclohexane, 1,1-bis(t -butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, 1,1-bis(t-butylperoxy)butane, 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, α,α'-bis(t-butylperoxy)diisopropyl Pyrbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide, m-toluoylbenzoyl peroxide, benzoyl peroxide, di-n-propyl Dipropyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis(4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethoxyhexyl peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-s-butyl peroxydicarbonate, di(3-methyl-3-methoxybutyl) peroxydicarbonate, α,α'-bis(neodecanoylperoxy)diisopropylbenzene, cumyl peroxyneodecanoate, 1,1,3,3-Tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate , t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxyisobutyrate, t-butylperoxymalate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-butylperoxyacetate, t-butylperoxy-m-tolube organic peroxide initiators such as benzoate, t-butyl peroxybenzoate, bis(t-butylperoxy)isophthalate, 2,5-dimethyl-2,5-bis(m-toluylperoxy)hexane, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butylperoxyallyl monocarbonate, t-butyltrimethylsilyl peroxide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 2,3-dimethyl-2,3-diphenylbutane; 2-Phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 1-[(1-cyano-1-methylethyl)azo]formamide, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis(2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2'-Azobis[N-(4-chlorophenyl)-2-methylpropionamidine]dihydridochloride, 2,2'-Azobis[N-(4-hydrophenyl)-2-methylpropionamidine]dihydrochloride, 2,2'-Azobis[2-methyl-N-(phenylmethyl)propionamidine]dihydrochloride, 2,2'-Azobis[2-methyl-N-(2-propenyl)propionamidine]dihydrochloride, 2,2'-Azobis[N-(2-hydroxyethyl)-2-methylpropionamidine dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(3,4,5,6-tetrahydropyrimidin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(5- hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane] dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide], 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl) )ethyl]propionamide], 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis(2-methylpropionamide), 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane), dimethyl-2,2-azobis(2-methylpropionate), 4,4'-azobis(4-cyanopentanoic acid), 2,2'-azobis[2-(hydroxymethyl)propionitrile], and the like. These thermal polymerization initiators may be used alone or in combination of two or more.

[0056] Examples of photopolymerization initiators include 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzil dimethyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl dimethyl ketone ... Acetophenones such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc.; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3',4,4'-tetrabenzoylbenzoate, 4-benzoyl-4'-methyl-diphenyl sulfide, 4-benzoyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer, etc. Benzophenones such as (t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl]benzenemethanaminium bromide, and (4-benzoylbenzyl)trimethylammonium chloride; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-(3-dimethylthioxanthone), 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-(3-dimethylthioxanthone), 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 4-isopropyl ... Examples of the photopolymerization initiator include thioxanthones such as bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; thioxanthones such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; oxime esters; cationic photopolymerization initiators; and intramolecular hydrogen abstraction photopolymerization initiators. These photopolymerization initiators may be used alone or in combination of two or more.

[0057] [Optional ingredients] In addition to the surface conditioner, resin or monomers constituting the resin, and dispersion medium, as well as the polymerization initiator described above, the resin composition of the present invention may further contain known additives to the extent that the effects of the present invention are not impaired. Examples of additives include pigments, plasticizers, dispersants, thickeners, antifoaming agents, preservatives, UV absorbers, and fragrances. The content of such additives is not particularly limited, but is preferably 0.01 to 30% by mass, more preferably 0.1 to 20% by mass, based on the resin.

[0058] The form of use of the surface conditioner according to the present invention is not particularly limited. For example, a resin composition may be prepared by mixing a monomer constituting a resin with a dispersion medium, and then adding the surface conditioner to obtain a dispersion. Alternatively, a resin composition may be prepared by dispersing a surface conditioner in a dispersion medium, and then adding a monomer constituting a resin to the dispersion. Alternatively, a suitable combination of these forms may be used. Alternatively, a resin composition containing a resin may be prepared by adding the surface conditioner, resin, and dispersion medium in any order.

[0059] [Coating] According to the present invention, there is also provided a coating film made of the resin composition. That is, the present invention also provides a coating film formed by applying the resin composition. As described above, the resin composition according to the present invention exhibits the effects of the surface conditioner according to the present invention, and therefore the coating film according to the present invention also exhibits the effects of the surface conditioner and has high smoothness.

[0060] The coating film according to the present invention can be obtained by applying the resin composition according to the present invention to an object to be coated, followed by drying and, if necessary, polymerization. There are no particular limitations on the drying and polymerization conditions. For example, in the case of solution polymerization, the polymerization temperature can be appropriately set depending on the type of polymerization initiator used, but is preferably 50 to 120°C. There are also no particular limitations on the polymerization time, but it is preferably 1 to 10 hours.

[0061] When polymerization is carried out by irradiation with ultraviolet light, a mercury lamp (e.g., a high-pressure mercury lamp or a low-pressure mercury lamp), a metal halide lamp, etc. can be used as the irradiation light source. The irradiation conditions of ultraviolet light are not particularly limited, but the cumulative light dose is preferably 100 mJ / cm. 2 More than 200mJ / cm is preferable. 2 The above is more preferable. The irradiation time is not particularly limited, but is preferably 0.01 to 300 seconds.

[0062] [Coating] The present invention also provides a coated article comprising a substrate and a coating film according to the present invention formed on the substrate. As described above, the coating film according to the present invention exhibits the effects of the surface conditioner according to the present invention, and therefore a coated article having such a coating film on the substrate can also exhibit the effects of the surface conditioner according to the present invention.

[0063] Specific examples of objects to be coated and coated with coating films include buildings, structures (bridges, tanks, etc.), ships, road vehicles, electrical machinery, metal products, wood products, etc. The shape and thickness of the coating film are not particularly limited, and a desired thickness can be adopted depending on the application.

[0064] The material of the substrate on which the coating film is formed is not particularly limited, and may be organic materials such as metals and plastics (resins), inorganic materials such as ceramics and glass, paper, wood, etc. When the substrate is made of resins such as polyethylene terephthalate (PET), acrylic resins, polyolefin resins such as polypropylene, and talc-containing chlorinated polypropylene, the surface conditioner of the present invention can particularly reduce the effects on the substrate and can maintain adhesion between the resin composition containing the surface conditioner of the present invention and the substrate.

[0065] The method for applying the resin composition of the present invention to an object to be coated to form a coating film can be any conventionally known coating method without any particular limitations. Thus, the present invention also provides a method for forming a coating film, which includes a step of applying the resin composition to an object to be coated to form a coating film. In the present invention, the concept of a coating film also includes a coating film without an object to be coated, i.e., a film consisting only of the resin composition. [Example]

[0066] The present invention will be described in more detail using the following examples and comparative examples, although the technical scope of the present invention is not limited to the following examples.

[0067] <Synthesis of surface conditioner> [Synthesis Example 1: Synthesis of diol EO adduct] The diol compound (CH3-(CH2)) is prepared by the method described on page 1 of JP-A-50-159595. a -CH2(OH)-(CH2) b -CH2(OH)-(CH2) c -CH3; a to c are each independently an integer of 0 to 10, and the sum of a to c is 8 to 10) was synthesized, and then EO was added to the diol compound in an amount adjusted to achieve the desired number of moles of EO added, thereby preparing a diol EO adduct.

[0068] Specifically, the case where 3 moles of EO are added to a diol compound will be described. Note that, hereinafter, the number of moles (numerical value) of EO added to the diol compound will be added before the term "EO adduct" when referring to the diol EO adduct (for example, a compound with 3 moles of EO added will be referred to as a "diol 3EO adduct").

[0069] Diol compounds (CH3-(CH2) a -CH2(OH)-(CH2) b -CH2(OH)-(CH2) c-CH3; a-c are each independently an integer between 0 and 10, and the sum of a-c is 8-10) is a compound obtained by liquid-phase oxidation of n-paraffins having 12 to 14 carbon atoms with a molecular oxygen-containing gas, in which an average of two hydroxyl groups are randomly bonded to primarily secondary carbons per molecule. The carbon numbers of the diol compound were analyzed by gas chromatography, and it was confirmed that the diol compound was present in a mass ratio of C12 / C13 / C14 / other high-boiling substances = 3 / 42 / 53 / 2. NMR analysis confirmed that the diol compound was not a primary alcohol, and that it contained two hydroxyl groups.

[0070] A diol compound (CH3-(CH2)) was placed in a stainless steel autoclave equipped with a stirrer, thermometer, and EO inlet tube. a -CH2(OH)-(CH2) b -CH2(OH)-(CH2) c 394.3 parts by mass of -CH3 (a-c are each independently integers between 0 and 10, and the sum of a-c is 8-10) was charged and purged with nitrogen. Then, 0.8 parts by mass of BF3·OEt2 was charged, and EO was added at 3 moles per mole of raw alcohol at an initial nitrogen pressure of 0.05 MPa and 65±5°C. Next, the diol-3EO adduct ethoxylate of the raw alcohol obtained above and 4 parts by mass of an adsorption treatment agent (Kyoward 500SH, manufactured by Kyowa Chemical Industry Co., Ltd.) were charged into a Pyrex beaker and stirred for 1 hour with nitrogen bubbling at 60±5°C. The adsorption treatment agent was then filtered, and the filtrate was charged into a recovery flask. Low-boiling components were removed by evaporation, yielding a diol-3EO adduct.

[0071] [Compounds used in Examples and Comparative Examples] Diol 3EO adduct (a to c are each independently an integer of 0 to 10, and the sum of a to c is 8 to 10; n + m = 3) Diol 5EO adduct (a to c are each independently an integer of 0 to 10, and the sum of a to c is 8 to 10; n + m = 5) Diol 7EO adduct (a to c are each independently an integer of 0 to 10, and the sum of a to c is 8 to 10; n + m = 7) Diol 9EO adduct (a to c are each independently an integer of 0 to 10, and the sum of a to c is 8 to 10; n + m = 9) Diol 12EO adduct (a to c are each independently an integer of 0 to 10, and the sum of a to c is 8 to 10; n + m = 12) Diol 40EO10PO adduct (a-c are each independently an integer of 0-10, and the sum of a-c is 8-10; n+m=50) Surfynol 465 (acetylene glycol surfactant, EO addition mole number: 10.5, manufactured by Nissin Chemical Industry Co., Ltd.); comparative compound Surfynol 485 (acetylene glycol surfactant, EO addition mole number: 30, manufactured by Nissin Chemical Industry Co., Ltd.); comparative compound Primary monoalcohol 59EO adduct (EO adduct to primary monoalcohol with 12-13 carbon atoms); comparative compound Secondary monoalcohol 40EO adduct (CH3-(CH2) p -CH2(-O(CH2O) r H)-(CH2) q -CH3; p and q each independently represent an integer of 0 to 10, and the sum of p and q is 8 to 10; r=40); comparative compound.

[0072] <Evaluation> [Foaming power / antifoaming property] For a 1% by mass aqueous solution of each compound, 200 mL of the sample solution of a specified concentration is dropped onto the liquid surface from a height of 900 mm under specified temperature conditions for 30 seconds using the Ross-Miles method (JIS K 3362; 2008 8.5.1). The height of the foam generated (immediately afterwards) is measured as the foaming power, and the height after 5 minutes is measured as the defoaming power. The evaluation results are shown in Table 1.

[0073] [Contact angle] For each compound, the contact angle of a 0.1% by mass aqueous solution and a 1% by mass aqueous solution was measured. Specifically, under dry conditions (25°C / 50% RH), a contact angle meter (Kyowa Interface Science Co., Ltd., Model: CA-XP) was used to create approximately 1 μL droplets on the tip of a needle using a 0.1% by mass aqueous solution and a 1% by mass aqueous solution, respectively, and these were then brought into contact with the surface of a parafilm (Bemis) to create droplets. The contact angle was the angle on the liquid-containing side, defined as the angle between the tangent to the liquid surface and the parafilm surface at the point where the parafilm and liquid come into contact. The evaluation results are shown in Table 1.

[0074] [Static surface tension] The surface tension (mN / m) of 0.1% by mass and 1% by mass aqueous solutions of each compound was measured at 25°C (50% RH) using a surface tensiometer (K100, manufactured by KRUSS) based on the Wilhelmy method (plate method). The lower the surface tension, the higher the wettability of the coated object. The evaluation results are shown in Table 1.

[0075] [Dynamic surface tension] A 0.1% by mass aqueous solution and a 1% by mass aqueous solution of each compound were prepared, and the dynamic surface tension was measured at 25°C (50% RH) using the maximum bubble pressure method with a bubble pressure dynamic surface tensiometer (KRUSS, BP100). Specifically, the values ​​at 15 Hz and 0.08 Hz were measured for the 0.1% by mass aqueous solution and the 1% by mass aqueous solution of each compound. The evaluation results are shown in Table 1.

[0076] [Critical micelle concentration (CMC)] A 5% by mass aqueous solution of each compound was prepared, and the 5% by mass aqueous solution was diluted with water to 0.01% by mass using a surface tensiometer (KRUSS, Surface Tensiometer K100) based on the Wilhelmy method (plate method), and the CMC at 25°C (50% RH) was measured. The evaluation results are shown in Table 1.

[0077] [Table 1]

[0078] As shown in Table 1, the static and dynamic surface tension results show that the surface conditioners of the present invention in Examples 1 to 6 and the comparative compounds in Comparative Examples 1 to 4 have similar surface tensions. On the other hand, the surface conditioners of the present invention in Examples 1 to 6 have smaller contact angles than the comparative compounds in Comparative Examples 1 to 4, demonstrating improved wettability to the substrate. Furthermore, the surface conditioners of the present invention in Examples 3 to 6 have smaller CMCs than the comparative compounds in Comparative Examples 1 and 2, demonstrating the ability to reduce surface tension with a small amount added.

[0079] Furthermore, in the foaming power and defoaming property tests, it was found that the surface conditioners of the present invention in Examples 1 to 5 had lower foaming power immediately after foaming and higher defoaming power after 5 minutes compared to the comparative compounds in Comparative Examples 1 to 4. It was found that the surface conditioner of the present invention in Example 6 had better foaming power and defoaming power (foam breaking power) than the comparative compounds in Comparative Examples 3 and 4, which had similar numbers of moles of alkylene oxide added.

[0080] These results demonstrate that the surface conditioner of the present invention can provide high surface tension reduction and excellent bubble breaking properties even when added in small amounts. This suggests that the surface conditioner of the present invention can impart good wettability and good smoothness to the substrate, even in coating films formed from resin compositions containing the surface conditioner.

Claims

1. The following formula (1): 【Chemistry 1】 In formula (1), R １ and R ２ is CH ３ It is the basis, a to c are each independently an integer from 0 to 10, and the sum of a to c is from 4 to 14, R ３ are each independently a linear or branched alkylene group having 1 to 6 carbon atoms, m and n each independently represent a number from 0 to 50, and the sum of m and n is from 3 to 50; Here, m and n are the (R ３ When m and / or n is 2 or more, R constituting each polyalkylene glycol group represents the number of moles of R ３ The types may be different, R ４ are each independently hydrogen or a linear or branched alkyl group having 1 to 8 carbon atoms; A surface conditioner comprising a compound represented by the formula:

2. In the formula (1), R 3 is an ethylene group; 2. The surface conditioner according to claim 1, wherein m and n each independently represent a number from 0 to 15, and the sum of m and n is 3 to 15.

3. 3. The surface conditioner according to claim 1, wherein in the formula (1), the sum of a to c is 8 or more and 10 or less.

4. The surface conditioner according to claim 1 or 2, which is a leveling agent.

5. A resin composition comprising the surface conditioner according to claim 1 or 2, a resin or a monomer constituting the resin, and a dispersion medium.

6. The resin composition according to claim 5 , wherein the surface conditioner is contained in an amount of 0.1 parts by mass or more relative to 100 parts by mass of the resin.

7. A coating film formed by applying the resin composition according to claim 6.

8. A method for forming a coating film, comprising the step of applying the resin composition according to claim 6 to an object to be coated to form a coating film.

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