Monomer composition, polymer, water repellent agent composition, and water repellent agent-treated product

Abstract

To provide a monomer composition having high water repellency of a polymer and high solubility of a monomer in a solvent.SOLUTION: A monomer composition comprising 50 to 99% by mass of a hydroxyurethane group-containing (meth) acrylate represented by the following formula (1) and 1 to 50% by mass of a hydroxyurethane group-containing (meth) acrylate represented by the following formula (2): SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a monomer composition, a polymer, a water repellent composition, and a water repellent-treated product. [Background technology]

[0002] A (meth)acrylate polymer containing a long-chain alkyl group and a hydroxyurethane group can form a dense film with aligned long-chain alkyl groups on the surface of a substrate because the hydroxyurethane structure induces crystallization of the side chains. Therefore, a composition containing the polymer imparts excellent water repellency to the substrate (for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2023-145051 Summary of the Invention [Problem to be solved by the invention]

[0004] On the other hand, (meth)acrylates containing long-chain alkyl groups and hydroxyurethane groups have low solubility in solvents, so when polymerizing the (meth)acrylate, there is a risk of monomer precipitation during the polymerization reaction. Therefore, when the resulting polymer is applied to a substrate, the film surface is not smooth enough, and the water repellency may not be as high as expected. This monomer precipitation is particularly likely to occur when the copolymerization ratio of the (meth)acrylate is high.

[0005] A common method for suppressing monomer precipitation is to increase the polymerization temperature. However, increasing the polymerization temperature generates impurities such as Michael adducts and ester hydrolysates, which reduce the water repellency and smoothness of the coating film. Furthermore, the melting point of the composition can be lowered by blending a low-melting-point acrylate, thereby increasing the solubility of the (meth)acrylate. However, this method reduces the density of the side chains, and the water repellency of the polymer does not increase as much as expected.

[0006] Therefore, a new method has been sought for improving the solubility of (meth)acrylates containing long-chain alkyl groups and hydroxyurethane groups in solvents while maintaining the water repellency of the polymer.

[0007] The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a monomer composition containing a (meth)acrylate containing a long-chain alkyl group and a hydroxyurethane group, wherein the polymer has high water repellency and high solubility of the monomer in solvents; a polymer obtained from the monomer composition; and a water repellent composition and a water repellent-treated product each containing the polymer. [Means for solving the problem]

[0008] One embodiment of the present invention for solving the above problems relates to a monomer composition, a polymer, a water repellent composition, and a water repellent-treated product as set forth in the following items [1] to [4]. [1] 50 to 99% by mass of a hydroxyurethane group-containing (meth)acrylate represented by the following formula (1), and The composition contains 1 to 50% by mass of a hydroxyurethane group-containing (meth)acrylate represented by the following formula (2) (wherein the total of the compound represented by formula (1) and the compound represented by formula (2) is 100% by mass), Monomer composition. [ka] [ka] (In formula (1) and formula (2), R 1 and R 4 are independently a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, or an iodine atom; A and B are independently an alkylene group having 1 to 10 carbon atoms; X and Y are independently 0 or 1; R 2 and R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; R 3 and R 6 are independently an alkyl group having 12 to 24 carbon atoms. [2] A polymer obtained by polymerizing a monomer contained in the monomer composition according to [1], A polymer, wherein the mass ratio (a) / (c) of the structural unit (a) derived from the compound represented by formula (1) and the compound represented by formula (2) to the structural unit (c) derived from another copolymerizable vinyl group-containing monomer is 100 / 0 to 30 / 70. [3] A water repellent composition comprising the polymer according to [2]. [4] A water-repellent treated object, which is obtained by adhering the polymer according to [2] to the surface of an object to be treated. [Effects of the Invention]

[0009] According to the present invention, there are provided a monomer composition containing a (meth)acrylate containing a long-chain alkyl group and a hydroxyurethane group, wherein the polymer has high water repellency and the monomer has high solubility in solvents; a polymer obtained from the monomer composition; and a water repellent composition and a water repellent-treated product each containing the polymer. DETAILED DESCRIPTION OF THE INVENTION

[0010] In this specification, a numerical range indicated by "to" includes the numerical values ​​before and after "to."

[0011] In this specification, (meth)acrylate means acrylate or methacrylate (similarly to (meth)acrylate), (meth)acrylic means acrylic or methacrylic, and (meth)acryloyl means acryloyl or methacryloyl.

[0012] <Monomer composition and method for producing same> One embodiment of the present invention relates to a monomer composition containing a hydroxyurethane group-containing (meth)acrylate represented by the following formula (1) and a hydroxyurethane group-containing (meth)acrylate represented by the following formula (2).

[0013] [ka]

[0014] [ka]

[0015] In formula (1) and formula (2), R 1 and R 4 are independently a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, or an iodine atom. Among these, a hydrogen atom and a methyl group are preferred from the viewpoint of facilitating the polymerization reaction of the monomer composition, and a methyl group is more preferred from the viewpoint of solubility.

[0016] In formula (1) and formula (2), R 2 and R 5 R independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. The alkyl group having 1 to 12 carbon atoms may be linear, or when the number of carbon atoms is 3 or more, it may be branched. 3 and R 6 From the viewpoint of making it difficult to inhibit the crystallization of the side chain by R 2 and R 5 are each independently preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0017] In formula (1) and formula (2), R 3 and R 6 R independently represents an alkyl group having 12 to 24 carbon atoms. The alkyl group having 12 to 24 carbon atoms may be a straight chain or a branched chain. 3 and R 6 When R is polymerized, it induces the crystallization of the side chains, forming a dense film with aligned alkyl groups on the surface of the workpiece. 3 and R 6 From the viewpoint of further enhancing the water repellency of the polymer film and facilitating industrial production, R 3 and R 6 is preferably an alkyl group having 12 to 22 carbon atoms, and more preferably an alkyl group having 18 to 22 carbon atoms. 3 and R 6 is preferably a straight-chain alkyl group.

[0018] A and B independently represent an alkylene group having 1 to 10 carbon atoms, and X and Y independently represent 0 or 1. From the viewpoint of sufficient precipitation from a good solvent using an aliphatic hydrocarbon solvent, A and B preferably have 1 to 6 carbon atoms, and more preferably have 1 to 4 carbon atoms. From the viewpoint of sufficient precipitation from a good solvent using an aliphatic hydrocarbon solvent, X and Y are preferably 0.

[0019] The compound represented by formula (1) may be used alone or in combination of two or more. Similarly, the compound represented by formula (2) may be used alone or in combination of two or more.

[0020] When the total amount of the compound represented by formula (1) and the compound represented by formula (2) is taken as 100% by mass, the monomer composition contains 50 to 99% by mass of the compound represented by formula (1) and 1 to 50% by mass of the compound represented by formula (2). The greater the amount of the compound represented by formula (1), the more water-repellent the polymer film can be. The greater the amount of the compound represented by formula (2), the more the solubility of the monomer in hydrocarbon solvents can be. From the viewpoint of achieving a balance between these, the monomer composition preferably contains 50 to 95% by mass of the compound represented by formula (1) and 5 to 50% by mass of the compound represented by formula (2), and even more preferably contains 70 to 90% by mass of the compound represented by formula (1) and 10 to 30% by mass of the compound represented by formula (2).

[0021] The compounds represented by formula (1) and formula (2) can be synthesized, for example, by an addition reaction between a compound having a (meth)acryloyl group and a five-membered cyclic carbonate group, represented by the following formula (3), and an amine compound.

[0022] [ka]

[0023] In formula (3), R 7 represents a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, or an iodine atom. Among these, a hydrogen atom and a methyl group are preferred, and a methyl group is more preferred from the viewpoint of solubility.

[0024] In formula (3), C represents an alkylene group having 1 to 10 carbon atoms. From the viewpoint of sufficient precipitation from a good solvent using an aliphatic hydrocarbon solvent, C preferably has 1 to 6 carbon atoms, and more preferably has 1 to 4 carbon atoms.

[0025] In formula (3), Z represents 0 or 1. From the viewpoint of solubility, Z is preferably 0.

[0026] Specific examples of the compound represented by formula (3) include the following compounds (3-1) to (3-3).

[0027] [ka]

[0028] The amine compound is an amine compound represented by formula (4). NH 8 R 9 ...Equation (4)

[0029] In formula (4), R 8 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. The alkyl group having 1 to 12 carbon atoms may be a straight chain, or when the number of carbon atoms is 3 or more, it may be a branched chain. R 8 is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0030] In formula (4), R 9 represents an alkyl group having 12 to 24 carbon atoms. The alkyl group having 12 to 24 carbon atoms may be a straight chain or a branched chain. R 9 is preferably an alkyl group having 12 to 22 carbon atoms, and more preferably an alkyl group having 18 to 22 carbon atoms. 9 is preferably a straight-chain alkyl group.

[0031] The reaction between the five-membered cyclic carbonate compound represented by formula (3) and the amine compound represented by formula (4) can be carried out by mixing the two and, if desired, increasing the temperature by a known method. If necessary, a known polymerization inhibitor may be added. This reaction is preferably carried out at a temperature of 0 to 100°C, more preferably at a temperature of 5 to 50°C, and even more preferably at a temperature of 5 to 40°C.

[0032] The reaction is carried out in an aliphatic hydrocarbon solvent. The aliphatic hydrocarbon solvent may be linear or branched. Examples of aliphatic hydrocarbon solvents include hexane, 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, 2,2-dimethylbutane, heptane, octane, and nonane. Among these, hexane, 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, 2,2-dimethylbutane, and heptane are preferred, with hexane and heptane being more preferred. Furthermore, acetone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene, xylene, tetrahydrofuran, and the like may be used in combination as a mixed solvent.

[0033] In the above reaction, from the viewpoint of synthesis efficiency, the hydroxyurethane group-containing (meth)acrylate represented by formula (2) can be synthesized in one step. Therefore, the reaction product obtained by the above reaction is an isomer mixture containing the compound represented by formula (1) and the compound represented by formula (2).

[0034] Therefore, after the reaction, a step of adjusting the composition ratio of the compound represented by formula (1) to the compound represented by formula (2) in the reaction product may be carried out. The step of adjusting the composition ratio can be carried out by a known method such as filtration, reprecipitation, or distillation.

[0035] <Filtration process> Since the filtrate portion of the reaction solution contains a high proportion of the compound represented by formula (2), by filtering only the residue, a monomer composition containing a high proportion of the compound represented by formula (1) can be obtained. The filtration temperature is preferably 40 to 5°C to suppress impurities such as Michael adducts and ester hydrolysates, and more preferably 20 to 25°C from the viewpoint of filtering out the compound represented by formula (2).

[0036] <Reprecipitation step> In the reprecipitation process, the residue obtained from the filtration step is dissolved in a good solvent, and then an aliphatic hydrocarbon solvent is added to prepare crude crystals. Specifically, by adding an aliphatic hydrocarbon solvent to the reaction solution, crude crystals containing the reaction product, the hydroxyurethane group-containing (meth)acrylate represented by formula (1), are selectively precipitated.

[0037] The aliphatic hydrocarbon solvent used for reprecipitation (precipitation) may be linear or branched. Examples of the aliphatic hydrocarbon solvent include hexane, 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, 2,2-dimethylbutane, heptane, octane, and nonane. Among these, hexane, 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, 2,2-dimethylbutane, and heptane are preferred, and hexane and heptane are more preferred.

[0038] The amount of the aliphatic hydrocarbon solvent is preferably 600 to 1200 parts by mass, more preferably 700 to 1000 parts by mass, and even more preferably 800 to 900 parts by mass, relative to 100 parts by mass of the amine compound before the reaction.

[0039] During reprecipitation, chloroform, tetrahydrofuran, toluene, or the like, which is a good solvent for the compound represented by formula (1) and the compound represented by formula (2), is used together with an aliphatic hydrocarbon solvent, which is a poor solvent.

[0040] The amount of the compound represented by formula (1) and the compound represented by formula (2) (residue obtained by the filtration step) dissolved in the good solvent is preferably 30 to 80 parts by mass per 100 parts by mass of the good solvent in order to effectively remove the compound represented by formula (2), and more preferably 60 to 80 parts by mass from the viewpoint of efficiency.

[0041] The temperature during reprecipitation is preferably 50 to 20°C from the viewpoint of suppressing the formation of impurities such as Michael adducts and ester hydrolysates, and more preferably 40 to 20°C in order to obtain a monomer composition containing a higher proportion of the compound represented by formula (1).

[0042] Furthermore, by carrying out further reprecipitation or the like, the composition ratio of the compound represented by formula (1) and the compound represented by formula (2) can be adjusted.

[0043] <Distillation step> The filtrate portion of the reaction solution contains a high proportion of the compound represented by formula (2), and therefore, by distilling off the filtrate, a monomer composition containing a high proportion of the compound represented by formula (2) can be obtained. The distillation temperature is preferably 60 to 20°C from the viewpoint of suppressing the formation of impurities such as Michael adducts and ester hydrolysates, and more preferably 40 to 30°C from the viewpoint of distillation efficiency. By increasing the distillation temperature, it is possible to suppress the remaining solvent, and by setting the distillation temperature to a moderately high temperature, it is possible to suppress gelation.

[0044] The degree of vacuum is preferably 20 to 100 torr. From the viewpoint of distillation efficiency, 20 to 50 torr is more preferable. By increasing the degree of vacuum, gelation can be suppressed, and by setting the distillation temperature to a moderately high temperature, residual solvent can be suppressed.

[0045] The distillation time is preferably 10 to 180 minutes. From the viewpoint of suppressing the formation of impurities such as Michael adducts and ester hydrolysates, 40 to 120 minutes is more preferable. By extending the distillation time, the amount of solvent remaining can be suppressed, and by setting the distillation time to a suitable time that is not too long, gelation can be suppressed.

[0046] <Method for adjusting the composition ratio of a composition comprising a compound represented by formula (1) and a compound represented by formula (2)> The composition ratio of the composition consisting of the compound represented by formula (1) and the compound represented by formula (2) can be adjusted by any method. For example, to obtain a composition containing 90 to 99 mass% of the compound represented by formula (1) and 1 to 10 mass% of the compound represented by formula (2), it is preferable to perform a reprecipitation step after the filtration step. Furthermore, to obtain a composition containing 80 to 90 mass% of the compound represented by formula (1) and 10 to 20 mass% of the compound represented by formula (2), it is preferable to perform only the filtration step. Furthermore, to obtain a composition containing 65 to 80 mass% of the compound represented by formula (1) and 20 to 35 mass% of the compound represented by formula (2), it is preferable to perform only the evaporation step without performing the filtration step and the reprecipitation step.

[0047] <Polymer> The above-mentioned monomer mixture can be used to produce a polymer by radical polymerization of a compound represented by formula (1) and a compound represented by formula (2). This polymer can be used as a polymer for a water repellent. The polymerization method is not particularly limited, and known polymerization methods such as solution polymerization, emulsion polymerization, and suspension polymerization can be used.

[0048] A polymer according to another embodiment of the present invention comprises a constitutional unit derived from a compound represented by formula (1) and a constitutional unit derived from a compound represented by formula (2).

[0049] From the viewpoint of enhancing water repellency, the polymer preferably contains a process unit derived from at least one other monomer that is copolymerizable with the compound represented by formula (1) and the compound represented by formula (2), and preferably has a constituent unit derived from a vinyl group-containing monomer represented by the following formula (4):

[0050] [ka] (Formula (4), R 10 represents a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, or an iodine atom; D represents an oxygen atom or a nitrogen atom; R 11are independently a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 22 carbon atoms, and n is 1 when D is an oxygen atom, and is 2 when D is a nitrogen atom.

[0051] (Vinyl group-containing monomer represented by formula (4)) Examples of other vinyl group-containing monomers copolymerizable with the compound represented by formula (1) and the compound represented by formula (2) include (meth)acrylic acid ester compounds, (meth)acrylamide compounds, aromatic alkenyl compounds, halogenated vinyl compounds excluding fluorine atom-containing compounds, vinyl cyanide compounds, etc. Among these, (meth)acrylic acid ester compounds or (meth)acrylamide compounds are preferred, and vinyl monomers represented by formula (4) are preferred.

[0052] In formula (4), R 10 is a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, or an iodine atom; D is an oxygen atom or a nitrogen atom; R 11 is a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, and n is 1 when D is an oxygen atom, and 2 when D is a nitrogen atom. The hydrocarbon group may have a substituent, or may have a linking group in the hydrocarbon chain. The compound represented by formula (4) can be prepared by the reaction of R 11 is a hydrocarbon group having a substituent or a linking group, and R 11 is a hydrocarbon group having no substituent or linking group.

[0053] R 11 Examples of the compound in which is a hydrogen atom include (meth)acrylic acid and (meth)acrylamide.

[0054] R 11 Examples of the hydrocarbon group having no substituent or linking group in the above formula include linear, branched, and cyclic alkyl groups having 1 to 22 carbon atoms.

[0055] R 11Examples of the compound represented by formula (4) having a linear or branched alkyl group having 1 to 22 carbon atoms as the alkyl group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, hexadecyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, docosyl (meth)acrylate, dimethyl(meth)acrylamide, and diethyl(meth)acrylamide. Among these, methyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, and isostearyl (meth)acrylate are preferred, and stearyl (meth)acrylate is more preferred, from the viewpoints of facilitating enhancement of water repellency and ease of copolymerization with the compound represented by formula (1) and the compound represented by formula (2).

[0056] R 11 The substituent in the formula (I) is a cyclic hydrocarbon group having no linking group, and examples thereof include monocyclic or polycyclic alkyl groups having 3 to 22 carbon atoms.

[0057] R 11 Examples of the compound represented by formula (4) having a cyclic hydrocarbon group having 1 to 22 carbon atoms as the alkyl group include cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, 1-adamantyl (meth)acrylate, etc. Among these, cyclohexyl (meth)acrylate and isobornyl (meth)acrylate are preferred from the viewpoint of making it easier to maintain water repellency.

[0058] R 11When the hydrocarbon group in R has a substituent or a linking group, examples of the substituent and linking group include a hydroxyl group, an ether group, an epoxy group, a carbonyl group, an ester group, an amide group, an isocyanate group, a urethane group, a urea group, a vinyl group, an amino group, an onium salt group, a heterocyclic group, an aryl group, an organosiloxy group, a polydimethylsiloxane group, etc. Among these substituents and linking groups, a polydimethylsiloxane group is preferred. 5 When the hydrocarbon group in the formula (1) has a polydimethylsiloxane group as a substituent, the molecular weight of the compound represented by formula (4) is preferably 1,000 to 30,000.

[0059] R 11Examples of the compound represented by formula (4) having an alkyl group having 1 to 22 carbon atoms and having a substituent or a linking group as the alkyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, methoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, glycidyl (meth)acrylate, 2-isocyanatoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, trimethylammonium ethyl (meth)acrylate, Examples of suitable polymers include tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, 4-hydroxyphenyl (meth)acrylate, "Placcel FM Series" (manufactured by Daicel Corporation, ε-caprolactone adduct of 2-hydroxyethyl methacrylate, trade name), 3-(trimethoxysilyl)propyl (meth)acrylate, "Silaplane FM-0721 (manufactured by JNC Corporation, polydimethylsiloxane group-containing macromonomer (molecular weight 5,000), trade name)," "Silaplane FM-0725 (manufactured by JNC Corporation, polydimethylsiloxane group-containing macromonomer (molecular weight 10,000)), "Silaplane FM-7721 (manufactured by JNC Corporation, polydimethylsiloxane group-containing bifunctional macromonomer (molecular weight 5,000)), diacetone (meth)acrylamide, and N-methylol (meth)acrylamide.

[0060] Examples of aromatic alkenyl compounds used as vinyl group-containing monomers include styrene, α-methylstyrene, p-methoxystyrene, and the like.

[0061] Examples of the vinyl halide compounds, excluding fluorine atom-containing compounds, used as the vinyl group-containing monomer include vinyl chloride, vinyl bromide, vinyl iodide, and the like.

[0062] Examples of vinyl cyanide compounds used as vinyl group-containing monomers include (meth)acrylonitrile.

[0063] In the solution polymerization method, each monomer is dissolved in an arbitrary solvent in the presence of a polymerization initiator, and the mixture is heated and stirred after nitrogen substitution, thereby allowing the polymerization reaction to proceed.

[0064] In the emulsion polymerization method, the respective monomers are emulsified in water or a mixture of organic solvent and water in the presence of a polymerization initiator and a surfactant, and the mixture is heated and stirred after nitrogen substitution to allow the polymerization reaction to proceed.

[0065] Examples of polymerization initiators that can be used include organic peroxides, azo compounds, and persulfates. Specific examples of polymerization initiators include tert-butyl peroxypivalate, tert-hexylperoxyneodecanate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, di-3,5,5-trimethylhexanoyl peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylpropionamidine) dihydrochloride, and ammonium persulfate. The amount of polymerization initiator used can be determined appropriately depending on the combination of monomers used, reaction conditions, and the like.

[0066] The arrangement of the structural units derived from the compound represented by formula (1) and the structural units derived from the compound represented by formula (2) in the polymer is not particularly limited. The polymer may be any of a random polymer, a block polymer, a graft polymer, etc.

[0067] <Polymer composition ratio> In the polymer, the mass ratio (a) / (c) of the structural units (a) derived from the compounds represented by formula (1) and formula (2) to the structural units (c) derived from the vinyl group-containing monomer is preferably in the range of 100 / 0 to 30 / 70, more preferably 90 / 10 to 30 / 70 from the viewpoint of improving water repellency and solubility in various solvents, and even more preferably 80 / 20 to 50 / 50. The more structural units (a), the higher the water repellency.

[0068] <Water repellent composition> The polymer can be mixed with a liquid medium to form a water repellent composition. By applying the water repellent composition to an object to be treated, the polymer can be easily attached to the object to be treated.

[0069] The liquid medium is not particularly limited as long as it dissolves or disperses the polymer. Examples of liquid media include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, water, ethanol, n-propanol, isopropyl alcohol, propylene glycol, dipropylene glycol, tripropylene glycol, dipropylene glycol monomethyl ether, ethyl acetate, butyl acetate, tetrahydrofuran, dimethylformaldehyde, toluene, xylene, aliphatic hydrocarbon solvents, and isoparaffinic solvents. Among these liquid media, aliphatic hydrocarbon solvents are preferred because they are less likely to cause changes or deterioration in the texture of the treated object. Examples of aliphatic hydrocarbon solvents include n-hexane, isohexane, n-heptane, cyclopentane, cyclohexane, and methylcyclohexane. Of these, n-hexane, n-heptane, and cyclohexane are preferred. These liquid media may be used alone or in combination of two or more.

[0070] <Water repellent treated material> The polymer can be applied to the surface of a substrate to produce a water-repellent-treated object, imparting water repellency to the substrate. In this case, the water repellent composition is preferably applied to the substrate. Examples of applicable substrates include natural fibers such as cotton, linen, and silk; recycled fibers such as rayon and cupra; semi-synthetic fibers such as acetate and triacetate; synthetic fibers such as polyamide, polyester, polyacrylonitrile, polypropylene, polyvinyl chloride, and polyvinyl alcohol; natural leather; synthetic leather; fur; paper; wood; and blends thereof, as well as fabrics, clothing, and shoes made from these. The substrates also include glass fiber, glass, brick, cement, metal, and plastic. Among these, synthetic fibers, natural fibers, and natural leather are preferred due to their high water repellency.

[0071] The water repellent composition can be applied to the object to be treated by a common method such as spray coating, bar coating, or dip coating. After application, it is preferable to dry the object to be treated by volatilizing the liquid medium at room temperature or by heat treatment, as appropriate. The temperature conditions during drying are not particularly limited, but in consideration of thermal deterioration of the object to be treated, a temperature of 20°C to 200°C is preferred, and 50 to 150°C is more preferred. [Example]

[0072] The present invention will be described in more detail below with reference to examples and comparative examples.

[0073] 1. Preparation of isomer mixture (monomer composition) An isomer mixture (monomer composition) was prepared by the following method.

[0074] Monomers A-1 to A-4 and monomers B-1 to B-4 are represented by the formulas (1) and (2), respectively, where X, Y, and R 1 ~R 6 are compounds having the structures shown in Table 1.

[0075] [Table 1]

[0076] 1-1. Example 1 100 parts by mass of (2-oxo-1,3-dioxolan-4-yl)methyl methacrylate (manufactured by NOF Corporation, trade name: Blenmer DO-MA), 100 parts by mass of stearylamine, and 100 parts by mass of heptane were placed in a reaction vessel equipped with a stirrer and a thermometer, and the mixture was allowed to react at room temperature for 12 hours. 1 The completion of the reaction was confirmed by 1 H NMR spectrum measurement, based on the disappearance of the peak of the raw material (2-oxo-1,3-dioxolan-4-yl)methyl methacrylate.

[0077] The resulting mixture was filtered at room temperature using Advantec filter paper, and the resulting residue, an isomer mixture (reaction product), was analyzed by proton NMR. The isomer mixture contained 87% by mass of Monomer A-1 and 13% by mass of its isomer, Monomer B-1. This isomer mixture was reprecipitated (deposited) using heptane / chloroform, the residue was filtered, and the solvent was removed using a rotary evaporator. The resulting isomer mixture was analyzed by proton NMR, and the isomer mixture contained 93% by mass of Monomer A-1 and 7% by mass of its isomer, Monomer B-1.

[0078] Proton NMR was performed in chloroform-d. In this spectrum, four protons in the hydroxyl group and the two -CH2-OC(=O)-R structures of Monomer A-1 are observed between 4.025 and 4.221 ppm. On the other hand, two protons in the -CH2-OH structure of Monomer B-1 are observed between 3.734 and 3.791 ppm. This compound gives a proton ratio of 5 / 2 for the four protons in the hydroxyl group and the two -CH2-OC(=O)-R structures of Monomer A-1: ​​the two protons in the -CH2-OH structure of Monomer B-1. The ratio of Monomer A-1 to Monomer B-1 was calculated from the observed proton ratio.

[0079] 1-2. Example 2 An isomer mixture was prepared in the same manner as in Example 1, except that the residue after filtration was not reprecipitated. The resulting isomer mixture contained 87% by mass of Monomer A-1 and 13% by mass of its isomer, Monomer B-1.

[0080] 1-3. Example 3 An isomer mixture was prepared in the same manner as in Example 1, except that the solvent was distilled off from the reaction solution after the reaction without filtering or reprecipitation. The resulting isomer mixture contained 70% by mass of Monomer A-1 and 30% by mass of its isomer, Monomer B-1.

[0081] 1-4. Example 4 An isomer mixture was prepared in the same manner as in Example 1, except that the reaction temperature was changed from room temperature to 50°C and the solvent was distilled off from the reaction solution after the reaction without filtering it. The resulting isomer mixture contained 51% by mass of Monomer A-1 and 49% by mass of its isomer, Monomer B-1.

[0082] 1-5. Example 5 An isomer mixture was prepared in the same manner as in Example 2, except that stearylamine was replaced with behenylamine. The resulting isomer mixture contained 88% by mass of Monomer A-2 and 12% by mass of its isomer, Monomer B-2.

[0083] 1-6. Example 6 An isomer mixture was prepared in the same manner as in Example 2, except that stearylamine was replaced with dodecylamine. The resulting isomer mixture contained 84% by mass of Monomer A-3 and 16% by mass of its isomer, Monomer B-3.

[0084] 1-7. Example 7 An isomer mixture was prepared in the same manner as in Example 2, except that (2-oxo-1,3-dioxolan-4-yl)methyl methacrylate was replaced with (2-oxo-1,3-dioxolan-4-yl)methyl acrylate. The resulting isomer mixture contained 83% by mass of Monomer A-4 and 17% by mass of its isomer, Monomer B-4.

[0085] 1-8. Comparative Example 1 An isomer mixture was prepared in the same manner as in Example 1, except that the reprecipitation purification was performed twice instead of once. The resulting isomer mixture contained 99.4% by mass of Monomer A-1 and 0.6% by mass of its isomer, Monomer B-1.

[0086] 1-9. Comparative Example 2 An isomer mixture was prepared in the same manner as in Example 1, except that the solvent was removed from the filtrate obtained by the reprecipitation method using a rotary evaporator. The isomer mixture contained 28% by mass of Monomer A-1 and 72% by mass of its isomer, Monomer B-1.

[0087] 2. Evaluation 2-1. Solubility Ten parts by mass of each sample (isomer mixture) was added to 90 parts by mass of a toluene / methanol mixed solvent, and the temperature was gradually raised while stirring until the sample was completely dissolved. Based on the temperature at which the sample dissolved, the solubility was evaluated according to the following criteria. ◎ (Excellent) Dissolved at 30℃ 〇 (Excellent) Dissolved at 35℃ × (bad) Dissolved at 40°C or higher

[0088] 2-2. Water repellency A 500 mL four-neck flask equipped with a thermometer, stirrer, and reflux condenser was charged with 230 g of cyclohexane, and the atmosphere inside the flask was replaced with nitrogen. Next, a monomer solution consisting of 30.5 g of the obtained isomer mixture and 29 g of cyclohexane, and a polymerization initiator solution consisting of 0.5 g of tert-hexyl peroxyneodecanate and 10 g of cyclohexane were prepared. The temperature inside the reaction vessel was raised to 55°C, and the monomer solution and polymerization initiator solution were simultaneously added dropwise over 2 hours. After the dropwise addition was completed, the mixture was reacted at 55°C for 5 hours, then heated to 70°C and reacted for an additional 2 hours to obtain a solution containing a polymer. The resulting solution was diluted with cyclohexanone to prepare a solution (water repellent composition) with a polymer concentration of 5.0% by mass.

[0089] A4 filter paper was used as the evaluation substrate. The evaluation substrate was cut into a size of 7 cm length x 5 cm width and immersed in each solution to apply the water repellent composition to the evaluation substrate. The evaluation substrate was then dried by heating at 100°C for 1 hour to prepare a test piece (water repellent-treated product).

[0090] The test specimen was attached to a tinplate test piece (200 x 50 x 0.3 mm, folded on all four sides) and fixed at an arbitrary angle, and 0.7 g of water was dropped from a height of 5 cm. The water repellency was evaluated according to the following criteria based on the angle at which the dropped water droplet completely slid off the test paper (sliding angle). The angle of the test piece was changed in 5° increments when measuring the sliding angle. ◎ (Excellent) The sliding angle was 25° or less 〇 (Excellent) The sliding angle was 30° × (bad): The sliding angle was 35° or more.

[0091] Table 2 shows the amount of monomer contained in each sample (isomer mixture) and the evaluation results.

[0092] [Table 2]

[0093] As is clear from the results in Table 2, in Examples 1 to 7, the solubility of the monomer in the solvent was high, and the polymer exhibited high water repellency when applied to a substrate.

[0094] In Comparative Example 1, the content of the hydroxyurethane group-containing (meth)acrylate represented by formula (2) was low, and therefore the solubility in solvents was poor.

[0095] In Comparative Example 2, the amount of the hydroxyurethane group-containing (meth)acrylate structural unit represented by formula (1) was too small, and therefore the water repellency of the polymer was poor. [Industrial Applicability]

[0096] The monomer composition of the present invention has an increased solubility in a solvent, thereby improving the smoothness of a coating film and enabling the preparation of a polymer with high water repellency. Therefore, the monomer composition of the present invention is useful as a material for a water repellent composition.

Claims

1. 50 to 99% by mass of a hydroxyurethane group-containing (meth)acrylate represented by the following formula (1), and The composition contains 1 to 50% by mass of a hydroxyurethane group-containing (meth)acrylate represented by the following formula (2) (where the total of the compound represented by formula (1) and the compound represented by formula (2) is taken as 100% by mass), Monomer composition. 【Chemistry 1】 【Chemistry 2】 (In formula (1) and formula (2), R １ and R ４ are independently a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, or an iodine atom; A and B are independently an alkylene group having 1 to 10 carbon atoms; X and Y are independently 0 or 1; R ２ and R ５ each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; R ３ and R ６ each independently represents an alkyl group having 12 to 24 carbon atoms.

2. A polymer obtained by polymerizing the monomer composition according to claim 1, A polymer, wherein the mass ratio (a) / (c) of the structural unit (a) derived from the compound represented by formula (1) and the compound represented by formula (2) to the structural unit (c) derived from another copolymerizable vinyl group-containing monomer is 100 / 0 to 30 / 70.

3. A water repellent composition comprising the polymer of claim 2.

4. A water-repellent treated object, which is obtained by adhering the polymer according to claim 2 to the surface of an object to be treated.

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