Active energy ray-curable water / oil-repellent composition, and water / oil-repellent base material

Abstract

[Solution] This active energy ray-curable water / oil-repellent composition contains a urethane compound (A) and a (meth)acrylate compound (B) having three or more (meth)acryloyl groups per molecule. The urethane compound (A) contains a structural unit derived from a hydroxyl group-containing (meth)acrylate (a), a structural unit derived from an organic isocyanate compound (b) having two or more isocyanate groups per molecule, and a structural unit derived from a straight chain saturated alcohol (c) having 12-22 carbon atoms. The ratio of hydroxyl group equivalent weight of the straight chain saturated alcohol (c) / isocyanate group equivalent weight of the organic isocyanate compound (b) is 0.17-0.67.

Description

Active energy ray-curable water / oil repellent composition and water / oil repellent substrate

[0001] The present invention relates to an active energy ray-curable water / oil repellent composition and a water / oil repellent substrate.

[0002] It has been known that fluorine-based polymers having perfluoroalkyl groups are useful as coating agents that impart both water- and oil-repellent properties to the surface of a wide variety of substrates, such as glass, plastics, fibers, and building materials. For example, Patent Documents 1 and 2 disclose fluorine-based active energy ray-curable water- and oil-repellent compositions. However, fluorine-based polymers have become less popular in recent years due to factors such as the generation of inert gases when heated and the accumulation of some components in the fluorine-based polymers in the human body. Under these circumstances, Patent Document 3, for example, discloses a non-fluorine-based active energy ray-curable water- and oil-repellent coating agent.

[0003] JP 2016-204463 A JP 2019-203069 A JP 2023-11394 A

[0004] However, non-fluorine-based active energy ray-curable water- and oil-repellent coating agents have sufficient water repellency but have not been satisfactory in terms of oil repellency, i.e., they have not been excellent in both water and oil repellency.

[0005] The present invention has been made in view of the problems inherent in the prior art, and an object of the present invention is to provide an active energy ray-curable composition and a water- and oil-repellent substrate that are excellent in both water repellency and oil repellency.

[0006] One aspect of the present invention that solves the above-mentioned problems is as follows: (1) An active energy ray-curable water / oil repellent composition comprising a urethane compound (A) and a (meth)acrylate compound (B) having three or more (meth)acryloyl groups in one molecule, wherein the urethane compound (A) comprises a structural unit derived from a hydroxyl group-containing (meth)acrylate (a), a structural unit derived from an organic isocyanate compound (b) having two or more isocyanate groups in one molecule, and a structural unit derived from a linear saturated alcohol (c) having 12 to 22 carbon atoms, and wherein the hydroxyl group equivalent of the linear saturated alcohol (c) / the isocyanate group equivalent of the organic isocyanate compound (b) is 0.17 to 0.67.

[0007] (2) The active energy ray-curable water / oil repellent composition according to (1) above, wherein the content of the urethane compound (A) and the (meth)acrylate compound (B) is, in mass ratio, (A) / ((A)+(B))=0.05 to 0.5.

[0008] (3) The active energy ray-curable water / oil repellent composition according to (1) or (2), wherein the (meth)acrylate compound (B) has a structure represented by the following general formula (1) or (2):

[0009]

[0010] [In general formulas (1) and (2), X １ ~X １０ each independently represents a (meth)acryloyl group or a hydroxyl group, X １ ~X ６ At least three of X represent a (meth)acryloyl group; ７ ~X １０ At least three of these represent (meth)acryloyl groups.

[0011] (4) The active energy ray-curable water / oil repellent composition according to any one of (1) to (3), which comprises, together with or instead of the (meth)acrylate compound (B), an acrylate mixture (C) containing two or more acrylates having one or more acryloyl groups in one molecule, and the two or more acrylates in the acrylate mixture (C) have an average of three or more acryloyl groups.

[0012] (5) A water- and oil-repellent substrate having a water- and oil-repellent layer on the substrate, the water- and oil-repellent layer being a cured product of the active energy ray-curable water- and oil-repellent composition according to claim 1 or 2, and having a thickness of 0.05 to 50 μm.

[0013] According to the present invention, it is possible to provide an active energy ray-curable composition and a water- and oil-repellent substrate that are excellent in both water- and oil-repellent properties.

[0014] Hereinafter, embodiments of the present disclosure will be described. The present invention is not limited to the examples in the following embodiments.

[0015] In this specification, a numerical range indicated using "to" indicates a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in stages in this specification, the upper or lower limit of a numerical range in a certain stage can be arbitrarily combined with the upper or lower limit of a numerical range in another stage. In the numerical ranges described in this specification, the upper or lower limit of the numerical range may be replaced with a value shown in the examples. In this specification, when multiple substances corresponding to each component are present in the composition, the content of each component in the composition means the total amount of the multiple substances present in the composition, unless otherwise specified. Included in this term. Unless otherwise specified, an element may refer to either a single element or multiple elements.

[0016] <Active Energy Ray-Curable Water / Oil Repellent Composition> The active energy ray-curable water / oil repellent composition of this embodiment contains a urethane compound (A) and a (meth)acrylate compound (B) having three or more (meth)acryloyl groups per molecule. The urethane compound (A) contains a structural unit derived from a hydroxyl group-containing (meth)acrylate (a), a structural unit derived from an organic isocyanate compound (b) having two or more isocyanate groups per molecule, and a structural unit derived from a linear saturated alcohol (c) having 12 to 22 carbon atoms. The hydroxyl group equivalent of the linear saturated alcohol (c) / the isocyanate group equivalent of the organic isocyanate compound (b) is 0.17 to 0.67. The active energy ray-curable water / oil repellent composition of this embodiment is described below. In this specification, "(meth)acrylate" means acrylate and / or methacrylate.

[0017] [Urethane Compound (A)] The urethane compound (A) is a component that exhibits water- and oil-repellent effects in the active energy ray-curable water- and oil-repellent composition, and is a urethane compound having a (meth)acryloyl group that reacts with active energy rays and a linear saturated alkyl group having 12 to 22 carbon atoms. The urethane compound (A) contains a structural unit derived from a hydroxyl group-containing (meth)acrylate (a), a structural unit derived from an organic isocyanate compound (b) having two or more isocyanate groups per molecule, and a structural unit derived from a linear saturated alcohol (c) having 12 to 22 carbon atoms. For example, the urethane compound (A) can be obtained by reacting the hydroxyl group-containing (meth)acrylate (a), the organic isocyanate compound (b) having two or more isocyanate groups per molecule, and the linear saturated alcohol (c) having 12 to 22 carbon atoms.

[0018] Examples of the hydroxyl group-containing (meth)acrylate (a) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerin mono(meth)acrylate, glycerin di(meth)acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, 2-(meth)acryloyloxyethyl acid phosphate, and epoxy (meth)acrylates obtained by addition reaction of (meth)acrylic acid with the epoxy group of an epoxy resin. These may be used alone or in combination of two or more. Among these, 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate are more preferred, and 2-hydroxyethyl (meth)acrylate is even more preferred, in terms of reactivity with isocyanate groups and photocurability. Furthermore, hydroxyl group-containing (meth)acrylates other than those mentioned above may also be used as the hydroxyl group-containing (meth)acrylate (a).

[0019] The organic isocyanate compound (b) is not particularly limited as long as it has two or more isocyanate groups in one molecule. For example, diisocyanate compounds such as tolylene diisocyanate, hydrogenated tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, lysine diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and hydrogenated xylylene diisocyanate, as well as biuret polyisocyanate compounds obtained by reacting these various diisocyanate compounds with water, adduct polyisocyanate compounds obtained by reacting various diisocyanate compounds with polyhydric alcohols such as trimethylolpropane, and polymers obtained by isocyanurating various compounds, etc. These may be used alone or in combination of two or more. Among these exemplified compounds, from the viewpoint of controlling reactivity, isophorone diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, hexamethylene diisocyanate, and isocyanurates of these diisocyanates are more preferred, and isocyanurate of hexamethylene diisocyanate is even more preferred.

[0020] The linear saturated alcohol (c) has one or more hydroxyl groups per molecule in order to react with the hydroxyl group-containing (meth)acrylate (a) via the organic isocyanate compound (b). Furthermore, a saturated alcohol is preferred in order to exhibit good water and oil repellency. It preferably has 12 to 22 carbon atoms, more preferably 14 to 21 carbon atoms, and even more preferably 16 to 20 carbon atoms. A linear saturated alcohol with 12 or more carbon atoms can exhibit good water and oil repellency, while a linear saturated alcohol with 22 or less carbon atoms exhibits good reactivity with the organic isocyanate compound. Examples of linear saturated alcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, eicosyl alcohol, behenyl alcohol, and octyl alcohol. These may be used alone or in combination of two or more.

[0021] As the linear saturated alcohol (c), commercially available products can be used, and examples thereof include Conol 1275, Conol 20F, Conol 20P, Conol 1495, Conol 1695, Conol 30RC, Conol 30F, Conol 30S, Conol 30SS, Conol 2265, Conol 2280 (manufactured by New Japan Chemical Co., Ltd., trade name: "Conol" (registered trademark)), Kalcol 2098, Kalcol 4098, Kalcol 6098, Kalcol 8098, Kalcol 200GD, Kalcol 6870, Kalcol 6850, Kalcol 8688, Kalcol 8665, and Kalcol 220-80 (manufactured by Kao Corporation, trade name: "Kalcol" (registered trademark)).

[0022] Furthermore, when reacting the urethane compound (A) with the hydroxyl group-containing (meth)acrylate (a), the organic isocyanate compound (b), and the linear saturated alcohol (c), the hydroxyl group equivalent of the linear saturated alcohol (c) / the isocyanate group equivalent of the organic isocyanate compound (b) is adjusted to 0.17 to 0.67. Adjusting the hydroxyl group equivalent of the linear saturated alcohol (c) / the isocyanate group equivalent of the organic isocyanate compound (b) to 0.17 to 0.67 reduces the amount of linear saturated alcohol (c) that remains unreacted with the hydroxyl group-containing (meth)acrylate (a), thereby achieving good water and oil repellency. The hydroxyl group equivalent of the linear saturated alcohol (c) / the isocyanate group equivalent of the organic isocyanate compound (b) is preferably adjusted to 0.22 to 0.60, and more preferably adjusted to 0.33 to 0.50. It is also preferable to first react components (b) and (c), and then react component (a). After confirming that the NCO% is saturated, the hydroxyl group-containing (meth)acrylate (a) is reacted, and the isocyanate group of the organic isocyanate compound (b) disappears, thereby obtaining a urethane compound that exhibits water- and oil-repellent effects. Note that "NCO% is saturated" means that components (a) and (b) have completely reacted, and the NCO% does not change any further, except for a decrease in the NCO% due to moisture.

[0023] [(Meth)acrylate Compound (B)] The (meth)acrylate compound (B) used in the active energy ray-curable water / oil repellent composition of this embodiment is a component that, as a cured film in the water / oil repellent composition, exhibits effects as a coating film, such as adhesion to a substrate and solvent resistance. The (meth)acrylate compound (B) has three or more (meth)acryloyl groups in one molecule. By having three or more (meth)acryloyl groups in one molecule, it is possible to obtain a tough coating film that is sufficiently curable and excellent in solvent resistance. If the (meth)acrylate compound (B) does not have sufficient curability, poor curing is likely to occur even when irradiated with active energy rays. As a result, even if the composition appears cured, oil repellency, solvent resistance, etc. are likely to be deteriorated.

[0024] The (meth)acrylate compound (B) preferably has a structure represented by the following general formula (1) or (2).

[0025]

[0026] [In general formulas (1) and (2), X １ ~X １０ each independently represents a (meth)acryloyl group or a hydroxyl group, X １ ~X ６ At least three of X represent a (meth)acryloyl group; ７ ~X １０ At least three of these represent (meth)acryloyl groups.

[0027] In particular, the (meth)acrylate compound (B) is preferably one or more selected from the group consisting of dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol triacrylate, and pentaerythritol tetraacrylate. The (meth)acrylate compound (B) may be a mixture of multiple compounds having the structure represented by the above general formula (1) or the following general formula (2).

[0028] [Acrylate mixture (C)] In order to obtain better curability, it is preferable to use an acrylate mixture (C) containing two or more acrylates having one or more acryloyl groups per molecule together with or instead of the (meth)acrylate compound (B). More preferably, the average number of acryloyl groups in the two or more acrylates in the acrylate mixture (C) is three or more. For example, it is preferable to use an acrylate mixture (C) containing two or more acrylates having one or more acryloyl groups per molecule but not containing a methacryloyl group. Among these, a mixture of two or more selected from dipentaerythritol monoacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol monoacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, and pentaerythritol pentaacrylate is preferred, and those mixtures in which the number of acryloyl groups contained therein is adjusted to three or more on average per molecule are more preferred.

[0029] In the active energy ray-curable water / oil repellent composition of this embodiment, the contents of the urethane compound (A) and the (meth)acrylate compound (B) are preferably adjusted so that the mass ratio is (A) / ((A)+(B))=0.05 to 0.5. The value of this ratio is more preferably 0.08 to 0.3, and even more preferably 0.1 to 0.2. When the ratio is adjusted to the range of (A) / ((A)+(B))=0.01 to 0.5, it is possible to obtain a good active energy ray-curable water / oil repellent composition that combines good water / oil repellency with properties such as substrate adhesion and solvent resistance.

[0030] Examples of active energy rays in this embodiment include known and commonly used rays such as electron beams, α rays, β rays, γ rays, infrared rays, visible light, and ultraviolet rays. Among these, electron beams and ultraviolet rays have been relatively well studied, and ultraviolet rays in particular have the advantage that irradiation equipment therefor is inexpensive and readily available. The light irradiation dose is, for example, 100 to 10,000 mJ / cm. ２It is preferable to set the exposure dose to 200 to 7,000 mJ / cm. ２ More preferably, it is 300 to 5,000 mJ / cm ２ It is more preferable to set the following.

[0031] When the active energy ray-curable water / oil repellent composition of the present embodiment is cured with active energy rays, if the above-mentioned electron beam is used, it is not necessary to mix a photopolymerization initiator. When curing with ultraviolet rays, it is necessary to mix a photopolymerization initiator with the active energy ray-curable water / oil repellent composition.

[0032] The photopolymerization initiator is not particularly limited, but examples thereof include carbonyl-based photopolymerization initiators, sulfide-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, quinone-based photopolymerization initiators, sulfochloride-based photopolymerization initiators, and thioxanthone-based photopolymerization initiators.

[0033] Examples of the carbonyl-based photopolymerization initiator include benzophenone, benzil, benzoin, ω-bromoacetophenone, chloroacetone, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, 2-chlorobenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bisdiethylaminobenzophenone, Michler's ketone, benzoin methyl ether, benzoin isobutyl ether, benzoin-n-butyl ether, benzoin methyl ether, benzoin iso ... dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, methyl benzoyl formate, 2,2-diethoxyacetophenone, 1,1'-[methylenebis(4,1-phenylene)]bis(2-methyl-2-hydroxy-1-propanone), 4-N,N'-dimethylacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, and the like.

[0034] Examples of sulfide-based photopolymerization initiators include diphenyl disulfide, dibenzyl disulfide, tetraethyl thiuram disulfide, and tetramethyl ammonium monosulfide.

[0035] Examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide.

[0036] Examples of the quinone-based photopolymerization initiator include quinone-based photopolymerization initiators such as benzoquinone and anthraquinone.

[0037] Examples of sulfochloride-based photopolymerization initiators include 2-naphthalenesulfonyl chloride.

[0038] Examples of the thioxanthone-based photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, and 2-methylthioxanthone.

[0039] Among these exemplified compounds, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, phenylglyoxylic acid methyl ester, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one are preferred, with 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one being particularly preferred. From the viewpoints of curability, cost, and the like, the amount of the photopolymerization initiator blended is preferably 3 to 15 mass% based on the resin solids content of the active energy ray-curable water / oil repellent composition. The photopolymerization initiators may be used alone or in combination of two or more.

[0040] In order to enhance the effect of the photopolymerization initiator, an initiator aid such as p-dimethylaminobenzoic acid isoamyl ester, p-dimethylamino-benzoic acid ethyl ester, N-methyldiethanolamine, bisethylaminobenzophenone, ethyl-4-dimethylaminobenzoate, or 2-ethylhexyl-4-dimethylaminobenzoate can also be used.

[0041] The active energy ray-curable water / oil repellent composition of this embodiment may optionally contain a (meth)acrylate compound (B) having three or more (meth)acryloyl groups in one molecule and a photopolymerizable monomer other than the (meth)acrylate in the (meth)acrylate mixture. In this case, however, it is preferable that the photopolymerizable monomer has a radically polymerizable ethylenically unsaturated bond as a functional group for polymerizing with the urethane compound (A) and the (meth)acrylate compound (B). Examples of the photopolymerizable monomer include, but are not limited to, photopolymerizable monomers having an acryloyl group, methacryloyl group, vinyl group, allyl group, propenyl group, isopropenyl group, vinyl ether group, maleimide group, etc. Preferably, the photopolymerizable monomer is a monofunctional (meth)acrylate and / or polyfunctional (meth)acrylate.

[0042] The active energy ray-curable water / oil repellent composition of this embodiment is usually prepared as an organic solvent solution for convenience of use, and any conventionally known organic solvent can be used as long as it has good solubility with the respective components and is non-reactive. For example, toluene, xylene, methanol, ethanol, isobutanol, n-butanol, methyl ethyl ketone, hexane, heptane, etc. can be used alone or as a mixture of two or more thereof, and the amount used is desirably such that the resin solids content of the active energy ray-curable water / oil repellent composition falls within the range of 1 to 60 mass %.

[0043] The active energy ray-curable water / oil repellent composition of this embodiment can be applied (painted) to a substrate, heated to volatilize the solvent in the case of a solvent-based composition, and then irradiated with active energy rays to cure the composition, thereby forming a coating film (water / oil repellent layer). The heating temperature is generally 50 to 100°C, but is not limited thereto and can be determined as desired depending on the film thickness and dilution solvent.

[0044] <Water- and oil-repellent substrate> The water- and oil-repellent substrate of this embodiment has a water- and oil-repellent layer on a substrate, and the water- and oil-repellent layer is a cured product of the active energy ray-curable water- and oil-repellent composition of this embodiment described above, and has a thickness of 0.05 to 50 μm. For example, the water- and oil-repellent substrate of this embodiment is obtained by applying the active energy ray-curable water- and oil-repellent composition of this embodiment described above to a surface of a substrate to a thickness of 0.05 to 50 μm in terms of resin solid content, and then curing the composition by irradiation with active energy rays.

[0045] When the active energy ray-curable water / oil repellent composition is applied to a substrate to prepare a water / oil repellent substrate, the thickness of the water / oil repellent layer formed on the substrate is 0.05 to 50 μm, preferably 0.07 to 40 μm, and more preferably 0.1 to 30 μm. If the film thickness is in the range of 0.05 to 50 μm, the coated surface is smooth and stable water / oil repellency can be exhibited.

[0046] Specific examples of substrates to which the active energy ray-curable water / oil repellent composition can be applied include film substrates such as polyethylene film, polypropylene film, polyethylene terephthalate film, and polyethylene naphthalate film, as well as paper substrates such as fine paper, medium-quality paper, art paper, cast-coated paper, and coated paper, polymer products such as plastic molded articles, wood-based products, fibers, ceramics, glass, metals, composites and laminates thereof, etc. In order to improve adhesion to the cured film to be formed, the surface of the substrate may be activated by corona treatment, plasma treatment, chemical treatment, etc.

[0047] Examples of methods for applying the active energy ray-curable water / oil repellent composition include brush coating, spray coating, dip coating, flow coating, roll coating, curtain coating, spin coating, and inkjet coating.

[0048] The water- and oil-repellent layer obtained as described above has a static water contact angle (also simply referred to as water contact angle) of 100° or more, particularly 105° or more, measured by measuring the angle between the liquid surface and a solid surface when a 2 μL droplet of ion-exchanged water comes into contact with the surface one second after contact. It is preferable that the water- and oil-repellent surface has a static hexadecane contact angle (also simply referred to as hexadecane contact angle) of 35° or more, particularly 40° or more, measured by measuring the angle between the liquid surface and a solid surface when a 2 μL droplet of hexadecane comes into contact with the surface one second after contact.

[0049] The present embodiment will be described in more detail below with reference to examples, but the present embodiment is not limited to the following examples. Furthermore, "parts" and "%" shown in the examples represent parts by mass and % by mass unless otherwise specified.

[0050] <Synthesis of urethane compound (A)> [Production Example 1] A flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube was charged with 570 parts of Coronate HX (manufactured by Tosoh Corporation, trade name: isocyanurate of hexamethylene diisocyanate) as an organic isocyanate compound (b) having two or more isocyanate groups in one molecule, and 135 parts of Conol 30SS (manufactured by New Japan Chemical Co., Ltd., trade name: stearyl alcohol) as a linear saturated alcohol (c) having 12 to 22 carbon atoms, and the temperature was raised to 85 ° C. and kept warm for 7 hours to react. Then, after confirming that the NCO% was saturated, 290 parts of BHEA (manufactured by Nippon Shokubai Co., Ltd., trade name: 2-hydroxyethyl acrylate) as a hydroxyl group-containing (meth)acrylate (a) was charged, and the reaction was continued for 7 hours. IR measurement confirmed that the isocyanate group had disappeared, and a urethane compound (A-1) was obtained. The R value ((hydroxyl group equivalent of linear saturated alcohol (c) / isocyanate group equivalent of organic isocyanate compound (b)), the same applies hereinafter) was 0.17.

[0051] [Production Example 2] In a flask equipped similarly to Production Example 1, 570 parts of Coronate HX (manufactured by Tosoh Corporation, trade name: isocyanurate of hexamethylene diisocyanate) as an organic isocyanate compound (b) having two or more isocyanate groups in one molecule, 270 parts of Conol 30SS (manufactured by New Japan Chemical Co., Ltd., trade name: stearyl alcohol) as a linear saturated alcohol (c) having 12 to 22 carbon atoms were charged, and the temperature was raised to 85 ° C. and kept warm for 7 hours to react. Then, after confirming that the NCO% was saturated, 232 parts of BHEA (manufactured by Nippon Shokubai Co., Ltd., trade name: 2-hydroxyethyl acrylate) as a hydroxyl group-containing (meth)acrylate (a) were charged, and the reaction was carried out by keeping the temperature for 7 hours. IR measurement confirmed that the isocyanate group had disappeared, and a urethane compound (A-2) was obtained. The R value was 0.33.

[0052] [Production Example 3] In a flask equipped similarly to Production Example 1, 570 parts of Coronate HX (manufactured by Tosoh Corporation, trade name: isocyanurate of hexamethylene diisocyanate) as an organic isocyanate compound (b) having two or more isocyanate groups in one molecule, 540 parts of Conol 30SS (manufactured by New Japan Chemical Co., Ltd., trade name: stearyl alcohol) as a linear saturated alcohol (c) having 12 to 22 carbon atoms were charged, and the temperature was raised to 85 ° C. and kept warm for 7 hours to react. Then, after confirming that the NCO% was saturated, 116 parts of BHEA (manufactured by Nippon Shokubai Co., Ltd., trade name: 2-hydroxyethyl acrylate) as a hydroxyl group-containing (meth)acrylate (a) were charged, and the reaction was carried out by keeping the temperature for 7 hours. IR measurement confirmed that the isocyanate group had disappeared, and a urethane compound (A-3) was obtained. The R value was 0.67.

[0053] [Production Example 4] In a flask equipped similarly to Production Example 1, 570 parts of Coronate HX (manufactured by Tosoh Corporation, trade name: isocyanurate of hexamethylene diisocyanate) as an organic isocyanate compound (b) having two or more isocyanate groups in one molecule, 270 parts of Conol 30SS (manufactured by New Japan Chemical Co., Ltd., trade name: stearyl alcohol) as a linear saturated alcohol (c) having 12 to 22 carbon atoms were charged, and the temperature was raised to 85 ° C. and kept warm for 7 hours to react. Then, after confirming that the NCO% was saturated, 288 parts of 4HBA (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: 4-hydroxybutyl acrylate) as a hydroxyl group-containing (meth)acrylate (a) were charged, and the reaction was carried out by keeping the temperature for 7 hours. IR measurement confirmed that the isocyanate group had disappeared, and a urethane compound (A-4) was obtained. The R value was 0.33.

[0054] [Production Example 5] A flask equipped similarly to Production Example 1 was charged with 504 parts of HDI (hexamethylene diisocyanate, manufactured by Tosoh Corporation, trade name: HDI) as an organic isocyanate compound (b) having two or more isocyanate groups per molecule, and 270 parts of Conol 30SS (manufactured by New Japan Chemical Co., Ltd., trade name: stearyl alcohol) as a linear saturated alcohol (c). The temperature was raised to 85°C and the mixture was kept at that temperature for 7 hours to allow the reaction to proceed. After confirming that the NCO % had reached saturation, 580 parts of BHEA (trade name: 2-hydroxyethyl acrylate, manufactured by Nippon Shokubai Co., Ltd.) as a hydroxyl group-containing (meth)acrylate (a) was charged and the mixture was kept at that temperature for 7 hours to allow the reaction to proceed. IR measurement confirmed that the isocyanate groups had disappeared, yielding a urethane compound (A-5). The R value was 0.17.

[0055] [Production Example 6] In a flask equipped similarly to Production Example 1, 570 parts of Coronate HX (manufactured by Tosoh Corporation, trade name: isocyanurate of hexamethylene diisocyanate) as an organic isocyanate compound (b) having two or more isocyanate groups in one molecule, 326 parts of Conol 2280 (manufactured by New Japan Chemical Co., Ltd., behenyl alcohol 80-85% by mass) as a linear saturated alcohol (c) having 12 to 22 carbon atoms were charged, and the temperature was raised to 85 ° C. and kept at 45 ° C. for 7 hours to react. Then, after confirming that the NCO% was saturated, 232 parts of BHEA (manufactured by Nippon Shokubai Co., Ltd., trade name: 2-hydroxyethyl acrylate) as a hydroxyl group-containing (meth)acrylate (a) were charged, and the reaction was carried out by keeping the temperature for 7 hours. IR measurement confirmed that the isocyanate group had disappeared, and a urethane compound (A-6) was obtained. The R value was 0.33.

[0056] [Production Example 7] In a flask equipped similarly to Production Example 1, 570 parts of Coronate HX (manufactured by Tosoh Corporation, trade name: isocyanurate of hexamethylene diisocyanate) as an organic isocyanate compound (b) having two or more isocyanate groups in one molecule, 81 parts of Conol 30SS (manufactured by New Japan Chemical Co., Ltd., trade name: stearyl alcohol) as a linear saturated alcohol (c) having 12 to 22 carbon atoms were charged, and the temperature was raised to 85 ° C. and kept warm for 7 hours to react. Then, after confirming that the NCO% was saturated, 313.2 parts of BHEA (manufactured by Nippon Shokubai Co., Ltd., trade name: 2-hydroxyethyl acrylate) as a hydroxyl group-containing (meth)acrylate (a) were charged, and the reaction was carried out by keeping the temperature for 7 hours. IR measurement confirmed that the isocyanate group had disappeared, and a urethane compound (A-7) was obtained. The R value was 0.10.

[0057] [Production Example 8] In a flask equipped similarly to Production Example 1, 570 parts of Coronate HX (manufactured by Tosoh Corporation, trade name: isocyanurate of hexamethylene diisocyanate) as an organic isocyanate compound (b) having two or more isocyanate groups in one molecule, 675 parts of Conol 30SS (manufactured by New Japan Chemical Co., Ltd., trade name: stearyl alcohol) as a linear saturated alcohol (c) having 12 to 22 carbon atoms were charged, and the temperature was raised to 85 ° C. and kept warm for 7 hours to react. Then, after confirming that the NCO% was saturated, 58 parts of BHEA (manufactured by Nippon Shokubai Co., Ltd., trade name: 2-hydroxyethyl acrylate) as a hydroxyl group-containing (meth)acrylate (a) were charged, and the reaction was carried out by keeping the temperature for 7 hours. IR measurement confirmed that the isocyanate group had disappeared, and a urethane compound (A-8) was obtained. The R value was 0.83.

[0058] [Production Example 9] In a flask equipped similarly to Production Example 1, 570 parts of Coronate HX (manufactured by Tosoh Corporation, trade name: isocyanurate of hexamethylene diisocyanate) as an organic isocyanate compound (b) having two or more isocyanate groups in one molecule, 130 parts of Kalcol 0898 (manufactured by Kao Corporation, trade name: octyl alcohol) as a linear saturated alcohol (C) having 12 to 22 carbon atoms were charged, and the temperature was raised to 85 ° C. and kept warm for 7 hours to react. Then, after confirming that the NCO% was saturated, 232 parts of BHEA (manufactured by Nippon Shokubai Co., Ltd., trade name: 2-hydroxyethyl acrylate) as a hydroxyl group-containing (meth)acrylate (a) were charged, and the reaction was carried out by keeping the temperature for 7 hours. IR measurement confirmed that the isocyanate group had disappeared, and a urethane compound (A-9) was obtained. The R value was 0.33.

[0059] The components used in the above Production Examples 1 to 9 and their amounts charged are shown in Table 1 below. The meanings of the abbreviations in Table 1 are as follows: HEA: 2-hydroxyethyl acrylate (manufactured by Nippon Shokubai Co., Ltd., trade name: BHEA) 4HBA: 4-hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Ltd., trade name: 4-HBA) HDI nurate: isocyanurate of hexamethylene diisocyanate (manufactured by Tosoh Corporation, trade name: Coronate HX) HDI: hexamethylene diisocyanate (manufactured by Tosoh Corporation, trade name: HDI)

[0060]

[0061] Example 1 A flask equipped similarly to that in Production Example 1 was charged with 10 parts of the urethane compound (A-1) obtained in Production Example 1, 90 parts of KAYARAD DPHA (a mixture of pentaacrylate and hexaacrylate having the structure represented by general formula (1), manufactured by Nippon Kayaku Co., Ltd.) as a (meth)acrylate compound (B) having three or more (meth)acryloyl groups in one molecule, 110 parts of toluene, and 10 parts of Omnirad 184 (a photopolymerization initiator, manufactured by IGM B.V., 1-hydroxycyclohexylphenylketone), and the mixture was heated to 50°C and mixed for 1 hour to obtain an active energy ray-curable water / oil repellent composition.

[0062] Example 2 A flask equipped similarly to that of Production Example 1 was charged with 10 parts of the urethane compound (A-2) obtained in Production Example 2, 90 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of pentaacrylate and hexaacrylate having the structure represented by general formula (1)) as a (meth)acrylate (D) having three or more (meth)acryloyl groups in one molecule, 110 parts of toluene, and 10 parts of Omnirad 184 (manufactured by IGM B.V., photopolymerization initiator, 1-hydroxycyclohexylphenylketone), and the mixture was heated to 50°C and mixed for 1 hour to obtain an active energy ray-curable water / oil repellent composition.

[0063] Example 3 A flask equipped similarly to that of Production Example 1 was charged with 10 parts of the urethane compound (A-3) obtained in Production Example 3, 90 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of pentaacrylate and hexaacrylate having the structure represented by general formula (1)) as a (meth)acrylate compound (B) having three or more (meth)acryloyl groups in one molecule, 110 parts of toluene, and 10 parts of Omnirad 184 (manufactured by IGM B.V., photopolymerization initiator, 1-hydroxycyclohexylphenylketone), and the mixture was heated to 50°C and mixed for 1 hour to obtain an active energy ray-curable water / oil repellent composition.

[0064] Example 4 A flask equipped similarly to that of Production Example 1 was charged with 10 parts of the urethane compound (A-4) obtained in Production Example 4, 90 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of pentaacrylate and hexaacrylate having the structure represented by general formula (1)) as a (meth)acrylate compound (B) having three or more (meth)acryloyl groups in one molecule, 110 parts of toluene, and 10 parts of Omnirad 184 (manufactured by IGM B.V., photopolymerization initiator, 1-hydroxycyclohexylphenylketone), and the mixture was heated to 50°C and mixed for 1 hour to obtain an active energy ray-curable water / oil repellent composition.

[0065] Example 5 A flask equipped similarly to that of Production Example 1 was charged with 7.5 parts of the urethane compound (A-5) obtained in Production Example 5, 92.5 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of pentaacrylate and hexaacrylate having the structure represented by general formula (1)) as a (meth)acrylate compound (B) having three or more (meth)acryloyl groups in one molecule, 110 parts of toluene, and 10 parts of Omnirad 184 (manufactured by IGM B.V., photopolymerization initiator, 1-hydroxycyclohexylphenylketone), and the mixture was heated to 50°C and mixed for 1 hour to obtain an active energy ray-curable water / oil repellent composition.

[0066] Example 6 A flask equipped similarly to that of Production Example 1 was charged with 10 parts of the urethane compound (A-6) obtained in Production Example 6, 90 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of pentaacrylate and hexaacrylate having the structure represented by general formula (1)) as a (meth)acrylate compound (B) having three or more (meth)acryloyl groups in one molecule, 110 parts of toluene, and 10 parts of Omnirad 184 (a photopolymerization initiator manufactured by IGM B.V., 1-hydroxycyclohexylphenylketone), and the mixture was heated to 50°C and mixed for 1 hour to obtain an active energy ray-curable water / oil repellent composition.

[0067] Example 7 A flask equipped similarly to that of Production Example 1 was charged with 10 parts of the urethane compound (A-2) obtained in Production Example 2, 90 parts of KAYARAD PET-30 (manufactured by Nippon Kayaku Co., Ltd., a mixture of triacrylate and tetraacrylate having the structure represented by general formula (2)) as a (meth)acrylate compound (B) having three or more (meth)acryloyl groups in one molecule, 110 parts of toluene, and 10 parts of Omnirad 184 (manufactured by IGM B.V., photopolymerization initiator, 1-hydroxycyclohexylphenylketone), and the mixture was heated to 50°C and mixed for 1 hour to obtain an active energy ray-curable water / oil repellent composition.

[0068] Comparative Example 1 A flask equipped similarly to that of Production Example 1 was charged with 10 parts of the urethane compound (A-7) obtained in Production Example 7, 90 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of pentaacrylate and hexaacrylate having the structure represented by general formula (1)) as a (meth)acrylate compound (B) having three or more (meth)acryloyl groups in one molecule, 110 parts of toluene, and 10 parts of Omnirad 184 (manufactured by IGM B.V., photopolymerization initiator, 1-hydroxycyclohexylphenyl ketone), and the mixture was heated to 50°C and mixed for 1 hour to obtain an active energy ray-curable water / oil repellent composition.

[0069] Comparative Example 2 A flask equipped similarly to that of Production Example 1 was charged with 10 parts of the urethane compound (A-8) obtained in Production Example 8, 90 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of pentaacrylate and hexaacrylate having the structure represented by general formula (1)) as a (meth)acrylate compound (B) having three or more (meth)acryloyl groups in one molecule, 110 parts of toluene, and 10 parts of Omnirad 184 (manufactured by IGM B.V., photopolymerization initiator, 1-hydroxycyclohexylphenyl ketone), and the mixture was heated to 50°C and mixed for 1 hour to obtain an active energy ray-curable water / oil repellent composition.

[0070] Comparative Example 3 A flask equipped similarly to that of Production Example 1 was charged with 10 parts of the urethane compound (A-9) obtained in Production Example 9, 90 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of pentaacrylate and hexaacrylate having the structure represented by general formula (1)) as a (meth)acrylate compound (B) having three or more (meth)acryloyl groups in one molecule, 110 parts of toluene, and 10 parts of Omnirad 184 (manufactured by IGM B.V., photopolymerization initiator, 1-hydroxycyclohexylphenylketone), and the mixture was heated to 50°C and mixed for 1 hour to obtain an active energy ray-curable water / oil repellent composition.

[0071] The performance evaluation was carried out according to the following method. An untreated polyethylene terephthalate (hereinafter abbreviated as PET) film having a thickness of 100 μm was used as a substrate for forming a water- and oil-repellent layer for evaluation, and the active energy ray-curable water- and oil-repellent compositions of Examples 1 to 7 and Comparative Examples 1 to 3 were coated onto the film so that the film thickness after coating was 1 μm. After coating, the solvent was evaporated at 70° C. for 1 minute, and the film was irradiated with 200 mJ / cm using an ultraviolet irradiator (one high-pressure mercury lamp, 80 W / cm). ２ The coating was cured by irradiating it with ultraviolet light of 1000 kJ / cm2 to obtain a water- and oil-repellent layer for evaluation.

[0072] (Evaluation Method) [Evaluation of Water and Oil Repellency] Using a contact angle meter DropMaster (manufactured by Kyowa Interface Science Co., Ltd.), the contact angle of the water and oil repellent layer for evaluation obtained above with water (water contact angle) and with oleic acid at 25°C (hexadecane contact angle) were measured. The measurements were carried out 30 minutes after UV irradiation. The water contact angle was measured as the angle between the liquid surface and the cured film surface 1 second after a 2 μL droplet of ion-exchanged water came into contact with the liquid. The hexadecane contact angle was measured as the angle between the liquid surface and the cured film surface 1 second after a 2 μL droplet of hexadecane came into contact with the liquid.

[0073] [Solvent Resistance] The surface of the prepared water- and oil-repellent layer for evaluation was rubbed with gauze soaked in methyl ethyl ketone at a load of 1.0 kgf, and the number of times the gauze was rubbed back and forth until the water- and oil-repellent layer for evaluation was dissolved by the solvent or peeled off from the substrate was measured.

[0074] The performance evaluation results of each Example and Comparative Example are summarized in Tables 2 and 3 below. The meanings of the abbreviations in Tables 2 and 3 are as follows: DPHA: A mixture of dipentaerythritol penta- and hexaacrylates (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) PET-30: A mixture of pentaerythritol tri- and tetraacrylates (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD PET-30)

[0075]

[0076]

[0077] It can be seen from Tables 2 and 3 that in Examples 1 to 7, both the water contact angle and the hexadecane contact angle were large. That is, in Examples 1 to 7, both the water repellency and the oil repellency were excellent. In contrast, in Comparative Examples 1 to 3, both or either the water contact angle or the hexadecane contact angle was small. That is, in Comparative Examples 1 to 3, at least one of the water repellency and the oil repellency was poor.

[0078] The disclosure of this application relates to the subject matter described in Japanese Patent Application No. 2024-089039, filed May 31, 2024, the entire disclosure of which is incorporated herein by reference. It should be noted that, in addition to what has already been described, various modifications and variations may be made to the above-described embodiments without departing from the novel and advantageous features of the present disclosure. Accordingly, all such modifications and variations are intended to be included within the scope of the appended claims.

Claims

1. An active energy ray-curable water / oil repellent composition comprising a urethane compound (A) and a (meth)acrylate compound (B) having three or more (meth)acryloyl groups in one molecule, wherein the urethane compound (A) comprises a structural unit derived from a hydroxyl group-containing (meth)acrylate (a), a structural unit derived from an organic isocyanate compound (b) having two or more isocyanate groups in one molecule, and a structural unit derived from a linear saturated alcohol (c) having 12 to 22 carbon atoms, and wherein the hydroxyl group equivalent of the linear saturated alcohol (c) / the isocyanate group equivalent of the organic isocyanate compound (b) = 0.17 to 0.

67.

2. The active energy ray-curable water / oil repellent composition according to claim 1, wherein the content of the urethane compound (A) and the (meth)acrylate compound (B) is (A) / ((A)+(B))=0.05 to 0.5 in terms of mass ratio.

3. The active energy ray-curable water / oil repellent composition according to claim 1 or 2, wherein the (meth)acrylate compound (B) has a structure represented by the following general formula (1) or (2): [In general formulas (1) and (2), X １ ~X １０ each independently represents a (meth)acryloyl group or a hydroxyl group, X １ ~X ６ At least three of X represent a (meth)acryloyl group; ７ ~X １０ At least three of these represent (meth)acryloyl groups.

4. The active energy ray-curable water / oil repellent composition according to claim 1 or 2, which comprises, together with or instead of the (meth)acrylate compound (B), an acrylate mixture (C) containing two or more acrylates having one or more acryloyl groups in one molecule, and the two or more acrylates in the acrylate mixture (C) have an average of three or more acryloyl groups.

5. A water- and oil-repellent substrate having a water- and oil-repellent layer on the substrate, the water- and oil-repellent layer being a cured product of the active energy ray-curable water- and oil-repellent composition according to claim 1 or 2, and having a thickness of 0.05 to 50 μm.

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