Anti-mildew agents

Abstract

The anti-mildew agent comprises a blocked isocyanate. The blocked isocyanate is provided with a blocked residue (A) of a polyisocyanate, an anti-mildew / non-blocked blocked group (B), and a non-anti-mildew / non-blocked blocked group (C). The blocked residue (A) of the polyisocyanate is formed by blocking an isocyanate group of a polyisocyanate having a plurality of isocyanate groups. The anti-mildew-non-blocking blocking group (B) is formed by blocking at least some of the plurality of isocyanate groups in a non-renewable manner. The non-anti-mildew-blocking blocking group (C) is formed by blocking at least some of the plurality of isocyanate groups in a renewable manner. The anti-mildew-non-blocking blocking group (B) contains a quaternary ammonium group.

Description

TECHNICAL FIELD

[0001] The present application relates to an antifungal agent. BACKGROUND

[0002] In the past, water-dispersible blocked isocyanates have been known. Water-dispersible blocked isocyanates are used as, for example, a fiber treatment agent, a hydrophobic agent, a coating composition, and an adhesive.

[0003] More specifically, the following water-dispersible blocked isocyanate has been proposed. That is, the water-dispersible blocked isocyanate is obtained by reacting an isocyanurate derivative of hexamethylene diisocyanate, 3,5-dimethylpyrazole (DMP), and 1,1,3,3-tetramethylguanidine (TMG). In the above reaction, the proportion of DMP is 20 moles with respect to 100 moles of isocyanate groups. In addition, the proportion of TMG is 80 moles with respect to 100 moles of isocyanate groups. Furthermore, in the above reaction, 1 mole of TMG is neutralized with 2 moles of acetic acid (for example, see Patent Document 1 (Example 2)).

[0004] PRIOR ART DOCUMENTS PATENT DOCUMENTS Patent Document 1: International Publication No. 2022 / 059774 SUMMARY

[0005] PROBLEMS TO BE SOLVED BY THE INVENTION On the other hand, in various industrial fields using the above-described water-dispersible polyisocyanate, it is required to impart antifungal properties to products. In the above-described patent document, it is described that the water-dispersible polyisocyanate has antibacterial properties. However, the antibacterial properties and the antifungal properties are different in the mechanism of action. Furthermore, the resin obtained using the above-described water-dispersible polyisocyanate does not have sufficient antifungal properties.

[0006] The present application is an antifungal agent capable of imparting excellent antifungal properties to a resin.

[0007] MEANS FOR SOLVING THE PROBLEMS The present application [1] includes an antifungal agent, which is an antifungal agent containing a blocked isocyanate, the above-described blocked isocyanate having a blocked residue of a polyisocyanate (A), an antifungal-non-blocked blocking group (B), and a non-antifungal-blocked blocking group (C), the above-described blocked residue of a polyisocyanate (A) being formed by blocking isocyanate groups of a polyisocyanate having a plurality of isocyanate groups, the above-described antifungal-non-blocked blocking group (B) being formed by blocking at least a part of the plurality of the above-described isocyanate groups in a non-regenerable manner, the above-described non-antifungal-blocked blocking group (C) being formed by blocking at least a part of the plurality of the above-described isocyanate groups in a regenerable manner, and the above-described antifungal-non-blocked blocking group (B) containing a quaternary ammonium group.

[0008] The present application [2] includes the antifungal agent described in the above [1], wherein the aforementioned blocked isocyanate is not subjected to quaternary ammonium treatment.

[0009] The present application [3] includes the antifungal agent described in the above [1] or [2], wherein the aforementioned blocked isocyanate is a reaction product of raw material components, the raw material components including: a polyisocyanate (a) having a plurality of isocyanate groups for forming the aforementioned blocked residue (A); an antifungally non-blocking blocking agent (b) capable of reacting with at least a part of the plurality of aforementioned isocyanate groups for forming the aforementioned antifungally non-blocking blocking group (B); and a non-antifungally blocking blocking agent (c) capable of reacting with at least a part of the plurality of aforementioned isocyanate groups for forming the aforementioned non-antifungally blocking blocking group (C), the aforementioned antifungally non-blocking blocking agent (b) including a quaternary ammonium group-containing compound.

[0010] The present application [4] includes the antifungal agent described in the above [3], wherein the ratio of the aforementioned antifungally non-blocking blocking agent (b) is 5 moles or more and 95 moles or less with respect to 100 moles of isocyanate groups of the aforementioned polyisocyanate (a).

[0011] The present application [5] includes the antifungal agent described in the above [3], wherein the aforementioned quaternary ammonium group-containing compound includes a trialkylalkanolammonium compound.

[0012] The present application [6] includes the antifungal agent described in any one of the above [1] to [5], wherein the aforementioned polyisocyanate includes an aromatic aliphatic polyisocyanate derivative.

[0013] Effects of Invention The antifungal agent of the present application includes a blocked isocyanate. The blocked isocyanate has a blocked residue (A) of a polyisocyanate, an antifungally non-blocking blocking group (B), and a non-antifungally blocking blocking group (C). Moreover, the antifungally non-blocking blocking group (B) includes a quaternary ammonium group. Therefore, the aforementioned antifungal agent has excellent antifungal properties. In addition, the aforementioned antifungal agent can be fixed to a resin with a relatively high degree of freedom. DETAILED DESCRIPTION

[0014] 1. Antifungal agent (1) Blocked isocyanate The antifungal agent includes a blocked isocyanate. The blocked isocyanate is a compound having a latent isocyanate group. The latent isocyanate group is a functional group that can be regenerated into an isocyanate group (active isocyanate group) by de-blocking.

[0015] More specifically, the blocked isocyanate has a blocked residue of polyisocyanate (A), a mold resistance-non-blocking group (B), and a mold resistance-blocking group (C).

[0016] (2) Blocked residue of polyisocyanate (A) The blocked residue of polyisocyanate (A) is the main molecular skeleton of the blocked isocyanate. The blocked residue of polyisocyanate (A) is the remaining portion formed by blocking the isocyanate group of polyisocyanate (described later). Note that blocking includes end-blocking and non-end-blocking.

[0017] (3) Mold resistance-non-blocking group (B) The mold resistance-non-blocking group (B) is formed by blocking at least a part of the isocyanate group of polyisocyanate (described later) in a manner that cannot be regenerated. That is, the mold resistance-non-blocking group (B) is a terminal blocking group that cannot be deblocked.

[0018] In addition, the mold resistance-non-blocking group (B) has mold resistance. More specifically, the mold resistance-non-blocking group (B) contains a quaternary ammonium group.

[0019] Note that the quaternary ammonium group is a cationic group in which four atoms other than hydrogen atoms are bonded to one nitrogen atom. By using a quaternary ammonium group, a blocked isocyanate having excellent water dispersibility can be obtained. The quaternary ammonium group is neutralized by a counter ion, for example.

[0020] As the quaternary ammonium group, for example, a trialkylammonium group can be given. As the trialkylammonium group, for example, a trialkylammonium group having 1 to 8 carbon atoms in an alkyl group can be given, and preferably a trialkylammonium group having 1 to 4 carbon atoms in an alkyl group can be given. As the trialkylammonium group, more specifically, for example, a trimethylammonium group, a triethylammonium group, a dimethylethylammonium group, a methyldiethylammonium group, a tripropylammonium group, and a tributylammonium group can be given. These can be used alone or in combination of two or more. As the trialkylammonium group, preferably a trimethylammonium group can be given.

[0021] As the counter ion of the quaternary ammonium group, for example, a chloride ion, a bromide ion, an iodide ion, an acetate ion, a carbonate ion, a phosphate ion, a hydroxide ion, a citrate ion, a tartrate ion, a bitartrate ion, and a lactate ion can be given. These can be used alone or in combination of two or more. As the counter ion, preferably a chloride ion, a bromide ion, and an acetate ion can be given, and more preferably a chloride ion can be given.

[0022] The mold resistance-non-blocking group (B) is chemically bonded to the blocked residue of polyisocyanate (A).

[0023] The proportion of the non-mold-resistant blocking group (B) is, for example, 2 moles or more, preferably 5 moles or more, more preferably 10 moles or more, and further preferably 15 moles or more, relative to 100 moles of the isocyanate groups of the polyisocyanate (described later) that forms the blocking residue (A), from the viewpoint of mold resistance, water dispersibility, and storage stability. In addition, the proportion of the non-mold-resistant blocking group (B) is, for example, 98 moles or less, preferably 95 moles or less, more preferably 80 moles or less, and further preferably 60 moles or less, relative to 100 moles of the isocyanate groups of the polyisocyanate (described later) that forms the blocking residue (A), from the viewpoint of durability, and further preferably 40 moles or less, further preferably 30 moles or less, and particularly preferably 25 moles or less, from the viewpoint of water dispersibility and storage stability.

[0024] In addition, the proportion of the non-mold-resistant blocking group (B) is, for example, 2 moles or more, preferably 5 moles or more, more preferably 10 moles or more, and further preferably 15 moles or more, relative to 100 moles of the total of the non-mold-resistant blocking group (B) and the non-mold-resistant blocking group (C), from the viewpoint of mold resistance, water dispersibility, and storage stability. In addition, the proportion of the non-mold-resistant blocking group (B) is, for example, 98 moles or less, preferably 95 moles or less, more preferably 80 moles or less, and further preferably 60 moles or less, relative to 100 moles of the total of the non-mold-resistant blocking group (B) and the non-mold-resistant blocking group (C), from the viewpoint of durability, and further preferably 40 moles or less, further preferably 30 moles or less, and particularly preferably 25 moles or less, from the viewpoint of water dispersibility and storage stability.

[0025] In addition, the proportion of the non-mold-resistant blocking group (B) is, for example, 2.0 parts by mass or more, and preferably 4.5 parts by mass or more, relative to 100 parts by mass of the polyisocyanate (described later) that forms the blocking residue (A). In addition, the proportion of the non-mold-resistant blocking group (B) is, for example, 20.0 parts by mass or less, and preferably 15.0 parts by mass or less, relative to 100 parts by mass of the polyisocyanate (described later) that forms the blocking residue (A).

[0026] (4) Non-mold-resistant blocking group (C) The non-mold-resistant blocking group (C) is formed by blocking at least a portion of the isocyanate groups of the polyisocyanate (described later) in a regenerable manner. That is, the non-mold-resistant blocking group (C) is a latent isocyanate group (blocked isocyanate group) that can be deblocked.

[0027] Further, the non-mold-resistant end-capping blocking group (C) does not have mold resistance. As the non-mold-resistant end-capping blocking group (C), a known latent isocyanate group (end-capping isocyanate group) can be given.

[0028] The non-mold-resistant end-capping blocking group (C) is chemically bonded to the blocking residue (A) of the polyisocyanate.

[0029] As for the proportion of the non-mold-resistant end-capping blocking group (C) relative to 100 moles of the isocyanate group of the polyisocyanate (described later) that forms the blocking residue (A), from the viewpoint of durability, for example, 2 moles or more, preferably 5 moles or more, more preferably 20 moles or more, further preferably 40 moles or more, more preferably 60 moles or more, further preferably 70 moles or more, and particularly preferably 75 moles or more are desirable. In addition, as for the proportion of the non-mold-resistant end-capping blocking group (C) relative to 100 moles of the isocyanate group of the polyisocyanate (described later) that forms the blocking residue (A), from the viewpoints of mold resistance, water dispersibility, and storage stability, for example, 98 moles or less, preferably 95 moles or less, more preferably 90 moles or less, and further preferably 85 moles or less are desirable.

[0030] In addition, as for the proportion of the non-mold-resistant end-capping blocking group (C) relative to 100 moles of the total of the mold-resistant non-end-capping blocking group (B) and the non-mold-resistant end-capping blocking group (C), from the viewpoint of durability, for example, 2 moles or more, preferably 5 moles or more, more preferably 20 moles or more, further preferably 40 moles or more, more preferably 60 moles or more, further preferably 70 moles or more, and particularly preferably 75 moles or more are desirable. In addition, as for the proportion of the non-mold-resistant end-capping blocking group (C) relative to 100 moles of the total of the mold-resistant non-end-capping blocking group (B) and the non-mold-resistant end-capping blocking group (C), from the viewpoints of mold resistance, water dispersibility, and storage stability, for example, 98 moles or less, preferably 95 moles or less, more preferably 90 moles or less, and further preferably 85 moles or less are desirable.

[0031] In addition, the proportion of the non-mold-resistant end-capping blocking group (C) is, for example, 18.0 parts by mass or more, and preferably 22.0 parts by mass or more, relative to 100 parts by mass of the polyisocyanate (described later) that forms the blocking residue (A). In addition, the proportion of the non-mold-resistant end-capping blocking group (C) is, for example, 33.0 parts by mass or less, and preferably 30.0 parts by mass or less, relative to 100 parts by mass of the polyisocyanate (described later) that forms the blocking residue (A).

[0032] Non-mold-resistant end-capping blocking group (C) is de-capped (dissociated) by heating and regenerated as an isocyanate group. The dissociation temperature of non-mold-resistant end-capping blocking group (C) is, for example, 50°C or higher. In addition, the dissociation temperature of non-mold-resistant end-capping blocking group (C) is, for example, 150°C or lower, preferably 140°C or lower, and further preferably 130°C or lower.

[0033] (5) Mold-resistant end-capping blocking group (D) The blocked isocyanate can further have a mold-resistant end-capping blocking group (D). With the mold-resistant end-capping blocking group (D), the reactivity (curability) of the blocked isocyanate can be improved.

[0034] The mold-resistant end-capping blocking group (D) is formed by at least a part of the isocyanate groups of a polyisocyanate (described later) being blocked in a regenerable manner. That is, the mold-resistant end-capping blocking group (D) is a latent isocyanate group (blocked isocyanate group) that can be de-capped.

[0035] In addition, the mold-resistant end-capping blocking group (D) has mold resistance. More specifically, as the mold-resistant end-capping blocking group (D), a tertiary ammonium salt can be given.

[0036] The tertiary ammonium salt is formed, for example, by neutralizing a tertiary amino group with an acid.

[0037] Note that the tertiary amino group is an amino group in which three atoms other than a hydrogen atom are bonded to one nitrogen atom with a single bond. In other words, an amino group in which two or three atoms other than a hydrogen atom are bonded to one nitrogen atom with a double bond or a triple bond is not a tertiary amino group. In addition, the tertiary amino group can be included in a heterocyclic structure.

[0038] As the tertiary amino group, for example, a dialkylamino group can be given. As the dialkylamino group, for example, a dialkylamino group in which the number of carbon atoms of an alkyl group is 1 to 8 can be given, and preferably a dialkylamino group in which the number of carbon atoms of an alkyl group is 1 to 4 can be given. As the dialkylamino group, more specifically, for example, a dimethylamino group, a diethylamino group, a dipropylamino group, a diisopropylamino group, a dibutylamino group, a diisobutylamino group, a di-sec-butylamino group, and a di-tert-butylamino group can be given. These can be used alone or in combination of two or more. As the dialkylamino group, preferably a dimethylamino group can be given.

[0039] As the acid for neutralizing the tertiary amino group, for example, an organic acid and an inorganic acid can be given, and preferably an organic acid can be given. As the organic acid, for example, a carboxylic acid can be given. As the carboxylic acid, for example, acetic acid, propionic acid, and lactic acid can be given. These can be used alone or in combination of two or more.

[0040] The mold-resistant end-capping blocking group (D) is chemically bonded to the blocking residue (A) of the polyisocyanate.

[0041] The proportion of the anti-mold end-capping group (D) is, for example, 0.1 moles or more, preferably 1 mole or more, relative to 100 moles of the isocyanate groups of the polyisocyanate (described later) that forms the blocked residue (A), from the viewpoint of anti-mold properties, water dispersibility, and storage stability. In addition, the proportion of the anti-mold end-capping group (D) is, for example, 20 moles or less, preferably 10 moles or less, relative to 100 moles of the isocyanate groups of the polyisocyanate (described later) that forms the blocked residue (A), from the viewpoint of anti-mold properties, water dispersibility, and storage stability.

[0042] In addition, the proportion of the anti-mold end-capping group (D) is, for example, 1 mole or more, preferably 5 moles or more, more preferably 10 moles or more, relative to 100 moles of the anti-mold non-end-capping group (B). In addition, the proportion of the anti-mold end-capping group (D) is, for example, 40 moles or less, preferably 35 moles or less, more preferably 30 moles or less, relative to 100 moles of the anti-mold non-end-capping group (B), from the viewpoint of anti-mold properties, water dispersibility, and storage stability.

[0043] In addition, the proportion of the anti-mold end-capping group (D) is, for example, 0.1 parts by mass or more, preferably 1.3 parts by mass or more, relative to 100 parts by mass of the polyisocyanate (described later) that forms the blocked residue (A). In addition, the proportion of the anti-mold end-capping group (D) is, for example, 15.0 parts by mass or less, preferably 12.0 parts by mass or less, relative to 100 parts by mass of the polyisocyanate (described later) that forms the blocked residue (A).

[0044] The anti-mold end-capping group (D) can be de-encapped (dissociated) by heating and regenerated into an isocyanate group. However, the anti-mold end-capping group (D) can not be de-encapped (dissociated) and not regenerated into an isocyanate group depending on the temperature conditions.

[0045] More specifically, the dissociation temperature of the anti-mold end-capping group (D) is preferably higher than the dissociation temperature of the non-anti-mold end-capping group (C). The higher the dissociation temperature of the anti-mold end-capping group (D) is compared to the dissociation temperature of the end-capping group of the non-anti-mold end-capping group (C), the more the dissociation of the anti-mold end-capping group (D) is suppressed, and the non-anti-mold end-capping group (C) is preferentially dissociated. Therefore, in the case where the resin (described later) is formed by the dissociation of the non-anti-mold end-capping group (C), the anti-mold end-capping group (D) can be fixed to the resin.

[0046] The dissociation temperature of the non-mold-resistant blocking group (C) is, for example, 200°C or lower, preferably 180°C or lower, and more preferably 160°C or lower.

[0047] The difference between the dissociation temperature of the non-mold-resistant blocking group (C) and the dissociation temperature of the mold-resistant blocking group (D) is, for example, 1°C or higher, and preferably 10°C or higher. In addition, the difference between the dissociation temperature of the non-mold-resistant blocking group (C) and the dissociation temperature of the mold-resistant blocking group (D) is, for example, 50°C or lower, and preferably 40°C or lower.

[0048] (6) Hydrophilic group (E) The blocked isocyanate can further have a hydrophilic group (E). With the hydrophilic group (E), the water dispersibility of the blocked isocyanate can be improved.

[0049] The hydrophilic group (E) is formed by blocking at least a part of the isocyanate groups of the polyisocyanate (described later) in a manner that cannot be regenerated. That is, the hydrophilic group (E) is a terminal blocking group that cannot be deblocked.

[0050] As the hydrophilic group (E), for example, anionic groups and nonionic groups can be given, and preferably nonionic groups can be given. As the nonionic groups, for example, polyoxyethylene groups can be given. In the polyoxyethylene groups, the number of repetitions of the oxyethylene units is, for example, 3 or higher, and preferably 5 or higher. In addition, the number of repetitions of the oxyethylene units is, for example, 100 or lower, and preferably 50 or lower.

[0051] The hydrophilic group (E) is chemically bonded to the blocking residue (A) of the polyisocyanate.

[0052] Regarding the proportion of the hydrophilic group (E), with respect to 100 moles of the isocyanate groups of the polyisocyanate (described later) that form the blocking residue (A), from the viewpoints of mold resistance, water dispersibility, and storage stability, for example, 0.1 moles or higher, and preferably 1 mole or higher. In addition, regarding the proportion of the hydrophilic group (E), with respect to 100 moles of the isocyanate groups of the polyisocyanate (described later) that form the blocking residue (A), from the viewpoints of mold resistance, water dispersibility, and storage stability, for example, 20 moles or lower, and preferably 10 moles or lower.

[0053] Further, the proportion of the hydrophilic group (E) is, for example, 1 mol or more, preferably 3 mol or more, and more preferably 5 mol or more, relative to 100 moles of the antifungal-non-blocking blocking group (B). Further, the proportion of the hydrophilic group (E) is, for example, 30 mol or less, preferably 25 mol or less, and more preferably 20 mol or less, relative to 100 moles of the antifungal-non-blocking blocking group (B), from the viewpoint of antifungality, water dispersibility, and storage stability.

[0054] Further, the proportion of the hydrophilic group (E) is, for example, 0.1 parts by mass or more, and preferably 1.0 parts by mass or more, relative to 100 parts by mass of the polyisocyanate (to be described later) that forms the blocking residue (A). Further, the proportion of the hydrophilic group (E) is, for example, 65.0 parts by mass or less, and preferably 32.0 parts by mass or less, relative to 100 parts by mass of the polyisocyanate (to be described later) that forms the blocking residue (A).

[0055] 2. Method for producing blocked isocyanate (1) Raw material components The blocked isocyanate can be obtained as a reaction product of the following raw material components. The raw material components of the blocked isocyanate include, for example, a polyisocyanate (a), an antifungal-non-blocking blocking agent (b), and a non-antifungal-blocking blocking agent (c).

[0056] (2) Polyisocyanate (a) The polyisocyanate (a) is a raw material compound for forming the blocking residue (A). The polyisocyanate (a) has a plurality of isocyanate groups. As the polyisocyanate (a), for example, a polyisocyanate monomer and a polyisocyanate derivative can be given.

[0057] As the polyisocyanate monomer, for example, an aliphatic polyisocyanate, an aromatic polyisocyanate, and an aromatic-aliphatic polyisocyanate can be given.

[0058] As the aliphatic polyisocyanate, for example, ethylene diisocyanate, trimethylene diisocyanate, 1,4-butanediisocyanate, 1,5-pentanediisocyanate, 1,6-hexanediisocyanate, trimethylhexanediisocyanate, and 2,6-diisocyanatomethylhexanoate can be given. They can be used alone or in combination with two or more.

[0059] In addition, as the aliphatic polyisocyanate monomer, an alicyclic polyisocyanate monomer can also be given. As the alicyclic polyisocyanate monomer, for example, 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, methylene bis(cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, norbornane diisocyanate, and bis(isocyanatomethyl)cyclohexane can be given. These can be used alone or in combination of two or more.

[0060] As the aromatic polyisocyanate, for example, toluene diisocyanate, phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, and 4,4'-diphenyl ether diisocyanate can be given. These can be used alone or in combination of two or more.

[0061] As the aromatic aliphatic polyisocyanate, for example, xylene diisocyanate, tetramethyl xylene diisocyanate, and ω,ω'-diisocyanato-1,4-diethylbenzene can be given. These can be used alone or in combination of two or more.

[0062] The polyisocyanate derivative is derived from the above polyisocyanate monomer. As the polyisocyanate derivative, for example, isocyanurate-modified product, iminooxadiazinedione-modified product, triol-addition product, allophanate-modified product, biuret-modified product, urea-modified product, oxadiazine-trione-modified product, carbodiimide-modified product, uretdione-modified product, and uretonimine-modified product can be given. These can be used alone or in combination of two or more. As the polyisocyanate derivative, isocyanurate-modified product is preferable.

[0063] The polyisocyanate (a) can be used alone or in combination of two or more. From the viewpoint of curability (reactivity), the polyisocyanate (a) preferably contains a polyisocyanate derivative, and more preferably consists of a polyisocyanate derivative.

[0064] As the polyisocyanate derivative, from the viewpoint of light resistance, an aliphatic polyisocyanate derivative (hereinafter, aliphatic polyisocyanate derivative) derived from an aliphatic polyisocyanate and an aromatic aliphatic polyisocyanate derivative (hereinafter, aromatic aliphatic polyisocyanate derivative) derived from an aromatic aliphatic polyisocyanate are preferable.

[0065] As the polyisocyanate derivative, from the viewpoint of achieving a balance of mold resistance, storage stability, curability, and light resistance, an aromatic aliphatic polyisocyanate derivative is more preferable.

[0066] In other words, the polyisocyanate (a) preferably contains an aromatic aliphatic polyisocyanate derivative. As the aromatic aliphatic polyisocyanate derivative, a derivative of xylylene diisocyanate can be preferably mentioned, and an isocyanurate-modified product of xylylene diisocyanate can be more preferably mentioned.

[0067] The average isocyanate group number of the polyisocyanate (a) is, for example, 2 or more, and preferably 2.5 or more. In addition, the average isocyanate group number of the polyisocyanate (a) is, for example, 4 or less, and preferably 3.5 or less.

[0068] The isocyanate group content (NCO%) of the polyisocyanate (a) is, for example, 5% by mass or more, and preferably 7% by mass or more. In addition, the isocyanate group content (NCO%) of the polyisocyanate (a) is, for example, 30% by mass or less, and preferably 25% by mass or less.

[0069] (3) Antifungal non-blocking agent (b) The antifungal non-blocking agent (b) is a raw material compound for forming an antifungal non-blocking group (B). The antifungal non-blocking agent (b) can react with at least a part of the isocyanate groups of the above-described polyisocyanate (a) to form the antifungal non-blocking group (B).

[0070] The antifungal non-blocking agent (b) contains one or more active hydrogen groups in one molecule, and one or more antifungal groups in one molecule.

[0071] The active hydrogen group is a functional group (non-blocking group) that is bonded to the isocyanate group in a manner that cannot be dissociated. As the active hydrogen group, for example, a hydroxyl group, an amino group, and a mercapto group can be mentioned, and a hydroxyl group can be preferably mentioned. The number of active hydrogen groups is preferably one per one molecule of the antifungal non-blocking agent (b).

[0072] The antifungal group is a functional group that exhibits antifungal properties. As the antifungal group, for example, the above-described quaternary ammonium group can be mentioned. The number of antifungal groups is preferably one per one molecule of the antifungal non-blocking agent (b).

[0073] As the antifungal non-blocking agent (b), more specifically, a quaternary ammonium group-containing compound can be mentioned. The quaternary ammonium group-containing compound is, for example, a compound that has one active hydrogen group in one molecule, and one quaternary ammonium group in one molecule. As the quaternary ammonium group-containing compound, more specifically, a trialkylalkanolammonium compound can be mentioned.

[0074] The trialkylalkanolammonium compound, for example, has 3 alkyl groups and 1 alkanol group in 1 molecule. As the alkyl group, for example, an alkyl group having 1 to 4 carbon atoms can be mentioned, and preferably a methyl group can be mentioned. As the alkanol group, for example, an alkanol group having 1 to 20 carbon atoms can be mentioned, and preferably an alkanol group having 1 to 10 carbon atoms can be mentioned. That is, as the trialkylalkanolammonium compound, for example, a compound having 3 alkyl groups each having 1 to 4 carbon atoms and 1 alkanol group having 1 to 20 carbon atoms in 1 molecule can be mentioned, and preferably a compound having 3 methyl groups and 1 alkanol group having 1 to 10 carbon atoms in 1 molecule can be mentioned.

[0075] More specifically, as the trialkylalkanolammonium compound, for example, choline chloride, choline bromide, choline iodide, choline acetate, choline carbonate, choline phosphate, choline hydroxide, choline citrate, choline tartrate, choline bitartrate, and choline lactate can be mentioned. They can be used alone or in combination of two or more.

[0076] From the viewpoint of storage stability, choline bromide and choline acetate can be preferably mentioned. In addition, from the viewpoint of low cost, choline chloride can be preferably mentioned.

[0077] In the raw material components, the proportion of the antifungal non-blocked blocking agent (b) with respect to 100 moles of the isocyanate groups of the polyisocyanate (a) is, for example, 2 moles or more, preferably 5 moles or more, more preferably 10 moles or more, and further preferably 15 moles or more, from the viewpoints of antifungality, water dispersibility, and storage stability. In addition, the proportion of the antifungal non-blocked blocking agent (b) with respect to 100 moles of the isocyanate groups of the polyisocyanate (a) is, for example, 98 moles or less, preferably 95 moles or less, more preferably 80 moles or less, and further preferably 60 moles or less, from the viewpoint of durability, and further preferably 40 moles or less, further preferably 30 moles or less, and particularly preferably 25 moles or less, from the viewpoints of water dispersibility and storage stability.

[0078] In addition, in the raw material components, the proportion of the antifungal non-blocked blocking agent (b) with respect to 100 parts by mass of the polyisocyanate (a) is, for example, 2.0 parts by mass or more, preferably 4.5 parts by mass or more, and more preferably 6.0 parts by mass or more, from the viewpoints of antifungality, water dispersibility, and storage stability. In addition, the proportion of the antifungal non-blocked blocking agent (b) with respect to 100 parts by mass of the polyisocyanate (a) is, for example, 20.0 parts by mass or less, preferably 15.0 parts by mass or less, and more preferably 12.5 parts by mass or less, from the viewpoints of antifungality, water dispersibility, and storage stability.

[0079] (4) Antifungal non-blocked blocking agent (c) The non-mold-resistant blocking agent (c) is a raw compound for forming a non-mold-resistant blocking group (C). The non-mold-resistant blocking agent (c) is capable of reacting with at least a part of the isocyanate groups of the above-described polyisocyanate (a) to form the non-mold-resistant blocking group (C).

[0080] The non-mold-resistant blocking agent (c) is a blocking agent containing one or more blocking groups in one molecule.

[0081] The blocking group is a functional group that blocks and inactivates the isocyanate group of the polyisocyanate (a). By the reaction of the blocking group with the isocyanate group, a latent isocyanate group can be formed.

[0082] As the blocking group, for example, guanidine group, imidazole group, alcohol group, phenol group, active methylene group, amine group, imine group, oxime group, carbamic acid group, urea group, amide group, imide group, triazole group, pyrazole group, thiol group, bisulfite, imidazoline group, and pyrimidine group can be mentioned. They can be used alone or in combination of two or more. The number of the blocking group is preferably one per one molecule of the mold-resistant non-blocking agent (b).

[0083] As the non-mold-resistant blocking agent (c), more specifically, known blocking agents (excluding the tertiary amino group-containing compound (d1) described later. The same applies hereinafter.) can be mentioned.

[0084] As the non-mold-resistant blocking agent (c), more specifically, for example, imidazole-based compounds, alcohol-based compounds, phenol-based compounds, active methylene-based compounds, 1-2 amine-based compounds, imine-based compounds, oxime-based compounds, carbamic acid-based compounds, urea-based compounds, amide-based compounds, imide-based compounds, triazole-based compounds, pyrazole-based compounds, thiol-based compounds, bisulfite, imidazoline-based compounds, and pyrimidine-based compounds can be mentioned.

[0085] As the imidazole-based compounds, for example, imidazole (IMZ), benzimidazole, 2-methylimidazole, 4-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, and 2-amino-imidazole can be mentioned.

[0086] As the alcohol-based compound, for example, methanol, ethanol, 2-propanol, n-butanol, sec-butanol, 2-ethylhexanol, 1-octanol, 2-octanol, cyclohexanol, ethylene glycol, benzyl alcohol, 2,2,2-trifluoroethanol, 2,2,2-trichloroethanol, 2-(hydroxymethyl)furan, 2-methoxyethanol, methoxypropanol, 2-ethoxyethanol, n-propoxyethanol, 2-butoxyethanol, 2-ethoxyethoxyethanol, 2-ethoxybutoxyethanol, butoxyethoxyethanol, 2-butoxyethyl ethanol, 2-butoxyethoxyethanol, N,N-dibutyl-2-hydroxyacetamide, N-hydroxysuccinimide, N-morpholinoethanol, 2,2-dimethyl-l,3-dioxolane-4-methanol, 3-oxazolidinethanol, 2-hydroxymethylpyridine, furfuryl alcohol, 12-hydroxystearic acid, triphenylsilanol, and 2-hydroxyethyl methacrylate can be given.

[0087] As the phenol-based compound, for example, phenol, cresol, ethylphenol, n-propylphenol, isopropylphenol, n-butylphenol, sec-butylphenol, t-butylphenol, n-hexylphenol, 2-ethylhexylphenol, n-octylphenol, n-nonylphenol, di-n-propylphenol, diisopropylphenol, isopropylcresol, di-n-butylphenol, di-sec-butylphenol, di-t-butylphenol, di-n-octylphenol, di-2-ethylhexylphenol, di-n-nonylphenol, nitrophenol, bromophenol, chlorophenol, fluorophenol, dimethylphenol, styrenated phenol, methyl salicylate, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 2-ethylhexyl hydroxybenzoate, 4-[(dimethylamino)methyl]phenol, 4-[(dimethylamino)methyl]nonylphenol, bis(4-hydroxyphenyl)acetic acid, 2-hydroxypyridine, 2-hydroxyquinoline, 8-hydroxyquinoline, 2-chloro-3-pyridinol, and pyridine-2-thiol can be given.

[0088] As the active methylene-based compound, for example, Michler's acid, dialkyl malonate, alkyl acetoacetate, 2-acetoacetoxyethyl methacrylate, acetylacetone, and ethyl cyanoacetate can be given. As the dialkyl malonate, for example, dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-t-butyl malonate, di-2-ethylhexyl malonate, methyl n-butyl malonate, ethyl n-butyl malonate, methyl sec-butyl malonate, ethyl sec-butyl malonate, methyl t-butyl malonate, ethyl t-butyl malonate, diethyl methylmalonate, dibenzyl malonate, diphenyl malonate, benzyl methyl malonate, ethyl phenyl malonate, t-butyl phenyl malonate, and isopropylidene malonate can be given. As the alkyl acetoacetate, for example, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, n-butyl acetoacetate, t-butyl acetoacetate, benzyl acetoacetate, and phenyl acetoacetate can be given.

[0089] As the 1 to 2 order amine-based compounds, for example, dibutylamine, diphenylamine, aniline, N-methylaniline, carbazole, bis(2,2,6,6-tetramethylpiperidyl)amine, di-n-propylamine, diisopropylamine (DiPA), isopropylethylamine, 2,2,4-trimethylhexamethyleneamine, 2,2,5-trimethylhexamethyleneamine, N-isopropylcyclohexylamine, dicyclohexylamine, bis(3,5,5-trimethylcyclohexyl)amine, piperidine, 2,6-dimethylpiperidine, t-butylmethylamine, t-butylethylamine, t-butylpropylamine, t-butylbutylamine, t-butylbenzylamine, t-butylphenylamine, 2,2,6-trimethylpiperidine, 2,2,6,6-tetramethylpiperidine, (dimethylamino)-2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethyl-4-piperidine, 6-methyl-2-piperidine, and 6-aminohexanoic acid can be given.

[0090] As the imine-based compounds, for example, ethyleneimine, polyethyleneimine, and 1,4,5,6-tetrahydropyrimidine can be given.

[0091] As the oxime-based compounds, for example, formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime (MEKO), cyclohexanone oxime, diacetyl monoxime, benzophenone oxime, 2,2,6,6-tetramethylcyclohexanone oxime, diisopropyl ketone oxime, methyl t-butyl ketone oxime, diisobutyl ketone oxime, methyl isobutyl ketone oxime, methyl isopropyl ketone oxime, methyl 2,4-dimethylpentyl ketone oxime, methyl 3-ethylheptyl ketone oxime, methyl isoamyl ketone oxime, n-pentyl ketone oxime, 2,2,4,4-tetramethyl-1,3-cyclobutanedione monoxime, 4,4'-dimethoxybenzophenone oxime, and 2-heptanone oxime can be given.

[0092] As the carbamic acid-based compounds, for example, N-phenyl phenylcarbamate can be given.

[0093] As the urea-based compounds, for example, urea, thiourea, and ethylene urea can be given.

[0094] In other words, the amide-based compounds are lactam-based compounds. As the amide-based compounds, for example, acetanilide, N-methylacetamide, acetamide, ε-caprolactam, δ-valerolactam, γ-butyrolactam, pyrrolidone, 2,5-piperazinedione, and lauryllactam can be given.

[0095] As the imide-based compounds, for example, succinimide, maleimide, and phthalimide can be given.

[0096] As the triazole-based compounds, for example, 1,2,4-triazole and benzotriazole can be given.

[0097] As the pyrazole-based compound, for example, pyrazole, 3-methylpyrazole, 3-methyl-5-phenylpyrazole, 3,5-diphenylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3,5-dimethylpyrazole, and 3,5-dialkylpyrazole can be given. The 3,5-dialkylpyrazole has no substituent at the 4-position of the pyrazole ring. As the 3,5-dialkylpyrazole, for example, 3,5-dimethylpyrazole (DMP), 3,5-diisopropylpyrazole, and 3,5-di-t-butylpyrazole can be given.

[0098] As the thiol-based compound, for example, butyl mercaptan, dodecyl mercaptan, and hexyl mercaptan can be given.

[0099] As the bisulfite, for example, sodium bisulfite can be given.

[0100] As the imidazoline-based compound, for example, 2-methylimidazoline and 2-phenylimidazoline can be given.

[0101] As the pyrimidine-based compound, for example, 2-methyl-l,4,5,6-tetrahydropyrimidine can be given.

[0102] Further, as the non-antifungal end-capping blocking agent (c), for example, benzoxazolone, chitosan anhydride, and tetrabutylphosphonium acetate can be given.

[0103] They can be used alone or in combination of two or more. The non-antifungal end-capping blocking agent (c) preferably contains a pyrazole-based compound, and more preferably consists of a pyrazole-based compound. As the pyrazole-based compound, 3,5-diphenylpyrazole and 3,5-dialkylpyrazole can be given, and more preferably 3,5-dialkylpyrazole can be given, and further preferably 3,5-dimethylpyrazole (DMP) can be given.

[0104] In the raw material component, the proportion of the non-antifungal end-capping blocking agent (c) with respect to 100 moles of the isocyanate groups of the polyisocyanate (a) is, for example, 2 moles or more from the viewpoint of durability, preferably 5 moles or more, more preferably 20 moles or more, and further preferably 40 moles or more, and further preferably 60 moles or more, and further preferably 70 moles or more, and particularly preferably 75 moles or more from the viewpoint of water dispersibility and storage stability. In addition, the proportion of the non-antifungal end-capping blocking agent (c) with respect to 100 moles of the isocyanate groups of the polyisocyanate (a) is, for example, 98 moles or less from the viewpoint of antifungal property, water dispersibility, and storage stability, preferably 95 moles or less, more preferably 90 moles or less, and further preferably 85 moles or less.

[0105] Further, in the raw material components, the proportion of the non-mold-resistant end-capping blocking agent (c) with respect to 100 parts by mass of the polyisocyanate (a) is, for example, 18.0 parts by mass or more, preferably 22.0 parts by mass or more, and more preferably 25.0 parts by mass or more, from the viewpoint of mold resistance, water dispersibility, and storage stability. Further, the proportion of the non-mold-resistant end-capping blocking agent (c) with respect to 100 parts by mass of the polyisocyanate (a) is, for example, 33.0 parts by mass or less, preferably 30.0 parts by mass or less, and more preferably 27.0 parts by mass or less, from the viewpoint of mold resistance, water dispersibility, and storage stability.

[0106] (5) Mold-resistant end-capping blocking group forming raw material (d) The raw material components can further include a raw material compound for forming the above-described mold-resistant end-capping blocking group (D) (hereinafter, referred to as a mold-resistant end-capping blocking group forming raw material) (d).

[0107] The mold-resistant end-capping blocking group forming raw material (d) includes, for example, a tertiary amino group-containing compound (dl) and an acid (d2).

[0108] The tertiary amino group-containing compound (dl) is a raw material compound for adding a tertiary amino group to an end-capped isocyanate. The tertiary amino group-containing compound (dl) can react with at least a part of the isocyanate groups of the above-described polyisocyanate (a) to add a tertiary amino group to the polyisocyanate (a).

[0109] The tertiary amino group-containing compound (dl) includes, for example, one or more of the above-described end-capping groups in one molecule, and one or more of the above-described tertiary amino groups in one molecule.

[0110] As the tertiary amino group-containing compound, more specifically, a guanidine compound represented by the following general formula (1) can be given.

[0111] [Chemical Formula 1] Chemical Formula 1 (In the formula, R 1 ~R 5 represents a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom. Among them, R 1 and R 2 both represent a hydrocarbon group having 1 to 12 carbon atoms, and / or R 4 and R 5 both represent a hydrocarbon group having 1 to 12 carbon atoms. Further, R 1 and R 3 may be bonded to each other to form a heterocyclic ring. Further, R 4 and R 1 may be bonded to each other to form a heterocyclic ring. Further, R 5 and R3 They can bond with each other to form heterocyclic rings. In the above general formula (1), R 1 ~R 5 They can be the same as each other or different from each other. R 1 ~R 5 It represents a hydrocarbon group or hydrogen atom with 1 to 12 carbon atoms.

[0112] Among them, R 1 and R 2 These two represent hydrocarbon groups with 1 to 12 carbon atoms, and / or, R 4 and R 5 These two represent hydrocarbon groups with 1 to 12 carbon atoms. Therefore, guanidine compounds represented by general formula (1) contain at least one tertiary amino group.

[0113] As R 1 ~R 5 The hydrocarbon group represented has 1 to 12 carbon atoms. Examples of such groups include alkyl groups with 1 to 12 carbon atoms and aryl groups with 6 to 12 carbon atoms.

[0114] Examples of alkyl groups having 1 to 12 carbon atoms include chain alkyl groups having 1 to 12 carbon atoms and cyclic alkyl groups having 3 to 12 carbon atoms.

[0115] Examples of linear alkyl groups having 1 to 12 carbon atoms include straight-chain or branched linear alkyl groups having 1 to 12 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, hexyl, heptyl, octyl, nonyl, isononyl, decyl, undecyl, and dodecyl.

[0116] Examples of cyclic alkyl groups having 3 to 12 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and cyclododecyl.

[0117] Examples of aryl groups with 6 to 12 carbon atoms include phenyl, tolyl, xylyl, naphthyl, azulel, and biphenyl.

[0118] Hydrocarbon groups with 1 to 12 carbon atoms in R 1 ~R 5 They can be the same as each other or different from each other.

[0119] Additionally, R 1 and R 3 They can bond with each other to form heterocyclic rings.

[0120] R 1 and R 3The heterocycle formed by the bonding of each other is a nitrogen-containing heterocycle having a -N=C-N- structure, and examples thereof include 3- to 20-membered heterocycles, preferably 3- to 10-membered heterocycles, more preferably 3- to 8-membered heterocycles, and further preferably 5- to 7-membered heterocycles. In addition, the heterocycle can be monocyclic or polycyclic in which a plurality of monocycles share one edge. In addition, the heterocycle can be a conjugated heterocycle.

[0121] In addition, R 4 and R 1 may be bonded to each other to form a heterocycle. Furthermore, R 5 and R 3 may be bonded to each other to form a heterocycle.

[0122] In addition, the heterocycle formed by R 1 , R 3 , R 4 and R 5 may be polycyclic in which a plurality of monocycles share one edge. The heterocycle formed in this case is a nitrogen-containing heterocycle having a -N=C-N- structure, and examples thereof include 6- to 20-membered heterocycles, preferably 6- to 15-membered heterocycles, more preferably 6- to 12-membered heterocycles, and further preferably 10- to 12-membered heterocycles. In addition, the heterocycle can be a conjugated heterocycle. Note that, in the case where R 1 , R 3 , R 4 and R 5 form a heterocycle, R 2 preferably represents a hydrogen atom. As such a heterocycle structure, specifically, a triazabicyclo ring structure can be given.

[0123] In General Formula (1) above, R 1 to R 5 preferably represent a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, more preferably an alkyl group having 1 to 12 carbon atoms or a hydrogen atom, and further preferably a chain alkyl group having 1 to 12 carbon atoms or a hydrogen atom.

[0124] wherein R 1 and R 2 both represent a hydrocarbon group having 1 to 12 carbon atoms, and / or R 4 and R 5 both represent a hydrocarbon group having 1 to 12 carbon atoms.

[0125] It is particularly preferable that, in General Formula (1) above, R 1 , R 2 , R 4 and R 5 represent a chain alkyl group having 1 to 12 carbon atoms, and R 3 represents a hydrogen atom.

[0126] As the guanidine compound represented by the above general formula (1), specifically, 3,3-dialkylguanidine, 1,1,3,3-tetraalkylguanidine, and 1,5,7-triazabicyclo[4.4.0]dec-5-ene can be given.

[0127] The guanidine compound represented by the above general formula (1) can be used alone or in combination with two or more kinds.

[0128] The tertiary amino group-containing compound (d1) is not limited to the above guanidine compound. As the tertiary amino group-containing compound (d1), in addition to the above guanidine compound, for example, N-dimethylaminoethanol (DMAE), N-methyldiethanolamine (MDEA), N-methylpiperazine (MPZ), N-methylhomopiperazine (MHPZ), 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), N,N,N'-trimethylethylenediamine (TMEDA), and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TABD) can be given.

[0129] The tertiary amino group-containing compound (d1) can be used alone or in combination with two or more kinds. From the viewpoints of the mold resistance and the water dispersibility, as the tertiary amino group-containing compound (d1), preferably, the guanidine compound represented by the above general formula (1) can be given, and more preferably, 1,1,3,3-tetraalkylguanidine can be given, and more preferably, 1,1,3,3-tetramethylguanidine (TMG) can be given.

[0130] In the raw material components, the proportion of the tertiary amino group-containing compound (d1) with respect to 100 moles of the isocyanate groups of the polyisocyanate (a) is, for example, 0.1 mole or more, and preferably 1 mole or more, from the viewpoints of the mold resistance, the water dispersibility, and the storage stability. In addition, the proportion of the tertiary amino group-containing compound (d1) with respect to 100 moles of the isocyanate groups of the polyisocyanate (a) is, for example, 20 moles or less, and preferably 10 moles or less, from the viewpoints of the mold resistance, the water dispersibility, and the storage stability.

[0131] In addition, in the raw material components, the proportion of the tertiary amino group-containing compound (d1) with respect to 100 parts by mass of the polyisocyanate (a) is, for example, 0.1 parts by mass or more, and preferably 1.3 parts by mass or more, and more preferably 1.5 parts by mass or more, from the viewpoints of the mold resistance, the water dispersibility, and the storage stability. In addition, the proportion of the tertiary amino group-containing compound (d1) with respect to 100 parts by mass of the polyisocyanate (a) is, for example, 15.0 parts by mass or less, and preferably 12.0 parts by mass or less, and more preferably 10.0 parts by mass or less, from the viewpoints of the mold resistance, the water dispersibility, and the storage stability.

[0132] The acid (d2) is a raw material compound that neutralizes at least a part of the tertiary amino group described above to form a tertiary ammonium salt. The acid (d2) is not particularly limited as long as it can neutralize the tertiary amino group described above, and, for example, the acid described above as the antifungal property-terminating blocking group (D) can be given. As the acid (d2), acetic acid, propionic acid, and lactic acid can be given, and acetic acid is more preferable.

[0133] The proportion of the acid (d2) with respect to the tertiary amino group of the tertiary amino group-containing compound (d1) in the raw material components is, for example, 0.5 equivalents or more, and preferably 0.8 equivalents or more. In addition, the proportion of the acid (d2) with respect to 100 moles of the tertiary amino group of the tertiary amino group-containing compound (d1) is, for example, 5.0 equivalents or less, and preferably 3.0 equivalents or less.

[0134] (6) Hydrophilic compound (e) The raw material components can further include a hydrophilic compound (e) for forming the hydrophilic group (E) described above.

[0135] The hydrophilic compound (e) has an active hydrogen group and a hydrophilic group. As the hydrophilic compound (e), for example, a nonionic hydrophilic compound can be given, and a polyoxyethylene compound is preferable. The polyoxyethylene compound has at least 3 continuous oxyethylene groups.

[0136] As the polyoxyethylene compound, for example, a polyoxyethylene group-containing polyol, a polyoxyethylene group-containing polyamine, a mono-end-capped polyoxyethylene glycol, and a mono-end-capped polyoxyethylene diamine can be given.

[0137] The polyoxyethylene compound can be used alone or in combination of two or more.

[0138] The polyoxyethylene compound preferably includes a mono-end-capped polyoxyethylene glycol, and more preferably includes a monoalkoxy polyoxyethylene glycol.

[0139] One end of the monoalkoxy polyoxyethylene glycol is capped with, for example, an alkyl group having 1 to 20 carbon atoms, and preferably an alkyl group having 1 to 4 carbon atoms. A hydroxyl group is present at the other end of the monoalkoxy polyoxyethylene glycol.

[0140] As the monoalkoxy polyoxyethylene glycol, for example, a methoxy polyoxyethylene glycol (MeOPEG) and an ethoxy polyoxyethylene glycol can be given, and a methoxy polyoxyethylene glycol is preferable.

[0141] In the polyoxyethylene compound, the number of repetitions of the oxyethylene unit is, for example, 3 or more, and preferably 5 or more. In addition, the number of repetitions of the oxyethylene unit is, for example, 100 or less, and preferably 50 or less.

[0142] The number average molecular weight of the polyoxyethylene compound is, for example, 200 or more, and preferably 400 or more. In addition, the number average molecular weight of the polyoxyethylene compound is, for example, 2,000 or less, and preferably 1,500 or less. Note that the number average molecular weight of the polyoxyethylene compound can be measured by gel permeation chromatography.

[0143] The proportion of the hydrophilic compound (e) in the raw material components is, for example, 0.1 moles or more, and preferably 1 mole or more, relative to 100 moles of the isocyanate groups of the polyisocyanate (a), from the viewpoints of mold resistance, water dispersibility, and storage stability. In addition, the proportion of the hydrophilic compound (e) is, for example, 20 moles or less, and preferably 10 moles or less, relative to 100 moles of the isocyanate groups of the polyisocyanate (a), from the viewpoints of mold resistance, water dispersibility, and storage stability.

[0144] In addition, the proportion of the hydrophilic compound (e) in the raw material components is, for example, 0.1 parts by mass or more, and preferably 1.0 parts by mass or more, and more preferably 1.5 parts by mass or more, relative to 100 parts by mass of the polyisocyanate (a), from the viewpoints of mold resistance, water dispersibility, and storage stability.

[0145] In addition, the proportion of the hydrophilic compound (e) is, for example, 65.0 parts by mass or less, and preferably 32.0 parts by mass or less, and more preferably 30.0 parts by mass or less, relative to 100 parts by mass of the polyisocyanate (a), from the viewpoints of mold resistance, water dispersibility, and storage stability.

[0146] (7) Reaction of raw material components In the reaction of the raw material components, the components described above can be reacted simultaneously, or the components described above can be reacted sequentially.

[0147] Preferably, first, the polyisocyanate (a) and the mold resistance-non-blocking blocking agent (b) are mixed in the above-described ratio, and they are reacted (primary reaction step).

[0148] The reaction environment of the primary reaction step is, for example, a non-reactive gas atmosphere. As the non-reactive gas, for example, nitrogen or argon can be given. The reaction pressure of the primary reaction step is, for example, a pressurized condition or an atmospheric pressure condition, and is preferably an atmospheric pressure condition.

[0149] The reaction temperature of the primary reaction step is, for example, 40°C or higher, and preferably 50°C or higher. In addition, the reaction temperature of the primary reaction step is, for example, 100°C or lower, and preferably 80°C or lower. The reaction time of the primary reaction step is, for example, 0.5 hours or more, and preferably 1.0 hours or more. In addition, the reaction time of the primary reaction step is, for example, 24 hours or less, and preferably 12 hours or less.

[0150] The progress of the reaction can be judged by confirming the disappearance or reduction of the isocyanate group, for example, using infrared spectroscopic analysis, and the like. Alternatively, for example, the isocyanate group content can be measured using a known titration method, and the reduction of the isocyanate group content can be confirmed, whereby the progress of the reaction can be judged.

[0151] As a result, the anti-mold non-blocked blocking group (B) is formed. In addition, a part of the isocyanate groups of the polyisocyanate (a) (the remaining part with respect to the above part) remains in a free state without being blocked by the anti-mold non-blocked blocking agent (b).

[0152] That is, in the primary reaction step, a reaction product (primary reaction product) having the anti-mold non-blocked blocking group (B) and the free isocyanate group is obtained.

[0153] Next, in the method, the primary reaction product and the non-anti-mold blocked blocking agent (c) are mixed at the above-mentioned ratio, and they are reacted (secondary reaction step).

[0154] The reaction environment of the secondary reaction step is, for example, a non-active gas atmosphere. As the non-active gas, for example, nitrogen and argon can be given. The reaction pressure of the secondary reaction step is, for example, a pressurized condition and an atmospheric pressure condition, and is preferably an atmospheric pressure condition.

[0155] The reaction temperature of the secondary reaction step is, for example, 0°C or higher, and is preferably 20°C or higher. In addition, the reaction temperature of the secondary reaction step is, for example, 80°C or lower, and is preferably 60°C or lower. The reaction time of the secondary reaction step is, for example, 0.5 hours or more, and is preferably 1.0 hours or more. In addition, the reaction time of the secondary reaction step is, for example, 24 hours or less, and is preferably 12 hours or less.

[0156] The end of the reaction can be judged by confirming the disappearance or reduction of the isocyanate group, for example, using infrared spectroscopic analysis, and the like.

[0157] As a result, the non-anti-mold blocked blocking group (C) is formed.

[0158] In addition, in the above-mentioned primary reaction step and secondary reaction step, the isocyanate groups of the polyisocyanate (a) are blocked by the anti-mold non-blocked blocking group (B) and the non-anti-mold blocked blocking group (C). As a result, the blocked residue of the polyisocyanate (A) is formed.

[0159] That is, in the secondary reaction step, a blocked isocyanate having a blocked residue of a polyisocyanate (A), a mold-resistant non-blocking blocking group (B), and a non-mold-resistant blocking blocking group (C) (secondary reaction product) is obtained.

[0160] Such a blocked isocyanate has a blocked residue of a polyisocyanate (A), a mold-resistant non-blocking blocking group (B), and a non-mold-resistant blocking blocking group (C). Furthermore, the mold-resistant non-blocking blocking group (B) contains a quaternary ammonium group. Therefore, the above-mentioned blocked isocyanate has excellent mold resistance and can be fixed to a resin with a relatively high degree of freedom.

[0161] (8) Quaternization treatment In the above-mentioned method, the mold-resistant non-blocking blocking group (B) is formed by reacting the polyisocyanate (a) with the mold-resistant non-blocking blocking agent (b), but for example, the mold-resistant non-blocking blocking group (B) can be formed without using the mold-resistant non-blocking blocking agent (b).

[0162] More specifically, for example, a compound containing a tertiary amino group can be used instead of a compound containing a quaternary ammonium group, and the tertiary amino group thereof is subjected to quaternization treatment, thereby forming the mold-resistant non-blocking blocking group (B).

[0163] In such a case, for example, in the above-mentioned primary reaction step, a compound containing a tertiary amine (b1) is used instead of the mold-resistant non-blocking blocking agent (b) (for example, a compound containing a quaternary ammonium group), and they are reacted (primary reaction step).

[0164] As the compound containing a tertiary amine (b1), for example, the above-mentioned compound containing a tertiary amine as a mold-resistant blocking blocking group forming raw material can be mentioned. They can be used alone or in combination with two or more.

[0165] Note that the mixing ratio of the compound containing a tertiary amine (d1) is in accordance with the mixing ratio of the above-mentioned mold-resistant non-blocking blocking agent (b). In addition, the reaction conditions in the primary reaction step are the same as above. Thus, a reaction product having a tertiary amino group and a free isocyanate group (primary reaction product) is obtained.

[0166] Next, in this method, as in the above, the primary reaction product and the mold-resistant blocking blocking agent (c) are mixed at the above-mentioned ratio, and they are reacted (secondary reaction step). Thus, a reaction product having a blocked residue of a polyisocyanate (A), a non-mold-resistant blocking blocking group (C), and a tertiary amino group (secondary reaction product) is obtained.

[0167] Then, in this method, the tertiary amino group of the secondary reaction product is subjected to quaternization treatment by a known method (quaternization treatment step).

[0168] In the quaternary ammonium treatment step, for example, a tertiary amino group is reacted with a quaternary ammonium agent (b2). As the quaternary ammonium agent (b2), for example, chloromethane, allyl chloride, benzyl chloride, dimethyl sulfate, dimethyl carbonate, propylene oxide, butylene oxide, styrene oxide, epibromohydrin, chloroethanol, 3-chloro-l,2-propanediol, 3-chloro-2-hydroxypropyltrimethylammonium chloride, glycidyltrimethylammonium chloride, glycidol, butyl glycidyl ether, and allyl glycidyl ether, and glycidyl methacrylate can be given. These can be used alone or in combination of two or more. As the quaternary ammonium agent (b2), chloromethane is preferable.

[0169] The proportion of the quaternary ammonium agent (b2) with respect to the tertiary amino group of the tertiary amino group-containing compound (bl) is, for example, 0.5 equivalents or more, and preferably 0.8 equivalents or more. In addition, the proportion of the quaternary ammonium agent (b2) with respect to 100 moles of the tertiary amino group of the tertiary amino group-containing compound (bl) is, for example, 5.0 equivalents or less, and preferably 3.0 equivalents or less.

[0170] The reaction environment of the quaternary ammonium treatment step is, for example, a non-active gas atmosphere. As the non-active gas, for example, nitrogen and argon can be given. The reaction pressure of the quaternary ammonium treatment step is, for example, a pressurized condition and an atmospheric pressure condition, and is preferably an atmospheric pressure condition.

[0171] The reaction temperature of the quaternary ammonium treatment step is, for example, 0°C or higher, and is preferably 20°C or higher. In addition, the reaction temperature of the quaternary ammonium treatment step is, for example, 80°C or lower, and is preferably 60°C or lower. The reaction time of the quaternary ammonium treatment step is, for example, 0.5 hours or more, and is preferably 1.0 hour or more. In addition, the reaction time of the quaternary ammonium treatment step is, for example, 24 hours or less, and is preferably 12 hours or less.

[0172] As a result, a blocked isocyanate (quaternary ammonium treatment product) having a blocked residue (A) of a polyisocyanate, an anti-mold non-blocking group (B), and a non-anti-mold blocking group (C) is obtained.

[0173] Such a quaternary ammonium treatment product also has a blocked residue (A) of a polyisocyanate, an anti-mold non-blocking group (B), and a non-anti-mold blocking group (C). Furthermore, the anti-mold non-blocking group (B) contains a quaternary ammonium group. Therefore, the blocked isocyanate described above has excellent anti-mold properties, and can be fixed to a resin with a relatively high degree of freedom.

[0174] On the other hand, from the viewpoint of obtaining particularly excellent mold resistance, a blocked isocyanate which has not been subjected to quaternary ammonium treatment can be preferably cited, and more specifically, a reaction product of raw material components including a polyisocyanate (a), a mold resistance-nonblocked blocking agent (b), and a mold resistance-blocked blocking agent (c) can be cited.

[0175] (9) Reaction of mold resistance-blocked blocking group forming raw material (d) The raw material components can include a mold resistance-blocked blocking group forming raw material (d). In such a case, as needed, the compound containing a tertiary amino group (dl) is incorporated in the above-described ratio in the primary reaction step and / or the secondary reaction step. Preferably, the compound containing a tertiary amino group (dl) is incorporated in the above-described ratio together with the mold resistance-nonblocked blocking agent (c) in the secondary reaction step.

[0176] In the secondary reaction step, if the compound containing a tertiary amino group (dl) is incorporated, at least a part of the free isocyanate groups of the primary reaction product is blocked in a regenerable manner by the mold resistance-nonblocked blocking agent (c). In addition, at least a part of the free isocyanate groups of the primary reaction product is blocked by the compound containing a tertiary amino group (dl).

[0177] As a result, a secondary reaction product containing a mold resistance-nonblocked blocking group (C) from the mold resistance-nonblocked blocking agent (c) and a tertiary amino group from the compound containing a tertiary amino group (dl) is obtained.

[0178] Furthermore, in such a case, after the above-described secondary reaction step, the acid (d2) is incorporated in the above-described ratio with respect to the secondary reaction product, and they are reacted. Thereby, at least a part of the tertiary amino groups is neutralized by the acid, and a tertiary ammonium salt is formed (neutralization step).

[0179] The reaction environment of the neutralization step is, for example, a non-active gas atmosphere. As the non-active gas, for example, nitrogen and argon can be cited. The reaction pressure of the neutralization step is, for example, a pressurized condition and an atmospheric pressure condition, and is preferably an atmospheric pressure condition.

[0180] The reaction temperature of the neutralization step is, for example, 0°C or higher, and is preferably 20°C or higher. In addition, the reaction temperature of the neutralization step is, for example, 80°C or lower, and is preferably 60°C or lower. The reaction time of the neutralization step is, for example, 0.5 hours or longer, and is preferably 1.0 hours or longer. In addition, the reaction time of the neutralization step is, for example, 24 hours or shorter, and is preferably 12 hours or shorter.

[0181] Thereby, the tertiary amino group is neutralized by the acid, and a mold resistance-blocked blocking group (D) containing a tertiary ammonium salt is formed.

[0182] That is, in the above-described method, a blocked isocyanate having a blocked residue of a polyisocyanate (A), a mold-resistant non-blocking blocking group (B), a non-mold-resistant blocking blocking group (C), and a mold-resistant blocking blocking group (D) (neutralization reaction product) is obtained.

[0183] Such a blocked isocyanate has a blocked residue of a polyisocyanate (A), a mold-resistant non-blocking blocking group (B), and a non-mold-resistant blocking blocking group (C), and also has a mold-resistant blocking blocking group (D). Therefore, such a blocked isocyanate has particularly excellent mold resistance and curability.

[0184] (10) Reaction of the hydrophilic compound (e) The raw material component can include the hydrophilic compound (e). In such a case, as necessary, the hydrophilic compound (e) is incorporated in the above-described ratio in the primary reaction step and / or the secondary reaction step. Preferably, the hydrophilic compound (e) is incorporated in the above-described ratio together with the mold-resistant non-blocking blocking agent (b) in the primary reaction step.

[0185] In the primary reaction step, if the hydrophilic compound (e) is incorporated, at least a part of the free isocyanate groups of the polyisocyanate compound (a) is blocked in a non-regenerable manner by the mold-resistant non-blocking blocking agent (b). In addition, at least a part of the free isocyanate groups of the polyisocyanate compound (a) is blocked in a non-regenerable manner by the hydrophilic compound (e).

[0186] As a result, a primary reaction product containing a mold-resistant non-blocking blocking group (B) from the mold-resistant non-blocking blocking agent (b) and a hydrophilic group (E) from the hydrophilic compound (e) is obtained.

[0187] Then, as described above, the primary reaction product is reacted with the non-mold-resistant blocking blocking agent (c) to obtain a secondary reaction product (secondary reaction step).

[0188] Thus, a blocked isocyanate having a blocked residue of a polyisocyanate (A), a mold-resistant non-blocking blocking group (B), a non-mold-resistant blocking blocking group (C), and a hydrophilic group (E) (secondary reaction product) is obtained.

[0189] Such a blocked isocyanate has a blocked residue of a polyisocyanate (A), a mold-resistant non-blocking blocking group (B), and a non-mold-resistant blocking blocking group (C), and also has a hydrophilic group (E). Therefore, such a blocked isocyanate has particularly excellent water dispersibility.

[0190] (11) Reaction of the mold-resistant blocking blocking group forming raw material (d) and the hydrophilic compound (e) The raw material components can include an antifungal non-blocking group forming raw material (d) and a hydrophilic compound (e). In such a case, preferably, the hydrophilic compound (e) is combined with the antifungal non-blocking blocking agent (b) in the above-described ratio in the first reaction step. Also, preferably, the tertiary amino group-containing compound (d1) is combined with the non-antifungal blocking blocking agent (c) in the above-described ratio in the second reaction step. Also, as with the above, the second reaction product is neutralized with the acid (d2).

[0191] Thus, a blocked isocyanate (neutralized reaction product) having a blocked residue of a polyisocyanate (A), an antifungal non-blocking blocking group (B), a non-antifungal blocking blocking group (C), an antifungal blocking blocking group (D), and a hydrophilic group (E) is obtained.

[0192] Such a blocked isocyanate has a blocked residue of a polyisocyanate (A), an antifungal non-blocking blocking group (B), and a non-antifungal blocking blocking group (C), and also has an antifungal blocking blocking group (D) and a hydrophilic group (E). Therefore, such a blocked isocyanate has particularly excellent antifungal properties, curability, and water dispersibility.

[0193] In the blocked isocyanate, the content of free isocyanate groups (free isocyanate groups) from the polyisocyanate (a) is substantially 0.

[0194] That is, the free isocyanate groups from the polyisocyanate (a) have all reacted with any one of the antifungal non-blocking blocking agent (b) and the non-antifungal blocking blocking agent (c) (in addition, as necessary, the antifungal blocking blocking group forming raw material (d) and the hydrophilic compound (e)).

[0195] More specifically, the free isocyanate groups from the polyisocyanate (a) have all preferably each reacted with any one of the antifungal non-blocking blocking agent (b) and the non-antifungal blocking blocking agent (c). Thus, the free isocyanate groups (free isocyanate groups) from the polyisocyanate (a) are all blocked.

[0196] The obtained blocked isocyanate has a blocked residue of a polyisocyanate (A), an antifungal non-blocking blocking group (B), and a non-antifungal blocking blocking group (C).

[0197] Further, the free isocyanate groups from the polyisocyanate (a) are preferably each reacted with any one of the anti-mold non-blocking blocking agent (b), the non-anti-mold blocking blocking agent (c), and the anti-mold blocking blocking group forming raw material (d). Thus, the free isocyanate groups (free isocyanate groups) from the polyisocyanate (a) are all blocked. The resulting blocked isocyanate has the blocking residue of the polyisocyanate (A), the anti-mold non-blocking blocking group (B), and the non-anti-mold blocking blocking group (C), and also has the anti-mold blocking blocking group (D).

[0198] Further, the free isocyanate groups from the polyisocyanate (a) are preferably each reacted with any one of the anti-mold non-blocking blocking agent (b), the non-anti-mold blocking blocking agent (c), the anti-mold blocking blocking group forming raw material (d), and the hydrophilic compound (e). Thus, the free isocyanate groups (free isocyanate groups) from the polyisocyanate (a) are all blocked. The resulting blocked isocyanate has the blocking residue of the polyisocyanate (A), the anti-mold non-blocking blocking group (B), and the non-anti-mold blocking blocking group (C), and also has the anti-mold blocking blocking group (D), and the hydrophilic group (E).

[0199] (12) Other modes The reaction order of the raw material components is not limited to the above order. That is, the polyisocyanate (a), and the anti-mold non-blocking blocking agent (b) and the non-anti-mold blocking blocking agent (c) can be reacted in any order. Further, the anti-mold blocking blocking group forming raw material (d) and / or the hydrophilic compound (e) can be combined at any timing and reacted.

[0200] Further, each of the above reactions can be carried out in the absence of a solvent, or, for example, in the presence of an organic solvent. As the organic solvent, for example, ketones, nitriles, nitriles, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, glycol ether esters, ethers, halogenated aliphatic hydrocarbons, and polar aprotic solvents can be mentioned. The organic solvent can be used alone or in combination with two or more.

[0201] For example, in the case where the blocked isocyanate is not subjected to quaternary ammonium treatment, that is, in the case where the polyisocyanate (a), the anti-mold non-blocking blocking agent (b) containing a quaternary ammonium group-containing compound, and the non-anti-mold blocking blocking agent (c) are reacted, they are preferably reacted in the presence of an organic solvent. As the organic solvent, a hydrophilic solvent capable of dissolving the quaternary ammonium group-containing compound is used. As the hydrophilic solvent, for example, nitriles (for example, acetonitrile and propionitrile), and polar aprotic solvents (for example, acetone, N-methylpyrrolidone, dimethylformamide, N,N'-dimethylacetamide, dimethyl sulfoxide, and hexamethylphosphoramide) can be mentioned.

[0202] In any of the above-described reactions, when an organic solvent is used, for example, a solution of blocked isocyanate is obtained. In such a case, for example, water can be added to the blocked isocyanate solution and / or the blocked isocyanate dispersion to emulsify the blocked isocyanate, and further, the emulsion can be heated under reduced pressure, whereby the above-described organic solvent is removed. Thus, an aqueous dispersion of blocked isocyanate is obtained.

[0203] The solid content concentration of the solution and / or aqueous dispersion of blocked isocyanate is, for example, 1% by mass or more, and preferably 10% by mass or more. In addition, the solid content concentration of the solution and / or aqueous dispersion of blocked isocyanate is, for example, 80% by mass or less, and preferably 50% by mass or less.

[0204] 3. Antifungal agent The antifungal agent can contain only the above-described blocked isocyanate. For example, the antifungal agent can be a solid content formed from the blocked isocyanate. In addition, the antifungal agent can be a solution and / or aqueous dispersion of blocked isocyanate.

[0205] In addition, the antifungal agent can include an additive. As the additive, for example, a solvent, a catalyst, an epoxy resin, a coating property modifier, a leveling agent, an antifoaming agent, an antioxidant, an ultraviolet absorber, a thickening agent, an anti-settling agent, a plasticizer, a surfactant, a pigment, a filler, an organic fine particle, an inorganic fine particle, and an antiviral agent can be mentioned. The amount of the additive to be added is appropriately determined according to the purpose and use thereof.

[0206] In addition, the antifungal agent can include other isocyanate components in addition to the above-described blocked isocyanate (blocked isocyanate having a blocked residue of polyisocyanate (A), an antifungal non-blocking group (B), and a non-antifungal blocking group (C)). As the other isocyanate components, for example, an isocyanate not having the antifungal non-blocking group (B) and / or the non-antifungal blocking group (C) can be mentioned. The proportion of the other isocyanate components to be contained is not particularly limited, and is appropriately set according to the purpose and use thereof.

[0207] In addition, the above-described antifungal agent can be used in combination with a known antifungal agent. That is, the above-described antifungal agent can be mixed with another antifungal agent. Note that the mixing ratio is appropriately determined according to the purpose and use thereof.

[0208] 4. Effects The aforementioned antifungal agent comprises a capped isocyanate. The capped isocyanate possesses a polyisocyanate capped residue (A), an antifungal-resistant non-capped capped group (B), and a non-antifungal-resistant capped group (C). Furthermore, the antifungal-resistant non-capped capped group (B) comprises a quaternary ammonium group. Therefore, the aforementioned antifungal agent exhibits excellent antifungal properties and can be immobilized in the resin with a relatively high degree of freedom.

[0209] The aforementioned antifungal agents exhibit resistance to a variety of known molds. Examples of molds include, for instance, *Aspergillus niger*, *Penicillium citrinum*, *Aspergillus*, and *Chetomium globosum*. Other examples of molds include, for instance, *Cladosporium*, *Alternaria*, *Penicillium*, *Auoreobasidium*, *Trichoderma*, and *Paecilomyces variotii*.

[0210] 5. Resin (1) Curing agent The method for fixing an antifungal agent to a resin (the immobilized material) is described in detail below. When fixing an antifungal agent to a resin, the antifungal agent preferably also functions as a curing agent.

[0211] The average number of functional groups (including free isocyanate groups and potential isocyanate groups) of the curing agent is, for example, 2 or more, preferably 2.5 or more. Furthermore, the average number of functional groups (including free isocyanate groups and potential isocyanate groups) of the curing agent is, for example, 4 or less, preferably 3.5 or less.

[0212] More specifically, in this method, a main agent capable of reacting with free isocyanate groups and an antifungal agent serving as a curing agent are mixed to obtain a resin composition. Next, the resin composition is heated to decapsulate the latent isocyanate groups of the antifungal agent without dissociating at least a portion of the tertiary ammonium salt, thereby obtaining free isocyanate groups. Then, the free isocyanate groups are reacted with the main agent. This yields a resin in which the antifungal agent is immobilized in the molecule. Examples of resins include polyurethane resins, polyester resins, and acrylic resins, with polyurethane resins being preferred.

[0213] (2) Main agent The main agent is a component that reacts with the free isocyanate group obtained by de-blocking of the latent isocyanate group to form a resin. For example, in the case where the resin is a polyurethane resin, as the main agent, for example, a compound containing an active hydrogen group can be mentioned. The compound containing an active hydrogen group is a compound containing one or more active hydrogen groups in the molecule. As the compound containing an active hydrogen group, for example, a polyol compound and a polyamine compound can be mentioned. As the compound containing an active hydrogen group, a polyol compound is preferable.

[0214] As the polyol compound, for example, a low molecular weight polyol and a high molecular weight polyol can be mentioned.

[0215] The number average molecular weight of the low molecular weight polyol is, for example, less than 300, preferably less than 400. The low molecular weight polyol has two or more hydroxyl groups.

[0216] As the low molecular weight polyol, for example, a diol, a triol, a tetraol, a pentaol, a hexaol, a heptaol and an octaol can be mentioned. As the diol, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2,2-trimethylpentanediol, 3,3-dihydroxymethylheptane, an alkane (C7-20) diol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, bisphenol A, diethylene glycol, triethylene glycol, and dipropylene glycol can be mentioned. As the triol, for example, glycerol, trimethylolpropane, and triisopropanolamine can be mentioned. As the tetraol, for example, tetramethylolmethane (pentaerythritol), and diglycerol can be mentioned. As the pentaol, for example, xylitol can be mentioned. As the hexaol, for example, sorbitol, mannitol, allitol, iditol, dulcitol, arabitol, inositol, and dipentaerythritol can be mentioned. As the heptaol, for example, perillartine can be mentioned. As the octaol, for example, sucrose can be mentioned. The low molecular weight polyol can be used alone or in combination of two or more.

[0217] The number average molecular weight of the high molecular weight polyol is, for example, 300 or more, preferably 400 or more, more preferably 500 or more. The high molecular weight polyol has two or more hydroxyl groups.

[0218] As the high molecular weight polyol, for example, a polyether polyol, a polyester polyol, a polycarbonate polyol, a polyurethane polyol, an epoxy-based polyol, a vegetable oil polyol, a polyolefin polyol, an acrylic polyol, a vinyl monomer-modified polyol, and a fluorine-containing polyol can be mentioned.

[0219] As the polyether polyol, for example, polyoxyalkylene (C2-3) polyol and polytetramethylene ether polyol can be mentioned.

[0220] As the polyester polyol, for example, adipic acid-based polyester polyol, phthalic acid-based polyester polyol and lactone-based polyester polyol can be mentioned.

[0221] As the polycarbonate polyol, for example, ring-opening polymer of ethylene carbonate using the above low molecular weight polyol as an initiator, and amorphous polycarbonate polyol obtained by copolymerizing the above diol with the ring-opening polymer can be mentioned.

[0222] As the polyurethane polyol, for example, polyester polyurethane polyol, polyether polyurethane polyol, polycarbonate polyurethane polyol and polyester polyether polyurethane polyol can be mentioned.

[0223] As the epoxy-based polyol, for example, epoxy-based polyol obtained by reacting the above low molecular weight polyol with a polyfunctional epihalohydrin can be mentioned.

[0224] As the vegetable oil polyol, for example, castor oil, coconut oil and ester-modified castor oil polyol can be mentioned.

[0225] As the polyolefin polyol, for example, polybutadiene polyol and partially saponified ethylene-vinyl acetate copolymer can be mentioned.

[0226] As the acrylic polyol, for example, copolymer of a hydroxyl group-containing acrylate and a copolymerizable vinyl monomer copolymerizable with the hydroxyl group-containing acrylate can be mentioned.

[0227] The vinyl monomer-modified polyol can be obtained by reacting the above high molecular weight polyol with a vinyl monomer.

[0228] As the fluorine-containing polyol, for example, acrylic polyol obtained by incorporating a fluorine compound as a copolymerizable vinyl monomer in the copolymerization of the above acrylic polyol can be mentioned.

[0229] The high molecular weight polyol can be used alone or in combination of two or more.

[0230] The polyol compound can be used alone or in combination of two or more.

[0231] Among the polyol compounds, high molecular weight polyol is preferable, and polyurethane polyol and acrylic polyol are more preferable.

[0232] The main agent can contain an additive. As the additive, for example, a reaction solvent, a catalyst, an epoxy resin, a coating property modifier, a leveling agent, an antifoaming agent, an antioxidant, an ultraviolet absorber, a thickening agent, an anti-settling agent, a plasticizer, a surfactant, a pigment, a filler, an organic fine particle, an inorganic fine particle, and an antiviral agent can be mentioned. The blending amount of the additive is appropriately determined depending on the purpose and use thereof.

[0233] (3) Resin composition In the production of the resin composition, the above-mentioned main agent, and an antifungal agent as a curing agent are blended. The blending ratio is appropriately set depending on the purpose and use thereof. For example, the equivalent ratio of the latent isocyanate group of the antifungal agent to the active hydrogen group of the main agent (the compound containing the active hydrogen group) (latent isocyanate group / active hydrogen group) is, for example, 0.1 or more, preferably 0.5 or more, and more preferably 0.8 or more. In addition, the equivalent ratio of the latent isocyanate group of the antifungal agent to the active hydrogen group of the main agent (the compound containing the active hydrogen group) (latent isocyanate group / active hydrogen group) is, for example, 5 or less, preferably 3 or less, and more preferably 1.2 or less.

[0234] Then, the resin composition is applied to an object by a known application method, and dried, whereby a coating film is formed. Then, the coating film is heated, and, if necessary, cured.

[0235] The heating temperature and the heating time are set in such a manner that the blocking agent is dissociated from the latent isocyanate group.

[0236] The heating temperature is, for example, 50°C or more, and preferably 80°C or more. In addition, the heating temperature is, for example, 180°C or less, and preferably 150°C or less. The heating time is, for example, 10 seconds or more, and preferably 30 seconds or more. In addition, the heating time is, for example, 10 minutes or less, and preferably 5 minutes or less.

[0237] Thus, the latent isocyanate group (the antifungal non-blocking blocking group (C)) of the antifungal agent is deblocked, and regenerated as a free isocyanate group. Then, the free isocyanate group of the antifungal agent reacts with the main agent, and a cured product of the resin is obtained.

[0238] On the other hand, the quaternary ammonium group (the antifungal non-blocking blocking group (B)) remains in the antifungal agent. In addition, in the case where the antifungal agent contains the tertiary ammonium salt (the antifungal blocking blocking group (D)), at least a part of the tertiary ammonium salt remains in the antifungal agent.

[0239] Thus, by the above-mentioned reaction, the quaternary ammonium group (and the tertiary ammonium salt) in the antifungal agent is fixed to the resin. As a result, a resin (cured product) having excellent antifungal property is obtained.

[0240] Further, in the case of compounding in excess of the antifungal agent, the excess antifungal agent is not reacted with the main agent and is contained in the resin (cured product). As a result, particularly excellent antifungal properties are obtained using the excess antifungal agent.

[0241] As the use of such a resin composition (uncured product) and resin (cured product), for example, fiber treatment agent, water repellent agent, coating composition, adhesive, antistatic agent, papermaking treatment agent, paper wet strength agent, receiving layer of recording medium, electrodeposition coating composition, antifungal composition, encapsulated composition, optical member, and latex composition can be given. Among the uses of the resin composition (uncured product) and resin (cured product), fiber treatment agent, water repellent agent, coating composition, and adhesive are preferable, and fiber treatment agent and water repellent agent are more preferable.

[0242] Note that in the above description, the resin (cured product) having excellent antifungal properties is formed by the reaction of the main agent with the antifungal agent as the curing agent. However, the main agent and the antifungal agent can not react. In this case, the antifungal agent is encapsulated in the dried product of the main agent and / or the cured product of the main agent. Thus, the resin (cured product) having excellent antifungal properties is formed.

[0243] In addition, the antifungal agent can be cured alone. For example, the antifungal agent can be coated or impregnated on a substrate, and the blocking agent can be dissociated from the latent isocyanate group, thereby allowing the antifungal agent to self-crosslink and cure. In addition, for example, in the case where the substrate has an active hydrogen group, the substrate can be reacted with the antifungal agent to fix the antifungal agent to the substrate.

[0244] Example The following examples show the present application more specifically, but the present application is not limited thereto. In the following description, the specific numerical values of the compounding ratio (content ratio), physical property values, parameters, and the like used can be replaced with the upper limit values (numerical values defined in the form of "to or less than" or "less than") or lower limit values (numerical values defined in the form of "to or more than" or "more than") corresponding to the compounding ratio (content ratio), physical property values, parameters, and the like described in the "DETAILED DESCRIPTION OF THE INVENTION" above. Note that "parts" and "%" are based on mass unless otherwise specified.

[0245] Example 1 At room temperature (25°C), an isocyanurate derivative of xylylene diisocyanate (XDI) (polyisocyanate compound, trade name: TAKENATE D-131N, solid content 75 mass%, isocyanate group content 13.7%, manufactured by Mitsui Chemicals, Inc.) 50 parts by mass and acetonitrile (solvent) were put into a 500 mL reactor equipped with a stirrer, a thermometer, a condenser, and a nitrogen inlet tube.

[0246] Next, choline chloride was added to the reactor. The addition ratio of choline chloride was the number of moles shown in Table 1 with respect to 100 moles of the isocyanate groups possessed by the isocyanurate derivative of XDI.

[0247] Then, the contents of the reactor were warmed to 75°C using a sheathed resistance heater to react the isocyanurate derivative of XDI with choline chloride. The isocyanate group concentration was measured, and it was confirmed that a portion of the isocyanate groups were blocked with choline chloride.

[0248] Next, 3,5-dimethylpyrazole (DMP) was added to the reactor. The addition ratio of DMP was the number of moles shown in Table 1 with respect to 100 moles of the isocyanate groups possessed by the isocyanurate derivative of XDI.

[0249] Then, the FT-IR spectrum of the reaction solution was measured, and it was thereby confirmed that the remaining portion of the isocyanate groups were capped with DMP to form capped isocyanate groups. Thereby, a reaction solution containing capped isocyanate was obtained. Note that the capped isocyanate possessed a quaternary ammonium group from choline chloride, and had excellent water dispersibility.

[0250] Then, 150 parts by mass of water was added to 50 parts by mass of the reaction solution containing capped isocyanate. Then, the reaction solution and the water were stirred using a homomixer to emulsify them. Next, under reduced pressure, the solvent was distilled off from the emulsion, and a portion of the water was distilled off.

[0251] Thereby, an aqueous dispersion of capped isocyanate was obtained as an antifungal agent. The solid content concentration of the aqueous dispersion of capped isocyanate was 20 mass%.

[0252] Examples 2 to 3 The formulation described in Table 1 was changed. Other than that, an aqueous dispersion of capped isocyanate was obtained as an antifungal agent by the same method as Example 1.

[0253] Comparative Example 1 At room temperature (25°C), an isocyanurate derivative of hexamethylene diisocyanate (HDI) (polyisocyanate compound, trade name: TAKENATE (registered trademark) D-170N, solid content 100 mass%, isocyanate group content 20.7%, manufactured by Mitsui Chemicals, Inc.) 50 parts by mass, and acetonitrile (solvent) were put into a reactor having a capacity of 500 mL equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas inlet tube.

[0254] Next, 3,5-dimethylpyrazole (DMP) was added to the reactor. The addition ratio of DMP was the number of moles shown in Table 1 with respect to 100 moles of the isocyanate groups possessed by the isocyanurate derivative of XDI.

[0255] Next, 1, 1, 3, 3-tetramethylguanidine (TMG) was added to the reactor. The addition ratio of TMG was the number of moles shown in Table 1 with respect to 100 moles of isocyanate groups possessed by the isocyanurate derivative of HDI.

[0256] Then, FT-IR spectroscopy was performed, whereby it was confirmed that a part of the isocyanate groups were capped with DMP to form capped isocyanate groups. In addition, it was confirmed that the remaining part of the isocyanate groups were capped with TMG.

[0257] Next, acetic acid was added to the reaction solution and stirred. The addition ratio of acetic acid was the number of moles shown in Table 1 with respect to 1 mole of TMG. Thereby, the tertiary amino groups from TMG were neutralized with acetic acid to form tertiary ammonium salts (ammonium acetate salts).

[0258] Thereby, a reaction solution containing capped isocyanate was obtained. Note that the capped isocyanate has tertiary ammonium salts (ammonium acetate salts) formed from TMG and acetic acid, and thus has excellent water dispersibility.

[0259] Then, 150 parts by mass of water was added to 50 parts by mass of the reaction solution containing capped isocyanate. Then, the reaction solution and the water were stirred using a homomixer to emulsify them. Next, under reduced pressure, the solvent was distilled off from the emulsion and a part of the water was distilled off.

[0260] The water dispersion of capped isocyanate was prepared by the above method. The solid content concentration of the water dispersion of capped isocyanate was 20% by mass.

[0261] Comparative Example 2 The formulation described in Table 1 was changed. Other than that, the water dispersion of capped isocyanate was obtained by the same method as in Example 1.

[0262] <Assessment> <Antimycotic property (MIC test)> The antimycotic effect of the antimycotic agent was evaluated using the MIC (Minimum Inhibitory Concentration) test method. Details are shown below.

[0263] (1) Culture medium and surfactant solution In the MIC test (mold), the following PDA (Potato Dextrose Agar) culture medium, PDB (Potato Dextrose Broth) culture medium, and surfactant solution were used.

[0264] The PDA medium was prepared by dissolving "Difco Potato Dextrose Agar" (manufactured by Becton Dickinson and company) 39 g in 1000 mL of distilled water and adding chloramphenicol (manufactured by FUJIFILM Wako Pure Chemical Corporation, reagent special grade) diluted with ethanol to 50 mg / mL 1 mL.

[0265] The PDB medium was prepared by dissolving "Difco Potato Dextrose Broth" (manufactured by Becton Dickinson and company) 24 g in 1000 mL of distilled water and adding chloramphenicol (manufactured by FUJIFILM Wako Pure Chemical Corporation, reagent special grade) diluted with ethanol to 50 mg / mL 1 mL.

[0266] The surfactant solution was prepared by dissolving "sodium chloride" (manufactured by FUJIFILM Wako Pure Chemical Corporation, reagent special grade) 8.5 g, "polyoxyethylene (20) sorbitan monooleate" (manufactured by FUJIFILM Wako Pure Chemical Corporation, for molecular biology) 0.5 mL in 1000 mL of distilled water.

[0267] (2) Pre-culture In the MIC test (mold), the following mold strains were used. The mold strains were test mold strains that had been cultured at 25°C for 7 days or more using PDA medium that had been autoclaved at 121°C for 20 minutes.

[0268] Mold strain: Cladosporium cladosporioides (NBRC 4459, provided by the National Institute of Technology and Evaluation, Independent Administrative Agency, black mold) (3) Preparation of sample (mold-resistant agent-containing medium) Each mold-resistant agent was added to PDB medium that had been autoclaved at 121°C for 20 minutes. Then, a 2-fold dilution series of 11 stages was prepared so that the maximum concentration of the active ingredient was 4000 ppm. Thus, a mold-resistant agent-containing medium was obtained.

[0269] Note that the "maximum concentration of the active ingredient" in the MIC test method (mold) means the proportion (mass %) of the solid content of the mold-resistant agent in the mold-resistant agent-containing medium with respect to the total mass of the mold-resistant agent-containing medium.

[0270] (4) Preparation of mold liquid The test mold species was suspended in a surfactant solution that had been autoclaved at 121°C for 20 minutes. In addition, a mold liquid was prepared so that the number of spores was 1 x 10 5 / mL to 100 x 10 5 / mL using a hemocytometer. Thus, a mold liquid was obtained.

[0271] (5) MIC measurement (mold) To each of 2 mL of the prepared dilution series of the mold-resistant agent-containing medium, 100 μL of the mold liquid was inoculated, and incubation was performed at 7 days and 25°C. Then, the development of mold was confirmed by visual observation, and the minimum dilution concentration at which mold did not develop was taken as the MIC value.

[0272] Note that in the case where a substance was obtained in which the mycelium of mold was not confirmed to form a mass in the mold-resistant agent-containing medium by visual observation, mold was determined to not have developed. The measurement results are shown in Table 1.

[0273] Note that the permissible range of the MIC value of the MIC test (mold) was 3.9 ppm or more. In addition, in the case where the MIC value was 500 ppm or less, mold resistance was determined to be good.

[0274] [Table 1] Details of the abbreviations in the table are described below.

[0275] D-131N; isocyanurate derivative of xylylene diisocyanate (XDI), trade name: TAKENATE D-131N, solid content 75 mass%, isocyanate group content 13.7%, manufactured by Mitsui Chemicals, Inc. D-170N; isocyanurate derivative of hexamethylene diisocyanate (HDI), trade name: TAKENATE D-170N, solid content 100 mass%, isocyanate group content 20.7%, manufactured by Mitsui Chemicals, Inc. TMG; 1,1,3,3-tetramethylguanidine DMP; 3,5-dimethylpyrazole

Claims

1. An antifungal agent which is an antifungal agent comprising a blocked isocyanate, the blocked isocyanate has: a blocked residue (A) of a polyisocyanate, an antifungal-non-blocked blocking group (B), and a non-antifungal-blocked blocking group (C), the blocked residue (A) of a polyisocyanate is formed by blocking isocyanate groups of a polyisocyanate having a plurality of isocyanate groups, the antifungal-non-blocked blocking group (B) is formed by blocking at least a part of the plurality of isocyanate groups in a non-regenerable manner, the non-antifungal-blocked blocking group (C) is formed by blocking at least a part of the plurality of isocyanate groups in a regenerable manner, the antifungal-non-blocked blocking group (B) contains a quaternary ammonium group.

2. The antifungal agent of claim 1, wherein, The blocked isocyanate is not subjected to quaternization treatment.

3. The antifungal agent of claim 1 or 2, wherein, The blocked isocyanate is a reaction product of raw material components, the raw material components contain: a polyisocyanate (a) having a plurality of isocyanate groups for forming the blocked residue (A); an antifungal-non-blocked blocking agent (b) capable of reacting with at least a part of the plurality of isocyanate groups for forming the antifungal-non-blocked blocking group (B); and a non-antifungal-blocked blocking agent (c) capable of reacting with at least a part of the plurality of isocyanate groups for forming the non-antifungal-blocked blocking group (C), the antifungal-non-blocked blocking agent (b) contains a quaternary ammonium group-containing compound.

4. The antimold agent of claim 3, wherein, The proportion of the antifungal-non-blocked blocking agent (b) is 5 moles or more and 95 moles or less with respect to 100 moles of isocyanate groups of the polyisocyanate (a).

5. The antifungal agent as described in claim 3, wherein, The quaternary ammonium group-containing compound contains a trialkylalkanolammonium compound.

6. The antimold agent of claim 1, wherein The polyisocyanate contains an aromatic aliphatic polyisocyanate derivative.

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