Antifungal agent

Abstract

This antifungal agent contains a blocked isocyanate. The blocked isocyanate comprises a capped polyisocyanate residue (A), an antifungal non-blocked capped group (B), and a non-antifungal blocked capped group (C). The capped polyisocyanate residue (A) is produced by capping an isocyanate group in a polyisocyanate having a plurality of isocyanate groups. In the antifungal non-blocked capped group (B), at least some of the plurality of isocyanate groups are capped in a non-reproducible manner. In the antifungal blocked capped group (C), at least some of the plurality of isocyanate groups are capped in a reproducible manner. The antifungal non-blocked capped group (B) includes a quaternary ammonium group.

Description

Antifungal agents

[0001] The present invention relates to an antifungal agent.

[0002] Water-dispersible blocked isocyanates have been known and are used, for example, as fiber treatment agents, water repellents, coating compositions, and adhesives.

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

[0004] International Publication No. 2022 / 059774

[0005] On the other hand, in various industrial fields where the above-mentioned water-dispersible polyisocyanates are used, there is a demand for imparting antifungal properties to products. The above-mentioned patent document describes that water-dispersible polyisocyanates have antibacterial properties. However, the mechanisms of action of antibacterial properties and antifungal properties are different. Furthermore, resins obtained using the above-mentioned water-dispersible polyisocyanates do not have sufficient antifungal properties.

[0006] The present invention is an antifungal agent that can impart excellent antifungal properties to resins.

[0007] The present invention [1] relates to an antifungal agent containing a blocked isocyanate, wherein the blocked isocyanate comprises a polyisocyanate blocking residue (A), an antifungal unblocked blocking group (B), and a non-antifungal blocked blocking group (C), wherein the polyisocyanate blocking residue (A) is obtained by blocking the isocyanate groups of a polyisocyanate having a plurality of isocyanate groups, the antifungal unblocked blocking group (B) is obtained by non-regeneratively blocking at least a portion of the plurality of isocyanate groups, and the non-antifungal blocked blocking group (C) is obtained by regeneratively blocking at least a portion of the plurality of isocyanate groups, and the antifungal unblocked blocking group (B) contains a quaternary ammonium group.

[0008] The present invention [2] includes the antifungal agent according to the above [1], in which the blocked isocyanate has not been subjected to a quaternary treatment.

[0009] The present invention [3] comprises the antifungal agent according to the above [1] or [2], wherein the blocked isocyanate is a reaction product of raw material components, the raw material components having a plurality of isocyanate groups, and comprising: a polyisocyanate (a) for forming the blocking residue (A); an antifungal unblocked blocking agent (b) that reacts with at least a portion of the plurality of isocyanate groups to form the antifungal unblocked blocking group (B); and a non-antifungal unblocked blocking agent (c) that reacts with at least a portion of the plurality of isocyanate groups to form the non-antifungal blocked blocking group (C), and the antifungal unblocked blocking agent (b) comprises a quaternary ammonium group-containing compound.

[0010] The present invention [4] includes the antifungal agent according to the above [3], wherein the ratio of the antifungal non-blocking sealing agent (b) is 5 mol or more and 95 mol or less per 100 mol of isocyanate groups of the polyisocyanate (a).

[0011] The present invention [5] includes the antifungal agent according to the above [3], wherein the quaternary ammonium group-containing compound includes a trialkylalkanol ammonium compound.

[0012] The present invention [6] includes the antifungal agent according to any one of the above [1] to [5], wherein the polyisocyanate includes an araliphatic polyisocyanate derivative.

[0013] The antifungal agent of the present invention contains a blocked isocyanate. The blocked isocyanate comprises a blocking residue of a polyisocyanate (A), an antifungal non-blocked blocking group (B), and a non-antifungal blocked blocking group (C). The antifungal non-blocked blocking group (B) contains a quaternary ammonium group. Therefore, the antifungal agent has excellent antifungal properties. Furthermore, the antifungal agent can be fixed in a resin with a relatively high degree of freedom.

[0014] 1. Antifungal Agents (1) Blocked Isocyanate The antifungal agent contains a blocked isocyanate. A blocked isocyanate is a compound containing a latent isocyanate group. The latent isocyanate group is a functional group that can regenerate an isocyanate group (active isocyanate group) by deblocking.

[0015] More specifically, the blocked isocyanate comprises a polyisocyanate blocking residue (A), a fungicide-resistant non-blocking blocking group (B), and a non-fungicide-resistant non-blocking blocking group (C).

[0016] (2) Blocked Residue of Polyisocyanate (A) The blocked residue of polyisocyanate (A) is the main molecular skeleton of a blocked isocyanate. The blocked residue of polyisocyanate (A) is the remainder obtained by blocking the isocyanate groups of a polyisocyanate (described later). Note that the blocking includes both blocked and unblocked blocking.

[0017] (3) Antifungal-unblocked capping group (B) The antifungal-unblocked capping group (B) is formed by irreversibly blocking at least a portion of the isocyanate groups of a polyisocyanate (described later). That is, the antifungal-unblocked capping group (B) is an end-capping group that cannot be deblocked.

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

[0019] The quaternary ammonium group is a cationic group in which four atoms other than hydrogen atoms are bonded to one nitrogen atom. The quaternary ammonium group allows a blocked isocyanate to be obtained with excellent water dispersibility. The quaternary ammonium group is neutralized with, for example, a counter ion.

[0020] Examples of quaternary ammonium groups include trialkylammonium groups. Examples of trialkylammonium groups include trialkylammonium groups in which the alkyl group has 1 to 8 carbon atoms, and preferably trialkylammonium groups in which the alkyl group has 1 to 4 carbon atoms. More specific examples of trialkylammonium groups include trimethylammonium groups, triethylammonium groups, dimethylethylammonium groups, methyldiethylammonium groups, tripropylammonium groups, and tributylammonium groups. These can be used alone or in combination of two or more types. A preferred example of the trialkylammonium group is a trimethylammonium group.

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

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

[0023] The proportion of the antifungal non-blocked capping group (B) relative to 100 moles of isocyanate groups in the polyisocyanate (described below) forming the capping residue (A) is, from the viewpoints of antifungal properties, water dispersibility, and storage stability, for example, 2 moles or more, preferably 5 moles or more, more preferably 10 moles or more, and even more preferably 15 moles or more. Furthermore, the proportion of the antifungal non-blocked capping group (B) relative to 100 moles of isocyanate groups in the polyisocyanate (described below) forming the capping residue (A) is, from the viewpoint of durability, for example, 98 moles or less, preferably 95 moles or less, more preferably 80 moles or less, and even more preferably 60 moles or less, and from the viewpoint of water dispersibility and storage stability, even more preferably 40 moles or less, even more preferably 30 moles or less, and particularly preferably 25 moles or less.

[0024] The proportion of the antifungal non-blocked capping group (B) is, from the viewpoints of antifungal property, water dispersibility, and storage stability, for example, 2 moles or more, preferably 5 moles or more, more preferably 10 moles or more, and even more preferably 15 moles or more, per 100 moles of the total of the antifungal non-blocked capping group (B) and the non-antifungal non-blocked capping group (C). The proportion of the antifungal non-blocked capping group (B) is, from the viewpoint of durability, for example, 98 moles or less, preferably 95 moles or less, more preferably 80 moles or less, and even more preferably 60 moles or less, per 100 moles of the total of the antifungal non-blocked capping group (B) and the non-antifungal non-blocked capping group (C). From the viewpoint of water dispersibility and storage stability, the proportion is more preferably 40 moles or less, even more preferably 30 moles or less, and especially preferably 25 moles or less.

[0025] The proportion of the antifungal non-blocked capping group (B) is, for example, 2.0 parts by mass or more, preferably 4.5 parts by mass or more, per 100 parts by mass of the polyisocyanate (described below) that forms the capping residue (A).The proportion of the antifungal non-blocked capping group (B) is, for example, 20.0 parts by mass or less, preferably 15.0 parts by mass or less, per 100 parts by mass of the polyisocyanate (described below) that forms the capping residue (A).

[0026] (4) Non-fungal-resistant blocked capping group (C) The non-fungal-resistant blocked capping group (C) is obtained by blocking at least a portion of the isocyanate groups of a polyisocyanate (described below) in a reproducible manner. That is, the non-fungal-resistant blocked capping group (C) is a deblockable latent isocyanate group (blocked isocyanate group).

[0027] The non-fungal-resistant blocked capping group (C) does not have antifungal properties. Examples of the non-fungal-resistant blocked capping group (C) include known latent isocyanate groups (blocked isocyanate groups).

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

[0029] The proportion of the non-fungal-resistant blocked capping group (C) relative to 100 moles of isocyanate groups in the polyisocyanate (described below) forming the capping residue (A) is, from the viewpoint of durability, for example, 2 moles or more, preferably 5 moles or more, more preferably 20 moles or more, even more preferably 40 moles or more, and from the viewpoint of water dispersibility and storage stability, more preferably 60 moles or more, even more preferably 70 moles or more, particularly preferably 75 moles or more. Furthermore, the proportion of the non-fungal-resistant blocked capping group (C) relative to 100 moles of isocyanate groups in the polyisocyanate (described below) forming the capping residue (A) is, from the viewpoint of antifungal property, water dispersibility and storage stability, for example, 98 moles or less, preferably 95 moles or less, more preferably 90 moles or less, even more preferably 85 moles or less.

[0030] The proportion of the non-antifungal blocked capping group (C) is, from the viewpoint of durability, for example, 2 moles or more, preferably 5 moles or more, more preferably 20 moles or more, and even more preferably 40 moles or more, and from the viewpoint of water dispersibility and storage stability, preferably 60 moles or more, even more preferably 70 moles or more, and particularly preferably 75 moles or more, per 100 moles of the total of the antifungal non-block capping group (B) and the non-antifungal non-block capping group (C). The proportion of the non-antifungal blocked capping group (C) is, from the viewpoint of antifungal property, water dispersibility and storage stability, for example, 98 moles or less, preferably 95 moles or less, more preferably 90 moles or less, and even more preferably 85 moles or less, per 100 moles of the total of the antifungal non-block capping group (B) and the non-antifungal non-block capping group (C).

[0031] The proportion of the non-fungal-resistant blocked capping group (C) is, for example, 18.0 parts by mass or more, preferably 22.0 parts by mass or more, per 100 parts by mass of the polyisocyanate (described below) that forms the capping residue (A).The proportion of the non-fungal-resistant blocked capping group (C) is, for example, 33.0 parts by mass or less, preferably 30.0 parts by mass or less, per 100 parts by mass of the polyisocyanate (described below) that forms the capping residue (A).

[0032] The non-fungal-resistant blocked capping group (C) is deblocked (dissociated) by heating to regenerate the isocyanate group. The dissociation temperature of the non-fungal-resistant blocked capping group (C) is, for example, 50°C or higher. The dissociation temperature of the non-fungal-resistant blocked capping group (C) is, for example, 150°C or lower, preferably 140°C or lower, and more preferably 130°C or lower.

[0033] (5) Antifungal Block Cap Group (D) The blocked isocyanate may further comprise an antifungal block capping group (D). The antifungal block capping group (D) can improve the reactivity (curability) of the blocked isocyanate.

[0034] The antifungal blocked capping group (D) is obtained by reproducibly blocking at least a portion of the isocyanate groups of a polyisocyanate (described below). That is, the antifungal blocked capping group (D) is a deblockable latent isocyanate group (blocked isocyanate group).

[0035] The antifungal block capping group (D) also has antifungal properties. More specifically, the antifungal block capping group (D) may be a tertiary ammonium salt.

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

[0037] A tertiary amino group is an amino group in which three atoms other than hydrogen atoms are single-bonded to one nitrogen atom. In other words, an amino group in which atoms other than hydrogen atoms are double- or triple-bonded to one nitrogen atom is not a tertiary amino group. The tertiary amino group may also be contained in a heterocyclic structure.

[0038] An example of a tertiary amino group is a dialkylamino group. An example of a dialkylamino group is a dialkylamino group having an alkyl group with 1 to 8 carbon atoms, preferably a dialkylamino group having an alkyl group with 1 to 4 carbon atoms. More specific examples of dialkylamino groups include a dimethylamino group, a diethylamino group, a dipropylamino group, a diisopropylamino group, a dibutylamino group, a diisobutylamino group, a di-s-butylamino group, and a di-t-butylamino group. These can be used alone or in combination of two or more types. A preferred example of a dialkylamino group is a dimethylamino group.

[0039] Examples of acids that neutralize tertiary amino groups include organic acids and inorganic acids, and preferably organic acids. Examples of organic acids include carboxylic acids. Examples of carboxylic acids include acetic acid, propionic acid, and lactic acid. These acids can be used alone or in combination of two or more.

[0040] The antifungal blocking group (D) is chemically bonded to the blocking residue (A) of the polyisocyanate.

[0041] The proportion of the antifungal blocked capping group (D) is, for example, 0.1 mole or more, preferably 1 mole or more, relative to 100 moles of isocyanate groups in the polyisocyanate (described below) forming the capping residue (A), from the viewpoints of antifungal properties, water dispersibility, and storage stability. The proportion of the antifungal blocked capping group (D) is, for example, 20 moles or less, preferably 10 moles or less, relative to 100 moles of isocyanate groups in the polyisocyanate (described below) forming the capping residue (A), from the viewpoints of antifungal properties, water dispersibility, and storage stability.

[0042] The proportion of the antifungal blocked capping group (D) is, for example, 1 mole or more, preferably 5 moles or more, more preferably 10 moles or more, per 100 moles of the antifungal non-blocked capping group (B). From the viewpoints of antifungal properties, water dispersibility, and storage stability, the proportion of the antifungal blocked capping group (D) is, for example, 40 moles or less, preferably 35 moles or less, more preferably 30 moles or less, per 100 moles of the antifungal non-blocked capping group (B).

[0043] The proportion of the antifungal blocked capping group (D) is, for example, 0.1 parts by mass or more, preferably 1.3 parts by mass or more, per 100 parts by mass of the polyisocyanate (described below) that forms the capping residue (A).The proportion of the antifungal blocked capping group (D) is, for example, 15.0 parts by mass or less, preferably 12.0 parts by mass or less, per 100 parts by mass of the polyisocyanate (described below) that forms the capping residue (A).

[0044] The antifungal-blocked capping group (D) can be deblocked (dissociated) by heating to regenerate the isocyanate group. However, depending on the temperature conditions, the antifungal-blocked capping group (D) may not be deblocked (dissociated) to regenerate the isocyanate group.

[0045] More specifically, the dissociation temperature of the antifungal block capping group (D) is preferably higher than the dissociation temperature of the non-antifungal block capping group (C). If the dissociation temperature of the antifungal block capping group (D) is higher than the dissociation temperature of the blocking group of the non-antifungal block capping group (C), the non-antifungal block capping group (C) can be preferentially dissociated while suppressing the dissociation of the antifungal block capping group (D). Therefore, when a resin (described below) is formed by the dissociation of the non-antifungal block capping group (C), the antifungal block capping group (D) can be immobilized on the resin.

[0046] The dissociation temperature of the antifungal block capping group (D) is, for example, 60° C. or higher, preferably 100° C. or higher. The dissociation temperature of the non-antifungal block capping group (C) is, for example, 200° C. or lower, preferably 180° C. or lower, more preferably 160° C. or lower.

[0047] The difference between the dissociation temperature of the non-antifungal block capping group (C) and the dissociation temperature of the antifungal block capping group (D) is, for example, 1° C. or more, preferably 10° C. or more. The difference between the dissociation temperature of the non-antifungal block capping group (C) and the dissociation temperature of the antifungal block capping group (D) is, for example, 50° C. or less, preferably 40° C. or less.

[0048] (6) Hydrophilic Group (E) The blocked isocyanate may further include a hydrophilic group (E). The hydrophilic group (E) can improve the water dispersibility of the blocked isocyanate.

[0049] The hydrophilic group (E) is formed by irreversibly blocking at least a portion of the isocyanate groups of a polyisocyanate (described later), i.e., the hydrophilic group (E) is an end-capping group that cannot be deblocked.

[0050] Examples of the hydrophilic group (E) include anionic groups and nonionic groups, and preferably nonionic groups. Examples of the nonionic group include polyoxyethylene groups. In the polyoxyethylene group, the number of repeating oxyethylene units is, for example, 3 or more, preferably 5 or more. The number of repeating oxyethylene units is, for example, 100 or less, preferably 50 or less.

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

[0052] The proportion of the hydrophilic group (E) is, for example, 0.1 mole or more, preferably 1 mole or more, relative to 100 moles of isocyanate groups in the polyisocyanate (described later) forming the capping residue (A), from the viewpoints of antifungal properties, water dispersibility, and storage stability. The proportion of the hydrophilic group (E) is, for example, 20 moles or less, preferably 10 moles or less, relative to 100 moles of isocyanate groups in the polyisocyanate (described later) forming the capping residue (A), from the viewpoints of antifungal properties, water dispersibility, and storage stability.

[0053] The proportion of the hydrophilic group (E) is, for example, 1 mole or more, preferably 3 moles or more, more preferably 5 moles or more, per 100 moles of the antifungal non-blocking capping group (B). From the viewpoints of antifungal properties, water dispersibility, and storage stability, the proportion of the hydrophilic group (E) is, for example, 30 moles or less, preferably 25 moles or less, more preferably 20 moles or less, per 100 moles of the antifungal non-blocking capping group (B).

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

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

[0056] (2) Polyisocyanate (a) Polyisocyanate (a) is a raw material compound for forming the capping residue (A). Polyisocyanate (a) has multiple isocyanate groups. Examples of polyisocyanate (a) include polyisocyanate monomers and polyisocyanate derivatives.

[0057] Examples of polyisocyanate monomers include aliphatic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates.

[0058] Examples of aliphatic polyisocyanates include ethylene diisocyanate, trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and 2,6-diisocyanate methyl caproate. These can be used alone or in combination of two or more.

[0059] The aliphatic polyisocyanate monomer also includes an alicyclic polyisocyanate monomer. Examples of the alicyclic polyisocyanate monomer include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, methylenebis(cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, norbornane diisocyanate, and bis(isocyanatomethyl)cyclohexane. These can be used alone or in combination of two or more types.

[0060] Examples of aromatic polyisocyanates include tolylene diisocyanate, phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, and 4,4'-diphenyl ether diisocyanate. These can be used alone or in combination of two or more.

[0061] Examples of aromatic aliphatic polyisocyanates include xylylene diisocyanate, tetramethylxylylene diisocyanate, and ω,ω'-diisocyanate-1,4-diethylbenzene. These can be used alone or in combination of two or more.

[0062] The polyisocyanate derivative is derived from the polyisocyanate monomer described above. Examples of the polyisocyanate derivative include isocyanurate-modified products, iminooxadiazinedione-modified products, triol adducts, allophanate-modified products, biuret-modified products, urea-modified products, oxadiazinetrione-modified products, carbodiimide-modified products, uretdione-modified products, and uretonimine-modified products. These can be used alone or in combination of two or more types. A preferred example of the polyisocyanate derivative is an isocyanurate-modified product.

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

[0064] From the viewpoint of light resistance, preferred examples of the polyisocyanate derivative include polyisocyanate derivatives derived from aliphatic polyisocyanates (hereinafter referred to as “aliphatic polyisocyanate derivatives”) and polyisocyanate derivatives derived from araliphatic polyisocyanates (hereinafter referred to as “araliphatic polyisocyanate derivatives”).

[0065] As the polyisocyanate derivative, from the viewpoint of achieving a balance between mildew resistance, storage stability, curability, and light resistance, aromatic aliphatic polyisocyanate derivatives are more preferred.

[0066] In other words, the polyisocyanate (a) preferably includes an araliphatic polyisocyanate derivative. As the araliphatic polyisocyanate derivative, preferably, a derivative of xylylene diisocyanate is used, and more preferably, an isocyanurate-modified product of xylylene diisocyanate is used.

[0067] The polyisocyanate (a) has an average number of isocyanate groups of, for example, 2 or more, or preferably 2.5 or more. The polyisocyanate (a) has an average number of isocyanate groups of, for example, 4 or less, or preferably 3.5 or less.

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

[0069] (3) Antifungal-unblocked sealing agent (b) The antifungal-unblocked sealing agent (b) is a raw material compound for forming the antifungal-unblocked sealing group (B). The antifungal-unblocked sealing agent (b) reacts with at least a portion of the isocyanate groups of the polyisocyanate (a) to form the antifungal-unblocked sealing group (B).

[0070] The antifungal non-blocking sealant (b) contains one or more active hydrogen groups per molecule and one or more antibacterial groups per molecule.

[0071] The active hydrogen group is a functional group (non-blocking group) that non-detachably bonds to an isocyanate group. Examples of the active hydrogen group include a hydroxyl group, an amino group, and a mercapto group, and a hydroxyl group is preferred. The number of active hydrogen groups is preferably one per molecule of the antifungal non-blocking sealant (b).

[0072] The antibacterial group is a functional group that exhibits antifungal properties. Examples of the antibacterial group include the above-mentioned quaternary ammonium group. The number of antibacterial groups is preferably one per molecule of the antifungal non-blocking sealing agent (b).

[0073] More specifically, the antifungal non-blocking sealant (b) may be a quaternary ammonium group-containing compound. The quaternary ammonium group-containing compound is, for example, a compound having both one active hydrogen group and one quaternary ammonium group per molecule. More specifically, the quaternary ammonium group-containing compound may be a trialkylalkanolammonium compound.

[0074] The trialkylalkanolammonium compound has, for example, three alkyl groups and one alkanol group in one molecule. Examples of the alkyl group include an alkyl group having 1 to 4 carbon atoms, preferably a methyl group. Examples of the alkanol group include an alkanol group having 1 to 20 carbon atoms, preferably an alkanol group having 1 to 10 carbon atoms. That is, examples of the trialkylalkanolammonium compound include a compound having, in one molecule, three alkyl groups having 1 to 4 carbon atoms and one alkanol group having 1 to 20 carbon atoms, preferably a compound having, in one molecule, three methyl groups and one alkanol group having 1 to 10 carbon atoms.

[0075] More specifically, examples of trialkylalkanolammonium compounds include choline chloride, choline bromide, choline iodide, choline acetate, choline carbonate, choline phosphate, choline hydroxide, choline citrate, choline tartrate, choline bitartrate, and choline lactate, which can be used alone or in combination of two or more.

[0076] From the viewpoint of storage stability, choline bromide and choline acetate are preferred, and from the viewpoint of low cost, choline chloride is preferred.

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

[0078] In addition, the proportion of the antifungal non-blocking sealing agent (b) in the raw material components is, from the viewpoints of antifungal properties, water dispersibility, and storage stability, 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, per 100 parts by mass of the polyisocyanate (a). In addition, the proportion of the antifungal non-blocking sealing agent (b) is, from the viewpoints of antifungal properties, water dispersibility, and storage stability, 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, per 100 parts by mass of the polyisocyanate (a).

[0079] (4) Antifungal Unblocked Capper (c) The non-antifungal blocked capper (c) is a raw material compound for forming the non-antifungal blocked capping group (C). The non-antifungal blocked capper (c) reacts with at least a portion of the isocyanate groups of the polyisocyanate (a) to form the non-antifungal blocked capping group (C).

[0080] The non-fungal 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). The reaction between the blocking group and the isocyanate group forms a latent isocyanate group.

[0082] Examples of blocking groups include guanidine groups, imidazole groups, alcohol groups, phenol groups, active methylene groups, amine groups, imine groups, oxime groups, carbamic acid groups, urea groups, acid amide groups, acid imide groups, triazole groups, pyrazole groups, mercaptan groups, bisulfites, imidazoline groups, and pyrimidine groups. These can be used alone or in combination of two or more. The number of blocking groups is preferably one per molecule of the antifungal non-blocking sealing agent (b).

[0083] More specifically, the non-fungal resistant blocking agent (c) may be any known blocking agent (excluding the tertiary amino group-containing compound (d1) described later; the same applies hereinafter).

[0084] More specific examples of the non-fungal-resistant blocking sealant (c) include imidazole compounds, alcohol compounds, phenol compounds, active methylene compounds, primary and secondary amine compounds, imine compounds, oxime compounds, carbamic acid compounds, urea compounds, acid amide compounds, acid imide compounds, triazole compounds, pyrazole compounds, mercaptan compounds, bisulfites, imidazoline compounds, and pyrimidine compounds.

[0085] Examples of imidazole compounds include imidazole (IMZ), benzimidazole, 2-methylimidazole, 4-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, and 2-amine-imidazole.

[0086] Examples of alcohol compounds include methanol, ethanol, 2-propanol, n-butanol, s-butanol, 2-ethylhexyl alcohol, 1-octanol, 2-octanol, cyclohexyl alcohol, ethylene glycol, benzyl alcohol, 2,2,2-trifluoroethanol, 2,2,2-trichloroethanol, 2-(hydroxymethyl)furan, 2-methoxyethanol, methoxypropanol, 2-ethoxyethanol, n-propoxyethanol, 2-butoxyethanol, and 2-ethoxyethoxy. Examples of suitable hydroxypropyl methyl ethers include ethanol, 2-ethoxybutoxyethanol, butoxyethoxyethanol, 2-butoxyethylethanol, 2-butoxyethoxyethanol, N,N-dibutyl-2-hydroxyacetamide, N-hydroxysuccinimide, N-morpholineethanol, 2,2-dimethyl-1,3-dioxolane-4-methanol, 3-oxazolidineethanol, 2-hydroxymethylpyridine, furfuryl alcohol, 12-hydroxystearic acid, triphenylsilanol, and 2-hydroxyethyl methacrylate.

[0087] Examples of phenolic compounds include phenol, cresol, ethylphenol, n-propylphenol, isopropylphenol, n-butylphenol, s-butylphenol, t-butylphenol, n-hexylphenol, 2-ethylhexylphenol, n-octylphenol, n-nonylphenol, di-n-propylphenol, diisopropylphenol, isopropylcresol, di-n-butylphenol, di-s-butylphenol, di-t-butylphenol, di-n-octylphenol, di-2-ethylhexylphenol, di-n-nonyl Examples include phenol, 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.

[0088] Examples of active methylene compounds include Meldrum's acid, dialkyl malonate, alkyl acetoacetate, 2-acetoacetoxyethyl methacrylate, acetylacetone, and ethyl cyanoacetate. Examples of dialkyl malonate include 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 s-butyl malonate, ethyl s-butyl malonate, methyl t-butyl malonate, ethyl t-butyl malonate, diethyl methylmalonate, dibenzyl malonate, diphenyl malonate, benzylmethyl malonate, ethylphenyl malonate, t-butylphenyl malonate, and isopropylidene malonate. Examples of alkyl acetoacetates include methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, n-butyl acetoacetate, t-butyl acetoacetate, benzyl acetoacetate, and phenyl acetoacetate.

[0089] Examples of primary and secondary amine compounds include dibutylamine, diphenylamine, aniline, N-methylaniline, carbazole, bis(2,2,6,6-tetramethylpiperidinyl)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-aminocaproic acid.

[0090] Examples of imine compounds include ethyleneimine, polyethyleneimine, and 1,4,5,6-tetrahydropyrimidine.

[0091] Examples of oxime compounds include formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime (MEKO), cyclohexanone oxime, diacetyl monooxime, 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-amyl ketone oxime, 2,2,4,4-tetramethyl-1,3-cyclobutanedione monooxime, 4,4′-dimethoxybenzophenone oxime, and 2-heptanone oxime.

[0092] An example of the carbamic acid compound is N-phenylcarbamate phenyl.

[0093] Examples of urea-based compounds include urea, thiourea, and ethyleneurea.

[0094] In other words, the acid amide compound is a lactam compound. Examples of the acid amide compound include acetanilide, N-methylacetamide, acetic acid amide, ε-caprolactam, δ-valerolactam, γ-butyrolactam, pyrrolidone, 2,5-piperazinedione, and laurolactam.

[0095] Examples of the acid imide compounds include succinimide, maleimide, and phthalimide.

[0096] Examples of triazole compounds include 1,2,4-triazole and benzotriazole.

[0097] Examples of pyrazole compounds include 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. 3,5-Dialkylpyrazoles do not have a substituent at the 4-position of the pyrazole ring. Examples of 3,5-dialkylpyrazoles include 3,5-dimethylpyrazole (DMP), 3,5-diisopropylpyrazole, and 3,5-di-t-butylpyrazole.

[0098] Examples of mercaptan compounds include butyl mercaptan, dodecyl mercaptan, and hexyl mercaptan.

[0099] An example of the bisulfite is sodium bisulfite.

[0100] Examples of imidazoline compounds include 2-methylimidazoline and 2-phenylimidazoline.

[0101] An example of the pyrimidine compound is 2-methyl-1,4,5,6-tetrahydropyrimidine.

[0102] Non-fungal blocking sealants (c) also include, for example, benzoxazolone, isatoic anhydride, and tetrabutylphosphonium acetate.

[0103] These can be used alone or in combination of two or more. The non-fungal-resistant blocking sealant (c) preferably contains a pyrazole compound, and more preferably consists of a pyrazole compound. Examples of the pyrazole compound include preferably 3,5-diphenylpyrazole and 3,5-dialkylpyrazole, more preferably 3,5-dialkylpyrazole, and even more preferably 3,5-dimethylpyrazole (DMP).

[0104] In the raw material components, the proportion of the non-fungal blocking agent (c) relative to 100 moles of isocyanate groups in the polyisocyanate (a) is, from the viewpoint of durability, for example, 2 moles or more, preferably 5 moles or more, more preferably 20 moles or more, even more preferably 40 moles or more; from the viewpoint of water dispersibility and storage stability, it is, from the viewpoint of water dispersibility and storage stability, more preferably 60 moles or more, even more preferably 70 moles or more, particularly preferably 75 moles or more. Furthermore, the proportion of the non-fungal blocking agent (c) relative to 100 moles of isocyanate groups in the polyisocyanate (a) is, from the viewpoint of fungicide resistance, water dispersibility and storage stability, for example, 98 moles or less, preferably 95 moles or less, more preferably 90 moles or less, even more preferably 85 moles or less.

[0105] In addition, the proportion of the non-fungal-resistant blocking agent (c) in the raw material components is, from the viewpoints of antifungal properties, water dispersibility, and storage stability, 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, per 100 parts by mass of the polyisocyanate (a). In addition, the proportion of the non-fungal-resistant blocking agent (c) is, from the viewpoints of antifungal properties, water dispersibility, and storage stability, 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, per 100 parts by mass of the polyisocyanate (a).

[0106] (5) Antifungal Block Capped Group Forming Raw Material (d) The raw material components may further contain a raw material compound (d) for forming the above antifungal block capping group (D) (hereinafter referred to as antifungal block capping group forming raw material).

[0107] The antifungal block capping group forming raw material (d) contains, for example, a tertiary amino group-containing compound (d1) and an acid (d2).

[0108] The tertiary amino group-containing compound (d1) is a raw material compound for adding a tertiary amino group to the blocked isocyanate. The tertiary amino group-containing compound (d1) reacts with at least a portion of the isocyanate groups of the polyisocyanate (a) to add a tertiary amino group to the polyisocyanate (a).

[0109] The tertiary amino group-containing compound (d1) contains, for example, one or more of the above-mentioned blocking groups in one molecule and one or more of the above-mentioned tertiary amino groups in one molecule.

[0110] More specifically, the tertiary amino group-containing compound includes a guanidine compound represented by the following general formula (1). (In the formula, R １ ~R ５ represents a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom. １ and R ２ and both represent a hydrocarbon group having 1 to 12 carbon atoms, and / or R ４ and R ５ Both R and R represent a hydrocarbon group having 1 to 12 carbon atoms. １ and R ３ may be bonded to each other to form a heterocycle. ４ and R １ may be bonded to each other to form a heterocycle. ５ and R ３ may be bonded to each other to form a heterocycle.) In the above general formula (1), R １ ~R ５ may be the same or different from each other. １ ~R ５ represents a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom.

[0111] However, R １ and R ２ and both represent a hydrocarbon group having 1 to 12 carbon atoms, and / or R ４ and R ５ and each represent a hydrocarbon group having 1 to 12 carbon atoms. As a result, the guanidine compound represented by general formula (1) contains at least one tertiary amino group.

[0112] R １ ~R ５ Examples of the hydrocarbon group having 1 to 12 carbon atoms represented by the formula (I) include an alkyl group having 1 to 12 carbon atoms and an aryl group having 6 to 12 carbon atoms.

[0113] Examples of the alkyl group having 1 to 12 carbon atoms include a chain alkyl group having 1 to 12 carbon atoms and a cyclic alkyl group having 3 to 12 carbon atoms.

[0114] Examples of the chain alkyl group having 1 to 12 carbon atoms include linear or branched chain 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.

[0115] Examples of the cyclic alkyl group having 3 to 12 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and cyclododecyl.

[0116] Examples of the aryl group having 6 to 12 carbon atoms include phenyl, tolyl, xylyl, naphthyl, azulenyl, and biphenyl.

[0117] The hydrocarbon group having 1 to 12 carbon atoms is R １ ~R ５ may be the same or different from each other.

[0118] Also, R １ and R ３ can be bonded to each other to form a heterocycle.

[0119] R １ and R ３ The heterocycle formed by bonding to each other is a nitrogen-containing heterocycle having an -N=C-N- structure, and examples thereof include a 3- to 20-membered heterocycle, preferably a 3- to 10-membered heterocycle, more preferably a 3- to 8-membered heterocycle, and even more preferably a 5- to 7-membered heterocycle. The heterocycle may be, for example, a monocyclic ring, or a polycyclic ring in which multiple monocyclic rings share one side. The heterocycle may also be a conjugated heterocycle.

[0120] Also, R ４ and R １can be bonded to each other to form a heterocycle. ５ and R ３ can be bonded to each other to form a heterocycle.

[0121] Also, R １ , R ３ , R ４ and R ５ The heterocycle formed from may be a polycyclic ring in which a plurality of monocycles share one side. In this case, the heterocycle formed is a nitrogen-containing heterocycle having an -N=C-N- structure, and examples thereof include a 6- to 20-membered heterocycle, preferably a 6- to 15-membered heterocycle, more preferably a 6- to 12-membered heterocycle, and even more preferably a 10- to 12-membered heterocycle. The heterocycle may also be a conjugated heterocycle. Note that R １ , R ３ , R ４ and R ５ When R forms a heterocycle, ２ is preferably a hydrogen atom. Specific examples of such heterocyclic structures include triazabicyclo ring structures.

[0122] In the above general formula (1), R １ ~R ５ represents preferably 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 even more preferably a chain alkyl group having 1 to 12 carbon atoms or a hydrogen atom.

[0123] However, R １ and R ２ and both represent a hydrocarbon group having 1 to 12 carbon atoms, and / or R ４ and R ５ Both of and represent a hydrocarbon group having 1 to 12 carbon atoms.

[0124] Particularly preferably, in the above general formula (1), R １ , R ２ , R ４ and R ５ represents a chain alkyl group having 1 to 12 carbon atoms, and R ３ indicates a hydrogen atom.

[0125] Specific examples of the guanidine compound represented by the general formula (1) include 3,3-dialkylguanidine, 1,1,3,3-tetraalkylguanidine, and 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

[0126] The guanidine compounds represented by the above general formula (1) can be used alone or in combination of two or more kinds.

[0127] The tertiary amino group-containing compound (d1) is not limited to the above-mentioned guanidine compounds. Examples of the tertiary amino group-containing compound (d1) include, in addition to the above-mentioned guanidine compounds, 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).

[0128] The tertiary amino group-containing compound (d1) can be used alone or in combination of two or more kinds. From the viewpoint of antifungal properties and water dispersibility, the tertiary amino group-containing compound (d1) is preferably a guanidine compound represented by the above general formula (1), more preferably 1,1,3,3-tetraalkylguanidine, and even more preferably 1,1,3,3-tetramethylguanidine (TMG).

[0129] In the raw material components, the proportion of the tertiary amino group-containing compound (d1) is, for example, 0.1 mol or more, preferably 1 mol or more, per 100 mol of isocyanate groups in the polyisocyanate (a), from the viewpoints of antifungal properties, water dispersibility, and storage stability. Also, the proportion of the tertiary amino group-containing compound (d1) is, for example, 20 mol or less, preferably 10 mol or less, per 100 mol of isocyanate groups in the polyisocyanate (a), from the viewpoints of antifungal properties, water dispersibility, and storage stability.

[0130] In the raw material components, the proportion of the tertiary amino group-containing compound (d1) is, from the viewpoints of antifungal properties, water dispersibility, and storage stability, for example, 0.1 parts by mass or more, preferably 1.3 parts by mass or more, more preferably 1.5 parts by mass or more, per 100 parts by mass of the polyisocyanate (a). In addition, the proportion of the tertiary amino group-containing compound (d1) is, from the viewpoints of antifungal properties, water dispersibility, and storage stability, for example, 15.0 parts by mass or less, preferably 12.0 parts by mass or less, more preferably 10.0 parts by mass or less, per 100 parts by mass of the polyisocyanate (a).

[0131] The acid (d2) is a raw material compound for neutralizing at least a portion of the tertiary amino groups to form a tertiary ammonium salt. The acid (d2) is not particularly limited as long as it can neutralize the tertiary amino groups, and examples thereof include the acids described above as the antifungal blocking group (D). Preferred examples of the acid (d2) include acetic acid, propionic acid, and lactic acid, and more preferred examples include acetic acid.

[0132] In the raw material components, the proportion of the acid (d2) relative to the tertiary amino groups of the tertiary amino group-containing compound (d1) is, for example, 0.5 equivalents or more, preferably 0.8 equivalents or more, and the proportion of the acid (d2) relative to 100 moles of the tertiary amino groups of the tertiary amino group-containing compound (d1) is, for example, 5.0 equivalents or less, preferably 3.0 equivalents or less.

[0133] (6) Hydrophilic Compound (e) The raw material components may further contain a hydrophilic compound (e) for forming the hydrophilic group (E).

[0134] The hydrophilic compound (e) has an active hydrogen group and a hydrophilic group. Examples of the hydrophilic compound (e) include nonionic hydrophilic compounds, preferably polyoxyethylene compounds. The polyoxyethylene compound has at least three consecutive oxyethylene groups.

[0135] Examples of polyoxyethylene compounds include polyoxyethylene group-containing polyols, polyoxyethylene group-containing polyamines, one-end-capped polyoxyethylene glycols, and one-end-capped polyoxyethylene diamines.

[0136] The polyoxyethylene compounds can be used alone or in combination of two or more kinds.

[0137] The polyoxyethylene compound preferably includes a one-end-capped polyoxyethylene glycol, and more preferably includes a monoalkoxypolyoxyethylene glycol.

[0138] One end of the monoalkoxypolyoxyethylene glycol is capped with, for example, an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, and a hydroxyl group is located at the other end of the monoalkoxypolyoxyethylene glycol.

[0139] Examples of monoalkoxypolyoxyethylene glycols include methoxypolyoxyethylene glycol (MeOPEG) and ethoxypolyoxyethylene glycol, and preferably methoxypolyoxyethylene glycol.

[0140] In the polyoxyethylene compound, the number of repeating oxyethylene units is, for example, 3 or more, preferably 5 or more. The number of repeating oxyethylene units is, for example, 100 or less, preferably 50 or less.

[0141] The number average molecular weight of the polyoxyethylene compound is, for example, 200 or more, preferably 400 or more. The number average molecular weight of the polyoxyethylene compound is, for example, 2000 or less, preferably 1500 or less. The number average molecular weight of the polyoxyethylene compound can be measured by gel permeation chromatography.

[0142] In the raw material components, the ratio of the hydrophilic compound (e) is, for example, 0.1 mol or more, preferably 1 mol or more, relative to 100 mol of isocyanate groups of the polyisocyanate (a), from the viewpoints of antifungal properties, water dispersibility, and storage stability. The ratio of the hydrophilic compound (e) is, for example, 20 mol or less, preferably 10 mol or less, relative to 100 mol of isocyanate groups of the polyisocyanate (a), from the viewpoints of antifungal properties, water dispersibility, and storage stability.

[0143] In the raw material components, the ratio of the hydrophilic compound (e) is, from the viewpoints of antifungal properties, water dispersibility, and storage stability, for example, 0.1 parts by mass or more, preferably 1.0 parts by mass or more, and more preferably 1.5 parts by mass or more, per 100 parts by mass of the polyisocyanate (a). In addition, the ratio of the hydrophilic compound (e) is, from the viewpoints of antifungal properties, water dispersibility, and storage stability, for example, 65.0 parts by mass or less, preferably 32.0 parts by mass or less, and more preferably 30.0 parts by mass or less, per 100 parts by mass of the polyisocyanate (a).

[0144] (7) Reaction of Raw Material Components In the reaction of the raw material components, the above components may be reacted simultaneously or sequentially.

[0145] Preferably, first, the polyisocyanate (a) and the antifungal non-blocking sealant (b) are mixed in the above ratio and reacted (first reaction step).

[0146] The reaction environment of the first reaction step is, for example, an inert gas atmosphere. Examples of inert gases include nitrogen gas and argon gas. The reaction pressure of the first reaction step is, for example, pressurized or atmospheric, preferably atmospheric.

[0147] The reaction temperature of the primary reaction step is, for example, 40°C or higher, preferably 50°C or higher. The reaction temperature of the primary reaction step is, for example, 100°C or lower, preferably 80°C or lower. The reaction time of the primary reaction step is, for example, 0.5 hours or higher, preferably 1.0 hour or higher. The reaction time of the primary reaction step is, for example, 24 hours or lower, preferably 12 hours or lower.

[0148] The progress of the reaction can be determined by, for example, using infrared spectroscopy to confirm the disappearance or decrease of isocyanate groups. Alternatively, the progress of the reaction can be determined by, for example, measuring the isocyanate group content by a known titration method and confirming the decrease in the isocyanate group content.

[0149] As a result, a portion of the isocyanate groups of the polyisocyanate (a) are irreproducibly blocked with the antifungal, non-blocking blocking agent (b). As a result, antifungal, non-blocking blocking groups (B) are formed. Furthermore, a portion of the isocyanate groups of the polyisocyanate (a) (the remainder of the above portion) is not blocked with the antifungal, non-blocking blocking agent (b) and remains in a free state.

[0150] That is, in the primary reaction step, a reaction product (primary reaction product) having an antifungal non-blocked capping group (B) and a free isocyanate group is obtained.

[0151] Next, in this method, the primary reaction product and the non-fungal-resistant blocking sealant (c) are mixed in the above ratio and reacted (secondary reaction step).

[0152] The reaction environment of the secondary reaction step is, for example, an inert gas atmosphere. Examples of inert gases include nitrogen gas and argon gas. The reaction pressure of the secondary reaction step is, for example, pressurized or atmospheric, preferably atmospheric.

[0153] The reaction temperature of the secondary reaction step is, for example, 0°C or higher, preferably 20°C or higher. The reaction temperature of the secondary reaction step is, for example, 80°C or lower, preferably 60°C or lower. The reaction time of the secondary reaction step is, for example, 0.5 hours or higher, preferably 1.0 hour or higher. The reaction time of the secondary reaction step is, for example, 24 hours or lower, preferably 12 hours or lower.

[0154] The completion of the reaction can be determined by, for example, infrared spectroscopy, etc., by confirming the disappearance or reduction of the isocyanate groups.

[0155] This allows the free isocyanate groups of the primary reaction product to be reproducibly blocked with the non-fungal-resistant blocking agent (c), resulting in the formation of non-fungal-resistant blocking groups (C).

[0156] In the above-mentioned primary reaction step and secondary reaction step, the isocyanate groups of the polyisocyanate (a) are blocked with the antifungal non-blocked blocking group (B) and the non-antifungal non-blocked blocking group (C), thereby forming a blocked residue of the polyisocyanate (A).

[0157] That is, in the secondary reaction step, a blocked isocyanate (secondary reaction product) is obtained which comprises the blocking residue of polyisocyanate (A), the antifungal non-blocking blocking group (B), and the non-antifungal non-blocking blocking group (C).

[0158] Such blocked isocyanates comprise a polyisocyanate blocking residue (A), an antifungal non-blocked blocking group (B), and a non-antifungal blocked blocking group (C). The antifungal non-blocked blocking group (B) contains a quaternary ammonium group. Therefore, the blocked isocyanates have excellent antifungal properties and can be immobilized in resins with a relatively high degree of freedom.

[0159] (8) Quaternization Treatment In the above method, the antifungal non-blocked capping group (B) is formed by reacting the polyisocyanate (a) with the antifungal non-blocked capping agent (b). However, for example, the antifungal non-blocked capping group (B) may be formed without using the antifungal non-blocked capping agent (b).

[0160] More specifically, the antifungal non-blocking capping group (B) may be formed without using a quaternary ammonium group-containing compound, for example, by using a tertiary amino group-containing compound and subjecting the tertiary amino group to a quaternary treatment.

[0161] In such a case, for example, in the above-mentioned primary reaction step, a tertiary amine-containing compound (b1) is blended in place of the antifungal non-blocking sealant (b) (e.g., a quaternary ammonium group-containing compound), and they are reacted (primary reaction step).

[0162] Examples of the tertiary amine-containing compound (b1) include the tertiary amine-containing compounds described above as the raw material for forming the antifungal block capping group. These compounds can be used alone or in combination of two or more.

[0163] The proportion of the tertiary amine-containing compound (d1) conforms to the proportion of the antifungal non-blocking sealant (b) described above. The reaction conditions in the primary reaction step are the same as those described above. This produces a reaction product (primary reaction product) containing a tertiary amino group and a free isocyanate group.

[0164] Next, in this method, the primary reaction product and the antifungal blocking agent (c) are mixed in the above ratio and reacted (secondary reaction step), as in the above, to obtain a reaction product (secondary reaction product) comprising the polyisocyanate blocking residue (A), the non-antifungal blocking group (C), and a tertiary amino group.

[0165] Thereafter, in this method, the tertiary amino groups of the secondary reaction product are quaternized by a known method (quaternization treatment step).

[0166] In the quaternization treatment step, for example, a tertiary amino group is reacted with a quaternizing agent (b2). Examples of the quaternizing agent (b2) include methyl chloride, allyl chloride, benzyl chloride, dimethyl sulfate, dimethyl carbonate, propylene oxide, butylene oxide, styrene oxide, epibromohydrin, ethylene chlorohydrin, 3-chloro-1,2-propanediol, 3-chloro-2-hydroxypropyltrimethylammonium chloride, glycidyltrimethylammonium chloride, glycidol, butyl glycidyl ether, allyl glycidyl ether, and glycidyl methacrylate. These can be used alone or in combination of two or more. A preferred example of the quaternizing agent (b2) is methyl chloride.

[0167] The proportion of the quaternizing agent (b2) relative to the tertiary amino groups of the tertiary amino group-containing compound (b1) is, for example, 0.5 equivalents or more, preferably 0.8 equivalents or more, and the proportion of the quaternizing agent (b2) relative to 100 moles of the tertiary amino groups of the tertiary amino group-containing compound (b1) is, for example, 5.0 equivalents or less, preferably 3.0 equivalents or less.

[0168] The reaction environment of the quaternization treatment step is, for example, an inert gas atmosphere. Examples of inert gases include nitrogen gas and argon gas. The reaction pressure of the quaternization treatment step is, for example, pressurized conditions or atmospheric pressure conditions, preferably atmospheric pressure conditions.

[0169] The reaction temperature in the quaternization treatment step is, for example, 0°C or higher, preferably 20°C or higher. The reaction temperature in the quaternization treatment step is, for example, 80°C or lower, preferably 60°C or lower. The reaction time in the quaternization treatment step is, for example, 0.5 hours or higher, preferably 1.0 hour or higher. The reaction time in the quaternization treatment step is, for example, 24 hours or lower, preferably 12 hours or lower.

[0170] This quaternizes the tertiary amino group, forming a quaternary ammonium group (antifungal non-blocked capping group (B)). As a result, a blocked isocyanate (quaternized product) is obtained that comprises the polyisocyanate capping residue (A), the antifungal non-blocked capping group (B), and the non-antifungal non-blocked capping group (C).

[0171] Such a quaternized product also comprises a polyisocyanate blocking residue (A), an antifungal non-blocked blocking group (B), and a non-antifungal blocked blocking group (C). The antifungal non-blocked blocking group (B) contains a quaternary ammonium group. Therefore, the blocked isocyanate has excellent antifungal properties and can be fixed in a resin with a relatively high degree of freedom.

[0172] On the other hand, from the viewpoint of obtaining particularly excellent antifungal properties, a blocked isocyanate that has not been quaternized is preferably used, and more specifically, a reaction product of raw material components including a polyisocyanate (a), an antifungal non-blocking sealing agent (b), and a non-antifungal non-blocking sealing agent (c) is preferably used.

[0173] (9) Reaction of Antifungal Block Capped Group-Forming Raw Material (d) The raw material components may contain the antifungal block capped group-forming raw material (d). In such a case, if necessary, the tertiary amino group-containing compound (d1) is blended in the above-mentioned ratio in the primary reaction step and / or the secondary reaction step. Preferably, the tertiary amino group-containing compound (d1) is blended in the above-mentioned ratio together with the non-antifungal block capping agent (c) in the secondary reaction step.

[0174] In the secondary reaction step, when the tertiary amino group-containing compound (d1) is blended, at least a portion of the free isocyanate groups in the primary reaction product are reproducibly blocked with the non-fungal-resistant blocking capping agent (c). Also, at least a portion of the free isocyanate groups in the primary reaction product are blocked with the tertiary amino group-containing compound (d1).

[0175] As a result, a secondary reaction product is obtained containing the non-fungal-resistant blocked capping group (C) derived from the non-fungal-resistant blocked capping agent (c) and the tertiary amino group derived from the tertiary amino group-containing compound (d1).

[0176] In such a case, after the secondary reaction step, the acid (d2) is added to the secondary reaction product in the above-mentioned ratio, and the two are reacted to neutralize at least a portion of the tertiary amino groups with the acid to form a tertiary ammonium salt (neutralization step).

[0177] The reaction environment of the neutralization step is, for example, an inert gas atmosphere. Examples of inert gases include nitrogen gas and argon gas. The reaction pressure of the neutralization step is, for example, pressurized or atmospheric, preferably atmospheric.

[0178] The reaction temperature in the neutralization step is, for example, 0°C or higher, preferably 20°C or higher. The reaction temperature in the neutralization step is, for example, 80°C or lower, preferably 60°C or lower. The reaction time in the neutralization step is, for example, 0.5 hours or higher, preferably 1.0 hour or higher. The reaction time in the neutralization step is, for example, 24 hours or lower, preferably 12 hours or lower.

[0179] This neutralizes the tertiary amino group with the acid, forming an antifungal blocking group (D) containing a tertiary ammonium salt.

[0180] That is, the above method produces a blocked isocyanate (neutralization reaction product) comprising a polyisocyanate blocking residue (A), an antifungal non-blocked blocking group (B), a non-antifungal blocked blocking group (C), and an antifungal blocked blocking group (D).

[0181] Such blocked isocyanates comprise a polyisocyanate blocking residue (A), an antifungal non-blocking blocking group (B), a non-antifungal blocked blocking group (C), and further comprise an antifungal blocked blocking group (D), and therefore have particularly excellent antifungal properties and curing properties.

[0182] (10) Reaction of Hydrophilic Compound (e) The raw material components may contain the hydrophilic compound (e). In such a case, the hydrophilic compound (e) is blended in the above-mentioned ratio in the primary reaction step and / or the secondary reaction step, as necessary. Preferably, the hydrophilic compound (e) is blended in the above-mentioned ratio together with the antifungal non-blocking sealant (b) in the primary reaction step.

[0183] When the hydrophilic compound (e) is blended in the primary reaction step, at least a portion of the free isocyanate groups of the polyisocyanate compound (a) are irreproducibly blocked by the antifungal non-blocking blocking agent (b). Also, at least a portion of the free isocyanate groups of the polyisocyanate compound (a) are irreproducibly blocked by the hydrophilic compound (e).

[0184] As a result, a primary reaction product is obtained that contains antifungal-unblocked capping groups (B) derived from the antifungal-unblocked capping agent (b) and hydrophilic groups (E) derived from the hydrophilic compound (e).

[0185] Thereafter, as described above, the primary reaction product is reacted with the non-fungal-resistant blocking sealant (c) to obtain a secondary reaction product (secondary reaction step).

[0186] This results in a blocked isocyanate (secondary reaction product) comprising the polyisocyanate blocking residue (A), the antifungal non-blocking blocking group (B), the non-antifungal non-blocking blocking group (C), and the hydrophilic group (E).

[0187] Such blocked isocyanates comprise a polyisocyanate blocking residue (A), a fungicide-resistant non-blocked blocking group (B), a non-fungicide-resistant non-blocked blocking group (C), and further comprise a hydrophilic group (E), and therefore have particularly excellent water dispersibility.

[0188] (11) The reaction raw material components of the antifungal block capping group-forming raw material (d) and the hydrophilic compound (e) can contain the antifungal block capping group-forming raw material (d) and the hydrophilic compound (e). In such a case, preferably, in the first reaction step, the hydrophilic compound (e) is blended together with the antifungal non-blocking capping agent (b) in the ratio described above. Also, preferably, in the second reaction step, the tertiary amino group-containing compound (d1) is blended together with the non-fungal block capping agent (c) in the ratio described above. Also, similarly to the above, the secondary reaction product is neutralized with an acid (d2).

[0189] This results in a blocked isocyanate (neutralization reaction product) comprising the polyisocyanate blocking residue (A), the antifungal non-blocked blocking group (B), the non-antifungal blocked blocking group (C), the antifungal blocked blocking group (D), and the hydrophilic group (E).

[0190] Such blocked isocyanates comprise a polyisocyanate blocking residue (A), an antifungal non-blocked blocking group (B), a non-antifungal blocked blocking group (C), and further comprise an antifungal blocked blocking group (D) and a hydrophilic group (E). As a result, such blocked isocyanates have particularly excellent antifungal properties, curability, and water dispersibility.

[0191] In the blocked isocyanate, the content of free isocyanate groups derived from the polyisocyanate (a) is substantially zero.

[0192] That is, all of the free isocyanate groups derived from the polyisocyanate (a) have reacted with either the antifungal unblocked blocking agent (b) or the non-antifungal blocked blocking agent (c) (and, if necessary, the antifungal blocked blocking group forming raw material (d) and the hydrophilic compound (e)).

[0193] More specifically, all of the free isocyanate groups derived from the polyisocyanate (a) are preferably reacted with either the antifungal non-blocking blocking agent (b) or the non-antifungal blocked blocking agent (c), respectively. As a result, all of the free isocyanate groups derived from the polyisocyanate (a) are blocked. The resulting blocked isocyanate comprises the blocking residue of the polyisocyanate (A), the antifungal non-blocking blocking group (B), and the non-antifungal blocked blocking group (C).

[0194] Furthermore, all of the free isocyanate groups derived from the polyisocyanate (a) are preferably reacted with either the antifungal unblocked capping agent (b), the non-antifungal blocked capping agent (c), or the antifungal blocked capping group-forming raw material (d). This results in all of the free isocyanate groups derived from the polyisocyanate (a) being blocked. The resulting blocked isocyanate comprises the blocking residue of the polyisocyanate (A), the antifungal unblocked capping group (B), the non-antifungal blocked capping group (C), and further comprises the antifungal blocked capping group (D).

[0195] Preferably, all of the free isocyanate groups derived from the polyisocyanate (a) are reacted with any one of the antifungal unblocked capping agent (b), the non-antifungal blocked capping agent (c), the antifungal blocked capping group-forming raw material (d), and the hydrophilic compound (e). This results in all of the free isocyanate groups derived from the polyisocyanate (a) being blocked. The resulting blocked isocyanate comprises the blocking residue (A) of the polyisocyanate, the antifungal unblocked capping group (B), and the non-antifungal blocked capping group (C), as well as the antifungal blocked capping group (D) and the hydrophilic group (E).

[0196] (12) Other Forms The order of reaction of the raw material components is not limited to the above. That is, the polyisocyanate (a), the antifungal non-blocking capping agent (b), and the non-antifungal non-blocking capping agent (c) can be reacted in any order. Furthermore, the antifungal blocked capping group forming raw material (d) and / or the hydrophilic compound (e) can be added and reacted at any timing.

[0197] Furthermore, each of the above reactions may be carried out without a solvent, or may be carried out in the presence of, for example, an organic solvent. Examples of organic solvents include ketones, nitriles, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, glycol ether esters, ethers, halogenated aliphatic hydrocarbons, and polar aprotic solvents. The organic solvents may be used alone or in combination of two or more.

[0198] For example, when the blocked isocyanate is not quaternized, that is, when the polyisocyanate (a), the antifungal non-blocking sealant (b) containing a quaternary ammonium group-containing compound, and the non-antifungal non-blocking sealant (c) are reacted, they are preferably reacted in the presence of an organic solvent. The organic solvent used is a hydrophilic solvent capable of dissolving the quaternary ammonium group-containing compound. Examples of the hydrophilic solvent include nitriles (e.g., acetonitrile and propionitrile) and polar aprotic solvents (e.g., acetone, N-methylpyrrolidone, dimethylformamide, N,N'-dimethylacetamide, dimethyl sulfoxide, and hexamethylphosphonylamide).

[0199] When an organic solvent is added in any of the above reactions, a solution of blocked isocyanate is obtained. In such cases, for example, water can be added to the blocked isocyanate solution and / or blocked isocyanate dispersion to emulsify the blocked isocyanate, and the resulting emulsion can be heated under reduced pressure to remove the organic solvent. This results in an aqueous dispersion of blocked isocyanate.

[0200] The solids concentration of the blocked isocyanate solution and / or aqueous dispersion is, for example, 1% by mass or more, preferably 10% by mass or more, and for example, 80% by mass or less, preferably 50% by mass or less.

[0201] 3. Antifungal Agent The antifungal agent may contain the above-described blocked isocyanate. For example, the antifungal agent may be a solid component composed of the blocked isocyanate. Alternatively, the antifungal agent may be a solution and / or aqueous dispersion of the blocked isocyanate.

[0202] Furthermore, the antifungal agent may contain additives. Examples of additives include solvents, catalysts, epoxy resins, coating property improvers, leveling agents, antifoaming agents, antioxidants, UV absorbers, thickeners, anti-settling agents, plasticizers, surfactants, pigments, fillers, organic fine particles, inorganic fine particles, and antiviral agents. The amount of additive to be added is determined appropriately depending on the purpose and application.

[0203] Furthermore, the antifungal agent may contain other isocyanate components in addition to the above-mentioned blocked isocyanate (blocked isocyanate having a blocking residue of polyisocyanate (A), an antifungal unblocked blocking group (B), and a non-antifungal blocked blocking group (C)). Examples of other isocyanate components include isocyanates that do not have the antifungal unblocked blocking group (B) and / or the non-antifungal blocked blocking group (C). The content ratio of the other isocyanate components is not particularly limited and may be appropriately set depending on the purpose and application.

[0204] The antifungal agent may be used in combination with a known antifungal agent. That is, the antifungal agent may be mixed with another antifungal agent. The mixing ratio is determined appropriately depending on the purpose and application.

[0205] 4. Effects The antifungal agent contains a blocked isocyanate. The blocked isocyanate comprises a blocking residue of polyisocyanate (A), an antifungal unblocked blocking group (B), and a non-antifungal blocked blocking group (C). The antifungal unblocked blocking group (B) contains a quaternary ammonium group. Therefore, the antifungal agent has excellent antifungal properties and can be fixed in a resin with a relatively high degree of freedom.

[0206] The antifungal agent exhibits antifungal properties against various known molds. Examples of molds include black mold (Aspergillus niger), blue mold (Penicillium citrinum), black mold (Aspergillus), and Chetomium globosum. Examples of molds include Cladosporium, Alternaria, Penicillium, Aureobasidium, Trichoderma, and Paecilomyces variotii.

[0207] 5. Resin (1) Hardener A method for immobilizing an antifungal agent to a resin (substance to be immobilized) will be described in detail below. When the antifungal agent is immobilized to a resin, the antifungal agent preferably also serves as a hardener.

[0208] The average functionality of the isocyanate groups (including free isocyanate groups and latent isocyanate groups) of the curing agent is, for example, 2 or more, preferably 2.5 or more. The average functionality of the isocyanate groups (including free isocyanate groups and latent isocyanate groups) of the curing agent is, for example, 4 or less, preferably 3.5 or less.

[0209] More specifically, in this method, a base resin capable of reacting with free isocyanate groups is mixed with an antifungal agent as a curing agent to obtain a resin composition. The resin composition is then heated to deblock the latent isocyanate groups of the antifungal agent without dissociating at least a portion of the tertiary ammonium salt, thereby obtaining free isocyanate groups. The free isocyanate groups are then reacted with the base resin. This allows for the production of a resin in which the antifungal agent is fixed in the molecule. Examples of resins include polyurethane resins, polyester resins, and acrylic resins, with polyurethane resins being preferred.

[0210] (2) Main Agent The main agent is a component capable of reacting with the free isocyanate group obtained by deblocking the latent isocyanate group to form a resin. For example, when the resin is a polyurethane resin, the main agent may be, for example, an active hydrogen group-containing compound. The active hydrogen group-containing compound is a compound containing one or more active hydrogen groups in the molecule. Examples of the active hydrogen group-containing compound include polyol compounds and polyamine compounds. A preferred example of the active hydrogen group-containing compound is a polyol compound.

[0211] Examples of the polyol compound include low molecular weight polyols and high molecular weight polyols.

[0212] The number average molecular weight of the low-molecular-weight polyol is, for example, less than 300, or preferably less than 400. The low-molecular-weight polyol has two or more hydroxyl groups.

[0213] Low molecular weight polyols include, for example, dihydric alcohols, trihydric alcohols, tetrahydric alcohols, pentahydric alcohols, hexahydric alcohols, heptahydric alcohols, and octahydric alcohols. Examples of dihydric alcohols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2,2-trimethylpentanediol, 3,3-dimethylolheptane, alkane (C7-20) diols, 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. Examples of trihydric alcohols include glycerin, trimethylolpropane, and triisopropanolamine. Examples of tetrahydric alcohols include tetramethylolmethane (pentaerythritol) and diglycerin. Examples of pentahydric alcohols include xylitol. Examples of hexahydric alcohols include sorbitol, mannitol, allitol, iditol, dulcitol, altritol, inositol, and dipentaerythritol. Examples of heptahydric alcohols include perseitol. Examples of octahydric alcohols include sucrose. Low molecular weight polyols can be used alone or in combination of two or more.

[0214] The number average molecular weight of the high molecular weight polyol is, for example, 300 or more, preferably 400 or more, or more preferably 500 or more. The high molecular weight polyol has two or more hydroxyl groups.

[0215] Examples of high molecular weight polyols include polyether polyols, polyester polyols, polycarbonate polyols, polyurethane polyols, epoxy polyols, vegetable oil polyols, polyolefin polyols, acrylic polyols, vinyl monomer modified polyols, and fluorine-containing polyols.

[0216] Examples of polyether polyols include polyoxyalkylene (C2-3) polyols and polytetramethylene ether polyols.

[0217] Examples of polyester polyols include adipic acid-based polyester polyols, phthalic acid-based polyester polyols, and lactone-based polyester polyols.

[0218] Examples of polycarbonate polyols include ring-opening polymers of ethylene carbonate using the above-mentioned low-molecular-weight polyols as initiators, and amorphous polycarbonate polyols obtained by copolymerizing the above-mentioned dihydric alcohols with the ring-opening polymers.

[0219] Examples of polyurethane polyols include polyester polyurethane polyols, polyether polyurethane polyols, polycarbonate polyurethane polyols, and polyester polyether polyurethane polyols.

[0220] The epoxy polyol may be, for example, an epoxy polyol obtained by reacting the above-mentioned low-molecular-weight polyol with a polyfunctional halohydrin.

[0221] Vegetable oil polyols include, for example, castor oil, coconut oil, and ester-modified castor oil polyols.

[0222] Examples of polyolefin polyols include polybutadiene polyols and partially saponified ethylene-vinyl acetate copolymers.

[0223] Examples of acrylic polyols include copolymers of hydroxyl group-containing acrylates and copolymerizable vinyl monomers copolymerizable with the hydroxyl group-containing acrylates.

[0224] The vinyl monomer-modified polyol can be obtained by reacting the above-mentioned high molecular weight polyol with a vinyl monomer.

[0225] Examples of the fluorine-containing polyol include acrylic polyols in which a fluorine compound is blended as a copolymerizable vinyl monomer in the copolymerization of the acrylic polyol described above.

[0226] The high molecular weight polyols can be used alone or in combination of two or more kinds.

[0227] The polyol compounds can be used alone or in combination of two or more kinds.

[0228] Of the polyol compounds, preferably, high molecular weight polyols are used, and more preferably, polyurethane polyols and acrylic polyols are used.

[0229] The base resin may contain additives. Examples of additives include reaction solvents, catalysts, epoxy resins, coating property improvers, leveling agents, antifoaming agents, antioxidants, UV absorbers, thickeners, anti-settling agents, plasticizers, surfactants, pigments, fillers, organic fine particles, inorganic fine particles, and antiviral agents. The amount of additives to be added is determined appropriately depending on the purpose and application.

[0230] (3) Resin Composition In producing the resin composition, the above-mentioned main component and an antifungal agent serving as a curing agent are blended. The blending ratio is appropriately set depending on the purpose and application. For example, the equivalent ratio of the latent isocyanate groups of the antifungal agent to the active hydrogen groups of the main component (active hydrogen group-containing compound) (latent isocyanate groups / active hydrogen groups) is, for example, 0.1 or more, preferably 0.5 or more, and more preferably 0.8 or more. Furthermore, the equivalent ratio of the latent isocyanate groups of the antifungal agent to the active hydrogen groups of the main component (active hydrogen group-containing compound) (latent isocyanate groups / active hydrogen groups) is, for example, 5 or less, preferably 3 or less, and more preferably 1.2 or less.

[0231] The resin composition is then applied to an object by a known coating method and dried to form a coating film, which is then heated and aged as necessary.

[0232] The heating temperature and heating time are set so as to dissociate the blocking agent from the latent isocyanate groups.

[0233] The heating temperature is, for example, 50° C. or more, preferably 80° C. or more. The heating temperature is, for example, 180° C. or less, preferably 150° C. or less. The heating time is, for example, 10 seconds or more, preferably 30 seconds or more. The heating time is, for example, 10 minutes or less, preferably 5 minutes or less.

[0234] This unblocks the latent isocyanate groups (non-antifungal blocked capping groups (C)) of the antifungal agent, regenerating free isocyanate groups. The free isocyanate groups of the antifungal agent then react with the base resin, resulting in a cured resin.

[0235] On the other hand, the quaternary ammonium group (antifungal-unblocked capping group (B)) remains in the antifungal agent. Also, when the antifungal agent contains a tertiary ammonium salt (antifungal-blocked capping group (D)), at least a portion of the tertiary ammonium salt remains in the antifungal agent.

[0236] Therefore, the quaternary ammonium group (and tertiary ammonium salt) in the antifungal agent is fixed to the resin by the above reaction, resulting in a resin (cured product) with excellent antifungal properties.

[0237] Furthermore, when an excess amount of antifungal agent is added, the excess agent is contained in the resin (cured product) without reacting with the base resin, resulting in particularly excellent antifungal properties.

[0238] Examples of uses of such resin compositions (uncured products) and resins (cured products) include fiber treatment agents, water repellents, coating compositions, adhesives, antistatic agents, papermaking treatment agents, wet paper strength agents, receiving layers for recording media, electrodeposition coating compositions, antifungal compositions, encapsulated compositions, optical components, and latex compositions. Among the uses of the resin compositions (uncured products) and resins (cured products), preferred are fiber treatment agents, water repellents, coating compositions, and adhesives, and more preferred are fiber treatment agents and water repellents.

[0239] In the above description, a resin (cured product) with excellent antifungal properties is formed by reacting the base agent with the antifungal agent as a curing agent. However, the base agent and the antifungal agent do not have to react. In this case, the antifungal agent is encapsulated in the dried base agent and / or the cured base agent. Therefore, a resin (cured product) with excellent antifungal properties is formed.

[0240] The antifungal agent can also be cured by itself. For example, the antifungal agent can be applied to or impregnated into a substrate, and the blocking agent can be dissociated from the latent isocyanate group, thereby causing the antifungal agent to self-crosslink and cure. Furthermore, for example, when the substrate has an active hydrogen group, the antifungal agent can be reacted with the substrate to fix the antifungal agent to the substrate.

[0241] The present invention will be described in more detail below with reference to examples, but is not limited thereto. Specific numerical values ​​such as blending ratios (content ratios), physical property values, and parameters used in the following description can be replaced with the upper limit values ​​(numeric values ​​defined as "not more than" or "less than") or lower limit values ​​(numeric values ​​defined as "not less than" or "exceeding") of the corresponding blending ratios (content ratios), physical property values, and parameters described in the above "Modes for Carrying Out the Invention." Note that "parts" and "%" are based on mass unless otherwise specified.

[0242] Example 1 At room temperature (25°C), a 500 mL reactor equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas inlet tube was charged with 50 parts by mass of an isocyanurate derivative of xylylene diisocyanate (XDI) (polyisocyanate compound, trade name: Takenate D-131N, solids content 75% by mass, isocyanate group content 13.7%, manufactured by Mitsui Chemicals, Inc.) and acetonitrile (solvent).

[0243] Next, choline chloride was added to the reactor in the amount shown in Table 1 per 100 moles of isocyanate groups of the isocyanurate derivative of XDI.

[0244] The content of the reactor was then heated to 75°C using a mantle heater to react the isocyanurate derivative of XDI with choline chloride. The isocyanate group concentration was measured to confirm that some of the isocyanate groups had been blocked with choline chloride.

[0245] Next, 3,5-dimethylpyrazole (DMP) was added to the reactor in the amount shown in Table 1 per 100 moles of isocyanate groups in the isocyanurate derivative of XDI.

[0246] Subsequently, the FT-IR spectrum of the reaction solution was measured, and it was confirmed that the remaining isocyanate groups had been blocked with DMP, forming blocked isocyanate groups. This resulted in a reaction solution containing blocked isocyanate. The blocked isocyanate had a quaternary ammonium group derived from choline chloride and had excellent water dispersibility.

[0247] Then, 150 parts by mass of water was added to 50 parts by mass of the reaction solution containing the blocked isocyanate. The reaction solution and water were then emulsified by stirring using a homomixer. Next, the solvent was distilled off from the emulsion under reduced pressure, and a portion of the water was also distilled off.

[0248] This resulted in an aqueous dispersion of blocked isocyanate as an antifungal agent. The solids concentration of the aqueous dispersion of blocked isocyanate was 20% by mass.

[0249] Examples 2 and 3 The formulation was changed to that shown in Table 1. Except for this, an aqueous dispersion of blocked isocyanate was obtained as an antifungal agent in the same manner as in Example 1.

[0250] Comparative Example 1 At room temperature (25°C), a 500 mL reactor equipped with a stirrer, a thermometer, a cooler, and a nitrogen gas inlet tube was charged with 50 parts by mass of an isocyanurate derivative of hexamethine diisocyanate (HDI) (polyisocyanate compound, trade name: Takenate (registered trademark) D-170N, solids content 100% by mass, isocyanate group content 20.7%, manufactured by Mitsui Chemicals, Inc.) and acetonitrile (solvent).

[0251] Next, 3,5-dimethylpyrazole (DMP) was added to the reactor in the amount shown in Table 1 per 100 moles of isocyanate groups in the isocyanurate derivative of HDI.

[0252] Next, 1,1,3,3-tetramethylguanidine (TMG) was added to the reactor in the amount shown in Table 1 per 100 moles of isocyanate groups in the isocyanurate derivative of HDI.

[0253] Thereafter, FT-IR spectroscopy confirmed that some of the isocyanate groups had been blocked with DMP to form blocked isocyanate groups, and that the remaining isocyanate groups had been blocked with TMG.

[0254] Next, acetic acid was added to the reaction solution and stirred. The mole ratio of acetic acid added per mole of TMG was shown in Table 1. As a result, the tertiary amino group derived from TMG was neutralized by the acetic acid to form a tertiary ammonium salt (ammonium acetate salt).

[0255] This resulted in a reaction liquid containing a blocked isocyanate. The blocked isocyanate had excellent water dispersibility due to the presence of a tertiary ammonium salt (ammonium acetate salt) formed by TMG and acetic acid.

[0256] Then, 150 parts by mass of water was added to 50 parts by mass of the reaction solution containing the blocked isocyanate. The reaction solution and water were then emulsified by stirring using a homomixer. Next, the solvent was distilled off from the emulsion under reduced pressure, and a portion of the water was also distilled off.

[0257] In this way, an aqueous dispersion of blocked isocyanate was prepared. The solid content concentration of the aqueous dispersion of blocked isocyanate was 20% by mass.

[0258] Comparative Example 2 The formulation was changed to that shown in Table 1. Except for this, an aqueous dispersion of blocked isocyanate was obtained in the same manner as in Example 1.

[0259] <Evaluation> <Antifungal Activity (MIC Test)> The antifungal effect of the antifungal agent was evaluated by the MIC (Minimum Inhibitory Concentration) test method. Details are shown below.

[0260] (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.

[0261] PDA medium was prepared by dissolving 39 g of "Difco Potato Dextrose Agar" (manufactured by Becton, Dickinson and Company) in 1000 mL of distilled water and adding 1 mL of chloramphenicol (special grade reagent, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) diluted to 50 mg / mL with ethanol.

[0262] PDB medium was prepared by dissolving 24 g of "Difco Potato Dextrose Broth" (manufactured by Becton, Dickinson and Company) in 1000 mL of distilled water and adding 1 mL of chloramphenicol (Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent) diluted to 50 mg / mL with ethanol.

[0263] The surfactant solution was prepared by dissolving 8.5 g of "sodium chloride" (special grade reagent, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 0.5 mL of "polyoxyethylene (20) sorbitan monooleate" (molecular biology grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) in 1000 mL of distilled water.

[0264] (2) Pre-culture The following fungal species were used in the MIC test (mold): The test fungal species were cultured at 25°C for 7 days or more using PDA medium that had been autoclaved at 121°C for 20 minutes.

[0265] Mold species: Cladosporium cladosporioides (NBRC 4459, Distributor: National Institute of Technology and Evaluation, Black mold)

[0266] (3) Sample (antifungal agent-containing medium) preparation: Each antifungal agent was added to PDB medium sterilized by autoclave at 121°C for 20 minutes. Then, 11 two-fold dilution series were prepared with the maximum active ingredient concentration at 4000 ppm. Thus, antifungal agent-containing medium was obtained.

[0267] The "maximum concentration of the active ingredient" in the MIC test method (mold) refers to the ratio (mass %) of the mass of the solid content of the antifungal agent in the antifungal agent-containing medium to the total mass of the antifungal agent-containing medium.

[0268] (4) Preparation of fungal solution: A test fungus species was suspended in a surfactant solution that had been autoclaved at 121°C for 20 minutes. The number of spores was measured using a hemocytometer. ５ / mL ~ 100 x 10 ５ / mL. Thus, a mold solution was obtained.

[0269] (5) MIC Measurement (Mold) 100 μL of mold solution was inoculated into 2 mL of each of the prepared dilution series of antifungal agent-containing media, and cultured for 7 days at 25° C. Thereafter, mold growth was confirmed visually, and the minimum dilution concentration at which mold did not grow was taken as the MIC value.

[0270] When no clumps of fungal hyphae were visually observed in the medium containing the antifungal agent, it was determined that no fungal growth had occurred. The measurement results are shown in Table 1.

[0271] The acceptable range for the MIC value in the MIC test (mold) is 3.9 ppm or more. An MIC value of 500 ppm or less was determined to have good antifungal properties.

[0272]

[0273] Details of the abbreviations in the table are as follows: 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 hexamethine 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 comprising a blocked isocyanate, the blocked isocyanate comprising: a blocking residue of a polyisocyanate (A); an antifungal unblocked blocking group (B); and a non-antifungal blocked blocking group (C); the blocking residue of the polyisocyanate (A) is obtained by blocking the isocyanate groups of a polyisocyanate having a plurality of isocyanate groups; the antifungal unblocked blocking group (B) is obtained by blocking at least a portion of the plurality of isocyanate groups in a non-reproducible manner; and the non-antifungal blocked blocking group (C) is obtained by blocking at least a portion of the plurality of isocyanate groups in a reproducible manner; and the antifungal unblocked blocking group (B) comprises a quaternary ammonium group.

2. The anti-fungal agent according to claim 1, wherein the blocked isocyanate is not quaternized.

3. The antifungal agent according to claim 1 or 2, wherein the blocked isocyanate is a reaction product of raw material components, the raw material components comprising: a polyisocyanate (a) having a plurality of isocyanate groups and for forming the blocking residue (A); an antifungal unblocked blocking agent (b) which reacts with at least a portion of the plurality of isocyanate groups to form the antifungal unblocked blocking group (B); and a non-antifungal blocked blocking agent (c) which reacts with at least a portion of the plurality of isocyanate groups to form the non-antifungal blocked blocking group (C), and the antifungal unblocked blocking agent (b) comprises a quaternary ammonium group-containing compound.

4. The antifungal agent according to claim 3, wherein the ratio of the antifungal non-blocking sealing agent (b) is 5 moles or more and 95 moles or less per 100 moles of isocyanate groups of the polyisocyanate (a).

5. The antifungal agent according to claim 3, wherein the quaternary ammonium group-containing compound comprises a trialkylalkanol ammonium compound.

6. The antifungal agent according to claim 1, wherein the polyisocyanate comprises an araliphatic polyisocyanate derivative.

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