JP5620831B2 - Curable aqueous resin composition, aqueous coating agent and aqueous adhesive - Google Patents

Description

  The present invention relates to a curable aqueous resin composition, an aqueous coating agent, and an aqueous adhesive.

  Conventionally, organic solvent-based adhesives and coating agents have been mainly used in the fields of various adhesives and various coating agents such as paints and printing inks. However, in recent years, water-based adhesives and water-based coating agents using water-based resins have been demanded for reasons such as air pollution problems and work environment improvements. For this reason, studies have been made on making a water-based curing agent such as a polyisocyanate compound.

  By the way, since an isocyanate group shows high reactivity with water, when a polyisocyanate compound is used in a solvent containing water, there is a problem that long-term storage is difficult and pot life (usable time) is short. As a method for improving the pot life of a polyisocyanate compound, a method of blocking an isocyanate group with a blocking agent is known. For example, Patent Document 1 below discloses a hydrophobic polyisocyanate compound in which an isocyanate group is blocked with a pyrazole group for the purpose of achieving both reactivity and pot life. Further, Patent Documents 2 to 5 below disclose water-dispersible block polyisocyanate compounds into which hydrophilic groups have been introduced.

European Patent Application Publication No. 0159117A1 JP-A-51-77695 JP-A-55-82119 Japanese Patent Laid-Open No. 61-31422 Japanese National Patent Publication No. 11-512772

  Hydrophobic block polyisocyanate compounds have a problem that they are very difficult to emulsify and disperse and are difficult to apply to aqueous adhesives and aqueous coating agents. On the other hand, water-dispersible blocked polyisocyanate compounds with hydrophilic groups introduced can easily make the curing agent water-based, but the water resistance and adhesion of cured films formed compared to hydrophobic blocked polyisocyanate compounds Is inferior.

  The present invention has been made in view of the above circumstances, and has a sufficient storage stability, a curable aqueous resin composition capable of forming a cured film excellent in water resistance and adhesiveness, and the An object is to provide an aqueous coating agent and an aqueous adhesive used.

  As a result of intensive studies to solve the above problems, the present inventors have shown that an aqueous dispersion of a specific pyrazole block hydrophobic polyisocyanate obtained by using a specific surfactant exhibits stable emulsification and dispersion. By using an aqueous dispersion and an aqueous resin in combination, it has been found that a curable aqueous resin composition capable of forming a cured film having a long pot life and excellent water resistance and adhesiveness can be obtained. Completed the invention.

（式（ＩＩ）中、ｎは０〜３の整数を示し、ｎが１以上の場合、Ｒ^１は同一であっても異なっていてもよく、炭素数１〜６のアルキル基、炭素数２〜６のアルケニル基、炭素数７〜１２のアラルキル基、Ｎ−置換カルバミル基、フェニル基、−ＮＯ_２、ハロゲン原子又は−Ｃ（Ｏ）−Ｏ−Ｒ^２（式中Ｒ^２は水素原子又は炭素数１〜６のアルキル基である）を示す。）］ The present invention comprises a pyrazole block hydrophobic polyisocyanate aqueous dispersion containing a pyrazole block hydrophobic polyisocyanate represented by the following general formula (I) and a nonionic surfactant, and an aqueous resin. A curable aqueous resin composition is provided.
R (—NH—CO—Z) _m (I)
[In Formula (I), m represents an integer of 2 or more, R represents a residue obtained by removing m isocyanate groups from a polyisocyanate compound having m isocyanate groups, and Z may be the same or different. Often, it represents a residue obtained by removing a hydrogen atom from an active hydrogen-containing compound capable of reacting with an isocyanate group, and at least two of Z are pyrazole groups represented by the following general formula (II).

(In the formula (II), n represents an integer of 0 to 3, and when n is 1 or more, R ¹ may be the same or different, and is an alkyl group having 1 to 6 carbon atoms or 2 carbon atoms. -6 alkenyl group, C 7-12 aralkyl group, N-substituted carbamyl group, phenyl group, -NO ₂ , halogen atom or -C (O) -O-R ² (wherein R ² is a hydrogen atom or Which is an alkyl group having 1 to 6 carbon atoms.)]

  According to the curable aqueous resin composition of the present invention, a cured film having sufficient storage stability and excellent water resistance and adhesiveness can be formed by having the above configuration. According to the curable aqueous resin composition of the present invention, an aqueous coating agent having a sufficient pot life (usable time) can be realized, and a coating film excellent in water resistance and adhesiveness on various substrates. Can be formed. In addition, according to the curable aqueous resin composition of the present invention, an aqueous adhesive having a sufficient pot life (usable time) can be realized, and various kinds of coatings can be obtained even under an environment affected by moisture. The bonded body can be bonded with sufficient adhesive force.

  The liquid medium of the above-mentioned pyrazole block hydrophobic polyisocyanate aqueous dispersion is water or water, and when mixed with water, the liquid medium is divided into ketones, esters, ethers, aromatic hydrocarbons and aliphatic carbonization. A mixture containing at least one organic solvent selected from the group consisting of hydrogens is preferred.

  In addition, from the viewpoint of storage stability, the liquid medium of the aqueous pyrazole block hydrophobic polyisocyanate dispersion is preferably a mixture containing water and ethers.

  Furthermore, from the viewpoint of storage stability, the nonionic surfactant is preferably a nonionic surfactant having an HLB of 10 or more.

  Further, from the viewpoint of further improving the water resistance and adhesiveness of the cured film, it is preferable that all of Z in the general formula (I) are pyrazole groups represented by the general formula (II).

  The curable aqueous resin composition of the present invention can be a two-component type of the first composition containing the aqueous pyrazole block hydrophobic polyisocyanate dispersion and the second composition containing the aqueous resin. . In this case, the pot life can be further extended.

  The present invention also provides an aqueous coating agent comprising the curable aqueous resin composition of the present invention. According to the aqueous coating agent of the present invention, a coating film having a sufficient pot life and excellent in water resistance and adhesiveness can be formed on various substrates.

  The present invention also provides an aqueous adhesive comprising the curable aqueous resin composition of the present invention. According to the water-based adhesive of the present invention, various adherends can be bonded with a sufficient adhesive force even in an environment having a sufficient pot life and affected by moisture.

  According to the present invention, a curable aqueous resin composition having sufficient storage stability and capable of forming a cured film excellent in water resistance and adhesiveness, and an aqueous coating agent and an aqueous adhesive using the same Can be provided.

The curable aqueous resin composition of the present invention includes an aqueous dispersion of a pyrazole block hydrophobic polyisocyanate containing a pyrazole block hydrophobic polyisocyanate represented by the following general formula (I) and a nonionic surfactant, and an aqueous resin: It is characterized by including.
R (—NH—CO—Z) _m (I)
[In Formula (I), m represents an integer of 2 or more, R represents a residue obtained by removing m isocyanate groups from a polyisocyanate compound having m isocyanate groups, and Z may be the same or different. Often, it represents a residue obtained by removing a hydrogen atom from an active hydrogen-containing compound capable of reacting with an isocyanate group, and at least two of Z are pyrazole groups represented by the following general formula (II).

（式（ＩＩ）中、ｎは０〜３の整数を示し、ｎが１以上の場合、Ｒ^１は同一であっても異なっていてもよく、炭素数１〜６のアルキル基、炭素数２〜６のアルケニル基、炭素数７〜１２のアラルキル基、Ｎ−置換カルバミル基、フェニル基、−ＮＯ_２、ハロゲン原子又は−Ｃ（Ｏ）−Ｏ−Ｒ^２（式中Ｒ^２は水素原子又は炭素数１〜６のアルキル基である）を示す。）］

(In the formula (II), n represents an integer of 0 to 3, and when n is 1 or more, R ¹ may be the same or different, and is an alkyl group having 1 to 6 carbon atoms or 2 carbon atoms. -6 alkenyl group, C 7-12 aralkyl group, N-substituted carbamyl group, phenyl group, -NO ₂ , halogen atom or -C (O) -O-R ² (wherein R ² is a hydrogen atom or Which is an alkyl group having 1 to 6 carbon atoms.)]

  The pyrazole block hydrophobic polyisocyanate represented by the general formula (I) can be obtained by reacting a polyisocyanate compound having m isocyanate groups with an active hydrogen-containing compound capable of reacting with the isocyanate group. . In this case, a block is formed using a pyrazole compound represented by the following general formula (III) so that at least two of Z in the above general formula (I) are pyrazole groups represented by the above general formula (II). can do.

式（ＩＩＩ）中、ｎは０〜３の整数を示し、ｎが１以上の場合、Ｒ^１は同一であっても異なっていてもよく、炭素数１〜６のアルキル基、炭素数２〜６のアルケニル基、炭素数７〜１２のアラルキル基、Ｎ−置換カルバミル基、フェニル基、−ＮＯ_２、ハロゲン原子又は−Ｃ（Ｏ）−Ｏ−Ｒ^２（式中Ｒ^２は水素原子又は炭素数１〜６のアルキル基である）を示す。

In the formula (III), n represents an integer of 0 to 3, and when n is 1 or more, R ¹ may be the same or different, an alkyl group having 1 to 6 carbon atoms, 6 alkenyl group, aralkyl group having 7 to 12 carbon atoms, N-substituted carbamyl group, phenyl group, —NO ₂ , halogen atom or —C (O) —O—R ² (wherein R ² is a hydrogen atom or carbon atom) It is an alkyl group of the number 1-6.

Here, examples of the alkyl group having 1 to 6 carbon atoms represented by R ¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, and n. -A hexyl group etc. can be mentioned. Examples of the alkenyl group having 2 to 6 carbon atoms include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group. Examples of the aralkyl group having 7 to 12 carbon atoms include benzyl group, ethylphenyl group, propylphenyl group, butylphenyl group, methylnaphthyl group, and ethylnaphthyl group. In the present invention, n is preferably 1 or more from the viewpoint of easy availability of the pyrazole compound. From the same viewpoint, R ¹ is an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an aralkyl group having 7 to 9 carbon atoms, a phenyl group, —NO 2, a bromo group, —C (O ) -O-R ³ (R ³ is an alkyl group having 1 to 4 carbon atoms) is preferred.

  In the present invention, the pyrazole block hydrophobicity obtained by reacting the pyrazole compound represented by the general formula (III) with a ratio of 2 moles or more with respect to 1 mole of the polyisocyanate compound having m isocyanate groups. It is preferable to use a polyisocyanate. When m is 3 or more, it is preferable to use a pyrazole block hydrophobic polyisocyanate obtained by reacting at a ratio of (0.8 × m) mol or more.

  As the polyisocyanate compound having m isocyanate groups, known polyisocyanate compounds can be used. Examples thereof include diisocyanate compounds such as alkylene (preferably having 1 to 12 carbon atoms) diisocyanate, aryl diisocyanate and cycloalkyl diisocyanate, and modified polyisocyanate compounds such as dimers or trimers of these diisocyanate compounds.

  Specific examples of the diisocyanate compound include 2,4- or 2,6-tolylene diisocyanate, ethylene diisocyanate and mixtures thereof, propylene diisocyanate, 4,4-diphenylmethane diisocyanate, p-phenylene diisocyanate, tetramethylene diisocyanate, hexa Methylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene-1,6-diisocyanate, phenylene diisocyanate, tolylene or naphthylene diisocyanate, 4,4'-methylene-bis (phenylisocyanate), 2 , 4′-methylene-bis (phenylisocyanate), 3,4′-methylene-bis (phenylisocyanate), 4,4 Ethylene-bis (phenylisocyanate), ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylcyclohexane, ω, ω′-diisocyanate-1,4-dimethylbenzene , Ω, ω′-diisocyanate-1,3-dimethylcyclohexane, 1-methyl-2,4-diisocyanate cyclohexane, 4,4′-methylene-bis (cyclohexyl isocyanate), 3-isocyanate-methyl-3,5,5 -Trimethylcyclohexyl isocyanate, acid-diisocyanate dimer, ω, ω'-diisocyanate diethylbenzene, ω, ω'-diisocyanate dimethyltoluene, ω, ω'-diisocyanate diethyltoluene, fumaric acid bis (2-isocyanatoethyl) ester, 1 4- bis (2-isocyanate - prop-2-yl) include benzene and 1,3-bis (2-isocyanate Pro 2-yl) benzene. Examples of the triisocyanate compound include triphenylmethane triisocyanate, dimethyltriphenylmethane tetraisocyanate, and tris (isocyanatophenyl) -thiophosphate.

  The modified polyisocyanate compound derived from the diisocyanate compound is not particularly limited as long as it has two or more isocyanate groups. For example, biuret structure, isocyanurate structure, urethane structure, uretdione structure, allophanate structure, Examples thereof include polyisocyanates having a trimer structure and the like, and adducts of trimethylolpropane aliphatic isocyanate. Polymeric MDI (MDI = diphenylmethane diisocyanate) can also be used as the polyisocyanate compound.

  A polyisocyanate compound can be used individually by 1 type or in combination of 2 or more types.

  From the viewpoints of water resistance and adhesiveness of the resulting cured film, alkylene (preferably having 1 to 12 carbon atoms) diisocyanates and modified polyisocyanate compounds derived therefrom are preferred, and particularly preferred polyisocyanate compounds are 1,6-hexa Biuret, uretdione or isocyanurates of methylene diisocyanate (HDI). A commercial item can be used for the polyisocyanate compound. Examples of commercially available polyisocyanate compounds include Duranate THA-100 (manufactured by Asahi Kasei Chemicals) (solid content 100%), Duranate 24A-100 (manufactured by Asahi Kasei Chemicals) (solid content 100%), and the like.

  Examples of the pyrazole compound represented by the general formula (III) used to block at least two of the isocyanate groups of the polyisocyanate compound having m isocyanate groups include 3,5-dimethylpyrazole, Examples include 3-methylpyrazole, 3,5-dimethyl-4-nitropyrazole, 3,5-dimethyl-4-bromopyrazole, and pyrazole.

  These pyrazole compounds may be used alone or in combination of two or more. Among these, 3,5-dimethylpyrazole and 3-methylpyrazole are preferable from the viewpoint of water resistance and adhesiveness of the obtained cured film.

  The pyrazole block hydrophobic polyisocyanate represented by the above general formula (I) and m is 2 can be obtained by blocking all isocyanate groups with the pyrazole compound represented by the above general formula (III). In addition, the pyrazole block hydrophobic polyisocyanate represented by the above general formula (I), wherein m is an integer of 3 or more, represents at least two isocyanate groups of a polyisocyanate compound having 3 or more isocyanate groups. It can be obtained by blocking with a pyrazole compound represented by III). In this case, from the viewpoint of water resistance and adhesiveness of the resulting cured film, it is preferable that all isocyanate groups are blocked with a pyrazole compound, but the remaining isocyanate groups are blocked with a blocking agent other than the pyrazole compound. Also good.

  Examples of blocking agents other than pyrazole compounds include alcohols such as methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, tert-butyl alcohol; phenol, methylphenol, chloro Phenols such as phenol, p-iso-butylphenol, p-tert-butylphenol, p-iso-amylphenol, p-octylphenol, p-nonylphenol; malonic acid dimethyl ester, malonic acid diethyl ester, acetylacetone, methyl acetoacetate, aceto Active methylene compounds such as ethyl acetate; formaldoxime, acetoaldoxime, acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime, acetate Oximes such as phenone oxime and benzophenone oxime; lactams such as ε-caprolactam, δ-valerolactam, and γ-butyrolactam; N-substituted amides such as N-methylacetamide and acetanilide; imide compounds such as succinimide and phthalimide And imidazole compounds such as imidazole and 2-methylimidazole. You may use these individually by 1 type or in combination of 2 or more types. As the blocking agent other than the pyrazole compound, methyl ethyl ketone oxime is preferable from the viewpoint of easy blocking.

The pyrazole block hydrophobic polyisocyanate according to the present invention is preferably hydrophobic, but for the purpose of improving water dispersibility, a nonionic hydrophilic group having an ethylene oxide group, a carboxylate group (COO ⁻ ), and a sulfonate. An anionic hydrophilic group having a group (SO ₃ ⁻ ) or a phosphonate group (PO ₃ ⁻ ) may be included. Here, that the pyrazole block hydrophobic polyisocyanate is hydrophobic means that it does not self-emulsify in water. The state of self-emulsification in water means that 200 ml of an 18% by weight aqueous dispersion of blocked isocyanate is added to T.W. K. In HOMODISPER (manufactured by Primix Co., Ltd.), when treated at 2000 rpm × 10 minutes at room temperature, a uniform aqueous dispersion is obtained. When the aqueous dispersion is sealed in a glass container and allowed to stand at 45 ° C., It means a state where the mixture is uniformly emulsified and dispersed without separation or sedimentation for 12 hours or more.

  When the pyrazole block hydrophobic polyisocyanate according to the present invention contains a nonionic hydrophilic group having an ethylene oxide group, from the viewpoint of reducing the influence on the water resistance and adhesiveness of the resulting cured film, the ethylene oxide group The content is preferably 3% by mass or less, and most preferably not contained at all. Moreover, when the pyrazole block hydrophobic polyisocyanate according to the present invention contains an anionic hydrophilic group having a carboxylate group, a sulfonate group or a phosphonate group, the influence on the water resistance and adhesiveness of the resulting cured film is reduced. In view of the above, the content ratio of the carboxylate group, the sulfonate group or the phosphonate group is preferably 1% by mass or less, and most preferably not contained at all.

  The nonionic hydrophilic group having an ethyleneoxy group is derived by reacting a nonionic hydrophilic compound with a polyisocyanate compound.

  Nonionic hydrophilic compounds include, for example, (poly) ethylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol; block polymers and random copolymers of polyethylene glycol, polypropylene glycol, and polytetramethylene glycol , Polyoxy (2 to 4 carbon atoms) alkylene glycols such as random copolymers and block copolymers of ethylene oxide and propylene oxide, ethylene oxide and butylene oxide; polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, polyethylene glycol Monobutyl ether, polyethylene glycol polypropylene glycol monomethyl ether, polypropylene glycol Polyoxy (2 to 4 carbon atoms) polyoxy (2 to 4 carbon atoms) polyoxy (2 to 4 carbon atoms) polyoxy (2 to 4 carbon atoms) alkylene glycols having one end blocked with an alkoxy group having 2 to 4 carbon atoms (2 to 2 carbon atoms) 4) Alkyl ethers; polyoxy (2 to 3 carbon atoms) alkylene monoamines such as JEFFAMINE (M series) (manufactured by HUNTSMAN); polyoxys (carbon number) such as JEFFAMINE (D series, ED series, EDR series) (manufactured by HUNTSMAN) 2-3) alkylenediamines; and the like. The ethylene oxide group may be contained continuously or not continuously in the pyrazole block hydrophobic polyisocyanate.

  An anionic hydrophilic group having a carboxylate group, a sulfonate group or a phosphonate group is derived by reacting a polyisocyanate compound with an anionic hydrophilic compound. The anionic hydrophilic compound may be neutralized either before or after the reaction with the polyisocyanate compound or during the reaction.

  Examples of the anionic hydrophilic compound include acids such as aliphatic hydroxycarboxylic acids, aliphatic or aromatic aminocarboxylic acids, aliphatic hydroxysulfonic acids, aliphatic or aromatic aminosulfonic acids, aliphatic or aromatic aminophosphones, and the like. Examples include acids.

  Examples of the aliphatic hydroxycarboxylic acids include hydroxycarboxylic acids such as hydroxyacetic acid, 3-hydroxypropionic acid, 6-hydroxycaproic acid, 8-hydroxycaprylic acid, 10-hydroxydecanoic acid, glyceric acid, mevalonic acid, and pantoic acid. Dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolacetic acid, dimethylolvaleric acid, dimethylolcaproic acid and the like.

  Examples of the aliphatic or aromatic aminocarboxylic acids include glycine, N-methylglycine, 2-aminopropanoic acid, 3-aminopropanoic acid, 4-aminobutyric acid, 6-aminocaproic acid, 8-aminocaprylic acid, ornithine, Examples include lysine and 4-aminobenzoic acid.

  Examples of the aliphatic hydroxysulfonic acids include 2-hydroxyethanesulfonic acid and 4-hydroxybutanesulfonic acid.

  Examples of the aliphatic or aromatic aminosulfonic acids include taurine, N-methyltaurine, N-butyltaurine, sulfanilic acid, 2- (2-aminoethylamino) -ethanesulfonic acid, and 2,4-diaminosulfonic acid. Is mentioned.

  Examples of the aliphatic or aromatic aminophosphonic acids include aminomethylphosphonic acid, aminoethylphosphonic acid, aminopropylphosphonic acid, aminophenylphosphonic acid, and the like.

  The anionic hydrophilic compound preferably has a molecular weight of 500 or less. The compound used for neutralization of the anionic hydrophilic compound is not particularly limited, and examples thereof include amines such as trimethylamine, triethylamine, tri-n-propylamine, tributylamine, triethanolamine, potassium hydroxide, hydroxide Sodium, potassium carbonate, sodium carbonate, ammonia and the like can be used.

  Said nonionic hydrophilic compound and anionic hydrophilic compound can be used individually by 1 type or in combination of 2 or more types.

  Isocyanate groups other than those blocked with the pyrazole compound represented by the general formula (III) may be reacted with a known low molecular weight chain extender which is a low molecular weight compound having two or more active hydrogens.

  Examples of the low molecular weight chain extender having two or more active hydrogen atoms include ethylene glycol, propylene glycol (1,2-propanediol), 1,3-propanediol, 1,2-butanediol, 1,3 -Butylene glycol (1,3-butanediol), 1,4-butanediol, 2,3-butanediol, neopentyl glycol, 2,4,4-trimethyl-1,3-pentanediol, 1,6-hexane Low molecular weight polyhydric alcohols such as diol, cyclohexanediethanol, hydrogenated bisphenol A, trimethylolethane, trimethylolpropane, 1,2,6-hexanetriol, glycerin, pentaerythritol, sorbitol; ethylenediamine, propylenediamine, hexamethylenediamine, Diaminosic Hexyl methane, piperazine, 2-methylpiperazine, isophorone diamine, diethylenetriamine, triethylenetetramine, be mentioned low molecular weight polyamines such as hydrazine. Compounds having different functional groups such as N-methylethanolamine and N-methylisopropanolamine can also be used. Such a low molecular weight chain extender having two or more active hydrogen atoms preferably has a molecular weight of 400 or less, more preferably 300 or less.

  Said low molecular weight chain extender can be used individually by 1 type or in combination of 2 or more types.

  When using a low molecular weight chain extender, it is preferable that the content rate of the group introduce | transduced by a low molecular weight chain extender is 5 mass% or less of a pyrazole block hydrophobic polyisocyanate. When this ratio exceeds 5 mass%, the dispersion state of the pyrazole block hydrophobic polyisocyanate aqueous dispersion tends to deteriorate. In the case where the low molecular weight chain extender contains an ethylene oxide group, the content of the ethylene oxide group in the pyrazole block hydrophobic polyisocyanate is preferably 3% by mass or less, but most preferably not contained at all.

  The pyrazole block hydrophobic polyisocyanate represented by the above general formula (I) includes, for example, the above polyisocyanate compound, the pyrazole compound represented by the above general formula (III) as an active hydrogen-containing compound, and as necessary. The other blocking agent and the low molecular weight chain extender are reacted at a predetermined ratio at 20 to 150 ° C. for several minutes to several days.

  The reaction between the polyisocyanate compound and the active hydrogen-containing compound can be carried out by a conventionally known one-shot method (one-stage method) or multi-stage method. In this case, various known catalysts that promote the reaction can be used. Examples of such catalysts include organic tin compounds, organic zinc compounds, and organic amine compounds.

  Further, an organic solvent that does not react with an isocyanate group may be added at any stage of the reaction.

  It is preferable that the pyrazole block hydrophobic polyisocyanate according to the present invention does not contain a free isocyanate group.

  The pyrazole block hydrophobic polyisocyanate aqueous dispersion according to the present invention may contain one or more pyrazole block hydrophobic polyisocyanates represented by the above general formula (I).

  The aqueous pyrazole block hydrophobic polyisocyanate dispersion according to the present invention emulsifies and disperses the pyrazole block hydrophobic polyisocyanate represented by the above formula (I) in a liquid medium containing water with a nonionic surfactant. Can be obtained.

  Examples of the nonionic surfactant include alcohols, phenols, amines, amides, fatty acids, polyhydric alcohol fatty acid esters, fats and oils, and alkylene oxide adducts of polypropylene glycol.

  Examples of alcohols include linear or branched alcohols having 8 to 24 carbon atoms or alkenols, such as octanol, decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, oleyl. Examples include alcohol, linoleyl alcohol, erucyl alcohol, elaidyl alcohol, and palmitoleyl alcohol.

  Examples of phenols include phenol, cresol, butylphenol, octylphenol, nonylphenol, dodecylphenol, catechol, resorcinol, hydroquinone, pyrogallol (1,2,3-trihydroxybenzene), 1,2,4-trihydroxybenzene, and fluoro. Monocyclic phenols such as loglucinol (1,3,5-trihydroxybenzene), tetrahydroxybenzene; 2-cumylphenol, 3-cumylphenol, 4-cumylphenol, 2-phenylphenol, 3-phenyl Polycyclic phenols such as phenol, 4-phenylphenol, 1-naphthol, 2-naphthol, bisphenol A, bisphenol F, bisphenol S; or styrenes thereof (styrene, α-methylstyrene) Include polycyclic phenols such as vinyl toluene) adduct or benzyl chloride reactant.

  Examples of amines include linear or branched aliphatic amines having 8 to 44 carbon atoms, such as octylamine, 2-ethylhexylamine, cocoalkylamine, decylamine, laurylamine, myristylamine, cetylamine, stearyl. Examples thereof include amine, isostearylamine, behenylamine, oleylamine, linoleylamine, erucylamine, elaidylamine, palmitoleylamine, disacylalkylamine, and distearylamine.

  Examples of amides include linear or branched fatty acid amides having 8 to 44 carbon atoms such as caprylic acid amide, caproic acid amide, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, Examples include behenic acid amide, oleic acid amide, and isostearic acid amide.

  Examples of fatty acids include linear or branched fatty acids having 8 to 24 carbon atoms such as caprylic acid, caproic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, isostearic acid. An acid etc. are mentioned.

  Examples of the polyhydric alcohol fatty acid esters include a condensation reaction product of a polyhydric alcohol and a linear or branched fatty acid having 8 to 24 carbon atoms.

  Examples of the polyhydric alcohol include glycerin, pentaerythritol, sorbit, sorbitan, monoethanolamine, diethanolamine, and sugar.

  As fats and oils, vegetable oils such as soybean oil, sunflower oil, cottonseed oil, rapeseed oil, olive oil, castor oil, coconut oil, tall oil; animal fats such as beef fat, pork fat, shark liver oil, sperm whale oil; carnauba wax, Plant waxes such as candelilla wax; animal waxes such as beeswax and lanolin; mineral waxes such as montan wax; hardened oils such as beef tallow hardened oil and castor hardened oil.

  Among the above compounds, polycyclic phenols are preferable from the viewpoint of the dispersibility and stability of the aqueous dispersion, and (3 to 8 mol) of phenol, 4-cumylphenol, 4-phenylphenol, or 2-naphthol. A styrene adduct, (3-8 mol) α-methylstyrene adduct, or (3-8 mol) benzyl chloride reactant is more preferred.

  The styrene adduct can be obtained, for example, by reacting phenols with styrene at 120 to 150 ° C. for 1 to 10 hours. The molar ratio of phenols to styrenes is 1: 1 to 10, preferably 1: 3 to 8.

  Examples of the non-ionic surfactant alkylene oxide include ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,4-butylene oxide, styrene oxide, epichlorohydrin, and the like. Is mentioned. From the viewpoint of the dispersibility and stability of the aqueous dispersion, the alkylene oxide is preferably ethylene oxide or 1,2-propylene oxide, and more preferably ethylene oxide.

  Examples of the alkylene oxide addition method include a method of adding ethylene oxide alone, a method of adding propylene oxide after addition of ethylene oxide, a block addition method such as a method of adding ethylene oxide after addition of propylene oxide, and the like. Examples thereof include a random addition method for adding a mixture. Preferably, ethylene oxide is added alone.

  Nonionic surfactants include, for example, 3 to 200 mol of ethylene oxide in 1 mol of the above alcohols, phenols, amines, amides, fatty acids, polyhydric alcohol fatty acid esters, fats and oils, and polypropylene glycol. Can be obtained at 130-170 ° C.

  The number of moles of alkylene oxide added is preferably 3 to 200, more preferably 10 to 100, and still more preferably 10 to 50. If the number of moles of alkylene oxide added is less than 3 moles, the emulsion stability of the pyrazole block hydrophobic isocyanate aqueous dispersion tends to deteriorate, and if it exceeds 200 moles, the water resistance and adhesion of the resulting cured film will deteriorate. There is a tendency.

  From the viewpoint of obtaining a better aqueous dispersion, the nonionic surfactant preferably has an HLB of 10 or more. In this case, one kind of nonionic surfactant having an HLB of 10 or more may be used, and two or more kinds of activators may be combined to provide an HLB of 10 or more. The HLB of the nonionic surfactant is more preferably 13 or more, and even more preferably 15 or more. Here, HLB refers to Griffin HLB, and the hydrophilic group refers to an ethylene oxide group.

  One or more nonionic surfactants can be contained in the aqueous pyrazole block hydrophobic polyisocyanate dispersion according to the present invention.

  In the present invention, an anionic surfactant or a cationic surfactant can be used in combination for the purpose of improving the stability of the aqueous pyrazole block hydrophobic polyisocyanate dispersion.

  The anionic surfactant that can be used in combination is not particularly limited, and is a linear or branched C8-24 alcohol or alkenol anionized product, a linear or branched C8-24 alcohol or alkenol. Anionized products of alkylene oxide adducts, anionized products of alkylene oxide adducts of polycyclic phenols, anionized products of alkylene oxide adducts of linear or branched aliphatic amines having 8 to 44 carbon atoms, linear or branched An anionized product of an alkylene oxide adduct of a fatty acid amide having 8 to 44 carbon atoms in the chain, an anionized product of an alkylene oxide adduct of a linear or branched fatty acid having 8 to 24 carbon atoms, and the like. These anionic surfactants can be used alone or in combination of two or more.

  There is no restriction | limiting in particular as a cationic surfactant which can be used together, C8-C24 monoalkyltrimethylammonium salt, C8-C24 dialkyldimethylammonium salt, C8-C24 monoalkylamine acetate C8-24 dialkylamine acetate, C8-24 alkyl imidazoline quaternary salt, and the like. These cationic surfactants can be used alone or in combination of two or more.

  The blending ratio (mass basis) of the nonionic surfactant (A) and the anionic surfactant (B) is in the range of (A) :( B) = 50: 50 to 100: 0, preferably 90:10. ~ 100: 0. When the amount of the anionic surfactant exceeds 50 parts by mass with respect to 50 parts by mass of the nonionic surfactant, the water resistance and adhesiveness of the cured film tend to be lowered.

  The blending ratio (mass basis) of the nonionic surfactant (A) and the cationic surfactant (C) is in the range of (A) :( C) = 50: 50 to 100: 0, preferably 90:10. ~ 100: 0. When the compounding quantity of a cationic surfactant exceeds 50 mass parts with respect to 50 mass parts of nonionic surfactant, it exists in the tendency for the water resistance of a cured film and adhesiveness to fall.

  The blending ratio (mass basis) of the pyrazole block hydrophobic polyisocyanate and the nonionic surfactant according to the present invention is preferably in the range of 100: 50 to 100: 1, and more preferably in the range of 100: 20 to 100: 1. . When the compounding amount of the nonionic surfactant exceeds 50 parts by mass with respect to 100 parts by mass of the pyrazole block hydrophobic polyisocyanate, the water resistance and adhesiveness of the cured film tend to decrease, and the amount is less than 1 part by mass. , The stability of the pyrazole block hydrophobic polyisocyanate aqueous dispersion tends to decrease, and the stability of the curable aqueous resin composition tends to decrease when the two-pack type is used.

Examples of the liquid medium other than water include at least one organic solvent selected from the group of ketones, esters, ethers, aromatic hydrocarbons, and aliphatic hydrocarbons, which are separated when mixed with water. It is done. Those having low solubility in water and low density are preferable, for example, those having a density of 1.00 g / cm ³ (20 ° C.) or less and a solubility in water of 35 g / 100 ml (20 ° C.) or less. preferable.

  Examples of such organic solvents include ketones such as methyl isobutyl ketone (density 0.801 g / cm 3 (20 ° C.), solubility 1.91 g / 100 ml (20 ° C.)); ethyl acetate (density 0.897 g / cm 3, solubility 8 .3 g / 100 ml (20 ° C.), butyl acetate (density 0.88 g / cm 3, solubility 0.83 g / 100 ml (20 ° C.)), butyl glycol acetate (density 0.94 g / cm 3, solubility 1.1 g / 100 ml ( Esters such as 20 ° C.); ethyl ether (density 0.713 g / cm 3, solubility 6.9 g / 100 ml (20 ° C.)), dibutyl diglycol (diethylene glycol dibutyl ether) (density 0.884 g / cm 3, solubility 0. 3 g / 100 ml (20 ° C.)), diethylene glycol mono-2-ethylhexyl ether (Density 0.923 g / cm 3, solubility 0.3 g / 100 ml (20 ° C.)), ethylene glycol monohexyl ether (density 0.889 g / cm 3, solubility 0.99 g / 100 ml (20 ° C.)), diethylene glycol monohexyl ether ( Density 0.935 g / cm 3, solubility 1.7 g / 100 ml (20 ° C.), ethylene glycol mono-2-ethylhexyl ether (density 0.883 g / cm 3, solubility 0.2 g / 100 ml (20 ° C.)), dipropylene glycol Monopropyl ether (density 0.923 g / cm 3, solubility 4.8 g / 100 ml (20 ° C.)), propylene glycol monobutyl ether (density 0.880 g / cm 3, solubility 6.4 g / 100 ml (20 ° C.)), dipropylene glycol Monobutyl ether (density Ethers such as 917 g / cm 3 and solubility 3.0 g / 100 ml (20 ° C.); toluene (density 0.867 g / cm 3, solubility 0.47 g / l (20 ° C.)), o-xylene (density 0.88 g) / Cm3, water insoluble), m-xylene (density 0.86 g / cm3, water insoluble), p-xylene (density 0.86 g / cm3, water insoluble), mesitylene (density 0.86 g / cm3, water insoluble), etc. Aromatic hydrocarbons: Carbonized carbon containing 6 to 12 carbon atoms such as cyclohexane (density 0.8 g / cm 3, water almost insoluble), cyclooctane (density 0.834 g / cm 3, solubility 7.90 mg / l) Hydrogen; liquid paraffins, etc. are mentioned. These organic solvents can be used alone or in combination of two or more.

  By using the above organic solvent in combination, the effect of making fine particles is improved at the time of dispersion. Moreover, it becomes possible to reduce a viscosity by using an organic solvent together and to disperse with a small shearing force. If the viscosity is low, various emulsifying dispersers can be used. Furthermore, the organic solvent having a small density as described above can prevent the emulsion from being settled, and when used in combination with water, has an effect of improving the stability of the aqueous dispersion. When an organic solvent that does not separate layers when mixed with water or an organic solvent that has few layers when mixed with water is used, the effect of emulsifying and dispersing the pyrazole block hydrophobic polyisocyanate compound tends to decrease.

  In the present invention, from the viewpoint of the storage stability of the pyrazole block hydrophobic polyisocyanate compound and the storage stability of the curable aqueous resin composition when the two-component type is used, the liquid medium of the aqueous dispersion of the pyrazole block hydrophobic polyisocyanate is used. Is preferably a mixture containing water and ethers. In particular, when dibutyl diglycol or diethylene glycol mono-2-ethylhexyl ether is used as the ethers, the storage stability of the pyrazole block hydrophobic polyisocyanate compound, and the curable aqueous resin composition of the two-pack type The effect of storage stability is improved.

  As for the usage-amount of an organic solvent, it is preferable that the compounding ratio (mass basis) of a pyrazole block hydrophobic polyisocyanate compound and an organic solvent is 100: 20-300. More preferably, it is 100: 50-200. When the amount of the organic solvent used is less than 20 parts by mass with respect to 100 parts by mass of the pyrazole block hydrophobic polyisocyanate, a good aqueous dispersion tends to be not obtained. It is necessary to use a lot, which is disadvantageous in terms of performance and economy.

  As for the usage-amount of water, it is preferable that the compounding ratio (mass basis) of a pyrazole block hydrophobic polyisocyanate compound and water is 100: 30-1000. More preferably, it is 100: 50-700. When the amount of water used is less than 30 parts by mass relative to 100 parts by mass of the pyrazole block hydrophobic polyisocyanate, the viscosity tends to be high and the developability to water tends to be poor. There is a tendency that a dispersion cannot be obtained.

  The aqueous pyrazole block hydrophobic polyisocyanate dispersion according to the present invention can be produced, for example, as follows.

  The pyrazole block hydrophobic polyisocyanate represented by the above general formula (I) is dissolved in the above organic solvent (for example, toluene, methyl isobutyl ketone, butyl glycol acetate, dibutyl diglycol, diethylene glycol mono-2-ethylhexyl ether, etc.) Further, an aqueous dispersion can be obtained by dissolving the above-mentioned nonionic surfactant (for example, 30 mol adduct of tristyrenated phenol with ethylene oxide) and gradually adding water while stirring. it can.

  The obtained aqueous dispersion was homomixer (manufactured by Primix Co., Ltd.), homogenizer (manufactured by NIRO SOAVI) or (manufactured by APV GAULIN), nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.), Ultimizer (Sugino Machine Co., Ltd.) Manufactured), Starburst (manufactured by Sugino Machine Co., Ltd.), etc.

  The organic solvent may be distilled off under reduced pressure during or after the preparation of the aqueous dispersion, or may be left as it is.

  The average particle size of the particles in the obtained aqueous dispersion is preferably 1 μm or less. More preferably, it is 0.5 μm or less. When the particle diameter exceeds 1 μm, the stability of the aqueous pyrazole block hydrophobic polyisocyanate dispersion tends to decrease. The average particle diameter is measured by a laser diffraction type / scattering type particle size distribution measuring apparatus LA-920 (manufactured by Horiba, Ltd.), and the average particle diameter (μm) is obtained by calculating the particle diameter (median particle diameter) having a percentage integrated value of 50%. ).

  The aqueous pyrazole block hydrophobic polyisocyanate dispersion according to the present invention is preferably in an emulsified dispersion state. Here, the emulsified dispersion state refers to 200 ml of a 20% by mass aqueous dispersion mixed at a ratio in the preparation examples described later. K. In HOMODISPER (manufactured by Primix Co., Ltd.), when treated at 2000 rpm × 10 minutes at room temperature, a uniform aqueous dispersion is obtained. When the aqueous dispersion is sealed in a glass container and allowed to stand at 45 ° C., It means a state where the mixture is uniformly emulsified and dispersed without separation or sedimentation for 12 hours or more. In order to obtain this emulsified dispersion state, it is preferable to appropriately select a combination of a liquid medium of a pyrazole block hydrophobic polyisocyanate, a nonionic surfactant and an aqueous dispersion.

  The aqueous resin used in the present invention may be in the form of an aqueous solution type or an aqueous dispersion type such as an emulsified dispersion. As used herein, the aqueous resin refers to a 35% by weight aqueous resin aqueous solution or aqueous dispersion that is dissolved or emulsified and dispersed without separation or settling for 12 hours or more when sealed in a glass container and allowed to stand at 20 ° C. Means the state.

Examples of the aqueous resin include ethyleneoxy group, hydroxy group, quaternary ammonium group, amino group, imino group, carboxylate group (COO ⁻ ), sulfonate group (SO ₃ ⁻ ), phosphonate group (PO ₃ ⁻ ), knight. Examples thereof include those in which a hydrophilic group such as a rate group (NO ₂ ⁻ ) is bonded and / or incorporated in the main chain and / or side chain of the resin.

  The aqueous resin used in the present invention may or may not have an active hydrogen-containing group capable of reacting with an isocyanate group, but from the viewpoint of curability, water resistance, adhesiveness, etc. It is more preferable to have an active hydrogen-containing group (such as a hydroxy group or an amino group) that can react with an isocyanate group.

  Examples of the aqueous resin include vinyl acetate resins, styrene-butadiene resins, styrene-acrylonitrile resins, acrylic resins, fluoroolefin resins, silicon-modified vinyl polymers, vinyl alcohols such as polyvinyl alcohol; polyesters Synthetic resins other than vinyl polymers such as resin, polyurethane resin, phenol resin, melamine resin, epoxy resin, alkyd resin, polyamide resin, polyether resin, silicon resin; animal protein, Natural polymers such as starch, cellulose derivatives, dextrin and gum arabic can be mentioned. These aqueous resins can be used singly or in combination of two or more. Among these aqueous resins, polyurethane resins and acrylic resins are more preferable from the viewpoint of water resistance and adhesiveness of the obtained cured film.

  In the curable aqueous resin composition of the present invention, the blending ratio of the aqueous dispersion of the pyrazole block hydrophobic polyisocyanate and the aqueous resin according to the present invention is the above general formula (I) with respect to 100 parts by mass of the aqueous resin component. It is preferable to set so that the pyrazole block hydrophobic polyisocyanate represented by these may become 1-100 mass parts. If the ratio of the pyrazole block hydrophobic polyisocyanate is less than 1 part by mass with respect to 100 parts by mass of the aqueous resin component, it may be difficult to develop sufficient water resistance and adhesiveness. When the proportion of the pyrazole block hydrophobic polyisocyanate exceeds 100 parts by mass with respect to 100 parts by mass of the aqueous resin component, an effect commensurate with the amount used cannot be obtained, which may be economically disadvantageous.

  The curable aqueous resin composition of the present invention may be used as a clear composition containing no pigment, or may be used as a colored composition by blending various organic or inorganic pigments. .

  In addition, the curable aqueous resin composition of the present invention includes a filler, a leveling agent, a viscosity modifier, an antifoaming agent, an organic solvent, an ultraviolet absorber, an antioxidant, a surfactant, and a pigment dispersion as necessary. Agent, resin, antibacterial agent, antifungal agent, solvent, fluid additive, catalyst for promoting reaction of isocyanate group, cross-linking agent other than isocyanate (for example, epoxy, silane, oxazoline, carbodiimide, melamine, A crosslinking agent such as a glioxal) may be blended to such an extent that the effects of the present invention are not inhibited.

  The form of the curable aqueous resin composition of the present invention may be one in which the pyrazole block hydrophobic polyisocyanate aqueous dispersion according to the present invention and the aqueous resin are in one liquid, for example, the pyrazole block according to the present invention. A two-component type may be used which is divided into a liquid A containing a hydrophobic polyisocyanate aqueous dispersion and a liquid B containing an aqueous resin.

  When the curable aqueous resin composition of the present invention is a two-component type, the B solution containing the aqueous resin is preferably in a state where the aqueous resin is dissolved or emulsified and dispersed in a solvent containing water.

  The curable aqueous resin composition of the present invention can be used for applications such as coating agents such as paints and printing inks, adhesives, waterproofing agents, and sealing agents. In particular, it is preferably used as an aqueous coating agent or an aqueous adhesive. When used as an aqueous coating agent, the curable aqueous resin composition of the present invention can form a cured film with excellent water resistance, and when used as an aqueous adhesive, exhibits excellent performance with strong adhesive strength. Can do.

  When the curable aqueous resin composition of the present invention is used as a coating agent, the coating agent may further contain the aforementioned low molecular weight chain extender. In this case, the use amount of the low molecular weight chain extender may be appropriately adjusted in consideration of the performance of the cured film to be obtained, but is based on the mass of the pyrazole block hydrophobic polyisocyanate represented by the general formula (1). Is preferably 5% by mass or less. However, when the low molecular weight chain extender contains an ethyleneoxy group in the molecule, the ethyleneoxy group is preferably used so that it is 3% by mass or less of the above-mentioned pyrazole block hydrophobic polyisocyanate. Most preferred is not.

  The aqueous coating agent of the present invention comprises the curable aqueous resin composition of the present invention. According to the aqueous coating agent of the present invention, a cured coating film excellent in appearance and water resistance can be formed by coating on various substrates and curing.

  Examples of the coating method of the aqueous coating agent of the present invention include brush coating, roller coating, spray coating, dip coating, flow coater coating, and electrodeposition coating.

  As a method for curing the aqueous coating agent of the present invention, for example, heating is performed at about 50 to 300 ° C. for about 5 seconds to 2 hours using a hot air dryer, a thermostatic bath, an infrared dryer, a high-frequency dryer or the like. Can be mentioned.

  Examples of the substrate on which the cured coating film is formed include various metal substrates, inorganic substrates, plastic substrates, paper, wood-based substrates, leather, and fur.

  Typical metal substrates include metals such as iron, nickel, aluminum, chromium, zinc, tin, copper and lead; alloys of various metals such as stainless steel and brass; plating and chemical conversion with various metals or alloys. Examples include various surface-treated metals that have been treated.

  Examples of inorganic substrates include hardened bodies produced from calcium compounds such as calcium silicate, calcium aluminate, calcium sulfate, and calcium oxide; ceramics obtained by sintering metal oxides such as alumina, silica, and zirconia; Tiles obtained by firing clay minerals; various glasses. Specific examples of cured products produced from calcium compounds include cured products of cement compositions such as concrete and mortar, asbestos straight, lightweight cellular concrete (ALC) cured products, dolomite plaster cured products, gypsum plaster cured products, and silicic acid. A calcium plate etc. are mentioned.

  Plastic base materials include polystyrene, polycarbonate, polymethyl methacrylate, ABS resin, polyphenylene oxide, polyurethane, polyethylene, polyvinyl chloride, polypropylene, polybutylene terephthalate, polyethylene terephthalate, and other thermoplastic resin molded articles; unsaturated polyester resins, Examples thereof include molded products of various thermosetting resins such as a phenol resin, a crosslinkable polyurethane, a crosslinkable acrylic resin, and a crosslinkable saturated polyester resin.

  The aqueous adhesive of the present invention comprises the curable aqueous resin composition of the present invention. According to the aqueous adhesive of the present invention, adherends can be bonded to each other with excellent adhesive strength by applying to at least one of the adherends and curing.

  Examples of the application method of the aqueous adhesive of the present invention include application with a spatula, a brush, a spray, a roller, and the like.

  As a method for curing the water-based adhesive of the present invention, for example, heating is performed at about 50 to 300 ° C. for about 5 seconds to 2 hours using a hot air dryer, a thermostatic bath, an infrared dryer, a high frequency dryer or the like. Can be mentioned. By such heat treatment, the pyrazole blocked isocyanate group is converted into a highly active -N = C = O group, and the water resistance and adhesiveness of the cured film are enhanced by the high reactivity. Moreover, you may pressurize a to-be-adhered body as needed.

  Examples of the adherend include the same substrates as those on which the cured coating film is formed.

  The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples.

<Preparation of raw material isocyanate>
Duranate THA-100: Isocyanurate type of hexamethylene diisocyanate, NCO functional group number 3, manufactured by Asahi Kasei Chemicals, trade name, content 100%.
Duranate 24A-100: Bimuret type of hexamethylene diisocyanate, NCO functional group number 3, manufactured by Asahi Kasei Chemicals, trade name, content 100%.

<Preparation of organic solvent>
The following solvents were prepared as organic solvents for preparing an aqueous dispersion of block polyisocyanate.
(Hydrophobic organic solvent)
Dibutyl diglycol (diethylene glycol dibutyl ether) (density 0.884 g / cm ³ , solubility in water 0.3 g / 100 ml (20 ° C.)).
(Hydrophilic organic solvent)
Tripropylene glycol (density 1.02 g / cm ³ , optionally dissolved in water (20 ° C.)).
Methyl ethyl ketone (density 0.805 g / cm ³ , solubility 29 g / 100 ml (20 ° C.)).
Butyl glycol (density 0.9019 g / cm ³ , optionally dissolved in water (20 ° C.)).
n-methylpyrrolidone (density 1.028 g / cm ³ , optionally dissolved in water (20 ° C.)).

<Synthesis of block polyisocyanate>
(Synthesis example 1: pyrazole block hydrophobic polyisocyanate)
To the reaction vessel, 252 parts by mass of Duranate THA-100 and 5 parts by mass of methyl isobutyl ketone were added and heated to 60 to 70 ° C. Next, 144 parts by mass of 3,5-dimethylpyrazole is slowly charged and reacted at 60 to 70 ° C. until the isocyanate content confirmed by an infrared spectrophotometer becomes zero, whereby a pyrazole block hydrophobic polyisocyanate compound is obtained. A colorless transparent viscous liquid composition containing 98.8% by mass of was obtained.

(Synthesis Example 2: Pyrazole block hydrophobic polyisocyanate)
To the reaction vessel, 239 parts by mass of Duranate 24A-100 and 5 parts by mass of methyl isobutyl ketone were added and heated to 60 to 70 ° C. Next, 144 parts by mass of 3,5-dimethylpyrazole is slowly charged and reacted at 60 to 70 ° C. until the isocyanate content confirmed by an infrared spectrophotometer becomes zero, whereby a pyrazole block hydrophobic polyisocyanate compound is obtained. A colorless transparent viscous liquid composition containing 98.7% by mass of was obtained.

(Synthesis Example 3: Methylethylketoxime-containing pyrazole block hydrophobic polyisocyanate)
To the reaction vessel, 252 parts by mass of Duranate THA-100 and 5 parts by mass of methyl isobutyl ketone were added and heated to 60 to 70 ° C. Subsequently, 43.5 parts by mass of methyl ethyl ketoxime was added dropwise, and 96 parts by mass of 3,5-dimethylpyrazole was further added dropwise, and the reaction was carried out at 60 to 70 ° C. until the isocyanate content confirmed by an infrared spectrophotometer became zero. As a result, a colorless transparent viscous liquid composition containing 98.7% by mass of the pyrazole block hydrophobic polyisocyanate compound was obtained.

(Synthesis Example 4: 3 mass% ethyleneoxy group-containing pyrazole block hydrophobic polyisocyanate)
To the reaction vessel, 252 parts by mass of Duranate THA-100 and 5 parts by mass of methyl isobutyl ketone were added and heated to 60 to 70 ° C. Next, 109.6 parts by mass of 3,5-dimethylpyrazole was added dropwise and stirred for 1 hour. Further, 11.1 parts by mass of ethylene glycol was added dropwise and reacted at 60 to 70 ° C. until the isocyanate content confirmed by an infrared spectrophotometer became zero, whereby 98.7 parts by mass of the pyrazole block hydrophobic polyisocyanate compound was obtained. % Colorless transparent viscous liquid composition was obtained.

(Synthesis Example 5: Carboxylate group (COO ⁻ ) 1% by mass-containing pyrazole block hydrophobic polyisocyanate)
To the reaction vessel, 252 parts by mass of Duranate THA-100 and 5 parts by mass of methyl isobutyl ketone were added and heated to 60 to 70 ° C. Next, 127.2 parts by mass of 3,5-dimethylpyrazole was added dropwise and stirred for 1 hour. Further, 11.7 parts by mass of dimethylolpropionic acid was added dropwise and reacted at 60 to 70 ° C. until the isocyanate content confirmed by an infrared spectrophotometer became zero. Then, the colorless and transparent viscous liquid composition which contains 98.8 mass% of pyrazole block hydrophobic polyisocyanate compounds by neutralizing with 10.2 mass parts of 2- (dimethylamino) -2-methyl-1-propanol. Got.

(Comparative Synthesis Example 1: Methyl ethyl ketoxime block polyisocyanate)
To the reaction vessel, 252 parts by mass of Duranate THA-100 and 5 parts by mass of methyl isobutyl ketone were added and heated to 60 to 70 ° C. Next, 130.5 parts by mass of methyl ethyl ketoxime was slowly charged and reacted at 60 to 70 ° C. until the isocyanate content confirmed with an infrared spectrophotometer was zero, whereby 98.70% of the methyl ethyl ketoxime block polyisocyanate compound was obtained. A colorless transparent viscous liquid composition containing 7% by mass was obtained.

(Comparative Synthesis Example 2: 5 mass% ethyleneoxy group-containing pyrazole block polyisocyanate)
To the reaction vessel, 252 parts by mass of Duranate THA-100 and 5 parts by mass of methyl isobutyl ketone were added and heated to 60 to 70 ° C. Subsequently, 22 parts by mass of polyethylene glycol monomethyl ether (average number of moles of ethylene oxide addition 12) was slowly charged and reacted for 1 hour. Subsequently, 140.2 parts by mass of 3,5-dimethylpyrazole was slowly charged and reacted at 60 to 70 ° C. until the isocyanate content confirmed by an infrared spectrophotometer was zero, thereby making the pyrazole block hydrophilic poly (polysiloxane). A colorless transparent viscous liquid composition containing 98.8% by mass of an isocyanate compound was obtained.

(Comparative synthesis example 3: carboxylate group (COO ⁻ ) 1.5% by mass containing pyrazole block polyisocyanate)
To the reaction vessel, 252 parts by mass of Duranate THA-100 and 5 parts by mass of methyl isobutyl ketone were added and heated to 60 to 70 ° C. Next, 117.5 parts by mass of 3,5-dimethylpyrazole was added dropwise and stirred for 1 hour. Furthermore, 18.5 parts by mass of dimethylolpropionic acid was added dropwise and reacted at 60 to 70 ° C. until the isocyanate content confirmed by an infrared spectrophotometer was zero. Then, the colorless and transparent viscous liquid composition which contains 98.8 mass% of pyrazole block hydrophilic polyisocyanate compounds by neutralizing with 16.2 mass parts of 2- (dimethylamino) -2-methyl-1-propanol. Got.

(Comparative Synthesis Example 4: 3% by mass of ethyleneoxy group-containing ε-caprolactam block polyisocyanate)
To the reaction vessel, 252 parts by mass of Duranate THA-100 and 5 parts by mass of methyl isobutyl ketone were added and heated to 60 to 70 ° C. Then, 13.8 parts by mass of polyethylene glycol monomethyl ether (average number of moles of ethylene oxide added 12) was added dropwise and stirred for 1 hour. Furthermore, 166.7 parts by mass of ε-caprolactam was added dropwise and reacted at 60 to 70 ° C. until the isocyanate content confirmed with an infrared spectrophotometer became zero, whereby 98.9 of the hydrophilic blocked polyisocyanate compound was obtained. A colorless transparent viscous liquid composition containing 5% by mass was obtained.

(Comparative Synthesis Example 5: Carboxylate Group (COO ⁻ ) 0.8% by Mass Containing ε-Caprolactam Block Polyisocyanate)
To the reaction vessel, 252 parts by mass of Duranate THA-100 and 5 parts by mass of methyl isobutyl ketone were added and heated to 60 to 70 ° C. Next, 3.4 parts by mass of dimethylolpropionic acid was added dropwise and stirred for 1 hour. Further, 163.8 parts by mass of ε-caprolactam was added dropwise and reacted at 60 to 70 ° C. until the isocyanate content confirmed by an infrared spectrophotometer became zero. Then, the colorless and transparent viscous liquid composition containing 98.8 mass% of hydrophilic block polyisocyanate compounds was obtained by neutralizing with 2.3 mass parts of dimethylaminoethanol.

<Synthesis of surfactant>
(Synthesis Example 6: Stearyl alcohol 5 mol ethylene oxide adduct (HLB = 9.0), hereinafter abbreviated as “St5E”)
270 parts by mass (1 mol) of stearyl alcohol and 3.0 parts by mass of caustic soda were charged in an autoclave, heated to about 130 ° C., and then added with 220 parts by mass (5 mol) of ethylene oxide, and a temperature of 155 to 165 The reaction was performed at 0 ° C. and a pressure of 0.39 MPa or less. After completion of the alkylene oxide addition reaction, the mixture was cooled and neutralized to pH 7 with glacial acetic acid to obtain a light yellow solid nonionic surfactant.

(Synthesis Example 7: Stearyl alcohol 10 mol ethylene oxide adduct (HLB = 12.4), hereinafter abbreviated as “St10E”)
Synthesis was carried out in the same manner as in Synthesis Example 6 except that the number of moles of ethylene oxide added was changed to 10 moles to obtain a light yellow solid nonionic surfactant.

(Synthesis Example 8: Stearyl alcohol 28 mol ethylene oxide adduct (HLB = 16.4), hereinafter abbreviated as “St28E”)
Synthesis was carried out in the same manner as in Synthesis Example 6 except that the number of moles of ethylene oxide added was changed to 28 moles, to obtain a light yellow solid nonionic surfactant.

(Synthesis Example 9: 3 styrenated phenol 30 mol ethylene oxide adduct (HLB = 15.3), hereinafter abbreviated as “T30E”)
After adding 47 parts by mass (0.5 mol) of phenol and 0.1 part by mass of sulfuric acid to a reaction vessel and stirring, 47 parts by mass of phenol (0.5 mol) was added and heated under a nitrogen gas stream to raise the temperature. The temperature was 80 ° C. Further, the temperature is raised and 312 parts by mass (3 moles) of styrene monomer is added dropwise at 105 to 135 ° C., followed by addition reaction at 125 to 135 ° C. for about 3 hours, followed by cooling to obtain a brown transparent viscous liquid tristyrenated phenol. Obtained.

  406 parts by mass (1 mol) of the obtained tristyrenated phenol and 3.5 parts by mass of caustic soda were charged into an autoclave, heated to about 130 ° C., and then 1320 parts by mass (30 mol) of ethylene oxide was added at a temperature of 155. The reaction was carried out at ˜165 ° C. and a pressure of 0.39 MPa or less. After completion of the alkylene oxide addition reaction, the mixture was cooled and neutralized to pH 7 with glacial acetic acid to obtain a light yellow solid nonionic surfactant.

<Synthesis of aqueous resin component>
(Synthesis Example 10: aqueous dispersion of polyurethane resin)
In a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube, 120.0 g of polybutylene adipate diol (average molecular weight 3000), 5.9 g of 1,6-hexanediol, 2,2-dimethylol Add 6.7 g of propionic acid, 0.001 g of dibutyltin dilaurate and 60 g of methyl ethyl ketone, mix uniformly, add 33.6 g of dicyclohexylmethane diisocyanate, react at 80 ° C. for 2 hours, and content of free isocyanate groups with respect to non-volatile content A methyl ethyl ketone solution of a prepolymer having a content of 2.2% by mass was obtained. The solution was cooled to 30 ° C. and neutralized by adding 5.0 g of triethylamine, and then 330 g of water was gradually added and emulsified and dispersed. After adding 18.0 g of a 20% by weight aqueous solution of ethylenediamine to this emulsified dispersion and stirring for 2 hours, the solvent was removed while raising the temperature to 60 ° C. under reduced pressure, and an aqueous dispersion of a polyurethane resin having a nonvolatile content of 35% by weight. Got.

(Synthesis Example 11: aqueous dispersion of hydroxyl group-containing polyurethane resin)
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, 50.0 g of poly (3-methyl-1,5-pentanediol adipate) (average molecular weight 1000), polyethylene glycol (average molecular weight 1000) ) 10.0 g, 6.7 g of 2,2-dimethylolpropionic acid, 2.7 g of 1,4-butanediol, 0.001 g of dibutyltin dilaurate, and 60 g of methyl ethyl ketone, and after mixing uniformly, isophorone diisocyanate 44. 6 g was added and reacted at 80 ° C. for 2 hours to obtain a methyl ethyl ketone solution of a prepolymer having a free isocyanate group content of 2.9% by weight based on the nonvolatile content. The solution was cooled to 30 ° C. and neutralized by adding 5.1 g of triethylamine, and then 230 g of water was gradually added and emulsified and dispersed. To this emulsified dispersion, 6.0 g of a 20% by mass aqueous solution of ethylenediamine was added and stirred for 0.5 hour, and further 8.4 g of diethanolamine was added and stirred for 2 hours. Solvent removal was performed while raising the temperature to 60 ° C. under reduced pressure to obtain an aqueous dispersion of a hydroxyl group-containing polyurethane resin having a nonvolatile content of 35% by mass.

<Preparation of aqueous dispersion of block polyisocyanate>
(Preparation Example 1)
180 parts by mass of the composition obtained in Synthesis Example 1 as a pyrazole block hydrophobic polyisocyanate, 140 parts by mass of dibutyl diglycol as an organic solvent, and 20 parts by mass of St28E obtained in Synthesis Example 8 as a nonionic surfactant Mix and homogenize. Water was gradually added while stirring, and then a homogenizer treatment was performed at 30 MPa to obtain an aqueous pyrazole block hydrophobic polyisocyanate dispersion having a nonvolatile content of 20% by mass. The average particle size of the particles in this aqueous dispersion was 0.34 μm.

(Preparation Example 2)
The same procedure as in Preparation Example 1 was performed except that the nonionic surfactant was changed from St28E obtained in Synthesis Example 8 to T30E obtained in Synthesis Example 9, and a pyrazole block hydrophobic polyisocyanate water having a nonvolatile content of 20% by mass was obtained. A dispersion was obtained. The average particle size of the particles in this aqueous dispersion was 0.33 μm.

(Preparation Example 3)
The same procedure as in Preparation Example 1 was performed except that the nonionic surfactant was changed from St28E obtained in Synthesis Example 8 to St10E obtained in Synthesis Example 7, and a pyrazole block hydrophobic polyisocyanate water having a nonvolatile content of 20% by mass was obtained. A dispersion was obtained. The average particle size of the particles in this aqueous dispersion was 1.07 μm.

(Preparation Example 4)
Preparation Example 1 except that 15 parts by mass of St10E was used as a nonionic surfactant and 18 parts by mass of Arcard T-28 (manufactured by Lion Corporation, active ingredient 28%, stearyltrimethylammonium chloride) was used as a cationic surfactant. The same operation was performed to obtain an aqueous dispersion of a pyrazole block hydrophobic polyisocyanate having a nonvolatile content of 20% by mass. The average particle size of the particles in this aqueous dispersion was 1.02 μm.

(Preparation Example 5)
The pyrazole block hydrophobic polyisocyanate was changed from the composition obtained in Synthesis Example 1 to the composition obtained in Synthesis Example 2, and the nonionic surfactant was obtained in Synthesis Example 9 from St28E obtained in Synthesis Example 8. The same operation as in Preparation Example 1 was performed except that the T30E was changed to obtain a pyrazole block hydrophobic polyisocyanate aqueous dispersion having a nonvolatile content of 20% by mass. The average particle size of the particles in this aqueous dispersion was 0.32 μm.

(Preparation Example 6)
The pyrazole block hydrophobic polyisocyanate was changed from the composition obtained in Synthesis Example 1 to the composition obtained in Synthesis Example 3, and the nonionic surfactant was obtained in Synthesis Example 9 from St28E obtained in Synthesis Example 8. The same operation as in Preparation Example 1 was performed except that the T30E was changed to obtain a pyrazole block hydrophobic polyisocyanate aqueous dispersion having a nonvolatile content of 20% by mass. The average particle size of the particles in this aqueous dispersion was 0.31 μm.

(Preparation Example 7)
The pyrazole block hydrophobic polyisocyanate was changed from the composition obtained in Synthesis Example 1 to the composition obtained in Synthesis Example 4, and the nonionic surfactant was obtained in Synthesis Example 9 from St28E obtained in Synthesis Example 8. The same operation as in Preparation Example 1 was performed except that the T30E was changed to obtain a pyrazole block hydrophobic polyisocyanate aqueous dispersion having a nonvolatile content of 20% by mass. The average particle size of the particles in this aqueous dispersion was 0.31 μm.

(Preparation Example 8)
The pyrazole block hydrophobic polyisocyanate was changed from the composition obtained in Synthesis Example 1 to the composition obtained in Synthesis Example 5, and the nonionic surfactant was obtained in Synthesis Example 9 from St28E obtained in Synthesis Example 8. The same operation as in Preparation Example 1 was performed except that the T30E was changed to obtain a pyrazole block hydrophobic polyisocyanate aqueous dispersion having a nonvolatile content of 20% by mass. The average particle size of the particles in this aqueous dispersion was 0.30 μm.

(Preparation Example 9)
The same procedure as in Preparation Example 1 was performed except that the nonionic surfactant was changed from St28E obtained in Synthesis Example 8 to St5E obtained in Synthesis Example 6, and a pyrazole block hydrophobic polyisocyanate water having a nonvolatile content of 20% by mass was obtained. A dispersion was obtained. The average particle size of the particles in this aqueous dispersion was 1.30 μm.

(Preparation Example 10)
Except that the organic solvent was changed from dibutyl diglycol to tripropylene glycol, the same operation as in Preparation Example 1 was performed to obtain a pyrazole block hydrophobic polyisocyanate aqueous dispersion having a nonvolatile content of 20% by mass. The average particle size of the particles in this aqueous dispersion was 1.33 μm.

(Preparation Example 11)
The nonionic surfactant was changed from St28E obtained in Synthesis Example 8 to T30E obtained in Synthesis Example 9, and the organic solvent was changed from dibutyl diglycol to methyl ethyl ketone. An aqueous dispersion of 20% by mass pyrazole block hydrophobic polyisocyanate was obtained. The average particle size of the particles in this aqueous dispersion was 1.10 μm.

(Preparation Example 12)
The pyrazole block hydrophobic polyisocyanate was changed from the composition obtained in Synthesis Example 1 to the composition obtained in Synthesis Example 4, and the nonionic surfactant was obtained in Synthesis Example 9 from St28E obtained in Synthesis Example 8. The same operation as in Preparation Example 1 was carried out except that the organic solvent was changed from dibutyl diglycol to methyl ethyl ketone, to obtain a pyrazole block hydrophobic polyisocyanate aqueous dispersion having a nonvolatile content of 20% by mass. The average particle size of the particles in this aqueous dispersion was 1.24 μm.

(Comparative Preparation Example 1)
The block polyisocyanate was changed from the composition obtained in Synthesis Example 1 to the composition obtained in Comparative Synthesis Example 1, and the nonionic surfactant was obtained in Synthesis Example 9 from St28E obtained in Synthesis Example 8. The same operation as in Preparation Example 1 was carried out except that the organic solvent was changed from 140 parts by weight of butyl glycol acetate to 20 parts by weight of methyl ethyl ketone, and a methyl ethyl ketoxime block polyisocyanate aqueous dispersion having a nonvolatile content of 20% by weight was obtained. . The average particle size of the particles in this aqueous dispersion was 0.31 μm.

(Comparative Preparation Example 2)
The block polyisocyanate was changed from the composition obtained in Synthesis Example 1 to the composition obtained in Comparative Synthesis Example 2, and the surfactant was changed from St28E obtained in Synthesis Example 8 to Disponil SUS 87 (manufactured by Cognis Co., Ltd.). ) The same procedure as in Preparation Example 1 was carried out except that the organic solvent was changed from 140 parts by weight to 25 parts by weight of butyl glycol acetate, and the pyrazole block hydrophilic polymer having a nonvolatile content of 18.5% by weight was changed to 15 parts by weight. An isocyanate aqueous dispersion was obtained. The average particle size was 0.33 μm.

(Comparative Preparation Example 3)
After adding 25 parts by mass of N-methylpyrrolidone to the pyrazole block hydrophilic polyisocyanate composition (180 parts by mass) obtained in Comparative Synthesis Example 3 and stirring uniformly, water was gradually added while stirring, A homogenizer treatment was performed at 30 MPa to obtain a pyrazole block hydrophilic polyisocyanate aqueous dispersion having a nonvolatile content of 18% by mass. The average particle size was 0.32 μm.

(Comparative Preparation Example 4)
The ε-caprolactam block hydrophilic polyisocyanate composition (180 parts by mass) obtained in Comparative Synthesis Example 4 was gradually charged with water while being stirred, and then homogenized at 30 MPa, with a nonvolatile content of 18% by mass. An ε-caprolactam block hydrophilic polyisocyanate aqueous dispersion was obtained. The average particle size of the particles in this aqueous dispersion was 0.35 μm.

(Comparative Preparation Example 5)
The ε-caprolactam block hydrophilic polyisocyanate composition (180 parts by mass) obtained in Comparative Synthesis Example 5 was gradually charged with water while being stirred, and then homogenized at 30 MPa, with a nonvolatile content of 18% by mass. An ε-caprolactam block hydrophilic polyisocyanate aqueous dispersion was obtained. The average particle size of the particles in this aqueous dispersion was 0.38 μm.

(Comparative Preparation Example 6)
Vivijoule 3100 (manufactured by Sumika Bayer Urethane Co., Ltd., content: 100%, hydrophilic aliphatic polyisocyanate) (180 parts by mass) was gradually charged with stirring, and polyisocyanate water dispersion having a nonvolatile content of 18% by mass A liquid was obtained.

<Manufacture of functional materials>
Example 1
100 parts by mass of the polyurethane resin aqueous dispersion obtained in Synthesis Example 10 as the aqueous resin component and 7 parts by mass of the pyrazole block hydrophobic polyisocyanate aqueous dispersion obtained in Preparation Example 1 as the blocked isocyanate component A curable aqueous resin composition was prepared. The mixed solution obtained by mixing these was spray-coated on an iron plate so that the weight after drying was 3 g / m ^2, and dried at 80 ° C. for 1 minute. Thereafter, baking was performed at 130 ° C. for 30 minutes with a hot air dryer to obtain a functional material having a coating film (cured film). This material was evaluated for the following adhesion and water resistance. The obtained results are shown in “0 hours” in the table.

  The two-component curable aqueous composition prepared above was allowed to stand at 45 ° C. for 5 hours, and then subjected to the same treatment as above to obtain a functional material having a coating film (cured film). This material was evaluated for the following adhesion and water resistance. The obtained results are shown in “5 hours” in the table.

[Evaluation of adhesion]
Adhesive cellophane tape was applied to the coating film (cured film) and peeled off rapidly at an angle of 60 degrees. The appearance of the coating film at this time was observed and evaluated according to the following criteria.
AA: 90% or more of the coating film remained on the iron plate side.
A: More than 80% of the coating film remained on the iron plate side.
B: 50% or more and less than 80% of the coating film remained on the iron plate side.
C: The coating film remaining on the iron plate side was less than 50%.
In addition, as an evaluation of an intermediate position between A and B, an evaluation closer to A is expressed as “AB”, and an evaluation closer to B is expressed as “BA”. The same notation was used for the evaluation of the intermediate position between B and C.

[Evaluation of water resistance]
The functional material on which the coating film (cured film) was formed was immersed in ion-exchanged water at 25 ° C. for 48 hours. Thereafter, the appearance of the coating film was visually observed, and whitening and swelling were evaluated according to the following criteria.
A: No change is seen in the coating film.
B: A slight whitening or a slight swelling is observed in the coating film.
C: Significant whitening or significant swelling is observed in the coating film.
D: Significant whitening or blistering is observed in the coating film.
In addition, as an evaluation of an intermediate position between A and B, an evaluation closer to A is expressed as “AB”, and an evaluation closer to B is expressed as “BA”. The same notation was used for the evaluation of the intermediate position between B and C and the intermediate position between C and D.

  Moreover, about the prepared 2 liquid type curable aqueous resin composition, the stability of the block isocyanate aqueous dispersion and the storage stability of the mixture which mixed 2 liquid were evaluated by the following method.

[Stability of blocked isocyanate dispersion (stability 1)]
The block isocyanate aqueous dispersion was allowed to stand at 45 ° C., and the stability was evaluated from the number of weeks or days in which separation was observed.

[Storage stability of the mixture (stability 2)]
The appearance immediately after preparing the mixture and the appearance when allowed to stand at 45 ° C. for 12 hours were visually observed, and the storage stability was evaluated according to the following criteria. This test also evaluated the ease of use of the two-part curable aqueous resin composition (pot life (usable time), etc.) and the storage stability when the curable aqueous resin composition was made into one-part type. can do.
A: No change is seen at all.
B: Slight separation was observed.
C: Many separations occurred.

In addition, the abbreviation in a table | surface represents the following meaning.
DMP: 3,5-dimethylpyrazole, () indicates the number of moles.
MEKO: methyl ethyl ketoxime, () indicates the number of moles.
Caprolactam: ε-caprolactam, () indicates the number of moles.
T-28: Arcard T-28 (manufactured by Lion Corporation, active ingredient 28%, stearyltrimethylammonium chloride).
EO: Ethyleneoxy group, () shows EO content (% by mass) in the blocked isocyanate compound.
Carboxylate: Carboxylate group, () indicates the carboxylate group content (% by mass) in the blocked isocyanate compound.
BGAc: butyl glycol acetate.
DBDG: Dibutyl diglycol.
TPG: Tripropylene glycol.
MEK: methyl ethyl ketone.
Anionic activator: Disponil SUS 87 (manufactured by Cognis).
Bihijoule 3100: manufactured by Sumika Bayer Urethane Co., Ltd., hydrophilic aliphatic polyisocyanate.

(Examples 2 to 12, Comparative Examples 1 to 7)
The coating films (cured films) of Examples 2 to 12 and Comparative Examples 1 to 7 were operated in the same manner as in Example 1 except that the blocked polyisocyanate component in Example 1 was changed to those shown in Tables 1 to 5. Each functional material provided with

  In the same manner as in Example 1, the functional material, the blocked isocyanate aqueous dispersion, and the mixture were evaluated. The results are shown in Tables 1-5.

(Examples 13-24, Comparative Examples 8-14)
In Example 1-12 and Comparative Examples 1-7, it replaced with the polyurethane resin aqueous dispersion obtained by the synthesis example 10, and implemented except having used the hydroxyl group containing polyurethane resin aqueous dispersion obtained by the synthesis example 11. In the same manner as in Example 1, functional materials provided with the coating films (cured films) of Examples 13 to 24 and Comparative Examples 8 to 14 were obtained.

  In the same manner as in Example 1, the functional material, the blocked isocyanate aqueous dispersion, and the mixture were evaluated. The results are shown in Tables 6-10.

  As shown in the above results, the two-component curable aqueous resin composition prepared in Examples 1 to 26 forms a cured film having good adhesion and water resistance even after 5 hours of mixing. can do. In particular, in Examples 1-6, Examples 9-11, Examples 15-20, and Examples 23-25 using a hydrophobic polyisocyanate containing no hydrophilic group, the adhesiveness and water resistance were superior. It has been shown that a cured film can be formed.

  In comparison between Comparative Example 7 and Comparative Example 14, the hydroxyl group-containing polyurethane resin of Synthesis Example 11 is compared to the polyurethane resin of Synthesis Example 10 because it contains a hydroxy group and has a low molecular weight. It is shown that the water resistance is poor. On the other hand, in the Example used together with the pyrazole block hydrophobic polyisocyanate according to the present invention, the water resistance is equivalent due to the crosslinking of the hydrophobic polyisocyanate. From this, it is considered that the aqueous resin preferably has an active hydrogen-containing group capable of reacting with an isocyanate group from the viewpoint of improving performance.

In Comparative Examples 1 and 8 using a polyisocyanate all blocked with MEKO (hydrophobic group other than pyrazole), the adhesion and water resistance are inferior compared to the case of using a pyrazole blocked hydrophobic polyisocyanate. Moreover, even if it is a pyrazole block isocyanate, it exists in the tendency for water resistance to fall in Comparative Examples 2-3 and Comparative Examples 9-10 using hydrophilic polyisocyanate which many hydrophilic groups are contained. Furthermore, the isocyanate blocked with ε-caprolactam (hydrophobic group other than pyrazole) tends to decrease the water resistance and adhesiveness even if the content of the hydrophilic group is small. Moreover, in Comparative Examples 6 and 13 using hydrophilic aliphatic polyisocyanate, it can be seen that the performance is greatly reduced in 5 hours after mixing the two liquids, and the pot life (usable time) is short.

Claims (11)

Represented by the following formula (I), and, for dividing layer when the pyrazole blocked hydrophobic polyisocyanate not self-emulsifying, and a non-ionic surfactant, and water, mixed in water in water, ketones, esters And at least one organic solvent selected from the group consisting of ethers, aromatic hydrocarbons and aliphatic hydrocarbons, the blending ratio (mass basis) of the pyrazole block hydrophobic polyisocyanate and the organic solvent is 100: 20-300 pyrazole block hydrophobic polyisocyanate aqueous dispersion obtained by mixing ,
An aqueous resin,
A curable aqueous resin composition comprising:
R (—NH—CO—Z) _m (I)
[In Formula (I), m represents an integer of 2 or more, R represents a residue obtained by removing m isocyanate groups from a polyisocyanate compound having m isocyanate groups, and Z may be the same or different. Often, it represents a residue obtained by removing a hydrogen atom from an active hydrogen-containing compound capable of reacting with an isocyanate group, and at least two of Z are pyrazole groups represented by the following general formula (II).

(In the formula (II), n represents an integer of 0 to 3, and when n is 1 or more, R ¹ may be the same or different, and is an alkyl group having 1 to 6 carbon atoms or 2 carbon atoms. -6 alkenyl group, C 7-12 aralkyl group, N-substituted carbamyl group, phenyl group, -NO ₂ , halogen atom or -C (O) -O-R ² (wherein R ² is a hydrogen atom or Which is an alkyl group having 1 to 6 carbon atoms.)] The curable aqueous resin composition according to claim 1, wherein the organic solvent is an ether. The curable aqueous resin composition according to claim 1, wherein the nonionic surfactant is a nonionic surfactant having an HLB of 10 or more. The curable aqueous resin composition according to any one of claims 1 to 3 , wherein all Z in the general formula (I) is a pyrazole group represented by the general formula (II). The two-component type according to any one of claims 1 to 4 , which is a two-component type of a first composition containing the aqueous pyrazole block hydrophobic polyisocyanate dispersion and a second composition containing the aqueous resin. Curable aqueous resin composition. An aqueous coating agent comprising the curable aqueous resin composition according to any one of claims 1 to 5 . An aqueous adhesive comprising the curable aqueous resin composition according to any one of claims 1 to 5 . Ketones and esters which are represented by the following general formula (I) and which are separated when mixed with water, a pyrazole block hydrophobic polyisocyanate that does not self-emulsify in water, a nonionic surfactant, water, and water. And at least one organic solvent selected from the group consisting of ethers, aromatic hydrocarbons and aliphatic hydrocarbons, the blending ratio (mass basis) of the pyrazole block hydrophobic polyisocyanate and the organic solvent is A step of obtaining a pyrazole block hydrophobic polyisocyanate aqueous dispersion by mixing to be 100: 20 to 300,
A process for producing a pyrazole block hydrophobic polyisocyanate aqueous dispersion.
R (-NH-CO-Z) _m       ... (I)
[In Formula (I), m represents an integer of 2 or more, R represents a residue obtained by removing m isocyanate groups from a polyisocyanate compound having m isocyanate groups, and Z may be the same or different. Often, it represents a residue obtained by removing a hydrogen atom from an active hydrogen-containing compound capable of reacting with an isocyanate group, and at least two of Z are pyrazole groups represented by the following general formula (II).

(In the formula (II), n represents an integer of 0 to 3, and when n is 1 or more, R ¹ , Which may be the same or different, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an N-substituted carbamyl group, a phenyl group, —NO ₂ , Halogen atom or -C (O) -O-R ² (Where R ² Is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms). ]] The manufacturing method of the pyrazole block hydrophobic polyisocyanate aqueous dispersion of Claim 8 whose said organic solvent is ethers. The manufacturing method of the pyrazole block hydrophobic polyisocyanate aqueous dispersion of Claim 8 or 9 whose said nonionic surfactant is a nonionic surfactant more than HLB10. All of Z in the said general formula (I) is the pyrazole group represented by the said general formula (II), The pyrazole block hydrophobic polyisocyanate aqueous dispersion as described in any one of Claims 8-10. Production method.