JP2014125512A - Aqueous amine emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous amine emulsion which is environmentally friendly and is excellent in storage stability, and to provide an aqueous mixed emulsion containing aqueous amine emulsion and an aqueous epoxy resin emulsion which has a long usable time without deteriorating various physical properties of a cured product.SOLUTION: In an aqueous amine emulsion in which amine is emulsified and dispersed into an aqueous medium in the presence of an emulsifier, the average particle diameter is 500 nm or less.

Description

  The present invention relates to an aqueous amine emulsion and an aqueous paint containing the same.

  In order to reinforce the mechanical strength and impart water resistance of inorganic building materials, a two-pack type sealer using an aqueous epoxy resin emulsion as a main agent and an aqueous amine as a curing agent is widely used. In addition, solvent-based two-component paints with epoxy resin as the main component and amine as the curing agent are used for large steel structures. Progressing.

  The water-based amine curing agents that have been widely used for water-based epoxy resin emulsions are mostly water-soluble amines or self-emulsifiable amines. Aqueous amine curing agents often have short pot life due to their high reactivity.

  On the other hand, amine curing agents for solvent-based epoxy resins use amines with various organic compounds for the purpose of controlling physical properties such as the viscosity of the curing agent, reactivity with the epoxy resin, pot life, and physical properties of the cured product. Degeneration is widely performed. However, since such modified amines have relatively high hydrophobicity, many of them are poor in water solubility and self-emulsification. When emulsified and dispersed in an aqueous medium, a large amount of emulsifier must be used. The performance of the cured coating film is inevitably deteriorated due to uneven distribution of the emulsifier used in a large amount in the cured coating film or bleeding out on the surface of the coating film. For this reason, as a curing agent for aqueous epoxy resins, there is a limit to the extension of the usable time and the control of physical properties of the cured product by selecting a modified amine curing agent.

  With regard to making an epoxy resin aqueous, Patent Document 1 discloses that an aqueous epoxy resin emulsion can be obtained by phase inversion emulsification using an epoxy-amine addition compound as an emulsifier. Such aqueous epoxy resin emulsions are widely used for applications such as a two-component curable primer. An aqueous amine curing agent is widely used as a curing agent for the aqueous epoxy resin emulsion. When a conventional aqueous amine curing agent is used, the pot life is relatively short, about 1 hour. A short pot life not only causes inefficiency in the coating work, but also leads to disposal of the paint that has passed the pot life and has a problem in terms of effective use of resources.

  Patent Document 2 discloses a method of extending the pot life by completely neutralizing an aqueous amine curing agent with a carboxylic acid such as oxalic acid. However, since the amine is completely neutralized to reduce the nucleophilicity of the amine, a decrease in room temperature curability when applied is inevitable. Moreover, the method of this literature has a restriction | limiting in the selection of an amine, such as being unsuitable for an amine with low water solubility.

  Patent Document 3 discloses a method of adding a dispersion obtained from a diamine and a solid epoxy resin for the purpose of adjusting the viscosity of an aqueous amine curing agent comprising a water-soluble amine and a self-emulsifying amine and extending the pot life. Yes. According to this method, an aqueous amine curing agent containing no emulsifier can be obtained, so that a decrease in the performance of the cured coating film due to the emulsifier can be avoided. However, the method of this document can be applied only to water-soluble amines or self-emulsifiable amines, and cannot be applied to many hydrophobic modified amines, so it is difficult to control the physical properties of the cured product.

JP 2000-504372 A JP 59-6214 A JP-A-2005-200366

  An object of the present invention is to solve the above problems and to provide an aqueous amine emulsion excellent in storage stability. Another object of the present invention is to provide an aqueous mixed emulsion containing an amine and an epoxy resin, which has a long pot life and excellent substrate adhesion.

  The present invention and preferred embodiments of the present invention are as follows.

1. An aqueous amine emulsion in which an amine is emulsified and dispersed in an aqueous medium in the presence of an emulsifier (B1), and the average particle size is 500 nm or less.

2. 2. The aqueous amine emulsion as described in 1 above, further having a particle size dispersion of 1.0 to 2.0.

3. 3. The aqueous amine emulsion according to 1 or 2 above, wherein the emulsifier (B1) contains a reactive emulsifier having an epoxy group.

4). An aqueous mixed emulsion comprising the aqueous amine emulsion according to any one of 1 to 3 and an aqueous epoxy resin emulsion,
An aqueous mixed emulsion, wherein the aqueous epoxy resin emulsion is obtained by emulsifying and dispersing an epoxy resin in an aqueous medium in the presence of an emulsifier (B2), and has an average particle size of 500 nm or less.

5. 5. The aqueous mixed emulsion according to 4 above, wherein a particle size dispersion degree of the aqueous epoxy resin emulsion is 1.0 to 1.4.

6). 6. The aqueous mixed emulsion according to 4 or 5 above, wherein the emulsifier (B2) contains a reactive emulsifier having an epoxy group.

7). An aqueous paint containing the aqueous mixed emulsion according to any one of 4 to 6 above.

8). 4. A method of using the aqueous amine emulsion according to any one of 1 to 3 as a curing agent for an epoxy resin.

  The aqueous amine emulsion of the present invention has excellent storage stability, long pot life, and excellent permeability to inorganic building materials because the average particle size is within a predetermined range. Moreover, when an aqueous amine emulsion is produced using a reactive emulsifier, since the emulsifier does not bleed out from the cured coating film, there is no concern about environmental contamination, and it is possible to suppress deterioration of various physical properties of the cured coating film.

  In the present specification, an amine is a compound in which one or more hydrogen atoms of ammonia are substituted with a hydrocarbon residue, and the number of hydrocarbon residues may be one or two. It may be an individual. The hydrocarbon residue may be a part of a linear or branched aliphatic hydrocarbon structure, or a part of an aliphatic hydrocarbon structure in which a cyclic structure such as a 5-membered ring or a 6-membered ring is formed, Aromatic hydrocarbons may be used. Moreover, functional groups such as halogens such as fluorine, chlorine and bromine, hydroxyl groups and nitrile groups may be bonded to these aliphatic hydrocarbon residues and aromatic hydrocarbon residues.

  In the present specification, the modified amine refers to the above-mentioned amine for the purpose of controlling various physical properties such as viscosity, extending the pot life when used as a curing agent for epoxy resins, and controlling the physical properties of the cured product. This refers to an amine having a hydrocarbon residue newly introduced by a reaction, a Michael addition reaction, an addition reaction with an epoxy group, a condensation reaction with a ketone group, or the like.

  In the present specification, the “epoxy group” is a bonding group having an epoxy structure (a three-membered ring structure composed of carbon-oxygen-carbon), and the carbon-carbon part may be a part of a linear or branched hydrocarbon structure. It may be a part of a hydrocarbon structure in which a cyclic structure such as a 5-membered ring or a 6-membered ring is formed. In addition, halogens such as fluorine, chlorine and bromine, and functional groups such as hydroxyl groups and nitrile groups may be bonded to these hydrocarbon structures. Furthermore, an alkyl group such as a methyl group, an aryl group such as a phenyl group, a halogen, or the like may be bonded to the carbon atom forming the epoxy structure. Examples of these epoxy groups include glycidyl groups and bonding groups represented by the following formula (2). In particular, a glycidyl group is desirable because it is industrially produced from allyl alcohol and epichlorohydrin and is easily available.

（式中、Ｒ_１ 及びＲ_２ は炭素数１〜１２の炭化水素基を、ｍは０〜３の整数を表す。）

(In the formula, R ₁ and R ₂ represent a hydrocarbon group having 1 to 12 carbon atoms, and m represents an integer of 0 to 3).

<< Aqueous amine emulsion >>
In the aqueous amine emulsion of the present invention, the amine (A) is emulsified and dispersed in the aqueous medium (C1) in the presence of the emulsifier (B1), and the average particle size is 500 nm or less. The aqueous amine emulsion of the present invention can be used as a curing agent for an aqueous epoxy resin emulsion in which an epoxy resin (D) is emulsified and dispersed (details will be described later).

  First, each component contained in the aqueous amine emulsion of the present invention will be described.

<Amine (A)>
The amine (A) is emulsified and dispersed in the aqueous medium (C1) in the presence of the emulsifier (B1). In the present invention, the amine (A) is a compound having at least one amino group in one molecule and can be appropriately selected according to the use, but a compound having two or more amino groups is preferable. Moreover, when using the amine emulsion of this invention as a hardening | curing agent of an epoxy resin, it is preferable to include the thing whose active hydrogen equivalent is 50-1000 from points, such as sclerosis | hardenability of a cured coating film, and rust prevention property, More preferably, those within the range of 700 are included.

  The amine (A) is not particularly limited but is preferably highly hydrophobic. By using a highly hydrophobic amine, freedom of choice is available for control of pot life when amine (A) is used as a curing agent for epoxy resin, reactivity with epoxy resin, control of physical properties of cured product, etc. The degree becomes higher.

  Examples of the amine (A) include aliphatic polyamines, alicyclic polyamines, aromatic polyamines, polyamides, polyamidoamines, heterocyclic amines, and modified products thereof.

  A highly hydrophobic amine is an amine that is insoluble in an aqueous medium or has low solubility in an aqueous medium, and examples thereof include those having a hydrophobic group. Examples of the hydrophobic group include hydrocarbon groups such as aromatic groups, chain aliphatic groups, and alicyclic groups. Examples of the hydrophobic amine include amines having at least one alkyl group. The alkyl group preferably has 4 to 22 carbon atoms, more preferably 6 to 22 carbon atoms, or a hydrophilic aliphatic polyamine. Examples include amines hydrophobized by epoxy modification.

  Amine (A) may be used individually by 1 type, and may be used in combination of 2 or more type of amine. Further, a highly hydrophobic amine and a highly hydrophilic amine may be used in combination. Also in this case, it is more preferable that two or more amino groups are contained in one molecule of each amine.

  A commercially available product can be used as the amine (A). For example, Daitokural U-5396I, U-5728, X-7004 (manufactured by Daito Sangyo Co., Ltd.), JEFFAMINE ST-404, T-5000 ( Huntsman Co., Ltd.), ANCAMINE 2390 (Air Products and Chemicals Co., Ltd.), and Primine 1074 (Croda Co., Ltd.). These may be used individually by 1 type, or may mix and use 2 or more types.

<Emulsifier (B1)>
As the emulsifier (B1), a reactive emulsifier, a non-reactive emulsifier, or a combination thereof can be used, and a reactive emulsifier is preferably used. Here, “reactivity” of the reactive emulsifier means having a functional group that reacts with the curing agent of the epoxy resin or a functional group that reacts with the epoxy group. Hereinafter, each emulsifier will be described.

(Reactive emulsifier)
In the present invention, the reactive emulsifier means an emulsifier having a reactive functional group in the molecule, and means an emulsifier suitable for making soap free. Here, soap-free means a technique for reducing the amount of free emulsifier in the cured coating film.

  That is, the reactive emulsifier has a hydrophilic part (hydrophilic group, hydrophilic block, etc.) and a hydrophobic part (hydrophobic group, hydrophobic block, etc.). Further, the reactive emulsifier can react with the amine (A) or the epoxy resin (D), and has a functional group capable of co-curing with the epoxy resin (D) described later as the reactive functional group.

  As the reactive functional group that reacts with an amino group, for example, an ethylenically unsaturated group, an acetylenically unsaturated group, a carbonyl group, an isocyanate group, an isothiocyanate group, an epoxy group, or an oxetane group is preferable. In view of properties and reactivity, an epoxy group is more preferable. In this case, the reactive emulsifier (B1) can react with the amine (A). As the reactive functional group that reacts with the epoxy group, for example, an amino group, a mercapto group, a carboxyl group, and imidazoles are preferable, and in view of ease of synthesis, stability, and reactivity, an amino group is more preferable. . In this case, the reactive emulsifier (B1) can react with the epoxy resin (D). Therefore, when these reactive emulsifiers are used, the reactive emulsifier can be copolymerized with the epoxy resin (D) described later, and is immobilized on the epoxy resin and is unevenly distributed in the cured coating film. There is no problem of bleeding out on the surface, and there is no concern about environmental pollution.

  In addition, in the reactive emulsifier which reacts with an amino group and the reactive emulsifier which reacts with an epoxy group, the reactive emulsifier which reacts with an amino group is preferable when the ease of synthesis, stability, and reactivity are considered. Furthermore, either the reactive emulsifier that reacts with an amino group or the reactive emulsifier that reacts with an epoxy group may be used alone, or both may be used in combination. For example, a reactive emulsifier having a functional group that reacts with an amino group may be used to emulsify an epoxy resin, and a reactive emulsifier having a functional group that reacts with an epoxy group may be used to emulsify an amine.

  In the present invention, the reactive emulsifier preferably has an HLB value in the range of 10 to 17. The HLB value is calculated by the following formula.

  HLB = (molecular weight of hydrophilic part in molecule) / (molecular weight of hydrophilic part in molecule + molecular weight of hydrophobic part in molecule) × 100/5

  The reactive emulsifier may be any of anionic, nonionic or cationic types, but is preferably nonionic from the viewpoints of storage stability, curability, rust resistance of the cured coating film, and the like. Moreover, a reactive emulsifier may be used individually by 1 type, or 2 or more types may be mixed and used for it.

  Typical examples of the nonionic reactive emulsifier include a structure containing a polyalkylene oxide block containing a repeating structure such as ethylene oxide and propylene oxide as a hydrophilic part and an aromatic ring and / or an alkyl chain as a hydrophobic part. . The HLB value can be adjusted by changing the length of the polyalkylene oxide block, that is, the number of repeating alkylene oxides in consideration of the size of the hydrophobic site.

  Although not particularly limited, specific examples of reactive emulsifiers that react with amino groups include, for example, epoxy resins having at least two epoxy groups in the molecule (having hydrophobic or hydrophilic sites), for example, An epoxy / active hydrogen compound adduct having at least one epoxy obtained by reacting a compound having an active hydrogen such as an amine or a thiol compound (having a hydrophilic or hydrophobic site) can be mentioned.

  Although not particularly limited, specific examples of the reactive emulsifier that reacts with the epoxy group include, for example, a compound having at least two amino groups in the molecule (having a hydrophobic or hydrophilic site), for example, 1 An epoxy-amine compound adduct having at least one amino group obtained by reacting an epoxy resin having one epoxy group (having a hydrophilic or hydrophobic site) can be mentioned.

  The epoxy amine adduct, which is a reactive emulsifier that reacts with an amino group, will be described as an example. The epoxy amine adduct may be, for example, (1) a hydrophobic epoxy resin and a hydrophilic amine, or (2) a hydrophilic epoxy. They can be synthesized from a resin and a hydrophobic amine, and the combination thereof can be arbitrarily selected so that the HLB value is preferably in the range of 10-17.

  (1) In synthesizing a reactive emulsifier from a hydrophobic epoxy resin and a hydrophilic amine, the hydrophobic epoxy resin includes at least two epoxy groups in the molecule, an aromatic ring, an aliphatic ring, and a chain aliphatic group. An aromatic epoxy resin having a hydrocarbon group selected from the above, an alicyclic epoxy resin, an aliphatic epoxy resin, or the like can be used. Commonly used epoxy resins are usually classified as hydrophobic epoxy resins. As aromatic epoxy resins, bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin and bisphenol S type epoxy resin; novolak type epoxy resins such as phenol novolac type epoxy resin and cresol novolak type epoxy resin; Resin Co., Ltd. product name YX4000 biphenyl type epoxy resin; naphthalene, anthracene, epoxy resin having a polycyclic aromatic group such as terphenyl in the basic skeleton; tetraglycidyldiaminodiphenylmethane (TGDDM) triglycidylparaaminophenol, And triglycidyl metaaminophenol.

  Those having an epoxy group having a ring strain such as cyclohexene oxide structure and cyclopentene oxide structure in the molecule (structures shown in (1) to (5) described later in epoxy resin (D) described later), hydrogenated bisphenol Cycloaliphatic epoxy resins such as type epoxy resins; and linear or branched aliphatic epoxy resins such as alkylene diglycidyl ethers may be used.

  Hydrophobic epoxy resin can be selected according to the application, but bisphenol type epoxy resin may be used for general applications, and in particular, bisphenol A type epoxy resin (that is, bisphenol A diglycidyl ether) is used. Good. When synthesizing the reactive emulsifier, the hydrophobic epoxy resin may be used alone or in combination of two or more.

  The hydrophilic amine is preferably a monoamine or diamine having a hydrophilic group and having an amino group at the molecular end, and more preferably a monoamine. As the hydrophilic group, a polyoxyalkylene chain is usually preferable. Specific examples of the hydrophilic amine include polyalkylene glycol (polyoxyalkylene amine) having an amino group at the terminal. The polyoxyalkylene chain preferably contains an ethylene oxide unit and / or a propylene oxide unit, and particularly preferably contains 60% by mass or more of the ethylene oxide unit in the polyoxyalkylene chain. The length of the polyoxyalkylene chain (that is, the number of repeating oxyalkylenes) is selected so that the HLB of the reactive emulsifier becomes a predetermined value. Examples of commercially available products include JEFFAMINE M-1000 and M-2000 (manufactured by Huntsman). When synthesizing the reactive emulsifier, one kind of hydrophilic amine may be used alone, or two or more kinds may be mixed and used.

  (2) When a reactive emulsifier is synthesized from a hydrophilic epoxy resin and a hydrophobic amine, the hydrophilic epoxy resin has at least two epoxy groups and a hydrophilic group in the molecule. As the hydrophilic group, a polyoxyalkylene chain is usually preferable. Specifically, as the hydrophilic epoxy resin, for example, polyalkylene glycol having glycidyl groups at both ends of the molecule is preferable. The polyoxyalkylene chain preferably contains ethylene oxide units and / or propylene oxide units, and particularly preferably contains 60% by mass or more of ethylene oxide units in the polyoxyalkylene chain. The length of the polyoxyalkylene chain (that is, the number of repeating oxyalkylenes) is selected so that the HLB of the reactive emulsifier becomes a predetermined value. Specific examples include polyethylene glycol diglycidyl ether. When synthesizing the reactive emulsifier (B1), the hydrophilic epoxy resin may be used alone or in combination of two or more.

  The hydrophobic amine is preferably a monoamine or diamine having a hydrophobic group and having an amino group at the molecular end, and more preferably a monoamine. The hydrophobic group is preferably a hydrocarbon group such as an aromatic group, a chain aliphatic group, or an alicyclic group. Examples of the hydrophobic amine include amines having at least one alkyl group, and the alkyl group preferably has 4 to 22 carbon atoms, more preferably 6 to 22 carbon atoms. When synthesizing the reactive emulsifier, one kind of hydrophobic amine may be used alone, or two or more kinds may be mixed and used.

  Examples of the combination for synthesizing the reactive emulsifier include a combination of bisphenol A diglycidyl ether and JEFFAMINE M-1000, a combination of polyethylene glycol diglycidyl ether and hexadecylamine, and the like.

  The method of synthesizing the reactive emulsifier is not particularly limited, but a ratio of at least one epoxy group present in the molecule, for example, a mixture having a molar ratio of epoxy resin: amine = 2: 1 to 1: 1 is 80. It can be obtained by heating reaction at a temperature of ˜150 ° C.

(Non-reactive emulsifier)
In the aqueous amine emulsion of the present invention, non-reactive emulsifiers other than the reactive emulsifiers can also be used.

  It does not specifically limit as a non-reactive emulsifier, A well-known emulsifier can be used. Any of an anionic emulsifier, a nonionic emulsifier, and a cationic emulsifier may be used, but nonionic is preferable from the viewpoint of storage stability, curability, and rust prevention of a cured coating film. Nonionic emulsifiers include, for example, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene phenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octyl Examples include phenyl ether, polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monooleate, sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate, and polyoxyethylene sorbitan monolaurate. A non-reactive emulsifier may be used individually by 1 type, and may use 2 or more types together.

  A commercial item can be used as a non-reactive emulsifier, for example, Neugen EA-167D (made by Daiichi Kogyo Seiyaku Co., Ltd.) is mentioned.

<Aqueous medium (C1)>
“Aqueous medium (C1)” refers to, for example, general water such as distilled water, ion-exchanged water and pure water, or a mixed solvent of “water” and “water-soluble solvent”. The aqueous medium may further contain impurities such as oligomer resin as long as the object of the present invention is not impaired. The “water-soluble solvent” is not particularly limited as long as it is a water-soluble solvent. Specifically, alcohols such as methanol, ethanol and isopropanol, and lower aldehydes such as formaldehyde and acetaldehyde are used. Can be illustrated.

  The aqueous amine emulsion of the present invention is not particularly limited, but the amine (A) is preferably 1 to 70% by mass with respect to the total mass of the amine (A), the emulsifier (B1) and the aqueous medium (C1). Preferably, it is produced using 20 to 50% by mass and the emulsifier (B1) is preferably 0.3 to 20% by mass, more preferably 1 to 10% by mass.

  The aqueous amine emulsion of the present invention has an average particle size of 500 nm or less, preferably 50 to 500 nm, more preferably 100 to 500 nm, still more preferably 150 to 500 nm, and most preferably 200 to 500 nm. In the present invention, the “average particle diameter” means a particle diameter measured by a dynamic light scattering type measuring instrument and obtained by analysis by a cumulant method.

  When the average particle size of the aqueous amine emulsion is 500 nm or less, even when the aqueous amine emulsion is stored for a long period of time, the particles are not aggregated or settled and are excellent in stability. Furthermore, when using the aqueous | water-based amine emulsion of this invention as a hardening | curing agent of the water-based epoxy resin emulsion mentioned later, a pot life can be extended to moderate length. Furthermore, for example, when the aqueous amine emulsion of the present invention is used as a curing agent for an aqueous epoxy resin emulsion for an inorganic building material sealer, it has excellent permeability to inorganic building materials, so that adhesion to a substrate is improved and water resistance is improved. To do. Moreover, the adhesiveness and water resistance to a metal base material improve, and rust prevention performance improves. Therefore, the aqueous amine emulsion of the present invention is suitable, for example, as a raw material for a metal coating agent and its primer.

  The aqueous amine emulsion of the present invention preferably has a particle size dispersion of 1.0 to 2.0, more preferably 1.0 to 1.8, and 1.0 to 1.5. Most preferably it is. In the present specification, the “particle size dispersion degree” is a value obtained by Dw / Dn from the weight average particle size Dw and the number average particle size Dn calculated from the measurement result by the dynamic light scattering type measuring instrument. When the particle size dispersion degree of the aqueous amine emulsion is within this range, the coarsening of the particles is suppressed, and the storage stability of the aqueous amine emulsion is easily maintained.

  As a method of emulsifying and dispersing the amine (A) in the aqueous medium (C1), for example, the amine (A) and the reactive emulsifier (B1) are added to the aqueous medium (C1), and the mixture is stirred and mixed to be pre-emulsified. And a method of performing the emulsification such as microfluidization by a high shearing force using a dispersion apparatus after performing the above. Depending on the viscosity of the amine, the emulsification dispersion treatment may be performed by lowering the viscosity with an organic solvent such as acetone or ethyl acetate.

  In addition, for controlling the average particle size and the degree of particle size dispersion, a highly hydrophobic organic compound such as hexadecane or hexadecyl alcohol can be added as necessary.

  Examples of a dispersion apparatus used for emulsification, particularly main emulsification, include a batch mixer (manufactured by Silverson), a homogenizer (manufactured by IKA), a polytron (manufactured by Kinematica), and a TK auto homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). ) Etc. Batch type emulsifier, Ebara Milder (manufactured by Aihara Seisakusho Co., Ltd.), TK Fillmix, TK Pipeline Homo Mixer (manufactured by Special Machine Industries Co., Ltd.), Colloid Mill (manufactured by Shinko Pantech Co., Ltd.), Thrasher, Trigonal Wet Continuous emulsifiers such as fine pulverizer (Mitsui Miike Kako Co., Ltd.), Captron (Eurotech Co., Ltd.), Fine Flow Mill (Pacific Kiko Co., Ltd.), Static Mixer (Noritake Co.), Microfluidizer (Micro Fluidics), Nanomizer (Nanomizer), APV Gaurin (Gaurin) and other high-pressure milk Machine, membrane emulsifier such as membrane emulsifier (made by Chilling Industries Co., Ltd.), vibratory emulsifier such as Vibro mixer (made by Chilling Industries Co., Ltd.), ultrasonic emulsifier such as ultrasonic homogenizer (made by Branson) etc. Can be mentioned. Among these, preferred from the viewpoint of uniforming the particle size are a microfluidizer, APV gaurin, batch mixer, Ebara milder, and ultrasonic homogenizer.

  As a method of this emulsification, for example, a microfluidizer (manufactured by Microfluidics) may be used. For example, G10Z (minimum flow path width 87 μm) or H210Z (minimum flow path width 210 μm) is used as an interaction chamber, and H30Z (Minimum flow path width 200 μm) or H230Z (minimum flow path width 400 μm) is used as an auxiliary processing module, and the process pressure is processed at 2000 to 30000 psi, preferably 5000 to 20000 psi. By applying a shearing force to the emulsion by passing a flow path of several hundreds of μm under a pressure of 2000 to 30000 psi, the aqueous amine emulsion of the present invention can easily reach a predetermined particle diameter having a predetermined particle size dispersion degree. It is emulsified and dispersed, and the storage stability is improved.

<< Aqueous epoxy resin emulsion >>
Next, the aqueous epoxy resin emulsion will be described.

  The aqueous epoxy resin emulsion is obtained by emulsifying and dispersing the epoxy resin (D) in the aqueous medium (C2) in the presence of the emulsifier (B2).

  As the emulsifier (B2) used in the production of the aqueous epoxy resin emulsion, the same compound as the emulsifier (B1) used in the production of the amine emulsion can be used. Even if it is a reactive emulsifier, it is a non-reactive emulsifier. It may be. Especially, it is preferable to use the reactive emulsifier which can be used as said emulsifier (B1) also as an emulsifier (B2). When a reactive emulsifier that reacts with an amino group is used as the emulsifier (B2) of the aqueous epoxy resin emulsion, the emulsifier (B2) and the amine (A) can react. For this reason, during the curing reaction, the emulsifier (B2), which is a reactive emulsifier, can be copolymerized with the epoxy resin (D) described later, and is fixed to the epoxy resin and is unevenly distributed or cured in the cured coating film. There is no problem of bleeding out on the surface of the coating film, and there is no concern about environmental pollution.

  An emulsifier (B2) may be used individually by 1 type, and may use 2 or more types together.

  The emulsifier (B1) used for the aqueous amine emulsion and the emulsifier (B2) used for the aqueous epoxy resin emulsion may be the same or different. Of the emulsifier (B1) and the emulsifier (B2), at least one is preferably a reactive emulsifier, and more preferably a reactive emulsifier.

<Epoxy resin (D)>
In the present invention, the epoxy resin (D) can be appropriately selected according to the use, but preferably contains a resin having at least two epoxy groups in one molecule, such as curability of a cured coating film and rust prevention properties. From this point, it is preferable to include those having an epoxy equivalent of 100 to 1000, and more preferable to include those in the range of 150 to 700.

  As the epoxy resin (D), an epoxy resin having an aromatic ring, an alicyclic epoxy resin, and other various epoxy resins can be used. One type of epoxy resin may be used, or two or more types may be used. Moreover, it is preferable that the epoxy resin has at least one aromatic ring from the viewpoint of excellent mechanical strength and heat resistance of the cured product.

  Examples of the epoxy resin having an aromatic ring include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin and bisphenol S type epoxy resin; novolak type epoxy resins such as phenol novolak type epoxy resin and cresol novolak type epoxy resin. Biphenyl type epoxy resin such as trade name YX4000 manufactured by Japan Epoxy Resins Co., Ltd .; epoxy resin having a polycyclic aromatic group such as naphthalene, anthracene and terphenyl in the basic skeleton; other tetraglycidyl diaminodiphenylmethane (TGDDM) triglycidyl Examples include paraaminophenol and triglycidyl metaaminophenol. The epoxy resin having an aromatic ring usually has one or more, preferably two or more epoxy groups in the molecule, and the epoxy equivalent can be appropriately selected.

  As an epoxy resin having no aromatic ring, an alicyclic epoxy resin having an epoxy group having a ring strain such as a cyclohexene oxide structure and a cyclopentene oxide structure in the molecule (for example, in the following formulas (1) to (5) Compounds shown)

；水素化ビスフェノール型エポキシ樹脂（ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂およびビスフェノールＳ型エポキシ樹脂等のビスフェノール型エポキシ樹脂のベンゼン環が水素化されたもの）；ジシクロペンタジエンフェノールノボラックのグリシジルエーテル等のジシクロペンタジエン型エポキシ樹脂；シクロヘキサンジメタノールジグリシジルエーテル(cyclohexanedimethanol diglycidyl ether)、ブチルグリシジルエーテル、２−エチルヘキシルグリシジルエーテル、アリルグリシジルエーテル等の脂肪族アルキル−モノまたはジ−グリシジルエーテル；グリシジルメタクリレート、３級カルボン酸グリシジルエステル等のアルキルグリシジルエステル；スチレンオキサイド；フェニルグリシジルエーテル、クレジルグリシジルエーテル、ｐ−ｓ−ブチルフェニルグリシジルエーテル、ノニルフェニルグリシジルエーテル等の芳香族アルキルモノグリシジルエーテル；テトラヒドロフルフリルアルコールグリシジルエーテル等を挙げることができる。

Hydrogenated bisphenol type epoxy resin (hydrogenated benzene ring of bisphenol type epoxy resin such as bisphenol A type epoxy resin, bisphenol F type epoxy resin and bisphenol S type epoxy resin); glycidyl ether of dicyclopentadienephenol novolac Dicyclopentadiene type epoxy resin such as cyclohexanedimethanol diglycidyl ether, aliphatic alkyl-mono or di-glycidyl ether such as butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether; glycidyl methacrylate, Alkyl glycidyl esters such as tertiary carboxylic acid glycidyl ester; styrene oxide; phenyl glycidyl ether, cresyl g Aromatic alkyl monoglycidyl ethers such as ricidyl ether, p-s-butylphenyl glycidyl ether, and nonylphenyl glycidyl ether; tetrahydrofurfuryl alcohol glycidyl ether and the like.

  These epoxy resins having no aromatic ring are preferably used alone or in combination with other epoxy resins, particularly epoxy resins having an aromatic ring. Also in these cases, it is preferable that the epoxy resin is selected so as to include an epoxy resin having two or more epoxy groups in one molecule.

  Furthermore, brominated epoxy resins of the above various epoxy resins, those obtained by modifying the above various epoxy resins with a polyester resin, a phenol resin, a melamine resin, and the like can be exemplified.

  As the epoxy resin (D), it is preferable to select one or two or more types of epoxy resins according to the intended use. Generally, bisphenol type epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins are used. It is preferable to contain at least one selected from epoxy resins and novolac-type epoxy resins.

  A commercially available product can be used as the epoxy resin (D). For example, jER828 (manufactured by Mitsubishi Chemical Corporation), Epototo YD-011 (manufactured by Nippon Steel Chemical Co., Ltd.), YD-902LD (manufactured by Nippon Steel Chemical Co., Ltd.) ), EPPN201 (manufactured by Nippon Kayaku Co., Ltd.) and the like. These may be used individually by 1 type, or may mix and use 2 or more types.

  The epoxy resin may contain other known diluents, and vinyl ethers, oxetane compounds, polyols and the like can be used as appropriate.

  As the aqueous medium (C2) used for the production of the aqueous epoxy resin emulsion, the same aqueous medium (C1) used for the production of the aqueous amine emulsion can be used.

  The aqueous epoxy resin emulsion of the present invention is obtained by emulsifying and dispersing the epoxy resin (D) in the aqueous medium (C2) in the presence of the emulsifier (B2).

  The aqueous epoxy resin emulsion is not particularly limited, but the emulsifier (B2) is preferably 1 to 50% by mass, more preferably based on the total mass of the emulsifier (B2), the epoxy resin (D) and the aqueous medium (C2). Is produced using 10 to 30% by mass of the epoxy resin (D), preferably 1 to 70% by mass, more preferably 20 to 50% by mass.

  In the present invention, the average particle size of the aqueous epoxy resin emulsion is preferably 500 nm or less, particularly preferably 200 to 500 nm, and most preferably 200 to 300 nm. The aqueous epoxy resin emulsion has excellent storage stability and substrate adhesion when the average particle size is in the above range. The “average particle size” of the water-based epoxy resin emulsion is also measured by a dynamic light scattering type measuring device, and is the particle size obtained by analysis by the cumulant method.

  The particle size dispersion of the aqueous epoxy resin emulsion is preferably 1.0 to 1.4, more preferably 1.1 to 1.4, and most preferably 1.2 to 1.4. The particle size dispersion degree of the aqueous epoxy resin emulsion is also a value obtained by Dw / Dn from the weight average particle diameter Dw and the number average particle diameter Dn calculated from the measurement result by the dynamic light scattering type measuring instrument. When the particle size dispersion is within this range, the coarsening of the particles is suppressed, and the storage stability of the aqueous epoxy resin emulsion is easily maintained.

  As a method for emulsifying and dispersing the epoxy resin (D) in the aqueous medium (C2), for example, the emulsifier (B2) and the epoxy resin (D) are added to the aqueous medium (C2), and the mixture is stirred and pre-emulsified. And a method of performing the emulsification such as microfluidization by a high shearing force using a dispersion apparatus after performing the above. Depending on the viscosity of the epoxy resin, the emulsification dispersion treatment may be carried out by lowering the viscosity with an organic solvent such as acetone or ethyl acetate or a reactive diluent for epoxy resin.

  Examples of a dispersion apparatus used for emulsification, particularly main emulsification, include a batch mixer (manufactured by Silverson), a homogenizer (manufactured by IKA), a polytron (manufactured by Kinematica), and a TK auto homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). ) Etc. Batch type emulsifier, Ebara Milder (manufactured by Aihara Seisakusho Co., Ltd.), TK Fillmix, TK Pipeline Homo Mixer (manufactured by Special Machine Industries Co., Ltd.), Colloid Mill (manufactured by Shinko Pantech Co., Ltd.), Thrasher, Trigonal Wet Continuous emulsifiers such as fine pulverizer (Mitsui Miike Kako Co., Ltd.), Captron (Eurotech Co., Ltd.), Fine Flow Mill (Pacific Kiko Co., Ltd.), Static Mixer (Noritake Co.), Microfluidizer (Micro Fluidics), Nanomizer (Nanomizer), APV Gaurin (Gaurin) and other high-pressure milk Machine, membrane emulsifier such as membrane emulsifier (made by Chilling Industries Co., Ltd.), vibratory emulsifier such as Vibro mixer (made by Chilling Industries Co., Ltd.), ultrasonic emulsifier such as ultrasonic homogenizer (made by Branson) etc. Can be mentioned. Among these, preferred from the viewpoint of uniforming the particle size are a microfluidizer, APV gaurin, batch mixer, Ebara milder, and ultrasonic homogenizer.

  As a method of this emulsification, for example, a microfluidizer (manufactured by Microfluidics) may be used. For example, G10Z (minimum flow path width 87 μm) or H210Z (minimum flow path width 210 μm) is used as an interaction chamber, and H30Z (Minimum flow path width 200 μm) or H230Z (minimum flow path width 400 μm) is used as an auxiliary processing module, and the process pressure is processed at 2000 to 30000 psi, preferably 5000 to 20000 psi. A shearing force is applied to the emulsion by passing it through a flow path of several hundred μm under a pressure of 2000 to 30000 psi, so that the aqueous epoxy resin emulsion can be easily emulsified and dispersed to a predetermined particle size with a predetermined particle size dispersion degree. Storage stability is also increased.

<< Aqueous mixed emulsion >>
The aqueous mixed emulsion of the present invention contains the aqueous amine emulsion of the present invention, and can be produced by mixing the aqueous amine emulsion and the aqueous epoxy resin emulsion. The mixing ratio of the aqueous amine emulsion and the aqueous epoxy resin emulsion is not particularly limited. For example, when the aqueous amine emulsion is used as a curing agent, the active hydrogen group of the amine with respect to 1 equivalent of the epoxy group contained in the aqueous epoxy resin emulsion. Is preferably 0.5 to 1.5 equivalents, more preferably 0.8 to 1.2 equivalents. During the curing reaction, heating is performed as necessary.

<Water-based paint, other uses>
The aqueous amine emulsion according to the present invention can be used as a raw material for water-based paints, glass fiber sizing agents, cosmetics, agricultural chemicals, etc., but is preferably used for water-based paints and glass fiber sizing agents, and is used for water-based paints. Is more preferable.

  In these uses, in order to obtain a cured product as a coating film, a binder, etc. from the aqueous amine emulsion of the present invention, the aqueous amine emulsion of the present invention is used as a curing agent, and an aqueous mixture mixed with a main agent composed of an aqueous epoxy resin emulsion. After applying the emulsion to the object, the aqueous medium can be removed, for example, at room temperature or under heating if necessary, and further allowed to stand at room temperature or under heating as necessary to obtain a cured product. When an aqueous amine emulsion using a reactive emulsifier as the emulsifier (B1) and / or an aqueous epoxy resin emulsion using a reactive emulsifier as the emulsifier (B2) is used, when the amine and the epoxy resin are cured, the reactivity is increased. Since the emulsifier reacts and cures simultaneously with the epoxy resin, there is no problem such as bleeding out of the emulsifier, which is particularly preferable.

  Hereinafter, the water-based paint will be described. The aqueous paint of the present invention contains at least the aqueous amine emulsion of the present invention described above and an aqueous epoxy resin emulsion. The water-based paint of the present invention is preferably a two-component paint in which a paint main component containing an aqueous epoxy resin emulsion and a curing agent containing an aqueous amine emulsion are separately provided, and are mixed immediately before use for coating.

  The water-based paint according to the present invention only needs to contain the water-based amine emulsion of the present invention, and is further known pigments, fillers, rust inhibitors, thickeners, dispersants, antifoaming agents, antiseptics. An agent, a film forming aid, a curing accelerator and the like may be contained as necessary. In the case of a two-pack type paint, these additives may be contained in either a paint main agent containing an aqueous epoxy resin emulsion or a curing agent containing an aqueous amine emulsion, but is usually contained in a paint main agent.

  The pigment is not particularly limited and is usually classified into an organic pigment and an inorganic pigment.

  Examples of organic pigments include, for example, insoluble azo pigments such as fast erotic, diazo yellow, diazo orange and naphthol red, phthalocyanine pigments such as copper phthalocyanine, dye lakes such as fanal lake, tannin lake and katanol, isoindolino ero greenish and Illustrative examples include isoindolino pigments such as Isoendolino Yellow Dish, perylene pigments such as quinacridone pigments, perylene cut and perylene maroon.

  Examples of inorganic pigments include carbon black, white lead, red lead, yellow lead, silver vermilion, ultramarine, cobalt oxide, titanium dioxide, titanium yellow, strontium chromate, molybden red, molybten white, iron black, litbon, emerald green, guinea green. And cobalt blue.

  The filler refers to a substance added for the purpose of improving performance or reducing cost, and is not particularly limited. Specific examples include calcium carbonate, magnesium carbonate, silica, talc, clay, and alumina.

  A rust preventive means a substance added to suppress corrosion of a material, and is not particularly limited. For example, red lead, white lead, lead zinc, basic white lead sulfate, basic lead chromate, calcium lead acid, zinc chromate, lead acid cyanamide, powder, dichloromate, barium chromate, sodium nitrite, dicyclohexyl Examples thereof include ammonium nitrile, cyclohexylamine carbonate, rust preventive oil and the like.

  The thickener is not particularly limited. For example, a modified acrylic polymer can be exemplified as an alkali thickening type thickener, and a urethane-modified polyether and polyether can be exemplified as an association type thickening agent. Examples of the alkali thickening agent include hydroxyethyl cellulose (SP600 (trade name) manufactured by Daicel Chemical Industries), SN thickener 615 (trade name) manufactured by San Nopco Co., Ltd., and ASE 60 (commercial product) manufactured by R & H Co., Ltd. Name), KA10K (trade name) manufactured by Henkel Japan Co., Ltd., and the like. Examples of associative thickeners include SN812 (trade name) manufactured by San Nopco, RM8W (trade name) manufactured by R & H, UH752 (trade name) manufactured by ADEKA, and the like. .

  The dispersant is not particularly limited. For example, Primel 850 (trade name) manufactured by Rohm & Haas, Demol EP (trade name) manufactured by Kao Corporation, DISCOAT N-14 (trade name) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (R & H) Orotan 165A (trade name) manufactured by Sanyo Kogyo Co., Ltd. and SN Dispersant 5020 (trade name) manufactured by San Nopco Co., Ltd.

  The antifoaming agent is not particularly limited. Examples include hydrophobic silica, metal soap, amide, modified silicone, silicone compound, polyether, emulsion, and powder. For example, as a hydrophobic silica, Nopco SN deformer 777 (trade name) manufactured by San Nopco Co., Ltd., SN deformer VL (trade name) manufactured by San Nopco Co., Ltd., Nopco NXZ (manufactured by San Nopco Co., Ltd.) as a metal soap system Product name), Amop-based antifoaming agent, Nopco 267-A (trade name) manufactured by San Nopco Co., Ltd., and modified silicone-based antifoaming agent, Shin-Etsu Chemical's silicone KM80 (trade name), silicone compound-based antifoaming agent SN deformer 121N (trade name) manufactured by San Nopco Co., Ltd., SN deformer PC (trade name) manufactured by San Nopco Co., Ltd., and San Nopco Co., Ltd. as an emulsion defoamer. Nopco KF-99 (trade name) manufactured by Sannopco Co., Ltd. SN deformer 14-HP (trade) It can be exemplified the name), and the like.

  The preservative is not particularly limited. For example, ACTICIDE LG (trade name) manufactured by So Japan Co., Ltd., and ACTICIDE MBS (trade name) manufactured by So Japan Co., Ltd. can be exemplified.

  The film forming aid is not particularly limited. For example, 2,2,4-trimethylpentanediol-1,3-monoisobutarate (CS-12 (trade name) manufactured by Chisso Corporation), 2,2,4-trimethylpentanediol-1,3 -Diisobutarate (CS-16 (trade name) manufactured by Chisso Corporation), benzyl alcohol, butyl glycol, 2-ethylhexyl glycol, phenylpropylene glycol, dibutyl diglycol; dipropylene glycol mono n-butyl ether, Organic esters of polyhydric alcohol monoalkyl ethers such as tripropylene monoglycol n-butyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether, diethylene glycol mono n-butyl ether, 3-ethoxypropionic acid esters, acetic acid 3- Methoxy-3 Methyl - butyl, benzoic acid ester, adipic acid-based polyester can be exemplified.

  The curing accelerator is not particularly limited. For example, Accelerator 399, Accelerator 60, XTA-770, Decoupage MNP (trade name) manufactured by Huntsman, Daito Sangral HD-Acc43 (trade name), Tris (dimethylaminomethyl) phenol (trade name) manufactured by Daito Sangyo Co., Ltd. Examples thereof include tertiary amines such as Ancamine K-54 (trade name) manufactured by Air Products and Chemicals.

  The water-based paint according to the present invention can be applied to various base materials, for example, general base materials such as inorganic building materials and metals, and is particularly suitable for sealers for inorganic building materials and the like. As described above, since the aqueous amine emulsion of the present invention has an average particle size as small as 500 nm or less, it penetrates well into inorganic building materials and improves adhesion, so that the water resistance, mechanical strength, etc. of inorganic building materials can be improved. it can. Furthermore, when a reactive emulsifier having an epoxy group in the molecule is used as an emulsifier, the cured emulsifier is fixed in the cured coating film, so that it does not bleed out to the surface of the coating film. Decrease in physical properties and water resistance can be suppressed, and furthermore, there is no concern about environmental contamination due to the emulsifier.

  The water-based paint according to the present invention is also suitable as a primer for metal. As described above, since the aqueous amine emulsion of the present invention has a small average particle diameter of 500 nm or less, the adhesion of the resin to the base material can be improved, and the rust prevention performance can be improved.

  Usually, in order to improve the performance such as weather resistance, chemical resistance, stain resistance, water resistance, rust resistance, etc., the water-based paint according to the present invention is used as an undercoat, and the coating with this undercoat is applied. A top coat can be applied over the membrane. The top coat is not particularly limited as long as it is a known top coat.

  Examples of the top coat include polyester resin paints, silicon polyester resin paints, polyurethane resin paints, acrylic resin paints, and fluororesin paints.

  The water-based paint according to the present invention can be used for various applications, for example, for plastic molded products, home appliances, steel products, large structures, vehicles (for example, solid colors for repairing automobiles and metallic bases). Can be used for various undercoats such as for building use, for clear top use, for building use, for tile use, and for woodworking.

  Examples of the method for applying the water-based paint include dip coating (dipping coating), air spray, airless spray, electrostatic coating, roll coater coating, flow coater coating, roller coating, brush coating, and the like.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited only to these Examples. In the following examples, “part” and “%” mean “part by mass” and “% by mass”, respectively.

<Synthesis of Epoxy Reactive Emulsifier I>
A glass three-necked flask equipped with a thermometer, a stirrer, and a condenser tube was charged with jER828 (148 g) which is a hydrophobic epoxy resin and polyether monoamine JEFFAMINE M-1000 (200 g) which is a hydrophilic monoamine, and 150 Stirring at 6 ° C. for 6 hours gave 340 g of an epoxy-reactive emulsifier (HLB value is 11.8). When the obtained epoxy reactive emulsifier was analyzed by a high speed GPC apparatus HLC-8220GPC equipped with SuperMultipore HZ-M manufactured by Tosoh Corporation, the weight average molecular weight was 7200 in terms of styrene.

<Example 1>
The epoxy-reactive emulsifier I obtained above (3.0 g) is dissolved in 45 g of water, the amine curing agent Daitokural U-5396I (30 g) and hexadecane (1.2 g) are added, and the mixture is stirred at 400 rpm for 20 minutes. And pre-emulsified. The obtained preliminary emulsion was microfluidized at 10000 psi with a microfluidizer equipped with G10Z as an interaction chamber and H210Z as an auxiliary processing module to obtain the target aqueous amine emulsion (AM1).

<Example 2>
The epoxy-reactive emulsifier I (3.0 g) obtained above is dissolved in 45 g of water, the amine curing agent Ditocraal X-7004 (30 g) and hexadecane (1.2 g) are added, and the mixture is stirred at 400 rpm for 20 minutes. And pre-emulsified. The obtained preliminary emulsion was microfluidized at 10000 psi with a microfluidizer equipped with G10Z as an interaction chamber and H210Z as an auxiliary processing module to obtain the target aqueous amine emulsion (AM2).

<Example 3>
The epoxy-reactive emulsifier I obtained above (3.0 g) is dissolved in 45 g of water, the amine curing agent ANCAMINE 2390 (30 g) and hexadecane (1.2 g) are added, and the mixture is stirred at 400 rpm for 20 minutes for preliminary emulsification. Went. The obtained preliminary emulsion was microfluidized at 10000 psi with a microfluidizer equipped with G10Z as an interaction chamber and H210Z as an auxiliary processing module to obtain the desired aqueous amine emulsion (AM3).

<Example 4>
The epoxy-reactive emulsifier I obtained above (3.0 g) is dissolved in 45 g of water, amine Primine 1074 (30 g) and hexadecane (1.2 g) are added, and the mixture is stirred at 400 rpm for 20 minutes for preliminary emulsification. It was. The obtained preliminary emulsion was microfluidized at 10000 psi with a microfluidizer equipped with G10Z as an interaction chamber and H210Z as an auxiliary processing module to obtain the target aqueous amine emulsion (AM4).

<Example 5>
Non-reactive emulsifier Neugen EA-167D (Daiichi Kogyo Seiyaku Co., Ltd., 3.0 g) was dissolved in 45 g of water, and the amine curing agent Daitokural U-5396I (30 g) and hexadecane (1.2 g) were added, followed by 400 rpm. The mixture was stirred for 20 minutes and pre-emulsified. The obtained preliminary emulsion was microfluidized at 10,000 psi with a microfluidizer equipped with G10Z as an interaction chamber and H210Z as an auxiliary processing module to obtain the target aqueous amine emulsion (AM5).

<Example 6>
The epoxy-reactive emulsifier I obtained above (0.60 g) is dissolved in 45 g of water, the amine curing agent Daitoclar U-5596I (30 g) and hexadecane (1.2 g) are added, and the mixture is stirred at 400 rpm for 20 minutes. And pre-emulsified. The obtained preliminary emulsion was microfluidized at 10,000 psi with a microfluidizer equipped with G10Z as an interaction chamber and H210Z as an auxiliary processing module to obtain the target aqueous amine emulsion (AM6).

<Example 7>
The epoxy-reactive emulsifier I obtained above (0.36 g) is dissolved in 45 g of water, the amine curing agent Daitoclar U-5596I (30 g) and hexadecane (1.2 g) are added, and the mixture is stirred at 400 rpm for 20 minutes. And pre-emulsified. The obtained preliminary emulsion was microfluidized at 10,000 psi with a microfluidizer equipped with G10Z as an interaction chamber and H210Z as an auxiliary processing module, to obtain the target aqueous amine emulsion (AM7).

(Comparative Example 1)
The epoxy-reactive emulsifier I obtained above (3.0 g) is dissolved in 45 g of water, the amine curing agent Daitokural U-5396I (30 g) is added, and the mixture is stirred for 20 minutes at 1000 rpm with a disper. An amine emulsion (AM′8) was obtained.

(Comparative Example 2)
Non-reactive emulsifier Neugen EA-167D (3.0 g) is dissolved in 45 g of water, the amine curing agent Daitokural U-5396I (30 g) is added, and the mixture is stirred with a disper at 1000 rpm for 20 minutes to obtain an aqueous amine emulsion. (AM'9) was obtained.

(Comparative Example 3)
The epoxy-reactive emulsifier I obtained above (3.0 g) is dissolved in 45 g of water, the amine curing agent Daitokural X-7004 (30 g) is added, and the mixture is stirred for 20 minutes at 1000 rpm with a disper. An amine emulsion (AM′10) was obtained.

(Comparative Example 4)
The epoxy-reactive emulsifier I (3.0 g) obtained above was dissolved in 45 g of water, the amine curing agent ANCAMINE 2390 (30 g) was added, and the mixture was stirred at 1000 rpm for 20 minutes with a disper to obtain an aqueous amine emulsion ( AM'11) was obtained.

(Comparative Example 5)
The epoxy-reactive emulsifier I (3.0 g) obtained above was dissolved in 45 g of water, and amine Primer 1074 (30 g) was added, followed by stirring at 1000 rpm for 20 minutes with a disper to obtain an aqueous amine emulsion (AM ′ 12) was obtained.

(Comparative Example 6)
A commercially available aqueous amine emulsion (EB30 (product name) manufactured by Henkel Japan) was used (AM'13).

<Measurement of average particle size and particle size dispersion>
With respect to the aqueous amine emulsions obtained in Examples 1 to 7 and Comparative Examples 1 to 6, the average particle size and the particle size dispersion degree were measured by LASER PARTICLE ANALYZER PAR-III manufactured by Otsuka Electronics Co., Ltd. The results are shown in Table 1. In Comparative Examples 4 and 5, phase separation occurred, and the average particle size and particle size dispersion could not be measured.

<Storage stability test>
The aqueous amine emulsions obtained in Examples 1 to 7 and Comparative Examples 1 to 6 were allowed to stand at room temperature, and storage stability was determined based on the presence or absence of sedimentation and aggregation after 30 days. The results are shown in Table 1. The evaluation criteria are as follows.
○: No aggregation or sedimentation of particles.
X: Aggregation and sedimentation of particles are observed.

<Measurement of pot life>
The aqueous amine emulsion obtained above and the aqueous epoxy resin emulsion listed in Table 2 are mixed so that the active amine equivalent and the epoxy equivalent are 1: 1, and water is added so that the solid content of the mixture becomes 40%. Was added. The coating was applied to a glass plate every 30 minutes while stirring at 200 rpm at room temperature, and the time during which a transparent cured coating film could not be obtained after drying at room temperature was measured as the pot life and judged. The results are shown in Table 3. The judgment criteria are as follows.
○: The pot life is longer than 3 hours.
Δ: Pot life is 2 hours or more and 3 hours or less.
X: The pot life is less than 2 hours.

<Adhesion test to inorganic building materials>
The amine emulsion obtained above and the aqueous epoxy resin emulsion listed in Table 2 are mixed so that the active amine equivalent and the epoxy equivalent are 1: 1, and water is added so that the solid content of the mixture becomes 15%. And stirred at room temperature at 200 rpm for 15 minutes. Then, 2.0 g was applied to a 10 × 10 cm calcium plate (specific gravity 0.8), dried at room temperature for 1 day, cured at 130 ° C. for 6 hours, and further cured at room temperature for 3 days. After curing, a top coat (Odefresh Si) was further applied and dried at room temperature for 2 days. On the obtained test plate, a 2 mm square grid (10 × 10 = 100 squares) was scratched with a cutter knife, and after attaching cellophane tape, it was peeled off at an angle of 45 degrees and remained without peeling. The squares were counted and used as an adhesion test. The adhesion test was performed three times, and the average number of remaining cells was calculated and judged. The results are shown in Table 4. The evaluation criteria are as follows.
○: The number of remaining cells is 90 or more.
Δ: The number of remaining cells is 80 or more and less than 90.
X: The number of remaining squares is less than 80.

  As above-mentioned, the aqueous | water-based amine emulsion of Examples 1-7 uses a reactive emulsifier or a non-reactive emulsifier, and was obtained by microfluidization, and an average particle diameter is 500 nm or less. Also, the degree of particle size dispersion is narrow due to the microfluidization treatment. On the other hand, Comparative Examples 1 to 5 use a reactive emulsifier or a non-reactive emulsifier, but are epoxy resin emulsions obtained without microfluidization, and the average particle diameter exceeds 500 nm.

  As shown in Table 1, the aqueous amine emulsions obtained in Examples 1 to 7 did not show particle sedimentation or aggregation even when allowed to stand at room temperature for 30 days, and had good storage stability.

  On the other hand, in the amine emulsions of Comparative Examples 1 to 5 having an average particle diameter exceeding 500 nm, aggregation was observed after 3 days at room temperature.

  Therefore, it was shown that the aqueous amine emulsion can realize high storage stability by making the average particle size 500 nm or less by microfluidization, more preferably by narrowing the particle size dispersion degree.

  In addition, as shown in Table 3, the average particle diameter of both the aqueous amine emulsion and the aqueous epoxy resin emulsion contained in the aqueous mixed emulsion should be 500 nm or less by microfluidization, and more preferably a reactive emulsifier should be used. Can further extend the pot life.

  Furthermore, as shown in Table 4, the average particle diameter of both the aqueous amine emulsion and the aqueous epoxy resin emulsion is reduced to 500 nm or less by microfluidization, more preferably by using a reactive emulsifier. Adhesion can be improved.

  Therefore, it was shown that the aqueous amine emulsion can realize high base material permeability to inorganic building materials by making the average particle size 500 nm or less by microfluidization, and more preferably by narrowing the particle size dispersion degree. Moreover, it was shown that the adhesiveness is further improved by using a reactive emulsifier.

  Thus, the aqueous amine emulsions of Examples 1 to 7 are superior to the aqueous amine emulsions of Comparative Examples 1 to 6 in terms of storage stability, base material permeability and adhesion, and aqueous paints (sealers for inorganic building materials and It proved to be very useful as a coating agent for metals).

Claims (6)

  An aqueous amine emulsion in which an amine is emulsified and dispersed in an aqueous medium in the presence of an emulsifier (B1), and the average particle size is 500 nm or less.   Furthermore, the aqueous | water-based amine emulsion of Claim 1 whose particle size dispersion degree is 1.0-2.0.   The aqueous amine emulsion according to claim 1 or 2, wherein the emulsifier (B1) contains a reactive emulsifier having an epoxy group. An aqueous mixed emulsion comprising the aqueous amine emulsion according to any one of claims 1 to 3 and an aqueous epoxy resin emulsion,
An aqueous mixed emulsion, wherein the aqueous epoxy resin emulsion is obtained by emulsifying and dispersing an epoxy resin in an aqueous medium in the presence of an emulsifier (B2), and has an average particle size of 500 nm or less.   The aqueous mixed emulsion according to claim 4, wherein a particle size dispersion degree of the aqueous epoxy resin emulsion is 1.0 to 1.4.   An aqueous paint comprising the aqueous mixed emulsion according to claim 4.