JP2017043759A - One-packed hardening type epoxy emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide one-packed hardening type epoxy emulsion satisfactory in long period storage stability and low temperature curability and also giving excellent adhesion and hardness to a hardened matter.SOLUTION: Provided is one-packed type hardening type epoxy emulsion comprising: polyepoxide; and a hardening catalyst, in which the hardening catalyst is at least one kind selected from the group consisting of 1,8-diazabicyclo[5.4.0]-7-undecene salt and 1,5-diazabicyclo[4.3.0]-5-nonene salt, and also provided is a hardened matter obtained by hardening the one-packed type epoxy emulsion.SELECTED DRAWING: None

Description

  The present invention relates to a one-part curable epoxy emulsion. More specifically, the present invention relates to a one-part curable epoxy emulsion having excellent storage stability and good low-temperature curability.

Conventionally, when an aqueous dispersion of a compound having an epoxy group such as a glycidyl ether group and a compound having primary and secondary amino groups is mixed to obtain a paint, the reaction between the glycidyl ether group and the amino group proceeds even at room temperature. However, when stored for a long period of time, there is a problem that the viscosity of the paint increases and it cannot be used.
Therefore, in order to improve them, a one-component heat-curable aqueous epoxy resin composition comprising an aqueous dispersion containing an epoxy compound and a latent curing agent of a fine powder dihydrazide compound hardly soluble in water (for example, Patent Document 1) is known.

Japanese Patent Laid-Open No. 11-293092

However, although the technology of Patent Document 1 has improved the storage stability to some extent, there is a problem that a high temperature of 200 ° C. or higher is necessary for complete curing, and it is necessary to solve these problems particularly in paint applications. It was anxious.
An object of the present invention is to provide a one-part curable epoxy emulsion which has good long-term storage stability and low-temperature curability and gives cured products with excellent adhesion and hardness.
In addition, being excellent in storage stability in the present invention means that when left at 60 ° C., the particle size change of the emulsion is small and the viscosity change is small. Moreover, being excellent in low-temperature curability means that a baked cured product at 140 ° C. for 20 minutes is excellent in hardness (pencil hardness) and adhesion.
The above can be evaluated by the method described later.

  The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention comprises a polyepoxide (A) and a curing catalyst (B), and the (B) is 1,8-diazabicyclo [5.4.0] -7-undecene salt (B1) and 1 , 5-diazabicyclo [4.3.0] -5-nonene salt (B2) is a one-component curable epoxy emulsion (X) which is at least one selected from the group consisting of.

The one-component curable epoxy emulsion (X) of the present invention has the following effects.
(1) Excellent storage stability.
(2) Excellent temperature (high temperature, low temperature) dispersion stability.
(3) Good low-temperature curability.
(4) A cured product obtained by curing the emulsion is excellent in hardness and adhesion.

[Polyepoxide (A)]
The polyepoxide (A) in the present invention has at least two epoxy groups in the molecule, and includes an aromatic ring-containing polyepoxide (A1), an aliphatic polyepoxide (A2), an alicyclic ring-containing polyepoxide (A3), and a heterocyclic ring. Examples thereof include polyepoxide (A4) and (co) polymer (A5) having an epoxy group.

As the aromatic ring-containing polyepoxide (A1), polyvalent polyhydridyl ether (A11), aromatic ring-containing polyglycidylamine (A12), and other aromatic ring-containing polyepoxides (A13) having a valence of 10 to 10 or more. And mixtures thereof.
The polyhydric phenol constituting the polyglycidyl ether (A11) of the polyhydric phenol is a divalent to univalent or higher valent carbon number (hereinafter sometimes abbreviated as C) 6 or more and a number average molecular weight [hereinafter Mn Abbreviated. The measurement is based on a gel permeation chromatography (GPC) method under the conditions described below. ] 10,000 or less polyhydric phenols (bisphenol A, -F, -B, -AD and -S, halogenated bisphenol A, pyrogallol, phenol novolac, cresol novolac, etc.), and their polyglycidyl ethers Bisphenol A type polyglycidyl ether (polyglycidyl ether obtained from the reaction of 2 mol of bisphenol A and 3 mol or more of epichlorohydrin), bisphenol F type polyglycidyl ether, bisphenol S type polyglycidyl ether, phenol novolac type poly Examples thereof include glycidyl ether and cresol novolac type polyglycidyl ether.
Examples of other divalent to 10-valent or higher polyglycidyl ethers include polyglycidyl ethers of polyphenols obtained by the condensation reaction of phenol and glioxal, glutaraldehyde or formaldehyde, and polyphenols obtained by the condensation reaction of resorcin and acetone. Examples thereof include polyglycidyl ether.

  Examples of the aromatic ring-containing amine constituting the aromatic ring-containing polyglycidylamine (A12) include C6-30 aromatic ring-containing monovalent to tetravalent or higher aromatic ring-containing polyamines (aniline, 1,3- and / or Or 1,4-phenylenediamine, 2,4- and / or 2,6-tolylenediamine, and the like. Examples of the polyglycidylamine include diglycidylamine [N, N-diglycidylaniline and the like], Tetraglycidyl or higher polyglycidylamine [1,3- and / or 1,4-phenylenetetraglycidylamine, 2,4- and / or 2,6-tolylenetetraglycidylamine, 4,4′-diphenylmethanetetra Glycidylamine, m- and / or p-xylylenetetraglycidylamine, α, α, α ′, '- tetramethyl xylylene tetraglycidyl amine] and the like.

  Furthermore, other aromatic ring-containing polyepoxides (A13) include diglycidyl urethane compounds obtained by addition reaction of tolylene diisocyanate (hereinafter abbreviated as TDI) or diphenylmethane diisocyanate (hereinafter abbreviated as MDI) and glycidol, TDI or Addition of glycidyl group-containing polyurethane (pre) polymer obtained by reacting glycidol and polyol with MDI, addition of alkylene oxide of bisphenol A (hereinafter abbreviated as AO) [ethylene oxide (hereinafter abbreviated as EO) or propylene oxide (hereinafter abbreviated as PO)] The diglycidyl ether of a thing is mentioned.

Examples of the aliphatic polyepoxide (A2) include 2-8 valent polyglycidyl ethers of aliphatic polyhydric alcohols (A21), polyglycidyl esters of aliphatic polycarboxylic acids (A22) and aliphatic polyglycidylamines (A23) and These mixtures are mentioned.
Examples of the polyhydric alcohol constituting the polyglycidyl ether (A21) of the aliphatic polyhydric alcohol include C2 or more and Mn 1,000 or less [ethylene glycol, propylene glycol, tetramethylene glycol, polyethylene glycol, polypropylene glycol, triglyceride. Methylolpropane, glycerin, pentaerythritol, sorbitol (hereinafter abbreviated as EG, PG, TMG, PEG, PPG, TMP, GR, PE, SO, etc.), and the like. As their polyglycidyl ether, diglycidyl ether [ EG diglycidyl ether, PG diglycidyl ether, TMG diglycidyl ether, PEG (Mn 100 to 1,000) diglycidyl ether, PPG (Mn 100 to 1,500) diglycidyl ether Triglycidyl ether [TMP triglycidyl ether and GR triglycidyl ether, etc.], tetra- or higher polyglycidyl ether [PE tetraglycidyl ether, SO polyglycidyl ether, SO polyglycidyl ether, diPE polyglycidyl ether, poly (Polymerization degree 2-20) GR polyglycidyl ether etc.] etc. are mentioned.

Examples of the aliphatic polycarboxylic acid constituting the polyglycidyl ester of the aliphatic polycarboxylic acid (A22) include 2 to 6-valent C4-24 aliphatic polycarboxylic acids [succinic acid, adipic acid, sebacic acid, azelaic acid, Butanetetracarboxylic acid, (meth) acrylic acid, etc.], and polyglycidyl esters thereof include diglycidyl esters [diglycidyl succinate, diglycidyl adipate, diglycidyl sebacate, diglycidyl azelate, etc.], tetraglycidyl esters [ Butanetetracarboxylic acid tetraglycidyl etc.] and unsaturated carboxylic acid glycidyl ester [(meth) acrylic acid glycidyl ester etc.]. Examples of the polyglycidyl ester of the aliphatic polycarboxylic acid include polymers and copolymers of glycidyl esters of unsaturated carboxylic acids such as (meth) acrylic acid glycidyl ester.
Examples of the aliphatic polyglycidylamine (A23) include polyglycidylamines of 2 to 6 and C2-24 aliphatic amines such as tetraglycidylamine of ethylenediamine.

  Examples of the alicyclic ring-containing polyepoxide (A3) include polyepoxides having 2 to 6 valences and C6 to 36 alicyclic ring-containing compounds, and alicyclic ring-containing unsaturated hydrocarbon polyepoxides having 2 to 6 C6 to 24 per molecule. Polyepoxides of hydrocarbons having one or more double bonds [vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, etc.], polyepoxides of alicyclic ethers and alicyclic esters [bis (2,3- Epoxycyclopentyl) ether, EG bisepoxydicyclopentyl ale, 3,4-epoxy-6-methylcyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, bis (3,4-epoxy-6- Methylcyclohexylmethyl) adipate, etc.], the aromatic ring Nuclear hydrogenation product of organic polyepoxides is also included.

  Examples of the heterocyclic ring-containing polyepoxide (A4) include divalent to hexavalent C5-30, such as trisglycidylmelamine.

  As the (co) polymer (A5) having an epoxy group, an unsaturated monomer (a1) having an epoxy group, which will be described later, is a structural unit, and an unsaturated monomer (a2) other than (a1) if necessary. ) As a structural unit. The number average molecular weight (Mn) of (A5) is preferably 3,000 to 300,000, more preferably 6,000 to 200,000, and particularly preferably 12 from the viewpoints of hardness, adhesion, and low temperature curability. , 100,000 to 100,000.

Unsaturated monomer having an epoxy group (a1):
For example, glycidyl (meth) acrylate.

Examples of the unsaturated monomer (a2) other than (a1) include the following (a21) to (a26).
(A21) (Meth) acrylate:
Those having 4 to 30 carbon atoms [hereinafter sometimes abbreviated as C], such as alkyl (C1-18) (meth) acrylate, alkoxy (C1-4) alkyl (C1-18) (meth) acrylate;

(A22) (Meth) acrylamide compound:
C4-18, for example, N-alkyl (C1-5) (meth) acrylamide, N-alkenyl (C2-5) (meth) acrylamide, alkoxy (C1-4) alkyl (C1-5) (meth) acrylamide , N, N-dialkyl (C1-5) (meth) acrylamide, aminoalkyl (C1-5) (meth) acrylamide;

(A23) Vinyl ethers of C6-30, such as vinyl alkyl (C4-20) ethers;

(A24) Unsaturated hydrocarbon Aliphatic (C2-30, such as ethylene, propylene, isobutylene, isoprene), aromatic (C8-30, such as styrene, α-methylstyrene, p-methoxystyrene, vinyl Toluene, p-hydroxystyrene, p-acetoxystyrene), alicyclic (C8-30, eg vinylcyclohexane);
(A25) Vinyl ester:
C4-30, such as vinyl acetate, vinyl propionate.

(A26) Unsaturated carboxylic acid:
For example, C3-20 unsaturated monocarboxylic acid [(meth) acrylic acid (meaning acrylic acid and / or methacrylic acid; the same shall apply hereinafter), crotonic acid, cinnamic acid, vinylbenzoic acid, 3-methyl-3- Butenoic acid, 3-pentenoic acid, 4- and 5-hexenoic acid, vinyl acetic acid, etc.], monoalkyl (C1-8) esters of unsaturated dicarboxylic acids (C5-16, such as monoalkyl maleate, monoalkyl fumarate) Ester, citraconic acid monoalkyl ester), unsaturated dicarboxylic acid monoester having a hydroxyl group (C5-20, such as diethylene glycol monoester of maleic acid, diethylene glycol monoester of fumaric acid, diethylene glycol monoester of itaconic acid, etc.)]; C4-20 (Preferably C4-16) unsaturated dicar Phosphate [maleic acid, fumaric acid, citraconic acid, itaconic acid]; trivalent or more, and the like unsaturated polycarboxylic acids C5～20 (eg aconitic acid).

  Of the above (a2), from the viewpoints of hardness and adhesion, (a21), (a24), (a21) and (a24) are used in combination, and alkyl (C1-18) (meth) is particularly preferable. A combination of acrylate, styrene, alkyl (C1-18) (meth) acrylate and styrene.

  Among the polyepoxides (A), from the viewpoints of storage stability of the emulsion (X) described later, adhesion of the cured product, and hardness, an aromatic ring-containing polyepoxide (A1) is more preferable, and a polyhydric polyphenol is more preferable. Glycidyl ether (A11), particularly preferred are bisphenol A, bisphenol F, bisphenol S, phenol novolac and cresol novolac type polyglycidyl ether.

  Among the polyepoxides (A), Mn in the case of (A1) to (A4) is preferably from 500 to 20,000, more preferably from 700 to 10,000, particularly preferably from the viewpoint of the hardness and emulsifiability of the cured product. Is 900 to 7,000, most preferably 1,000 to 4,000.

Mn in the present invention is measured by the GPC method under the following conditions.
Apparatus: “Alliance” Nippon Waters Co., Ltd. Column: Guardcolumn Super H-L
TSKgel Super H4000
TSKgel Super H3000
TSKgel Super H2000
(The above columns are connected in series.)
Solvent: Tetrahydrofuran (THF)
Reference substance: Polystyrene sample solution: 0.25 wt% tetrahydrofuran (THF) solution Column temperature: 40 ° C.

The number of epoxy groups in (A) is preferably 2 to 30, more preferably 4 to 10, from the viewpoints of the adhesion of the cured product, the hardness, and the storage stability of the emulsion (X).
The epoxy equivalent of (A) (unit: g / eq. Only numerical values are shown below) is preferably 100 to 10,000 from the viewpoint of the storage stability of the emulsion (X), the adhesion of the cured product, and the hardness. More preferably, it is 200-2,000.

[Curing catalyst (B)]
The curing catalyst (B) in the present invention contains 1,8-diazabicyclo [5.4.0] -7-undecene salt (B1) and 1,5-diazabicyclo [4.3.0] -5-nonene salt (B2). At least one selected from the group consisting of:

  The curing catalyst (B) is a salt of 1,8-diazabicyclo [5.4.0] -7-undecene (hereinafter sometimes abbreviated as DBU) and the following (b1) to (b4), , 5-diazabicyclo [4.3.0] -5-nonene (hereinafter sometimes abbreviated as DBN) and the following salts (b1) to (b4).

(B1) Carboxylic acid:
(B1) is a C1-10 (preferably C1-4) carboxylic acid such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, odorous acid, lactic acid, apple Acid, citric acid, benzoic acid, salicylic acid, octylic acid, orthophthalic acid, terephthalic acid, isophthalic acid, gallic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, pyruvic acid, aconite Examples include acids.

(B2) Sulfonic acid:
Examples of (b2) include methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid.
(B3) Phenol:
Examples of (b3) include unsubstituted phenol (b31), substituted phenol (b32) [as the substituent, an alkyl or alkoxy group having 1 to 20 carbon atoms, a hydroxyl group and / or a halogen atom (a fluorine atom, a chlorine atom and Bromine atom etc.)], polynuclear phenol (b33), and novolak (b34).

(B31) Unsubstituted phenol:
Examples of (b31) include phenol and naphthol.
(B32) Substituted phenol:
As (b32), nonylphenol, hydroquinone, catechol, resorcin, bisphenol A, bisphenol F, bisphenol S, triphenol, nonylphenol, octylphenol, dinonylphenol, 1,4-bis (1-hydroxy-1-methyl-ethyl) benzene 4,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxybenzophenone, 2-methyl 1-naphthol, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6- Examples include dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and 2-hydroxy-6-naphthoic acid.
(B33) Polynuclear phenol:
Examples of (b33) include 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,3,3-tetrakis (4-hydroxyphenyl) propane and the like.
(B34) Novolak:
Examples of (b34) include phenol novolak, cresol novolak, resorcin novolak, bisphenol A novolak, and other novolaks obtained by condensation reactions of various phenols with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde, and glyoxal [for example, 2, 4 -Bis (hydroxymethyl) phenol, 2,6-bis (hydroxymethyl) phenol, 2,6-bis (hydroxymethyl) -4-methylphenol, 2,4-bis (hydroxymethyl) -6 methylphenol, 2, 6-hydroxymethyl] -4-t-butylphenol, etc.].

(B4) Acids other than the above (b1) to (b3):
Examples of (b4) include tetraphenylboric acid, tetrafluoroboric acid, hexafluorophosphoric acid, carbonic acid, hydrochloric acid, phosphoric acid, sulfuric acid, and nitric acid.

Among the above (b1) to (b4), formic acid, acetic acid, octyl are preferable from the viewpoint of storage stability, temperature dispersion stability, low-temperature curability, adhesion of the cured product, and hardness of the emulsion (X) described later. Acid, orthophthalic acid, toluenesulfonic acid, phenol, phenol novolac, tetraphenylboric acid, and more preferred are octylic acid and orthophthalic acid.
In addition, said (b) may be used individually by 1 type, or may use 2 or more types together.

[Nonionic surfactant (C)]
Examples of the nonionic surfactant (C) in the present invention include an alkylene oxide addition type nonionic surfactant (C1) and a polyvalent alcohol type nonionic surfactant (C2).

  The alkylene oxide addition type nonionic surfactant (C1) is a polyalkylene glycol obtained by directly adding AO to a higher alcohol, higher fatty acid, alkylamine or the like, or by adding AO to a glycol. By reacting higher fatty acids or the like with the alcohol, or by adding alkylene oxide (AO) to the esterified product obtained by reacting the higher alcohol with the polyhydric alcohol, or by adding AO to the higher fatty acid amide. can get.

  Examples of the AO include ethylene oxide (EO), propylene oxide (PO), and butylene oxide. Of these, EO and random or block adducts of EO and PO are preferred. The number of moles of AO added is preferably 10 to 50 moles, and 50 to 100% of the AO is preferably EO.

  Specific examples of the alkylene oxide addition type nonionic surfactant include oxyalkylene alkyl ethers (for example, octyl alcohol EO adduct, lauryl alcohol EO adduct, stearyl alcohol EO adduct, oleyl alcohol EO adduct, lauryl Alcohol EO / PO block adducts); polyoxyalkylene higher fatty acid esters (eg, oleic acid EO adduct, stearic acid EO adduct, lauric acid EO adduct); polyoxyalkylene polyhydric alcohol higher fatty acid esters (eg, Lauric acid diester of polyethylene glycol, oleic acid diester of polyethylene glycol, stearic acid diester of polyethylene glycol); polyoxyalkylene alkylphenyl ether (eg, nonylphenol EO) Adducts, nonylphenol EO / PO block adducts, octylphenol EO adducts, bisphenol A EO adducts, dinonylphenol EO adducts, styrenated phenol EO adducts); polyoxyalkylene alkylamino ethers and (eg, lauryl) Amine EO adducts, stearylamine EO adducts); polyoxyalkylene alkyl alkanolamides (for example, EO adducts of hydroxyethyl lauric acid amide, EO adducts of hydroxypropyl oleic acid amide, EO addition of dihydroxyethyl lauric acid amide) Thing) etc. are mentioned.

  Examples of the polyhydric alcohol type nonionic surfactant (C2) include polyhydric alcohol fatty acid ester, polyhydric alcohol fatty acid ester AO adduct, polyhydric alcohol alkyl ether, polyhydric alcohol alkyl ether AO adduct. .

  Specific examples of polyhydric alcohol fatty acid esters include pentaerythritol monolaurate, pentaerythritol monooleate, sorbitan monolaurate, sorbitan monostearate, sorbitan monolaurate, sorbitan dilaurate, sorbitan dioleate, sucrose monostearate, etc. Is mentioned. Specific examples of polyhydric alcohol fatty acid ester AO adducts include trimethylolpropane monostearate EO / PO random adduct, sorbitan monolaurate EO adduct, sorbitan monostearate EO adduct, sorbitan distearate EO adduct And sorbitan dilaurate EO / PO random adduct. Specific examples of the polyhydric alcohol alkyl ether include pentaerythritol monobutyl ether, pentaerythritol monolauryl ether, sorbitan monomethyl ether, sorbitan monostearyl ether, methyl glycoside, lauryl glycoside and the like. Specific examples of the polyhydric alcohol alkyl ether AO adduct include sorbitan monostearyl ether EO adduct, methyl glycoside EO / PO random adduct, lauryl glycoside EO adduct, stearyl glycoside EO / PO random adduct, and the like.

  Mn of (C) is preferably 500 to 20,000, more preferably 1,000 to 15, from the viewpoint of the dispersibility (emulsifying power) of (A) and (B) and the storage stability of emulsion (X). 000.

  (C) hydrophile-lipophile balance [hereinafter abbreviated as HLB. It shows a balance between hydrophilicity and lipophilicity (hydrophobicity). ] Is preferably 5 to 19 and more preferably 7 to 18 from the viewpoint of optimizing dispersibility (emulsifying power).

The HLB can be determined by the method of Oda described in “Introduction to Surfactants” (Takehiko Fujimoto, Sanyo Chemical Industries, Ltd., 2007, page 212).
That is, using the inorganic (hydrophilic) or organic (hydrophobic) numerical value of each functional group (see Tables 3, 3 and 11 of the above literature), the type of hydrophobic group in the surfactant (C) And the inorganic value is calculated | required from the content, and the organic value is calculated | required from the kind and content of a hydrophilic group, and HLB is calculated by the following formula | equation.

HLB = 10 × (inorganic / organic)

[One-part curable epoxy emulsion (X)]
The one-component curable epoxy emulsion (X) of the present invention contains the polyepoxide (A) and the curing catalyst (B), and the (B) is 1,8-diazabicyclo [5.4.0]. It is at least one selected from the group consisting of a -7-undecene salt (B1) and a 1,5-diazabicyclo [4.3.0] -5-nonene salt (B2).
In addition, the one-part curable epoxy emulsion (X) includes the aqueous dispersion (A0) of (A), the aqueous dispersion (B0) of (B) and / or aqueous from the viewpoint of industrial and storage stability. What contains a medium solution (B00) is preferable.
Here, the aqueous dispersion refers to a dispersion of (A) particles and, if necessary, (B) particles in an aqueous medium, and includes an emulsion.
The aqueous medium includes water and a mixture of water containing water as a main component (50% by weight or more) and an organic solvent described later.

Specific examples of the production method (X) include the following methods [1] to [4].
[1] Add an organic solvent to the polyepoxide (A) if necessary, and further add a nonionic surfactant (C), for example, at 35 to 45 ° C., and gradually add water dropwise while stirring. Phase inversion emulsification. Next, the organic solvent is distilled off by reducing the pressure while heating as necessary to obtain an aqueous dispersion (A0) of the polyepoxide (A).
On the other hand, if necessary, an organic solvent is added to the curing catalyst (B), and a nonionic surfactant (C) is further added, for example, at 35 to 45 ° C. while water is gradually added dropwise. Phase inversion emulsification. Next, the organic solvent is distilled off by reducing the pressure while heating as necessary to obtain an aqueous dispersion (B0) of the curing catalyst (B).
A method of producing an epoxy emulsion (X) by mixing these (A0) and (B0).

[2] An aqueous solution or water of a nonionic surfactant (C) is added to (A) to which an organic solvent is added if necessary, and dispersed with a normal disperser, and the organic solvent is distilled off as necessary. Thus, an aqueous dispersion (A0) of (A) is obtained.
On the other hand, (B), to which an organic solvent is added, if necessary, is added with the aqueous solution or water of (C) and dispersed by a normal disperser, and the organic solvent is distilled off as necessary to obtain an aqueous solution of (B). Dispersion (B0) is obtained.
A method of producing an epoxy emulsion (X) by mixing these (A0) and (B0).

[3] (B), to which an organic solvent is added, if necessary, is added with the aqueous solution or water of (C) and dispersed with a normal disperser, and the organic solvent is distilled off if necessary. An aqueous dispersion (B0) is obtained.
If necessary, (C) and / or (A) containing an organic solvent is added to the aqueous dispersion (B0) and dispersed from a normal disperser. If necessary, the organic solvent is distilled off, A method for producing an epoxy emulsion (X).

  In the production methods [1] to [3] above, the aqueous dispersion (B0) of (B) may be the aqueous medium solution (B00) of (B), or (B0) and (B00) may be used in combination. The aqueous medium solution (B00) of (B) can be obtained by mixing the curing catalyst (B) and the aqueous medium.

[4] (A) and (B), each of which is added with an organic solvent, if necessary, are added to the aqueous solution of (C) and dispersed by an ordinary disperser, and the organic solvent is distilled off as necessary. The method for producing the epoxy emulsion (X).
In any of the methods [1] to [4], the organic solvent may remain as long as the effects of the present invention are not impaired, but it is preferable to distill off the organic solvent from the viewpoint of storage stability. .
Of the above [1] to [4], the methods [1] and [2] are preferable from the viewpoint of industrial and storage stability, and the method [1] is more preferable.

Examples of the organic solvent in the above production method include those having C1-10, such as alcohol (methanol, isopropanol, etc.), ketone (acetone, methylmethylketone, etc.), tetrahydrofuran, dioxane, and ethyl acetate.
Of these, methanol, acetone, and methyl ethyl ketone are preferable from the viewpoint of solvent removal.

Based on the weight of the epoxy emulsion (X) of the present invention, the weight of (A) is preferably 10 to 79.9%, more preferably from the viewpoint of the storage stability of (X), the hardness of the cured product, and the adhesion. 20 to 50%.
Further, the weight of (B) based on the weight of the epoxy emulsion (X) is preferably 0.1 to 25% from the viewpoint of the storage stability, temperature dispersion stability, hardness of the cured product, and adhesion of (X). More preferably, it is 1 to 10%.

  Furthermore, the total weight of (A) and (B) based on the weight of the epoxy emulsion (X) is preferably 20 to 80%, more preferably 30 to 60, from the viewpoint of the storage stability and paintability of (X). %.

  Further, the weight of the nonionic surfactant (C) based on the total weight of (A) and (B) is preferably 0.1 to 30% from the viewpoint of storage stability and paintability of (X). More preferably, it is 2 to 10%.

The viscosity (mPa · s) of (X) at 25 ° C. is preferably 1,000 to 100,000, and more preferably 2,000 to 5,000, from the viewpoint of sagging prevention and handling properties.
In addition, the median particle diameter (unit: μm; only numerical values are shown below) of the particles (A) and (B) in (X) is preferably from the viewpoint of the viscosity and storage stability of (X). It is 0.1-50, More preferably, it is 0.2-20. The median particle diameter can be measured by a laser diffraction / scattering particle size distribution measuring apparatus described later.

[Additive (E)]
In the one-component curable epoxy emulsion (X) of the present invention, a surfactant other than the above (C), a filler, an antiseptic, a heat stabilizer, a weather stabilizer, if necessary, as long as the effects of the present invention are not impaired. 1 type, or 2 or more types of additives (E) chosen from the group which consists of a coloring agent, a thickener, a leveling agent, an antifoamer, a viscoelasticity modifier, and a dynamic surface tension regulator can be contained. .
The (E) can be added at any stage of the production process (X).
The total content of the additive (E) is usually 30% or less, preferably 0.01 to 20%, more preferably 0.1 to 10 based on the total weight of the epoxy emulsion (X) after addition of the additive. %.

Examples of the surfactant (E1) other than the above (C) include known anions and cationic surfactants.
The content of (E1) is usually 10% or less, preferably 0.01 to 3%, based on the total weight of the epoxy emulsion (X) after addition of the additive.

Examples of the filler (E2) include sodium carbonate and silica.
The content of (E2) is usually 10% or less, preferably 0.01 to 3%, based on the total weight of the epoxy emulsion (X) after addition of the additive.

Examples of the preservative (E3) include methyl paraben and ethyl paraben.
The content of (E3) is usually 10% or less, preferably 0.01 to 3%, based on the total weight of the epoxy emulsion (X) after addition of the additive.

Examples of the heat resistance stabilizer (E4) include tris (2,4-di-t-butylphenyl) phosphate, dioctadecyl-3,3′-thiodipropionate and the like.
The content of (E4) is usually 10% or less, preferably 0.01 to 3%, based on the total weight of the epoxy emulsion (X) after addition of the additive.

As the weather resistance stabilizer (E5), ultraviolet absorbers such as salicylic acid compounds (phenyl salicylate, p-tert-butylphenyl salicylate, etc.), benzophenones (2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, etc.), Benzotriazole compounds [2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, etc.], cyanoacrylate compounds (2-ethylhexyl- 2-cyano-3,3′-diphenyl acrylate, etc.); light stabilizers such as hindered amines [octylated diphenylamine, isooctyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) propionate, etc.] It is done.
The content of (E5) is usually 10% or less, preferably 0.1 to 3%, based on the total weight of the epoxy emulsion (X) after addition of the additive.

Colorants (E6) include pigments and dyes. Among pigments, inorganic pigments include titanium oxide, talc, zinc phosphate, carbon black, chromium oxide, ferrite, etc .; organic pigments include azo pigments (azo lake, monoazo, disazo, chelate azo, etc.), polycyclic And formula pigments (benzimidazolone, phthalocyanine, quinacridone, dioxazine, isoindolinone, thioindigo, perylene, quinophthalone, anthraquinone, etc.).
Examples of the dye include nigrosine and aniline.
The content of (E6) is usually 60% or less, preferably 1 to 40%, based on the total weight of the epoxy emulsion (X) after addition of the additive.

Examples of the thickener (E7) include montmorillonite and colloidal alumina.
The content of (E7) is usually 10% or less, preferably 0.01 to 5%, based on the total weight of the epoxy emulsion (X) after addition of the additive.

As the leveling agent (E8), Mn is preferably 100 to 1,000, polyolefin resin [polyethylene, polypropylene, etc.], olefin- (meth) acrylic acid copolymer [ethylene- (meth) acrylic acid copolymer, etc. ], Polyvinylpyrrolidone, etc. are mentioned.
The content of (E8) is usually 6% or less, preferably 0.01 to 3%, based on the total weight of the epoxy emulsion (X) after the addition of the additive.

Examples of the antifoaming agent (E9) include mineral oil defoaming agents and silicone oil defoaming agents.
The content of (E9) is usually 6% or less, preferably 0.01 to 3%, based on the total weight of the epoxy emulsion (X) after addition of the additive.

As the viscoelasticity adjusting agent (E10), a polymer type (Mn 10,000-500,000, for example, polycarboxylic acid, polysulfonic acid, polyether-modified carboxylic acid, polyether), association type (Mn 10,000-500). 1,000, for example, urethane-modified polyether).
The content of (E10) is usually 10% or less, preferably 0.01 to 5%, based on the total weight of the epoxy emulsion (X) after the addition of the additive.

Examples of the dynamic surface tension adjusting agent (E11) include acetylene glycol and fluorine-containing compound silicone-containing compounds. The dynamic surface tension adjusting agent has a function of reducing the surface tension.
The content of (E11) is usually 20% or less, preferably 0.01 to 10%, based on the total weight of the epoxy emulsion (X) after addition of the additive.

The one-part curable epoxy emulsion (X) of the present invention is excellent in storage stability, low-temperature curability, and physical properties (hardness, adhesion) of a cured product, and thus various uses (for example, for paints, adhesives, primers). In particular, it can be suitably used for paints.
In addition, as shown in the examples described later, since it has excellent temperature (high temperature, low temperature) dispersion stability, it has a characteristic that it is easy to store and manage the industrial (X).

[Cured product]
The cured product of the present invention is obtained by curing the one-component curable epoxy emulsion (X). The (X) can be applied using a spray coating machine, which is a conventional water paint coating equipment or solvent paint coating equipment, and does not require new equipment.
As a coating method, the wet film thickness (film thickness immediately after coating) is preferably 10 to 200 μm, more preferably 20 to 100 μm, from the viewpoint of coating effect and industry, with respect to the object to be coated (X). The method of spray-coating so that

The coated article is preferably 100 to 180 ° C., more preferably 120 to 160 ° C. from the viewpoint of curability of the cured product and industrial, and preferably 5 to 60 from the same viewpoint. Minute, more preferably 8 to 30 minutes, particularly preferably 10 to 20 minutes, a cured product can be formed.
The film thickness of the cured product after curing is preferably 10 to 150 μm, more preferably 15 to 50 μm, from the viewpoint of coating effect and industrial viewpoint.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this. In the following, “parts” represents parts by weight, and “%” represents% by weight.

[Aqueous dispersion of polyepoxide (A0)]
<Production Example 1>
A container is charged with 9.0 parts of methyl ethyl ketone (hereinafter abbreviated as MEK), and cresol novolac-type polyglycidyl ether (A-1) [trade name “EOCN-104S”, manufactured by Nippon Kayaku Co., Ltd., Mn 2,000, epoxy Equivalent 220, hereinafter the same] 66.5 parts were added and dissolved, and styrenated phenol EO 17 mol adduct (C-1) [trade name “Sunspear ST-36”, manufactured by Sanyo Chemical Industries, Ltd. Same as above] 3.5 parts was added and stirred at 40 ° C. for 30 minutes. Thereafter, 30 parts of water was added dropwise at the same temperature over 2 hours to effect phase inversion emulsification, and the solvent was removed at 50 ° C. under reduced pressure (30 kPa or less, the same applies hereinafter) for 2 hours to obtain an aqueous solution of (A-1). Dispersion (A0-1) (solid content concentration: 70%) was obtained. The median particle diameter of the particles in (A0-1) was 0.3 μm.

<Production Example 2>
In production example 1, except that (A-1) was replaced with bisphenol A type polyglycidyl ether (A-2) [trade name “JER1001”, manufactured by Mitsubishi Chemical Corporation, Mn950, epoxy equivalent 475, the same below] Obtained the aqueous dispersion (A0-2) (solid content concentration 70%) of (A-2) in the same manner as in Production Example 1. The median particle diameter of the particles in (A0-2) was 0.4 μm.

<Production Example 3>
56. MEK 6.0 parts was charged in a container, and bisphenol F type polyglycidyl ether (A-3) [trade name “JER4010P”, manufactured by Mitsubishi Chemical Corporation, Mn 8,800, epoxy equivalent 4,400, the same shall apply hereinafter] Add 0 parts to dissolve, add EO18 mol adduct (C-2) of bisphenol A [trade name “New Pole BPE-180”, manufactured by Sanyo Chemical Industries, Ltd., hereinafter the same] 14.0 parts And stirred at 40 ° C. for 30 minutes. Thereafter, 30 parts of water was added dropwise at the same temperature over 2 hours to phase inversion emulsification, and the solvent was removed at 50 ° C. under reduced pressure for 2 hours to obtain an aqueous dispersion (A0-3) (A-3) (Solid content concentration 70%) was obtained. The median particle diameter of the particles in (A0-3) was 0.5 μm.

<Production Example 4>
In an autoclave equipped with a reflux apparatus, 492 parts of an EO6 mol adduct of bisphenol A [trade name “New Pole BPE-60”, manufactured by Sanyo Chemical Industries, Ltd.] and 833 parts of epichlorohydrin were charged with stirring. The product was refluxed at 120 ° C. 203 parts of 40% aqueous sodium hydroxide solution was added dropwise over 4 hours. The dropping was performed while removing distilled water. After completion of dropping, unreacted epichlorohydrin was distilled off under reduced pressure conditions at 120 ° C. and cooled to 25 ° C. Further, 1,000 parts of toluene was charged.
Next, after adding 1,000 parts of water and stirring for 1 hour, stirring was stopped and liquid-separated by standing for 1 hour, the lower layer was extracted, and operation which removes a production | generation salt and a residual alkali was performed. This operation was performed 5 times in total.
Further, toluene was distilled off at 120 ° C. under reduced pressure to obtain an EO 6 mol adduct diglycidyl ether (A-4) (epoxy equivalent 302) of bisphenol A.
Next, 85 parts of (A-4) and 15 parts of water were stirred at a high speed for 3 minutes at 70 ° C. and 20,000 rpm using a disperser [trade name “CLEAMIX” manufactured by M Technique Co., Ltd.]. Thus, an aqueous dispersion (A0-4) of (A-4) (solid content concentration: 85%) was obtained. The median particle diameter of the particles in (A0-4) was 0.6 μm.

<Production Example 5>
In a separable flask equipped with a dropping funnel for monomer dispersion, a dropping funnel for initiator solution, a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, 369.4 parts of ion-exchanged water, Aqualon KH-1025 [No. Manufactured by Ichiko Pharmaceutical Co., Ltd.] 1.6 parts (solid content: 0.4 part) and 4.0 parts of sodium hydrogen carbonate were charged. The mixture was stirred while blowing nitrogen, and the temperature was raised to 70 ° C.

  Next, 201.3 parts of ion-exchanged water, 8.0 parts of a surfactant [Eleminol CLS-20, manufactured by Sanyo Chemical Industries, Ltd.], 48.8 parts of methyl methacrylate, 224.0 parts of styrene, , 60.0 parts of glycidyl methacrylate, 63.2 parts of butyl acrylate, and 4.0 parts of 1-dodecanethiol were prepared, and after the monomer dispersion was prepared and stirred, it was charged into the dropping funnel for monomer dispersion, Of this, 30.5 parts was added to the separable flask.

Next, an initiator solution consisting of 0.9 parts of ammonium persulfate and 8.1 parts of ion-exchanged water, a reducing agent solution consisting of 0.2 parts of sodium thiosulfate pentahydrate and 6.6 parts of ion-exchanged water. Were added to the dropping funnel for the initiator solution and the dropping funnel for the reducing agent solution, respectively, added to the separable flask in order, the polymerization was started, and the remaining temperature was maintained at 70 ± 2 ° C. The monomer dispersion was added dropwise at a constant rate over 3 hours. Thereafter, stirring was continued for 90 minutes at the same temperature, and then the mixture was cooled to room temperature to obtain 1000 parts (solid content concentration: 40% by weight) of the aqueous dispersion (A0-5) of (A-5).
The median particle diameter of the dispersed particles of (A-5) in (A0-5) was 0.2 μm.
Moreover, the epoxy equivalent of (A-5) was 938 g / eq, and Mn of (A-5) was 9,000.

  The results of Production Examples 1 to 5 are shown in Table 1.

[Curing catalyst (B)]
<Production Example 6>
A reaction vessel was charged with 25 parts of water and 75 parts of 1,8-diazabicyclo [5.4.0] -7-undecenephenol salt (B1-1) and stirred at 40 ° C. for 1 hour (B1-1). An aqueous medium solution (B00-1) (solid content concentration 75%) was obtained.

<Production Example 7>
In Production Example 6, 25 parts of water and 75 parts of (B1-1) were converted to 15 parts of water and 85 parts of 1,8-diazabicyclo [5.4.0] -7-undecene orthophthalate (B1-2). Except having replaced, it carried out similarly to manufacture example 6, and obtained the aqueous medium solution (B00-2) (solid content concentration 75%) of (B1-2).

<Production Example 8>
In the same manner as in Production Example 6, except that 75 parts of (B1-1) was replaced with 75 parts of 1,5-diazabicyclo [4.3.0] -5-nonenephenol salt (B2-1) in Production Example 6. , (B2-1) aqueous medium solution (B00-3) (solid content concentration 75%) was obtained.

<Production Example 9>
In the same manner as in Production Example 6, except that 75 parts of (B1-1) was replaced with 75 parts of 1,5-diazabicyclo [4.3.0] -5-nonene octylate (B2-2) in Production Example 6. Thus, an aqueous medium solution (B00-4) (solid content concentration 75%) of (B2-2) was obtained.

<Production Example 10>
A reaction vessel was charged with 25 parts of MEK and 25 parts of 1,8-diazabicyclo [5.4.0] -7-undecenephenol novolak salt (B1-3), and stirred at 40 ° C. for 1 hour (B1-3). An MEK dispersion (solid content concentration 50%) was obtained.
Further, 2 parts of (C-1) was added and stirred at 40 ° C. for 30 minutes. Thereafter, 73 parts of water was added dropwise at the same temperature over 2 hours to effect phase inversion emulsification, and the solvent was removed at 50 ° C. under reduced pressure for 2 hours to obtain an aqueous dispersion (B0-5) of (B1-3) (Solid content concentration 27%) was obtained. The median particle diameter of the particles in (B0-5) was 0.6 μm.

<Comparative Production Example 1>
In Production Example 6, 25.0 parts of water, 75.0 parts of (B1-1), 25.0 parts of water, 1,8-diazabicyclo [5.4.0] -7-undecene (ratio B-1) 75. An aqueous medium solution (ratio B00-1) (solid content concentration 75%) of (ratio B-1) was obtained in the same manner as in Production Example 6 except that the amount was changed to 0 part.

  The results of Production Examples 6 to 10 and Comparative Production Example 1 are shown in Table 2.

Examples 1-8, Comparative Examples 1-2
Formulated and mixed according to Table 3 (temperature 25 ° C., stirring time 30 minutes), and one-component curable epoxy emulsions (X-1) to (X-8), (ratio X-1) to (ratio X-2). Obtained. Each emulsion was evaluated for performance by the following test method. The results are shown in Table 3.

<Test method>
(1) Median particle diameter of emulsion particles The median particle diameter of emulsion particles is determined by using a laser diffraction / scattering particle size distribution measuring apparatus [trade name “LA-700”, manufactured by Horiba, Ltd.] applying light scattering theory. (Unit: μm).

(2) Storage stability of emulsion The storage stability was evaluated based on the operation of normal temperature storage stability of JIS K5600-2-7. That is, the median particle diameter and viscosity of the emulsion filled in 180 ml in a sealable glass container having a capacity of 225 ml and an inner diameter of 5 cm and allowed to stand at 60 ° C. for 20 days were evaluated.
(2-1) Median particle diameter The median particle diameter was measured by the measurement method of (1), and the degree of increase in median particle diameter before and after the test was evaluated according to the following evaluation criteria.
<Evaluation criteria>
A: Increase in median particle size is less than 10% B: Increase in median particle size is 10% or more and less than 20% Δ: Increase in median particle size is 20% or more and less than 50% X: Increase in median particle size is 50% or more (2 -2) Viscosity Viscosity at 25 ° C. was measured according to JIS K7117-1 using a BL type viscometer [model number “DVL-BII”, manufactured by Toki Sangyo Co., Ltd., rotation speed: 30 rpm, No. 3 spindle]. The degree of increase in viscosity before and after the test was evaluated according to the following evaluation criteria.
<Evaluation criteria>
A: Increase in viscosity is less than 10% B: Increase in viscosity is 10% or more and less than 20% B: Increase in viscosity is 20% or more and less than 50% X: Increase in viscosity is 50% or more

(3) Temperature (high temperature, low temperature) dispersion stability (3-1) High temperature dispersion stability 12 g of each emulsion (X) was placed in a 20 mL screw tube and allowed to stand at high temperature (70 ° C.) for 36 hours. The median particle diameter was measured before and after the test, and the degree of increase in the median particle diameter before and after the test was evaluated according to the following evaluation criteria.
<Evaluation criteria>
A: Increase in median particle size is less than 10% B: Increase in median particle size is 10% or more and less than 20% B: Increase in median particle size is 20% or more and less than 50% X: Increase in median particle size is 50% or more (3 -2) Low-temperature dispersion stability Each emulsion (X) 12g was put into a 20 mL screw jar, and left still for 36 hours at low temperature (10 degreeC). The median particle diameter was measured before and after the test, and the degree of increase in the median particle diameter before and after the test was evaluated according to the following evaluation criteria.
<Evaluation criteria>
A: Increase in median particle diameter is less than 10% B: Increase in median particle diameter is 10% or more and less than 20% B: Increase in median particle diameter is 20% or more and less than 50% X: Increase in median particle diameter is 50% or more

(4) Pencil hardness (evaluation of low-temperature curability)
The surface of a test steel sheet [0.5 mm × 80 mm × 150 mm cold rolled steel sheet (SPCC-SD) specified in JIS G3141] is degreased with methanol so that the thickness of the cured product after baking is 30 to 40 μm. The emulsion was applied, a test piece was prepared by low-temperature baking (140 ° C., 20 minutes), and the pencil hardness was evaluated according to the pencil method of JIS K-5600-5-4.

(5) Adhesion (evaluation of low temperature curability)
Test pieces were prepared by the above method (4), and the adhesion was evaluated by the number of peeled squares in 100 squares according to the cross-cut method of JIS K-5600-5-6.

  From the results of Tables 1 to 3, the one-part curable epoxy emulsion of the present invention is superior in storage stability, temperature dispersion stability and low-temperature curability compared to the comparative one, and the cured product obtained by curing the emulsion has a hardness. It can be seen that the adhesiveness is excellent.

  The one-part curable epoxy emulsion of the present invention is excellent in storage stability, temperature dispersion stability and low-temperature curability, and the cured product is excellent in hardness and adhesion. It can be suitably used widely as a paint, an adhesive, a primer and the like for bonding applications, or for coating and bonding applications such as buildings and home appliances, and is extremely useful.

Claims (8)

  Comprising a polyepoxide (A) and a curing catalyst (B), wherein the (B) comprises 1,8-diazabicyclo [5.4.0] -7-undecene salt (B1) and 1,5-diazabicyclo [4]. .3.0] -5-nonene salt (B2) is a one-part curable epoxy emulsion (X) that is at least one selected from the group consisting of.   The epoxy emulsion according to claim 1, wherein the polyepoxide (A) is an aromatic ring-containing polyepoxide (A1).   The curing catalyst (B) is at least one selected from the group consisting of phenol salts, octylates, p-toluenesulfonates, formates, acetates, orthophthalates, phenol novolac salts, and tetraphenylborate salts. The epoxy emulsion according to claim 1 or 2.   The epoxy emulsion according to any one of claims 1 to 3, wherein the weight of the curing catalyst (B) is 0.1 to 25% by weight based on the weight of (X).   5. The epoxy emulsion according to claim 1, wherein the total weight of (A) and (B) is 20 to 80% by weight based on the weight of (X).   The epoxy emulsion according to any one of claims 1 to 5, wherein the emulsion (X) contains a nonionic surfactant (C).   The epoxy emulsion according to claim 6, wherein the content of the nonionic surfactant (C) is 0.1 to 30% by weight based on the total weight of (A) and (B).   Hardened | cured material formed by hardening | curing the one-component curable epoxy emulsion (X) in any one of Claims 1-7.