JP2006306923A - Water-based epoxy resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-based epoxy resin composition which, in the form of a varnish, has good storage stability, does not emit odor during storage and processing, gives a processed article excellent in adhesion and corrosion resistance, and is desirably used for coating materials, adhesives, fiber binders, concrete primers, etc. <P>SOLUTION: The water-based epoxy resin composition comprises (A) a compound obtained by reacting a compound (a1) having a weight-average molecular weight of 500 to 60,000 and having a carboxy group in the molecule with a glycidyl-containing quaternary onium salt (a2) and (B) water. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention has good storage stability of varnish, does not generate odor during processing, and is excellent in adhesion, corrosion resistance, etc. of the obtained processed product, and suitable for paints, adhesives, fiber sizing agents, concrete primers, etc. It is related with the water-based epoxy resin composition which can be used for.

  Epoxy resin compositions are generally used in various fields such as paints, adhesives, laminates, and electrical / electronic parts because they are generally excellent in the mechanical properties, corrosion resistance, adhesion and the like of the cured products obtained. Epoxy resins are often diluted in organic solvents and used as compositions. However, due to recent environmental problems, the amount of organic solvents discharged from the compositions is reduced without impairing the above-mentioned high performance of epoxy resins. Is desired.

  In order to solve the above problem, a method for solving the above problem by using a water-based epoxy resin composition in which the solvent is mainly water has been used. For example, after introducing a carboxyl group into a phosphoric acid-modified epoxy resin, There is known a method of adding water to make it aqueous (for example, see Patent Document 1). However, in the method described in Patent Document 1, although the proportion of the organic solvent used in the aqueous epoxy resin composition can be reduced, the tertiary amine used for neutralization does not react with the resin. Therefore, there is a problem that it easily volatilizes during storage of varnish or during heat processing, and odor is generated, or the heating furnace used during processing is corroded, and a solution is required.

JP 7-157711 A (pages 2 to 4)

  In view of the above situation, the object of the present invention is that the storage stability of the varnish is good, no odor is generated during storage or processing, and the adhesion and corrosion resistance of the obtained workpiece are excellent, and the paint, adhesive, An object of the present invention is to provide an aqueous epoxy resin composition that can be suitably used for fiber sizing agents, concrete primers, and the like.

  As a result of intensive studies to solve the above problems, the inventor of the present invention is excellent in an aqueous epoxy resin composition using a polyaddition product of a specific carboxyl group-containing compound and a glycidyl group-containing quaternary onium salt as a binder resin. The inventors have found that the varnish stability and the coating film performance are compatible, that no odor is generated during storage or processing, and that there is no cause of corrosion of the heating furnace, and the present invention has been completed.

  That is, the present invention relates to a compound (A) obtained by reacting a compound (a1) having a weight average molecular weight of 500 to 60,000 and having a carboxyl group-containing compound in the molecule with a glycidyl group-containing quaternary onium salt (a2). And an aqueous epoxy resin composition characterized by containing water (B).

  According to the present invention, the storage stability of the varnish is good, no odor is generated during processing, and the obtained processed product has excellent adhesion, corrosion resistance, etc., paint, adhesive, fiber sizing agent, concrete primer, etc. The water-based epoxy resin composition which can be used suitably for can be provided.

Hereinafter, the present invention will be described in detail.
The compound (A) used in the present invention is a compound obtained by reacting a carboxyl group-containing compound (a1) and a glycidyl group-containing quaternary onium salt (a2) in a molecule having a weight average molecular weight of 500 to 60,000. is there.

  When the weight average molecular weight of the compound (a1) having a carboxyl group is less than 500, the resin obtained by the reaction with the glycidyl group-containing quaternary onium salt (a2) has a small molecular weight, and the corrosion resistance when used in paints and the like. When the molecular weight exceeds 60,000, the storage stability when the aqueous epoxy resin composition is obtained is unfavorable. A more preferred weight average molecular weight is 700 to 50,000. For the measurement of the weight average molecular weight, GPC (gel permeation chromatography) was used, 0.1 g of a sample was dissolved in 10 ml of THF (tetrahydrofuran), and 50 μl of this sample solution was injected into the column. It is the converted value as a standard substance.

  Although it does not restrict | limit especially as a structure of the said compound (a1), Adhesion with the base material of the processed material obtained when the obtained aqueous | water-based epoxy resin composition is used as a coating material, dimensional stability, etc. It is preferable to have an aromatic ring from the viewpoint of excellent resistance to corrosion, and from the point of excellent corrosion resistance, it may be a compound obtained by reaction of the epoxy resin (a1-1) and the carboxyl group-containing compound (a1-2). preferable.

  The epoxy resin (a1-1) is not particularly limited, and for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, biscresol F type epoxy resin, bisphenol S type epoxy. Examples thereof include polyvalent epoxy resins such as resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, p-tert-butylphenol novolak type epoxy resins, nonylphenol novolac type epoxy resins, t-butylcatechol type epoxy resins, and more. Examples of the epoxy resin include aliphatic alcohols such as butanol, aliphatic alcohols having 11 to 12 carbon atoms, phenol, p-ethylphenol, o-cresol, m-cresol, p-cresol, and p-tarsha. Examples include condensates of monohydric phenols such as butylphenol, s-butylphenol, nonylphenol, and xylenol with epihalohydrin, condensates of monovalent carboxylic acids such as neodecanoic acid with epihalohydrin, and the like. Examples of polyhydric aliphatic epoxy resins such as condensates with polyglycidyl ethers of vegetable oils such as soybean oil and castor oil include ethylene glycol, propylene glycol, 1 , 4-butanediol, 1,6-hexanediol, glycerin, erythritol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, trimethylolpropane and epihalo Condensates of polyhedrin and the like, which be one kind, can be used together even two or more. Among these, bisphenol A type epoxy resins are preferable because they have good reactivity with the carboxyl group-containing compound (a1-2) described later, and the processed products using the resulting aqueous epoxy resin composition have good corrosion resistance. It is preferable to use a bisphenol F type epoxy resin.

  Further, the epoxy equivalent of the epoxy resin (a1-1) is not particularly limited, but is excellent in compatibility between the obtained compound (A) and water (B), and is an aqueous epoxy resin composition. It is preferable that it is 110-1,300 g / eq from the point that varnish stability is favorable.

Although it does not restrict | limit especially as a manufacturing method of the said epoxy resin (a1-1), For example, it obtains by making polyhydric phenol (x1) and / or polyhydric carboxylic acid (x2), and an epihalohydrin react. Can do. Specific examples of the production method include the following two methods.
(i) A polycondensation reaction between a polyhydric phenol (x1) and / or a polycarboxylic acid (x2) and an epihalohydrin.
(ii) A method in which the polycondensate obtained in (i) is further subjected to an extension reaction with polyhydric phenols (x1) and / or polycarboxylic acids (x2).

  Examples of the polyhydric phenols (x1) include divalent phenols such as resorcin, hydroquinone, and catechol, which may have a substituent, and bisphenols such as bisphenol A, bisphenol F, bisphenol AD, and tetrabromobisphenol A. And alkylphenol novolaks such as phenol novolak and cresol novolak, and dicyclopentadiene phenol resin. These can be used alone or as a mixture of two or more. Further, biphenols, compounds obtained by hydrogenating aromatic nuclei of the polyhydric phenols, and polyhydric phenols having condensed aromatic rings such as naphthalenediol can be used in combination.

  Examples of the polyvalent carboxylic acids (x2) include aliphatic divalent carboxylic acids such as malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, decanoic acid, dodecanedioic acid, and glutaric acid, phthalic acid, and isophthalic acid. Aromatic divalent carboxylic acids such as acid, terephthalic acid and naphthalenedicarboxylic acid, hydrogenated products thereof, dimer acid, etc., and those in which the aromatic ring is substituted with an alkyl group or halogen or those which are nuclear hydrogenated Further, these can be used alone or as a mixture of two or more.

  Examples of the epihalohydrin include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, β-methylepibromohydrin, and the like. Among these, the polyhydric phenols (x1) and / or the above Epichlorohydrin is preferable from the viewpoint of excellent reactivity with the polyvalent carboxylic acids (x2).

  The production method of (i) is not particularly limited. For example, 1 equivalent of a hydroxyl group of a polyhydric phenol (x1) or 1 equivalent of a carboxyl group of a polycarboxylic acid (x2) (when used in combination) Is added in an amount of 0.3 to 10 equivalents of the epihalohydrin, and the reaction is carried out in the presence of a base at 40 to 100 ° C. under normal pressure or reduced pressure using a solvent as necessary. The method of performing is mentioned.

  Examples of the solvent include alcohols such as isopropyl alcohol and butanol, ethers such as dioxane, aprotic polar solvents such as dimethyl sulfoxide and 1,3-dimethylimidazolidinone.

  The base is not particularly limited, and examples thereof include potassium hydroxide, sodium hydroxide, barium hydroxide, magnesium oxide, sodium carbonate, potassium carbonate, etc. Among these, potassium hydroxide and sodium hydroxide are preferable. . Further, these bases can be suitably used either in aqueous solution or in solid form.

  After the obtained reaction product is washed with water or without washing with water, epihalohydrin and other added solvents are removed at 110 to 250 ° C. under a pressure of 10 mmHg or less under reduced pressure. Furthermore, in order to obtain an epoxy resin with less hydrolyzable halogen, the crude epoxy resin obtained after recovering the epihalohydrin is dissolved again in a solvent such as toluene or methyl isobutyl ketone, and an alkali metal such as sodium hydroxide or potassium hydroxide. An aqueous solution of hydroxide can also be added and reacted further to ensure ring closure. In this case, the amount of alkali metal hydroxide used is usually 0.5 to 10 mol, preferably 1.2 to 5.0 mol, per 1 mol of hydrolyzable chlorine remaining in the crude epoxy resin. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 3 hours. For the purpose of improving the reaction rate, a phase transfer catalyst such as a quaternary ammonium salt or crown ether may be present. The amount of the phase transfer catalyst used is preferably in the range of 0.1 to 3.0% by weight based on the crude epoxy resin.

  After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and a solvent such as toluene and methyl isobutyl ketone is distilled off under heating and reduced pressure to obtain a high-purity epoxy resin.

  As the production method of (ii), for example, the reaction product obtained in (i) uses the polyhydric phenols (x1) and / or the polyhydric carboxylic acids (x2) as an extender, and a catalyst is present. Below, the method of heat-stirring at 120-220 degreeC is mentioned. In this reaction, the reaction can be carried out in the presence of an appropriate catalyst. The catalyst is not particularly limited, and examples thereof include onium salts, phosphines, alkali metal hydroxides, and the like. Moreover, the use ratio of the reaction product obtained in (i) and the polyhydric phenols (x1) and / or the polyhydric carboxylic acids (x2) is the epoxy equivalent of the target epoxy resin (a1-1). It is preferable to calculate from

  The polyhydric phenols (x1) and / or polyhydric carboxylic acids (x2) used as the extender are the same as the polyhydric phenols (x1) and polyhydric carboxylic acids (x2) used in the reaction (i). It may be different or different.

  In this extension reaction, a phosphoric acid compound can be used in combination as necessary. Examples of the phosphoric acid compound include orthophosphoric acid, pyrophosphoric acid, polyphosphoric acid, diethyl phosphate, triethyl phosphate, and triphenyl phosphate.

  Next, it describes about the carboxyl group-containing compound (a1-2) made to react with an epoxy resin (a1-1). The carboxyl group-containing compound (a1-2) is not particularly limited as long as it is a compound having a carboxyl group capable of reacting with the glycidyl group in the epoxy resin (a1-1) obtained above. Although various compounds can be used freely, the varnish stability of the reaction product (A) of the resulting compound (a1) and the glycidyl group-containing quaternary amine salt (a2) described later is 2 in the molecule. A compound containing at least two carboxyl groups is preferred.

  Examples of the carboxyl group-containing compound (a1-2) include malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, decanoic acid, dodecanedioic acid, glutaric acid, maleic acid, fumaric acid, pimelic acid, and suberin. Aliphatic divalent carboxylic acids such as acids, aromatic divalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid and diphenic acid, hydrogenated products thereof, dimer acids, etc. Those substituted with a group or halogen, or those hydrogenated with a nucleus can be used, and these can be used alone or as a mixture of two or more. These may be the same as or different from the above (x2).

  Furthermore, a reaction product of a divalent or higher glycidyl compound and a carboxyl group-containing compound can also be used. Examples of the divalent or higher glycidyl compound include a condensate of bisphenols and epihalohydrin, a condensate of dihydroxybenzenes and epihalohydrin, a condensate of dibasic acid and epihalohydrin, and the carboxyl group-containing compound includes malonic acid, Aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid, decanoic acid, dodecanedioic acid, glutaric acid, maleic acid, fumaric acid, pimelic acid, suberic acid, phthalic acid, isophthalic acid, terephthalic acid , Aromatic divalent carboxylic acids such as naphthalenedicarboxylic acid and diphenic acid, hydrogenated products thereof, dimer acids, etc., and those in which the aromatic ring is substituted with an alkyl group or halogen or those that are nuclear hydrogenated are also used Furthermore, these can be used alone or as a mixture of two or more. These may be the same as or different from the above (x2).

  The reaction ratio between the divalent or higher glycidyl compound and the carboxyl group-containing compound is the equivalent (eq) of the carboxyl group in the carboxyl group-containing compound with respect to 1 equivalent (eq) of the epoxy group in the divalent or higher glycidyl compound. If it is 1.01 or more, it can be used without particular limitation.

  As the carboxyl group-containing compound (a1-2), divalent carboxylic acids, among them, from the point of gelation during synthesis and the excellent storage stability of the aqueous epoxy resin composition using the resulting compound (A), Aliphatic carboxylic acids, aromatic carboxylic acids and dimer acids are particularly preferred.

  Examples of the polyaddition reaction between the epoxy resin (a1-1) and the carboxyl group-containing compound (a1-2) include, for example, in the presence of a catalyst such as an acid, a base, a metal salt, or a metal oxide, or no catalyst. In the molten state or in the presence of a solvent, there may be mentioned a method. The reaction temperature at this time is 50 to 160 ° C. from the viewpoint that the reaction time is appropriate, the increase in viscosity during the reaction is suppressed, and the reaction with the glycidyl group-containing quaternary onium salt described later is easy. It is preferable that it is 60 to 140 degreeC especially. As said solvent, the epoxy resin (a1-1) which is a raw material, the carboxyl group-containing compound (a1-2) and the compound (a1) which is a reaction product are uniformly dissolved, and inert to (a1) Is not particularly limited, for example, hydrocarbons such as toluene, xylene, cyclohexane, decalin, ethyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, ethoxyethyl propionate, 3 -Esters such as methoxybutyl acetate, methoxypropyl acetate, cellosolve acetate, alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol, methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve, isobutyl cellosolve, tert -Butyl cello solo Cellosolves such as monoglyme, diglyme and triglyme, propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monoisobutyl ether, propylene glycol mono tert-butyl ether Among these, alcohols, cellosolves, glymes, and propylene glycol monoalkyl ethers are preferable among these.

  When the epoxy resin (a1-1) and the carboxyl group-containing compound (a1-2) are reacted, a monovalent phenol compound, amine compound, glycidyl compound, and acid anhydride are used in combination as necessary. I can do things.

  Examples of the monovalent phenolic compound include phenols optionally substituted with hydrocarbons and halogens, and examples of the monovalent amine compound include dibutylamine and di-2-ethylhexylamine. And monovalent alkanolamines such as monovalent alkylamines, diethanolamine, diisopropanolamine, N-methylethanolamine and 1-methylaminopropanediol, and cyclic monovalent amines such as morpholine, piperazine and 4-methylpiperazine. . Monovalent glycidyl compounds include monovalent phenols such as phenol, p-ethylphenol, o-cresol, m-cresol, p-cresol, p-tertiarybutylphenol, s-butylphenol, nonylphenol, xylenol, and epihalohydrins. Condensates with glycidyl ether such as butyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, etc. These may be used alone or in combination of two or more. .

  The compound (a1) obtained by the above reaction may be used for the next step as it is, and if necessary, a purification step such as deactivation of the catalyst, removal of the solvent, distillation of the residual monomer, etc. is performed. Also good.

  The glycidyl group-containing quaternary onium salt (a2) used in the present invention can be used without particular limitation as long as it is a quaternary onium salt having a glycidyl group in the molecule.

  Examples of the glycidyl group-containing onium salt (a2) include glycidyl acrylate, glycidyl methacrylate, epoxy group-containing vinyl monomers such as alicyclic monoepoxide having a vinyl group, and acrylic acid monomers having a quaternary onium salt, A copolymer with a vinyl monomer having a quaternary onium salt such as a methacrylic acid monomer having a quaternary onium salt, or the following general formula (1)

（式中、Ｒは水素原子又はメチル基であり、Ｑは窒素原子又はリン原子であり、Ｘは塩素原子、臭素原子又はヨウ素原子であり、Ｒ_１、Ｒ_２、Ｒ_３はそれぞれアルキル基又はアリール基であり、これらは同一でも異なっていても良い。）
で表される化合物が挙げられる。

(In the formula, R is a hydrogen atom or a methyl group, Q is a nitrogen atom or a phosphorus atom, X is a chlorine atom, a bromine atom or an iodine atom, and R ₁ , R ₂ and R ₃ are each an alkyl group or An aryl group, which may be the same or different.)
The compound represented by these is mentioned.

  Examples of the alicyclic monoepoxide having a vinyl group include Celoxide 2000 (trade name: manufactured by Daicel Chemical Industries, Ltd.). Examples of the acrylic acid monomer having a quaternary onium salt include, for example, DMAEA-Q ( Kojin Co., Ltd., N, N-dimethylaminoethyl acrylate-methyl chloride salt, 79% aqueous solution) and DMAPAA-Q (Kojin Co., Ltd., N, N-dimethylaminopropylacrylamide-methyl chloride salt, 75% Aqueous solution) and the like.

  In addition, as the glycidyl group-containing quaternary onium salt (a2), a compound obtained by copolymerizing an epoxy group-containing vinyl monomer and an acrylic monomer having acrylamide or a tertiary amine and then quaternizing with an alkyl halide may be used. it can.

Among these, it is preferable to use the compound represented by the general formula (1) from the viewpoint of excellent compatibility between the obtained compound (A) and water (B). It is preferable to use a compound in which R ₁ , R ₂ , and R _{3 in the} general formula (1) are the same or different linear alkyl groups having 1 to 4 carbon atoms, wherein R is a hydrogen atom, and Q is SY-GTA80 in which nitrogen atom, R ₁ , R ₂ , R ₃ are methyl groups and X is a chlorine atom [trade name, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., NV = 80% aqueous solution, epoxy equivalent (solid content): 151 g / eq] is most preferred.

  The reaction between the compound (a1) and the glycidyl group-containing quaternary onium salt (a2) can be carried out without solvent or in a suitable solvent. The solvent is not particularly limited as long as it uniformly dissolves the compound (a1) and the glycidyl group-containing quaternary onium salt (a2) and is inert to the reaction product (A). Instead, for example, alcohols such as water, methanol, ethanol, isopropanol, n-butanol, isobutanol, hydrocarbons such as toluene, xylene, cyclohexane, decalin, ethyl acetate, n-butyl acetate, isobutyl acetate, n acetate -Esters such as amyl, ethoxyethyl propyronate, 3-methoxybutyl acetate, methoxypropyl acetate, cellosolve acetate, methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve, isobutyl cellosolve, cellosolves such as tert-butyl cellosolve, Monoglai , Glymes such as diglyme and triglyme, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monoisobutyl ether, propylene glycol mono tert-butyl ether, etc. It can also be used as a solvent. Among these, the solution of the reaction product obtained can be used as it is as the aqueous epoxy resin composition of the present invention, so that water alone or a mixed solvent of water and alcohols, cellosolves and glymes is used. It is preferable to use it.

  The reaction ratio between the compound (a1) and the glycidyl group-containing quaternary onium salt (a2) is not particularly limited, but the processed product of the resulting aqueous epoxy resin composition has good water resistance, and From the viewpoint of good storage stability of the composition, the number of equivalents (eq) of carboxyl groups in (a1) to 1 equivalent (eq) of epoxy groups in (a2) is usually 0.1 or more and 200 or less, Preferably they are 0.5 or more and 50 or less. More preferably, it is 0.7 or more and 10 or less, and most preferably the ratio is 0.8 or more and 5 or less.

  The compound (A) obtained by the reaction may be used as it is, or may be subjected to a purification step such as removal of a solvent as necessary.

  The water (B) used in the present invention is used for uniformly dissolving or dispersing the compound (A), and deionized water is preferable. Water (B) is added at the time of the reaction of the compound (a1) having an amino group in the molecule and the glycidyl group-containing quaternary onium salt (a2) [reaction to obtain the compound (A)] or after completion of the reaction. By stirring and mixing, the aqueous epoxy resin composition of the present invention can be obtained.

  As the aqueous epoxy resin composition of the present invention, a hydrophilic auxiliary can be used as necessary. Examples of hydrophilic auxiliaries include lower alcohols such as methanol, ethanol and isopropanol, cellosolves such as methyl cellosolve, ethyl cellosolve, n-propyl cellosolve, isopropyl cellosolve, butyl cellosolve, isobutyl cellosolve, and tert-butyl cellosolve, Glymes such as monoglyme, diglyme and triglyme, propylene such as propylene glycol monomethyl ether, polypropylene glycol monoethyl ether, propylene glycol monopropyl ether, polypropylene glycol mono n-butyl ether, polypropylene glycol monoisobutyl ether, polypropylene glycol mono-tert-butyl ether Examples include glycol monoalkyl ethers and diacetone alcohol It is.

  Among these, isopropanol, propyl cellosolve, butyl cellosolve, isobutyl cellosolve, tert-butyl cellosolve, diglyme, propylene glycol monomethyl ether, propylene glycol monopropyl ether, diacetone alcohol are used because of their good solubility in the compound (A). It is preferable. Moreover, these adjuvants are the compound (a1) which has a carboxyl group in a molecule | numerator at the time of reaction after reaction of an epoxy resin (a1-1) and a carboxyl group-containing compound (a1-2), or a reaction, and glycidyl. It can be added during or after the reaction with the group-containing quaternary onium salt (a2).

  Moreover, as a water-based epoxy resin composition of this invention, you may use together other polyester-type water resin, acrylic water-based resin, etc. as needed in the range which does not impair the characteristic of this invention.

  Furthermore, the aqueous epoxy resin composition of the present invention can be used in combination with a curing agent (C) in order to improve the performance of the obtained workpiece, such as adhesion to the substrate and corrosion resistance.

  The curing agent (C) is not particularly limited as long as it is a compound capable of undergoing a curing reaction with the hydroxyl group in the compound (A). It is preferable to use an amino resin (c1), an isocyanate compound (c2), and a phenol resin (c3) from the viewpoint of excellent performance.

  Examples of the amino resin (c1) include a melamine resin derived from melamine and an aldehyde compound, a guanamine resin derived from an aldehyde compound such as benzoguanamine and acetoguanamine, and a urea derived from an aldehyde compound such as urea and thiourea. Examples thereof include resins. These can be used alone or in combination of two or more.

  Further, as the amino resin (c1), those in which amino components such as melamine and urea are co-condensed, and those in which methylol groups in the resin are substituted with alcohols such as methanol, propanol, isopropanol, butanol and isobutanol are also used. can do.

  The use ratio of the amino resin (c1) is preferably 1 to 40 parts by weight, more preferably 2 parts by weight of the solids in the amino resin with respect to 100 parts by weight of the resin solids in the aqueous epoxy resin composition. -30 parts by weight.

  The isocyanate compound (c2) is not particularly limited. For example, as the diisocyanate, aromatic compounds such as phenylene diisocyanate, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylylene diisocyanate, and metaxylylene diisocyanate. Aliphatic isocyanates, hexamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate and other aliphatic diisocyanates, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated metaxylylene diene Cycloaliphatic diisols such as isocyanate and norbornene diisocyanate Aneto such and the like, and solvent-free, it can be used those which are diluted in a solvent.

  Examples of the polyisocyanate other than the diisocyanate include polymethylene polyphenyl isocyanate, dimethyltriphenylmethane tetraisocyanate, triphenylmethane triisocyanate, and tris (isocyanatophenyl) -triphosphate.

  Furthermore, as the isocyanate compound (c2), those subjected to various modification reactions using the above isocyanate for the purpose of reducing vapor pressure, adjusting the viscosity, the number of functional groups, reactivity, and imparting special physical properties are also used. can do. Examples of these are urethane prepolymers that are reaction products with alcohols, allophanate-modified isocyanates obtained by addition reaction of isocyanate groups, biuret-modified isocyanates, uretdione-modified isocyanates, isocyanurate-modified isocyanates, Examples thereof include a carbodiimide-modified product, an uretonimine-modified product, an acylurea diisocyanate product, and the like utilizing an isocyanate group condensation reaction.

  Examples of the urethane prepolymers include diols composed of dimers of unsaturated alcohols such as ethylene glycol, polyethylene glycol, polypropylene glycol, and oleyl alcohol, trimethylolpropane, glycerin, 1,2,6-hexanetriol, Examples thereof include compounds having an isocyanate group at the terminal, obtained by reacting a polyol such as polyester polyol with the isocyanate compound.

  These isocyanate compounds (c2) may be used alone or as a mixture of two or more.

  Although it does not restrict | limit especially as said isocyanate compound (c2) and a usage rate, From the point which is excellent in the said performance of the hardened | cured material obtained, it is isocyanate with respect to 100 weight part of resin solid content in an aqueous epoxy resin composition. The solid content in the compound (c2) is preferably 1 to 30 parts by weight, more preferably 3 to 25 parts by weight.

  The phenol resin (c3) is not particularly limited as long as it is a compound obtained by condensation reaction of a phenol and an aldehyde compound in the presence of a catalyst, and can be used alone or in combination of two or more.

  Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-tert-butylphenol, m-tert-butylphenol, p-tert-butylphenol, p-cyclohexylphenol, nonylphenol, and xylenol. Monohydric phenols, bisphenols such as bisphenol A, bisphenol F, tetramethylbisphenol F, bisphenol AD, bisphenol Z, naphthalenediols such as 1,5-dioxynaphthalene, 1,6-dioxynaphthalene, biphenols, Examples thereof include tetramethylbiphenol, and these can be used alone or in combination of two or more.

  As the catalyst, a basic catalyst or an acid catalyst can be used. Examples of the basic catalyst include alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, amines, ammonia and the like, and a resol-type condensate is obtained. Examples of the acid catalyst include hydrochloric acid, phosphoric acid, oxalic acid, and the like, and a novolac type condensate is obtained.

  Although it does not specifically limit as a usage-ratio of the said phenol resin (c3), It is preferable to use by 1-40 weight part of solid content in a phenol resin with respect to 100 weight part of resin solid content of an aqueous | water-based epoxy resin composition, Furthermore, Preferably it is 2-30 weight part.

  In addition, the aqueous epoxy resin composition of the present invention includes various additives such as a repellency inhibitor, an anti-sagging agent, a spreading agent, an antifoaming agent, a curing accelerator, an ultraviolet absorber, and a light stabilizer as necessary. May be blended.

  Although it does not restrict | limit especially as a use of the water-based epoxy resin composition of this invention, For example, it can use suitably as a coating material, an adhesive agent, a fiber sizing agent, a concrete primer, etc.

  When the aqueous epoxy resin composition of the present invention is used for coating applications, it is preferable to incorporate various fillers such as rust preventive pigments, colored pigments, extender pigments, various additives, and the like as necessary. Examples of the anticorrosion pigment include zinc powder, aluminum phosphomolybdate, zinc phosphate, aluminum phosphate, barium chromate, aluminum chromate, graphite and other scaly pigments, and the coloring pigment includes carbon black, oxidation pigment, etc. Examples thereof include titanium, zinc sulfide, and bengara. Examples of extender pigments include barium sulfate, calcium carbonate, talc, and kaolin. The blending amount of these fillers is 10 to 70 parts by weight with respect to a total of 100 parts by weight of the compound (A), water (B) and the curing agent (C) blended as necessary. It is preferable from the viewpoints of film performance and painting workability.

  The coating method in the case of using the aqueous epoxy resin composition of the present invention for coating is not particularly limited, and may be performed by roll coating, spraying, brushing, spatula, bar coater, dip coating, electrodeposition coating method. As the processing method, room temperature drying to heat curing can be performed. In the case of heating, a coating film can be obtained by reacting at 50 to 250 ° C., preferably 60 to 230 ° C., for 2 to 30 minutes, preferably 5 to 20 minutes.

  In addition, when the aqueous epoxy resin composition of the present invention is used as an adhesive, it is not particularly limited, and can be performed by applying the sprayed, brushed, or spatula to the base material, and then matching the adhesive surface of the base material. In addition, the bonding portion can form a strong adhesive layer by fixing or pressing the periphery. Steel plates, concrete, mortar, wood, resin sheets, resin films are suitable as the base material, and various surface treatments such as physical treatment such as polishing, electrical treatment such as corona treatment, and chemical treatment such as chemical conversion treatment are performed as necessary. More preferably, it is applied after application.

  Further, when the aqueous epoxy resin composition of the present invention is used as a fiber sizing agent, it can be carried out without any particular limitation. For example, it is applied to a fiber immediately after spinning using a roller coater and wound as a fiber strand. Thereafter, a method of drying is mentioned. The fiber to be used is not particularly limited. For example, inorganic fibers such as glass fiber, ceramic fiber, asbestos fiber, carbon fiber, and stainless steel fiber, natural fibers such as cotton and hemp, synthetic fibers such as polyester, polyamide, and urethane. Examples of the shape of the base material include short fibers, long fibers, yarns, mats, and sheets. The amount used as the fiber sizing agent is preferably 0.1 to 2% by weight as the resin solid content with respect to the fiber.

  Moreover, when using the water-based epoxy resin composition of this invention as a concrete primer, it is not specifically limited, It can carry out with a roll, a spray, a brush, a spatula, and a scissors.

  Hereinafter, the present invention will be described in more detail with reference to examples. In the examples, “parts” and “%” are based on weight unless otherwise specified.

In addition, the measurement of the weight average molecular weight of (a1) was performed on condition of the following using GPC.
A sample solution was prepared by dissolving 0.1 g of a sample in 10 ml of THF, 50 μl of this sample solution was injected into a column, and the retention time was measured under the following conditions. The weight average molecular weight is a conversion value using polystyrene having a known molecular weight as a standard substance.
Equipment: HLC-8220GPC (manufactured by Tosoh Corporation)
Column: TSG-GUARDCOLUMN + TSG-GEL G2000HXL × 2 + TSG-GEL G3000HXL + TSG-GEL G4000HXL (all manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Mobile phase, flow rate: THF (1 ml / min)
Peak detection method: RI

Example 1
In a four-necked flask equipped with a thermometer, a stirrer, and a nitrogen gas inlet tube, 300 parts of EPICLON 850-S (bisphenol A type epoxy resin, epoxy equivalent 188 g / eq, manufactured by Dainippon Ink & Chemicals, Inc.) and bisphenol A 27 parts were charged and uniformized by heating and stirring to 80 ° C. Here, 0.1 part of an 80% aqueous solution of tetrabutylphosphonium chloride as a catalyst was added and further stirred at 140 ° C. for 3 hours. Thereto were added 2.5 parts of triphenylphosphine and 172 parts of adipic acid, and the mixture was further stirred at 140 ° C. for 4 hours to obtain a compound (a1-i) having a weight average molecular weight of 2,500. 200 parts of butyl cellosolve was added here, and after confirming that the solution became uniform, the liquid temperature was cooled to 90 ° C. Subsequently, 94 parts of SY-GTA80 (glycidyl group-containing quaternary onium salt-80% aqueous solution, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) was added and further reacted at 90 ° C. for 3 hours. Finally, 565 parts of ion-exchanged water was added to obtain a white liquid aqueous epoxy resin composition having a nonvolatile content of 40%. This is defined as (E-1).

Example 2
In Example 1, 86 parts of bisphenol A, 2.5 parts of triphenylphosphine, and 112 parts of adipic acid were used to obtain a compound (a1-ii) having a weight average molecular weight of 5,000. Next, it carried out similarly except having changed into 192.5 parts of butyl cellosolve, 65 parts of SY-GTA80, and 567.2 parts of ion-exchange water, and obtained the white liquid aqueous epoxy resin composition of 40% of non volatile matters. This is defined as (E-2).

Example 3
A compound (a1-iii) having a weight average molecular weight of 10,000 was obtained in the same manner as in Example 1 except that 86 parts of bisphenol A, 2.4 parts of triphenylphosphine, and 100 parts of adipic acid were used. . Further, a white liquid aqueous epoxy resin having a non-volatile content of 25% was obtained in the same manner as in Example 1 except that 315.6 parts of butyl cellosolve, 49.8 parts of SY-GTA, and 1253 parts of ion-exchanged water were used. A composition was obtained. This is defined as (E-3).

Example 4
In Example 1, except for changing to 86 parts of bisphenol A, 2.3 parts of triphenylphosphine, and 74.7 parts of adipic acid, the compound (a1-iv) having a weight average molecular weight of 21,000 was obtained in the same manner as in Example 1. Obtained. Further, a white liquid aqueous epoxy resin composition having a nonvolatile content of 20% was obtained in the same manner as in Example 1 except that SY-GTA80 was changed to 17.4 parts, butyl cellosolve 358 parts, and ion-exchanged water 1554 parts. This is defined as (E-4).

Example 5
In a four-necked flask equipped with a thermometer, a stirrer, and a nitrogen gas inlet tube, 300 parts of EPICLON 850-S (bisphenol A type epoxy resin, epoxy equivalent 188 g / eq, manufactured by Dainippon Ink & Chemicals, Inc.) and bisphenol A 35 parts and 46 parts of bisphenol F were charged, and uniformized by heating and stirring to 80 ° C. Here, 0.1 part of an 80% aqueous solution of tetrabutylphosphonium chloride as a catalyst was added and further stirred at 140 ° C. for 3 hours. To this, 2.1 parts of triphenylphosphine and 92 parts of adipic acid were added, and the mixture was further stirred at 140 ° C. for 4 hours to obtain a compound (a1-v) having a weight average molecular weight of 16,000. 375 parts of butyl cellosolve was added here, and after confirming that the solution became uniform, the liquid temperature was cooled to 90 ° C. Subsequently, 34.3 parts of SY-GTA80 was charged and further reacted at 90 ° C. for 3 hours. Finally, 1619 parts of ion-exchanged water was added to obtain a white liquid aqueous epoxy resin composition having a nonvolatile content of 20%. This is defined as (E-5).

Example 6
In a four-necked flask equipped with a thermometer, a stirrer, and a nitrogen gas introduction tube, 300 parts of EPICLON 830-S (bisphenol F type epoxy resin, epoxy equivalent 170 g / eq, manufactured by Dainippon Ink & Chemicals, Inc.) and bisphenol A 35 parts and 59.8 parts of bisphenol F were charged, and the mixture was uniformly heated to 80 ° C. with stirring. Here, 0.2 parts of 80% tetrabutylphosphonium chloride aqueous solution was charged as a catalyst and further stirred at 140 ° C. for 3 hours. 2.4 parts of triphenylphosphine and 90 parts of adipic acid were added thereto, and the mixture was further stirred at 140 ° C. for 5 hours to obtain a compound (a1-vi) having a weight average molecular weight of 14,000. 385 parts of butyl cellosolve was added here, and after confirming that the solution became uniform, the liquid temperature was cooled to 90 ° C. Subsequently, 35.2 parts of SY-GTA80 was charged and further reacted at 90 ° C. for 3 hours. Finally, 1660 parts of ion-exchanged water was added to obtain a white liquid aqueous epoxy resin composition having a nonvolatile content of 20%. This is defined as (E-6).

Comparative Example 1
In a four-necked flask equipped with a thermometer, a stirrer, and a nitrogen gas inlet tube, 300 parts of Denacol EX-201 (diglycidyl ether of resorcin, epoxy equivalent 123 g / eq, manufactured by Nagase ChemteX Corporation), 281 parts of succinic acid Was made uniform by heating and stirring to 80 ° C. Here, 2.9 parts of triphenylphosphine was charged as a catalyst, heated to 140 ° C. and reacted for 5 hours to obtain a compound having a weight average molecular weight of 450. 290 parts of butyl cellosolve was added here, and after confirming that the solution became uniform, the liquid temperature was cooled to 90 ° C. Subsequently, 140 parts of SY-GTA80 was charged and further reacted at 90 ° C. for 3 hours. Finally, 441.5 parts of ion-exchanged water was added to obtain a white liquid aqueous epoxy resin composition having a nonvolatile content of 40%. This is defined as (E′-1).

Comparative Example 2
150 parts of EPICLON 850-S, 35 parts of bisphenol A, and 46 parts of bisphenol F were charged into a four-necked flask equipped with a thermometer, a stirrer, and a nitrogen gas introduction tube, and the mixture was uniformly heated to 80 ° C. with stirring. Here, 0.2 parts of 80% tetrabutylphosphonium chloride aqueous solution was charged as a catalyst and further stirred at 140 ° C. for 3 hours. 1.5 parts of triphenylphosphine and 72.5 parts of adipic acid were added thereto, and the mixture was further stirred at 140 ° C. for 5 hours to obtain a compound having a weight average molecular weight of 70,000. 616 parts of butyl cellosolve was added here, and after confirming that the solution became uniform, the liquid temperature was cooled to 80 ° C. Subsequently, 10.7 parts of SY-GTA80 was charged and further reacted at 90 ° C. for 3 hours. Finally, 2000 parts of ion-exchanged water was added to obtain a white liquid aqueous epoxy resin composition having a nonvolatile content of 15%. This is defined as (E′-2).

Table 1 shows the aqueous epoxy resin compositions (E-1) to (E-6) and (E′-1) and (E′-2) obtained in Examples 1 to 6 and Comparative Examples 1 and 2. The property value and the change in appearance when stored in a dryer at 40 ° C. are shown. In Table 1, varnish storage stability was measured by weighing 90 g of an aqueous epoxy resin composition into a 100 ml mayonnaise bottle, storing it in a dryer at 40 ° C., and visually observing the appearance after a predetermined elapsed time.
○: No precipitation or separation. X: Separation is observed. XX: Aggregate generation.
Moreover, the mayonnaise bottle 6 months after the stability test was opened, and a sensory test was conducted for odor.
○: No odor. X: Odor is present.

Footnotes in Table 1 NV (%): non-volatile content (%) in aqueous epoxy resin composition

Test Examples 1 to 13 and Comparative Test Examples 1 to 6
Next, water-based paints were prepared using the obtained water-based epoxy resin compositions at the mixing ratios shown in Tables 2 to 4, and dried with a bar coater on the cold-rolled steel sheet that had been surface-treated with # 400 sandpaper. After coating so that the film thickness was 20 μm, the coating film properties were evaluated. The lacquer coating properties shown in Table 2 are the test results after curing at 100 ° C. × 20 minutes + 25 ° C. × 5 days, and the coating properties (curing agent combined system) shown in Tables 3 to 5 are 160 ° C. × 20 minutes. It is a test result after baking. Each test method and evaluation criteria are as follows.

Paint stability: 90 g of the prepared paint was weighed into a 100 ml mayonnaise bottle, stored at room temperature (25 ° C.), and visually observed after a predetermined time. (Similarly, when a curing agent was used, a stability test was conducted with a paint containing a predetermined amount of a curing agent and a curing catalyst.)
○: No precipitation or separation. X: Separation is observed. XX: Aggregate generation.

Impact strength: Measured according to JIS K-5600-5-3 (1999), DuPont type, with a half-shock and a load of 500 g.
◯: No crack or the like at 50 cm. X: Generation | occurrence | production of a crack etc. is recognized by 50 cm.

Cross cut test: According to JIS K-5600-5-6 (1999), cuts were made at intervals of 1 mm, and the state of the coating film was visually observed after peeling off after applying the tape.
○: No peeling. X: Peeling is seen.

MEK rubbing: A cloth impregnated with MEK was rubbed with a certain force until the surface of the substrate appeared.
○: 100 round trips or more. X: A base material is reached within 100 reciprocations.

Moisture resistance: The test piece was placed in a tester having a temperature of 48 ° C. and a humidity of 98%, and the swelling generated on the coating film surface after 300 hours was observed.
◯: No swelling occurs. X: Swelling occurred.

  SST: Performed according to JIS K-5600-7-1 (1999). After putting a crosscut into the test piece with a cutter, placing it in a tester and conducting a 300 hr test, the swell width of the coating film from the crosscut portion is noted. The unit is mm.

Footnotes in Table 2 P-W-2: Anti-corrosive pigment manufactured by Kikuchi Dye Co., Ltd. NS # 100: Calcium carbonate manufactured by Nitto Flour Chemical Co., Ltd. SW: Talc BYK-341 manufactured by Nihon Talc Co., Ltd. ): Weight ratio of filler to solid content of paint NV (%): Non-volatile content of paint (resin + filler)

Footnotes in Table 3 S-695: Water-soluble methyl etherified melamine resin “Watersol S-695” manufactured by Dainippon Ink and Chemicals, Inc., 65% nonvolatile content
Curing catalyst: Dainippon Ink & Chemicals, Inc. Becamine P-198

Footnotes in Table 4 DNW-500: manufactured by Dainippon Ink & Chemicals, Inc. Water-soluble isocyanate “Bernock DNW-500” non-volatile content 80%, NCO content 13.5%

Footnotes in Table 5 Hitanol 4010: Resol “Hitanol 4010” manufactured by Hitachi Chemical Co., Ltd.

As is clear from Tables 2 to 5, the aqueous epoxy resin composition of the present invention was excellent in storage stability of varnish, and was further excellent in storage stability of paint and physical properties of coating film when used for coating. Furthermore, since no volatile component contains an amine, no odor was generated during storage and during heat processing, and corrosion of the heating furnace did not occur.

Claims (6)

A compound (A) obtained by reacting a compound (a1) having a weight average molecular weight of 500 to 60,000 and having a carboxyl group in the molecule with a glycidyl group-containing quaternary onium salt (a2), and water (B) An aqueous epoxy resin composition characterized by containing. The glycidyl group-containing quaternary onium salt (a2) is represented by the following general formula (1)

(In the formula, R is a hydrogen atom or a methyl group, Q is a nitrogen atom or a phosphorus atom, X is a chlorine atom, a bromine atom or an iodine atom, and R ₁ , R ₂ and R ₃ are each an alkyl group or An aryl group, which may be the same or different.)
The aqueous epoxy resin composition according to claim 1, which is a compound represented by the formula: The aqueous epoxy resin composition according to claim ₂ , wherein R ₁ , R ₂ and R _{3 in the} general formula (1) are the same or different linear alkyl groups having 1 to 4 carbon atoms. The aqueous epoxy resin composition according to claim 1, wherein the compound (a1) having a carboxyl group in the molecule is a compound obtained by a reaction between the epoxy resin (a1-1) and the carboxyl group-containing compound (a1-2). Furthermore, the water-based epoxy resin composition of any one of Claims 1-4 containing a hardening | curing agent (C). The aqueous epoxy resin composition according to claim 5, wherein the curing agent (C) is at least one compound selected from the group consisting of an amino resin (c1), an isocyanate compound (c2), and a phenol resin (c3).