JP2007045940A - Aqueous epoxy resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous epoxy resin composition free from generation of odor in storage and processing, gives processed products having excellent adhesiveness and processing quality and can suitably be used as coating, adhesive, fiber sizing agent, concrete primer or the like. <P>SOLUTION: The aqueous epoxy resin composition comprises (A) a compound that has a weight-average molecular weight of 500 to 60,000 and is obtained by reaction between (a1) a compound having a functional group (x) reactive with glycidyl group and (a2) a quaternary onium salt bearing glycidyl group and (B) alkoxysilane. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

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

  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 problem of the present invention is that no odor is generated during storage or processing of varnish, and excellent in adhesion, workability, etc. of the obtained workpiece, paint, adhesive, fiber sizing agent, concrete primer It is providing the water-based epoxy resin composition which can be used suitably for the above.

  As a result of intensive studies to solve the above problems, the present inventor obtained by reacting a compound having a weight average molecular weight of 500 to 60,000 and a functional group that reacts with a glycidyl group with a glycidyl group-containing quaternary onium salt. It is found that an aqueous epoxy resin composition containing a compound obtained and an alkoxysilane is excellent in coating film performance, has no odor during storage or processing, and does not have a cause of corrosion in a heating furnace. It came to complete.

  That is, the present invention is a compound obtained by reacting a compound (a1) having a weight average molecular weight of 500 to 60,000 and having a functional group (x) that reacts with a glycidyl group and a glycidyl group-containing quaternary onium salt (a2) ( An aqueous epoxy resin composition comprising A) and alkoxysilane (B) is provided.

  Furthermore, the present invention provides a compound (a1) having a weight average molecular weight of 500 to 60,000 and having a functional group (x) that reacts with a glycidyl group, a glycidyl group-containing quaternary onium salt (a2), and a glycidyl group-containing alkoxysilane. An aqueous epoxy resin composition comprising a compound (C) obtained by reacting (b1) with water and water is also provided.

  Furthermore, the present invention provides a modified epoxy resin (a1 ′) having a weight average molecular weight of 500 to 60,000 obtained by reacting an epoxy resin (a1-1) with an amino group-containing alkoxysilane (b2) and a glycidyl group. The present invention also provides an aqueous epoxy resin composition comprising a compound (E) obtained by reacting a quaternary onium salt (a2) with water and water.

  According to the present invention, no odor is generated during storage or processing of the varnish, and it has excellent adhesion and processability of the obtained workpiece, and is suitably used for paints, adhesives, fiber sizing agents, concrete primers, and the like. An aqueous epoxy resin composition that can be used can be provided.

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

  When the weight average molecular weight of the compound (a1) having the functional group (x) that reacts with the glycidyl group is less than 500, the molecular weight of the resin obtained by reaction with the glycidyl group-containing quaternary onium salt (a2) described later is When the molecular weight exceeds 60,000, the storage stability when used as an aqueous epoxy resin composition is poor, preferably not small enough to be satisfactory in corrosion resistance and adhesion to a substrate when used in paints, etc. Absent. 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 that it has an aromatic ring from the point which is excellent in it, and the compound obtained by reaction with the compound which has a functional group (x) which reacts with an epoxy resin (a1-1) and a glycidyl group from the point which is excellent in corrosion resistance It is preferable that

  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 Include condensates of Dorin, they be one kind, it may be used in combination of two or more. Among these, bisphenol A type epoxy is preferable because it has good reactivity with a compound having a functional group that reacts with a glycidyl group, which will be described later, and the corrosion resistance of a processed product using the obtained aqueous epoxy resin composition is good. It is preferable to use a resin, 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, and the varnish stability of the aqueous epoxy resin composition. Is preferably 110 to 1,300 g / eq from the viewpoint of good.

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

  Examples of the polyhydric phenols include divalent phenols such as resorcin, hydroquinone, and catechol, which may have a substituent, bisphenols such as bisphenol A, bisphenol F, bisphenol AD, and tetrabromobisphenol A, and phenol novolacs. And alkylphenol novolaks such as cresol novolac, dicyclopentadiene phenol resin and the like, and 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 include malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, decanoic acid, dodecanedioic acid, glutaric acid and other aliphatic divalent carboxylic acids, phthalic acid, isophthalic acid, terephthalic acid Examples include acids, aromatic divalent carboxylic acids such as naphthalenedicarboxylic acid, hydrogenated products thereof, dimer acids, and the like, and those in which an aromatic ring is substituted with an alkyl group or a halogen or those that are nuclear hydrogenated, Furthermore, 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 and / or the polyvalent carboxylic acids are included. Epichlorohydrin is preferable from the viewpoint of excellent reactivity with acids.

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

  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.

  Examples of the production method of (ii) include, for example, the reaction product obtained in (i) using the polyhydric phenols and / or the polyhydric carboxylic acids as an extender, and in the presence of a catalyst, 120 to 220 A method in which the mixture is heated and stirred at 0 ° C. is exemplified. 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, it is preferable to calculate the use ratio of the reaction product obtained in (i) and the polyhydric phenols and / or the polyhydric carboxylic acids from the epoxy equivalent of the target epoxy resin (a1-1). .

  The polyhydric phenols and / or polyhydric carboxylic acids used as the extender may be the same as or different from the polyhydric phenols and polycarboxylic acids used in the reaction (i). .

  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 compound which has the functional group (x) which reacts with a glycidyl group made to react with an epoxy resin (a1-1). The compound is a modifier (extender) of the epoxy resin (a1-1), and introduces a site that reacts with the glycidyl group-containing quaternary onium salt (a2) described later in the structure of the resulting compound. is there. The functional group (x) that reacts with the glycidyl group is not particularly limited as long as it is a functional group that can react with the glycidyl group in the epoxy resin (a1-1) obtained above. From the point that 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 good, it may be an amino group, a hydroxyl group or a carboxyl group. An amino group is most preferable from the viewpoint of excellent corrosion resistance of the obtained workpiece. Therefore, as the compound (a1), the above-mentioned epoxy resin (a1-1), amino group-containing compound (a1-2), hydroxyl group-containing compound (a1-3), or carboxyl group-containing compound (a1-4) It is preferable that it is a compound obtained by reaction with.

  The amino group-containing compound (a1-2) is not particularly limited as long as it is a compound having an amino group capable of reacting with the glycidyl group in the epoxy resin (a1-1) obtained above. Various compounds can be used freely. From the viewpoint of good reactivity between the resulting compound (a1) and the glycidyl group-containing quaternary amine salt (a2) described later, it is a primary amino group-containing compound. Preferably there is.

  Examples of the amino group-containing compound (a1-2) include primary alkylamines such as butylamine, octylamine, oleylamine, 2-ethylhexylamine, monoethanolamine, 2-ethoxyethanolamine, and 2-hydroxypropanolamine. Primary alkanolamines, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-xylenediamine, p-xylenediamine and other aliphatic polyamines, 1,3-diaminocyclohexane, isophoronediamine and other alicyclic polyamines, polyamine By reaction of Mannich base consisting of polycondensates of aldehydes with aldehyde compounds and mono- or polyhydric phenols, aromatic polyamines such as diaminodiphenylmethane, polyamines and polycarboxylic acids or dimer acids. Polyamide polyamines such as obtained and the like. Among these, from the viewpoint of excellent compatibility between the obtained compound (A) and water and excellent storage stability of the aqueous epoxy resin composition, primary alkylamines and / or primary alkanolamines are preferable. Monoethanolamine and 2-ethoxyethanolamine are particularly preferable.

  Examples of the polyaddition reaction of the epoxy resin (a1-1) and the amino 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 viscosity during the reaction is suppressed, and the reaction with the glycidyl group-containing quaternary onium salt (a2) described later is easy. It is preferable that it is 60 degreeC-140 degreeC especially. As the solvent, the raw material epoxy resin (a1-1), the amino group-containing compound (a1-2) and the reaction product compound (a1) 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 cellosorob Rosolves, glymes such as monoglyme, diglyme, 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.

  As a preparation ratio of the epoxy resin (a1-1) and the amino group-containing compound (a1-2), the compound (A) obtained by the reaction with the glycidyl group-containing quaternary onium salt (a2) described later and water From the point of being excellent in compatibility and excellent in adhesion to the substrate of the resulting aqueous epoxy resin composition, (active hydrogen equivalent in (a1-2)) / (epoxy equivalent in (a1-1)) > 1 is preferable, and the ratio is particularly preferably 1.1 or more and 3.3 or less.

  When the epoxy resin (a1-1) and the amino group-containing compound (a1-2) are reacted, a monovalent active hydrogen compound or the like can be used in combination as necessary.

  Examples of the monovalent active hydrogen compound include monovalent alkylamines such as dibutylamine and di-2-ethylhexylamine, diethanolamine, diisopropanolamine, N-methylethanolamine, 1-methylaminopropanediol and the like. And cyclic monovalent amines such as valent alkanolamines, morpholine, piperazine and 4-methylpiperazine.

  The compound (a1) obtained by the above reaction may be used for the next step as it is, or may be subjected to a purification step such as deactivation of the catalyst or removal of the solvent, if necessary.

  Moreover, as a hydroxyl-containing compound (a1-3), if it is a compound which has a hydroxyl group which can react with the glycidyl group in the epoxy resin (a1-1) obtained above, it will not be restrict | limited especially, 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 excellent in the molecule. It is preferable that the compound contains two or more phenolic hydroxyl groups.

  Examples of the hydroxyl group-containing compound (a1-3) include bisphenols such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, and bisphenol Z, dihydroxybenzenes such as hydroquinone, resorcin, and catechol, and 1,5 dioxynaphthalene. , 1,6-dioxynaphthalene, and the like, biphenol, dicyclopentadiene-phenol condensate, and tricyclopentadiene N-phenol condensate, in which the aromatic ring is substituted with an alkyl group or halogen Or may be hydrogenated, or may be used alone or in combination of two or more.

  Also, novolaks obtained from phenols, bisphenols, dihydroxybenzenes, dihydroxynaphthalenes and ketones can be used.

  Furthermore, a reaction product of a divalent or higher glycidyl group-containing compound and the hydroxyl group-containing compound (a1-3) can also be used. Examples of the divalent or higher glycidyl group-containing compound include a condensate of bisphenols and epihalohydrin, a condensate of dihydroxybenzenes and epihalohydrin, and a condensate of dibasic acid and epihalohydrin.

  The reaction ratio of the reaction product of the divalent or higher glycidyl compound and the hydroxyl group-containing compound is equivalent to the equivalent of the phenolic hydroxyl group in the phenolic hydroxyl group-containing compound to one equivalent (eq) of the epoxy group in the divalent or higher glycidyl compound. If (eq) is 1.01 or more, it can be used without particular limitation.

  As the hydroxyl group-containing compound (a1-3), bisphenols and dihydroxybenzenes are preferred because they are excellent in compatibility between the resulting compound (A) and water (B) and are excellent in storage stability of the aqueous epoxy resin composition. And bisphenols are particularly preferable.

  As a method for the polyaddition reaction between the epoxy resin (a1-1) and the hydroxyl group-containing compound (a1-3), for example, in the presence of a catalyst such as an acid, a base, a metal salt, or a metal oxide, or without a catalyst. And a method performed in a molten state or in the presence of a solvent. The reaction temperature at this time is 50 to 160 ° C. from the viewpoint that the reaction time is appropriate, the viscosity during the reaction is suppressed, and the reaction with the glycidyl group-containing quaternary onium salt (a2) described later is easy. It is preferable that it is 60 degreeC-140 degreeC especially. As the solvent, the raw material epoxy resin (a1-1), the hydroxyl group-containing compound (a1-3) and the reaction product compound (a1) are uniformly dissolved, and are inert to (a1). There is no particular limitation as long as it is, 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- Cellulose such as butyl cello solob Glymes such as sorbs, monoglyme, diglyme, 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.

  When the epoxy resin (a1-1) and the hydroxyl group-containing compound (a1-3) are reacted, monovalent phenols, monovalent amine compounds, and monovalent glycidyl compounds are used in combination as necessary. I can do things.

  Examples of the monovalent phenols include phenols that may be nucleus-substituted with hydrocarbons and halogens. Examples of the monovalent amine compounds include 1-butylamine, di-2-ethylhexylamine and the like. And monovalent alkanolamines such as divalent 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, or may be subjected to a purification step such as deactivation of the catalyst or removal of the solvent, if necessary.

  Examples of the carboxyl group-containing compound (a1-4) 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.

  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, and a condensate of dibasic acid and epihalohydrin. Examples of the carboxyl group-containing compound include 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.

  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 (a1-4), divalent carboxylic acid, among them, from the concern 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 of the epoxy resin (a1-1) and the carboxyl group-containing compound (a1-4) 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 viscosity during the reaction is suppressed, and the reaction with the glycidyl group-containing quaternary onium salt (a2) described later is easy. It is preferable that it is 60 degreeC-140 degreeC especially. As said solvent, the epoxy resin (a1-1) which is a raw material, a carboxyl group-containing compound (a1-4) 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 (a1-4) 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 -Amyl, ethoxyethyl propyronate, 3-methoxybutyl acetate, methoxypropyl acetate, cellosolve acetate and other esters, 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 the functional group (x) reacting with the glycidyl group in (a1) relative to 1 equivalent (eq) of the epoxy group in (a2) is usually 0. .1 or more and 200 or less, preferably 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.

  Although it does not specifically limit as alkoxysilane (B) used by this invention, From the point which is excellent in the storage stability of an aqueous epoxy resin composition, glycidyl group containing alkoxysilane (b1), amino group containing alkoxysilane ( b2) and (meth) acryloxy group-containing alkoxysilane (b3) are preferred, and they may be used alone or in combination of two or more.

  Examples of the glycidyl group-containing alkoxysilane (b1) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ-glycidoxypropyl. Examples thereof include methyldiethoxysilane, γ-glycidoxypropyltriisopropenyloxysilane, and γ-glycidoxypropyltriiminooxysilane. As products already on the market, for example, KBM-403, KBE-403, KBE-402 (all manufactured by Shin-Etsu Chemical Co., Ltd.), SH6040, AY43-026 (all manufactured by Toray Dow Corning Silicone Co., Ltd.) ) And the like.

  Examples of the amino group-containing alkoxysilane (b2) include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (Β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldiethoxysilane, N-cyclohexyl-γ-aminopropyltrimethoxysilane, N-cyclohexyl-γ -Aminopropyltriethoxysilane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane, γ- (2-aminoethyl) -aminopropylmethyldimethoxysilane, γ-anilinopropyltrimethoxysilane and the like. As products already on the market, for example, KBM-602, KBM-603, KBE-603, KBM-903, KBE-903 (all manufactured by Shin-Etsu Chemical Co., Ltd.), SH6020, AY43-059, SZ6023 (whichever As well as Toray Dow Corning Silicone Co., Ltd.).

  Examples of the (meth) acryloxy group-containing alkoxysilane (b3) include 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropylmethyl. Examples thereof include diethoxysilane and 3-methacryloxypropyltriethoxysilane. Examples of products already on the market include KBM-5103, KBM-502, KBE-502, KBM-503, KBE503 (all manufactured by Shin-Etsu Chemical Co., Ltd.), SZ6030, AY43-310M (all are Toray Dow Corning Silicone Co., Ltd.).

  The compounding amount of the alkoxysilane (B) is not particularly limited, but it reacts with the glycidyl group from the viewpoint of excellent adhesion and corrosion resistance of the processed product and excellent balance with workability. 1 to 50 parts by weight, preferably 1 to 30 parts by weight, and particularly preferably 5 to 30 parts by weight with respect to 100 parts by weight of the compound (a1) having the functional group (x).

  The aqueous epoxy resin composition of the present invention can be produced, for example, by adding and mixing the alkoxysilane (B) after synthesizing the compound (A).

  When water is introduced into the aqueous epoxy resin composition of the present invention, it is preferable to use deionized water. Water is used to dissolve or disperse the compound (A), and the reaction between the compound (a1) and the glycidyl group-containing quaternary onium salt (a2) [reaction to obtain the compound (A)] or after completion of the reaction It can be added, and it can be set as an aqueous epoxy resin composition by uniformly stirring and mixing.

The aqueous epoxy resin composition of the present invention has found a method using an aqueous compound (A) and an alkoxysilane (B) in order to obtain a processed product having excellent performance balance such as adhesion, workability, and corrosion resistance. However, not only the method of externally adding alkoxysilane as described above, but also when using an alkoxysilane having a specific functional group, it is possible to introduce a silane structure into the resin (so-called internal addition). Thus, similar performance can be imparted to the obtained workpiece.
Hereinafter, this method will be described.

  First, a compound (a1) having a weight average molecular weight of 500 to 60,000 and having a functional group (x) that reacts with a glycidyl group, a glycidyl group-containing quaternary onium salt (a2), and a glycidyl group-containing alkoxysilane (b1) It describes about the compound (C) obtained by making these react.

  When the glycidyl group-containing alkoxysilane (b1) is used, the glycidyl group-containing quaternary onium salt (a2) after the reaction between the epoxy resin (a1-1) and the compound having a functional group (x) that reacts with the glycidyl group. Compound (C) can be obtained by reacting with glycidyl group-containing quaternary onium salt (a2) before the reaction. At this time, since a heating reaction is performed, the glycidyl group-containing alkoxysilane (b1) is directly bonded to a silane having an alkoxy group having 2 or more carbon atoms or a silicon atom because of the concern of hydrolysis and dehydration condensation. It is preferable to use a glycidyl group-containing alkoxysilane having 2 or less alkoxy groups. The amount of the glycidyl group-containing alkoxysilane (b1) to be added is appropriately selected within a range in which a glycidyl group-containing quaternary onium salt (a2) is sufficiently introduced into the molecule and an aqueous resin can be obtained. Is preferred. Examples of the glycidyl group-containing alkoxysilane (b1) include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ-glycidoxypropylmethyldiethoxysilane.

  As the compound (a1) having a weight average molecular weight of 500 to 60,000 and a functional group (x) that reacts with a glycidyl group or a glycidyl group-containing quaternary onium salt (a2), the above-mentioned external addition method is used. It is the same as that explained in full detail in that case, and the same also applies to the preferred glycidyl group-containing quaternary onium salt (a2).

  Water is used to uniformly dissolve or disperse the compound (C) obtained above. Deionized water is preferably used at this time. Water can be added when the reaction is carried out using the glycidyl group-containing quaternary onium salt (a2) or after completion of the reaction.

  When the content of alkoxysilane is increased to improve the adhesion of the resulting aqueous epoxy resin composition, as described above, the method of externally adding to the obtained compound (C) may be used in combination. The type of alkoxysilane added at this time may be the same as or different from the glycidyl group-containing alkoxysilane (b1) introduced into the molecule.

  Next, the compound (a1 ′) having a weight average molecular weight of 500-60,000 obtained by reacting the epoxy resin (a1-1) with the amino group-containing alkoxysilane (b2) and a glycidyl group-containing quaternary onium salt ( It describes about the compound (D) obtained by making a2) react.

  When the amino group-containing alkoxysilane (b2) is used, it can be used in the same manner as the amino group-containing compound (a1-2). Among them, it is preferable to use a primary amino group-containing alkoxysilane. At this time, since a heating reaction is performed, the number of alkoxysilanes having an alkoxy group having 2 or more carbon atoms, or alkoxy groups directly bonded to silicon atoms, because of the concern of hydrolysis of alkoxysilane and gelation by dehydration condensation reaction It is preferable to use an amino group-containing alkoxysilane having 2 or less. Further, the addition amount of the amino group-containing alkoxysilane (b2) can be increased or decreased depending on the molecular weight setting of the target compound (a1 ′). Furthermore, it can be used in combination with the amino group-containing compound (a1-2). Examples of the amino group-containing alkoxysilane (b2) include γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, and N- (β-aminoethyl) -γ-. Examples include aminopropylmethyldiethoxysilane.

  The epoxy resin (a1-1) and glycidyl group-containing quaternary onium salt (a2) used here are the same as those described in detail in the method of external addition described above, and are preferably glycidyl group-containing quaternary onium salts. The same applies to (a2).

  In order to uniformly dissolve or disperse the compound (D) obtained above, water is used. Deionized water is preferable for use at this time. Water is added when the epoxy resin (a1-1) is reacted with the amino group-containing alkoxysilane (b2), when the reaction is performed using the glycidyl group-containing quaternary onium salt (a2), or after the reaction is completed. I can do it.

  When the content of alkoxysilane is increased to improve the adhesion of the resulting aqueous epoxy resin composition, as described above, a method of externally adding to the obtained compound (D) may be used in combination. The type of alkoxysilane added at this time may be the same as or different from the amino group-containing alkoxysilane (b2) introduced into the molecule.

  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, triglyme, 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, and other propylene 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 from the viewpoint of good solubility in compound (A), compound (C) and compound (D) It is preferable to use glycol monopropyl ether or diacetone alcohol. These auxiliaries are added during or after the production of the compound (a1), or at the time of the reaction of the compound (a1) with the glycidyl group-containing quaternary onium salt (a2) or after the completion of the reaction. Can do.

  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 in order to improve the performance of the obtained workpiece, for example, the adhesion to the substrate and the corrosion resistance.

  The curing agent is not particularly limited as long as it is a compound capable of undergoing a curing reaction with a hydroxyl group in the compound (A), compound (C), or compound (D). It is preferable to use an amino resin, an isocyanate compound, or a phenol resin from the viewpoint that the obtained cured product is excellent in the aforementioned performance.

  Examples of the amino resins include melamine resins derived from melamine and aldehyde compounds, guanamine resins derived from aldehyde compounds such as benzoguanamine and acetoguanamine, and urea resins derived from aldehyde compounds such as urea and thiourea. Can be mentioned. These can be used alone or in combination of two or more.

  Further, as the amino resin, 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 may be used. it can.

  The amino resin is used in a proportion of preferably 1 to 40 parts by weight, more preferably 2 to 30 parts by weight, based on 100 parts by weight of the resin solids in the aqueous epoxy resin composition. Part.

  Although it does not specifically limit as said isocyanate compound, For example, aromatic isocyanates, such as phenylene diisocyanate, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylylene diisocyanate, metaxylylene diisocyanate, as diisocyanate, for example. Aliphatic diisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated metaxylylene diisocyanate, norbornene Alicyclic diisocyanates such as diisocyanates S and the like, and solvent-free, 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, it is also possible to use those subjected to various modification reactions for the purpose of reducing the vapor pressure, adjusting the viscosity, the number of functional groups, the reactivity, and imparting special physical properties using the above isocyanate. it can. 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 may be used alone or as a mixture of two or more.

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

  The phenol resin is not particularly limited as long as it is a compound in which a phenol and an aldehyde compound are subjected to a condensation reaction 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, biphenol, 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 novolak type condensate can be obtained.

  The proportion of the phenol resin used is not particularly limited, but it is preferably 1 to 40 parts by weight of solid content in the phenol resin with respect to 100 parts by weight of resin solid content of the aqueous epoxy resin composition, more preferably 2 -30 parts by weight.

  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 rust preventive pigment include zinc powder, aluminum phosphomolybdate, zinc phosphate, aluminum phosphate, barium chromate, aluminum chromate, and scaly pigments such as graphite. Color pigments include carbon black, oxidized Examples thereof include titanium, zinc sulfide, and bengara. Examples of extender pigments include barium sulfate, calcium carbonate, talc, and kaolin. As a compounding quantity of these fillers, it is 10-70 weight part with respect to a total of 100 weight part of a compound (A), a compound (C), or a compound (D), and the hardening | curing agent mix | blended as needed. It is preferable from the viewpoints of coating film performance, painting workability and the like.

  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, the fiber immediately after spinning is applied using a roller coater and wound as a fiber strand. Thereafter, a method of drying is mentioned. The fiber used is not particularly limited. For example, inorganic fibers such as glass fiber, ceramic fiber, asbestos fiber, carbon fiber, and stainless 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, sheets, and the like. 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 88 parts were charged and uniformed by heating and stirring to 80 ° C. Here, 0.1 part of a 50% aqueous solution of tetramethylammonium chloride as a catalyst was added, and further stirred at 140 ° C. for 3 hours, and then 29 parts of monoethanolamine (primary alkanolamine, manufactured by Mitsui Chemicals, Inc.) was added. It was made to react for a time and the compound (a1-i) of the weight average molecular weight 22,000 was obtained. 207 parts of butyl cellosolve was added here, and after confirming that the solution became uniform, the liquid temperature was cooled to 80 ° C. Subsequently, 17.9 parts of SY-GTA (glycidyl group-containing quaternary onium salt-80% aqueous solution, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) was added and further reacted at 80 ° C. for 3 hours. Further, 1173.6 parts of ion-exchanged water was added, and then 35 parts of KBM-403 (3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to form a white liquid with a non-volatile content of 25.2%. An aqueous epoxy resin composition was obtained. This is defined as (E-1).

Example 2
In Example 1, it carried out similarly except having changed KBM-403 to 40 parts, and obtained the white liquid aqueous epoxy resin composition of 25.4% of non volatile matters. This is defined as (E-2).

Example 3
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 86 parts were charged and uniformed 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. 2.4 parts of triphenylphosphine and 100 parts of adipic acid were added thereto, and the mixture was further stirred at 140 ° C. for 4 hours to obtain a compound (a1-ii) having a weight average molecular weight of 10,000. Here, 315.6 parts of butyl cellosolve was charged, and after confirming that the solution became uniform, the liquid temperature was cooled to 90 ° C. Subsequently, 49.8 parts of SY-GTA was charged and further reacted at 90 ° C. for 3 hours. 1253 parts of ion-exchanged water was added thereto, and finally 5 parts of KBM-403 was added to obtain a white liquid aqueous epoxy resin composition having a nonvolatile content of 25.2%. This is defined as (E-3).

Example 4
The same procedure as in Example 1 was carried out until the compound (a1-i) was obtained. 207 parts of butyl cellosolve was charged therein, and after confirming that the solution was uniform, the solution temperature was cooled to 90 ° C. Subsequently, 26.39 parts of KBM-403 was charged and further stirred at 90 ° C. for 1 hour. Further, 17.9 parts of SY-GTA was added and reacted at 80 ° C. for 3 hours. Finally, 1620.3 parts of ion-exchanged water was added to obtain a white liquid aqueous epoxy resin composition having a nonvolatile content of 20.0%. This is defined as (E-4).

Example 5
In the same manner as in Example 4 until SY-GTA was added, followed by addition of 1173.6 parts of ion-exchanged water, followed by addition of 8.61 parts of KBM-403 at 40 ° C. or lower and stirring until uniform. As a result, a white liquid aqueous epoxy resin composition having a nonvolatile content of 25.2% was obtained. This is defined as (E-5).

Example 6
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 88 parts were charged and uniformed by heating and stirring to 80 ° C. Here, 0.1 part of a 50% aqueous solution of tetramethylammonium chloride as a catalyst was added, and further stirred at 140 ° C. for 3 hours, and then 14.5 parts of monoethanolamine, KBE-903 (3-aminopropyltriethoxysilane, 12.6 parts (manufactured by Shin-Etsu Chemical Co., Ltd.) were charged and reacted at 110 ° C. for 2 hours to obtain a compound (a1-iii) having a weight average molecular weight of 20,000. 207 parts of butyl cellosolve was added here, and after confirming that the solution became uniform, the liquid temperature was cooled to 80 ° C. Subsequently, 11.0 parts of SY-GTA was charged and further reacted at 80 ° C. for 3 hours. Further, 1721.9 parts of ion-exchanged water was added to obtain a white liquid aqueous epoxy resin composition having a nonvolatile content of 18.0%. This is defined as (E-6).

Comparative Example 1
In Example 1, the process until SY-GTA is reacted is carried out in the same manner, and 1514.7 parts of ion-exchanged water is further added to obtain a white liquid aqueous epoxy resin composition having a nonvolatile content of 20.0%. It was. This is defined as (E′-1).

Table 1 shows the property values of the aqueous epoxy resin compositions (E-1) to (E-6) and (E′-1) obtained in Examples 1 to 6 and Comparative Example 1, and the inside of a dryer at 40 ° C. Changes in appearance when stored. 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 1-6 and Comparative Test Examples 1-2
Next, a water-based paint was prepared using the obtained water-based epoxy resin composition at a blending ratio shown in Table 2, and the dry film thickness was measured with a bar coater on a cold-rolled steel sheet that had been surface-treated with a # 400 sandpaper. After coating to 20 μm, the coating film physical properties were evaluated. In addition, the physical property of the lacquer coating film of Table 2 is a test result after 100 degreeC x 20 minutes +25 degreeC x 5 days post-curing. 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.
○: 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.

Flexibility: In accordance with JIS K-5600-5-1 (1999), the coating film was observed to be cracked and peeled off from the substrate when bent by a cylindrical mandrel (diameter 2 mm).
○: No cracking or peeling occurred. X: Cracking or peeling 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 manufactured by Nihon Talc Co., Ltd. BYK-341: Additive manufactured by BYK Chemie PWC (% ): Weight ratio of filler to solid content of paint NV (%): Non-volatile content of paint (resin + filler)

Claims (17)

A compound (A) obtained by reacting a compound (a1) having a weight average molecular weight of 500 to 60,000 and having a functional group (x) that reacts with a glycidyl group and a glycidyl group-containing quaternary onium salt (a2); An aqueous epoxy resin composition containing silane (B). An aqueous epoxy resin composition using 1 to 30 parts by weight of alkoxysilane (B) with respect to 100 parts by weight of the compound (A). 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 3, 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 functional group (x) that reacts with the glycidyl group in the compound (a1) is an amino group, a hydroxyl group, or a carboxyl group. The aqueous epoxy resin composition according to claim 1, wherein the functional group (x) that reacts with the glycidyl group in the compound (a1) is an amino group. The compound (a1) is obtained by reaction of the epoxy resin (a1-1) with an amino group-containing compound (a1-2), a hydroxyl group-containing compound (a1-3), or a carboxyl group-containing compound (a1-3). The aqueous epoxy resin composition according to claim 5, which is a compound. The alkoxysilane (B) is a glycidyl group-containing alkoxysilane (b1), an amino group-containing alkoxysilane (b2), or a (meth) acryloxy group-containing alkoxysilane (b3). An aqueous epoxy resin composition. The aqueous epoxy resin composition according to claim 1, which is a resin composition for aqueous paint. A compound (a1) having a weight average molecular weight of 500 to 60,000 and having a functional group (x) that reacts with a glycidyl group, a glycidyl group-containing quaternary onium salt (a2), and a glycidyl group-containing alkoxysilane (b1) An aqueous epoxy resin composition comprising a compound (C) obtained by reaction and water. 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 10, which is a compound represented by the formula: The aqueous epoxy resin composition according to claim 11, 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. It is a resin composition for water-based paints, The water-based epoxy resin composition of any one of Claims 10-12. A compound (a1 ′) having a weight average molecular weight of 500 to 60,000 obtained by reacting an epoxy resin (a1-1) with an amino group-containing alkoxysilane (b2), a glycidyl group-containing quaternary onium salt (a2), An aqueous epoxy resin composition comprising a compound (D) obtained by reacting water and water. 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 14, which is a compound represented by the formula: The aqueous epoxy resin composition according to claim 15, 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 any one of claims 14 to 16, which is a resin composition for aqueous paints.