JP2006206675A - Epoxy resin composition and its cured product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition that gives an epoxy resin cured product particularly exhibiting good alkali resistance and excellent flexibility without detriment to excellent corrosion resistance and is therefore suitably employed for a coating material, a lining material, a concrete primer, a concrete sealer and the like, and its cured product. <P>SOLUTION: The epoxy resin composition comprises an epoxy resin (X) obtained by glycidyl etherification of a modified polyhydric phenols (A) obtained by reacting a polyhydric phenols (a1) with a polyvalent vinyl ethers (a2), and a modified aliphatic polyamines (Y). The cured product thereof is also provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention does not impair the excellent corrosion resistance of the cured epoxy resin, has particularly good alkali resistance and excellent flexibility, and can be suitably used for coating materials, lining materials, concrete primers, concrete sealers, etc. The present invention relates to an epoxy resin composition and a cured product thereof.

  Epoxy resins are widely used in paints, lining materials, adhesives, electrical and electronic applications, etc., because they can be cured with various curing agents to obtain cured products with excellent corrosion resistance. It has the essential problem of being inferior. Especially in paint applications, concrete and mortar linings and primers, concrete sealers, etc., are often used outdoors, so the substrate tends to expand and contract due to changes in temperature or vibration, and cracks occur in the cured product. Therefore, there is a demand for an excellent flexibility without impairing the excellent corrosion resistance of the cured epoxy resin.

  As means for solving these problems, for example, a method using a urethane-modified epoxy resin has been proposed (see, for example, Patent Document 1). The cured product obtained using the urethane-modified epoxy resin, for example, is improved to some extent than the cured product obtained using the bisphenol-type epoxy resin, but does not meet the performance requirements in recent years. There is a shortage of alkali resistance required when used in concrete structural materials, and improvements are required.

JP-A-8-311152 (pages 2 to 4)

  Accordingly, an object of the present invention is to provide an epoxy resin that does not impair the excellent corrosion resistance of the cured epoxy resin, has particularly good alkali resistance, has excellent flexibility, and can be suitably used for coating materials, lining materials, and the like. The object is to provide a composition and a cured product thereof.

  As a result of diligent research to solve the above-mentioned problems, the present inventors have found that an epoxy resin obtained by glycidyl etherification of a modified polyphenol obtained by reacting a polyhydric phenol with a polyvalent vinyl ether and a modified aliphatic polyamine The present inventors have found that an epoxy resin composition containing the above can solve the above problems, and completed the present invention.

  That is, the present invention relates to an epoxy resin (X) obtained by glycidyl etherification of a modified polyphenol (A) obtained by reacting a polyhydric phenol (a1) with a polyvalent vinyl ether (a2) and a modified fat. The epoxy resin composition characterized by containing group polyamines (Y) and the hardened | cured material which hardened this are provided.

  The epoxy resin composition of the present invention can be cured at room temperature, and the resulting cured product is excellent in flexibility and excellent in corrosion resistance, particularly alkali resistance. Since it has such physical properties, it can satisfy the required performance of coating materials, lining materials, etc., and can be suitably used especially for scenes used as concrete structural materials, and is extremely useful.

Hereinafter, the present invention will be described in detail.
The epoxy tree composition of the present invention is an epoxy resin (X) obtained by glycidyl etherification of a modified polyhydric phenol (A) obtained by reacting a polyhydric phenol (a1) with a polyvalent vinyl ether (a2). And modified aliphatic polyamines (Y).

  In the epoxy resin (X), an aromatic hydroxyl group in the polyhydric phenol (a1) and a vinyl ether group in the polyvalent vinyl ether (a2) are subjected to an addition reaction, and the polyhydric phenol is chain extended by an acetal group. The resulting modified polyhydric phenols (A) have a chemical structure obtained by converting the hydroxyl group into glycidyl ether with epihalohydrin.

  The reaction between the hydroxyl group and the vinyl ether group is represented by the following chemical reaction formula:

で表され、アセタール基を生成する。

And produces an acetal group.

  The polyhydric phenol (a1) is not particularly limited as long as it is an aromatic compound containing more than one aromatic hydroxyl group in one molecule. For example, hydroquinone, resorcin, catechol, and substitution thereof Dihydroxybenzenes such as group-containing compounds; 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxy Dihydroxynaphthalenes such as naphthalene and substituents thereof; bis (4-hydroxyphenyl) methane (bisphenol F), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (3-Methyl-4-hydroxyphenyl) propane (bisph Nord C), 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z), 1,1-bis (4-hydroxyphenyl) -1-phenylethane (bisphenol AP), bis (4-hydroxyphenyl) sulfone Bisphenols such as (bisphenol S) and these substituent-containing compounds; bisnaphthols such as bis (2-hydroxy-1-naphthyl) methane and bis (2-hydroxy-1-naphthyl) propane; phenol / formaldehyde polycondensation , Orthocresol / formaldehyde polycondensate, 1-naphthol / formaldehyde polycondensate, 2-naphthol / formaldehyde polycondensate, phenol / acetaldehyde polycondensate, orthocresol / acetaldehyde polycondensate, 1-naphthol / acetaldehyde polycondensate Compound, 2-naphthol / acetaldehyde polycondensate, phenol / salicylaldehyde polycondensate, orthocresol / salicylaldehyde polycondensate, 1-naphthol / salicylaldehyde polycondensate, 2-naphthol / salicylaldehyde polycondensate and the like Phenols (naphthols) / aldehyde polycondensates such as those containing these substituents; phenol / dicyclopentadiene polyadduct, phenol / tetrahydroindene polyadduct, phenol / 4-vinylcyclohexene polyadduct, phenol / 5-vinylnoborn-2-ene polyadduct, phenol / α-pinene polyadduct, phenol / β-pinene polyadduct, phenol / limonene polyadduct, orthocresol / dicyclopentadiene polyadduct, orthocresol / Tetrahydroindene weight , Orthocresol / 4-vinylcyclohexene polyadduct, orthocresol / 5-vinylnoborn-2-ene polyadduct, orthocresol / α-pinene polyadduct, 1-naphthol / dicyclopentadiene polyadduct, 1- Naphthol / 4-vinylcyclohexene polyadduct, 1-naphthol / 5-vinylnorbornadiene polyadduct, 1-naphthol / α-pinene polyadduct, 1-naphthol / β-pinene polyadduct, 1-naphthol / limonene heavy adduct Phenols (naphthols) / dienes polyadducts such as adducts, orthocresol / β-pinene polyadducts, orthocresol / limonene polyadducts, etc., and substituents thereof; phenol / p-xylene dichloride Polycondensate, 1-naphthol / p-xylene dichloride polycondensate, 2-naphthol / p Xylene dichloride polycondensate, phenol / bischloromethylbiphenyl polycondensate, orthocresol / bischloromethylbiphenyl polycondensate, 1-naphthol / bischloromethylbiphenyl polycondensate, 2-naphthol / bischloromethylbiphenyl polycondensate And polycondensates of these substituent-containing products such as phenols / aralkyl resins. Examples of substituents in these substituent-containing products include alkyl groups, aryl groups, cycloalkyl groups, alkoxy groups, alkoxycarbonyl groups, acyl groups, and halogen atoms.

  Among these polyhydric phenols, liquid low-viscosity epoxy resins can be obtained even when the vinyl ether modification rate is increased, and divalent phenols are preferred because they can be suitably used for paints and lining materials. Among dihydric phenols, since a cured product having excellent flexibility and water resistance can be obtained, bisphenols such as bisphenol A and bisphenol F are preferable, and hydroquinone, when considering the fluidity of the resulting epoxy resin composition, Particularly preferred are dihydroxybenzenes such as resorcin and catechol, and dihydroxynaphthalenes such as 1,6-dihydroxynaphthalene.

  The polyvalent vinyl ethers (a2) are not particularly limited as long as they are compounds containing more than one vinyl ether group in one molecule. For example, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol diester Vinyl ether, Tetraethylene glycol divinyl ether, Polyethylene glycol divinyl ether, Propylene glycol divinyl ether, Dipropylene glycol divinyl ether, Tripropylene glycol divinyl ether, Tetrapropylene glycol divinyl ether, Polypropylene glycol divinyl ether, Polytetramethylene glycol di Divinyl ethers containing (poly) oxyalkylene groups such as vinyl ether; Divinyl ether, triglycerol divinyl ether, 1,3-butylene glycol divinyl ether, 1,4-butanedidiol divinyl ether, 1,6-hexanediol divinyl ether, 1,9-nonanediol divinyl ether, 1,10- Divinyl ethers having an alkylene group such as decanediol divinyl ether, neopentyl glycol divinyl ether, and hydroxypivalate neopentyl glycol divinyl ether; 1,4-cyclohexanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, tricyclo Decanediol divinyl ether, tricyclodecane dimethanol divinyl ether, pentacyclopentadecane dimethanol divinyl ether, pentacyclope Divinyl ethers containing a cycloalkane structure such as tadecanediol divinyl ether; bisphenol A divinyl ether, ethylene oxide modified bisphenol A divinyl ether, propylene oxide modified bisphenol A divinyl ether, bisphenol F divinyl ether, ethylene oxide modified bisphenol F divinyl ether , Divinyl ethers such as propylene oxide modified bisphenol F divinyl ether; trivalent vinyl ethers such as trimethylolpropane trivinyl ether, ethylene oxide modified trimethylolpropane trivinyl ether, propylene oxide modified trimethylolpropane trivinyl ether, pentaerythritol trivinyl ether ; Pentaerythritol Examples thereof include tetravalent vinyl ethers such as tetravinyl ether, pentaerythritol ethoxytetravinyl ether and ditrimethylolpropane tetravinyl ether; and polyvalent vinyl ethers such as dipentaerythritol hexa (penta) vinyl ether.

  Among the polyvalent vinyl ethers, divinyl ethers are preferred because a low-viscosity liquid epoxy resin can be obtained even when the vinyl ether modification rate is increased and can be suitably used for paints and lining materials. As the divinyl ether, an appropriate one may be selected in consideration of the desired properties of the obtained epoxy resin. If low viscosity, flexibility, etc. are desired, divinyl ether containing a polyoxyalkylene skeleton is used. Are preferred. If excellent corrosion resistance is desired, divinyl ethers containing a cycloalkane skeleton are preferred.

  The modified polyphenols (A) can be obtained by subjecting the polyhydric phenol (a1) and the polyvalent vinyl ethers (a2) to an acetalization reaction.

  The acetalization reaction method is not particularly limited as long as it conforms to the reaction conditions of an aromatic hydroxyl group and a vinyl ether group. For example, the polyhydric phenols (a1) and the polyvalent vinyl ethers ( and a method of heating while stirring and mixing. In this case, an organic solvent and a catalyst can be used as needed. The organic solvent that can be used is not particularly limited, for example, aromatic organic solvents such as benzene, toluene, xylene, ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, Examples thereof include alcohol organic solvents such as ethanol, isopropyl alcohol, and normal butanol, and may be appropriately selected in consideration of properties such as solubility of raw materials and products used, reaction conditions, and economics. The amount of the organic solvent used is preferably in the range of 5 to 500% by weight with respect to the raw material weight.

  The reaction usually proceeds sufficiently even without a catalyst, but depending on the type of raw material used, the desired properties of the resulting modified polyphenols (A), the desired reaction rate, etc., a catalyst may be used. Also good. The type of the catalyst is not particularly limited as long as it is usually a catalyst used for the reaction between a hydroxyl group and a vinyl ether group. For example, inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid, toluenesulfonic acid , Methanesulfonic acid, xylenesulfonic acid, trifluoromethanesulfonic acid, oxalic acid, formic acid, trichloroacetic acid, trifluoroacetic acid and other organic acids, aluminum chloride, iron chloride, tin chloride, gallium chloride, titanium chloride, aluminum bromide, bromide Examples include Lewis acids such as gallium, boron trifluoride ether complex, and boron trifluoride phenol complex. The addition amount can be in the range of 10 ppm to 1% by weight with respect to the total weight of the raw material. However, in the catalyst addition system, it is necessary to select the type, addition amount, and reaction conditions so as not to cause a vinyl group nucleus addition reaction to the aromatic ring.

  The reaction conditions between the aromatic hydroxyl group and the vinyl ether group are usually room temperature to 200 ° C., preferably 50 to 150 ° C., and may be heated and stirred for about 0.5 to 30 hours. At this time, in order to prevent the self-polymerization of vinyl ethers, it is preferable to react in an oxygen-containing atmosphere. The progress of the reaction can be traced by measuring the residual amount of the raw material using gas chromatography, liquid chromatography or the like. Further, when an organic solvent is used, it can be removed by distillation or the like, and when a catalyst is used, it can be deactivated with a deactivator or the like, if necessary, and removed by washing with water or filtering. However, in the case of an organic solvent or catalyst (including a deactivated catalyst residue) that does not adversely affect the epoxidation reaction in the next step, there is no need for purification.

  The reaction ratio between the polyhydric phenols (a1) and the polyvalent vinyl ethers (a2) in the above reaction is not particularly limited as long as at least one aromatic hydroxyl group remains in one molecule of the reaction product. Without limitation, types and combinations of raw material polyhydric phenols (a1) and polyvalent vinyl ethers (a2), desired vinyl ether modification rate of the obtained modified polyhydric phenols (A), molecular weight, hydroxyl group equivalent, etc. It may be determined in accordance with the physical property value of and the acetal conversion rate depending on the reaction conditions. For example, when the effect such as flexibility due to the vinyl ether modification is remarkably enhanced, the amount of the polyvalent vinyl ether (a2) may be increased. Specifically, the vinyl ether group in the polyvalent vinyl ether (a2) is [the aromatic hydroxyl group in the polyvalent phenol (a1)] / the aromatic hydroxyl group in the polyhydric phenol (a1) / [Vinyl ether group in the polyvalent vinyl ether (a2)] = 80/20 to 50/50 (molar ratio) is preferable. Further, in the case of reaction conditions such that the conversion rate of vinyl ether is low due to the influence of side reaction, the ratio [aromatic hydroxyl group in polyhydric phenol (a1)] / [polyhydric vinyl ether (a2) Of vinyl ether groups] = 50/50 (molar ratio), and the vinyl ether group excess charge condition may be used. On the other hand, when it is desired to emphasize the balance of physical properties such as curability and corrosion resistance, the above ratio is [aromatic hydroxyl group in polyhydric phenol (a1)] / [vinyl ether group in polyhydric vinyl ether (a2)] = A range of 95/5 to 80/20 (molar ratio) is preferable.

Next, the method for producing the epoxy resin (X) used in the present invention will be described in detail. The production method is not particularly limited. For example, sodium hydroxide or potassium hydroxide is added to a dissolved mixture of the modified polyhydric phenol (A) obtained above and epihalohydrin such as epichlorohydrin or epibromohydrin. The method of making it react at 20-120 degreeC for 1 to 10 hours, adding alkali metal hydroxides, such as these, is mentioned. The amount of the epihalohydrin added is usually in the range of 0.3 to 20 equivalents relative to 1 equivalent of the hydroxyl group in the raw material modified polyphenol (A). When the epihalohydrin is less than 2.5 equivalents, an epoxy group and an unreacted hydroxyl group are likely to react with each other. Therefore, a group formed by an addition reaction between an epoxy group and an unreacted hydroxyl group (—CH ₂ CR (OH) CH ₂ —, A high molecular weight product containing R: a hydrogen atom or an organic carbon group) is obtained. On the other hand, in the case of 2.5 equivalents or more, the content of the low molecular weight epoxy resin having a structure in which the hydroxyl group in the raw material modified polyphenol (A) is substituted with a glycidyl group is increased. What is necessary is just to adjust the quantity of epihalohydrin suitably according to desired characteristics (viscosity, epoxy equivalent, etc. of an epoxy resin).

  As the alkali metal hydroxide, an aqueous solution thereof may be used. In that case, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and water and epihalohydrin are continuously added under reduced pressure or normal pressure. May be distilled off, and the liquid may be further separated to remove water and the epihalohydrin to be continuously returned to the reaction system.

  Further, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride is added as a catalyst to a dissolved mixture of the modified polyphenol (A) and epihalohydrin at 50 to 150 ° C. for 1 to 5 hours. A method of adding a solid or aqueous solution of an alkali metal hydroxide to the halohydrin etherified product of the phenol obtained by the reaction and reacting again at 20 to 120 ° C. for 1 to 10 hours to dehydrohalogenate (ring closure) may be used. .

  Furthermore, alcohols such as methanol, ethanol, isopropyl alcohol and butanol, ketones such as acetone and methyl ethyl ketone, ethers such as dioxane, aprotic polar solvents such as dimethyl sulfone and dimethyl sulfoxide, etc. are used in order to facilitate the reaction. It is preferable to carry out the reaction by adding. The amount of the solvent used is usually 5 to 50% by weight, preferably 10 to 30% by weight, based on the amount of epihalohydrin. Moreover, when using an aprotic polar solvent, it is 5-100 weight% normally with respect to the quantity of epihalohydrin, Preferably it is 10-60 weight%.

  After the epoxidation 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. Further, in order to obtain an epoxy resin with less hydrolyzable halogen, the crude epoxy resin obtained after recovering epihalohydrin or the like is dissolved again in a solvent such as toluene or methyl isobutyl ketone, and an alkali such as sodium hydroxide or potassium hydroxide is obtained. An aqueous solution of a metal hydroxide can be added and further reacted to ensure ring closure. In this case, the amount of the alkali metal hydroxide used is usually 0.5 to 10 mol, preferably 1.2 to 5.0 mol, with respect to 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. When the phase transfer catalyst is used, the amount 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 the target epoxy resin (X) is obtained by distilling off a solvent such as toluene and methyl isobutyl ketone under heating and reduced pressure.

  Of course, it is possible to use rational means such as preparing the modified polyhydric phenols (A) and charging raw materials such as epihalohydrins as they are without removing them from the reactor and continuously converting them to glycidyl ether.

  The epoxy resin (X) obtained above has the following general formula (1)

（式中、Ｘは２価の有機基を示し、両末端の酸素原子（＊）は芳香族環と直接結合している。）
で表されるジアセタール構造を分子内に含有するエポキシ樹脂である。該エポキシ樹脂（Ｘ）の官能基濃度（エポキシ当量）や官能基数（１分子中のエポキシ基の平均個数）に関しても、特に限定されるものではないが、なかでもエポキシ当量に関しては、２００〜２，０００ｇ／ｅｑ．の範囲が粘度、硬化性、柔軟性、耐食性等のバランスに優れることから好ましく、官能基濃度に関しては、１＜官能基数（個）≦２０の範囲が同様な特性バランスに優れることから好ましい。

(In the formula, X represents a divalent organic group, and the oxygen atoms (*) at both ends are directly bonded to the aromatic ring.)
It is an epoxy resin containing a diacetal structure represented by The functional group concentration (epoxy equivalent) and the number of functional groups (average number of epoxy groups in one molecule) of the epoxy resin (X) are not particularly limited, but the epoxy equivalent is 200-2. , 000 g / eq. Is preferable from the viewpoint of excellent balance of viscosity, curability, flexibility, corrosion resistance, and the like, and regarding the functional group concentration, a range of 1 <number of functional groups (pieces) ≦ 20 is preferable because of excellent characteristics balance.

  In addition, the viscosity of the epoxy resin (X) at 25 ° C. is preferably in the range of 5,000 to 100,000 mPa · s from the viewpoint of fluidity, workability, freedom of composition blending, and the like.

  In the epoxy resin composition of the present invention, other epoxy resins other than the epoxy resin (X) can be used in combination as long as the effects of the present invention are not impaired. When used together, the proportion of the epoxy resin (X) in the total epoxy resin is preferably 30% by weight or more, particularly preferably 40% by weight or more. The epoxy resin that can be used in combination with the epoxy resin (X) is not particularly limited, and various epoxy resins can be used. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, Bisphenol AD type epoxy resin, resorcinol type epoxy resin, hydroquinone type epoxy resin, catechol type epoxy resin, dihydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, liquid epoxy resin such as tetramethylbiphenyl type epoxy resin, phenol novolac type epoxy resin, Cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol alla Kill type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy resin, Biphenyl modified novolac type epoxy resin, tetrabromobisphenol A type epoxy resin, brominated phenol novolac type epoxy resin and the like can be mentioned. Also included are reactive diluent type epoxy resins such as butyl glycidyl ether, alkylphenol glycidyl ether, and aliphatic chain carboxylic acid glycidyl ester, and liquid epoxy resins such as alicyclic epoxy resins. Moreover, the said other epoxy resin may be used independently and may mix 2 or more types.

  The modified aliphatic polyamines (Y) used in the present invention are used as a curing agent for the epoxy resin (X) obtained above, suppress skin damage caused by amine vapor, and have a large blending ratio with the epoxy resin. In order to facilitate handling, various modifications were performed using a polyamine compound (y1) having two or more aliphatic amino groups as a raw material. The modification method is not particularly limited, and examples thereof include a method by polycondensation of carboxylic acids and polyamine compound (y1), Michael reaction, thiourea reaction, reaction with various adducts, Mannich modification described later, and the like. Is mentioned. Among these, it is preferable to use an epoxy adduct-modified polyamine or a Mannich-modified polyamine which is a reaction product with an epoxy resin from the viewpoint of excellent curability, and it is particularly preferable to use a Mannich-modified polyamine from the viewpoint of excellent low-temperature curability.

  The Mannich-modified polyamine is obtained by reacting a polyamine compound (y1), formaldehydes (y2), and a phenol compound (y3), and generally has good curability among amine curing agents, and Since it has an aromatic ring derived from the phenol compound (y3) in the molecule, it is intended to improve the water resistance and mechanical properties of the resulting cured product, and by using it in combination with the above-mentioned epoxy resin (X), Even if it does not use a hardening accelerator, it is preferable from the point that hardening reaction advances rapidly at normal temperature.

  The polyamine compound (y1) is not particularly limited, and various compounds can be used. Examples thereof include alkylene diamines such as ethylene diamine and hexamethylene diamine; diethylene triamine, triethylene tetramine, tetraethylene pentamine. Polyalkylene polyamines such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, isophoronediamine, 1,4-bis (3-aminopropyl) piperazine and the like; m- Examples include polyamines having an aromatic ring such as xylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone, and these may be used alone or as a mixture of two or more.

  Furthermore, polyamide polyamines obtained by polycondensation of a part of amino groups with aliphatic dicarboxylic acids using the so-called raw amines (unmodified) exemplified above are also used as polyamine compounds (y1). I can do it. Examples of the aliphatic dicarboxylic acid that can be used at this time include dimer acid composed of tall oil fatty acid, linolenic acid, linoleic acid, and the like.

  The polyamine compound (y1) may be selected appropriately in consideration of the desired properties of the resulting cured product. If excellent flexibility is desired, a polyalkylene polyamine and a modified product thereof are used. It is preferable. If excellent corrosion resistance is desired, amines having an aromatic ring are preferably used.

  Examples of the formaldehydes (y2) include formaldehyde-releasing substances such as formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, and acetone. Among these, formaldehyde is preferable because of excellent reactivity.

  Examples of the phenol compound (y3) include phenol, alkyl-substituted phenol, cresol, halogen-substituted phenol, anisole, bisphenol A, bisphenol F and the like, and these may be used alone or in combination of two or more. Among these, phenol is preferred because of excellent curability and excellent corrosion resistance of the cured product.

  A method for obtaining a Mannich-modified polyamine by reacting these polyamine compounds (y1), formaldehydes (y2), and phenol compounds (y3) is not particularly limited. For example, polyamine compounds (y1) and phenol compounds Formaldehydes (y2) are added to the mixture with (y3) at 80 ° C. or lower, preferably 60 ° C. or lower, and then heated to 80 to 180 ° C., preferably 90 to 150, and the distillate is removed from the reaction system. However, the method obtained by making it react for 1 to 10 hours, etc. are mentioned. The obtained Mannich-modified polyamine may be used alone or as a mixture of two or more.

  The epoxy adduct-modified polyamine is obtained by increasing the molecular weight using an epoxy resin as an adduct agent, and is considered as an intermediate form of a curing reaction, and has excellent corrosion resistance and adhesion of a cured product obtained in an epoxy resin / curing agent system. The reaction proceeds at room temperature in the same manner as Mannich-modified polyamine without impairing the performance.

  As the polyamine compound that can be used at this time, any of the above-mentioned compounds can be used, and as the epoxy resin, any of the above-mentioned epoxy resins that can be used in the present invention can be used. Furthermore, you may use the epoxy resin (X) used by this invention obtained above. Among these, if excellent flexibility is desired, it is preferable to use a polyalkylene polyamine and a modified product thereof or the epoxy resin (X) used in the present invention. If excellent corrosion resistance is desired, amines having an aromatic ring are preferably used.

  The method for producing the adduct-modified polyamine is not particularly limited, and is mixed with the epoxy resin at a charging ratio such that a part of the amino group in the polyamine compound (y1) used as a raw material remains, and is 80 to 180. There may be mentioned a method in which the reaction is carried out by raising the temperature to 0 ° C., preferably 90 to 150. The obtained adduct-modified polyamine may be used alone or as a mixture of two or more.

  In order to further improve the curability, Mannich modification and adduct modification may be combined. That is, it may be a Mannich-modified compound of a polyamine adduct obtained by reacting a polyamine compound (y1) with an epoxy resin and a Mannich reaction between formaldehydes (y2) and a phenol compound (y3). .

  The amount of the modified aliphatic polyamines (Y) used is that the curing proceeds smoothly and good cured properties are obtained, so that the modified aliphatic polyamines ( The amount by which active hydrogen groups in Y) are 0.7 to 1.5 equivalents is preferred.

  Since the epoxy resin composition of the present invention has good curability without using a curing accelerator, it is not necessary to use a curing accelerator, but it further increases the reaction rate and imparts workability, etc. For this purpose, a curing accelerator may be used. Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts, and the like. The above combination is also possible.

  An inorganic filler can be blended in the epoxy resin composition of the present invention. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide.

  Various compounding agents, such as a silane coupling agent, a mold release agent, a pigment, an emulsifier, can be added to the epoxy resin composition of this invention as needed.

  A flame retardant imparting agent can be added to the epoxy resin composition of the present invention as necessary. Various flame retardants can be used, for example, halogen compounds such as decabromodiphenyl ether and tetrabromobisphenol A, phosphorus atom-containing compounds such as red phosphorus and various phosphoric acid ester compounds, melamine or derivatives thereof, etc. Examples thereof include inorganic flame retardant compounds such as nitrogen atom-containing compounds, aluminum hydroxide, magnesium hydroxide, zinc borate, and calcium borate.

  An organic solvent can be used for the epoxy resin composition of this invention as needed. The organic solvent is used to lower the viscosity and improve the fluidity and moldability, and the type is not particularly limited. Illustrative examples include methanol, toluene, xylene, diethyl ether, acetone, methyl ethyl ketone, dimethylformamide and the like. As the amount used, it is preferable that the solid content value of the epoxy resin composition is in the range of 20 to 95% by weight.

  The epoxy resin composition of the present invention comprises an epoxy resin (X), a modified aliphatic polyamine (Y), and other epoxy resins used in combination as necessary, additives, and the like according to the viscosity of the resulting composition. It can obtain by mixing uniformly using. The shape of the epoxy resin composition of the present invention is not limited at all, and even if the epoxy resin (X) to be used is liquid, the epoxy resin to be used together, the modified aliphatic polyamines (Y), the filler species and Depending on the amount used, the resulting epoxy resin composition may not become liquid at room temperature. What is necessary is just to select the shape of this composition suitably according to a use application, desired performance, etc.

  The use of the epoxy resin composition of the present invention is not particularly limited, and examples thereof include paints, adhesives, lining materials, etc. Among these, as a lining material from the viewpoint of excellent flexibility and corrosion resistance. It can be used suitably, and can be used suitably as a primer or sealer for concrete structural materials from the point which is especially excellent in alkali resistance.

  When the epoxy resin composition of the present invention is used as a resin composition according to the above-mentioned use, for example, epoxy resin (X), other epoxy resins used in combination as necessary, pigments, colorants, additives Etc., add organic solvent as necessary, mix thoroughly using equipment such as paint shaker, mixing mixer, ball mill, etc., and disperse uniformly, and further add modified aliphatic polyamines (Y) to this And a method of preparing the mixture with a desired viscosity with an organic solvent or the like.

  The resin composition obtained by the above method can be applied to various substrates by various methods, and the method is not particularly limited. For example, a gravure coater, a knife coater, a roll coater, a comma coater And coating methods such as spin coater, bar coater, brush coating, dipping coating, spray coating and electrostatic coating.

  Further, the curing method after coating is not particularly limited, and a cured product can be obtained by any of room temperature curing and heat curing, and a molded product, a laminate, a cast product, a structure, an adhesive, a coating, It has a form such as a film or a film.

  Next, the present invention will be specifically described with reference to examples and comparative examples. The parts and% described below are based on weight unless otherwise specified.

  Synthesis Example 1 Synthesis of epoxy resin (X-1) represented by the following structural formula

  A flask equipped with a thermometer and a stirrer was charged with 228 g (1.00 mol) of bisphenol A and 172 g (0.85 mol) of triethylene glycol divinyl ether (manufactured by ISP: trade name Rapi-Cure DVE-3) at 120 ° C. It took 1 hour until the temperature was raised, and further reacted at 120 ° C. for 6 hours to obtain 400 g of a transparent semi-solid raw material resin. Its hydroxyl equivalent is 364 g / eq. Met.

  Next, 400 g of the raw material resin obtained above, 925 g (10 mol) of epichlorohydrin, and 185 g of n-butanol were charged and dissolved. Thereafter, the temperature was raised to 65 ° C. while purging with nitrogen gas, and then the pressure was reduced to an azeotropic pressure, and 122 g (1.5 mol) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Stirring was then continued under these conditions for 0.5 hour. During this time, the distillate distilled azeotropically was separated with a Dean-Stark trap, the aqueous layer was removed, and the reaction was conducted while returning the organic layer to the reaction system. Thereafter, unreacted epichlorohydrin was distilled off under reduced pressure. 1000 g of methyl isobutyl ketone and 100 g of n-butanol were added to the crude epoxy resin thus obtained and dissolved. Further, 20 g of a 10% aqueous sodium hydroxide solution was added to this solution and reacted at 80 ° C. for 2 hours. Then, washing with 300 g of water was repeated three times until the pH of the washing solution became neutral. Next, the system was dehydrated by azeotropic distillation, and after microfiltration, the solvent was distilled off under reduced pressure to obtain the desired epoxy resin (X-1). The epoxy equivalent of the obtained epoxy resin (X-1) was 462 g / eq. The viscosity was 12,000 mPa · s (25 ° C., Canon Fenske method), and the average value of n in the formula calculated from the epoxy equivalent was 1.35.

Synthesis Example 2 Synthesis of Epoxy Resin (X-2) A raw material resin was obtained in the same manner as in Synthesis Example 1 except that the amount of triethylene glycol divinyl ether (DVE-3) was changed to 101 g. The raw material resin has a hydroxyl equivalent of 262 g / eq. Met.

  Next, 395 g of the target epoxy resin (X-2) was obtained in the same manner as in Synthesis Example 1 except that the raw material resin was changed to 329 g. The epoxy equivalent of the obtained epoxy resin (X-2) was 350 g / eq. The viscosity was 90,000 mPa · s (25 ° C., E-type viscometer), and the average value of n in the formula calculated from the epoxy equivalent was confirmed to be 0.84.

Synthesis Example 3 Synthesis of Dimer Acid-Modified Epoxy Resin (X′-1) A flask equipped with a thermometer, a condenser tube, and a stirrer was charged with a bisphenol A liquid epoxy resin (Dainippon Ink Chemical Co., Ltd .: trade name EPICLON). 850S, epoxy equivalent 185 g / eq.) 457 g and dimer acid (Tsuno Food Industries, trade name: Tsunodyme 216) 243 g were charged and heated to 80 ° C. while purging with nitrogen gas, and 0.14 g of triphenylphosphine (catalyst) Was added and reacted at 140 ° C. for 2 hours to obtain 700 g of a semisolid epoxy resin. This epoxy resin is an epoxy resin (X′-1) having a structure in which a molecular chain is extended by an ester bond by reacting a carboxylic acid of a dimer acid with an epoxy group, and an epoxy equivalent is 451 g / eq. The viscosity was 170 mPa · s (150 ° C., ICI viscometer).

Examples 1-4 and Comparative Examples 1-8
As epoxy resins, the two types of epoxy resins (X-1) and (X-2) obtained in Synthesis Examples 1 and 2 and the dimer acid-modified epoxy resin (X′-) obtained in Synthesis Example 3 for comparison are used. 1) EPICLON TSR-250-80BX (X′-2) (manufactured by Dainippon Ink & Chemicals, Inc., epoxy equivalent 850 g / eq) was used as the urethane-modified epoxy resin. Furthermore, EPICLON 726 (Dainippon Ink & Chemicals, Inc., epoxy equivalent 154 g / eq) was used as a reactive diluent. Further, as a curing agent, Mannich modified polyamine racamide WH-614 (manufactured by Dainippon Ink & Chemicals, Inc .: Mannich type curing agent using triethylenetetramine, active hydrogen equivalent 51 g / eq.), Mannich modified polyamine racamide WH-630 (Manufactured by Dainippon Ink & Chemicals, Inc .: Mannich type curing agent using m-xylenediamine, active hydrogen equivalent 79 g / eq.), Adduct-modified polyamine racamide WH-108-S (active hydrogen equivalent 57 g / eq.). Evaluated. The epoxy resin and the curing agent are blended at an epoxy equivalent / active hydrogen equivalent = 1/1, further diluted with xylene so that the non-volatile content becomes 50%, and then sufficiently stirred at room temperature. A composition was prepared. The blending ratio of the composition is summarized in Table 1.

Evaluation method of coating film A test piece for evaluating the strength and flexibility of the coating film was prepared as follows. First, the epoxy resin composition obtained above was applied to a polypropylene plate so that the film thickness after drying was 250 μm. This was left to dry in a constant temperature room at 25 ° C. for 1 week, and then peeled off from the polypropylene plate. A test piece of 100 mm × 10 mm was cut out from this, and a tensile test was performed at a tensile rate of 5 mm / min in an atmosphere at 23 ° C. The results are shown in Table 1.

Corrosion resistance evaluation results The corrosion resistance evaluation on the concrete surface was performed as follows. First, the epoxy resin composition obtained above was applied to a concrete test plate (manufactured by Test Piece Co., Ltd., JIS mortar 20 × 70 × 150 mm) using a brush so as to be 150 g / cm ² . This was left to dry in a constant temperature room at 25 ° C. for 1 week, then immersed in distilled water and a 10% aqueous sodium hydroxide solution, and the change with time of the surface was visually evaluated in accordance with ASTM D714-87. The results are shown in Table 1.

Claims (8)

Epoxy resin (X) and modified aliphatic polyamines (Y) formed by glycidyl etherification of modified polyphenols (A) obtained by reacting polyhydric phenols (a1) and polyvalent vinyl ethers (a2) The epoxy resin composition characterized by containing. The epoxy resin composition according to claim 1, wherein the modified aliphatic polyamine (Y) is a Mannich-modified polyamine or an epoxy adduct-modified polyamine. The epoxy resin composition according to claim 1, wherein the modified aliphatic polyamines (Y) are Mannich-modified polyamines. The epoxy resin composition according to claim 1, wherein the polyhydric phenols (a1) are dihydric phenols and the polyhydric vinyl ethers (a2) are divinyl ethers. The epoxy resin composition according to claim 1, wherein the polyvalent vinyl ether (a2) contains a polyoxyalkylene skeleton and / or a cycloalkane skeleton. It is a lining material, The epoxy resin composition in any one of Claims 1-5 The epoxy resin composition according to any one of claims 1 to 5, which is a primer or sealer for a concrete structural material. A cured product obtained by curing the epoxy resin composition according to claim 1.