TW201609763A - Aluminum chelate-based latent curing agent and production method therefor - Google Patents

Abstract

An aluminum chelate-based latent curing agent that allows a thermal peak temperature during thermal curing of a glycidyl ether-type epoxy resin to be lowered to 120 DEG C or less, preferably 80 DEG C or less, having a structure wherein an aluminum chelate-based curing agent and a di- or triarylsilanol compound are held in a cationic emulsion-polymerized porous epoxy resin forming a polymer capsule material. The cationic emulsion-polymerized porous epoxy resin is obtained by cationic emulsion polymerization, in a water phase containing a dispersant, of an oil phase having an aluminum chelate-based curing agent, a di- or triarylsilanol compound, and an epoxy compound dissolved or dispersed in an organic solvent.

Description

Aluminum chelate latent curing agent and preparation method thereof

The present invention relates to an aluminum chelate-based latent curing agent in which an aluminum chelate-based curing agent is held by a cationic emulsion-polymerized porous epoxy resin as a polymer capsule material.

In the past, a microcapsule-type aluminum chelate-based latent curing agent which is obtained by holding an aluminum chelate-based curing agent in a porous resin has been proposed as a curing agent for exhibiting a low-temperature-fastening activity of an epoxy resin (Patent Document) 1) The porous resin is obtained by interfacial polymerization of a polyfunctional isocyanate compound. However, in the case of a thermosetting epoxy resin composition in which the aluminum chelate latent curing agent, decane coupling agent, and epoxy resin are blended, if polymerization (hardening) reaction is initiated by heating, There is a problem that the silanolate anion produced by the decane coupling agent is added to the β-position carbon of the epoxy group of the epoxy propyl ether type epoxy compound to cause polymerization to stop the reaction, and thus it is used as an epoxy resin to be blended. A high-cost alicyclic epoxy compound that does not easily cause such a problem must be used.

Therefore, as an aluminum chelate latent curing agent which can cure a glycidyl ether type epoxy compound at a low temperature without using an alicyclic epoxy compound, the following aluminum chelate latent curing agent is proposed: Used as a porous resin for polymer capsule materials while maintaining aluminum chelation a system hardener and a specific stanol compound having a high steric hindrance chemical structure for interfacial polymerization of a polyfunctional isocyanate compound and polyfunctionality in the presence of a radical polymerization initiator The radically polymerizable compound is obtained by radical polymerization (Patent Document 2). By the aluminum chelate latent curing agent, the polymerization stop reaction can be suppressed, and the aluminum chelate-based curing agent and the cationic active species can be formed, so that the epoxypropyl ether type ring can be made to a certain extent. The oxygen compound is hardened at a low temperature.

Patent Document 1: Japanese Laid-Open Patent Publication No. 2006-70051

Patent Document 2: Japanese Laid-Open Patent Publication No. 2010-168449

However, since the low-temperature rapid hardening ability of the aluminum chelate-based latent curing agent disclosed in Patent Document 2 depends on the glass transition point of the polymer capsule material composed of the isocyanate interfacial polymerizable porous resin which is considered to be the outermost hardest, it exists. It is difficult to set the exothermic peak temperature when the epoxy propyl ether type epoxy compound is thermally cured to a level of not less than 120 ° C, preferably not more than 80 ° C.

An object of the present invention is to provide an aluminum chelate compound which can lower the exothermic peak temperature when the epoxy propyl ether type epoxy resin is thermally cured to a temperature of 120 ° C or less, preferably 80 ° C or less. Sex hardener.

The present inventors have found a cationic emulsion-polymerized porous epoxy resin obtained by cationic emulsion polymerization while being inhibited by polymerization due to moisture in a polymerization system. As the characteristics of the polymer capsule material, the glass transition temperature of the cationic emulsion-polymerized porous epoxy resin itself is more dependent on the cationic emulsion polymerization porous due to the polymerization inhibition caused by the moisture in the emulsion polymerization system. Under the assumption that the surface of the epoxy resin is reduced in mechanical strength or solvent resistance, the cationically emulsified polymerized porous epoxy resin is used as an aluminum chelate latent curing agent. The polymer capsule material exhibiting latentness can achieve the object of the invention, thereby completing the present invention.

That is, the present invention provides an aluminum chelate-based latent curing agent characterized in that an aluminum chelate-based hardener and a diaryl stanol compound or a triaryl stanol compound are held as a cation as a polymer capsule material. Emulsified polymerized porous epoxy resin. Here, a preferred cationically polymerizable porous epoxy resin is obtained by subjecting an oil phase to cationic emulsion polymerization in an aqueous phase containing a dispersant, which is an aluminum chelate-based hardener or a diaryl group. The stanol compound or the triaryl stanol compound and the epoxy compound are dissolved or dispersed in an organic solvent.

Further, the present invention provides a process for producing the above-described aluminum chelate latent curing agent characterized by comprising an aluminum chelate hardener and a diaryl stanol compound or a triaryl stanol The compound is held in a cationic emulsion-polymerized porous epoxy resin as a polymer capsule material, and the cationic emulsion-polymerized porous epoxy resin is obtained by cationic emulsion polymerization of an oil phase in an aqueous phase containing a dispersant. The phase is formed by dissolving or dispersing an aluminum chelate-based curing agent, a diaryl stanol compound, a triaryl stanol compound, and an epoxy compound in an organic solvent.

Further, the present invention provides a thermosetting epoxy resin composition comprising the above-mentioned aluminum chelate latent curing agent, epoxy resin, and diaryl stanol compound or triaryl group A stanol compound.

In the cationic emulsion-polymerized porous epoxy resin which is a polymer capsule material of the aluminum chelate-based latent curing agent of the present invention, the mechanical strength of the surface is lowered or resistant due to polymerization inhibition by moisture. The solvent is reduced. Therefore, the aluminum chelate latent hardener exhibits latent property, and on the other hand, the epoxy compound penetrates into the capsule wall by heating, or the aluminum chelate hardener oozes out from the capsule wall, thereby achieving Thermal activity and low temperature rapid hardening. Further, since the stanol compound having a specific high steric hindrance chemical structure is held by the cationic emulsion-polymerized porous epoxy resin (in other words, it is protected), the polymerization stop reaction can be suppressed, and an aluminum chelate-based hardener can be formed. With cationic active species. Therefore, the thermosetting epoxy resin composition containing the aluminum chelate latent curing agent of the present invention can be used as a ring at an exothermic peak temperature of not more than 120 ° C, preferably not more than 80 ° C. The epoxy resin epoxy acrylate type epoxy resin is hardened at a low temperature.

Fig. 1 is a particle size distribution diagram of the aluminum chelate latent curing agent of Example 1.

2 is a particle size distribution diagram of the aluminum chelate latent curing agent of Example 2.

Fig. 3 is a particle size distribution diagram of the aluminum chelate latent curing agent of Example 3.

Fig. 4 is an electron micrograph (magnification: 10,000 times) of the aluminum chelate latent curing agent of Example 3.

Fig. 5 is an electron micrograph of the aluminum chelate latent curing agent of Example 3 (magnification: 15000 times).

Fig. 6 is a DSC chart of a thermosetting epoxy resin composition in which the aluminum chelate latent curing agent of Examples 1 to 3 was blended.

Fig. 7 is a DSC chart of a thermosetting epoxy resin composition in which the aluminum chelate latent curing agent of Examples 3 to 5 is blended.

Figure 8 is a graph showing the particle size distribution of the aluminum chelate latent curing agent of Example 6.

Fig. 9 is a particle size distribution diagram of the aluminum chelate latent curing agent of Example 7.

Figure 10 is a graph showing the particle size distribution of the aluminum chelate latent curing agent of Example 8.

Figure 11 is a DSC chart of a thermosetting epoxy resin composition incorporating the aluminum chelate latent curing agent of Examples 3, 6-8.

<<Aluminum chelate latent hardener>>

The aluminum chelate latent curing agent of the present invention is an aluminum chelate hardener and a diaryl stanol compound or a triaryl stanol compound which is held in a cationic emulsion polymerized porous epoxy as a polymer capsule material. Resin. More specifically, it is not a microcapsule of a simple structure in which the periphery of the core of the aluminum chelate-based curing agent is coated with a shell of a cationically emulsion-polymerized porous epoxy resin, but is a cationically emulsion-polymerized porous epoxy system. Among the fine pores present in the resin matrix, an aluminum chelate-based hardener and a structure of a diaryl stanol compound or a triaryl stanol compound are held.

Since the aluminum chelate latent curing agent of the present invention is produced by a cationic emulsion polymerization method, its shape is spherical, and its particle diameter is preferably 0.1 to 10 μm in terms of hardenability and dispersibility. Moreover, in terms of hardenability and latent property, the size of the hole is preferably 0.1~50nm.

Further, the aluminum chelate-based latent curing agent has a tendency that if the degree of crosslinking of the cationically polymerizable porous epoxy resin to be used is too small, the latent property is lowered, and if it is too large, the thermal responsiveness is lowered. Therefore, it is preferred to use a cationic emulsion-polymerized porous epoxy resin whose crosslinking degree is adjusted depending on the purpose of use. Here, the degree of crosslinking of the cationically emulsion-polymerized porous epoxy resin can be measured by a micro compression test.

The aluminum chelate latent curing agent preferably does not substantially contain an organic solvent used in cationic emulsion polymerization, and is specifically 1 ppm or less in terms of hardening stability.

In order to achieve good hardening ability and good latent property, the content of the aluminum chelate-based hardener is 100 parts by mass relative to the cationically polymerizable porous epoxy resin in the aluminum chelate latent curing agent of the present invention. Preferably, it is 50 to 300 parts by mass, more preferably 100 to 200 parts by mass. Further, in order to achieve good hardening ability and good latent property, the content of the diaryl stanol compound or the triaryl stanol compound is also preferably from 10 to 200 parts by mass, more preferably from 50 to 150 parts by mass.

<Cationic emulsion polymerized porous epoxy resin>

The cationically polymerizable porous epoxy resin which is a polymer capsule material constituting the aluminum chelate latent curing agent of the present invention is preferably obtained by cationic emulsion polymerization of an oil phase in an aqueous phase containing a dispersing agent. The oil phase is obtained by dissolving or dispersing an aluminum chelate-based curing agent, a diaryl stanol compound, a triaryl stanol compound, and an epoxy compound in an organic solvent. This cationic emulsion polymerization has the meaning of a method for producing an aluminum chelate-based latent curing agent of the present invention. That is, the aluminum chelate latent curing agent of the present invention can be hardened by an aluminum chelate compound And a diaryl stanol compound or a triaryl stanol compound which is produced by holding a cationic emulsion-polymerized porous epoxy resin as a polymer capsule material by using an oil Obtained by emulsion polymerization in an aqueous phase containing a dispersant, which dissolves or disperses an aluminum chelate-based hardener, a diaryl stanol compound or a triaryl stanol compound, and an epoxy compound in an organic solvent. Made.

<Aluminum chelate hardener>

The aluminum chelate-based curing agent functions as a curing agent which reacts with a stanol compound to cationically polymerize an epoxy compound, and performs cationic emulsion polymerization of the blended epoxy compound to form a polymer capsule material. Examples of such an aluminum chelate-based curing agent include a compound in which three β-ketoenol anions represented by the formula (1) are coordinated to aluminum.

Here, R ^1, R ² and R ³ are each independently alkyl or alkoxy. Examples of the alkyl group include a methyl group and an ethyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, and an oleyl group.

Specific examples of the aluminum chelate-based curing agent represented by the formula (1) include: Tris(acetonitrile)aluminum, tris(acetateacetate)aluminum, monoethylammonium acetonate acetoacetate (ethyl acetate), ethyl acetoacetate, aluminum acetoacetate, ethyl acetate Aluminum isopropoxide, alkyl acetoacetate, aluminum diisopropylate, and the like.

<Diaryl stanol compound or triaryl stanol compound>

The diaryl stanol compound or the triaryl stanol compound is a highly sterically hindered stanol compound having a chemical structure of the following formula (A), unlike a conventional decane coupling agent having a trialkoxy group.

(Ar) _m Si(OH) _n (A)

Wherein m is 2 or 3, preferably 3, wherein the sum of m and n is 4. Therefore, the stanol compound of the formula (A) is a monool or a diol. "Ar" is a aryl group which may be substituted, and examples of the aryl group include a phenyl group, a naphthyl group (for example, 1-naphthyl group or 2-naphthyl group), an anthracenyl group (for example, 1-fluorenyl group, 2-anthracene group). Or 9-fluorenyl, benzo[a]-9-fluorenyl), phenylallyl (eg, 3-phenylallyl or 9-phenylallyl), fluorenyl (eg, 1) - mercapto), fluorenyl, fluorenyl, biphenyl (for example, 2-biphenyl, 3-biphenyl or 4-biphenyl), thienyl, furyl, pyrrolyl, imidazolyl, pyridyl Wait. Among them, a phenyl group is preferred from the viewpoint of availability and cost. The m Ar atoms may all be the same or different, and are preferably the same in terms of easiness.

These aryl groups may have 1 to 3 substituents, and examples thereof include halogen (chlorine, bromine, etc.), trifluoromethyl, nitro, sulfo, carboxyl, alkoxycarbonyl (methoxycarbonyl, ethoxycarbonyl). Or an electron attracting group such as a mercapto group, or an alkyl group (methyl, ethyl, propyl, etc.), an alkoxy group (methoxy group, ethoxy group, etc.), a hydroxyl group, an amine group, a monoalkylamino group (monomethylamine, etc.), dialkylamine A push group such as a dimethyl group or the like. Further, by using an electron attracting group as a substituent, the acidity of the hydroxyl group of the stanol can be increased, and on the contrary, the acidity can be lowered by using a push electron group as a substituent, so that the hardening activity can be controlled. Here, the substituent of each of m pieces of Ar may be different, but in terms of ease of obtaining m Ar, the preferable substituents are the same. Further, it is also possible that only a part of Ar has a substituent, and other Ar has no substituent. Specific examples of the phenyl group having a substituent include 2-methylphenyl, 3-methylphenyl or 4-methylphenyl; 2,6-dimethylphenyl, 3,5-di Methylphenyl, 2,4-dimethylphenyl, 2,3-dimethylphenyl, 2,5-dimethylphenyl or 3,4-dimethylphenyl; 2,4,6 - trimethylphenyl; 2-ethylphenyl or 4-ethylphenyl.

Preferred among the stanol compounds of the formula (A) include triphenyl decyl alcohol or diphenyl decane diol. More preferred is triphenyl stanol.

<epoxy compound>

As the epoxy compound of the cationically polymerizable porous epoxy resin constituting the aluminum chelate latent curing agent, a mixed system of an aluminum chelate latent hardener and a stanol compound can be preferably used. Epoxy propyl ether type epoxy resin which cannot be used. The epoxy propyl ether type epoxy resin may be in the form of a liquid or a solid, and has an epoxy equivalent of usually about 100 to 4,000, and preferably has two or more epoxy groups in the molecule. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, ester type ring Oxygen resin, etc. Among them, a bisphenol A type epoxy resin can be preferably used in terms of resin characteristics. Further, these epoxy resins also contain a prepolymer such as a monomer or an oligomer. Further, an alicyclic epoxy resin may be used within the range which does not impair the effects of the present invention.

<Oxycyclobutane compound>

In the aluminum chelate latent curing agent of the present invention, in addition to the above epoxy compound, in order to make the exothermic peak steep, an oxocyclobutane compound may be used in combination. Preferred examples of the oxycyclobutane compound include 3-ethyl-3-hydroxymethyloxycyclobutane and 1,4-bis{[(3-ethyl-3-oxocyclobutane)methoxyl Methyl}benzene, 4,4'-bis[(3-ethyl-3-oxocyclobutane)methoxymethyl]biphenyl, 1,4-phthalic acid bis[(3-B 3-oxocyclobutanyl)methyl]ester, 3-ethyl-3-(phenoxymethyl)oxycyclobutane, 3-ethyl-3-(2-ethylhexyloxymethyl) Oxycyclobutane, bis[1-ethyl(3-oxocyclobutane)]methyl ether, 3-ethyl-3-{[3-(triethoxyindolyl)propoxy]- Base oxycyclobutane, oxycyclobutane sesquioxane, phenol novolac oxycyclobutane, and the like. In the case of using an oxycyclobutane compound, the amount thereof is preferably from 10 to 100 parts by mass, more preferably from 20 to 70 parts by mass, per 100 parts by mass of the epoxy compound.

<organic solvent>

The organic solvent constituting the oil phase is preferably a volatile organic solvent which is an aluminum chelate-based hardener, a diaryl stanol compound or a triaryl stanol compound, and an epoxy compound. A good solvent for each (the solubility of each is preferably 0.1 g/ml or more (organic solvent) or more), and is substantially insoluble with respect to water (water solubility is 0.5 g/ml (organic solvent) or less), and atmospheric pressure The lower boiling point is 30~100 °C. Specific examples of such a volatile organic solvent include alcohols, acetates, ketones and the like. Among them, in terms of high polarity, low boiling point, and poor water solubility, acetates are preferred, and ethyl acetate is particularly preferred.

In order not to disperse the particle size and the hardening property, and to prevent deterioration of the hardening property, the volatile organic solvent is used in an amount relative to the aluminum chelate hardener, the diaryl stanol compound or the triaryl stanol compound, The total amount of the epoxy compound is preferably 100 parts by mass. It is 10 to 500 parts by mass, more preferably 20 to 200 parts by mass.

Further, since the amount of the volatile organic solvent used is relatively large in the range of the amount of the volatile organic solvent used, the viscosity of the solution which becomes the oil phase can be lowered, and if the viscosity is lowered, the stirring efficiency is improved. The oil phase droplets in the reaction system are made finer and more uniform, and as a result, the obtained latent hardener particle size can be controlled to a size of about several micrometers to several micrometers, and the particle size distribution can be made monodisperse. The viscosity of the solution to be an oil phase is preferably set to 1 to 500 mPa. s.

<Content of each component in the oil phase>

In order to achieve latentization and low-temperature rapid hardening property by cationic emulsion polymerization, the content of the diaryl stanol compound or the triaryl stanol compound is preferably 5 to 500 by mass based on 100 parts by mass of the aluminum chelate-based curing agent. More preferably, it is 20 to 200 parts by mass. Moreover, in order to achieve the suppression of the latent release and the hardening property by cationic emulsion polymerization, the blending amount of the epoxy compound is preferably from 5 to 500 parts by mass, more preferably from 20 to 200 parts by mass.

<aqueous phase>

An aqueous phase for emulsifying and polymerizing an oil phase obtained by dissolving or dispersing an aluminum chelate-based curing agent, a diaryl stanol compound, a triaryl stanol compound, and an epoxy compound in an organic solvent, and containing a known emulsification Agent. Examples of the known emulsifier include alkylbenzenesulfonate, glycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, sucrose fatty acid ester, soybean lecithin, egg yolk lecithin, and soap tree (Quillaja). Saponin), casein sodium, and the like. In addition, a dispersing agent such as polyvinyl alcohol, carboxymethyl cellulose or gelatin may be used in combination. The amount of the emulsifier used is usually 0.001 to 10.0% by mass of the aqueous phase.

Regarding the blending amount of the oil phase with respect to the water phase, in order to prevent the oil phase droplets from being dispersed more The agglomeration caused by the refinement is preferably 5 to 90 parts by mass, more preferably 10 to 70 parts by mass, per 100 parts by mass of the aqueous phase.

The emulsification conditions in the case of cationic emulsion polymerization include the following conditions: in the case where the size of the oil phase is preferably 0.5 to 30 μm, stirring conditions (stirring device homogenizer; stirring speed 6000 rpm or more), and usually at atmospheric pressure, at temperature Heat and stir at 30~80 °C for 2~12 hours.

After completion of the cationic emulsion polymerization, the polymer fine particles are separated by filtration, and dried naturally or vacuum-dried, whereby an aluminum chelate-based latent curing agent usable in the present invention can be obtained. Here, the aluminum chelate can be controlled by changing the kind or amount of the aluminum chelate-based curing agent of the formula (1), the cationic emulsion polymerization conditions, or the kind or amount of the stanol compound of the formula (A). The ability of the compound to cure the latent hardener. For example, if the cationic emulsion polymerization temperature is lowered, the exothermic peak temperature can be lowered, and if the cationic emulsion polymerization temperature is raised, the exothermic peak temperature can be raised.

Further, in the structure of the aluminum chelate latent curing agent, it is considered that an aluminum chelate-based hardener is also present on the surface, but is inertized by the water present in the polymerization system during cationic emulsion polymerization, and aluminum chelate Among the hardeners of the system, only the inside of the porous resin is kept active, and it is considered that the resulting hardener is a latent obtainable.

The aluminum chelate latent curing agent of the present invention can provide a low-temperature rapid hardening to the extent that the exothermic peak temperature is 80 ° C or less by adding a diaryl stanol compound or a triaryl stanol compound to the epoxy resin. A thermosetting epoxy resin composition. Such a thermosetting epoxy resin composition is also an integral part of the invention.

Furthermore, regarding the aluminum chelate compound in the thermosetting epoxy resin composition of the present invention The content of the squeezing agent is preferably from 1 to 70 parts by mass, based on 100 parts by mass of the epoxy resin, in order to sufficiently cure the resin composition and impart good mechanical properties (for example, flexibility) to the cured product. It is 1 to 50 parts by mass. As the epoxy resin, the epoxy compound described above can be used, and a glycidyl ether type epoxy compound is preferably used.

The content of the diaryl stanol compound or the triaryl stanol compound in the thermosetting epoxy resin composition of the present invention is 1 to 50 parts by mass, preferably 1 to 30 parts by mass based on 100 parts by mass of the epoxy resin. Share. If it is this range, it will not be hardened, and the fall of the resin characteristic after hardening can be suppressed. As the diaryl stanol compound or the triaryl stanol compound, a diaryl stanol compound or a triaryl stanol compound described above can be used, and triphenyl stanol or diphenyl stanol is preferably used.

The thermosetting epoxy resin composition of the present invention may further contain a filler such as a decane coupling agent, cerium oxide or mica, a pigment, an antistatic agent or the like as needed.

The decane coupling agent has a function of starting cationic polymerization of a thermosetting resin (for example, a thermosetting epoxy resin) together with an aluminum chelate-based curing agent as described in paragraphs 0007 to 0010 of JP-A-2002-212537. Therefore, the effect of promoting the hardening of the epoxy resin is obtained by using a small amount of such a decane coupling agent in combination. As such a decane coupling agent, those having 1 to 3 lower alkoxy groups in the molecule may have a group reactive with a functional group of the thermosetting resin, for example, a vinyl group, a styryl group, or an acrylonitrile group. A group, a methacryloxy group, an epoxy group, an amine group, a fluorenyl group or the like. Further, since the latent curing agent of the present invention is a cationic hardener, the coupling agent having an amine group or a mercapto group can be used when the amine group or the mercapto group does not substantially capture the generated cationic species.

Specific examples of such a decane coupling agent include vinyl tris(β-甲 Oxyethoxy ethoxy) decane, vinyl triethoxy decane, vinyl trimethoxy decane, γ-styryl trimethoxy decane, γ-methyl propylene methoxy propyl trimethoxy decane, γ- Propylene methoxypropyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-ring Oxypropyl propyl propyl methyl diethoxy decane, N-β-(aminoethyl)-γ-aminopropyltrimethoxy decane, N-β-(aminoethyl)-γ- Aminopropylmethyldimethoxydecane, γ-aminopropyltriethoxydecane, N-phenyl-γ-aminopropyltrimethoxydecane, γ-mercaptopropyltrimethoxydecane, Γ-chloropropyltrimethoxydecane, and the like.

In the case where a small amount of a decane coupling agent is used in combination, if the content is too small, the effect of addition cannot be expected, and if it is too large, the polymerization stop reaction caused by the stanol anion generated from the decane coupling agent is generated, so that it is relative to the aluminum chelate. The compound latent curing agent is used in an amount of from 1 to 300 parts by mass, preferably from 1 to 100 parts by mass, per 100 parts by mass.

The thermosetting epoxy resin composition of the present invention thus obtained has an aluminum chelate-based latent curing agent as a curing agent, and therefore has a one-part type, but is excellent in storage stability. Further, although it contains a glycidyl ether type epoxy compound which cannot be sufficiently cured with an aluminum chelate latent curing agent, it does not impair the cationic polymerization catalyst promoting ability in the aluminum chelate latent curing agent. In the case of a sterol compound having a high steric hindrance, the thermosetting epoxy resin composition can be subjected to low temperature fast curing cationic polymerization at an exothermic peak of not more than 80 °C.

Example

Hereinafter, the present invention will be specifically described.

Example 1 (Production of aluminum chelate latent curing agent)

800 parts by weight of distilled water, surfactant (NUREX R, Nippon Oil Co., Ltd.) 0.05 parts by mass of 4 parts by mass of polyvinyl alcohol (PVA-205, Kuraray Co., Ltd.) as a dispersing agent was placed in a 3 liter interfacial polymerization vessel equipped with a thermometer, and uniformly mixed to prepare an aqueous phase.

Further, the oil phase was further introduced into the aqueous phase, and the mixture was emulsified and mixed by a homogenizer (10000 rpm/5 minutes), and then subjected to cationic emulsion polymerization at 60 ° C for 6 hours, wherein the oil phase system was used as an aluminum chelate-based hardener. 100% by weight of a solution of 24% isopropanol (Alumichelate D, Chuanyan Precision Chemical Co., Ltd.) of monoethyl acetonide aluminum acetoacetate (acetic acid ethyl acetate), bisphenol A as epoxy propyl ether type epoxy resin 100 parts by mass of a type epoxy resin (EP828, Mitsubishi Chemical Corporation) and 50 parts by mass of triphenyl decyl alcohol (Tokyo Chemical Industry Co., Ltd.) were dissolved in 100 parts by mass of ethyl acetate.

After completion of the reaction, the polymerization reaction solution was allowed to cool to room temperature, and the polymerized particles were separated by filtration by filtration and naturally dried to obtain 90 parts by mass of a spherical aluminum chelate-based latent curing agent. The particle size distribution of the volume conversion was measured using a laser particle size distribution measuring device (MT3300EXII, Nikkiso Co., Ltd.) for the obtained aluminum chelate latent hardener. The results obtained are shown in Fig. 1. From this result, it is understood that the aluminum chelate-based latent curing agent is controlled to have a single-micron size.

Example 2 (Production of aluminum chelate latent curing agent)

70 parts by mass of spherical aluminum chelate was obtained in the same manner as in Example 1 except that the epoxy propyl ether type epoxy resin (EP828, Mitsubishi Chemical Corporation) was reduced from 100 parts by mass to 80 parts by mass. A latent hardener. The particle size distribution of the volume conversion was measured using a laser particle size distribution measuring device (MT3300EXII, Nikkiso Co., Ltd.) for the obtained aluminum chelate latent hardener. The results obtained are shown in Fig. 2. According to the result, the aluminum is known The chelate latent hardener is controlled to a single micron size.

Example 3 (Production of aluminum chelate latent curing agent)

50 parts by mass of spherical aluminum chelate was obtained in the same manner as in Example 1 except that the epoxy propyl ether type epoxy resin (EP828, Mitsubishi Chemical Corporation) was reduced from 100 parts by mass to 60 parts by mass. A latent hardener. The particle size distribution of the volume conversion was measured using a laser particle size distribution measuring device (MT3300EXII, Nikkiso Co., Ltd.) for the obtained aluminum chelate latent hardener. The results obtained are shown in Fig. 3. Further, an electron micrograph is shown in Fig. 4 (x 10000) and Fig. 5 (x 15000). Based on these results, it was found that the aluminum chelate latent curing agent was controlled to have a single micron size. Further, it is understood that the shape of the aluminum chelate latent curing agent is substantially spherical.

(DSC evaluation)

4 parts by mass of the aluminum chelate-based latent curing agent of Example 1, 2 or 3, 80 parts by mass of bisphenol A type epoxy resin (EP828, Mitsubishi Chemical Corporation), and triphenyl stanol 8 parts by mass were uniformly mixed to prepare a thermosetting epoxy resin composition. The resulting thermosetting epoxy resin composition was subjected to thermal analysis using a differential thermal analysis device (DSC) (DSC6200, Seiko Instruments Inc.). The results obtained are shown in Table 1 and Figure 6. Here, regarding the hardening property of the aluminum chelate latent curing agent, the exothermic onset temperature means the hardening start temperature, the exothermic peak temperature means the hardening most active temperature, the exothermic end temperature means the hardening end temperature, and the total exotherm In order to achieve good low-temperature rapid hardenability, it is practically required to be 250 J/g or more.

In addition, the "EP828 blending amount (parts by mass)" in Table 1 means 100 parts by mass of the epoxy propyl ether type ring relative to the aluminum chelate-based hardener when preparing the aluminum chelate latent curing agent. Oxygen resin (EP828, Mitsubishi Chemical Corporation) blending amount (parts by mass), not The blending amount of the epoxy propyl ether type epoxy resin used in the preparation of the thermosetting epoxy resin composition.

According to Table 1 and FIG. 6, it is understood that the exothermic start temperature of the aluminum chelate latent curing agent of Examples 1 to 3 is 70 ° C or lower, and the exothermic peak temperature is about 120 ° C or lower. In particular, when the aluminum chelate-based latent curing agent is prepared, when the amount of the epoxy propyl ether type epoxy resin is 80 parts by mass or less based on 100 parts by mass of the aluminum chelate-based curing agent, The exothermic start temperature is about 50 ° C, and the exothermic peak temperature is also about 80 ° C, and the low-temperature rapid hardenability is improved.

Example 4

An aluminum chelate latent curing agent was prepared in the same manner as in Example 3 except that the cationic emulsion polymerization temperature was changed to 60 ° C from 60 ° C to prepare a thermosetting epoxy resin composition.

Example 5

An aluminum chelate latent curing agent was prepared in the same manner as in Example 3 except that the cationic emulsion polymerization temperature was changed from 60 ° C to 80 ° C, and a thermosetting epoxy resin composition was prepared.

(DSC evaluation)

4 parts by mass of the aluminum chelate-based latent curing agent of Example 4 or 5, 80 parts by mass of bisphenol A type epoxy resin (EP828, Mitsubishi Chemical Corporation), and triphenyl stanol 8 mass The parts were uniformly mixed to prepare a thermosetting epoxy resin composition, and the same procedure as in Example 3 was carried out. Thermal analysis was performed using a differential thermal analysis device (DSC) (DSC6200, Seiko Instruments Inc.). The results obtained are shown in Table 2 and Figure 7. The results of Example 3 are also shown.

According to Table 2 and FIG. 7, it is understood that when the cationic emulsion polymerization temperature at the time of preparation of the aluminum chelate-based latent curing agent is increased, the DSC pattern tends to be broad.

Example 6

In addition to the bisphenol A type epoxy resin (EP828, Mitsubishi Chemical Corporation), a bisphenol F type epoxy resin (EP807, Mitsubishi Chemical Corporation) was used as the epoxy propyl ether type epoxy resin, and Example 3 An aluminum chelate latent hardener was prepared in the same manner.

Example 7

In addition to the bisphenol A type epoxy resin (EP828, Mitsubishi Chemical Corporation), a phenol novolak type epoxy resin (EP152, Mitsubishi Chemical Corporation) was used as the epoxy propyl ether type epoxy resin, and Example 3 An aluminum chelate latent hardener was prepared in the same manner.

Example 8

In addition to the bisphenol-type epoxy resin (EP828, Mitsubishi Chemical Corporation), a dicyclopentadiene type epoxy resin (EP4088S, ADEKA Co., Ltd.) was used as the epoxy propyl ether type epoxy resin, In Example 3, an aluminum chelate latent curing agent was prepared in the same manner.

(Particle size distribution)

For the aluminum chelate latent hardener obtained in Examples 6 to 8, a laser particle size was used. The distribution measuring device (MT3300EXII, Nikkiso Co., Ltd.) measures the particle size distribution of the volume conversion. The results obtained are shown in Table 3, Figure 8 (Example 6), Figure 9 (Example 7), and Figure 10 (Example 8). Based on these results, it is understood that the aluminum chelate-based latent curing agents are controlled to have a single micron size.

(DSC evaluation)

4 parts by mass of the aluminum chelate-based latent curing agent of Examples 3 and 6 to 8, 80 parts by mass of bisphenol A type epoxy resin (EP828, Mitsubishi Chemical Corporation), and triphenylstanol The thermosetting epoxy resin composition was prepared by uniformly mixing 8 parts by mass, and thermal analysis was carried out in the same manner as in Example 3 using a differential thermal analyzer (DSC) (DSC6200, Seiko Instruments Inc.). The results obtained are shown in Table 4 and Figure 11. The results of Example 3 are also described for reference.

According to Table 4 and FIG. 11, it is understood that the exothermic onset temperature is 50 ° C regardless of the type of the epoxy propyl ether type epoxy resin used in the preparation of the aluminum chelate latent curing agent. To the extent below, the exothermic peak temperature is also about 80 °C.

[Industrial availability]

The aluminum chelate-based latent curing agent of the present invention is useful as a latent curing agent for a glycidyl ether type epoxy-based adhesive for low-temperature short-time bonding.

Claims (14)

An aluminum chelate-based latent curing agent, an aluminum chelate-based curing agent, a diaryl stanol compound or a triaryl stanol compound is held in a cationic emulsion-polymerized porous epoxy resin as a polymer capsule material. The aluminum chelate-based latent curing agent of the first aspect of the invention is an aluminum chelate-based curing agent in an amount of 50 to 300 parts by mass based on 100 parts by mass of the cationic emulsion-polymerized porous epoxy resin. The aluminum chelate latent curing agent according to the first or second aspect of the invention, which contains 10 to 200 parts by mass of a diaryl stanol compound with respect to 100 parts by mass of the cationic emulsion polymerizable porous epoxy resin. Or a triaryl stanol compound. The aluminum chelate latent curing agent according to any one of claims 1 to 3, wherein the cationic emulsion polymerized porous epoxy resin is used for cationic emulsification of an oil phase in an aqueous phase containing a dispersing agent. In the case of polymerization, the oil phase is obtained by dissolving or dispersing an aluminum chelate-based curing agent, a diaryl stanol compound, a triaryl stanol compound, and an epoxy compound in an organic solvent. The aluminum chelate-based latent curing agent according to the fourth aspect of the invention, wherein the oil phase contains 5 to 500 parts by mass of an epoxy compound based on 100 parts by mass of the aluminum chelate-based curing agent. An aluminum chelate latent curing agent according to claim 4 or 5, wherein the epoxy compound is a glycidyl ether type epoxy resin. An aluminum chelate latent curing agent according to item 6 of the patent application, wherein the epoxy propyl ether type epoxy resin is selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac Phenol novolac epoxy resin, cresol novolac At least one of the group consisting of epoxy resins, dicyclopentadiene epoxy resins, and ester epoxy resins. The aluminum chelate latent curing agent according to any one of claims 4 to 7, wherein the organic solvent has a boiling point of 30 to 100 ° C at atmospheric pressure. The aluminum chelate latent curing agent according to any one of claims 4 to 8, wherein the oil phase is contained in an amount of 5 to 500 parts by mass based on 100 parts by mass of the aluminum chelate hardener. An aryl stanol compound or a triaryl stanol compound. The aluminum chelate latent hardener according to any one of claims 1 to 9, wherein the diaryl stanol compound or the triaryl stanol compound is triphenyl decyl alcohol or diphenyl decane alcohol. A manufacturing method for producing an aluminum chelate latent curing agent according to item 1 of the patent application, wherein an aluminum chelate hardener and a diaryl stanol compound or a triaryl stanol compound are retained as a cationic emulsion-polymerized porous epoxy resin of a polymer capsule material obtained by cationic emulsion polymerization of an oil phase in an aqueous phase containing a dispersant, the oil phase system The aluminum chelate-based curing agent, the diaryl stanol compound, the triaryl stanol compound, and the epoxy compound are dissolved or dispersed in an organic solvent. A thermosetting epoxy resin composition containing the aluminum chelate latent curing agent, epoxy resin, and diaryl stanol compound or triaryl decane according to any one of claims 1 to 10. Alcohol compound. For example, the thermosetting epoxy resin composition of claim 12, wherein the epoxy resin is A epoxidized propyl ether type epoxy compound. The thermosetting epoxy resin composition of claim 12 or 13, which further comprises an oxycyclobutane compound.