JPH08301985A - One-pack curing epoxy resin composition, curing method, and curing agent powder - Google Patents

Abstract

PURPOSE: To provide a one-pack curing epoxy resin composition having a good storage stability and low-temperature curability, a curing method therefor, and a curing agent powder thereof. CONSTITUTION: This epoxy resin composition is formed by dispersing a thermosetting curing agent powder in an epoxy resin, the powder having an average particle size of 1-100μm, and the composition is covered with 0.5-100 pts.wt. wax for each 100 pts.wt. thermosetting curing agent powder.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a one-component curable epoxy resin composition, a curing method using the same, and a thermosetting curing agent powder used in the one-component curable epoxy resin composition.

[0002]

2. Description of the Related Art Epoxy resin adhesives used for various purposes have already been mixed with a two-pack type in which an epoxy resin and a curing agent are mixed immediately before use and an epoxy resin and a curing agent. There is a one-pack type.

The two-pack type epoxy resin adhesive has the advantage that it cures at room temperature and is widely used at present.
Epoxy resin and curing agent must be stored separately and, if necessary, mixed before use, which makes storage and handling complicated, and the pot life after mixing is limited, Since it cannot be prepared in a large amount, when a large amount of epoxy resin-based adhesive is required, the compounding frequency becomes high and the working efficiency is lowered.

In order to solve the above-mentioned drawbacks, one-pack type epoxy resin adhesives using, for example, a boron fluoride-amine complex, dicyandiamide, an imidazole compound, etc. as a curing agent have been investigated. However, although these curing agents have excellent storage stability, they require a high temperature for curing,
Those that cure at a relatively low temperature have poor storage stability and are not practically satisfactory, and heretofore, curing agents for one-pack type epoxy resin adhesives that have storage stability and low temperature curability have been used. There wasn't.

US Pat. No. 4,066,625 describes
An epoxy resin-amine compound adduct in which an amine compound is subjected to an addition reaction with an epoxy compound to be polymerized and insolubilized to improve storage stability is disclosed in JP-A-1-564731 and JP-A-3-296525. U.S. Pat. No. 3,693,657 discloses a one-pack type epoxy in which an amine-polyamine adduct has a storage stability and a low temperature curing property. Each is disclosed as a curing agent for a resin adhesive, and in addition, a hydrazide-based latent curing agent, a nylon salt, and the like are being studied. But,
Since active groups that react with the interface with the epoxy resin are not completely blocked in these curing agents, it is impossible to effectively utilize the active groups to promote the curing of the epoxy resin when mixed with the epoxy resin. There is a problem such as.

Currently, as a method of blocking the active group, a method of treating the above-mentioned epoxy resin-amine compound adduct, urea type adduct, etc. with an acid such as hydrochloric acid, acetic acid, etc., or an isocyanate compound is treated. Etc. are being considered. However, the curing agents obtained by these methods have drawbacks such as abrupt deterioration of storage stability due to a small amount of water present in the epoxy resin, and one-pack type epoxy which can be practically satisfied. A curing agent for resin adhesive has not been obtained yet.

[0007]

SUMMARY OF THE INVENTION In view of the above, the present invention is a one-part curable epoxy resin composition having good storage stability and low temperature curability, a curing method using the same, and one part thereof. An object of the present invention is to provide a thermosetting curing agent powder used in a curable epoxy resin composition.

[0008]

The gist of the present invention is a one-pack curable epoxy resin composition comprising a thermosetting curative powder dispersed in an epoxy resin. The powder has an average particle diameter of 1 to 100 μm and is coated with 0.5 to 100 parts by weight of wax with respect to 100 parts by weight of the thermosetting curing agent powder.

The thermosetting type curing agent powder used in the present invention has an average particle size of 1 to 100 μm. The average particle diameter is a volume average value measured by the Coal counter method. If it is less than 1 μm, secondary aggregation easily occurs,
The effect of substantially improving the reactivity decreases, and when it exceeds 100 μm, it becomes unsuitable because it exceeds the general tape thickness.
It is limited to the above range.

The above-mentioned thermosetting type curing agent powder may be a fine powder obtained by pulverizing a thermosetting type curing agent, or may be a thermosetting type curing agent which has already been pulverized into a fine powder. Good. As the pulverization method, a dry method such as a jet mill such as a ball mill and a counter jet mill; a pin mill such as a contraplex mill is preferable because a drying step is unnecessary.

Examples of the thermosetting type curing agent which has already been pulverized into a fine powder include commercially available ones such as Amicure VDH and Amicure PN-23 manufactured by Ajinomoto Co., Inc. If these are used, no further grinding is necessary.

The thermosetting curing agent used in the present invention is not particularly limited, and preferably aromatic (poly) amine, (cyclic) aliphatic polyamine, acid anhydride, polyamide, boron fluoride-amine. Complexes, phenolic resins, epoxy resin-amine compound adducts, urea type adducts, amine-polyamine adducts, hydrazide latent curing agents, nylon salts, dicyanamides, imidazoles, acids or isocyanates whose surface has been treated with aromatics (polyethers). ) Amine, acid or isocyanate surface-treated (cyclic) aliphatic polyamines, acid or isocyanate surface-treated acid anhydrides, acid or isocyanate surface-treated polyamides, acid or isocyanate surface-treated surfaces Boron Fluoride-Amine Complex, Phenol Surface Treated with Acid or Isocyanate Fat, epoxy surface with an acid or an isocyanate treated resin - amine compound adduct, acid or urea type adduct having a surface treated with an isocyanate,
Amine-polyamine adduct surface-treated with acid or isocyanate, hydrazide latent curing agent surface-treated with acid or isocyanate, nylon salt surface-treated with acid or isocyanate, surface-treated with acid or isocyanate And at least one selected from the group consisting of dicyanamide and imidazole whose surface is treated with an acid or an isocyanate.

The aromatic (poly) amine is not particularly limited, and examples thereof include metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldimethyldiphenylmethane and the like.

The (cyclic) aliphatic polyamine is not particularly limited, and examples thereof include diamines such as Jeffamine and the like manufactured by Texaco Chemical Co., in which the hydroxyl group contained in polypropylene glycol is substituted with an amino group, triamine; diethylenetriamine; poly. Oxyethylenediamine; Metaxylenediamine; Bis (4-amino-3)
-Methylcyclohexyl) methane; aminoethylpiperazine and the like.

The acid anhydride is not particularly limited, and examples thereof include phthalic anhydride, ethylene glycol bisanhydrotrimellitate, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct and the like. To be

The above polyamide is not particularly limited,
For example, those obtained by reacting a dimer acid such as polymide manufactured by Sanyo Chemical Co., Ltd. with a polyamine such as diethylenetriamine and triethylenetetramine can be mentioned.

The epoxy resin-amine compound adduct is not particularly limited, and examples thereof include Amicure PN-23 and Amicure MY-24 manufactured by Ajinomoto Co. in which an amine compound such as imidazole is subjected to an addition reaction with an epoxy resin. The above urea-type adduct is not particularly limited, and for example, Fuji Chemical Co., Ltd. Fujicure FXE-1000, FX obtained by addition reaction of an amine compound with urea, isocyanate and the like.
R-1030 etc. are mentioned. The amine-polyamine adduct is not particularly limited, and examples thereof include HT-939 manufactured by Ciba-Geigy.

The hydrazide-based latent curing agent is not particularly limited, and examples thereof include Amicure VDH, Amicure LDH, Amicure UDH and the like manufactured by Ajinomoto Co., Inc. The nylon salt is not particularly limited, and examples thereof include Amicure ATU-C manufactured by Ajinomoto Co., Inc. As the above-mentioned imidazole, you may use imidazole type hardening | curing agent cure azole 2E4MZ (2-ethyl-4-methyl imidazole) by Shikoku Chemicals. Epoxy resin-amine compound adduct whose surface is treated with an acid or isocyanate, and urea type adduct whose surface is treated with an acid or isocyanate are not particularly limited.
Novacure HX manufactured by Asahi Kasei using hydrochloric acid, acetic acid, etc.
Surface treatment type latent curing agents such as −3721, Novacure HX-3741 and the like can be mentioned.

The thermosetting type curing agent powder used in the present invention is coated with wax. In the present invention, since the wax has a configuration in which the thermosetting curing agent powder is surrounded (hereinafter, referred to as “ordered mixture structure”), good storage stability is achieved without vacuum defoaming the epoxy resin. It is possible to obtain a one-pack type epoxy resin composition having properties and fast curing at low temperature.

In the present invention, it is preferable to spray coat the molten wax while flowing the thermosetting curing agent powder in an air stream. The above spray coating, for example, Freund Sangyo Co., Ltd. Spiral Flow, Paulex Co., Multiplex, Hosokawa Micron Co. Agromaster granulation / coating device while flowing the thermosetting curing agent powder in an air stream, The previously melted wax can be sprayed in the air stream using a nozzle.

In the present invention, the thermosetting curing agent powder is prepared by a physical method in which the finely powdered wax is dispersed in the gas phase and mechanical mechanical energy mainly composed of impact force is applied for coating. The body may be coated with the above wax. The coating by the above-mentioned physical method can be performed using, for example, a Theta composer manufactured by Tokuju Kosakusho, a hybridization system manufactured by Nara Machinery Co., Ltd., and the like.

When the coating by the physical method is adopted, it is preferable that the finely divided wax has an average particle diameter smaller than that of the thermosetting curing agent powder. When the average particle size of the finely divided wax exceeds the average particle size of the thermosetting curing agent powder, it becomes difficult to obtain an ordered mixture structure.

Since the thermosetting type curing agent powder is coated with the wax and is separated from the epoxy group contained in the epoxy resin, the reaction between the epoxy group and the thermosetting type curing agent powder. Does not occur at normal operating temperatures.

The wax used in the present invention preferably has a melting point of 50 to 160 ° C. and is difficult to dissolve in an epoxy resin. If the above-mentioned conditions are used, the epoxy group and the thermosetting-type curing agent powder are rapidly melted by heating and a crosslinking reaction occurs.

The above wax is not particularly limited, but is preferably an amide compound having 12 to 44 carbon atoms, a bisamide compound having 12 to 44 carbon atoms, and 12 to 44 carbon atoms.
N-substituted urea compound, carboxylic acid having 10 to 30 carbon atoms or salt thereof, alcohol having 16 to 72 carbon atoms, 20 carbon atoms
It is composed of at least one selected from the group consisting of an ester compound having 60 to 60 carbon atoms, a polyolefin having 20 to 7,000 carbon atoms, and a ketone having 20 to 60 carbon atoms.

The amide compound having 12 to 44 carbon atoms is not particularly limited, and examples thereof include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic acid amide, erucic acid amide,
Ricinoleic acid amide, N-stearyl stearic acid amide, N-oleyl oleic acid amide, N-stearyl oleic acid amide, N-stearyl erucic acid amide, N-
Examples include oleyl palmitate amide, methylol stearic acid amide, and methylol behenic acid amide.

The bisamide compound having 12 to 44 carbon atoms is not particularly limited and includes, for example, methylene bis-stearic acid amide, ethylene bis-stearic acid amide,
Ethylene bis behenic acid amide, hexamethylene bis stearic acid amide, hexamethylene bis stearic acid amide, hexamethylene bis behenic acid amide, N,
N'-distearyl adipic acid amide, N, N'-distearyl sebacic acid amide, N, N'-methylenebisoctadecanoic acid amide, ethylene bisoleic acid amide,
Hexamethylenebisoleic acid amide, N, N′-dioleyl adipate amide, N, N′-dioleyl sebacic acid amide, m-xylylenebisstearic acid amide,
N, N'-distearylisophthalic acid amide etc. are mentioned.

The N-substituted urea compound having 12 to 44 carbon atoms is not particularly limited and includes, for example, N-butyl-N'-
Stearyl urea, N-phenyl-N'-stearyl urea, N-stearyl-N'-stearyl urea and the like can be mentioned.

The carboxylic acid having 10 to 30 carbon atoms or salt thereof is not particularly limited, and examples thereof include caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, erucic acid, ricinoleic acid. , Barium stearate, calcium stearate,
Examples thereof include zinc stearate, aluminum stearate and magnesium stearate.

The alcohol having 16 to 72 carbon atoms is not particularly limited, and examples thereof include cetyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, mannitol and the like.

The ester compound having 20 to 60 carbon atoms is not particularly limited, and examples thereof include myristyl myristate, stearyl stearate, octyldodecyl behenate, behenyl behenate, distearyl phthalate, dicyclohexyl phthalate, sorbitan monopalmi. Tate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan sesquioleate, sorbitan monobehenate, polyethylene glycol monolaurate, (poly) ethylene glycol distearate, propylene glycol monostearate, pentaerythritol Monostearate, stearic acid monoglyceride, palmitic acid monoglyceride, oleic acid monoglyceride, oleic stearic acid monodiglyceride Id, stearic acid mono diglyceride chloride, behenic acid monoglyceride, stearyl methacrylate, behenyl methacrylate, hydrogenated castor oil and the like.

The above-mentioned polyolefin having 20 to 7,000 carbon atoms is not particularly limited, and examples thereof include polyethylene, polypropylene, copolymers thereof, etc. modified with (anhydrous) maleic acid, a carboxyl group, a glycidyl group and the like. Can be mentioned.

The ketone having 20 to 60 carbon atoms is not particularly limited, and examples thereof include distearyl ketone, dicapryl ketone, dilauryl ketone, dimyristyl ketone, dipalmityl ketone, dioleyl ketone and dibehen ketone.

The epoxy resin used in the present invention is not particularly limited, and examples thereof include glycidyl ether type epoxy resin of bisphenol A, glycidyl ether type epoxy resin of glycerin, glycidyl ether type epoxy resin of polyalkylene oxide, and oxybenzoic acid. Glycidyl ether type epoxy resin, dimer acid glycidyl ether type epoxy resin, phenol novolac glycidyl ether type epoxy resin, brominated bisphenol A glycidyl ether type epoxy resin, bisphenol F glycidyl ether type epoxy resin, polybutadiene with peracetic acid Examples thereof include epoxidized alicyclic epoxy resins and modified products thereof. These may be liquid or solid.

The amount of the thermosetting curing agent powder added can be determined from the rapid curing property and the physical properties of the one-pack type epoxy resin composition obtained from the thermosetting curing agent powder, and preferably, 0.1 to 100 parts by weight of the epoxy resin
It is 100 parts by weight. If it is less than 0.1 parts by weight, it takes a long time to obtain sufficient curability, and if it exceeds 100 parts by weight, the viscosity when mixing the epoxy resin and the thermosetting curing agent powder is increased. Is high and accompanied by fever,
It becomes difficult to control the curability.

In the present invention, when curing the epoxy resin, a curing agent other than the thermosetting curing agent powder may be added. The curing agent other than the thermosetting curing agent powder is not particularly limited, and examples thereof include aliphatic amines such as ethylenediamine, diethylenetriamine, dicyandiamide and guanidine; cyclic aliphatic compounds such as di (4-aminocyclohexyl) methane and isophoronediamine. Amines; aromatic amines such as m-phenylenediamine, p, p'-bis (4-aminophenyl) methane; phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylated hexahydrophthalic anhydride, anhydrous Polycarboxylic acid anhydrides such as trimellitic acid; phenol resins, melamine resins, urea resins and the like.

In the present invention, an inorganic powder may be added to the thermosetting curing agent powder to improve storage stability, properties after mixing with an epoxy resin, and the like. By adding the inorganic powder, it is possible to prevent aggregation that occurs due to pressurization during storage, and to prevent sedimentation and aggregation that occur during storage after heating with the epoxy resin and during heating.

The above-mentioned inorganic powder is not particularly limited,
For example, inorganic silicic acid, kaolin, atabal guide, diatomaceous earth, talc, bentonite, activated clay, zeolite, clay, asbestos, wollastonite, mica, titanium oxide, calcium carbonate, barium sulfate, carbon black, aluminum hydroxide, etc. Can be mentioned.

When the one-pack type curable epoxy resin composition of the present invention is cured, for example, a reactive diluent, a non-reactive diluent, a solvent, an anti-settling agent, a pigment, a filler, a plasticizer, and flexibility. You may add auxiliary materials, such as an imparting agent and coal tar.

The second aspect of the present invention is a curing method in which the one-part curable epoxy resin composition of the first aspect is applied to at least one surface of a substrate at room temperature and then heated and cured. According to this method, the wax that coats the thermosetting curing agent powder is rapidly melted by heating, and the crosslinking reaction between the epoxy group in the epoxy resin and the thermosetting curing agent powder proceeds rapidly. To do.

The present invention 3 is a thermosetting curing agent powder for a one-component curing type epoxy resin composition used for the preparation of the one-component curing type epoxy resin composition of the present invention 1, having an average particle diameter of 1 to 1. 1
It is 00 μm, and is coated with 0.5 to 100 parts by weight of wax based on 100 parts by weight of the total amount.

The above-mentioned thermosetting curing agent powder for one-component curing type epoxy resin composition is, for example, an insulating sealant, a film adhesive, an anisotropic conductive adhesive, a flocked tile adhesive, a water pipe repair. Adhesives, powder paints, dip paints for capacitors,
It can be applied to a wide range of application fields such as urethane paints, water pipe inner surface coating materials, casting materials, molding materials, laminated materials, and composite materials.

[0043]

The one-part curable epoxy resin composition of the present invention is formed by coating the wax with the thermosetting hardener powder constituting the one-part curable epoxy resin composition. The product performance can be sufficiently maintained and the storage stability can be dramatically improved.

[0044]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

Example 1 Amycure PN-23 manufactured by Ajinomoto Co., Inc. was placed in a granule coating apparatus AGM-2 manufactured by Hosokawa Micron Co., Ltd. at 400 g and rotated at 1200 rpm. 30 g of the stearyl oleic acid amide thus melted was sprayed to obtain a one-component curing type curing agent 1 for epoxy resin.

Example 2 A one-part curable epoxy resin curing agent 2 was obtained in the same manner as in Example 1 except that the amount of stearyl oleic acid amide was changed to 90 g.

Example 3 Example 1 except that 30 g of paraffin wax having a melting point of 75 ° C. was used instead of stearyl oleic acid amide.
In the same manner as described above, a one-component curing type curing agent 3 for epoxy resin was obtained.

Example 4 A one-component curing type epoxy resin curing agent 4 was obtained in the same manner as in Example 1 except that Ajinomoto Amicure PN-23 was used instead of Ajinomoto Amicure VDH.

Example 5 A one-component curing type epoxy resin curing agent 5 was obtained in the same manner as in Example 4 except that the amount of stearyl oleic acid amide was changed to 90 g.

Example 6 13.5 g of Amicure VDH manufactured by Ajinomoto Co. and an average particle size of 8
3.5 g of stearic acid amide of μm was put into the theta composer lab manufactured by Tokuju Kosakusho Co., Ltd.
m and the rotor was rotated at 5000 rpm for 20 minutes to obtain a curing agent 6.

Example 7 Imidazole type curing agent Curezol 2 manufactured by Shikoku Chemicals Co., Ltd.
E4MZ (2-ethyl-4-methylimidazole) is a current jet mill CI-1 manufactured by Nisshin Engineering Co., Ltd.
It was crushed with 0 to obtain crushed imidazole having an average particle size of 50 μm. 13.5 g of pulverized imidazole and stearic acid amide having an average particle size of 35 μm were put into a theta composer lab manufactured by Tokuju Seisakusho Co., Ltd., vessel 200 rpm, rotor 500
It was rotated at 0 rpm for 20 minutes to obtain a curing agent 7.

Comparative Example 1 Untreated Amicure PN-23 (manufactured by Ajinomoto Co., Inc.) was used as a curing agent. Comparative Example 2 Untreated Amicure VDH (manufactured by Ajinomoto Co., Inc.) was used as a curing agent. Comparative Example 3 Untreated imidazole 2E4MZ was used as a curing agent.

A curing agent for a one-component curing type epoxy resin is shown in Table 1.
By mixing with the epoxy resin "EP828" manufactured by Yuka Shell Epoxy Co., Ltd., the respective formulations were obtained. The curability and storage stability of each compounded product were evaluated. The results are shown in Table 1.

(Evaluation of Hardenability) Mild Steel Plate-130
After heating in an oven at ℃ for 1 hour, JIS K 685
The shear adhesive strength was measured according to the measuring method defined by 0, and the curability was evaluated. (Storage stability) The gelling time was defined as the time until it stopped flowing at 60 ° C and the bottle containing the formulation was turned over, and the gelling time was evaluated as the storage stability.

[0055]

[Table 1]

[0056]

EFFECTS OF THE INVENTION Since the one-pack curable epoxy resin composition of the present invention has the above-mentioned constitution, the storage stability is dramatically improved and the cured product performance is also good.

Claims (3)

[Claims] 1. A one-pack curing type epoxy resin composition comprising a thermosetting curing agent powder dispersed in an epoxy resin, wherein the thermosetting curing agent powder has an average particle diameter of 1 to 1. 100
A one-part curable epoxy resin composition having a thickness of μm and being coated with 0.5 to 100 parts by weight of wax with respect to 100 parts by weight of the thermosetting curing agent powder. 2. The one-part curable epoxy resin composition according to claim 1 is applied to at least one surface of a substrate at room temperature and then heated to cure the epoxy resin composition. A method for curing a one-component curing type epoxy resin composition. 3. Wax having an average particle size of 1 to 100 μm and 0.5 to 100 per 100 parts by weight of the total amount.
A thermosetting curing agent powder for a one-component curing type epoxy resin composition, characterized by being coated with parts by weight.