JPS607653B2 - Hydrous epoxy resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water-containing epoxy resin, and in particular to a water-containing epoxy resin obtained by crosslinking and curing a water-in-oil composition in which water is dispersed in a composition comprising a glycidyl-type epoxy resin and amines. This invention relates to a water-containing epoxy resin that has poor water escape properties.

Epoxy resin products cured at room temperature are generally obtained by curing a composition comprising a glycidyl-type epoxy resin and an amine, and are known to have good chemical resistance, physical properties, and adhesive properties.

However, even resins with these characteristics do not have sufficient flame resistance and combustion resistance, so improvements in this point are being considered by adding halogenated compounds, metal oxides, and phosphorus compounds. It is known that the above compounds decompose due to heat and generate gases harmful to the human body, and it is desired to improve this point. The inventors of the present invention have studied various methods of enclosing water in epoxy resin, and as a result, have completed the present invention, which has excellent flame resistance and flame resistance.

The present invention uses a mixture of a glycidyl-type epoxy compound and one or more selected from primary amine compounds, secondary amine compounds, modified amine compounds, or mixtures of polymercaptans and tertiary amines with an HLB value of 2 to 2. This is a water-containing epoxy resin characterized by dispersing water in the presence of a nonionic surfactant having a surfactant of 10.

Specifically, the glycidyl-type epoxy compounds used in the present invention include diglycidyl ether of bisphenol A (1) Nopola-Soku type engineered poxy resin (□)
Futacetic acid diglycidyl ester (n-o~2)
(m) Diglycidyl ether of water-added bisphenol A (W)<n-.

~2> Dimethylcricidyl ether of bisphenol A (n-o~2) (V) Dimethylglycidyl ester of phthalic acid (n-o~2) (W), etc. These epoxy compounds A single type may be used, but several types can also be used in combination, and one type can be used in combination with a solid type or a chain type.

Further, as the primary amine compound or the secondary amine compound, an aliphatic, cycloaliphatic, aromatic or mulberry ring compound polyamine can be used, such as ethylenediamine, jethylenetriamine, bis(hexamethylene)triamine, tetraethylene bentamine, bentaethylenehexamine, diethylaminopropylamine,
1,2-diaminocyclohexane, menthendiamine,
Isophoronediamine, N-aminoethylpiverazine, m
-xylylenediamine, tetrachlor-P-xylylenediamine, metaphenylenediamine, 4,4-methylenedianiline, methylenepis (0-chloroaniline), diaminodiphenyl sulfone, 3,6-diaminopitadine, N-methyl Piverazine, hydroxyethylpiverazine, piverizine, pyrrolidine, morpholine and the like can be mentioned.

Examples of modified amine compounds include adducts of primary amines or secondary amines and epoxy compounds, adducts of ethylene oxide or propylene oxide, adducts of organic acid compounds, or cyanoethylated polyamines. There is free -NH2 or > in the molecule.
It has NH.

These amines and modified amine compounds may be used alone, or several types may be used in combination. Polymercaptans include polyols, polyesters,
Examples include polyhydric acids such as mercaptoester and trimercaptomethyltrioxane.

These polymercaptans may be used alone or in combination with a tertiary amine compound. Examples of tertiary amine compounds include linear diamine, N/N/N''N'tetramethyl 1'3-butanediamine, alkyl tert monoamine, tetramethylguanidine, triethanolamine, dialkylaminoethanol, 2-dimethylaminoethanol, etc. 2-Hydroxypropane, heptamethylisohiguanide, N-N'-dimethylpiverazine, N-methylmorpholine, hexamethylenetetramine, N.N-bis[(2-hydroxy)propyl]piverazine, triethylenediamine, 1- Hydroxyethyl-2-hebutadecylglyoxalidine, pyridine, pyrazine, quinoline, penzyldimethylamine, alphamethyl penzyldimethylamine, 2-(dimethylaminomethyl)phenol, 2,446-tris(dimethylaminomethyl) Phenol, 2,4,6-tris(
Tri-2-ethylhexylate (dimethylaminomethyl)phenol, 2-ethyl-4-methylimidazole or mixtures thereof can be used. The use of a polymercaptan and a tertiary amine compound is characterized in that a water-containing resin with high elasticity is obtained.

Nonionic surfactants used in the present invention include, for example, polyoxyethylene alkyl phenol, small oxyethylene alkyl phenol ether, oxyethylene oxypropylene block polymer, sorbitan alkyl ester, ester of polyhydric alcohol and fatty acid. , higher alkylhenals, etc., and those having an HLB of 2 to 10 or less are used.

Only a single type of these can be used, or several types can be used in combination, and if necessary, a pond-based surfactant can be used in combination, but the HLB value of the mixed surfactant used in combination is It is used in a range of 2 to 10 or less. In carrying out the present invention, a glycidyl-type epoxy compound and a water-insoluble primary amine compound, secondary amine compound, or modified amine compound are mixed, and a /ionic surfactant and water are added to achieve high-speed loss. Although it is easiest to add the epoxy compound, amines, nonionic surfactant, and water, the order of adding the epoxy compound, amines, nonionic surfactant, and water does not necessarily have to be in accordance with the above and can be selected arbitrarily. It is also possible to mix in a high-speed rope feeder and then mix the amines in a low-speed condenser.

When using polymercaptans, it is easiest to mix glycidyl-type epoxy resin, polymercaptans, tertiary amine, nonionic surfactant, and water and perform high-speed distillation. Mix the above ingredients, nonionic surfactant, and water in advance in a high-speed light frame.
The tertiary amine can also be mixed at low speed. In addition, when the primary amine compound, secondary amine compound, and modified amine compound are water-soluble, they are used after being made into a water-insoluble amine compound by a known method. The addition ratio of the glycidyl type epoxy compound and the primary amine compound, secondary amine compound, or modified amine compound is such that a crosslinking reaction can be carried out, preferably in a stoichiometric ratio.
Glycidyl-type epoxy compound, polymercaptan and third
The mixing ratio of the amine compound is 10 parts by weight of the epoxy compound, 30 to 250 parts by weight of the polymercaptan, and 10 parts by weight of the epoxy compound.
The amount of the amine compound is preferably 2 to 15 parts by weight.
The amount of water used varies depending on the amount and type of nonionic surfactant used and the type of reaction mixture, and is not particularly limited.
If it is 0% or more, the cured product will be flame retardant, and if it is 60% or more, the physical properties of the cured product will deteriorate, so it is preferably 20 to 60%.

The amount of nonionic surfactant is 0.5 to 1 of the amount of reaction mixture.
0% is preferred. HLB of nonionic surfactant used
The value is preferably 2 to 10 from the viewpoint of moisture retention of the cured product. Furthermore, if the HLB value is 2 or less, the resin lacks hydrophilicity, making it difficult to disperse and having poor stability, resulting in immediate separation of the resin and water.

On the other hand, if it is 10 or more, the hydrophilicity is high and the resin tends to be dispersed in water, making it impossible to obtain the desired water-containing epoxy resin. The components of the water-containing epoxy resin of the present invention include a reactive diluent, a non-reactive diluent, a reactive softening agent, a non-reactive softening agent, coal tar, and a hardening agent. General epoxy modifiers such as .
Calcium carbonate, aluminum hydroxide, kaiseki powder, water temperature,
It can contain fillers such as glass fiber, asbestos, and wood flour, and it can also contain protective colloids or thickeners such as methylcellulose, hydroxyethylcellulose, CMC, gelatin, polyvinyl alcohol, and polyacrylamide. .

The hydrated epoxy resin of the present invention can be used for cast products, molded products, laminated products,
It can be used in paints, adhesives, corrosion-resistant linings, flooring materials, wall materials, resin concrete, etc.

In these applications, pigments, fillers, diluents, maneuverability agents, hardening accelerators, protective colloids, thickeners, aggregates, water-moistened aggregates, coal tar, etc. are also added as necessary. Of course it is possible. Next, examples of the present invention will be given, but the present invention is not limited thereto.

Example 1 Epon828 (epoxy compound manufactured by Shell Chemical Co., corresponds to the above structural formula 1, n = 0, epoxy equivalent 190) 10
4 parts by weight of EH220 (Asahi Denka Kogyo Co., Ltd., aliphatic modified amine compound, amine equivalent: 80), Emulgen 903 (polyoxyethylene nonylphenol ether surfactant, manufactured by Kao Atlas Co., Ltd., HLB 7. 8)
A water-in-oil type emulsion is obtained by gradually adding 55 parts by weight of water while stirring 5 parts by weight at high speed.

The emulsion was a stable water-containing epoxy resin that did not separate water during or after the reaction. Example 2 5 parts by weight of diaminodiphenylmethane, 34 parts by weight of dibutyl phthalate, 5 parts by weight of Epon 82815, and 1 part by weight of salicylic acid are thoroughly stirred and heated to cause an addition reaction to produce an adduct type modified amine compound.

60 parts by weight of the obtained modified amine compound, Epon828
Stirring 10 parts by weight of Emulgen 905 (polyoxyethylene nonylphenol ether surfactant order: LB9.2, manufactured by Kao Atlas Co., Ltd.) at high speed and gradually adding 8 parts by weight of water will result in a stable solution. A water-in-oil emulsion, ie a water-containing epoxy resin, is obtained. Example 3 Shodin 506 (epoxy compound manufactured by Showa Denko Co., Ltd., corresponding to the above structural formula m, n = 0, epoxy equivalent 140
) 10 parts by weight, 4 parts by weight of 4,4'-methylene dianiline, Nonipol 20 (polyoxyethylene nonylphenol surfactant manufactured by Sanyo Chemical Industries, Ltd., HLB5)
．． 7) Add 7 parts by weight to 4 parts in advance at 50°C at high speed.
A stable emulsion is obtained by gradually adding 10 parts by weight of a 2% aqueous solution of Cellocyz QP300 (hydroxyethylcellulose manufactured by U.C.C.) heated at 0:00 to 0:00.

No water separation occurred when the emulsion was left to harden at 90 oo for 24 hours. Example 4 100 parts by weight of Epiclone 800 (epoxy compound manufactured by Dainippon Ink and Chemicals Co., Ltd., corresponding to the above structural formula V, n = 0, epoxy equivalent 210), 8122036 parts by weight, Emalgen 9032 parts by weight, Tween 81 (Kao Atlas A stable water-in-oil type emulsion can be obtained by gradually adding 6 parts by weight of water while stirring 2 parts by weight of polyoxyethylene sorbitan monooleate surfactant (HLBIO) manufactured by Co., Ltd. at high speed.

The emulsion was left at 40 qo for 24 hours to obtain a stable water-containing epoxy resin. Example 5 EP4081 (epoxy compound manufactured by Asahi Denka Kogyo Co., Ltd.,
Corresponds to the above structural formula W, n = 0, epoxy equivalent 220) 1
0 parts by weight of blood, 5 parts by weight of Emaluge PP-150 (oxyethylene oxypropylene block polymer surfactant manufactured by Kao Atlas Co., Ltd.) are heated at high speed and 45 parts by weight of water is gradually added to form stable water droplets in oil. A mold emulsion is obtained.

Add 50 parts by weight of EH551 (Asahi Denka Kogyo Co., Ltd., a modified aromatic amine compound containing a curing accelerator, amine equivalent weight 110) to parts by weight of Emulsion 15, stir thoroughly at low speed, and stabilize by curing at room temperature. A water-containing epoxy resin was obtained. Example 6 DEN431 (epoxy compound manufactured by Dow Chemical Company, corresponds to the above structural formula 0, n = 0.2, epoxy equivalent weight 175) 1
69 parts by weight of Araldite HY Satoshi 0 (modified aromatic amine compound manufactured by Ciba Corporation, amine equivalent weight 120), 10 parts by weight of Nonipol 2010, Arasel 186 (glycerol fatty acid ester surfactant manufactured by Kao Atlas Corporation, HLB)
2.8) A stable emulsion can be obtained by gradually adding 5 parts by weight of a 2% aqueous solution of Cerocize QP300, which has been preheated to 40 qo, while stirring 2 parts by weight at a high speed at 40 qo.

The emulsion was cured at room temperature to obtain a stable hydrous epoxy resin. Example 7 Parts by weight of EP408110 and 2 parts by weight of Emulgen 404 (polyoxyethylene oleyl ether surfactant manufactured by Kao Atlas Co., Ltd., HLB 8.8) were mixed at high speed while 5 parts by weight of water was gradually added. When added to water, a stable water-in-oil emulsion is obtained.

Sanmid X2000 (
4 parts by weight of fatty acid-modified xylylene diamine manufactured by Sanwa Kagaku Kogyo Co., Ltd. and having an amine equivalent of 85) were stirred at a low speed and cured at room temperature to obtain a stable hydrous epoxy resin. Example 8 Parts by weight of Epon 82810, Sanmide 30
5 parts by weight of polyamide amine manufactured by Sanwa Kagaku Kogyo Co., Ltd., amine value 210, 5 parts by weight of Tononipol 20, and 5 parts by weight of Span 80 (sorbitan monooleate surfactant manufactured by Kao Atlas Co., Ltd., HLB 4.3). When 165 parts by weight of water is added while stirring at high speed, a stable water-in-oil type emulsion is obtained.

The emulsion was cured at room temperature to obtain a stable water-containing epoxy resin. Example 9 100 parts by weight of Epon 828, 50 parts by weight of Thiokol LP-3 (polymercaptan manufactured by Toray Thiokol Co., Ltd.), and 4 parts by weight of water were gradually added while stirring at high speed to form a stable water-in-oil type. An emulsion is obtained.

One part by weight of tris(dimethylaminomethyl)phenol was stirred into the emulsion at a low speed and reacted at room temperature to obtain a stable hydrous epoxy resin. Example 10
Parts by weight of Epon 82810, 100 parts by weight of Takuron 180 (coal tar manufactured by Yoshida Refinery Co., Ltd.), EH2
A stable water-in-oil type emulsion is obtained by gradually adding 10 parts by weight of water while stirring 204 parts by weight, 5 parts by weight of Emulgen 903, and 805 parts by weight of SPAN 805 at high speed.

The emulsion was cured at room temperature to obtain a stable water-containing epoxy resin. Example 11 Parts by weight of Epon 82810 and 5 parts by weight of Emulgen 905 are stirred at high speed.

EH240 (modified aliphatic amine compound manufactured by Asahi Denka Kogyo Co., Ltd., amine equivalent: 80) was added to 105 parts by weight of the obtained mixture.
Parts by weight of 4, sand for cement mortar with a moisture content of 10% 7
0 parts by weight were mixed in a mortar mixer and cured at room temperature to obtain a stable water-containing epoxy resin. Test Examples The performance of the water-containing resins obtained in Examples is shown in the table.

table.

Claims (1)

[Claims] 1 (a) a glycidyl-type epoxy compound and (b) (b-
1) Mixture of polymercaptan and tertiary amine (b-2
) Primary amine compound (b-3) Secondary amine compound (b-4) One or more amines selected from modified amine compounds are dispersed in water in the presence of a nonionic surfactant having an HLB of 2 to 10. Seshime,
A water-containing epoxy resin characterized by retaining water in a cured epoxy resin.