JPH0124165B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a polybutadiene-modified epoxy resin aqueous dispersion composition. Conventionally, epoxy resins are generally used in the form of resin liquids containing organic solvents and diluents, so the resin liquid becomes too viscous to be used at relatively high concentrations, making it extremely difficult to handle. to reduce to;
In addition, the odor and irritation of organic solvents contained in the resin liquid,
Due to flammability and other reasons, epoxy resins are dispersed in water to avoid these disadvantages. These epoxy resin water dispersion compositions are easily cured with curing agents such as amines or acids in the same way as conventional epoxy resin liquids, and are expected to be widely used in fields such as paints, adhesives, building materials, and civil engineering applications. . However, conventional epoxy resin aqueous dispersion compositions have the disadvantage that they tend to form sediment over time, particularly when left at low temperatures, and a solution has been sought. As a solution to this problem, there is a method of using surfactants such as emulsifiers or protective colloids, but when ionic surfactants are used, the epoxy groups open during the emulsification process and during storage, resulting in reaction with the curing agent. It is known that the properties of the cured product are reduced. When a nonionic surfactant is used as a protective colloid, for example, as in JP-A-46-29625, the crosslinking point decreases as in the case of using the ionic surfactant mentioned above. Although no significant performance deterioration was observed due to the addition of these surfactants, the properties of the cured product were clearly inferior to those of the cured product of solvent diluted epoxy resin. Therefore, it has been desired to develop a stable aqueous epoxy resin dispersion that can reduce the amount of emulsifiers and protective colloids used. As an attempt to do this, research has recently been carried out on water dispersions made from graft reaction products of acrylic acid derivatives on epoxy resins, but problems such as complicating the manufacturing process have arisen and sufficient improvements have not yet been made. It was hot. On the other hand, cured epoxy resins have excellent mechanical properties and adhesive properties, but have drawbacks in peeling strength, flexibility, and impact strength. In order to improve the drawbacks of such epoxy resins, polyethylene glycol, coal tar, dibutyl phthalate, polyglycol glycidyl ether, organic fatty acid glycidyl ester, polyester, polyamide, polyether, etc. have been used in combination as flexibility imparting agents. ing. Furthermore, urethane-modified epoxy resins and terminal-carboxynitrile-modified polybutadienes are mixed with epoxy resins, but in general, when such mixtures are used, one of the mixed components dissolves or settles in water during the emulsification process and storage. However, the stability of the aqueous dispersion was significantly impaired. The present inventors have developed a polybutadiene-modified epoxy resin aqueous dispersion composition that eliminates the above-mentioned conventional drawbacks, that is, it has excellent aging stability, especially low-temperature stability, with little or no use of emulsifiers or protective colloids. completed the present invention as a result of intensive research to find a polybutadiene-modified epoxy resin aqueous dispersion composition that provides good peeling strength, flexibility, and impact strength. That is, in the present invention, the polybutadiene homopolymer and/or copolymer (A) having a carboxyl group and the epoxy resin (B) are mixed in an amount of 1.8 per equivalent of the carboxyl group in (A).
It consists of a polybutadiene-modified epoxy resin obtained by heat-reacting an amount of (B) corresponding to ~30 equivalents of epoxy groups, water and a surfactant, and the weight ratio of each component is polybutadiene-modified epoxy resin/water =
90/10~1/99, water/surfactant=100/15~
This is a polybutadiene-modified epoxy resin aqueous dispersion composition characterized in that the ratio is in the range of 100/0. The polybutadiene homopolymers and/or copolymers having carboxyl groups in the molecule used in the present invention are commercially available Nippon Soda brand names Nisso-PB-C-1000, C-2000,
Gutdoritsuchi's product name: Hycar-CTB, CTBX,
CTBN, General Tire's product name Telogen
CT, S, Philips product name Butarez CTL,
There is HTPB. Also, Nippon Soda's product name for polybutadiene homopolymers and copolymers with hydroxyl groups at the ends.
Nisso PB-G-1000, 2000, 3000, Arco product name Poly-BD, Philips Butarez
Resins obtained by half-esterifying HT, Hycar-HTB from Gutduritsu, Telogen HT from General Tire, etc. with an acid anhydride such as maleic anhydride in a conventional manner are also butadiene with a carboxyl group at the end. Can be used as homopolymers and copolymers. Furthermore, a modified resin obtained by adding maleic anhydride to a polybutadiene homopolymer and/or copolymer having no terminal functional groups can also be used. Furthermore, the double bonds of the above polymer may be partially or completely saturated by hydrogenation. As the epoxy resin (B) used in the present invention, (a) Bisphenol A type epoxy resin, for example, Epicote, a trade name of Ciel Chemical Co., Ltd.
827, 828, 834, 836, 1001, 1004,
1007; Product name of Ciba Geigy Co., Ltd. Araldide
GY252, GY250, GY260, GY280,
6071, 6084, 6097; Dow Chemical Co., Ltd. product name DER330, 6097;
331, 337, 661, 664; Trade names of Dainippon Ink and Chemicals Co., Ltd. Epicron 800, 1010, 1000, 3010, (b) Novolac type epoxy resins, such as those of Ciel Chemical Co., Ltd. Product name: Epicote 152
154; Product name DEN-431 of Dow Chemical Co., Ltd.
438, 439; Ciba Geigy Co., Ltd. product name EPN-1138,
ECN-1235; Trade name of Dainippon Ink Chemical Co., Ltd. Epicron N
-740, N-680, N-695, N-565, N-577, (c) Hydrogenated bisphenol A diglycidyl ether resin, for example, Asahi Denka Kogyo Co., Ltd.'s product name Adekal Resin EP- 4080, (d) Bisphenol A side chain type diglycidyl ether resin, for example, Asahi Denka Kogyo Co., Ltd.'s trade name Adekal Resin EP-
4000, (e) Urethane-modified epoxy resin, for example, Asahi Denka Kogyo Co., Ltd.'s trade name ADEKA RIN EPU
-4, EPU-6, EPU-8, (f) Resorcin diglycidyl ether epoxy resins, such as SUMI-epoxy ELR-130,
ELR-150, (g) Glycidyl ester type epoxy resin, for example, Ciba Geigy's trade name Araldide CY
-182, Ciel Chemical Co., Ltd. trade name Epicote E-190,
E-871, Showa Denko Co., Ltd.'s product name S-500,
Same S-508, Same S-509, Same S-601X, Same S-
603X, S-607X, S-609X, S-729,
Same S-540, Same S-550, Dainippon Ink & Chemicals Co., Ltd. trade name Epiclon 200, Same 400, Same 1400, (h) p-oxybenzoic acid diglycidyl ether ester resin, e.g. SUMI-epoxy resin ELP−160, (i) Alicyclic epoxy resin Union Carbide Company product name ERL−
4221, 4289, 4206, 4234, 4205, Ciba Geigy Co., Ltd. product name Araldide CY
-179, CY-177, CY-185, CY-175, Chitsuso Co., Ltd. product name CX-221, CX-289,
CX-206, CX-301, CX-313, (j) Brominated bisphenol A type epoxy resin Product name of Ciel Chemical Co., Ltd. Epicote DX-
245, 1045-B-80, Ciba Geigy Co., Ltd. product name Araldide
8011, 8047, Dainippon Ink & Chemicals Co., Ltd.'s product name Epicron 152, 1120, Dow Chemical Co., Ltd.'s product name DER-542,
511, 580, (k) Glycidylamine epoxy resin e.g.
SUMI-epoxy ELM-120, SUMI-epoxy ELN-125, etc. can be used. In the reaction of the carboxyl group-containing polybutadiene homopolymer and/or copolymer (A) with the epoxy resin (B), the reaction temperature is 100 to 250°C, preferably 130 to 190°C, and the reaction time is usually 1 to 8°C.
The time is preferred, particularly 2 to 5 hours.
This reaction is mainly a reaction between an epoxy group and a carboxyl group, and an ester bond is produced.
(A hydroxyl group is simultaneously generated in this ester residue.) The ratio of the epoxy resin used is 1.8 to 30 equivalents, preferably 2.0 to 20 equivalents, of epoxy groups per equivalent of carboxyl group. If the amount of epoxy group used relative to carboxyl group is less than 1.8 equivalents, the molecular weight of the reactant increases, the viscosity increases significantly, and gelation sometimes occurs, which is not preferable. On the other hand, if the above-mentioned maximum limit of 30 equivalents is exceeded, the amount of unreacted epoxy resin remaining increases, and the peeling strength, flexibility and impact strength of the cured product are significantly reduced. In order to accelerate the reaction of epoxy groups to carboxyl groups, shorten the time of exposure to high temperatures, and prevent undesirable increases in viscosity or gelation due to thermal polymerization of polybutadiene-based polymers, an accelerator is added to the reaction system. It is also possible to accelerate the reaction. Reaction accelerators used for this purpose include, for example, 2-ethylimidazole, tetraethylammonium bromide, benzyldimethylamine, triethylenediamine, triethylamine, diethylamine, butylamine, choline chloride, caustic potash, and alkali carbonate. is added in an amount of 0.01 to 5 mol% based on the epoxy group. In addition, in order to further suppress thermal polymerization, radical polymerization inhibitors such as hydroquinone, parabenzoquinone, and anthraquinone may be used.
It is recommended to add 100 to 1000 ppm. The atmosphere of the reaction system may be an inert gas, and by conducting the reaction in the presence of air, thermal polymerization of the carbon-carbon double bond can be more reliably suppressed. . Further, if necessary, a suitable solvent may be added, and in this case it is effective in handling the reactants. The aqueous dispersion using this polybutadiene-modified epoxy resin can be manufactured by various methods, but for example, it can be manufactured as follows. The aforementioned polybutadiene-modified epoxy resin may be gradually added to water at 10 to 80°C, preferably nonionic water at 20 to 50°C, and mixed and dispersed using a high-speed mixer or homogenizer. The weight ratio of water and resin [water]/[resin] is 99/1 to 10/90
Preferably it is in the range of 60/40 to 40/60. Most of the polybutadiene-modified epoxy resins used in the present invention can be made into a water dispersion by the above method, but if the resin has a particularly high viscosity and it is extremely difficult to make an aqueous dispersion, it is possible to add an organic solvent to the resin. It is. Typical organic solvents include aromatic hydrocarbons such as xylene and toluene, ketones such as methyl ethyl ketone and methyl isobutyl ketone, hydroxy ethers such as butyl cellosolve and ethyl cellosolve, acetic esters such as ethyl acetate and butyl acetate, Examples include reactive diluents such as phenyl glycidyl ether and butyl glycidyl ether. The amount of organic solvent used is 0 to 30 PHR, preferably 0 to 30 PHR, based on the resin.
It is 10PHR. The polybutadiene-modified epoxy resin aqueous dispersion composition of the present invention is quite stable even without the presence of emulsifiers and protective colloids, but when long-term storage stability is required, it is recommended to use surfactants such as emulsifiers and protective colloids. preferable. Nonionic surfactants are preferable;
The HLB value is preferably 8 to 18. Typical surfactants include polyethylene glycol nonyl phenol ether, polyethylene glycol benzyl phenyl ether, poly(oxyethylene) benzylated phenyl ether, methylocellulose, hydroxyethylcellulose, hydroxypropylcellulose, and polyvinyl alcohol. The amount added is 15 to water.
Weight% or less, preferably 0.3% or more and 5% by weight
It is as follows. Since the polybutadiene-modified epoxy resin aqueous dispersion composition of the present invention has at least an unreacted epoxy group and a hydroxyl group in its molecules, it can be heat-cured by itself. By blending in the appropriate amount, the curing and crosslinking reaction can easily proceed under desired conditions ranging from room temperature to high temperature, and it is possible to provide a cured product having excellent flexibility and impact resistance. Known epoxy curing agents in this case include aliphatic amines such as diethylenetriamine and triethylenetetramine, aromatic amines such as metaphenylenediamine and diaminodiphenylsulfolane, and adducts of the above various amines with epoxy resins or acrylonitrile. Or polyamides which are reactants with dimer acid, monoethylamine complexes of _BF3 , etc.
Examples include BF ₃ -based complex compounds such as a pyridine complex of BF ₃ , complex compounds such as triethanolamine porate, and compounds having one or more -SH group or -CONH group in the molecule. As for the addition method, the water-insoluble curing agent is added in the form of an emulsion in advance. Water-soluble substances can be added themselves. The amount of these curing agents used is an amount equivalent to the epoxy equivalent of the polybutadiene-modified epoxy resin to the functional group equivalent ratio of the curing agent of 0.5 to 1.5, preferably
The amount is equivalent to 0.8 to 1.2. The polybutadiene-modified epoxy resin aqueous dispersion composition of the present invention improves the storage stability, particularly the low-temperature stability, of the epoxy resin aqueous dispersion, and also contains the polybutadiene-modified epoxy resin aqueous dispersion composition of the present invention as a main component. Cured resin has the mechanical properties and adhesive properties inherent to epoxy resin, and provides a cured product with significantly improved peeling strength, flexibility, and impact strength, which were considered disadvantageous, and is useful for paints, adhesives, It is a useful material for building materials and civil engineering applications. Specific examples of water-based paints of the aqueous dispersion composition of the present invention include thick coating paints, anticorrosion paints, concrete surface finishing paints, and the like. As an adhesive, it is used to bond cloth, wood, particle board, paper, etc. As civil engineering materials, tunnel water stop materials, expansion joint materials,
This includes uses such as mortar pouring material. It is also used as a building material, such as as a crack filler, sealant, and wall material. Next, the aqueous dispersion composition of the present invention will be explained in more detail with reference to Examples, Production Examples, Comparative Examples, Applied Examples, and Applied Comparative Examples, but these are not intended to limit the present invention. The following parts shall mean parts by weight unless otherwise specified. Production example 1 Nisso-PB-C-1000 (average molecular weight 1560, acid value
60) 100 parts of bisphenol A diglycidyl ether (epoxy equivalent: 190) were reacted at 145°C for 3.5 hours while blowing nitrogen to give an acid value of 0.1.
The following pale yellow transparent resin was obtained. Production example 2 Nisso-PB-C-1000 (average molecular weight 1560, acid value
60) Add 1.0 g of triethylamine to 60 parts and 140 parts of bisphenol A diglycidyl ether (epoxy equivalent: 190) and react at 145°C for 2 hours to obtain a pale yellow transparent resin (resin) with an acid value of 0.1 or less. Ta. Production example 3 Nisso-PB-C-2000 (average molecular weight 1964, acid value
37.1) 100 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (epoxy equivalent: 140) were reacted at 150°C for 2 hours while blowing nitrogen, resulting in a brown transparent product with an acid value of 0.1 or less. A resin (resin) was obtained. Production example 4 Nisso-PB-C-1000 (average molecular weight 1560, acid value
60) 100 parts of hydrogenated bisphenol A diglycidyl ether (epoxy equivalent: 240) were reacted at 150°C for 3.5 hours while blowing nitrogen to give an acid value of 0.1.
The following colorless transparent resin (resin) was obtained. Example 1 500 parts of the resin obtained in Production Example 1 and 50 parts of xylene were mixed, and 25 parts of polyethylene glycol nonyl phenyl ether (degree of polymerization 20) and 1 part of carboxymethyl cellulose were dissolved in 225 parts of water in an aqueous medium. The mixture was dispersed using a high-speed stirrer at 50°C to obtain an aqueous dispersion composition. Example 2 500 parts of the resin obtained in Production Example 2 was dispersed in an aqueous medium prepared by dissolving 6 parts of polyvinyl alcohol and 2 parts of polyethylene glycol benzyl phenyl ether in 250 parts of water at 40°C using a high-speed stirrer. Body composition was obtained. Example 3 An aqueous dispersion composition was obtained from 500 parts of the resin obtained in Production Example 3 in the same manner as in Example 2. Example 4 An aqueous dispersion composition was obtained from 500 parts of the resin obtained in Production Example 4 in the same manner as in Example 1. Comparison 1 500 parts of bisphenol A diglycidyl ether was dispersed in the same manner as in Example 1 to obtain an aqueous dispersion composition. Comparison 2 500 parts of bisphenol A diglycidyl ether was dispersed in the same manner as in Example 2 to obtain an aqueous dispersion composition. Table 1 shows the storage stability of the aqueous dispersion compositions at 5°C.

[Table] The storage stability of the polybutadiene-modified epoxy resin aqueous dispersion composition of the present invention, especially the storage stability at low temperatures, is clearly better than that of an unmodified epoxy resin aqueous dispersion. Application example: 100 parts of the aqueous dispersion obtained in Example 1 stored at room temperature for 15 days was added with 17.6 parts of dimer acid polyamide resin (Fuji Kasei, trade name: Tomide T-2500).
The mixture was cast, coated with a doctor blade, and cured at 20°C for 7 days. (cured product). The cured product was pale yellow and transparent and exhibited the properties shown in Table 2. Application comparison example To 100 parts of the aqueous dispersion obtained in Comparison 1 stored at room temperature for 15 days, 72.4 parts of dimer acid polyamide resin (Fuji Kasei product name: Tomide T-2500) was added, followed by pour molding and doctor blade coating. Then, a curing reaction was carried out at 20°C for 7 days (cured product-).
The cured product was pale yellow and transparent and exhibited the properties shown in Table 2.

【table】

【table】

[Table] Notes 1 to 3 were based on JISK-5400 (General Test Methods for Paints).

Claims (1)

[Claims] 1 Polybutadiene homopolymer and/or copolymer (A) having a carboxyl group and epoxy resin (B) in an amount of 1.8 to 1 per equivalent of carboxyl group in (A)
Consists of a polybutadiene-modified epoxy resin obtained by heat-reacting an amount of (B) equivalent to 30 equivalents of epoxy groups, water and a surfactant, and the weight ratio of each component is polybutadiene-modified epoxy resin/water = 90/10.
1/99, water/surfactant = 100/15 to 100/0.