JP2539920B2 - Thermosetting aqueous resin composition - Google Patents

Description

Detailed Description of the Invention [Object of the Invention] (Field of Industrial Application) The present invention relates to a novel aqueous dispersion of thermosetting resin, in particular, thermosetting which gives a film excellent in water resistance, solvent resistance and mechanical properties. Water-based resin composition.

Recently, water-based paints are becoming water-based in view of environmental pollution and safety and hygiene, and water-based paints are replacing conventional solvent-based paints. Under these circumstances, water-based paints are also required to have high coating performance, and among them, the improvement of coating durability is indispensable. The present invention relates to a thermosetting aqueous resin composition comprising a colloidal alumina sol (A), an aqueous resin (B) having a quaternary ammonium salt group, and an epoxy resin (C).

(Prior Art) Conventionally, an aqueous thermosetting resin dispersion has been used for metals, woodworking, plastics, concrete, and the like. These are used in combination with a solution type resin and a crosslinking agent such as an epoxy resin, a melamine resin, and a polyfunctional urethane resin. However, the solution type resin is not preferable because it has a risk of fire due to ignition and is toxic to the human body. Therefore, an aqueous type resin is preferable in these respects, but it is difficult to obtain a resin having a high level of physical properties comparable to a solution type resin. The water-based resin will be further classified into an aqueous solution type and a water dispersion type. The aqueous solution type is obtained by, for example, neutralizing a resin having a carboxylic acid group with an alkali, and the aqueous dispersion type is obtained by emulsion polymerization in the presence of an emulsifier. Further, they are classified into anionic type, nonionic type, and cationic type, respectively. Epoxy resin, melamine resin,
It is used in combination with a cross-linking agent such as a polyfunctional urethane resin, but most are of the two-liquid type. Further, when a melamine resin or the like is used in combination, there is a drawback that not only formalin is released upon heat treatment but also remaining on the base material or the film. Further, when a curing catalyst is used, the pot life becomes short and the workability deteriorates. Further, as the polyfunctional urethane resin and the like, a one-liquid type in which an isocyanate group is blocked has been developed, but it has a drawback that the heating temperature becomes high.

(Problems to be Solved by the Invention) The present invention has improved the above-mentioned drawbacks and, even though it is a one-pack type, it cures at a relatively low temperature, and since it does not use a commonly used emulsifier, it has excellent water resistance. In addition, it provides a completely new industrial coating material that is characterized by forming a solvent-resistant and flexible film and providing excellent adhesion to wood, plastic film, and inorganic substrates. .

[Structure of Invention]

(Means for Solving the Problems) The present invention comprises a colloidal alumina sol (A), an aqueous resin (B) having a quaternary ammonium salt group, and an epoxy resin (C). The epoxy resin (C) and the alumina sol ( The mixing ratio of A) and the composite resin of the aqueous resin (B) is
A thermosetting aqueous resin composition having a weight percentage ratio of 95/5 to 5/95 is provided.

The colloidal alumina sol (A) in the present invention is a colloidal solution of alumina and has a rod shape. The size is 100mμ
It is about 10mμ and is usually supplied as an aqueous dispersion, which can be used as it is. As the alumina sol, for example, trade name Alumina sol-10
0, Aluminasol-200 (manufactured by Nissan Chemical Industries, Ltd.), and Aluminasol AS series (Catalyst Chemical Co., Ltd.)
Commercially available products can be used.

The aqueous resin (B) having a quaternary ammonium salt group can be obtained by various methods, but the examples are shown below, but the invention is not limited thereto.

Examples of the vinyl polymer having a quaternary ammonium salt group include (a) an α, β-monoethylene unsaturated compound having an amino group or a nitrogen-containing heterocycle and / or a derivative thereof and an α, β-monoethylenic compound. A method in which a mixture containing an unsaturated compound is copolymerized in an organic solvent and then neutralized with an acid, and the solvent is converted to water. (B) A vinyl monomer containing a halogenated alkyl group and α, β -Copolymerization of a mixture containing monoethylenically unsaturated compounds in an organic solvent, followed by quaternary chlorination with an amine compound,
A method of converting a solvent into water, (c) a mixture containing a vinyl monomer having an epoxy group is polymerized in an organic solvent, and then quaternized with an acid-neutralized amine compound, and the solvent is changed to water. There are a conversion method, a method of polymerizing a mixture containing (d) a vinyl monomer having a quaternary ammonium salt group in an aqueous medium, and the like.

Examples of the α, β-monoethylenically unsaturated compound having an amino group or a nitrogen-containing heterocycle of (a) above include allylamine, N, N-dimethylaminoethyl methacrylate,
Examples thereof include N, N-diethylaminoethyl methacrylate and vinyl pyridine.

As the acid (a), inorganic acid radicals, organic acid radicals and the like can be used. For example, inorganic acid radicals include PO ₄ ^3- , HPO _{4
^{2-, H 2 PO 4 -Cl -}} , Br -, SO 4 2-, HSO 4 -, NO 3 - Examples of the organic acid radical ^{_{CH 3 COO -, C 2 H}} 5 COO -, CH 3 CH (OH) ^{_{COO -, C 6 H 5 SO}} 3 - , and the like.

Examples of the vinyl monomer having a halogenated alkyl group (b) include chloromethylstyrene, chloroethylstyrene, 3-chloro-2-hydroxypropyl methacrylate and the like.

Examples of the amine compounds (b) and (c) include ethanolamines such as pyridine, ammonia, triethylamine, dimethylethanolamine and triethanolamine.

Examples of the vinyl monomer having an epoxy group (c) include glycidyl acrylate, glycidyl methacrylate, and methylglycidyl acrylate.

As the polymerizable organic monomer, for example, those listed below are used, but a mixture thereof is usually used in view of physical properties and applications. Alkyl ester (C1-22) esters of acrylic acid: For example, methyl acrylate, ethyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate and the like can be mentioned.

Alkyl esters of methacrylic acid (having 1 to 22 carbon atoms): Examples include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate and the like.

Hydroxyl group-containing vinyl monomers: For example, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, etc. may be mentioned. In addition, α, β-monoethylenically unsaturated carboxylic acid amide derivatives containing an N-substituted methylol group are particularly effective for increasing the reactivity with alumina sol. Among these, N-methylol acrylamide, N-methylol methacrylamide, N
-Dimethylol methacrylamide, and its derivatives include N-n-butoxymethylmethacrylamide, N-n-butoxymethylacrylamide, N-ethoxymethylacrylamide, N-ethoxymethylmethacrylamide, N-methoxymethylacrylamide, N- Methoxymethyl methacrylamide etc. are mentioned.

Other monomers: For example, silicon (meth) acrylate, fluoroalkyl (meth) acrylate, styrene, vinyltoluene, acrylonitrile, vinyl chloride,
Examples include vinyl acetate, vinylidene chloride and vinylpyrrolidone.

The vinyl monomer having a quaternary ammonium salt of (d) is, for example, a vinyl monomer having an epoxy group, an amine compound and a protonic acid are reacted with each other, or α, β having a heterocyclic ring containing an amino group or a nitrogen group. It is obtained by reacting a monoethylenically unsaturated compound with a protic acid or a halide. Examples of the vinyl monomer having an epoxy group include those described in (c) above. As the amine compound, (b),
Examples include those described in (c). Examples of the protic acid include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid and boric acid; organic acids such as formic acid, acetic acid, propionic acid, butyric acid and lactic acid. Among them, those having a dissociation constant (pKa value) of 1 × 10 ⁻⁵ or more are preferable. Examples of the α, β-monoethylenically unsaturated compound having an amino group or a nitrogen-containing heterocycle include those described in (a) above. Examples of halides include methyl iodide, methyl bromide, and monochlorotrimethylsilane.

As the organic solvent used in the polymerization reaction of the present invention, any solvent that can dissolve the polymer can be used, and a water-miscible organic solvent is preferable. For example, methanol,
Alcohols such as ethanol and isopropanol;
Acetone, ketones such as methyl isobutyl ketone; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether, etc. Can be mentioned. Further, water or the like can be used together if necessary.

Examples of polymerization catalysts that can be used include organic peroxides such as benzoyl peroxide, perbutyl octate, and t-butyl hydroperoxide, azobisisobutyronitrile, azobiscyanovaleric acid, 2,2, 'azobis ( Two
And azo compounds such as amidinopropane) dihydrochloride.

In the presence of the above-mentioned water-based aqueous resin, α, β-
An aqueous resin obtained by polymerizing a monoethylenically unsaturated compound and / or its derivative can also be used.

As the epoxy resin (C), bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin,
Examples thereof include hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, straight chain aliphatic type epoxy resin, alicyclic type epoxy resin, and epoxidized polybutadiene.

Alumina sol used is based on 100 parts by weight of aqueous resin
It can be used in an amount of 0.1 to less than 1000 parts by weight. It is preferably 1 to 100 parts by weight. If less than 0.1 parts by weight, OH on the surface of alumina sol
This is because the reactivity of the group with the epoxy group is too small and the durability of the coating film becomes poor, a strong organic-inorganic bond cannot be obtained, and the durability of the coating film is poor. On the other hand, if the amount exceeds 1000 parts by weight, the continuous coating property is insufficient and cracks occur, resulting in poor durability of the coating film.

Epoxy resin has an epoxy group in its molecule,
A stronger film can be formed by cross-linking by the addition reaction of amino groups in the composite resin of the aqueous resin containing alumina sol. Such epoxy resins include polyphenol glycidyl ethers having an average molecular weight of at least about 350, preferably about 350-3000 and an epoxy equivalent of 150-3000, preferably 200-2000. The mixing ratio of the epoxy resin described above and the composite resin which is an aqueous resin containing alumina sol is 99/1 to 100% by weight.
5/95, preferably 95/5 to 50/50. When the amount of the epoxy resin used exceeds the above range, the dispersion stability is poor and the original performance cannot be sufficiently exhibited, and when the amount is less than the above range, the effect as a crosslinking agent becomes insufficient and the durability of the coating film deteriorates. .

The reason why the composition of the present invention brings about an excellent effect on the physical properties of the coating film is not always clear, but the OH group present on the surface of the alumina sol and the epoxy group contained in the aqueous resin react to form a strong cross-linking bond. It is presumed that a strong organic-inorganic composite bond can be formed by reacting with the OH groups on the surface of the alumina sol and the OH groups on the surface of the metal substrate and the inorganic substrate that remain when the metal substrate is applied and heated. To be done.

The thermosetting water-dispersible resin composition according to the present invention is mainly composed of the composite resin obtained as described above, but it is cross-linked and cured by a functional group remaining in the composite resin and an addition reaction. , A stronger film can be formed and water resistance, alkali resistance, acid resistance, and solvent resistance can be imparted.

If necessary, additives such as pigments, fillers, plasticizers, pigment dispersants, solvents, thickeners, preservatives, defoamers and leveling agents can be used in combination in the composition of the present invention.

In addition, the composition of the present invention may contain a cation system and, if necessary,
Alternatively, it can be mixed with a nonionic aqueous resin dispersion.

The composition of the present invention can be applied to plastic substrates, metals, papers, cloths, inorganic substrates and the like. It is especially effective for metals and inorganic substrates. As described above, the thermosetting resin aqueous dispersion composition obtained by the present invention is transparent and highly flexible, and has the advantages of epoxy resin, such as coating formability and curability, and the hardness, solvent resistance, and nonflammability of alumina sol. It is a completely new industrial coating material with features such as properties.

 Next, examples will be shown. However, all parts are parts by weight.

Example 1 1) Butyl methacrylate 45 parts 2) N, N dimethylaminoethyl methacrylate 50 parts 3) N-methylol acrylamide 5 parts 4) Isopropyl alcohol 150 parts 5) AIBN (azobisisobutyronitrile) 2 parts 6) Water 20 parts 7) Acetic acid 20 parts 8) Water 50 parts 9) Aluminazole-200 10 parts 10) Epon 828 (Epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.) 1800 parts 11) Water 4184 parts Reaction previously saturated with nitrogen gas 1) to 5) in a can
Was charged and heated to 80 ° C to polymerize. Then, stirring was continued for 4 hours, and when the nonvolatile content reached 40%, 6) and 7) were added dropwise in 10 minutes. After that, the mixture of 8) and 9) was added dropwise over 20 minutes,
Then, 10) was added and the mixture was stirred at room temperature for about 30 minutes. And 1
1) was added to obtain a thermosetting resin aqueous dispersion having a solid content of 30%. When this water-based resin was applied to a glass plate at a thickness of about 100 μm and heat-treated at 110 ° C. for 30 minutes and immersed in toluene, it swelled only slightly. Furthermore, when it was applied to a calcium silicate plate and tested for cellophane tape adhesion, it was good. Moreover, even if this product was stored at a constant temperature of 50 ° C for 1 month, it was stable without separation.

Example 2 1) 3-chloro-2-hydroxypropyl methacrylate 60 parts 2) Butyl methacrylate 35 parts 3) N-butoxymethyl acrylamide 5 parts 4) Isopropyl alcohol 80 parts 5) AIBN 5 parts 6) Triethylamine 34 parts 7) Water 40 parts 8) Water 40 parts 9) Aminazol-100 (Note 2) 10 parts 10) Epon 828 5 parts 11) Water 39 parts In a reaction vessel previously saturated with nitrogen gas 1) to 5)
1/2 was charged, heated to 80 ° C, and the remaining 1/2 was added dropwise over 2 hours. Continue to stir for 4 hours, nonvolatile content 54
%, 6), 7) is added dropwise over 10 minutes, and 8),
The mixture of 9) was added dropwise over 20 minutes, then 10) was added, and the mixture was stirred at room temperature for about 30 minutes. Then, 11) was added to obtain a thermosetting resin aqueous dispersion having a solid content of 30%. When this water-based resin was applied to a glass plate at a thickness of about 100 μm and heat-treated at 110 ° C. for 30 minutes and immersed in toluene, it swelled only slightly. Furthermore, when it was applied to a calcium silicate plate and tested for cellophane tape adhesion, it was good. Further, this product was stable without being separated even if it was stored at 50 ° C at a constant temperature for 1 month.

Note 2) Alumina sol-100 (Nissan Chemical Co., Ltd., solid content 10
%) Example 3 1) Butyl methacrylate 6 parts 2) Glycidyl metal acrylate 3.5 parts 3) 2-Hydroxymethacrylate 0.5 parts 4) Isopropyl alcohol 10 parts 5) AIBN 0.1 parts 6) Pyridine 2 parts 7) Acetic acid 1.5 parts 8) Water 4 parts 9) Epon 828 990 parts 10) Alumina sol-100 1000 parts 11) Water 1649 parts 1 to 5) in a reaction vessel previously saturated with nitrogen gas.
Was charged and heated to 80 ° C to polymerize. Then, stirring was continued for 4 hours, and when the nonvolatile content became 50%, 6), 7) and 8) were added, and the reaction was carried out at 80 ° C for 2 hours. Then, 9) was added and the mixture was stirred at room temperature for about 30 minutes. Then, the mixture of 10) and 11) was added dropwise over 20 minutes to obtain an aqueous thermosetting resin dispersion having a solid content of 30%. When this water-based resin was applied to a glass plate at a thickness of about 100 μm and heat-treated at 110 ° C. for 30 minutes and immersed in toluene, it swelled only slightly. Furthermore, when it was applied to a calcium silicate plate and tested for cellophane tape adhesion, it was good. Moreover, even if this product was stored at a constant temperature of 50 ° C for 1 month, it was stable without separation.

Example 4 1) Methacryloyloxyethyl trimethyl ammonium chloride 6 parts 2) Butyl methacrylate 3.5 parts 3) N-methoxymethyl acrylamide 0.5 parts 4) Isopropyl alcohol 7.5 parts 5) Water 7.5 parts 6) V-50 (Note 3) 0.1 parts 7) Water 1.5 parts 8) Alumina sol-100 500 parts 10) Epon 828 5 parts 11) Water 118 parts 1) to 6) in a reaction vessel previously saturated with nitrogen gas.
1/2 was charged, heated to 80 ° C, and the remaining 1/2 was added dropwise over 2 hours. Continue to stir for 4 hours, nonvolatile content 40
%, The mixture of 7) and 8) was added dropwise over 20 minutes,
Then, 9) was added and the mixture was stirred at room temperature for about 30 minutes. And 1
0) was added to obtain a thermosetting resin aqueous dispersion having a solid content of 10%. When this water-based resin was applied to a glass plate at a thickness of about 100 μm and heat-treated at 110 ° C. for 30 minutes and immersed in toluene, it swelled only slightly. Further, it was applied to a calcium silicate plate and tested for cellophane tape adhesion. Moreover, even if this product was stored at a constant temperature of 50 ° C for 1 month, it was stable without separation.

Note 3) 2,2, 'azobis (2-amidinopropane) dihydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.) Example 5 1) Butyl methacrylate 45 parts 2) N, N dimethylaminoethyl metal acrylate 50 parts 3 ) N-methylol acrylamide 5 parts 4) Isopropyl alcohol 150 parts 5) AIBN 2 parts 6) Water 20 parts 7) Acetic acid 20 parts 8) Water 50 parts 9) Aluminasol-200 10 parts 10) Epon 828 100 parts 11) Water 218 Part 1) to 5) in a reaction can that was previously saturated with nitrogen gas
Was charged and heated to 80 ° C to polymerize. Then, stirring was continued for 4 hours, and when the nonvolatile content reached 40%, 6) and 7) were added dropwise in 10 minutes. After that, the mixture of 8) and 9) was added dropwise over 20 minutes,
Then, 10) was added and the mixture was stirred at room temperature for about 30 minutes. And 1
1) was added to obtain a thermosetting resin aqueous dispersion having a solid content of 30%. When this water-based resin was applied to a glass plate at a thickness of about 100 μm and heat-treated at 110 ° C. for 30 minutes and immersed in toluene, it swelled only slightly. Furthermore, when it was applied to a calcium silicate plate and tested for cellophane tape adhesion, it was good. Moreover, even if this product was stored at a constant temperature of 50 ° C for 1 month, it was stable without separation.

Example 6 1) Butyl methacrylate 4.5 parts 2) N, N dimethylaminoethyl metal acrylate 5 parts 3) N-methylol acrylamide 0.5 parts 4) Isopropyl alcohol 15 parts 5) AIBN 0.2 parts 6) Water 100 parts 7) Acetic acid 2 Part 8) Methyl methacrylate 5 parts 9) 2-Ethylhexyl methacrylate 5 parts 10) V-50 0.1 parts 11) Alumina sol-200 100 parts 12) Epon 828 10 parts 13) Water 52.7 parts In a reaction vessel previously saturated with nitrogen gas. 1) -5)
Was charged and heated to 80 ° C to polymerize. Then, stirring was continued for 4 hours, and when the nonvolatile content reached 40%, 6) and 7) were added dropwise in 10 minutes. Then, 10) is added and the mixture of 8) and 9) is added to 20
The mixture was added dropwise over minutes and polymerized. Then after adding 11), 1
2) was added and the mixture was stirred at room temperature for about 30 minutes. Then, 13) was added to obtain a thermosetting resin aqueous dispersion having a solid content of 10%. This water-based resin is applied to a glass plate for about 100 microns and the temperature is 110 ° C ×
When heat-treated for 30 minutes and immersed in toluene, it swelled slightly. Furthermore, when it was applied to a calcium silicate plate and tested for cellophane tape adhesion, it was good. Moreover, even if this product was stored at a constant temperature of 50 ° C for 1 month, it was stable without separation.

Comparative Example 1 1) Butyl methacrylate 4.5 parts 2) N, N dimethylaminoethyl metal acrylate 5.0 parts 3) N-methylol acrylamide 0.5 parts 4) Isopropyl alcohol 15 parts 5) AIBN 0.2 parts 6) Water 2 parts 7) Acetic acid 2 Part 8) Epon 828 90 parts 9) Water 214 parts In a reaction vessel that has been saturated with nitrogen gas in advance 1) to 5)
Was charged and heated to 80 ° C to polymerize. Continued 4
Stirring was continued and when the nonvolatile content reached 40%, 6) and 7) were added dropwise in 10 minutes. Then, 8) was added and the mixture was stirred at room temperature for about 30 minutes. Then, 9) was added to obtain a thermosetting resin aqueous dispersion having a solid content of 30%. When this water-based resin was applied to a glass plate at a thickness of about 100 μm and heat-treated at 110 ° C. for 30 minutes and immersed in toluene, it swelled only slightly. Further, when it was applied to a calcium silicate plate and tested for adhesiveness to cellophane tape, some peeling was observed.
It was stable without storage even after storage for months.

Comparative Example 2 1) Butyl methacrylate 4.5 parts 2) N, N dimethylaminoethyl methacrylate 5 parts 3) N-methylol acrylamide 0.5 parts 4) Isopropyl alcohol 15 parts 5) AIBN 0.2 parts 6) Water 2 parts 7) Acetic acid 2 parts 8 ) Alumina sol-200 20 parts 9) Epon 828 1000 parts 10) Water 2317 parts 1) to 5) in a reaction vessel previously saturated with nitrogen gas.
Was charged and heated to 80 ° C to polymerize. Then, stirring was continued for 4 hours, and when the nonvolatile content reached 40%, 6) and 7) were added dropwise in 10 minutes. After that, 8) was added, 9) was added, and the mixture was stirred for 30 minutes. Then, 10) was added to obtain a thermosetting resin aqueous dispersion having a solid content of 30%. This water-based resin was coated on a glass plate in a thickness of about 100 μm, heat-treated at 110 ° C. for 30 minutes and immersed in toluene, and swelled considerably. Further, when it was applied to a calcium silicate plate and tested for adhesion with cellophane tape, peeling was observed, and this was separated at a constant temperature of 50 ° C for 2 weeks.

Comparative Example 3 1) Butyl methacrylate 45 parts 2) N, N dimethylaminoethyl metal acrylate 50 parts 3) N-methylol acrylamide 5 parts 4) Isopropyl alcohol 150 parts 5) AIBN 2 parts 6) Water 20 parts 7) Acetic acid 20 Part 8) Alumina sol-200 200 parts 9) Epon 828 5 parts 10) Water 128 parts For reactors saturated with nitrogen gas in advance 1) to 5)
Was charged and heated to 80 ° C to polymerize. Then, stirring was continued for 4 hours, and when the nonvolatile content reached 40%, 6) and 7) were added dropwise in 10 minutes. After that, 8) was added, 9) was added, and the mixture was stirred for 30 minutes. Then, 10) was added to obtain a thermosetting resin aqueous dispersion having a solid content of 30%. This water-based resin was coated on a glass plate in a thickness of about 100 μm, heat-treated at 110 ° C. for 30 minutes and immersed in toluene, and swelled considerably. Further, when it was applied to a calcium silicate plate and tested for adhesiveness to cellophane tape, peeling was observed, and it was stable even if stored for 1 month at a constant temperature of 50 ° C without separation.

〔The invention's effect〕

From the above results, the alumina sol composite thermosetting water-based epoxy dispersion resin of the present invention is excellent in solvent resistance and adhesiveness with an inorganic base material, and further, because it is a cation type, it is excellent in corrosion resistance to a substrate, It has been found to be extremely useful for paints for metals, inorganic building materials, and organic building materials because of its good resistance to parasitics.

Claims (1)

(57) [Claims] 1. A colloidal alumina sol (A), an aqueous resin (B) having a quaternary ammonium salt group and an epoxy resin (C). The epoxy resin (C), the alumina sol (A) and the aqueous resin (B). The thermosetting water-based resin composition, wherein the compounding ratio with the composite resin is from 95/5 to 5/95 in terms of weight percentage ratio.