JPH03174401A - Aqueous acrylic resin emulsion composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in water-resistant adhesiveness even to a water-nonabsorptive substrate by mixing a specified aqueous copolymer emulsion with MgO, Mg(OH)2 or MgCO3. CONSTITUTION:40-80wt.% alkyl acrylate obtained from a 1-8C monohydric aliphatic alcohol and acrylic acid is emulsionpolymerized with 20-60wt.% hard vinyl monomer selected from among styrene, methyl methacrylate, ethyl methacrylate,, propyl methacrylate, butyl methacrylate, (meth)acrylonitrile and vinyl acetate and 0-10wt.% another vinyl monomer to obtain an aqueous copolymer emulsion (A) of a min. film-forming temperature of 60 deg.C or below, a resin solid concentration of 20-65wt.% and a particle diameter of a copolymer particle of 0.03-3mum. Component A is mixed with 0.1-30 pts.wt., per 100 pts. wt. resin solid of component A, at least one member (B) selected from among MgO, Mg(OH)2 and MgCO3.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides adhesion with sufficient water resistance to non-water-absorbing substrates such as glass, non-water-absorbing ceramics, and tile metal plates. This invention relates to an aqueous acrylic resin emulsion composition, which is useful as an adhesive, a joint material, and a paint.

[Conventional technology]

Epoxy resin, silicone resin, urethane resin,
Alternatively, a mixture of these with calcium carbonate powder or the like is used. These resin adhesives have good adhesion and water resistance, and are unlikely to blister or peel off even when immersed in water for a long period of time.

Even when acrylic resin water-based emulsions, which have good adhesion to water-absorbing substrates such as wood, concrete, and paper, are used as adhesives, joint materials, and paints for tiles and glass, the films are poor in water resistance, and if immersed, the film will peel off. It peels off more easily than the base material, and there are concerns about reliability.

In order to improve these drawbacks, nonionic surfactants, reactive surfactants, or protective colloids are used during emulsion polymerization of vinyl monomers, crosslinking techniques are introduced, silane coupling agents, and silicone colloids are used. Attempts have been made to use polyvinyl alcohol containing polyvinyl alcohol, but none of them have a sufficient effect of improving water-resistant adhesive strength.

[Problem to be solved by the invention]

The object of the present invention is to provide adhesives, joint materials, and paints that exhibit excellent water resistance and adhesion to non-water-absorbing substrates such as tiles and glass.

[Specific means to solve the problem]

The present invention provides an acrylic resin aqueous emulsion composition that provides adhesion with excellent water resistance by blending MgO, Ag(OH)z, or MgC0z into an acrylic resin aqueous emulsion. That is, the present invention uses component A: (a) 40 to 80% by weight of an acrylic acid alkyl ester of a monohydric aliphatic alcohol having 1 to 8 carbon atoms and acrylic acid, (bl styrene, methyl methacrylate, methacrylate Consists of 20 to 60% by weight of a vinyl monomer selected from ethyl acid, propyl methacrylate, butyl methacrylate, acrylonitrile, methacrylonitrile, and vinyl acetate, and (c) 0 to 10% by weight of other vinyl monomers. Copolymer aqueous emulsion B component obtained by emulsion polymerization of a monomer mixture and having a minimum film-forming temperature of 60°C or less: Magnesium hydroxide, magnesium oxide, and magnesium carbonate with a particle size of 200 microns (μm) ) The following inorganic compounds Provide an acrylic resin aqueous emulsion composition in which component B is blended in a ratio of 0.1 to 30 parts by weight with respect to 100 parts by weight of resin solid content of the copolymer aqueous emulsion of component A. It is something to do.

(Component A) The aqueous acrylic resin emulsion of component A is
a> Acrylic acid lower alkyl ester 40-80% by weight
(b) Emulsion polymerization of 20 to 60% by weight of hard monomers and 0 to 10% by weight of other monomers (c1) at a temperature of 40 to 120°C in the presence of an anionic surfactant. It can be obtained by

The lower alkyl acrylate ester of component (a) that provides the aqueous copolymer emulsion of component A is one whose homopolymer has a glass transition point of 0° C. or lower, and H is methyl acrylate, hexyl acrylate, acrylic acid n
-propyl, isopropyl acrylate, n-acrylate
Butyl, t-butyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hexyl acrylate, etc. can be used, and these impart flexibility to the film.

(As the hard monomer for the BL component, one or more selected from styrene, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, acrylonitrile, methacrylonitrile, and vinyl acetate is used. The homopolymer of this hard monomer has a glass transition point (Tg) of 20 to 150°C, and imparts rigidity to the film.

Other monomers of component (c) include unsaturated acids such as acrylic acid, methacrylic acid, maleic anhydride, and itaconic acid, glycidyl methacrylate, acrylamide, methacrylamide, N-phenylmaleic anhydride, and 2-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate,
Functional polymers such as 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, methylol group-containing unsaturated monomers, phosphorus-containing monomers, monomers added for 7g adjustment, etc. of ethylene, vinyl chloride, etc. It is.

Examples of anionic surfactants include sodium laurate sulfonate, sodium stearate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfonate,
Organic sulfonic acid sodium salts such as sodium alkane sulfonates and sodium alkylbenzenesulfonates; fatty acid metal salts such as aliphatic soaps, fatty acid sarcosides, and rosin acid soaps; K+, oxidation-KH4'', and alkanolamines in place of these Na'' Sulfate ester type anionic surfactants or fatty acid derivatives having ions can be used.

These anionic emulsifiers have a solid content of 0.2 to 5 parts by weight per 100 parts by weight of the resulting aqueous emulsion copolymer.
．． It is used in a proportion of 0 parts by weight.

A nonionic surfactant such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, or polyoxyethylenated castor oil may be used together with the anionic emulsifier.

Emulsion polymerization is carried out in a conventional manner, and the fat solid content concentration in the resulting copolymer aqueous emulsion is 20 to 65% by weight.
The particle size of the copolymer particles is generally 0.03 to 3 microns.

The minimum film-forming temperature of the aqueous copolymer emulsion is preferably 60° C. or lower, preferably 40° C. or lower in terms of workability. Further, it is necessary that it is stable against mixing of component B.

However, it is possible to thicken the emulsion composition system by using a small amount of emulsion for the purpose of aggregation.

(Component B) As component B, magnesium oxide, magnesium hydroxide, or magnesium carbonate may be used alone or in combination. Aluminum sulfate, calcium chloride, barium chloride, and zinc chloride tend to gel when mixed into an emulsion, making it difficult to apply with a trowel or brush. Aluminum hydroxide has a small contribution to improving water resistance.

The BtE content is blended at a ratio of 0.1 to 30 parts by weight based on 100 parts by weight of the resin solid content of the emulsion. If the blending amount is small, the water resistant adhesion of the film will not be sufficient. On the other hand, if the amount is too large, the viscosity of the compounded product becomes high, making it difficult to apply.

Further, the particle size of component B is preferably 200 μm or less from the viewpoint of workability. If the diameter is 200 μm or more, it is difficult to mix uniformly.
, and when used in paints, it is difficult to obtain a smooth coating film.

(Optional components) In addition to the above A and B components, film forming aids, antifoaming agents, fillers, pigments, rust preventives, antifreeze agents, thickeners, wetting agents, dispersants, and other additives may be added. May be combined.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that parts and percentages in the examples are based on weight unless otherwise specified.

Emulsion Example 1 Temperature controller, anchor stirrer, reflux condenser, supply container,
The following raw materials were charged into a reaction vessel equipped with a thermometer and a nitrogen inlet tube.

water 20
0 parts 3.9 parts of a 35% aqueous solution of the sodium salt of the sulfuric acid half ester of p-nonylphenol (anionic emulsifier A) reacted with 20 moles of ethylene oxide Next, after purging the inside of the reaction vessel with nitrogen gas, the following supplies were added. 10% of Part I was added and the mixture was heated to 90°C.

Feed I Water 11
0 parts 35% aqueous solution of the above anionic emulsifier 19 parts n-butyl methacrylate 192 parts methyl methacrylate 192 parts methacrylic acid
16 parts Additionally, after charging 10% of 2.5 parts of potassium persulfate dissolved in 85 parts of water (Feed ■) into the vessel, the remaining Feed ■ total and 90% of Feed H % was fed into the container over 3.5 hours, and after the feeding was completed, the feed material I was kept at the same temperature for 2 hours to polymerize the anionic resin aqueous emulsion with a solid content of 50% by weight (minimum film forming temperature 21 °C) was obtained.

Examples 2 to 7 Aqueous emulsions of copolymer particles having the physical properties shown in Table 1 were obtained by changing the type of vinyl monomer and the type and amount of emulsifier as shown in Table 1.

In addition, the nonionic surfactant was prepared in Example 1 in the reaction container.
-3, Comparative Examples 1-7 100 parts by weight of the aqueous copolymer emulsion obtained in Example 1 were added with the inorganic compounds shown in Table 2 (magnesium oxide, magnesium hydroxide, magnesium carbonate, aluminum hydroxide, aluminum sulfate, chloride). Emulsion compositions for glass coating were prepared with or without 1.0 part by weight of barium, zinc chloride, calcium chloride.

This emulsion composition was
It was coated on a glass plate of 2 mm x 2 mm to obtain a film with a thickness of 0.5 vs. and left at 20° C. for 2 days to obtain a film.

This film was subjected to a base peel test, and the water resistance of the film was tested by placing it in water (investigating the number of days it took for the film to lift off the glass plate).

The results are shown in Table 2.

(Left below) Examples 4 to 8, Comparative Examples 8 to 10 1 weight of SN Deformer 414 (antifoaming agent, trade name manufactured by San Nopco) per 100 parts by weight of the aqueous copolymer emulsion obtained in Example 1 above. Part, butyl cellosolve (coating agent,
(manufactured by Kuraray), 100 parts by weight of heavy calcium carbonate powder, 5 parts by weight of a 3% aqueous solution of Shichirosize QP-4400H (dispersant, trade name manufactured by Union Carbide), and the inorganic compounds shown in Table 3 (magnesium oxide, Acrylic resin aqueous emulsion M Kaimono was prepared with or without blending magnesium hydroxide, aluminum hydroxide) in the amounts shown in the table.

This composition was applied onto a glass plate in the same manner as in Examples 1 to 3, and water resistant adhesion was examined.

The results are shown in Table 3.

(Left below) Examples 9 to 14, Comparative Examples 11 to 16 100 parts by weight of the copolymer aqueous emulsions obtained in Examples 2 to 7 were mixed with 1 part by weight of magnesium oxide to prepare a coating composition, and the coating composition was prepared. The water resistance of the film was evaluated in the same manner as in Example 1.

The results are shown in Table 4.

For comparison, an emulsion containing no magnesium oxide was also evaluated, and the results are shown in the same table.

(Leaving space below) Example 15, Comparative Example 17 100 parts by weight of the aqueous copolymer emulsion obtained in Example 1 was blended with 1 part by weight of magnesium oxide having different thread diameters to prepare a coating composition, and this was applied to Example 4. It was applied to a glass plate in the same manner as in steps 8 to 8, and the state of the film and the stability of the formulation were examined.

The results are shown in Table 5.

Table 5 Example 16 To 100 parts by weight of the copolymer aqueous emulsion obtained in Example 1,
A coating composition is prepared by blending 2 parts of magnesium oxide,
This was applied onto a steel plate using an applicator to form a film with a thickness of 0.5 m, and was left to dry at 20°C for 2 days.

This test piece was immersed in water (JIS K-366
3) However, no blisters or blisters were observed on the film even after two weeks had passed. Furthermore, it was difficult to remove the film on the steel plate by hand.

For comparison, the film on the tiA board obtained from the emulsion of Example 1, which did not contain MgO, blistered after being immersed in water for 5 to 7 days, and the film was easily peeled off when the film was pulled by hand.

〔effect〕

The aqueous acrylic resin emulsion composition containing MgO or Mg (OH) t of the present invention exhibits excellent water resistance and adhesion to non-water-absorbing materials such as glass, ceramic tiles, and steel plates.

This composition is an adhesive for inorganic materials such as tiles and glass,
It is useful as a binder for mamatic paints, ricin paints, putty, joint materials, etc. Of course, it also provides a film with good water-resistant adhesion to water-absorbing materials such as wood, concrete, paper, cloth, etc., and is also useful as adhesives, paints, and joint materials for these materials.

Claims (1)

[Claims] 1), Component A: (a) an acrylic acid alkyl ester consisting of a monohydric aliphatic alcohol having 1 to 8 carbon atoms and acrylic acid;
0% by weight, (b) 20 to 60% by weight of a hard vinyl monomer selected from styrene, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, acrylonitrile, methacrylonitrile, vinyl acetate, and ( c) Copolymer aqueous emulsion B component having a minimum film forming temperature of 60°C or less obtained by emulsion polymerization of a monomer mixture consisting of 0 to 10% by weight of other vinyl monomers: magnesium hydroxide, magnesium oxide, At least one compound selected from the group of magnesium carbonate,
and an inorganic compound having a particle size of 200 μm or less; an aqueous acrylic resin in which component B is blended in a ratio of 0.1 to 30 parts by weight with respect to 100 parts by weight of the solid resin content of the aqueous copolymer emulsion of component A; Emulsion composition. 2) The aqueous acrylic resin emulsion composition according to claim 1, wherein the aqueous acrylic resin emulsion is anionic.