JPS5922903A - Aqueous resin dispersion composition - Google Patents

Abstract

PURPOSE:To obtain titled composition most suitable as anchor coatings by mixing, in a specific proportion, an aqueous solution of a cationic resin with a resin aqueous dispersion prepared by dispersing an ethylene copolymer resin of a specific acid value in combination with a specific protective colloid-forming agent. CONSTITUTION:The objective composition can be obtained by mixing (A) a resin aqueous dispersion prepared by dispersing an ethylene copolymer resin of an acid value >=1 (e.g. an ethylene-acrylic acid copolymer) in combination with an amino group-contg. water-soluble acrylic resin [e.g., N,N-dimethylaminoethyl (meth)acrylate] with (B) an aqueous solution (or dispersion) of a cationic resin (e.g., an amino group-added epoxy resin) in a weight ratio (on a solid basis) A/B of 60/40-99.5/0.5. For forming a coating film, the above composition is coated on a base such as of paper, and dried on heating to a point higher than the minimum film-forming temperature.

Description

Detailed Description of the Invention The present invention can be used as a coating agent for aluminum foil or steel plates, or when producing resin-coated metals by melt-laminating films of polyethylene or ethylene-vinyl acetate copolymer on the surface of these metals. This relates to an aqueous resin dispersion composition suitable as an anchor coating agent to be used.〇Sulfethylene resin having a carboxyl group such as ethylene/acrylic acid copolymer or maleic anhydride grafted polyethylene is mixed with caustic soda, ammonium, ethanolamine,
The acid groups of the resin are partially or completely neutralized with a basic substance such as mol 7 oleine, and the anionic resin aqueous dispersion is dispersed by applying mechanical shearing force to hot water, and then the anionic resin aqueous dispersion is used as a metal coating agent. , is known to be used as an anchor coating agent (
(Japanese Patent Publication No. 49-49303, 32984-1984, 161684-54).

For example, in the above-mentioned Japanese Patent Application Laid-Open No. 54-161684, an aqueous dispersion of a sodium salt of ethylene/methacrylic acid copolymer is applied to the surface of an aluminum foil and dried to form an adhesion-promoting film on the aluminum foil. It is stated that the laminated material obtained by melt-laminating a film of ethylene/vinyl acetate copolymer on a film has excellent heat sealing properties and gas barrier properties, and is therefore excellent as a packaging material for milk, lactic acid bacteria drinks, etc. There is. The above-mentioned anionic aqueous dispersion provides a film with excellent adhesion to metals, but the reality is that improvements are desired in terms of metal corrosion.

Rust inhibitors are a way to improve the corrosion resistance of metals! Possible methods include a method of blending it into an aqueous dispersion, and a method of blending a cationic resin aqueous solution or aqueous dispersion, which provides a film with better corrosion resistance than an anionic resin aqueous dispersion. However, the former method of blending a rust preventive agent causes the rust preventive agent to bleed out from the surface of the film, reducing the adhesion between the metal and the film, and is not preferable from a sanitary standpoint when a laminated material is used as a food container. .

The latter method of adding an aqueous solution or dispersion of a cationic resin has not been carried out because the addition causes the resin to aggregate and gel.

The present invention is directed to an aqueous dispersion composition that does not cause aggregation or gelation of the resin when an aqueous solution or dispersion of the latter cationic resin is added, that is, component (a): an ethylene copolymer resin having an acid value of 1 or more. An aqueous dispersion in which a water-soluble acrylic resin containing an amino group is dispersed in water as a condensation colloid ■Ingredients: An aqueous solution or aqueous dispersion of a cationic resin The above ingredients and (
The solid content weight ratio of the odor component [capacity/(6)] is 99.510.
The present invention provides an aqueous resin dispersion composition characterized in that the resin composition is blended at a ratio of s to 60/400.

In the aqueous resin dispersion of component (4) used in the practice of the present invention, 100 parts by weight of an ethylene copolymer resin having an acid value of 1 or more, preferably 15 to 200, and 2 to 2 parts by weight of a water-soluble acrylic resin containing an amino group. 30 parts by weight, preferably 5-15
The protective colloid is dispersed in 60 to 1000 parts by weight, preferably 100 to 300 parts by weight, of water.

Ethylene copolymer resins having an acid value of 1 or more to be dispersed include random copolymers of ethylene and ethylenically unsaturated carboxylic acids, copolymers obtained by graft copolymerizing polyethylene with ethylenically unsaturated carboxylic acids, and These copolymers include those in which some of the acid groups are neutralized.

The ethylenically unsaturated carboxylic acids include (1) monocarboxylic acids such as aliphatic carboxylic acids containing usually 6 or less carbon atoms, preferably 4 or less carbon atoms, such as acrylic acid, methacrylic acid, crotonic acid, and isotalotonic acid; (2) As dicarboxylic acids, for example, aliphatic carboxylic acids such as maleic acid, fumaric acid, mesaconic acid, citraconic acid, and itaconic acid, 5-norbornene-2,3-dicarboxylic acid, nuclear methyl substituted products thereof, and endomethylene thereof. Examples include halogen-substituted groups, and the like. The acid in (2) may be an anhydride.

When the copolymer is a random copolymer, the content of these ethylenically unsaturated carboxylic acids is 2 to 50% by weight (
Ethylene is used in an amount of 98-50% by weight), and in the case of a graft copolymer, 0.1-10% by weight.

The ethylene copolymer resin has an acid value of 1 or more and 450 or less, preferably 15-200. If the acid value is less than 1, the adhesion between the obtained film and metal or resin will be insufficient. In addition, the slip property of the film obtained when the acid value exceeds 450,
Poor anti-blocking properties.

Specifically, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-acrylic acid-methyl methacrylate copolymer, ethylene-acrylic acid-ethyl acrylate copolymer, ethylene-acrylic acid-n
・Butyl acrylate copolymer, ethylene-acrylic acid-2/ethylhexyl acrylate copolymer, ethylene-acrylic acid=methyl methacrylate copolymer, ethylene-acrylic acid-butyl methacrylate copolymer, ethylene-methacrylic acid - Methyl acrylate copolymer, ethylene-methacrylic acid-methyl methacrylate copolymer, etc. and partial metal salts thereof; Ethylene-acrylic acid-vinyl acetate copolymer, ethylene-methacrylic acid-vinyl acetate copolymer; Polyethylene acrylic acid or methacrylic acid grafted products of ethylene-vinyl acetate copolymer, maleic anhydride grafted products of polyethylene, acrylic acid or methacrylic acid grafted products of ethylene-acrylic acid ester copolymer, maleic anhydride grafted product of ethylene-vinyl acetate copolymer,
Examples include acrylic acid or methacrylic acid, a partially saponified product of ethylene-vinyl acetate copolymer, or a maleic anhydride graft product.

A part of these resin components may be replaced with chlorinated polyethylene, petroleum resin, abietic acid rosin, chlorinated rubber, paraffin wax, carbana wax, or the like.

Next, a water-soluble acrylic resin containing an amine group, which is a protective colloid agent for dispersing the ethylene copolymer resin having an acid group in water, is used as a water-soluble acrylic resin containing N,N-dimethylamine ethyl (
meth)acrylate, N,N-dimethylaminoethyl (
meth)acrylate, N.

N-dimethylaminoethyl (meth)acrylamide, N
, acrylate 10 having an amino group such as N-dimethylamino-2.hydroxypropyl (meth)acrylate
-80 mol%, preferably 20-70 mol%, and other copolymerizable monomers, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylic acid- 2. Acrylates such as ethylhexyl, lauryl (meth)acrylate, stearate (meth)acrylate, cyclohexyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate;
Copolymers with lipophilic monomers such as acrylic acid, methacrylic acid, styrene, and vinyl chloride, and these copolymers with formic acid,
It is partially or completely neutralized by acid washing such as acetic acid or hydrochloric acid.

As a method for post-dispersing the ethylene copolymer having acid groups in water using this protective colloid agent, known dispersion means such as a patch mixer such as a kneader, a homomixer, a colloid mill, etc. can also be used. The ethylene copolymer resin is continuously supplied from a hopper of a twin-screw extruder, heated and melt-kneaded, and furthermore, at least one copolymer resin is provided in a compression zone and/or a metering zone of the extruder. A preferred method is to knead the protective colloid agent with an aqueous solution of the protective colloid agent supplied under pressure of 20 kg/- or more through the supply port.

The protective colloid agent is 2 to 30% of ethylene copolymer resin.
% by weight is used. If the concentration is less than 2% by weight, the resulting aqueous dispersion will have poor stability, and the formed film will have poor adhesion to metals, resin films, fibers, and paper; This is because, if it exceeds 100%, the resulting film will be sticky at room temperature or have poor adhesion to fine inorganic materials, metals, and other substrates.

(4) When the pf of the dispersion of the component is 8 or less, the storage stability is excellent.

Next, as the aqueous solution or aqueous dispersion of the cationic resin as component (B), amine group-added epoxy resin, amine group-containing acrylic ester copolymer, nitrogen-containing basic resin such as polyamide, or partially A resin neutralized with an acid, an aqueous solution of cationic polyurethane, or an aqueous dispersion in which these resins are dispersed in water using a dispersant (
% Opening and Closing No. 53-91938, Japanese Patent Publication No. 53-46874, Japanese Patent Publication No. 56-149420, etc.).

Such a basic resin or a partially neutralized salt thereof is a copolymer of acrylamide and methyl methacrylate; an amino group-added epoxy resin obtained by reacting diglycidyl ether of bisphenol A with jetanolamine is partially neutralized with propionic acid. Resin prepared by reacting a urethane prepolymer with a polyalkylene polyamine and further adding epihalohydrin to an antimine resin.

The blending ratio of the aqueous resin dispersion as component (1) and the aqueous solution or aqueous dispersion of the cationic resin as component (6) is 60/4 to 99.510 in terms of solid content weight ratio ((A)/(B)). It is 5. If the ratio is less than 60/40, the corrosion resistance of the film applied and dried on the metal surface will be poor. On the other hand, if it exceeds 99.''10.5, the adhesive strength between the metal and the coating film decreases.

Component (2) and component (6) can be easily mixed using a stirrer.

Resin aqueous dispersion of the present invention aluminum foil, paper, fiber,
As a method for coating a base material such as a resin film, a roll method, a spray method, a dipping method, etc. are selected depending on the purpose and the base material. After coating on the substrate, a film is formed on the substrate by heating and drying the aqueous dispersion composition to a temperature higher than the lowest film forming temperature.

Drying is performed using hot air, infrared heaters, etc. at 70-180°C.
C, preferably 80 to 170C.

The film provides waterproof and thermal adhesive properties to the base material. It is also possible to melt-laminate a film of polyethylene, ethylene/vinyl acetate copolymer, or the like on this film at 280 to 310°C to produce a composite material of aluminum foil and these resins. In such a case, since the adhesive is a film formed from an aqueous dispersion composition and is used as a hot-melt adhesive, there are no environmental and sanitary restrictions when using conventional solvent-based adhesives.

Furthermore, when the aqueous dispersion composition dries to form a film, the acid groups of the ethylene copolymer and the amino groups of the protective colloid react to form a film of the crosslinked structure, which improves the strength of the film itself. Moreover, due to the acid groups of the ethylene copolymer, it has a high adhesive strength with base materials such as aluminum foil. Furthermore, the corrosion resistance against metals is improved by adding the cationic resin (Component (2)).

Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that the parts and percentages in the examples are based on the limited roasted weight that does not particularly invert.

Example I N,N-dimethylamine ethyl methacrylate 62.9
parts (0.4 mol), butyl methacrylate 71 parts (
0.5 mol), 25.4 parts (0.1 mol) of lauryl methacrylate, and 200 parts of isopropyl alcohol were placed in a 4-tubular flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel, and after purging with nitrogen gas, 2.2'
-Azobisin 0.9 part of butyronitrile was added as a polymerization initiator, and a polymerization reaction was carried out at 80°C for 4 hours. Next, after neutralizing with 24 parts (0.4 mol) of acetic acid, water was added while distilling off the isopropyl alcohol, to finally obtain a viscous aqueous dispersant solution with a solid content of 35%.

Examples 2 to 6 A copolymer was obtained using the monomers shown in Table 1, and this was mixed with acid (0
An aqueous solution of a protective colloid agent was obtained in the same manner as in Example 1, except that the solution was neutralized with 4 mol)

Table 1 The abbreviations in the table are as follows.

DMMA: N,N-dimethylamine ethyl methacrylate E A: Ethyl acrylate BMA Nibutyl methacrylate LMA Nilauryl methacrylate SMA: Stearyl methacrylate 4-Vp: 4-vinylpyridine Example 1 Ethylene-acrylic acid copolymer manufactured by Dow Chemical Co. E
AA Xo-2375, 33” (trade name, acid value 156
, melt index (MI) 300, density 0.954
f/CC) at a rate of 100 parts/hour using a co-rotating intermeshing twin screw extruder (Ikegai Iron Works product name: PCM).
45, three-thread shallow groove type, L/D=30) hopper.

Further, from the supply port provided in the pent part of the same extruder, 20 parts of the protective colloid aqueous solution obtained in Example 1 was further diluted with 80 parts of water, and an aqueous solution was added at a rate of 100 parts/hour using a gear pump (discharge pressure 3 Kf/dG). > While continuously supplying pressure at
Continuous extrusion was performed at a screw rotation speed of 25 Orpm to obtain a milky white polymer aqueous dispersion (solid content concentration 40%).

The average particle size of the dispersed polymer particles in this aqueous polymer dispersion was determined by microscopic observation and was approximately 3 μm. Further, the minimum film forming temperature (MFT) of this polymer aqueous dispersion was 50° C., and the pH was 4.86.

Examples 2 to 6 Milky white polymer aqueous dispersions shown in Table 2 were obtained in the same manner as in Example 1, except that the protective colloids obtained in Examples 2 to 6 were used.

Examples 7 to 9 An ethylene-acrylic acid copolymer with an acrylic acid content of 20% Example 7 Acrylic acid (7%) grafted low-degree polyethylene “XEA-7” manufactured by Esso Chemical Co., Ltd. (trade name, acid value 78 , MI25
, density 0.925 t/CC) - Example 8: Mitsubishi Yuka ■
Made of low-density polyethylene "Yukalon MV-30" (product name, acid value 0, MI45, density 0.917?/CC)
- Example 9: A milky white polymer dispersion shown in Table 2 was obtained in the same manner as in Example 1 above, except that the following was used.

Examples 10 to 12 Milky white aqueous products shown in Table 2 were prepared in the same manner as in Example 1, except that the amount of protective colloid used was changed from 6 parts to 4 parts, 12 parts, and 25 parts with respect to 100 parts of ethylene/acrylic acid copolymer. A dispersion was obtained.

(Left below) Q3) Production example of cationic resin Example 1 Melamine 350 S', 780 f of a 37% aqueous solution of formaldehyde, and 10 f of caustic soda were mixed in a stirrer, a thermometer,
Pour into a 5t round bottom flask equipped with a reflux condenser.
Then, it was heated at 70°C for 4 hours @ then methanol 1
Add 700F to the flask together with 2f of oxalic acid,
After refluxing for 0 minutes, the flask was cooled to 20°C to complete the reaction.

Insoluble matter was filtered off through a glass filter, and the filtrate was distilled under reduced pressure using a 50-carp filter until the temperature reached 90°C.
The mixture was added until the concentration reached 0% to obtain a cationic melamine resin colloidal solution with a pH of 4.3.

Example 1 100 parts of the resin aqueous dispersion of the component obtained in Example 1 and a cationic polymer flocculant made by Kyoritsu Organic Industrial Research Institute - Himoroku M-173'' (trade name, a combination of methacrylic ester and acrylamide) were added. A homogeneous aqueous dispersion composition was prepared by vigorously stirring a 5% aqueous solution (Zoo part) of the polymer (polymer) with a disperser for 5 minutes at 3,000 rpm.

This aqueous dispersion composition was evaluated by the following method.

The results are shown in Table 1.

O stability 200 m/s of the composition in a constant temperature room at 23°C and 65% relative humidity.
The OO film-forming aqueous dispersion composition, which was evaluated as good if there was no separation of the aqueous phase and resin phase when it was placed in a beaker and left for one month, was placed on an aluminum foil (Mitsubishi Aluminum Diafoil (trade name); thickness 17μ) with a bar coater and dried with hot air at 100℃ for 1 minute to obtain a wall thickness of 3.
When obtaining a μ film, those that formed a continuous film were evaluated as good, and those that showed whitening, cracks, etc. in the film were evaluated as poor.

0 The coated surfaces of the aluminum foils, which have been tested for adhesion and film-forming properties with metal, were placed on top of each other, and heated with a heat sealer at a pressure of 2 Ky/-23°C, 6
Pressure-sensitive adhesion was performed for 1 second under the condition of 5% HR.

This heat-sealed sample was cut into a 15 m width sample piece, and this was cut out using an autograph (Shimadzu L5-2
000 type), a tension test was conducted at a tensile speed of 300 m/min according to the method described in JIS K-6854.

The surface of a steel plate of length 153 x width 10c++1 treated with zinc phosphate was degreased with acetone, immersed in an aqueous dispersion composition, air-dried, and then heated and dried in a gear oven at 150°C for 5 minutes. , 201/W per unit area? A coating film was obtained. A low-density polyethylene film (thickness 5
0 micron) at 160°C, cooled, and cut a slit with a length of 5 cWI in the center of the coating film using a knife to reach the steel plate, and then soaked in 4% saline solution. for two weeks at room temperature, and the longest distance from the slit where rust existed was measured.

0 slip property Based on ASTM D1894-73, a load of 200 tons was applied to a film formed by coating and drying on an aluminum foil.
The coefficient of dynamic friction was measured when the sled was moved at 150 m/min.

Film formation conditions: Coating amount: 15 f/m" (dry) Drying conditions: Zoo°C x 5 minutes Measurement atmosphere: 23°C, 65HR% Comparative Example 1 In Example 1, the resin aqueous dispersion obtained in Production Example 1 was replaced with Commercially available "Surlyn" aqueous dispersion, i.e. partially neutralized ethylene-methacrylic acid copolymer (melt index (190°C) 0.9, methacrylic acid content 15% by weight, neutralizing agent water) Aqueous dispersion (solid content concentration 30% by weight, viscosity 500 cps (
When mixed with a 5% aqueous solution of Himoroku M-173,
The resin immediately aggregated.

Examples 2 to 15, Comparative Examples 2 to 7 In Example 1, the aqueous resin dispersion of component (4) and (6
Aqueous dispersion compositions were prepared and evaluated in the same manner except that the cationic resin aqueous solution of component (2) shown in Table 3 was used and the blending ratio was changed as shown in the table. The results are shown in the same table.

(Leaving space below) Example 16 Ethylene-vinyl acetate copolymer 'Yukalon EVA V-203M' manufactured by Mitsubishi Yuka Corporation (trade name ) was extrusion laminated at 240°C (thickness 15μ) and then cooled to 20°C to obtain a multilayer material.

The multilayer material was evaluated in the same manner as the above-mentioned method for evaluating the adhesion with metal. In other words, the EVA film surfaces are 1
When the adhesive was adhered for 1 second at 20 DEG C. and a pressure of 2 Kf/-, and then the adhesive portion was peeled off, the film was peeled off from the interface between the aluminum foil and the aqueous resin dispersion. The peel strength at that time was 2.4 Kf/15 bites.

Patent applicant: Mitsubishi Yuka Co., Ltd. Agent: Patent Attorney Hidetoshi Furukawa Agent: Patent Attorney Masahisa Nagatani

Claims (1)

[Claims] 1) Capacity component: An aqueous resin dispersion in which an ethylene copolymer resin having an acid value of 1 or more is dispersed in water using a water-soluble acrylic resin containing an amine group as a protective colloid agent. ) Component: Aqueous solution or aqueous dispersion of cationic resin Components (6) and (9) above are combined in solid weight ratio [(B)/(B)] of 60
/ 40 to 99-5 / o, a resin aqueous dispersion composition formed by mixing at a ratio of 5.