JPH04153239A - Aqueous resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in cohesion to, e.g. a PE resin, water resistance, chemical resistance, applicability, mechanical stability, etc., and useful as a protectant, a water repellent, a water-resisting agent, a mold release or the like by mixing specified aqueous dispersions in a specified ratio. CONSTITUTION:An aqueous dispersion of a copolymer comprising 99-60wt.% ethylene and 1-40wt.% ethylenically unsaturated carboxylic acid (e.g. Premacol 5990, a product of Dow Chemical Co.) is mixed with an aqueous dispersion of a wax (e.g. paraffin wax) in a ratio of (95-5):(5-95) by weight.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is applicable to paper and textile products, various metals, various plastics, wood, and the printed surfaces of these materials, as a protective agent, active agent, water repellent, and release agent. The present invention relates to a water-based resin composition used for purposes such as molding agents and supports for various functional materials.

[Conventional technology]

Conventional paper and textile products, various metals, various plastics,
Organic solvent-based coating agents have traditionally been used for wood and their printed surfaces, but water-based coatings have been used due to issues such as pollution, environmental contamination, work environment problems, and ease of use. It's changing. The water-based resin ranges from natural rubber, various synthetic rubber, urethane, acrylic, vinyl chloride, vinyl acetate, epoxy, styrene, polyethylene, etc.
The resins have been expanded to include polyamide, phenol, and silicone resins, and are being used to take advantage of the characteristics of each resin. Among these, water-based polyethylene systems, water-based polyurethane systems, etc. are beginning to be applied in a wide range of fields due to their excellent properties. Examples of water-based polyethylene systems include Japanese Patent Publication No. 42-23085, Japanese Patent Publication No. 49-137223, As proposed in JP-A-52-148534, etc., a copolymer consisting of ethylene and ethylenically unsaturated carboxylic acid is self-emulsified using a basic substance.
It has been applied to adhesives, coating agents, etc., as in Publication No. 225, U, S, and P-3632720. These are adhesion,
It is characterized by water resistance and chemical resistance.

Waxes have traditionally been used in molten state, solvent dispersion, aqueous dispersion by mechanical methods, etc. for paper product processing, pharmaceuticals, cosmetics, etc.
Its properties are used in all kinds of fields, including stationery, electrical work, textile processing, heat storage, and ink.

[Problem to be solved by the invention]

However, if you want to make it water-based and use it as a protective agent, water repellent/water resistant agent, mold release agent, etc., the adhesion, water resistance, and chemical resistance of polyethylene resins will not be enough to achieve that purpose. I can't.

In addition, using other water-based resins cannot achieve the purpose; on the other hand, wax-based resins can be used in solvent dispersion or hot-melt methods, but they do not provide the adhesion and physical properties of a coating agent. I can't do anything.

Furthermore, in the case of an aqueous system, it cannot be used in practice unless the coatability and mechanical stability are improved by the use of surfactants and protective colloids. There has been a desire for the emergence of a water-based resin that has both of these characteristics.

In the present invention, both of these drawbacks can be compensated for, and by applying a water-based resin composition, a remarkable improvement in performance can be expected.

[Means to solve the problem]

The authors of this book@Meisha et al. have focused on this point and have arrived at the present invention as a result of extensive research. That is, the present invention
It can be obtained with an aqueous resin composition whose main components are an aqueous dispersion of a copolymer consisting of 9 to 60% by weight of ethylene and 1 to 40% by weight of ethylenically unsaturated carboxylic acid, and an aqueous dispersion of wax. I can do it.

Examples of the ethylene-unsaturated carboxylic acid copolymer used in the present invention include random copolymers, copolymers in which unsaturated galponic acid is grafted onto polyethylene, and terpolymers with a third component added thereto. .

Examples of the unsaturated carboxylic acids include acrylic acid, methacrylic acid, crotonic acid, and isocrotonic acid, which usually have 6 or less carbon atoms; examples of the dicarboxylic acids include maleic acid, fumaric acid, and itaconic acid. can be mentioned.

In order to form an aqueous dispersion of these copolymers, a method of using a surfactant, a method of self-emulsification, a method of mechanical dispersion, etc. are used depending on the purpose of use. The surfactant is generally an anionic surfactant, a nonionic surfactant, a combination thereof, or a combination of these and a basic substance. If the copolymerization ratio of unsaturated carboxylic acid is about 10% by weight or more, a self-emulsification method can be used, and these can be dispersed by neutralizing with a basic substance. As the base used for this neutralization, alkali metals such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, and amines such as ammonia, morpholine, triethylamine, and amino alcohol are generally used.

In the mechanical dispersion method, when the copolymerization ratio of unsaturated carboxylic acid is about 10% by weight or less, a surfactant is used as an auxiliary aid.

In order to make these into an aqueous dispersion, and in consideration of the later action as a reactive group, the copolymerization ratio of unsaturated carboxylic acid must be 1% by weight or more, and if it is 40% by weight or more, the blocking property becomes strong and it is not practical. It disappears.

The aqueous dispersion of wax may be either a generally known natural wax or a synthetic wax, and is selected depending on the required performance.

For example, natural waxes include animal-based wool wax, vegetable-based candelilla wax, carnauba wax, mineral-based montan wax, paraffin wax, microcrystalline wax, etc., and synthetic waxes include polyethylene wax and its derivatives, and ethylene wax. Polymers, polypropylene wax and its derivatives, montan wax derivatives, paraffin wax derivatives, microcrystalline wax derivatives, aliphatic alcohols and acids, fatty acid esters, etc., and outside the classification, α-olefin wax, castor wax, etc. These can be used alone or in combination to exhibit their respective characteristics.

These waxes can be obtained mainly by mechanical dispersion methods, such as galaric acid emulsifiers, sand grinders, K-day mills, and the like.

Surfactants, protective colloids, and oligomers used for dispersing and stabilizing the wax can be used as long as they are used in an amount of 30% by weight or less based on the wax, and smaller amounts are preferable. There are no particular limitations on the method for producing this dispersion and the drugs used in combination.

The aqueous resin of the present invention thus obtained can be used in combination with other resin systems, such as solvents, surfactants, plasticizers, thickeners, antifungal agents, and colorants, as is done in general resin emulsions. , use of fragrances, other organic and inorganic additives, etc.
Furthermore, a crosslinking agent can be used according to a conventional method as required.

〔Example〕

The present invention will be explained below with reference to production examples and examples.

[Manufacturing Example 1] 200 g of Brimacol 5990 (manufactured by Dow Chemical Company, carboxylic acid-containing polyethylene resin) was added to a pressure emulsifying machine.
Add 18g of % ammonia water and 580g of water, and heat to 150°C.
The mixture was emulsified for 30 minutes. The resulting aqueous dispersion has a non-volatile content of 2
It was 5.2% and pH 8.6.

[Production Example-2] Add 200 g of Yucalon A-500W (manufactured by Mitsubishi Yuka Co., Ltd., carboxylic acid-containing polyethylene resin), 22 g of 28% ammonia water, and 580 g of water to a pressure emulsifying machine, and heat at 150 ° C.
It was emulsified. The resulting aqueous dispersion had a nonvolatile content of 25.0%,
The pH was 9.2.

[Production Example-3] To 200 g of paraffin wax with a melting point of 55°C, 5 g of Tohol N-120 (nonionic activator manufactured by Toho Chemical Co., Ltd.) was added as an activator, and after rough emulsification at 80°C, the emulsification was performed using a high-pressure emulsifying machine “Gararin”. (manufactured by GAULIN, USA, model 15-M) at a discharge pressure of 500 Kgr/cm''G. The resulting aqueous dispersion had a nonvolatile content of 50.3% and a pH of 7.8.

[Manufacturing Example-4] Polyethylene oxide AC-680 (manufactured by Allied Signal) was two-phase dispersed in a bottle mill, then a wetting property improver was added, and finely dispersed in a sand grinder. The resulting aqueous dispersion had a nonvolatile content of 40.5% and a pH of 6.2.

[Production Example-5] Ethylene-acrylic acid-vinyl acetate copolymer, ACT○R14
50 (manufactured by Allied Signal) was similarly coarsely dispersed using a bottle mill, and then finely dispersed using a sand grinder. The resulting aqueous dispersion had a nonvolatile content of 35.3%, a pH of 6,
It was 8.

[Example] The polyethylene derivative-based dispersions obtained in Production Examples 1 to 2 and the wax-based dispersions obtained in Production Examples 3 to 5 were mixed in various ratios to produce Examples 1 to 1 shown in Table-1. A blended emulsion of No. 5 was obtained, and the physical properties of the emulsion and the physical properties of the film (
Elongation, strength, water resistance) and coated surface performance were measured. The results are summarized in Table-1. For comparison, the physical properties and performance of each emulsion alone are also shown.

[Effects of the Invention] As shown in Table 1, by using a mixture of the polyethylene derivative dispersion and the wax dispersion according to the present invention, compared to the case of using the polyethylene derivative dispersion alone,
Bringing significant improvements to film properties and coated surface properties,
It has become possible to provide industrially useful resins.

Patent applicant: Toho Chemical Industry Co., Ltd. hand Continued Supplementary Positive book (spontaneous) i month 1991 10 days 1990 Patent Application No. No. 85 2゜ name of invention Water-based resin composition 3゜ person who makes corrections Relationship with the incident

Claims (1)

[Claims] (1) Add the following aqueous dispersions [1] and [2] to [1]:[2]
] = 95-5: A water-based resin composition characterized by being mixed at a ratio of 5-95 (weight ratio). [1]: 99-60% by weight ethylene and 1-40% by weight
An aqueous dispersion of a copolymer consisting of ethylenically unsaturated carboxylic acid. [2]: Wax aqueous dispersion.