KR20190045497A - ater-based the manufacture of crosslink structure acrylic emulsion method and including the composition of the acrylic emulsion varnish - Google Patents

Abstract

According to an embodiment of the present invention, a method for manufacturing an acrylic emulsion resin comprises: a step (A) of mixing a surfactant and ion-exchanged water and raising the temperature by stirring the mixture; a step (B) of adding an initiator and acrylic monomer mixture pre-emulsion to the mixture and carrying out a reaction; a step (C) of aging the mixture and controlling pH of the mixture; and a step (D) of adjusting a physical property by adding a cross-linking polymer to the mixture. The present invention enables an amateur to rapidly and conveniently induce construction by making a one-component type which can be used alone with advantages of a conventional two-component type. The present invention can improve overall adhesion and weather protection by denaturing a molecular structure from a simple linear shape to a specific network shape.

Description

The present invention relates to a process for preparing an eco-friendly acrylic emulsion resin having a network structure and an eco-friendly acrylic emulsion resin paint prepared thereby.

More particularly, the present invention relates to a process for producing an environmentally friendly acrylic emulsion resin having excellent mechanical strength, water resistance, alkali resistance, flame resistance and stain resistance, and an environmentally friendly acrylic emulsion resin paint prepared therefrom.

Generally, a waterproof coating material refers to a preparation which forms a waterproof coating by applying a waterproofing agent in the form of an aqueous or oily liquid in the form of a liquid and drying the water or the solvent. Here, the emulsion type waterproof coating is also called an emulsion resin type waterproof coating, and it is a waterproof coating which forms a waterproof layer by coating the emulsion resin on the base.

Such a water-dispersible acrylic emulsion resin paint is advantageous in that it is environmentally friendly because it has less cracks due to self-shrinkage when it is cured and does not use an organic solvent. However, it is known that it is difficult to apply in a place where the material is soft and the area is large. Specifically, the acrylic emulsion waterproofing paint satisfies the basic waterproofing performance but has disadvantages such as chemical resistance, stain resistance, weather resistance, durability, elasticity and tensile strength.

In order to solve these drawbacks, Korean Patent Registration No. 10-0666140 " Environmentally friendly polyurethane waterproof flooring resin composition " is proposed. The proposed document relates to an environmentally friendly polyurethane waterproofing resin composition using water as a curing agent and selectively using eco-friendly raw materials and functional photocatalysts. The first polyol compound, the aromatic polyisocyanate compound, the chain extender, the plasticizer, And an additive and a coloring pigment are mixed to form a main component, and a curing agent containing a second polyol compound, a water-soluble flame retardant, water and an appropriate coloring dye as main components is blended therein.

However, in the case of the two-pack type urethane waterproof coating, there is a problem that the quality of the waterproofing material is not uniform due to the incorrect mixing of the liquid and powder in the field.

Korean Patent Registration No. 10-0666140 entitled " Environment-friendly polyurethane waterproofing resin composition "

SUMMARY OF THE INVENTION Accordingly, the present invention has been made to solve the above-mentioned problems of the prior art, and it is an object of the present invention to provide a two-component type in which a conventional base and a curing agent are mixed, while maintaining merits of mechanical strength, water resistance, alkali resistance, Friendly acrylic emulsion resin having a network structure capable of improving the overall adhesion and weatherability by modifying the molecular structure from a linear to a network type, And to provide an eco-friendly acrylic emulsion resin paint prepared therefrom.

In order to achieve the above object, the present invention provides a method for producing a water-soluble polymer, comprising the steps of (A) mixing a surfactant with ion-exchanged water and raising the temperature of the mixture while stirring; (B) adding the initiator and acrylic monomer mixture pre-emulsion to the mixture and reacting; (C) aging the mixture and then adjusting the pH of the mixture; And (D) adjusting the physical properties of the mixture by adding a crosslinking polymer to the mixture.

At this time, the acrylic monomer mixture pre-emulsion according to the present invention is characterized by comprising an acrylic or methacrylic monomer having an aliphatic group, an acid monomer, a surfactant, and ion exchange water.

The acrylic or methacrylic monomer having an aliphatic group according to the present invention may be at least one selected from the group consisting of methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, Acrylate, ethyl acrylate, n-propyl methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, lauryl methacrylate, And the mixture is composed of 60 to 90% by weight based on 100 parts by weight of the acrylic monomer mixture pre-emulsion.

The acid monomer according to the present invention is a mixture of one or more kinds selected from the group consisting of methacrylic acid, acrylic acid, maleic anhydride and itaconic acid, and is used in an amount of 0.5 to 10 parts by weight per 100 parts by weight of the acrylic monomer mixture pre- 3.0% by weight.

Also, the surfactant according to the present invention is a mixture of at least one member selected from the group consisting of sodium dodecylbenzene sulfonate, sodium dodecylbenzene sulfonate, nonionic ether sulfate and dialkylsulfonic acid ester, and the acrylic monomer mixture And 0.5 to 3.0 parts by weight based on 100 parts by weight of the total of the pre-emulsions.

Further, the initiator according to the present invention is characterized by being a mixture of at least one selected from ammonium persulfate, sodium persulfate, and potassium persulfate.

The step (B) of the present invention may be carried out by adding 5 to 10% by weight to 100 parts by weight of the acrylic monomer mixture pre-emulsion to be added to the mixture heated to 80 to 85 ° C, And the second reaction is carried out while the remaining 90 to 95 wt% is added dropwise for 1 to 4 hours.

The step (C) of the present invention is characterized in that the pH of the aged mixture is adjusted to 7 to 10.

The step (D) according to the present invention is characterized in that the crosslinked polymer is added in an amount of from 0.5 to 3.0% by weight to 97 to 99.5% by weight of the mixture, and then the mixture is stirred for 30 to 60 minutes.

The acrylic emulsion resin produced by the process according to the present invention has a glass transition temperature of -20 to + 20 캜 and a particle size of 50 to 150 nm.

It should be understood, however, that the terminology or words of the present specification and claims should not be construed in an ordinary sense or in a dictionary, and that the inventors shall not be limited to the concept of a term It should be construed in accordance with the meaning and concept consistent with the technical idea of the present invention based on the principle that it can be properly defined. Therefore, the embodiments described in the present specification and the configurations shown in the drawings are merely the most preferred embodiments of the present invention, and not all of the technical ideas of the present invention are described. Therefore, It is to be understood that equivalents and modifications are possible.

INDUSTRIAL APPLICABILITY As described in the above-mentioned constitution and operation, the present invention provides a one-component type which has mechanical strength, water resistance, alkali resistance, flame resistance and stain resistance and can be used singly, , The molecular structure is modified from a simple linear to a special network type, thereby improving the overall adhesion and weatherability.

Hereinafter, preferred embodiments according to the present invention will be described in detail.

The present invention relates to a one-pack type waterproof coating material, and is an eco-friendly acrylic emulsion resin coating material having a network structure, which is produced sequentially through steps (A) to (D). Hereinafter, a process for producing an environmentally friendly acrylic emulsion resin having a network structure will be described based on examples.

First, in step (A) according to the present invention, 0.2 to 1.0% by weight of a surfactant is mixed with 99.0 to 99.8% by weight of ion-exchanged water, and the mixture is heated to 75 to 85 ° C with stirring at 80 to 130 RPM .

On the other hand, it is preferable to use at least one surfactant selected from the group consisting of sodium dodecylbenzene sulfonate, sodium dodecylbenzene sulfonate, nonionic ether sulfate and dialkylsulfonic acid ester.

(B) according to the present invention is characterized in that 0.2 to 0.3 wt% of an initiator which is a mixture of one or more selected from the group consisting of ammonium persulfate, sodium persulfate and potassium persulfate is added to the mixture heated to 80 to 85 DEG C in the step (A) And 99.7 to 99.8% by weight of an acrylic monomer or a methacrylic monomer having an aliphatic group, an acid monomer, a surfactant, and an acrylic monomer mixture preform emulsion composed of ion-exchanged water.

Here, when the acrylic monomer mixture pre-emulsion is added all at once, there arises a problem of gelation due to a sudden reaction of a large number of monomers. Accordingly, 5 to 10% by weight of the acrylic monomer mixture pre-emulsion to be added to the mixture is preliminarily added in an amount of 5 to 10% by weight based on 100 parts by weight of the pre-emulsion, and then the first reaction is carried out for 5 to 20 minutes. It is important to react.

The acrylic or methacrylic monomer having an aliphatic group may be at least one selected from the group consisting of methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, lauryl methacrylate, Acrylate, n-butyl acrylate, isopropyl acrylate, butyl acrylate, butyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, ethyl acrylate, normal propyl methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate and lauryl methacrylate Mixtures of two or more are used.

The acrylic or methacrylic monomer is preferably 60 to 90% by weight based on 100 parts by weight of the acrylic monomer mixture pre-emulsion total.

Further, the acid monomer is a mixture of one or more selected from the group consisting of methacrylic acid, acrylic acid, maleic anhydride, and itaconic acid. The amount of the acid monomer is preferably 0.5 to 3.0% by weight based on 100 parts by weight of the acrylic monomer mixture pre-emulsion total.

And the surfactant is one or a mixture of two or more selected from sodium dodecylbenzene sulfonate, sodium dodecylbenzene sulfonate, nonionether sulfate and dialkylsulfonate ester. Such a surfactant is preferably 0.5 to 3.0 parts by weight based on 100 parts by weight of the acrylic monomer mixture pre-emulsion total.

(C) according to the present invention is characterized in that the mixture of step (B) is allowed to stand at 65 to 75 ° C for 60 to 120 minutes and aged. Then, the pH of the aged mixture is adjusted to 7 to 10, do.

That is, the process of aging the mixture of step (B) may further assist the removal of the unreacted residual monomers, so that the addition of the initiator after the addition of the initiator may help to remove residual monomers, Suitable for removal. Since the aged mixture is acidic with a pH of 2 to 6, it is preferable to adjust the pH to 7 to 10 to suit the storage stability of the mixture.

Next, step (D) according to the present invention may be performed by adding 0.5 to 3.0% by weight of a crosslinked polymer to 97 to 99.5% by weight of the mixture of step (C), stirring the mixture for 30 to 60 minutes, To prepare an acrylic emulsion resin.

If the content of the cross-linking polymer exceeds 3.0% by weight, the property of the physical property may not be improved or may be decreased. Therefore, it is preferable to add 0.5 to 3.0% by weight based on 100% by weight of the mixture. The crosslinked polymer may be one or a mixture of two or more selected from the group consisting of phenol formaldehyde, epoxy, unsaturated polyester, melamine, amide and urea.

The paint having the predetermined pigment added to the acrylic emulsion resin prepared by the present invention has a glass transition temperature of -20 to + 20 캜 and a particle size of 50 to 150 nm, and has a special network-like molecular structure and excellent overall adhesion and weatherability Do.

Hereinafter, a specific example of the present invention will be described, and the effect of the acrylic emulsion resin paint is validated.

<< Test method >>

The reaction process of modifying the molecular structure affecting the performance of the paint to a special network type was prepared for each example according to each condition, and the properties according to the rules according to the guidelines were measured.

<Sample Preparation>

First, 3 g of the surfactant and 600 g of ion-exchanged water were mixed, and the mixed mixture was heated to 80 캜 while stirring at 100 RPM to prepare the first to third embodiments. In each of the examples, 4 g of the initiator and 1400 g of the acrylic monomer mixture pre-emulsion were added and reacted. After aging at 70 ° C for 90 minutes, the pH of the aged mixture was adjusted to 9, 30 g of crosslinked polymer was added, Followed by stirring to complete the resin.

<Reaction Conditions>

In the first embodiment, 1400 g of the acrylic monomer mixture pre-emulsion was added and reacted. In the second embodiment, 1400 g of the acrylic monomer mixture pre-emulsion was added dropwise for 3 hours while the third example was carried out while the acrylic monomer mixture pre- 100 g was added to 1400 g of the emulsion, followed by a first reaction for 15 minutes and a second reaction with dropping the remaining 1300 g for 3 hours.

<Test Results>

Test Items Test Methods Example 1 Example 2 Example 3 Mirror gloss KS M ISO 2813
200 μm on glass plate 63 65 68 Scratching hardness
(Pencil method) KS M ISO 15184
Pencil light pencil hardness B H 2H Abrasion resistance (mg)
(Abrasive wheel method) JIS K 5600-5-9
Wear Wheel CS-17
Load 500g ㅧ 2 ㅇ 1000 rotations 71 73 82 My method KS M ISO 2812
7 days immersion in tap water clear clear clear Alkali resistance KS M ISO 2812 Sodium carbonate 5% aqueous solution for 48 hours clear clear clear Acid resistance KS M ISO 2812 Immersion in 5% sulfuric acid aqueous solution for 48 hours clear clear clear Water temperature After immersing in 50 ° C hot water for 48 hours, drying clear clear clear Formaldehyde dissipation JIS K 5970 Desiccator method 0.10 mg / L
Below 0.10 mg / L
Below 0.10 mg / L
Below Network structure Morphology

As a result of the test, it can be seen that the performance of Example 3 in which the acrylic monomer mixture pre-emulsion was added all at once or slowly added dropwise and subjected to a modification reaction in the form of a special network was divided into first and second groups in comparison with Example 1 and Example 2 .

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention as defined by the appended claims. It is therefore intended that such variations and modifications fall within the scope of the appended claims.

Claims (10)

(A) mixing a surfactant and ion-exchanged water and raising the temperature of the mixture while stirring;
(B) adding the initiator and acrylic monomer mixture pre-emulsion to the mixture and reacting;
(C) aging the mixture and then adjusting the pH of the mixture; And
(D) adding a cross-linking polymer to the mixture to adjust the physical properties of the cross-linked polymer. The method according to claim 1,
Wherein the acrylic monomer mixture pre-emulsion is composed of an acrylic or methacrylic monomer having an aliphatic group, an acid monomer, a surfactant, and ion-exchanged water. 3. The method of claim 2,
The acrylic or methacrylic monomer having an aliphatic group may be selected from the group consisting of methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, lauryl methacrylate, stearyl methacrylate One or two selected from the group consisting of butyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, ethyl acrylate, normal propyl methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate and lauryl methacrylate By weight based on 100 parts by weight of the total amount of the acrylic monomer mixture pre-emulsion, and 60 to 90% by weight based on 100 parts by weight of the acrylic monomer mixture pre-emulsion aggregate. 3. The method of claim 2,
The acid monomer is a mixture of one or more kinds selected from the group consisting of methacrylic acid, acrylic acid, maleic anhydride and itaconic acid, and is composed of 0.5 to 3.0% by weight based on 100 parts by weight of the acrylic monomer mixture pre-emulsion total Wherein the emulsion resin has a net-like structure. 3. The method of claim 2,
Wherein the surfactant is at least one selected from the group consisting of sodium dodecylbenzene sulfonate, sodium dodecylbenzene sulfonate, nonionic ether sulfate and dialkylsulfonic acid ester, and 100 parts by weight of the total of the acrylic monomer mixture preemulsions 0.5 to 3.0 parts by weight based on 100 parts by weight of the total weight of the emulsion. The method according to claim 1,
Wherein the initiator is one or a mixture of two or more selected from ammonium persulfate, sodium persulfate, and potassium persulfate. The method according to claim 1,
In the step (B), 5 to 10% by weight is added to 100 parts by weight of the acrylic monomer mixture pre-emulsion to be added to the mixture heated to 80 to 85 ° C, and then the first reaction is performed for 5 to 20 minutes. And 95% by weight of the organic solvent is added dropwise for 1 to 4 hours. The method according to claim 1,
Wherein the step (C) comprises adjusting the pH of the aged mixture to 7 to 10. The method for manufacturing an environmentally friendly acrylic emulsion resin according to claim 1, The method according to claim 1,
Wherein the step (D) comprises adding the cross-linked polymer in an amount of from 0.5 to 3.0% by weight to 97 to 99.5% by weight of the mixture, and then stirring the mixture for 30 to 60 minutes to control the physical properties. Way. An eco-friendly acrylic emulsion resin paint having a reticular structure, characterized in that the acrylic emulsion resin produced by the method of claim 1 has a glass transition temperature of -20 to + 20 ° C and a particle size of 50 to 150 nm.