KR101698054B1 - Polymer film containing reactive latex molecule - Google Patents

Abstract

The polymer film comprising the reactive latex particles according to the present invention has a multilayer structure including the first reactive latex particles and the second reactive latex particles including the metal oxide and has a low interfacial energy to have high flexural strength, water resistance and tensile strength .
In addition, the second reactive latex particles include metal oxide particles to prevent change in physical properties of the polymer film due to curing, and are excellent in antibacterial activity.

Description

A polymer film containing reactive latex particles {Polymer film containing reactive latex molecule}

The present invention relates to a polymer film comprising reactive latex particles.

Latex is a material that can be commonly contacted by the surrounding area, and is used as a raw material of an adhesive or a waterproofing agent, or is made of latex rubber, and is made of balloon, latex rubber gloves, latex bedding, and the like. In particular, in recent years, inks of latex have been used in mother companies for use in printing methods with improved water resistance.

However, in latex prepared using natural rubber, the protein contained in natural rubber causes an allergic reaction such as pain or rash to some users, which is a problem. To overcome this problem, a synthetic rubber which does not cause an allergic reaction Latex is manufactured and used.

Recently, as perception of environmental problems has been increasingly recognized in order to produce general synthetic rubber latex, a method of continuously producing polymer latex with polymer powder by an emulsion polymerization process which is an environmentally friendly method using water is used.

In the emulsion polymerization process described above, the aqueous solution of the flocculant such as inorganic salts or acids is first added to the polymer latex to affect the electrostatic stabilization of the polymer latex. As the latex particles break, the polymer particles in the latex coalesce and aggregate with each other, To prepare a coagulated polymer particle slurry. Since such a slurry forms a kind of multi-particle assemblage which does not form a physical bond, the slurry may break-up easily due to external shear force in such a state, In order to increase the strength of the slurry, it is aged so that one particle having a certain strength is formed by interpenetration between chains.

However, since most of the above processes use a large amount of coagulant to agglomerate very quickly, the process of entangling the polymer latex particles becomes quite disordered, so that the final particles become irregular and the particle size distribution becomes considerably wider. There is a problem that the production time of the latex film is increased and the water resistance and the tensile strength are lowered due to slow dehydration and drying in the production of the product due to the dehydration and drying ability deterioration due to the generation of a large amount of fine powder powders in the latex material. When the latex film is exposed to water and is weak to ultraviolet rays, when dried in the sun, moisture is evaporated and hardened due to ultraviolet rays, which may easily occur, and the antibacterial ability is lower than that of natural latex.

Therefore, there is a growing interest in the production of environmentally friendly polymer films to overcome the disadvantages of latex produced by emulsion polymerization. Water-soluble materials using emulsion polymerization techniques have been developed as a method to solve this problem, It is necessary to study a latex material produced by emulsion polymerization so that a thin film can be formed by fusing particles by evaporation of a dispersion medium due to heat when the film is formed in a homogeneous state.

Korean Patent No. 10-0512224 (published on April 25, 2001) Korean Patent No. 10-1168401 (published on March 31, 2010) Korean Patent Laid-Open No. 10-2014-0050708 (Published on 2014.04.29) Korean Published Patent Application No. 10-2012-0094021 (Publication date: Aug. 23, 2012)

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and it is an object of the present invention to provide a polymer film comprising reactive latex particles for preparing environmentally friendly polymer films, Technology contents.

In order to accomplish the above object, the present invention is characterized in that it has a multilayer structure including a base resin layer containing first reactive latex particles and a metal oxide resin layer containing a metal oxide and second reactive latex particles By weight based on the total weight of the polymer film.

The first reactive latex particle is a copolymer of an unsaturated monomer containing a carboxyl group and an unsaturated monomer containing an epoxy group, and the second reactive latex particle is a copolymer of an unsaturated monomer containing fluorine and silane.

The metal oxide may be at least one selected from aluminum oxide, antimony oxide, tin oxide, bismuth oxide, and titanium dioxide.

The polymer film comprising the reactive latex particles according to the present invention includes the second reactive latex particles including the first reactive latex particles and the metal oxide, and has a low interfacial energy of the multi-layer structure, so that the bending strength, the water resistance and the tensile strength are high.

In addition, it includes a metal oxide to prevent change in physical properties due to curing, and is superior in antibacterial activity to a conventionally produced polymer film.

1 is a TEM image of a section of a polymer film according to the present embodiment.
2 is an image of a polymer film according to the present embodiment.

Hereinafter, the present invention will be described in detail.

The polymer film comprising the reactive latex particles according to the present invention has a layered multi-layer structure including a base resin layer containing first reactive latex particles and a metal oxide resin layer comprising a metal oxide and second reactive latex particles.

More specifically, the first reactive latex particles may be formed by blending an unsaturated monomer containing a carboxyl group and an unsaturated monomer containing an epoxy group, followed by copolymerization to form a base resin layer.

For this purpose, the above unsaturated monomers containing a carboxyl group include aromatic vinyl monomers such as styrene and methylstyrene, methacrylate monomers containing a carboxyl group, monomers containing about 1 to 6 carbon atoms (Vinyl cyanide) monomer such as an alkyl methacrylate monomer having an alkyl group of an alkyl group, an alcohol acrylate group, an acrylonitrile group and a methacrylonitrile group, Or vinyl halide based monomers such as vinyl chloride and vinyl bromide, or the like, or an unsaturated monomer obtained by mixing two or more of these monomers.

The unsaturated monomer containing an epoxy group may be an aromatic vinyl monomer such as styrene or methylstyrene, a methacrylate monomer containing an epoxy group, a monomer having a carbon number of about 1 to 6, Vinyl cyanide type monomers such as alkyl methacrylate monomers having an alkyl group, alcohol acrylate type, acrylonitrile, and methacrylonitrile, Or a vinyl halide based monomer such as vinyl chloride or vinyl bromide, or the like, or an unsaturated monomer obtained by mixing two or more of these monomers.

The first reactive latex particles are prepared by dispersing an unsaturated monomer containing an carboxyl group and an unsaturated monomer containing an epoxy group in water using an anionic, cationic, nonionic surfactant or a mixture thereof, removing the surfactant And 5% by weight or less of an initiator and a coagulant based on the total weight of the first reactive latex particles to form a copolymer resin through emulsion polymerization to form a base resin layer, wherein the reactive functional group having a carboxyl group and an epoxy group It is possible to prepare a latex film without using sulfur or a vulcanization accelerator which is conventionally used because of the use of an unsaturated monomer, and a carboxyl group and an epoxy group undergo crosslinking reaction through an emulsion polymerization reaction to increase the bonding strength and mechanical strength of the resin layer Polymer chains are intertwined so that And it is connected to form a continuous form of the number of the base resin layer.

For reference, the mechanical properties may vary depending on the blending ratio of the unsaturated monomer containing an epoxy group and the unsaturated monomer containing a carboxyl group, and when the content of the unsaturated monomer containing an epoxy group is increased, The tensile strength is increased and the moisture permeability is increased when the proportion of the unsaturated monomer containing a carboxyl group is increased. Thus, the polymer can be produced at various mixing ratios depending on the intended use of the polymer film.

In preparing the reactive latex particles, additives such as ionic crosslinking agents, pigments, fillers, thickeners, and pH adjusters are dispersed in the range of 1 to 5 wt% based on the total weight of the reactive latex particles before emulsion polymerization in the course of dispersing the unsaturated monomer in the surfactant The flocculant may be a water-soluble inorganic acid such as hydrochloric acid, sulfuric acid or phosphoric acid, or an inorganic salt such as calcium chloride or magnesium sulfate, etc., And can be configured to control the amount of use depending on the critical coagulation concentration of the coagulant depending on the characteristics of the polymer film.

In addition, the second reactive latex particles may include at least one metal oxide nanoparticle selected from aluminum oxide, antimony oxide, tin oxide, and bismuth oxide, and the unsaturated monomer containing fluorine and silane may be blended with various fire retardants and monomers And copolymerize them to form a resin layer.

For this purpose, the second reactive latex particles can use unsaturated monomers including fluorine and silane, and can be obtained by reacting an aromatic vinyl monomer such as styrene, methylstyrene, etc., a methacrylate monomer Alkyl esters of methacrylic acid having an alkyl group of about 1 to 6 carbon atoms, ethyl acrylate, acrylonitrile, and methacrylonitrile. A vinyl cyanide monomer or a vinyl halide monomer such as vinyl chloride or vinyl bromide may be used alone or in combination of two or more. And an unsaturated monomer containing fluorine and silane in an amount of 10 to 90% by weight based on the total weight of the second reactive latex particles Preferably, the remaining unsaturated monomer is further mixed with the unsaturated monomer constituting the first reactive latex particles so as to form a resin layer.

In the second reactive latex particles, the unsaturated monomer containing fluorine and silane is copolymerized through an emulsion polymerization reaction after adding an initiator and a coagulant to form a resin layer on the upper surface of the base resin layer, Layered multi-layered polymer film.

In addition, the second reactive latex particles including the metal oxide nanoparticles may be coated on the base resin layer to form a resin layer to produce a layered polymer film.

To this end, the unsaturated monomer containing fluorine and silane constituting the second reactive latex is dispersed in water using an anionic, cationic or nonionic surfactant or a mixture thereof, and after removing the surfactant, the initiator and the flocculant Is added to the resin to form a copolymer through emulsion polymerization to form a resin layer containing the second reactive latex particles and a crosslinking reaction is caused between the carboxyl group and the epoxy group of the base resin layer by using an unsaturated monomer containing fluorine and silane In order to increase the bonding strength and mechanical strength of the resin layer, the polymer chains are intertwined and connected to form a continuous resin layer to form a polymer film. The same additives as those used for forming the base resin layer are added So as to further improve the physical properties of the metal oxide resin layer Can.

The polymer film produced as described above increases the binding force of the polymer film by interfacial contact between the particles and the particles or particles and the resin layer among the reactive latex particles or by interdiffusion of molecules, and the first reactive latex and the second reactive Functional materials capable of chemically crosslinking by ionic bonding, hydrogen bonding, covalent bonding or the like are attached to the latex to form a crosslinked network, and mechanical strength and solvent resistance can be improved.

Since the polymer film produced as described above contains metal oxide particles such as aluminum oxide, antimony oxide, tin oxide, bismuth oxide, titanium dioxide and the like and is produced using an unsaturated monomer containing fluorine and silane, A metal oxide resin layer capable of absorbing is formed on the surface to improve physical properties of the produced polymer film to improve durability and the antibacterial activity of the polymer film including titanium dioxide can be enhanced.

Further, since a polymer film is produced in the form of a multi-layer structure of a metal oxide resin layer and a base resin layer, it has a low interfacial energy and a high bending strength, water resistance and tensile strength.

The base resin layer and the metal oxide resin layer may be repeatedly laminated in the same manner for the production of a thicker film.

<Examples>

In order to produce the polymer film according to the present embodiment, the first reactive latex particles were composed of monoethylenically unsaturated monomers containing an unsaturated monomer containing a carboxyl group and an epoxy group and capable of copolymerization.

The unsaturated monomer containing a carboxyl group is obtained by using a polystyrene-butadiene copolymer obtained by copolymerizing styrene and butyl acrylate. The monoethylenically unsaturated monomer containing an epoxy group and capable of copolymerization is obtained by copolymerizing ethylene methyl glycine Dile methacrylate and ethylene methyl glycidyl methacrylate were added to water and copolymerized through emulsion polymerization.

As the second reactive latex particles, unsaturated monomers containing fluorine and silane groups were purchased from fluorine-containing acrylates and silane-containing methacrylate monomers, respectively. Through the emulsion polymerization reaction, titanium dioxide was added during copolymerization, Reactive latex particles were prepared.

Sodium lauryl sulfate (SLS), an anionic surfactant, was used as the emulsifying agent, and distilled deionized water (DDI), which was sterilized, was emulsified And used for polymerization.

The reactor used for the polymerization was a 500 mL flask with a pyrex upper and lower separation type, a reactor with a capacity of 1 L Pyrex upper and lower separation type five-necked flask, and a stirrer with a paddle type with four stainless steel wings. The motor was used in which the rotation speed was controlled from 0 to 400 rpm. A constant temperature water bath adjusted from 0 to 100 ° C was used to control the reaction temperature, and a temperature controller was used as the thermometer. During the reaction, a reflux condenser was installed to prevent the loss of monomer or water by evaporation, and the joint part was sealed with silicone oil.

Table 1 shows the composition of reactants and additives used to prepare reactive latex particles.

[Table 1]

In order to prepare an unsaturated monomer containing an epoxy group and having a composition shown in Table 1 by using the reactor described above, a poly (styrene-co-butyl acrylate, SB) to be used as a seed particle was prepared by using a semi-batch seed emulsion polymerization method ) Copolymer.

The composition of the styrene and butyl acrylate monomers was adjusted so that the glass transition temperature was 0 ° C and batch polymerization was conducted by adding an emulsifier and an initiator to water as a continuous phase.

In the second step, deionized distilled water, potassium persulfate, and sodium lauryl sulfate (SLS) were added to the prepared latex using a seed, and then a monomer mixture containing an epoxy group was added at a rate of 0.5 mL / min , And poly (styrene-co-butylacrylate-co-glycidyl methacrylate, SB-G) having an epoxy group introduced into the surface of the SB particles was prepared.

Then, a polystyrene-butadiene copolymer into which a carboxyl group was introduced and an ethylene methyl glycidyl methacrylate copolymer into which an epoxy group had been introduced were emulsion-blended and then poured onto a flat plate and dried at 50 ° C for 24 hours to form a base resin layer, A slurry of fluorine-containing acrylate and silane-containing methacrylate monomer copolymer on which titanium dioxide particles were supported was coated on the upper surface of the paper layer.

After the coating, the coating was dried at 50 ° C. for 24 hours to form a metal oxide resin layer, and then cured for 2 hours at 150 ° C. for chemical interface curing reaction of carboxyl groups, epoxy groups and fluorine and silane groups present on the surface of the particles A polymer film as shown in Figs. 1 and 2 was prepared.

Claims (3)

A base resin layer comprising a first reactive latex particle comprising a copolymer of an unsaturated monomer containing a carboxyl group and an unsaturated monomer containing an epoxy group; And
A polymer film comprising a metal oxide resin layer comprising a second reactive latex particle comprising a metal oxide and a copolymer of an unsaturated monomer containing fluorine and silane. delete The method according to claim 1,
Wherein the metal oxide is at least one selected from aluminum oxide, antimony oxide, tin oxide, bismuth oxide, and titanium dioxide.

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