KR100508685B1 - Preparing method of transparent elastomeric nanocomposite film and its preparing method - Google Patents

Abstract

The present invention relates to a method for producing a transparent polymer nanocomposite film, and more particularly, by increasing the affinity between the diene-based block copolymer and the layered compound by using a plasticizer having a low environmental hazard and a polar group such as phthalate, Higher molecular weight copolymers can be used than the diene block copolymers used in conventional nanocomposite film compositions, and the use of high-volatile low-boiling organic solvents can be eliminated, and the interlayer spacing of layered compounds is further increased. It is possible to extend the manufacturing process, and to prepare a film using a composition or composition containing the composition as described above, it is possible to omit the step of manufacturing a master batch in the production of conventional nanocomposites, thereby pursuing the simplicity of the manufacturing process. It can also be more heat resistant than conventional transparent nanocomposite films, The present invention relates to a method for producing a polymer nanocomposite film having improved mechanical strength and light transmittance and reduced environmental hazard.

Description

Preparation method of transparent elastomeric nanocomposite film and its preparing method

The present invention relates to a method for producing a transparent polymer nanocomposite film, and more specifically, by increasing the affinity between the diene block copolymer and the layered compound by using a plasticizer having a low harmfulness to the environment and having a polar group such as phthalate, Higher molecular weight copolymers can be used than the diene block copolymers used in conventional nanocomposite film compositions, and the use of high-volatile low-boiling organic solvents can be eliminated, and the interlayer spacing of layered compounds is further increased. It is possible to extend the manufacturing process, and to prepare a film using a composition or composition containing the composition as described above, it is possible to omit the step of manufacturing a master batch in the production of conventional nanocomposites, thereby pursuing the simplicity of the manufacturing process. It can also be more heat resistant than conventional transparent nanocomposite films, The present invention relates to a method for producing a polymer nanocomposite film having improved mechanical strength and light transmittance and reduced environmental hazard.

In general, transparent film materials are used in various products such as advertising labels, signs, toys, decorative products, various packaging, electronics packaging, food containers, etc. At present, plasticizers are added to resins such as polyvinyl chloride (PVC) to process them. It is used. However, the PVC-based resin composition contains environmentally harmful components, and there is an increasing demand for alternative materials. Among these alternative materials, diene-based block copolymers containing no environmentally harmful components are most preferred. However, since diene-based block copolymers are weak in mechanical strength, they are blended with silica and glass fibers when vulcanized to improve heat resistance and strength. An organic-inorganic hybrid material has been developed. In addition, the diene-based composite material is easily phase-separated, has a problem in compatibility with the inorganic filler, there is a problem in improving the physical properties of the composite, there is a problem lacking light transmittance.

Therefore, to improve the miscibility with inorganic fillers and to improve the physical properties of the composite, low molecular weight polystyrene is dissolved in an organic solvent and mixed with organic montmorillonite to form a polystyrene / organic montmorillonite master batch, and the master batch is A method for producing a styrenic block copolymer / organized montmorillonite nanocomposite by mixing with a block copolymer is known (Korean Patent Publication No. 2002-050493). The styrene-based block copolymer / organic montmorillonite nanocomposite prepared by the above method can obtain improved effects of mechanical properties such as transmittance and tensile strength compared to those of using high molecular weight compounds in the production of master batches. The light transmittance required for the production of a transparent film is low (85% or less), and the organic solvent is used, and thus the workability is poor due to its high volatility. In addition, since low molecular weight polystyrene is used, there is a problem in that the mechanical strength is weak when manufactured with a film.

In addition, known techniques include a method for producing a clay dispersed polymer resin nanocomposite [Korean Patent Publication No. 2002-019693], a clay dispersed polystyrene acrylonitrile copolymer resin, a polyacrylonitrile butadiene styrene copolymer resin, or polyvinyl. The method of adding polycaprolactone is known when manufacturing high molecular resin nanocomposites, such as a chloride resin, by a compounding method. However, in the above method, since the solution composition cannot be prepared because the molecular weight of polycaprolactone is 1,000 or more, film production is difficult.

As a result of research efforts to solve the above problems, the inventors of the present invention has a good compatibility with the diene-based block copolymer, easy to insert a nanocomposite to the layered compound, and shorten the nanocomposite film manufacturing process For the purpose of forming a film by solution processing, and researching a method of manufacturing a nanocomposite with improved mechanical strength and light transmittance, a layered compound and a diene-based inorganic filler are used when a plasticizer having a polar group such as phthalate is used. It was found that the miscibility of the block copolymer is improved, and thus, a transparent film having improved mechanical strength, light transmittance, and the like of the nanocomposite composition prepared according to the present invention has been completed.

Accordingly, the present invention provides a method for producing a film by a solution processing method using a polymer nanocomposite film composition comprising a diene block copolymer, a layered compound, and a plasticizer having a low environmental hazard and a polar group such as phthalate. have.

The present invention is prepared by mixing and stirring a mixture containing 5 to 95 parts by weight of a diene-based block copolymer, 0.1 to 30 parts by weight of a layered compound and 95 to 5 parts by weight of a plasticizer, and then the mixture itself or the mixture. Characterized in that the method for producing a polymer nanocomposite film comprising the step of applying a concentrated solution of the support and then drying.

The present invention will be described in more detail as follows.

The present invention increases the affinity between the diene block copolymer and the layered compound by using a specific plasticizer having a low environmental hazard, thereby making a higher molecular weight copolymer than the diene block copolymer used in the conventional nanocomposite film composition. It can be used, it is possible to exclude the use of the high-volatility low-boiling organic solvent used in the past, to further extend the interlayer spacing of the layered compound, and also to use the composition itself or a concentrate containing the composition By manufacturing the film, it is possible to omit the step of manufacturing the master batch during the manufacture of the conventional nanocomposite, which can pursue the simplicity of the manufacturing process, while improving heat resistance, mechanical strength and light transmittance and environmental hazards compared to the conventional transparent nanocomposite film. A method of making this reduced polymeric nanocomposite film.

The present invention will be described in detail as follows.

The plasticizer included in the polymer nanocomposite film composition of the present invention is a plasticizer having the same polar group as the phthalate, and is a phthalate-based, adipate-based, azelate-based, phosphate-based, sebacate, and meltate-based plasticizer, which is substituted with an alkyl group. To use, the plasticizer is characterized by low environmental hazard. These plasticizers contain polar groups such as phthalates, have excellent affinity with the inorganic layer compounds used, and easily penetrate between the layered compounds. They contain organic groups such as alkyl groups, and are therefore compatible with diene-based elastomers. Therefore, after mixing the composition consisting of the diene-based, plasticizer, inorganic layer compound can be processed into a transparent film immediately, unlike the conventional method for manufacturing nanocomposites, it is possible to omit the step of manufacturing the masterbatch to shorten the manufacturing process and At the same time, it is a characteristic part of the present invention that it is possible to improve the working environment and lower the harmfulness to the environment by not using the conventionally used PVC and organic solvents.

The polymer nanocomposite film composition of the present invention minimizes the generation of environmentally harmful components by using diene-based block copolymers, replacing polyvinyl chloride that has been used previously. The diene block copolymer may include styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, styrene-isoprene copolymer, acrylate-butadiene rubber, acrylonitrile-butadiene-styrene rubber, ethylene-propylene-diene-based polymer, One or a mixture of two or more of these polymers partially selected from hydrogenated, siloxane, alkylated, epoxidized and brominated may be used, preferably styrene having a styrene of 10% by weight or more and a molecular weight of 20,000 or more. Butadiene-styrene block copolymer (SBS), PDMS-SBS and SEBS are used, where SEBS is a polymer in which butadiene of SBS is partially hydrogenated, PDMS-SBS is a polydimethyl siloxane in which the butadiene block of SBS is partially It is a polymer substituted with a group. The amount of the diene copolymer as described above is 5 to 95 parts by weight. At this time, when the amount is less than 5 parts by weight, the strength is weak, and when it exceeds 95 parts by weight, film formation is difficult. Such polymers may be synthesized by a known method, or may be purchased and used in Kumho Petrochemical, Aldrich, LG Chemical, and the like.

The layered compound included in the polymer nanocomposite film composition of the present invention is a mineral or mineral belonging to the smectite group as a natural or synthetic clay mineral, and may use a mica type layer silicate mineral. , Montmorillonite or bentonite can be used. In particular, when the layered compound is a C ₆ to C ₃₀ alkyl chain or an lipophilic layered compound substituted with an aromatic vinyl group, a more preferable effect can be obtained. The layered compound as described above may be used in an amount of 0.1 to 30 parts by weight, and when the amount is less than 0.1 part by weight, the strength is weak. Such layered compounds can be purchased from Southern Clay Products Inc., USA.

In addition, as the plasticizer imparting the most important feature of the present invention, phthalate-based, adipate-based, azelate-based, phosphate-based, sebacate and melitate-based plasticizers substituted with alkyl groups can be used, and specifically, dibutyl phthalate (DBP). ), Diisobutyl phthalate (DIBP), dioctyl phthalate (DOP), diisooctyl phthalate (DIOP), diisononyl phthalate (DINP), polyadipate, dioctyl adipate (DOA), dioctyl azelate ( DOZ), Dioctyl sebacate (DOS), Trioctyl trimellitate (TOTM), Trixylyl phosphate (TXP), Trialkyl phosphate (TOP) and Epoxidized soya oil (ESO) 1 type, or 2 or more types of mixtures chosen from these etc. can be used. The plasticizer as described above can obtain a more preferable effect when using a phthalate-based or azelate-based plasticizer. The amount of the plasticizer used is 5 to 95 parts by weight. At this time, when the amount is less than 5 parts by weight, compatibility with the inorganic filler is weak. Such plasticizers may be synthesized by a known method, or may be purchased from Aldrich, LG Chemical, and the like.

In addition, the polymer nanocomposite film composition of the present invention is selected from polystyrene having a molecular weight of 20,000 or more, a polyolefin having a molecular weight of 2,000 to 100,000, a diphenylmethane diisocyanate (MDI) -based polyurethane having a molecular weight of 2,000 to 100,000, polypropylene oxide, derivatives thereof, and the like. Species or mixtures of two or more kinds may be additionally included, and the mechanical properties and processability of the polymer nanocomposite film prepared by additionally including the composition may be further improved. The amount used may be further included 0.1 to 70 parts by weight based on 100 parts by weight of the nanocomposite film composition.

In addition, an organic solvent may be used to improve the solubility of the film composition in the manufacture of the film. The working environment may be improved by using an organic solvent having a lower boiling point than the conventional organic solvent. An organic solvent in the range of 250 ° C. may be used, and when the boiling point is out of the range, there is a problem in poor workability. The solvent used may include one or two or more mixtures selected from ethyl acetate, toluene, butyl acetate having a boiling point of 100 ° C. or higher, isopropyl alcohol, cellulose acetate butylate, methyl isobutyl ketone, and methyl isoethyl ketone. A more preferable effect can be obtained when 5 to 70 parts by weight is additionally included with respect to 100 parts by weight.

In addition to the components of the composition as described above, a conventional additive selected from thickeners, antioxidants, dyes, pigments, stabilizers, anti-UV and flame retardants may be added in an amount of 0.01 to 30 parts by weight based on 100 parts by weight of the nanocomposite film composition.

The polymer nanocomposite film composition of the present invention comprising the composition as described above may be prepared by mixing the layered compound and the plasticizer and then adding and mixing the diene block copolymer, followed by mixing and stirring. And processing temperature and time can be changed according to a person skilled in the art, and generally can be stirred using a mechanical stirrer, a mixer, a mixer, a homogenizer, a magnetic stirrer, etc. in a temperature range of -10 to 180 ° C for 30 seconds to 14 days. .

The polymer nanocomposite film composition prepared as described above may be used in the manufacture of nanocomposite transparent film by itself or by concentrating. The composition or concentrate may be spin coated, bar coated, sprayed onto a support such as glass plate, paper, silicon wafer, OHP film, etc. After coating using a coating method such as coating and dip coating and dried in a normal pressure or vacuum oven in the temperature range of room temperature to 180 ℃, a transparent film having a thickness of about 3 ㎛ to 7 mm is formed.

That is, the polymer nanocomposite film composition prepared according to the present invention, unlike the known technique [Korean Patent Publication No. 2002-0050493], omitting the step of making a masterbatch can be prepared from the composition itself, the film is prepared, There is a feature that can significantly shorten the process.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the following Examples.

Example 1 Preparation of Nanocomposite Films by Vacuum Drying Method

10 g of styrene-butadiene-styrene (SBS) resin, 100 g of DOP, and 0.5 g of polystyrene resin were mixed, stirred at 40 ° C. for 48 hours, and then 0.3 g of Closite 6A was added to prepare a well mixed composition. The light transmittance of the prepared composition is at least 80%.

After adding 0.01 g of an antioxidant to the prepared solution, it was applied on a glass plate and dried in a vacuum oven at 100 ° C. to prepare a 0.5 mm thick transparent film. The film produced showed that the interlayer distance of silicate was extended by more than 1 nm (10 Å), demonstrating the nanocomposite of the polymer in the layered silicate, and showed excellent transparency with a transmittance of 85% or more.

The degree of insertion of the diene copolymer between the layers of the layered compound was measured as XRD, and the measurement results are as shown in FIG. 1A.

Examples 2 to 11 Preparation of Nanocomposite Films by Vacuum Drying Method

The diene copolymer, the layered compound, the plasticizer, the other additives and the composition conditions of the composition in Example 1 were changed as shown in Table 1 below to prepare a nanocomposite film composition.

In addition, the nanocomposite film was prepared by changing the film manufacturing conditions of Example 1 as shown in Table 1 below, and the measured physical properties are shown in Table 2 below.

Example 12 Preparation of Nanocomposite Films by Atmospheric Drying

40 g of styrene-butadiene-styrene, 4 g (10 phr) of polystyrene resin, and 1.2 g (3 phr) of organic montmorillonite were added to a Brabender mixer and mixed for 10 minutes at 100 ° C. and 60 rpm. The mixed sample was compression molded for 15 minutes using a preheated press at 100 ° C. and then cooled for 20 minutes to produce a film having a thickness of 2 mm, and the transmittance was excellent at 86%.

division Ingredient Temperature / hour (℃ / hour) Viscosity (cP) Diene copolymer (part by weight) Layered Compound (parts by weight) Plasticizer / Solvent (parts by weight) Other additives (parts by weight) Example 1 SBS ¹⁾ (8) 6A ⁴⁾ (2.6) DOP ⁸⁾ (88) PS-1 ¹⁴⁾ (1.2) 0.2 ²⁰⁾ 40/48 15 Example 2 SBS (16) 6A (2) DOP (80) PS-1 (1.8) 0.2 40/48 20 Example 3 SBS (20) 20A ⁵⁾ (3) DOP (76.9) - 0.1 40/48 17 Example 4 SEBS ²⁾ (16) 25A ⁶⁾ (5) DBP ⁹⁾ (75.9) PS-1 (3) 0.2 50/72 - Example 5 SBS (20) 6A (1) DOP (74) PS-2 ¹⁵⁾ (5) 0.1 70/48 - Example 6 SBS-PDMS ³⁾ (20) 6A (3) DPO (66.8) PS-2 (10) 0.2 120/48 - Example 7 SBS-PDMS (35.8) 6A (3) DOZ ¹⁰⁾ (61) - 0.2 120/48 - Example 8 SBS (20) 6A (1) DOP (60) / THF ¹¹⁾ (16.8) PP-MA ¹⁶⁾ (2) 0.2 40/108 - Example 9 SBS (19.7) 6A (5) DOP (75) PU ¹⁷⁾ (0.1) 0.2 40/48 - Example 10 SBS (15) / SBS-PDMS (5) 6A (7) DOP (60), o-toluenesulfonamide ¹²⁾ (9.8) PS-1 (3) 0.2 ²¹⁾ 40/48 - Example 11 SBS (25) VDAC-MMT ⁷⁾ (3) DOZ (15) / toluene ¹³⁾ (50) PS-3 ¹⁸⁾ (4) / CAB ¹⁹⁾ (3) - 40/72 - 1) SBS: Styrene-butadiene styrene, Kumho Petrochemical 2) SEBS: SBS partially modified butadiene, Kumho Petrochemical 3) SBS-PDMS: SBS where butadiene block is partially substituted with polydimethyl siloxane, in known method 4) 6A: Cloisite 6A, Southern Clay Inc. 5) 20A: Cloisite 20A, Southern Clay Inc. 6) 25A: Cloisite 25A, Southern Clay Inc. 7) VDAC-MMT: According to known methods Preparation 8) DOP: Dioctyl phthalate, Aldrich company 9) DBP: Dibutyl phthalate, Aldrich company 10) DOZ: Dioctyl azelate, Aldrich company 11) THF: Tetrahydrofuran, Aldrich company 12) o-toluenesulfonamide, Aldrich, Inc. 13) Toluene, Aldrich, Inc. 14) PS-1: PS 25,000, polystyrene with a number average molecular weight of 25,000, Aldrich Corporation15) PS-2: PS 50,000, polystyrene with a number average molecular weight of 50,000, manufactured according to a known method 16) PP-MA: Polypropylene- Maleate, Aldrich company 17) PU: Polyurethane, Aldrich company 18) PS -3: PS-tempo-terminated 50,000, tempo-terminated polystyrene with a number average molecular weight of 50,000, manufactured according to the known method 19) cellulose acetate butyrate, Aldrich 20) antioxidants: Irganox, Aldrich 21) phthalocyanine pigments: Aldrich

Experimental Example

The physical properties of the film produced by the following method as described above were measured by the following method, the results are shown in Table 2.

(1) Interlayer distance expansion: The interlayer distance of inorganic clay was measured by using wide angle X-ray scattering (WAXS), and it was calculated by the following equation.

Interlayer distance expansion (nm) = silicate interlayer distance in polymer composite-silicate itself interlayer distance

(2) Mechanical Properties: Tensile properties (tensile strength, tensile modulus, elongation at break) of nanocomposites prepared from inorganic clays and polymers were measured by ASTM D412.

(3) Thermal Properties: Measured using DMA (Dynamic Mechanical Analysis).

(4) Transmittance: The transmittance (%) at 600 nm was measured using a 2 mm thick cell for the solution and a 0.5 mm thick film for the film specimen.

(5) Thermo mechanical properties: measured by DMA (Dynamic Mechanical Analysis).

division Temperature / hour (℃ / min) Young's modulus (MPa) Tensile Strength (MPa) Break point elongation (%) Tg (℃) Interlayer distance extension Transmittance (%) BD ST Example 1 100/10 2.1 16 862 -72 108 10 > 85 Example 2 120/2 2.6 22 890 -68 110 14 85 Example 3 80/5 2.0 20 892 -69 109 9 86 Example 4 70/76 2.0 17 851 -72 108 5 87 Example 5 110/7 2.1 17 969 -71 110 3 85 Example 6 100/10 2.4 14 892 -71 115 5 90 Example 7 140/1 2.3 19 929 -67 114 13 90 Example 8 130 / 0.5 2.5 16 947 -71 110 7 87 Example 9 100/10 3.0 17 926 -72 107 9 88 Example 10 100/10 2.0 17 923 -72 107 10 91 Example 11 120/10 2.4 28 879 -65 114 > 12 90

As shown in Table 2, according to the present invention, not only the step of manufacturing the master batch can be omitted, but also the film manufacturing process can be shortened, and the light transmittance of the produced film is 85% or more, which is superior to that of the conventional nanocomposite film. In addition, it can be seen that the mechanical properties such as elastic modulus, tensile strength and breaking point elongation are excellent. In addition, even if the film is prepared by using a variety of conventional manufacturing methods such as applying a composition on the support as in Examples 1 to 11 and then manufacturing by vacuum drying, or manufacturing a film by compression molding as in Example 12 It can be seen that excellent physical properties.

As described in detail above, the transparent polymer nanocomposite film composition prepared according to the present invention has excellent affinity with the layered compound and is substituted with an alkyl group having a low environmental hazard, and is a phthalate-based, adipate-based, azelate-based, and phosphate-based compounds. , Sebacate and meritate, or o-toluenesulfonamide, epoxy and soya oil and the like by using a plasticizer to increase the nano-dispersity of the layered material, improved light transmittance, the nanocomposite film produced therefrom is a light transmittance and It is excellent in processability and excellent in mechanical properties, so it can be used in structural agents, coatings, modifiers, adhesives, adhesives, etc., and is particularly applicable as a transparent film material for PVC substitution.

1 is an X-ray diffraction measurement result showing the interlayer distance of the nanocomposite prepared in Example 1 of the present invention, (a) is a nanocomposite film (b) of Example 1 is a layered silicate itself.

Figure 2 is a transmission electron micrograph of the nanocomposite prepared in Example 1 of the present invention, (a) is a nanocomposite of Example 1, (b) is a nanocomposite of Example 13.

Claims (9)

A mixture containing 5 to 95 parts by weight of a diene block copolymer, 0.1 to 30 parts by weight of a layered compound and 95 to 5 parts by weight of a low environmentally harmful plasticizer is prepared by mixing and stirring in the range of -10 to 180 ° C., then the mixture itself or the Method of producing a polymer nanocomposite film comprising the step of applying a concentrated solution of the mixture on a support and then drying. The method of claim 1, wherein the plasticizer is dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, diisooctyl phthalate, diisononyl phthalate, poly adipate, dioctyl adipate, dioctyl azelate, dioctyl sebacate , Trioctyl trimellitate, trixylyl phosphate, trialkyl phosphate, o-toluenesulfonamide, and epoxidized soya oil. The method of claim 1, wherein the diene block copolymer is a styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, styrene-isoprene copolymer, acrylate-butadiene rubber, acrylonitrile-butadiene-styrene rubber, ethylene- A propylene-diene-based polymer and a method for producing a polymer nanocomposite film, characterized in that the polymer is one or a mixture of two or more selected from partially hydrogenated, siloxane, alkylated, epoxidized and brominated. The polymer nanocomposite of claim 1, wherein the layered compound is a natural or synthetic clay mineral, mineralogically belonging to a smectite group, and is a mica type layer silicate mineral. Method for producing a film. The method of manufacturing a polymer nanocomposite film according to claim 4, wherein the layered compound is a lipophilic layered compound substituted with a C ₆ -C ₃₀ alkyl chain or an aromatic vinyl group. The method of claim 1, wherein the nanocomposite film is selected from polystyrene having a molecular weight of 20,000 or more, a polyolefin having a molecular weight of 2,000 to 100,000, a diphenylmethane diisocyanate (MDI) -based polyurethane having a molecular weight of 2,000 to 100,000, polypropylene oxide and derivatives thereof. 0.1-70 weight part of 1 type or 2 or more types of mixtures are added with respect to 100 weight part of said nanocomposite film compositions, The manufacturing method of the polymer nanocomposite film characterized by the above-mentioned. The method of claim 1, wherein the nanocomposite film is one or a mixture of two or more selected from ethyl acetate, toluene, butyl acetate, isopropyl alcohol, cellulose acetate butylate, methyl isobutyl ketone and methyl isoethyl ketone having a boiling point of 100 ° C. or higher. 5 to 70 parts by weight based on 100 parts by weight of the nanocomposite film composition is further included. According to claim 1, wherein the nanocomposite film is a conventional additives selected from thickeners, antioxidants, dyes, pigments, stabilizers, UV inhibitors and flame retardants further comprises 0.01 to 30 parts by weight based on 100 parts by weight of the nanocomposite film composition. Method for producing a polymer nanocomposite film, characterized in that. delete