KR101182066B1 - Thermoplastic Transparent Resin for Transparent Extrusion Films, Thermoplastic Transparent Resin Composition for Transparent Extrusion Films comprising the Thermoplastic Transparent Resin, And Transparent Extrusion Films Prepared from thereof - Google Patents

Abstract

The present invention relates to thermoplastic transparent resins and thermoplastic transparent resin compositions for films, and films prepared therefrom, and more particularly, to (meth) acrylic acid alkyl ester compounds, aromatic vinyl compounds, vinyl cyan compounds, etc., in conjugated diene rubber latexes. In the graft copolymerization of the monomer mixture, the thermoplastic transparent resin capable of minimizing the deformation of the rubber by shearing and increasing the haze by improving the molecular weight and increasing the graft rate to sufficiently cover the rubber surface, and the thermoplastic transparent The thermoplastic transparent resin composition which mix | blended resin with hard resin is provided. According to the present invention, there is an effect of providing a film excellent in transparency, mechanical properties and processing properties from the above-mentioned thermoplastic transparent resin or thermoplastic transparent resin composition.

Optical film, thermoplastic transparent resin, rubber latex, molecular weight, haze

Description

Thermoplastic Transparent Resin for Transparent Extrusion Films, Thermoplastic Transparent Resin Composition for Transparent Extrusion Films comprising the Thermoplastic Transparent Resin, And Transparent Extrusion Films Prepared from Julia}

The present invention relates to thermoplastic transparent resins and thermoplastic transparent resin compositions for films, and films prepared therefrom, and more particularly, to (meth) acrylic acid alkyl ester compounds, aromatic vinyl compounds, vinyl cyan compounds, etc., in conjugated diene rubber latexes. In the graft copolymerization of the monomer mixture, the thermoplastic transparent resin capable of minimizing the deformation of the rubber by shearing and increasing the haze by improving the molecular weight and increasing the graft rate to sufficiently cover the rubber surface, and the thermoplastic transparent A thermoplastic transparent resin composition in which a resin is blended with a hard resin. According to the present invention, there is an effect of providing a film excellent in transparency, mechanical properties and processing properties from the above-mentioned thermoplastic transparent resin or thermoplastic transparent resin composition.

Recently, the use of transparent films has been made in various industrial fields. Automotive film, thermal expansion transparent film used for advertising, optical transparency film and the like are used in a variety of applications, and usage is also increasing. The required properties vary depending on the use of these films, but basically high transparency and mechanical properties are required.

Research on transparent resins using conjugated diene rubbers involves the introduction of (meth) acrylic acid alkyl ester compounds into acrylonitrile-butadiene-styrene (ABS) resins with excellent impact resistance, chemical resistance, and processability to impart transparency. Many are being developed. These resins have excellent mechanical properties such as toughness, excellent transparency, and low cost. However, most of these ABS-based resins are intended for injection molding products, and thus are not suitable for extrusion, and are not particularly suitable for producing a film having a thickness of several tens of micrometers.

In particular, such a transparent thermoplastic resin is required to express a colorless natural color because its yellow light has a significant effect on appearance and colorability. It is preferable to use a bulk polymerization or suspension polymerization without using an emulsifier, which is a factor that generates such a yellow light, but this method is not able to increase the rubber content in the resin, which leads to a limitation in improving the impact strength and is difficult to control the reaction heat. There is a problem.

In addition, the emulsion polymerization method is easy to adjust the content of rubber, the molecular weight of the matrix resin and the like, the heat of reaction is easy to control the resin design is free, but the use of an emulsifier is inevitable.

In Japanese Patent No. 2005-248096, a method for solving such a problem is proposed to add an alkaline earth metal salt of phosphoric acid during polymerization of a transparent thermoplastic resin or before powder recovery after aggregation, but its effect is insufficient in initial color and color stability. It was.

In addition, it is well known that the transparent thermoplastic resin produced by the emulsion polymerization method uses various kinds of electrolytes during polymerization. In order to solve the problem that these residual metals are relatively susceptible to oxidative degradation during processing, techniques for adding various stabilizers have been studied. For example, in Japanese Patent No. 2001-081271, sodium hypophosphite was added to prevent discoloration of the resin during processing in the manufacture of transparent thermoplastic resin, but relatively poor transparency, and toxic due to decomposition of sodium hypophosphite during processing at high temperature. There is a risk of generation of one phosphine gas.

In addition, Korean Patent Application Publication No. 2000-014173 discloses a thermoplastic transparent resin having excellent natural color, and Korean Patent Application Publication No. 2006-0016853 discloses a method for manufacturing a transparent resin having excellent color and weather resistance. As a product for molding, a phenomenon in which haze occurs due to shearing (shear) occurs depending on the processing conditions during extrusion, especially when the film is extruded for several tens of micrometers or less, the haze increases and becomes translucent. This haze generation occurs when the rubber is deformed by the shear and the surface is bent, especially in the film extrusion, the effect of the shear is increased.

In order to solve the problems of the prior art as described above, the present inventors graft copolymerization of a monomer mixture such as (meth) acrylic acid alkyl ester compound, aromatic vinyl compound, vinyl cyan compound, etc. The present invention provides a thermoplastic transparent resin, and a thermoplastic transparent resin composition blended with a hard resin to improve the molecular weight and increase the graft rate in the preparation of the film to sufficiently cover the rubber surface, thereby minimizing the deformation of the rubber due to shear and haze. It was confirmed that the increase of the can be completed based on the present invention.

That is, an object of the present invention is to improve the molecular weight and increase the graft rate of a monomer mixture of a (meth) acrylic acid alkyl ester compound, an aromatic vinyl compound, a vinyl cyan compound, and the like on a rubber surface by conjugated diene rubber latex. It is to provide a thermoplastic transparent resin that can sufficiently minimize the deformation of the rubber due to shearing and prevent the increase of haze.

Another object of the present invention is to provide a thermoplastic transparent resin composition for a film excellent in transparency, mechanical properties and processing properties by properly blending a hard resin to the above-mentioned thermoplastic transparent resin.

Another object of the present invention is to provide a film excellent in transparency, mechanical properties and processing properties by using the above-mentioned thermoplastic transparent resin or the thermoplastic transparent resin composition for a film.

In order to achieve the above object, according to the present invention,

(a) conjugated diene rubber latex;

(b) (meth) acrylic acid alkyl ester compounds and

(c) an aromatic vinyl compound; which is graft copolymerized as a graft copolymer,

It provides a thermoplastic transparent resin having a graft rate of 50 to 300% and a weight average molecular weight of 100,000 to 300,000.

In addition, according to the present invention,

a) the above-mentioned thermoplastic transparent resin; And

b) (meth) acrylic acid alkyl ester compounds; And aromatic vinyl compounds; As the resin composition comprising this copolymerized hard resin;

The graft ratio is 50 to 300%, and the weight average molecular weight is 100,000 to 300,000 to provide a thermoplastic transparent resin composition for a film.

In addition, according to the present invention,

Provided is a film made of the above-mentioned thermoplastic transparent resin or thermoplastic transparent resin composition for a film, and excellent in transparency, mechanical properties and processing characteristics.

Hereinafter, the present invention will be described in detail.

<Thermoplastic transparent resin manufacturing>

oil paint Graft  Copolymerization:

In the present invention, graft copolymerization of a monomer mixture of a (meth) acrylic acid alkyl ester compound, an aromatic vinyl compound, and a vinyl cyan compound to a conjugated diene rubber latex to prepare an emulsion graft copolymer, wherein the refractive index of the rubber latex and the monomer mixture It is a technical feature to set the monomer mixing ratio to optimize the refractive index of and optimize the graft rate, molecular weight and rubber content.

In consideration of this optimized rubber content and the mixing ratio of monomers, for example, when using polybutadiene rubber latex as the rubber latex, 3 to 45 weight of conjugated diene rubber latex based on 100 parts by weight of the rubber latex and the total monomer mixture It is preferable that a part consists of 10-60 weight part of (meth) acrylic-acid alkylester compound and 10-60 weight part of aromatic vinyl compounds.

If the content of the rubber latex is less than the range presented, the impact strength of the molded article is lowered, if the content exceeds the range presented there is a problem that the polymerization stability is lowered. Toughness and processability are poor in the above-described monomer content range, and transparency is poor in the above content range.

In addition, when using butadiene-styrene copolymer (SBR) rubber latex as the rubber latex, 3 to 45 parts by weight of the conjugated diene rubber latex based on 100 parts by weight of the rubber latex and the total monomer mixture (meth) acrylic acid alkyl ester compound 10 It is preferable to consist of from 60 to 60 parts by weight and 10 to 60 parts by weight of the aromatic vinyl compound.

If the content of the rubber latex is less than the range presented, the impact strength of the molded article is lowered, if the content exceeds the range presented there is a problem that the polymerization stability is lowered. Toughness and processability are poor in the above-described monomer content range, and transparency is poor in the above content range.

Also, when using butadiene-acrylonitrile copolymer (NBR) rubber latex as the rubber latex, from 3 to 45 parts by weight of (meth) acrylic acid alkyl ester based on 100 parts by weight of the rubber latex and the total monomer mixture It is preferable that it consists of 10-80 weight part of compounds and 4-50 weight part of aromatic vinyl compounds.

If the content of the rubber latex is less than the range presented, the impact strength of the molded article is lowered, if the content exceeds the range presented there is a problem that the polymerization stability is lowered. Toughness and processability are poor in the above-described monomer content range, and transparency is poor in the above content range.

In addition, the difference in refractive index between the rubber latex and the monomer mixture copolymer is 0.01 or less is appropriate considering the transparency, mechanical properties and processing characteristics.

Here, the conjugated diene rubber latex is preferably used having an average particle diameter of 0.2 to 0.5㎛. In this case, when the average particle diameter is less than 0.2 µm, toughness and haze are poor, and when the average particle diameter exceeds 0.5 µm, the whitening resistance is not good, which is not preferable.

Here, as said (meth) acrylic-acid alkylester compound, (meth) acrylic-acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid decyl ester, ( Methacrylic acid lauryl ester etc. can be used, Especially, it is more preferable to use methyl methacrylate.

As said aromatic vinyl compound, styrene, (alpha) -methylstyrene, (rho) -methylstyrene, vinyltoluene, etc. can be used, Especially, it is more preferable to use styrene.

As said vinyl cyan compound, acrylonitrile or methacrylonitrile is preferable.

The addition method of each component can use the batch administration method, and the method of administering whole quantity or a part continuously (sequential). In the present invention, it is preferable to take a complex form in which both batch administration and continuous administration methods are used. In the present invention, the transparent resin is preferably prepared by an emulsion polymerization method.

60-85 degreeC of polymerization temperature is preferable, and polymerization time of 3 to 10 hours is preferable.

In addition, in the polymerization reaction, 1 to 20 parts by weight of vinyl cyan compound, 1 to 20 parts by weight of acid anhydride, 0.2 to 0.6 parts by weight of emulsifier, 0.2 to 1.5 parts by weight of molecular weight regulator, It is preferable to add 0.02-0.3 weight part of polymerization initiators further.

If the vinyl cyan compound is 1 part by weight or less, there is a problem that the impact strength is lowered, and when the vinyl cyan compound is more than 20 parts by weight, there is a problem of making the color of the resin yellow. As the acid anhydride, monovalent or divalent or higher carboxylic acid anhydride can be used, and it is preferable to use maleic anhydride or a derivative thereof. As the emulsifier, alkylaryl sulfonates, alkali methylalkyl sulfates, sulfonated alkyl esters, fatty acid soaps, alkali salts of rosin acids, sodium oleate, and the like can be used alone or as a mixture of two or more thereof. As said molecular weight modifier, tertiary dodecyl mercaptan is preferable.

As the polymerization initiator, peroxides such as cumenehydroperoxide, diisopropylbenzenehydroperoxide, persulfate, etc., sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrophosphate, and acetic acid Oxidation-reduction catalyst systems in admixture with reducing agents such as sodium sulfate and the like can be used.

For reference, the monomer mixing amount according to the refractive index of the graft copolymer of the monomer mixture can be estimated using the following equation:

Refractive index of the graft copolymer = WtA x RIA + WtS x RIs + WtS x RIM

Where WtA is the weight percent of the vinyl cyan compound, RIA is the refractive index of the vinyl cyan polymer (1.52), WtS is the weight percent of the aromatic vinyl compound, RIs is the refractive index of the aromatic vinyl compound (1.592), and WtS is The weight percent of methacrylic acid alkyl ester compound, and RIM means the refractive index (1.49) of the methacrylic acid alkyl ester polymer.)

Not all monomers introduced in the graft polymerization process are grafted to the rubber latex, but the polymerization proceeds without being partially grafted. Therefore, in the conjugated diene-based resin using the same rubber as the present invention, the graft ratio has a great influence on the physical properties.

The graft rate, which is the ratio of the graft copolymer to the non-grafted copolymer prepared in the present invention, is preferably 50 to 300%, more preferably 70 to 250%, most preferably 100 to 150%. . When the graft rate is less than 50%, the rubber is deformed by shear at the surface during processing, so that light scatters at the surface, thereby increasing haze and transparency. On the other hand, if the graft rate is more than 300%, the stability during polymerization is not preferable.

In addition, the weight average molecular weight of the graft copolymer is preferably in the range of 100,000 to 300,000, more preferably in the range of 15 to 200,000. If the molecular weight is less than 100,000 it is difficult to extrude due to low melt strength (melt strength), the deformation of the rubber on the surface is easy to decrease the transparency, if the molecular weight exceeds 300,000 there is a problem that the flow is not good, difficult to process.

Cohesion:

In the present invention, the emulsion graft copolymer latex thus prepared is recovered as a dry powder type through a subsequent process of flocculation, dehydration and drying.

The inorganic salts of alkaline earth metals used as flocculants are preferably magnesium salts such as magnesium phosphate, magnesium sulfate and magnesium chloride and calcium salts such as calcium phosphate, calcium sulfate and calcium chloride.

The amount of the flocculant is preferably used in the range of 1 to 10 parts by weight based on 100 parts by weight of the latex solid content.

<Hard resin production>

In preparing the hard resin, a monomer mixture of 40 to 90 parts by weight of the (meth) acrylic acid alkyl ester compound and 10 to 60 parts by weight of the aromatic vinyl compound is polymerized based on 100 parts by weight of the total monomer content. At this time, it is more preferable to polymerize 60 to 80 parts by weight of the (meth) acrylic acid alkyl ester compound and 20 to 40 parts by weight of the monomer mixture based on 100 parts by weight of the total monomer content, based on 100 parts by weight of the total monomer content ( Most preferably, 65 to 75 parts by weight of the meta) acrylic acid alkyl ester compound and 25 to 35 parts by weight of the aromatic vinyl compound are mixed.

Furthermore, the vinyl cyan compound and acid anhydride may be further included, wherein the (meth) acrylic acid alkyl ester compound, aromatic vinyl compound, vinyl cyan compound, and acid anhydride that may be used are as described in the above-mentioned emulsion graft copolymerization step. . At this time, the vinyl cyan compound or acid anhydride is preferably added in the range of 5 to 7 parts by weight based on 100 parts by weight of the total monomer content.

The weight average molecular weight of the copolymer thus obtained is preferably in the range of 100,000 to 200,000, and more preferably in the range of 14 to 200,000. If the molecular weight is less than 100,000 it is difficult to extrude due to low melt strength (melt strength), the deformation of the rubber on the surface is easy to decrease the transparency, if the molecular weight exceeds 200,000 there is a problem that the flow is not good, difficult to process.

The thermoplastic transparent resin composition for a film of the present invention may include 15 to 50% by weight of the prepared thermoplastic transparent resin and 50 to 85% by weight of the hard resin. As said mixing ratio, it is more preferable to mix in the weight ratio of 25:75.

It is preferable that the thermoplastic transparent resin composition for films manufactured as described above further contains any one selected from the group consisting of ultraviolet absorbers, antioxidants, light stabilizers, dyes, pigments, and mixtures thereof, depending on the use and need.

The thermoplastic transparent resin composition or thermoplastic transparent resin composition for a film prepared in this way is added to a heat stabilizer, UV stabilizer, mold release material, silicone oil, etc. within a range that does not affect physical properties, and uniformly using a single screw extruder, a twin screw extruder, or a Banbury mixer. Disperse. It is then passed through a water bath and cut to prepare a resin in pellet form, and then to produce a film using a film extruder.

The film thus obtained has an extruded thickness of 60 to 80 μm, and may be applied as an automotive exterior film, an advertising thermally expandable transparent film, or an optically transparent film.

Thermoplastic transparent resin and the thermoplastic transparent resin composition for a film according to the present invention Graft copolymerization of monomer mixtures such as (meth) acrylic acid alkyl ester compounds and aromatic vinyl compounds in conjugated diene rubber latex improves the molecular weight and increases the graft rate to sufficiently cover the rubber surface to minimize deformation of rubber by shearing And by preventing the increase in haze has an effect of providing a film excellent in transparency, mechanical properties and processing properties.

Manufacturing example  1: Manufacture thermoplastic transparent resin

To 70 parts by weight of a rubber latex having a gel content of 70% and an average particle diameter of 0.3 µm and a refractive index of 1.516 prepared by emulsion polymerization, 100 parts by weight of ion-exchanged water, 0.5 parts by weight of sodium oleate emulsifier, 66.7 parts by weight of methyl methacrylate, and styrene 23.3 Parts by weight, acrylonitrile 5 parts by weight, tertiary dodecyl mercaptan 0.3 part by weight, sodium pyrophosphate 0.048 part by weight, dextrose 0.012 part by weight, ferrous sulfide 0.001 part by weight and cumene hydroperoxide 0.3 part by weight The graft copolymer was prepared by continuously adding and reacting for 10 hours at.

After the reaction, the temperature was raised to 80 ° C., and aged for 1 hour to complete the reaction. The latex was solidified with 3 parts by weight of an aqueous calcium chloride solution and washed to obtain a white powder. The graft rate of the graphite copolymer thus obtained was 110%, the weight average molecular weight was 180,000, and the refractive index was 1.516.

Manufacturing example  2: thermoplastic transparent resin manufacturer

0.7 parts by weight of tertiary dodecyl mercaptan The procedure of Preparation Example 1 was repeated except that the graft copolymer powder was obtained. The graft rate of the obtained graphite copolymer was 45%, the weight average molecular weight was 80,000, and the refractive index was 1.516.

Manufacturing example  3: manufacture of thermoplastic transparent resin

20 parts by weight of rubber latex, 55.6 parts by weight of methyl methacrylate, 19.4 parts by weight of styrene, and 0.2 parts by weight of tertiary dodecyl mercaptan were used. Repeated to obtain graft copolymer powder. The graft rate of the obtained graphite copolymer was 90%, the weight average molecular weight was 190,000, and the refractive index was 1.516.

Manufacturing example  4: thermoplastic transparent resin manufacturing

A thermoplastic transparent resin was prepared based on Example 1 in Korean Patent Laid-Open No. 2000-0014173.

Specifically, 90 parts by weight of ion-exchanged water, 0.2 parts by weight of sodium oleate, 14.38 parts by weight of methyl methacrylate, 5.63 parts by weight of styrene, 2.5 parts by weight of acrylonitrile, tertiary dode 0.2 part by weight of silmercaptan, 0.048 part by weight of sodium pyrophosphate, 0.012 part by weight of dextrose, 0.001 part by weight of ferrous sulfide and 0.04 part by weight of cumene hydroperoxide at 50 ° C., and the reaction temperature was added twice to 73 ° C. The reaction was carried out while rising.

Then, 70 parts by weight of ion-exchanged water, 0.4 parts by weight of sodium oleate, 43.12 parts by weight of methyl methacrylate, 16.88 parts by weight of styrene, 7.5 parts by weight of acrylonitrile, 0.25 parts by weight of tertiary dodecyl mercaptan, and pyrophosphoric acid A mixed emulsion solution containing 0.048 parts by weight of sodium, 0.012 parts by weight of dextrose, 0.001 parts by weight of ferrous sulfide, and 0.10 parts by weight of cumene hydroperoxide was continuously administered for 4 hours, and then heated to 76 ° C. and aged for 1 hour. Was terminated. The latex was solidified with 3 parts by weight of an aqueous calcium chloride solution and washed to obtain a white powder. The graft ratio of the thus obtained graphite copolymer was 38%, the weight average molecular weight was 100,000, and the refractive index was 1.516.

Manufacturing example  5: thermoplastic transparent resin manufacturing

A thermoplastic transparent resin was prepared based on the contents of Examples in Korean Laid-Open Patent Publication No. 2006-016853.

Specifically, 100 parts by weight of ion-exchanged water, 20 parts by weight of rubber latex having a refractive index of 1.516, 0.5 parts by weight of dioctylsulfo succinate as an emulsifier, 17.5 parts by weight of butyl acrylate, 12.5 parts by weight of styrene, and ethylene glycol di by a graft crosslinking agent. 0.28 parts by weight of methacrylate, 0.1 parts by weight of aryl methacrylate as a grafting agent, 0.1 parts by weight of sodium hydrogencarbonate as an electrolyte, and 0.06 parts by weight of potassium persulfate as a polymerization initiator were polymerized by continuous administration at 70 ° C. for 3 hours. At this time, to increase the polymerization conversion was further reacted at 80 ℃ for 1 hour to complete the intermediate layer.

100 parts by weight of ion-exchanged water, 0.5 parts by weight of sodium oleate as an emulsifier, 34.56 parts by weight of methyl methacrylate, 13.44 parts by weight of styrene as an aromatic vinyl derivative, and 2 parts of acrylonitrile as a vinyl cyan derivative. Parts, 0.5 part by weight of tertiary dodecyl mercaptan as a molecular weight regulator, 0.048 part by weight of sodium pyrophosphate as electrolyte, 0.012 part by weight of dextrose, 0.001 part by weight of ferrous sulfide, and 0.04 part by weight of cumene hydroperoxide as a polymerization initiator. Continuous administration and reaction at 5 ° C. for 5 hours. After the reaction, the temperature was raised to 80 ° C., and aged for 1 hour to terminate the reaction. The latex was solidified with 3 parts by weight of an aqueous calcium chloride solution and washed to obtain a white powder.

The graft rate of the thus obtained graphite copolymer was 35%, the weight average molecular weight was 90,000, and the refractive index was 1.518.

Manufacturing example  6: hard resin manufacturing

68.5 parts by weight of methyl methacrylate , 26.5 parts by weight of styrene, 5 parts by weight of acrylonitrile, 30 parts by weight of toluene as a solvent (based on 100 parts by weight of the monomer mixture) and 0.15 parts by weight of the differential dodecyl mercaptan as the molecular weight regulator One raw material was continuously added to a reaction tank at an reaction temperature of 148 ° C. to give an average reaction time of 3 hours to prepare a copolymer.

The polymer resin discharged from the reaction tank was heated in a preheating bath, the unreacted monomer was volatilized in a volatilization tank, and the copolymer resin was processed into pellets using a polymer transfer pump extrusion machine while maintaining the polymerization temperature at 210 ° C.

The obtained pellet had a weight average molecular weight of 200,000 and a final refractive index of 1.518.

Manufacturing example  7: hard resin manufacturing

70 parts by weight of methyl methacrylate 23 parts by weight of styrene, 7 parts by weight of maleic anhydride instead of acrylonitrile, 0.2 parts by weight of differential dodecyl mercaptan, and the reaction temperature was maintained at 155 ° C. The process of Preparation Example 4 was repeated and the copolymer resin was processed into pellets.

The weight average molecular weight of the pellets thus obtained was 140,000, and the final refractive index was 1.517.

Manufacturing example  8: hard resin manufacturing

The process of Preparation Example 4 was repeated except that 0.5 parts by weight of differential dodecyl mercaptan was used and the reaction temperature was maintained at 150 ° C., and the copolymer resin was processed into pellets.

The obtained pellet had a weight average molecular weight of 60,000 and a final refractive index of 1.516.

Example  One: Manufacturing example  1, film production by thermoplastic transparent resin alone

In this experiment, 0.2 parts by weight of antioxidant was administered to 100 parts by weight of the thermoplastic transparent resin of Preparation Example 1, and prepared in pellet form using a twin screw extruder at a cylinder temperature of 240 ° C. The pellet thus obtained was used to produce a 60 μm extruded film using an extruder comprising a T-die. About the produced extruded film, haze, toughness, and the number of bubbles (number) were observed, respectively, and the result obtained is put in Table 1 below.

Example  2: Manufacturing example  3, with thermoplastic transparent resin Manufacturing example  6, film production with hard resin

In the present experiment, the same experiment as in Example 1 was repeated except that 25 parts by weight of the thermoplastic transparent resin of Preparation Example 3 and 75 parts by weight of the hard resin of Preparation Example 6 were replaced with 100 parts by weight of the thermoplastic transparent resin of Preparation Example 1.

About the obtained extruded film, haze, toughness, and the number of bubbles (number) were observed, respectively, and the result obtained is put together in following Table 1.

Example 3: Film production from the thermoplastic transparent resin of Preparation Example 3 and the hard resin of Preparation Example 7

In the present experiment, the same experiment as in Example 1 was repeated except that 25 parts by weight of the thermoplastic transparent resin of Preparation Example 3 and 75 parts by weight of the hard resin of Preparation Example 7 were replaced with 100 parts by weight of the thermoplastic transparent resin of Preparation Example 1.

About the obtained extruded film, haze, toughness, and the number of bubbles (number) were observed, respectively, and the result obtained is put together in following Table 1.

Comparative example  One: Manufacturing example  2, the thermoplastic transparent resin alone film production

In this experiment, the same experiment as in Example 1 was repeated except that 100 parts by weight of the thermoplastic transparent resin of Preparation Example 2 was substituted for 100 parts by weight of the thermoplastic transparent resin of Preparation Example 1.

About the obtained extruded film, haze, toughness, and the number of bubbles (number) were observed, respectively, and the result obtained is put together in following Table 1.

Comparative example  2: Manufacturing example  3, film production by thermoplastic transparent resin alone

In this experiment, the same experiment as in Example 1 was repeated except that 100 parts by weight of the thermoplastic transparent resin of Preparation Example 3 was replaced with 100 parts by weight of the thermoplastic transparent resin of Preparation Example 1.

About the obtained extruded film, haze, toughness, and the number of bubbles (number) were observed, respectively, and the result obtained is put together in following Table 1.

Comparative example  3: Manufacturing example  3, with thermoplastic transparent resin Manufacturing example  8, film made of hard resin

In the present experiment, the same experiment as in Example 1 was repeated except that 25 parts by weight of the thermoplastic transparent resin of Preparation Example 3 and 75 parts by weight of the hard resin of Preparation Example 8 were replaced with 100 parts by weight of the thermoplastic transparent resin of Preparation Example 1.

About the obtained extruded film, haze, toughness, and the number of bubbles (number) were observed, respectively, and the result obtained is put together in following Table 1.

Comparative example  4: Manufacturing example  1, with thermoplastic transparent resin Manufacturing example  6, film production with hard resin

In the present experiment, the same experiment as in Example 1 was repeated except that 25 parts by weight of the thermoplastic transparent resin of Preparation Example 1 and 75 parts by weight of the hard resin of Preparation Example 6 were replaced with 100 parts by weight of the thermoplastic transparent resin of Preparation Example 1.

About the obtained extruded film, haze, toughness, and the number of bubbles (number) were observed, respectively, and the result obtained is put together in following Table 1.

Comparative example  5: Manufacturing example  4, film production by thermoplastic transparent resin alone

In this experiment, the same experiment as in Example 1 was repeated except that 100 parts by weight of the thermoplastic transparent resin of Preparation Example 4 was replaced with 100 parts by weight of the thermoplastic transparent resin of Preparation Example 1.

About the obtained extruded film, haze, toughness, and the number of bubbles (number) were observed, respectively, and the result obtained is put together in following Table 1.

Comparative example  6: Manufacturing example  5, with thermoplastic transparent resin Manufacturing example  6, film production with hard resin

In this experiment, the same experiment as in Example 1 was repeated except that 50 parts by weight of the thermoplastic transparent resin of Preparation Example 5 and 50 parts by weight of the hard resin of Preparation Example 6 were replaced with 100 parts by weight of the thermoplastic transparent resin of Preparation Example 1.

About the obtained extruded film, haze, toughness, and the number of bubbles (number) were observed, respectively, and the result obtained is put together in following Table 1.

Haze, toughness and processing characteristics (bubble number) measuring method in the above Examples and Comparative Examples are as follows:

1) Haze value: Haze value was measured according to ASTM 1003 method. For reference, the smaller the value, the better the transparency.

2) Toughness: The 60 μm film was measured by bending five times by hand. (○: never broken, Ⅹ: broken more than once)

3) Number of bubbles: When extruding a 60 μm film, bubbles were generated and the number of bubbles in a 10 cm × 10 cm area was measured and input. Bubbles should not occur in the specimen because they cannot be used as films.

division Hayes tenacity Bubbles () Example 1 0.9 ○ 0 Example 2 1.1 ○ 0 Example 3 1.3 ○ 0 Comparative Example 1 6.5 X 20 Comparative Example 2 7.8 ○ 0 Comparative Example 3 2.5 X 50 Comparative Example 4 0.6 X 0 Comparative Example 5 15.0 ○ 70 Comparative Example 6 40.4 ○ > 100

As can be seen in Table 1, Examples 1 to 3 according to the present invention was also excellent in transparency and excellent in toughness. In addition, no bubble generation was observed on the processing, showing excellent properties for film extrusion. Especially in the case of Example 3 in which maleic anhydride was introduced, the heat resistance (Tg) was also excellent at 117 ° C.

In contrast, in the case of Comparative Example 1, the graft ratio and the weight average molecular weight were low, resulting in poor transparency and toughness measurement results. In addition, bubble generation was also observed on the processing. In the case of Comparative Example 2, the rubber content was too high, the transparency was bad. In Comparative Example 3, the molecular weight was too low, resulting in poor toughness measurement results, and bubbles were also observed on the processing. In addition, in Comparative Example 4, it was observed that the rubber content was so low that the toughness of the film was very poor. In Comparative Example 5, the rubber content was high, the molecular weight was low, the graft rate was low, the transparency was bad, and the bubble generation was severe. In Comparative Example 6, the rubber content of the graft copolymer including the intermediate layer is high, the graft rate is low, so that the transparency is bad and the bubbles are severe.

Although described in detail above with reference to the specific embodiments of the present invention, it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention, and such modifications and modifications fall within the scope of the appended claims. It is natural.

Claims (12)

(a) conjugated diene rubber latex; (b) (meth) acrylic acid alkyl ester compounds and (c) an aromatic vinyl compound; a graft copolymer formed by graft copolymerization, The content of the (a) conjugated diene rubber latex is in the range of 3 to 10 parts by weight based on a total of 100 parts by weight of the (a) rubber latex and the monomer mixture of (b) and (c), The graft ratio is 50 to 300%, the weight average molecular weight is 150,000 to 200,000, the thermoplastic transparent resin for transparent extrusion film. The method of claim 1, The mixing amount of (a) to (c) is based on 100 parts by weight of the rubber latex and the total monomer mixture (a) 3 to 10 parts by weight of polybutadiene, (b) 20 to 80 parts by weight of (meth) acrylic acid alkyl ester compound, and (c) 8-50 weight part of aromatic vinyl compounds, Comprising: The thermoplastic transparent resin for transparent extrusion films characterized by the above-mentioned. The method of claim 1, The mixing amount of (a) to (c) is based on 100 parts by weight of the rubber latex and the total monomer mixture (a) 3 to 10 parts by weight of butadiene-styrene copolymer (SBR), (b) 20 to 80 parts by weight of (meth) acrylic acid alkyl ester compound, and (c) 8-50 weight part of aromatic vinyl compounds, Comprising: The thermoplastic transparent resin for transparent extrusion films characterized by the above-mentioned. The method of claim 1, The mixing amount of (a) to (c) is based on 100 parts by weight of the rubber latex and the total monomer mixture (a) 3 to 10 parts by weight of butadiene-acrylonitrile copolymer (NBR), (b) 20 to 80 parts by weight of (meth) acrylic acid alkyl ester compound, and (c) 8-50 weight part of aromatic vinyl compounds, Comprising: The thermoplastic transparent resin for transparent extrusion films characterized by the above-mentioned. The method of claim 1, The mixing amount of (a) to (c) is based on 100 parts by weight of the rubber latex and the total monomer mixture (a) 3 to 10 parts by weight of ethylene-propylene copolymer (EPDM), (b) 20 to 80 parts by weight of (meth) acrylic acid alkyl ester compound, and (c) 8-50 weight part of aromatic vinyl compounds, Comprising: The thermoplastic transparent resin for transparent extrusion films characterized by the above-mentioned. The method of claim 1, The monomer mixture further comprises at least one member selected from the group consisting of vinyl cyan compounds, maleic anhydride compounds, emulsifiers, molecular weight regulators, polymerization initiators, and mixtures thereof. (a) conjugated diene rubber latex; (b) (meth) acrylic acid alkyl ester compounds and (c) an aromatic vinyl compound; a graft copolymer formed by graft copolymerization, The content of the (a) conjugated diene rubber latex is in the range of 3 to 35 parts by weight based on a total of 100 parts by weight of the combination of (a) rubber latex and the monomer mixture of (b) and (c), Thermoplastic transparent resin having a graft ratio of 50 to 300% and a weight average molecular weight of 150,000 to 200,000; And A hard resin having a weight average molecular weight of 140,000 to 200,000 formed by copolymerization of an (meth) acrylic acid alkyl ester compound and an aromatic vinyl compound, and having a refractive index difference of 0.01 or less from the thermoplastic transparent resin; Thermoplastic transparent resin composition for a transparent extruded film comprising a. The method of claim 7, wherein The hard resin may include 40 to 90 parts by weight of (meth) acrylic acid alkyl ester compound and 10 to 60 of aromatic vinyl compound based on 100 parts by weight of the total monomer content. The thermoplastic transparent resin composition for transparent extruded films characterized by copolymerizing a weight part. The method of claim 7, wherein The resin composition is a thermoplastic transparent resin composition for a transparent extruded film, characterized in that consisting of 15 to 50 parts by weight of the thermoplastic transparent resin and 50 to 85 parts by weight of the hard resin. The method of claim 7, wherein The transparent thermoplastic resin composition for films further comprises at least one member selected from the group consisting of vinyl cyan compounds, acid anhydrides, ultraviolet absorbers, antioxidants, light stabilizers, dyes, pigments, and mixtures thereof. Thermoplastic transparent resin composition for extruded films. A transparent extruded film made of the thermoplastic transparent resin of any one of claims 1 to 6 and having excellent transparency, mechanical properties, and processing properties in a thickness range of 60 to 80 µm. A transparent extruded film made of the thermoplastic transparent resin composition for a film of claim 7 and having excellent transparency, mechanical properties and processing characteristics in a thickness range of 60 to 80 μm.