TW201742886A - Thermoplastic resin blend composition, master batch, and composition for forming biaxially stretched polyolefin-based film - Google Patents

Abstract

The present invention relates to a thermoplastic resin blend composition, and more particularly, to a thermoplastic resin blend composition including a polyolefin resin and a petroleum resin having a C1 to C18 alkyl group in its molecular structure. The above composition improves the compatibility between the polyolefin resin and the petroleum resin, so as to minimize the generation of fumes in the heating process using the polyolefin resin and the petroleum resin, particularly the master batch process and the film forming process.

Description

Composition of mixed thermoplastic resin

SUMMARY OF THE INVENTION The present invention is directed to a thermoplastic resin blending composition that minimizes the occurrence of fumes in the masterbatch process and the film forming process.

The materials used for film formation are roughly classified into natural materials such as paper, natural polymer materials, metal foils such as aluminum foil, and synthetic polymer materials typified by polypropylene and polyethylene. Among them, polypropylene has attracted the most attention due to its transparency, processability, impact resistance, moisture resistance and mechanical strength.

The type of the polypropylene film is classified into an unstretched film and a stretched film depending on whether or not it extends.

The unstretched film has a cast PP film (CPP) and an inflation polypropylene film (IPP), and the cast polypropylene film and the inflated polypropylene film are excellent in transparency and surface gloss. Further, the film is used as a sealing film for snack packaging, soft canned food packaging, and the like, in addition to a film excellent in strength and dimensional stability.

Oriented film refers to a film extending in the length direction and/or the width direction in an extrusion and cooling process, and is divided into a uniaxially stretched film and a biaxially stretched film according to the extension, and the above-mentioned biaxially stretched film is again divided into two Bi-Axially Oriented PP Film (BOPP) and Inflated oriented PP film (IOPP). Compared with the unstretched film, such a stretched film has mechanical strength such as tensile strength, tensile modulus, impact strength, tensile burst strength, and bending life, and heat resistance, cold resistance, transparency, and gas barrier property. And other characteristics.

In particular, the BOPP film is highly praised for its excellent mechanical strength, gloss and transparency, excellent chemical resistance, heat resistance, water resistance, durability, etc., and its demand is increasing worldwide in packaging. A membrane that has grown in the industry. The above BOPP film is roughly divided into general use and deposition, and the ordinary use is subdivided into printing, spacer paper, white pearl, pad, fiber packaging, cigarette packaging, etc. according to the use, and deposition is usually performed by aluminum vacuum deposition. The method is used in fields requiring gas barrier properties and water vapor barrier properties.

The BOPP film is formed by extruding a polypropylene (Polypropylene, PP) powder by a T-die to form an unstretched sheet, and then extending the unstretched sheet in the machine direction (MD) and the width direction (TD), respectively. A biaxially stretched PP film was produced.

Initially, the BOPP film uses polypropylene alone, but is used in combination with various resins or additives in order to secure various physical properties corresponding to the use.

Korean Laid-Open Patent Publication No. 2006-0071687 relates to a laminated BOPP film, which discloses a technique for improving the rigidity of the above film and improving the bonding strength and heat resistance in the lamination coating process, relative to the weight of the polypropylene 100. A petroleum resin such as a C5 fraction, a C9 fraction or a polydecene-based polymer is used in an amount of from 3 parts by weight to 30 parts by weight.

Referring to the preparation method of the above patent, the polypropylene and the petroleum resin are mixed into the extruder and then realized by an extrusion process. In this case, the mixing property of the polypropylene and the petroleum resin is low, so that the final result is obtained. The physical properties of the film are not uniform or the transparency of the film is lowered. Also, fumes are generated from petroleum resin due to heat applied in an extrusion process of 200 ° C to 250 ° C. Smoke refers to an aerosol of solid particles generated by condensation of combustion products in a vapor or a gas phase, which is classified as a harmful gas and generates malodor. Due to the above-mentioned smog, not only the working environment is deteriorated, the human body is harmful, but also the problem of environmental pollution and ecosystem pollution due to the smoke dispersed in the atmosphere.

Therefore, a dust collector for removing smoke or a discharge device for forcibly discharging the smoke has been proposed. With this method, the current working environment has been improved, but it still has fundamental problems of environmental pollution and ecosystem pollution along with the increase in process costs.

On the other hand, regarding the processing of the polymer, various molding processes such as an extrusion process or an injection process are used, and various plastic products are produced by such a molding process. In order to impart chromaticity or a special function to an article to be manufactured in the above-mentioned forming process, it is necessary to incorporate an additive of a desired function into the base material particles.

However, since the additive having the above functions is mostly in a powder or liquid state, it is difficult to use it in combination with particles, and the dispersion of the additive is poor due to poor kneading property, so that it is difficult to produce a product having a desired chromaticity or special function.

Therefore, a way of using a masterbatch is proposed. The master batch refers to a granule obtained by first concentrating the base base polymer particles and the additive to be added at a high concentration in order to improve the kneadability of the polymer particles as a raw material and the additive in a powder state or a liquid state, and thereafter mixing the master batch. Formal processing is performed with polymer particles.

The master batch is prepared by sequentially performing a mixing process, an extrusion process, a cooling process, and a cutting process for mixing materials, and the extrusion process is changed according to the T _{g of the} polymer, usually, in the case of polypropylene, at 200 The extrusion process was carried out at °C to 250 °C.

Therefore, even if a masterbatch is used and a BOPP film is prepared by using a polypropylene and a petroleum resin, it is necessary to perform an extrusion process performed at a temperature of 200 ° C or higher, so that it is impossible to avoid the generation of smoke in the extrusion process as mentioned in the above. .

[Pre-Technical Literature] [Patent Document] Korean Patent Publication No. 2006-0071687, June 27, 2006, a resin composition for preparing a biaxially stretched polypropylene film having heat resistance and high rigidity, a film prepared therefrom, and Coating

[Question to be solved by the invention]

In order to solve the above problems, the applicant of the present application has focused on performing continuous research on the concept of suppressing the generation of smoke in the extrusion process in the case of improving the lower thermal stability of the petroleum resin which is the cause of the generation of smoke, and the result is preparation. The petroleum resin obtained by introducing a linear alkyl group at one end was prepared by molding the petroleum resin with a polyolefin, and as a result, it was confirmed that the generation of smoke in the master batch process and the molding process was reduced, thereby completing the present invention.

Accordingly, an object of the present invention is to provide a thermoplastic resin blend composition comprising a polyolefin resin and a petroleum resin.

Further, another object of the present invention is to provide a masterbatch comprising the above thermoplastic resin blend composition for preparing a polymer molded article.

Further, it is still another object of the present invention to provide a thermoplastic formed composition comprising the above-mentioned resin blending for preparing a polymer molded article. [Means for solving the problem]

In order to achieve the above object, the present invention provides a thermoplastic resin blend composition comprising a polyolefin resin and a petroleum resin.

In this case, the above thermoplastic resin blending composition is characterized in that the above petroleum resin includes: a repeating unit (A) derived from a hydrogenated diene; and a hydrogenated diene derived from an alkyl group having at least one carbon of C1 to C18. Repeat unit (B).

Further, the thermoplastic resin blending composition is characterized in that the polyolefin-based resin and the petroleum resin are blended in a weight ratio of 1:0.5 to 9.5:0.5.

Further, the present invention provides a master batch comprising the above thermoplastic resin blend composition, the thermoplastic resin blend composition comprising a polyolefin resin and a petroleum resin.

Furthermore, the present invention provides a biaxially stretched polyolefin film forming composition comprising the above thermoplastic resin blending composition, wherein the thermoplastic resin blending composition comprises a polyolefin resin and a petroleum resin.

In this case, the biaxially stretched polyolefin film-forming composition is characterized in that the biaxially stretched polyolefin film is a BOPP (Biaxially oriented polypropylene) film. [Effects of the Invention]

The thermoplastic resin blending composition of the present invention uses a petroleum resin including an alkyl group to impart structural similarity with a repeating unit of a polyolefin to improve compatibility, whereby thermal stability can be greatly improved.

The high thermal stability and compatibility in this manner minimizes the occurrence of fumes in the heating process using polyolefin resins and petroleum resins, particularly in the masterbatch process and the film forming process.

The thermoplastic resin blending composition proposed in the present invention has an effect of reducing the generation of smoke in an extrusion process, and includes a polyolefin-based resin and a petroleum resin for improving adhesion and heat resistance.

Hereinafter, each component will be described in detail.

The polyolefin resin is obtained by polymerizing an olefin monomer, and includes polyethylene and polypropylene. The polyethylene may be high density polyethylene (HDPE, high density PE), medium density PE (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE, linear Low density PE). The polypropylene may be sPP (syndiotactic PP), iPP (isotactic PP), aPP (atactic PP), and partially irregular polypropylene (rirPP, regioirregular PP).

The polyethylene and the polypropylene may be a homopolymer or an ethylene-propylene copolymer, and if necessary, copolymerize any one of ethylene and propylene with a C3 to C20 α-olefin, acetic acid or acrylate. The monomer is copolymerized and used.

The above α-olefin may be used alone as 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1 Linear α-olefins such as tetradecene, 1-hexadecene and 1-octadecene, isobutylene, 3-methyl-1 butene, 2-methyl-1-butene, 3-methyl-1- Butylene, 4-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 5-methyl-1- Dendritic α-olefins such as hexene, 3,3-dimethyl-1-pentene, 3,4-dimethyl-1-pentene, 4,4-dimethyl-1-pentene, etc. The mixture is used in the same or mixed, and it is more preferable to use a linear α-olefin. For example, an ethylene-butene copolymer or an ethylene-octene copolymer may be used. In the case of a comonomer of acetic acid and an acrylate, it may be an ethylene-vinyl acetate (EVA) copolymer. , an ethylene-acrylate copolymer, an ethylene-methacrylate copolymer, and the like.

The polyolefin proposed in the present invention is preferably polypropylene.

The extrusion process of the polyolefin resin is usually carried out at 150 ° C to 300 ° C, more specifically, in the case of polypropylene, the extrusion process is performed at 200 ° C to 250 ° C, at which temperature, together with the above The petroleum resin used in combination with the polyolefin resin has a low thermal stability and a part of the chain of the hydrocarbon is heated, or in the case of the cyclic compound, ring-opening and thermal decomposition occur, so that the solid particles in the form of smoke (aerosol state) ) floating in the air. Such smoke is easily volatilized into the atmosphere, which deteriorates the working environment or affects human health and the ecosystem. Therefore, in the case of improving the thermal stability of the petroleum resin, the generation of the above-mentioned smoke can be reduced.

The increase in thermal stability can be carried out in various ways. In the present invention, a petroleum resin is used in the form of hydrogenation, which is prepared by increasing the molecular weight and molecular size and copolymerizing with other comonomers, i.e., olefins, in terms of thermodynamics. stable.

Specifically, it is described using dicyclopentadiene (also referred to as "DCPD") which is a typical petroleum resin. Referring to the following Reaction Scheme 1, DCPD has two double bonds, which are converted into polydicyclopentadiene by copolymerization with 1-hexene which is one of olefins, and are completely removed by hydrogenation. Form exists.

[Reaction formula 1]

At this time, DCPD has a ring structure of a cyclopentyl group, which is caused by strain due to an increase and decrease of a bonding angle (ie, an angle strain), due to accumulation of adjacent atomic bonds. Strain (ie, tortioanl strain) and strain caused by repulsion caused by atoms approaching each other (ie, steric strain) and low thermal stability are caused by heat applied during the extrusion process. Ring cleavage. Therefore, in the present invention, the above cyclopentyl group is made to have a relatively small strain of an alkyl group, and the molecular weight of the petroleum resin is increased by adjusting the amount of the alkyl group, and structural stability is improved, thereby improving the heat in the extrusion process. Stability reduces smoke generation.

Specifically, the petroleum resin proposed in the present invention is a hydrogenated petroleum resin comprising an alkyl group, preferably having a repeating unit (A) derived from hydrogenated diene and derived from an alkane having at least one carbon of C1 to C18. a petroleum resin of a repeating unit (B) of a hydrogenated diene.

The above repeating unit (A) is one or more diene derived from a group selected from the group consisting of dicyclopentadiene, pentadiene, butadiene, and propadiene.

The alkyl group in the above repeating unit (B) is derived from a group selected from the group consisting of propylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-decene, 1-ten One or more olefins of a group consisting of a diene, 1-tetradecene, 1-hexadecene, and 1-octadecene.

At this time, the above petroleum resin includes 60 mol% to 90 mol% of the repeating unit (A), and 10 mol% to 40 mol% of the repeating unit (B).

It is preferable that the above petroleum resin includes a repeating unit represented by the following Chemical Formula 1 and a repeating unit represented by the following Chemical Formula 2 [Chemical Formula 1] [Chemical Formula 2] (In the above Chemical Formula 1 and Chemical Formula 2, R1 is H or a methyl group, R2 is an alkyl group of C1 to C18, 0≤m≤10, and 0≤n≤10).

The above thermoplastic resin blending composition is characterized in that the above petroleum resin has a weight average molecular weight of from 500 g/mol to 5,000 g/mol, preferably from 500 g/mol to 3,000 g/mol, and a softening point of from 70 ° C to 150 ° C. The color (American Public Health Association (APHA) color) is from 1 to 100. If the weight average molecular weight is less than 500 g/mol, the use effect of the petroleum resin cannot be ensured, and if the weight average molecular weight exceeds 5000 g/mol, the compatibility is also insufficient. If the softening point is less than 70 ° C, the force will decrease. When the softening point exceeds 150 ° C, it is difficult to apply to the preparation process, which is not preferable.

Further, if the opacity (APHA color) exceeds 100, the chromaticity is deteriorated and it acts as a disadvantage in the preparation of the adhesive.

Further, the petroleum resin of the present invention may contain 10 mol% to 40 mol% of an olefin-derived component. When the content of the olefin is less than 10 mol%, it is difficult to exhibit an effect of improving the adhesion performance by the copolymerization of olefins and a heat resistance effect. When the content of the olefin exceeds 40 mol%, the subsequent performance is deteriorated.

The preparation of the petroleum resin of the present invention is not particularly limited in the present invention, and a known method can be used. It is preferably prepared after the thermal polymerization by a hydrogenation step. By thermally polymerizing the comonomer, the problem of difficulty in supplying and supplying raw materials of the C5-type olefin used as the main raw material in the prior petroleum resin can be solved, and the odor problem unsolved in the prior petroleum resin can also be solved. Further, in the case of preparing a petroleum resin by thermal polymerization as described above, it is not necessary to carry out a catalyst removal process which is a necessary process in the cationic catalyst method as a method for preparing a petroleum resin in the prior art, and in particular, it can be collected. The rate is greatly increased to over 90%, so it is better.

Specifically, the above petroleum resin is prepared by the following steps: a step S1, a polymer is prepared by thermal polymerization of a diene mixed with a solvent and an olefin having 2 to 20 carbon atoms; and a step S2 is performed in the above step S1. The polymer prepared in the reaction is hydrogenated by a hydrogenation catalyst.

Hereinafter, each step will be described in detail.

(Step S1) First, a diene is dissolved in a solvent before polymerization with an olefin, and then thermally polymerized with an olefin to prepare a petroleum resin.

In the above step S1, the olefin may include one or two or more double bonds, but is preferably one, and more preferably an α-olefin.

The above α-olefin may be used alone as 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1 Linear α-olefins such as tetradecene, 1-hexadecene and 1-octadecene, isobutylene, 3-methyl-1 butene, 2-methyl-1-butene, 3-methyl-1- Butylene, 4-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 5-methyl-1- A dendritic α-olefin such as hexene or the like, or the like, or a mixture thereof, and more preferably a linear α-olefin, preferably 1-hexene or 1-octene, which is excellent in price or supply and demand. - Terpenes and 1-dodecene.

In this case, the solvent may be used without limitation as long as it is a solvent capable of dissolving the diene, and toluene, dichloromethane, hexane, xylene, trichlorobenzene, alkylbenzene or the like is preferably used. . Further, the content of the solvent is not particularly limited as long as it can sufficiently dissolve the content of the diene and the olefin, and is approximately 2 to 10 mol with respect to 1 mol of the diene.

The above thermal polymerization reaction is carried out at a temperature of from 200 ° C to 320 ° C for 0.5 hours to 4 hours, and in the case of performing thermal polymerization in a manner of less than 200 ° C or 0.5 hours, the yield may be lower, at over 320 ° C or When a thermal polymerization is performed in a 4-hour manner, a gel is formed.

(Step S2) Next, the S2 step of subjecting the polymer prepared in the above step S1 to a hydrogenation reaction via a hydrogenation catalyst is carried out.

In the step S2, the hydrogenation catalyst may be one selected from the group consisting of nickel, palladium, cobalt, platinum, and ruthenium-based metal catalysts. In terms of improving the reactivity of the hydrogenation reaction, palladium (Pd) is more preferably used.

Preferably, from 0.001 mole to 0.5 moles of the above hydrogenation catalyst is used relative to 1 mole of diene. If the above hydrogenation catalyst is less than 0.001 mol with respect to 1 mol of the diene, the reactivity may be insufficient, and when the hydrogenation catalyst exceeds 0.5 mol, the catalyst is not used due to the use of a large amount of catalyst. Economic shortcomings.

The above S2 step can carry out the hydrogenation reaction at a temperature of from 150 ° C to 300 ° C at a pressure of from 50 bar to 150 bar. If the reaction is carried out in a manner of more than 150 bar or more than 300 ° C, the molecular structure is destroyed due to severe reaction conditions, and when the reaction is carried out at a temperature of less than 50 bar or less than 150 ° C, the reaction may not be sufficiently performed. The problem of performing the hydrogenation reaction.

The reaction product obtained by the hydrogenation reaction of the above S2 step can be subjected to a subsequent purification process.

The above-mentioned purification process is for removing and concentrating unreacted raw materials, reaction by-products, solvents, and the like which are present in the reaction product obtained in the above step, and various methods generally used in the preparation process of petroleum resins can be used. As an example, it is carried out by any one of distillation, recrystallization, extraction, sublimation or chromatography, and it is preferred to use a distillation method.

As an example of the distillation method used in the above-described purification process, various known methods such as simple distillation, fractional distillation, azeotropic distillation, and vacuum distillation can be used, and vacuum distillation is preferred.

At this time, in the case of the petroleum resin proposed in the present invention, in order to improve the thermal stability, vacuum distillation may be further performed by short path distillation after performing usual vacuum distillation in the refining process.

In this case, the short-path distillation apparatus refers to an apparatus for refining, concentrating a substance which is very weak in heat, or a substance having a large molecular weight and a high boiling point and being difficult to separate, and is different from a conventional distillation apparatus in an evaporator. The inside has a condenser and the distance between the evaporation region and the condensation region is short, so that the material having low thermal stability can be quickly removed, thereby improving the distillation efficiency. Therefore, the petroleum resin of the present invention can be effectively separated from a substance having a small molecular weight which is unstable in terms of heat and which causes smoke, by the above-described short-path distillation apparatus, whereby a petroleum resin having improved heat stability can be further prepared.

The above short-range distillation apparatus may be a product of MYERS-VACUUM, INCON, CHEMTECH SERVICE, ASAHI, ULVAC, VTA or UIC, but is not limited thereto.

As an example, when the distillation is carried out by the short-path distillation apparatus, the temperature can be 25 to 200 ° C, the distillation temperature is 150 to 300 ° C, and the degree of vacuum is 0.05 torr to 25 torr.

The polyolefin-based resin and the petroleum resin as described above can be applied to various fields, and from 1 part by weight to 50 parts by weight of the petroleum resin can be used with respect to 100 parts by weight of the polyolefin-based resin, and if the application ratio is changed with respect to such a mixing ratio Further, the mixing ratio between the above polyolefin resin and petroleum resin can also be changed.

In particular, the thermoplastic resin blending composition comprising a polyolefin-based resin and a petroleum resin proposed in the present invention can be formed into various articles of polyolefin type. In this case, the polyolefin-based molded article is prepared by mixing a polyolefin resin and a petroleum resin in a predetermined ratio to form a master batch (MB), and then using the master batch as a raw material polyolefin. The resin is mixed to prepare the above polyolefin-based molded article.

The use of the masterbatch in the production of the polyolefin-based molded article has the advantages of further improving the quality of the molded article and increasing the productivity, and improving the fluidity in the forming process by previously adding the additive in the master batch. .

Fig. 1 is a sequence diagram showing the composition added when a polyolefin-based molded article is produced by the master batch process proposed in the present invention.

Referring to Fig. 1, an extrusion process is performed by mixing a polyolefin-based resin with a petroleum resin, and a master batch is prepared by cooling.

The polyolefin resin and the petroleum resin used for the preparation of the master batch are contained in a weight ratio of from 1:0.5 to 1:1.5, preferably in a weight ratio of 1:1. When the content of the petroleum resin is more than the above range, it is difficult to mix with the polyolefin-based resin. On the contrary, when it is less than the above range, the use effect of the petroleum resin cannot be expected.

The polyolefin resin for the master batch may be in the form of a powder, a pellet, a plate or a sheet which is finely pulverized by a wet or dry ball mill, and is not particularly limited in the present invention.

The above mixing may be carried out by an extruder during the extrusion process or by a usual mixer before the extrusion process. In this case, a mixer equipped with a stirrer, a plastic recorder (Brabender Plasticorder), a Banbury Mixer, a Kneader, and a Roll Mill can be used. Mixing with Henschel mixer, V-type blender, drum blender, belt blender, etc.

The extrusion process is performed at 170 ° C to 200 ° C using a twin-screw extruder, a single-screw extruder, and after cooling the melt obtained after melt extrusion at normal temperature. The master batch was obtained by cutting with a pelletizer.

In particular, the masterbatch of the present invention hardly produces smoke generated when the prior petroleum resin is used because of the use of the petroleum resin as described above.

The master batch may be in the form of particles, a plate or a sheet, and may have various shapes.

The above mixing or extrusion process may be further added to additives well known in the film field, and as an example, pigments, fillers, antioxidants, gel formation inhibitors, ultraviolet absorbers, antistatic agents, lubricants, anti-knots may be further added. Additives such as blockers, impact reinforcing agents, dispersing agents, plasticizers. In this case, the selection and content of the above additives may be selected by those having ordinary knowledge in the art, and it is preferably adjusted so that the content in the final resin composition is 10% by weight or less.

As an example, the filler may be titanium oxide, barium sulfate, barium titanate, calcium carbonate, barium oxide, talc, clay, mica powder or the like, and preferably cerium oxide. Further, a lubricant such as a metal stearate such as zinc stearate or calcium stearate can be used.

Next, the above-prepared master batch and polypropylene resin are mixed at a constant ratio to prepare a composition for thermoplastic molding, and a molding process for preparing various articles is performed on the above-mentioned composition for thermoplastic molding.

In particular, the composition for forming a petroleum resin comprising the present invention hardly generates smoke generated when the prior petroleum resin is used in the forming process, and various advantages due to the use of the master batch can be obtained, that is, the ease of processing is improved, Product quality and other effects.

The molding process may be any one of processes as long as it is a thermoforming process, and may be changed depending on the application field of the polyolefin resin. For example, extrusion molding, blow molding, injection molding, compression molding, vacuum molding, or the like may be applied. Various forming processes such as die casting. At this time, the form of the product of the finally obtained thermoplastic resin blending composition can be changed according to the forming process.

According to an embodiment of the present invention, as an example, a biaxially stretched polyolefin-based film can be prepared by a tenter method using the above-mentioned master batch, wherein, in particular, biaxially oriented polypropylene can be prepared. BOPP) film.

Fig. 2 is a sequence diagram showing a preparation process for preparing a BOPP film using the petroleum resin of the present invention.

Referring to Fig. 2, a master batch (MB) is prepared by cooling a polypropylene (PP) resin and a petroleum resin in a powder state through a melt extrusion process. At this time, the polypropylene resin and the petroleum resin are mixed at a weight ratio of 1:0.5 to 1:1.5, preferably 1:1.

Next, the master batch and the polypropylene resin were mixed to prepare a composition for forming a BOPP film.

At this time, the composition for forming the BOPP film is a ratio of the polypropylene resin to the petroleum resin in the above composition in a weight ratio of 1:0.01 to 1:0.5, preferably 1:0.05 to 1:0.2, in order to prepare the BOPP film. The above polypropylene resin and petroleum resin are blended in a manner. The above mixing may be carried out in the same manner as the above-mentioned master batch before the melt extrusion molding process, and the mixing process by another mixer is performed.

Then, the BOPP film forming composition was subjected to a melt extrusion molding process using a T-die extruder, and then cooled on a cooling drum to prepare an unstretched sheet.

The unstretched sheet is extended by a subsequent extension process, fixed by a cooling process, and prepared by winding and cutting.

The extension process is performed when preparing the stretched film and can be eliminated when preparing the unstretched film.

As an example, as shown in FIG. 2, in the case of preparing a BOPP film as a biaxially stretched film, an MD (mechanical direction) stretching process and a TD (width direction) stretching process are sequentially performed. In the case of a uniaxially stretched film, only one of the above-described extension processes is performed.

Considered as the polypropylene material used in T _m and T _g of such extension process is performed.

The BOPP film preferably has a MD extension (machine direction extension) ratio of 4.0 times or more, preferably 5.0 times or more, and a TD extension (lateral extension) of 4.0 times or more, preferably 5.0 times or more, more preferably 8.0 times or more. ratio. The ratio of the above-described elongation ratio to the width of the stretched sheet obtained after stretching and the width of the stretched sheet obtained after stretching corresponds to a level extension ratio at which the film can be appropriately elongated without being broken, and is used for usual commercial use of BOPP. The scope.

The cooling process that is then performed is used to fix the extended state of the film, and generally refers to a process of lowering the temperature to a normal temperature.

The stretched film is taken up by a winding machine (wound roll) and then cut into an appropriate size according to the form of the product to be processed.

The BOPP film prepared through the above steps can be variously deformed depending on the raw materials used and the preparation process, and usually, the thickness thereof can be 50 μm or less, preferably 40 μm or less.

Further, the BOPP film can be formed into various films such as a CPP film, an IPP film, and an IOPP film in addition to the above BOPP film depending on the process variation. The polyolefin-based film prepared in this manner can be applied to various industrial fields.

Hereinafter, preferred embodiments and comparative examples of the present invention will be described. However, the following examples are merely preferred embodiments of the present invention, and the present invention is not limited to the following examples.

Preparation Example 1 : Preparation of DCPD/1 -hexene copolymerized petroleum resin A In a 1 L autoclave, 30% by weight of dicyclopentadiene (DCPD) was dissolved in toluene as a solvent to prepare a 50% mixture. To the mixture, 20% by weight of 1-hexene was added, and after the reactor was tightened, the reaction temperature was maintained at 270 ° C for 2 hours of thermal polymerization, after which the reaction was terminated. After completion of the reaction, the produced polymer was distilled at 240 ° C for 5 minutes to recover an unreacted fraction, and 55 g of a residual polymer was obtained. 1.5 g of toluene was added to 55 g of the obtained polymer as a hydrogenation solvent to completely dissolve the above polymer, and the mixture was placed in an autoclave of 1 L.

0.2 mol of a palladium catalyst was introduced thereto, and after the reactor was tightened, a hydrogenation reaction was performed for 90 minutes at a hydrogen pressure of 80 bar and a temperature of 230 °C. After completion of the reaction, 50 g of hydrogenated petroleum resin A was prepared by distilling the reaction liquid at 260 ° C for 10 minutes under a vacuum of 10 torr.

Whether the polymer before hydrogenation prepared above and the petroleum resin after hydrogenation were polymerized by measurement using a nuclear magnetic resonance spectrometer (500 NMR of Bruke, 14.1 telsa). That is, the ¹ H-NMR spectrum of the polymer before hydrogenation as measured by ¹ H-NMR showed an increase in peak (Peak) of methyl (-CH ₃ ) derived from 1-hexene between 0.85 ppm and 0.95 ppm. At the same time, a peak increase of -CH ₂ -chain representing 1-hexene between 1.20 ppm and 1.30 ppm is shown, so that DCPD and 1-hexene have been copolymerized.

Further, ¹ H-NMR of the hydrogenated petroleum resin by ¹ H-NMR showed an increase in peak (Peak) of methyl (-CH ₃ ) indicating a 1-hexene between 0.85 ppm and 0.95 ppm, and simultaneously It is shown that the peak value of the -CH ₂ - chain of 1-hexene is between 1.20 ppm and 1.30 ppm, and thus it is understood that the above-mentioned hydrogenated petroleum resin is a resin obtained by copolymerizing DCPD and 1-hexene, and at the same time, It was confirmed that the peak of the double bond between 4.9 ppm and 6.5 ppm was completely removed, whereby it was found that hydrogenation was completely achieved.

At this time, in the measurement method of ¹ H-NMR spectrum, the peak between 0.85 ppm and 0.95 ppm is the methyl group of the olefin, and the peak between 1.20 ppm and 1.30 ppm is the peak of the -CH ₂ - chain of the olefin, 4.9 The peak between ppm and 6.5 ppm is the peak of the double bond of the diene, and it can be confirmed whether the DCPD and the olefin (Olefin) have been copolymerized and whether the hydrogenation reaction has been carried out by comparing the values of the respective peaks.

Preparation Example 2: DCPD / 1- hexene copolymer petroleum resin B is prepared using 35% by weight of DCPD, 15 wt% of 1-hexene, except that, in the same manner and perform the above-described Preparation Example 1 Preparation of hydrogenated oil Resin B.

Preparation Example 3: DCPD / 1- hexene copolymer petroleum resin C was prepared using 25% by weight of DCPD, 25 wt% of 1-hexene, after the above distillation, additionally using a short path distillation apparatus (SPD) at 10 torr of Hydrogenated petroleum resin C was prepared in the same manner as in Preparation Example 1 except that the distillation was carried out at 260 ° C under vacuum.

Preparation Example 4: Preparation of DCPD / 1- octene copolymer petroleum resin D used 15% by weight of 1-octene instead of 1-hexene, except that, in the same manner performed in Example 1 above was prepared and hydrogenated petroleum resin prepared by D.

Preparation Example 5: Preparation of DCPD petroleum resin E used alone DCPD used alone, except that, in the same manner performed in Example 1 above was prepared and hydrogenated petroleum resin prepared E.

Experimental Example 1 : Physical property analysis of petroleum resin After measuring the physical properties of the petroleum resin prepared in the above Preparation Examples 1 to 5, the results are shown in Table 1 below.

(1) Softening point The softening point was measured by the Ring and ball softening method (American Society for Testing Materials (ASTM) E28). The resin was melted and put into an annular mold, placed in a beaker containing glycerin, and then placed in a ring containing a resin, and the temperature was raised by 2.5 ° C per minute to measure the temperature at which the resin melted and the ball fell (softening point). ).

(2) Molecular weight The weight average molecular weight, the number average molecular weight, and the z-average molecular weight in terms of polystyrene were measured by a gel permeation chromatography (GPC) (PL GPC-220). The hydrogenated petroleum resin to be measured was dissolved in 1,2,4-trichlorobenzene (this hydrogenated petroleum resin had a concentration of 1,4,4-trichlorobenzene of 0.34% by weight), and 288 μl was injected into GPC. The mobile phase of GPC was introduced using 1,2,4-trichlorobenzene at a flow rate of 1 mL/min, and analysis was performed at 130 °C. The column is connected in series with two guard columns (Guard column) and one PL 5 μl mixed-D. The measurement was carried out by using a differential scanning calorimeter to raise the temperature to 250 ° C at 10/min, and the analysis was carried out in an N ₂ atmosphere, and the analysis was carried out until the second scan (2nd scan), and the results are shown in Table 1.

The Mn described in the following Table 1 means the number average molecular weight, Mw means the weight average molecular weight, and the Polymer Dispersity Index (PDI) means Mw/Mn.

[Table 1]

Example 1 to Example 3 and Comparative Example 1 : Preparation of Masterbatch and BOPP Film A master batch was prepared using the petroleum resins of Preparation Examples 1 to 5, and process evaluation was performed. The specific method is as follows.

(1) Preparation of Masterbatch 50 g of PP powder resin, 2 g of ruthenium oxide (Rhodia Korea), 3 g of zinc stearate (Sinwon Chemical), and 50 g of petroleum resin of Preparation Examples 1 to 4 Invest in the super mixer in sequence. The above input was stirred at 360 rpm for 10 minutes and then stirred at 200 rpm for 5 minutes. The stirring temperature was 35 °C. The formulation obtained by the above stirring was put into a plastic extruder, and the above formulation was melt-extruded at 220 ° C, followed by cooling at normal temperature. Next, the pellets were cut into particles having an average diameter of 5 mm to obtain a master batch.

(2) Visual evaluation of smoke The volatile organic compounds (VOC) produced in the melt extrusion process of the master batch prepared in the above (1) were visually observed. VOC (olatile Organic Compounds), which are hydrocarbons including carbon and hydrogen, are all organic compounds which are discharged in the form of a gas in the atmosphere, and smoke generated by thermal decomposition of petroleum resin may be included in VOC. The degree of VOC observed by the naked eye is expressed in a scale of 0 to 5. At this time, 0 means that no VOC is generated, and a larger number means that the amount of generation is larger, and after three observations by three observers, the average is recorded. value.

[Table 2]

Referring to Table 2 above, it is understood that when the master batch preparation process of Examples 1 to 4 using the hydrogenated petroleum resin of the present invention is carried out, no smoke is generated or almost no smoke is generated. On the other hand, it was confirmed that the masterbatch of Comparative Example 1 using a petroleum resin obtained by polymerizing DCPD produced severe smoke.

(3) TGA evaluation In order to experimentally support the macroscopic results evaluated in the above (2), the amount of sample reduction corresponding to the time was measured after heating at 240 ° C for 1 hour using a thermogravimetric analyzer, and is shown below. Table 3 and Figure 3. At this time, in Table 3 below, the higher the content of the amount of reduction (Loss), the more the thermal decomposition of the master batch is, and as a result, the amount of VOC generated is high.

[table 3]

Referring to Table 3 and FIG. 3 described above, it was found that the masterbatch of the petroleum resin obtained by polymerizing DCPD of Comparative Example 1 was rapidly thermally decomposed after heating for 10 minutes.

On the other hand, the master batches of Examples 1 to 4 of the present invention exhibited thermal decomposition characteristics within 5% by weight. From the results, it was found that the petroleum resin proposed in the present invention is excellent in thermal stability.

(4) Evaluation of compatibility In order to confirm the compatibility of the polypropylene and the petroleum resin, after the master batch prepared in the above (1) was immersed in toluene, the surface of the master batch was examined by Scanning Electron Microscope (SEM). Image, and the result is shown in Fig. 4.

In the case where the compatibility between the polypropylene and the petroleum resin is poor, a large number of domains in which only the respective components exist are formed in the master batch. At this time, in the surface scanning microscope image, the domain was observed in the state of pores, and the larger the size of the pores and the larger the number, the worse the compatibility.

4(a) and 4(b) are surface scanning microscope images of the master batch prepared in Example 1 and Comparative Example 1, respectively. Referring to Fig. 4, it is understood that the surface of the master batch of Example 1 using petroleum resin is smooth, and therefore the compatibility between polypropylene and petroleum resin is excellent. On the other hand, it was found that a plurality of pores were dispersed throughout the master batch of Comparative Example 1, and thus a large number of domains were generated. From the results, it was found that the compatibility between the polypropylene and the pure petroleum resin was poor.

Experimental Example 2 : Preparation and Evaluation of BOPP Film A BOPP film was produced by using the master batch prepared in the above Examples 1 to 4 and Comparative Example 1, and it was confirmed at this time whether or not smoke was generated in the melt extrusion molding process.

At this time, in the production of the BOPP film, the PP powder was mixed in the weight ratio of 8:2 in the extruder equipped with the T-die, and the above-mentioned Examples 1 to 3 and Comparative Example 1 were respectively carried out. The master batch was then extruded at 270 ° C and passed through a chill roll to prepare an unstretched film. After performing MD extension (elongation ratio of 3.0) and TD extension (extension ratio of 3.0) on the above unstretched film, winding was performed to prepare a BOPP film.

[Table 4]

Referring to Table 4 above, in the case where the conventional petroleum resin was used as in Comparative Example 2, smoke was generated in the process of performing extrusion molding during the production process of the BOPP film.

However, it was confirmed that in Examples 5 to 8 using the master batch including the petroleum resin proposed in the present invention, no smoke was generated or almost no smoke was generated in the melt extrusion molding process.

From such a result, it is understood that the thermal stability of the petroleum resin having an alkyl group can be improved, and as a result, the generation of smoke can be greatly suppressed, thereby improving the working environment and reducing the harmfulness to the human body and the pollution of the ecosystem. [Industrial availability]

The thermoplastic shaped composition including the petroleum resin of the present invention can realize various applications throughout the industry.

no

Fig. 1 is a sequence diagram showing the composition added when a polyolefin-based molded article is produced by the master batch process proposed in the present invention. Fig. 2 is a sequence diagram showing the formation of a BOPP film according to an embodiment of the present invention. Figure 3 is a thermogravimetric analysis (TGA) graph of the masterbatch prepared in the examples and comparative examples. Figure 4 (a) is a surface scanning microscope image of the masterbatch prepared in Example 1. 4(b) is a surface scanning microscope image of the master batch prepared in Comparative Example 1.

Claims (15)

A thermoplastic resin blending composition comprising: a polyolefin-based resin; and a petroleum resin comprising a repeating unit A derived from a hydrogenated diene and a hydrogenated diene derived from an alkyl group having at least one carbon of C1 to C18 Repeat unit B. The thermoplastic resin blending composition according to claim 1, wherein the polyolefin-based resin is one selected from the group consisting of polyethylene, polypropylene, or the like. The thermoplastic resin blending composition according to claim 1, wherein the polyolefin-based resin is a copolymer of any one or more of ethylene and propylene and an α-olefin comonomer. The thermoplastic resin blending composition according to claim 3, wherein the α-olefin comprises a group selected from the group consisting of 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene , 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, isobutylene, 3-methyl-1butene, 2-methyl 1-butene, 3-methyl-1-butene, 4-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4-methyl 1-hexene, 5-methyl-1-hexene, 3,3-dimethyl-1-pentene, 3,4-dimethyl-1-pentene, 4,4-dimethyl One of a group consisting of a combination of 1-pentene and the like. The thermoplastic resin blending composition of claim 1, wherein the diene comprises a combination selected from the group consisting of dicyclopentadiene, pentadiene, butadiene, propadiene, and the like. One of the ethnic groups. The thermoplastic resin blending composition according to claim 1, wherein the petroleum resin has a softening point of 70 ° C to 150 ° C and a weight average molecular weight of 500 g / mol to 5000 g / mol. The thermoplastic resin blending composition according to claim 1, wherein the petroleum resin is prepared by copolymerizing a petroleum resin monomer and an olefin monomer in the presence of a catalyst. The hydrogenation reaction is carried out by adding a hydrogenation catalyst to the copolymer. The thermoplastic resin blending composition according to claim 7, wherein the petroleum resin monomer is selected from the group consisting of a mixed C5 fraction obtained by cracking naphtha, a mixed C9 fraction, a diene, and the like. One of the ethnic groups formed by the mixture. The thermoplastic resin blending composition according to claim 7, wherein the olefin monomer is an α-olefin. The thermoplastic resin blending composition according to claim 9, wherein the α-olefin comprises a group selected from the group consisting of 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene. , 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, isobutylene, 3-methyl-1butene, 2-methyl 1-butene, 3-methyl-1-butene, 4-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4-methyl One of a group consisting of a combination of hex-1-hexene, 5-methyl-1-hexene, and the like. The thermoplastic resin blending composition according to claim 7, wherein the hydrogenation catalyst is one or more selected from the group consisting of nickel, palladium, cobalt, platinum, and rhodium-based metal catalysts. The thermoplastic resin blending composition according to claim 1, which comprises from 1 part by weight to 50 parts by weight of the petroleum resin based on 100 parts by weight of the polyolefin-based resin. A masterbatch comprising the thermoplastic resin blending composition according to any one of claims 1 to 12, wherein the polyolefin-based resin and the petroleum resin are in a ratio of 1:0.5 to 1:1.5 The weight ratio is blended. A biaxially stretched polyolefin-based film forming composition comprising the thermoplastic resin blending composition according to any one of claims 1 to 12, wherein the polyolefin-based resin and the petroleum resin It is blended in a weight ratio of 1:0.01 to 1:0.5. The biaxially stretched polyolefin film-forming composition according to claim 14, wherein the biaxially stretched polyolefin film is a biaxially stretched polypropylene film.