WO2017213402A1 - Thermoplastic resin blend composition - Google Patents

Abstract

The present invention relates to a thermoplastic resin blend composition and, more specifically, to a thermoplastic resin blend composition comprising a polyolefin-based resin and a petroleum resin of which some parts within the molecular structure thereof have C1 to C18 alkyl groups. The composition increases the compatibility between the polyolefin-based resin and the petroleum resin, and such increased compatibility minimizes the generation of fumes during a heating process using polyolefin-based resins and petroleum resins, especially in a masterbatch and film forming process.

Description

Thermoplastic Blend Composition

This application claims the benefit of priority based on Korean Patent Application No. 10-2016-0070506 of June 7, 2016 and Korean Patent Application No. 10-2017-0069842 of June 5, 2017, All content disclosed in the literature is included as part of this specification.

The present invention relates to a thermoplastic resin blend composition capable of minimizing the generation of fumes in the master batch process and the film forming process.

Materials used for film forming are largely divided into natural materials of metal foil such as papers, natural polymer materials, aluminum foil, and synthetic polymer materials represented by polypropylene and polyethylene. Among them, polypropylene is most popular for its excellent transparency, processability, impact resistance, moisture resistance, and mechanical strength.

As a kind of polypropylene film, it is divided into a non-stretched film and a stretched film depending on whether or not it is stretched.

The unstretched film includes CPP film and IPP film (Inflation PP film). These films are excellent in transparency and surface gloss, and have excellent thermal adhesive strength and dimensional stability. They can be used for snack packaging and retort food packaging sealing films. Used as

Oriented film refers to a film stretched in the longitudinal direction and / or width direction in the extrusion and cooling process, divided into a uniaxially stretched film and a biaxially stretched film according to the stretching, the biaxially stretched film is again a BOPP film (Bi -It is divided into Axially Oriented PP Film and IOPP Film (Inflated oriented PP Film). Such a stretched film has characteristics such as mechanical strength and heat resistance, cold resistance, transparency, gas barrier properties such as tensile strength, tensile modulus, impact strength, tensile rupture strength, and bending life, compared to an unstretched film.

In particular, the BOPP film is well received for its excellent mechanical strength, gloss and transparency, excellent chemical resistance, heat resistance, water resistance, durability, etc., and is a film that is growing remarkably in the packaging industry due to increasing demand worldwide. The BOPP film is largely divided into general use and evaporation. General use is divided into production for printing, lamination, white pearl, mat, fiber packaging, tobacco packaging, and the like. Therefore, it is used in the field where gas barrier property and water vapor barrier property are required.

The BOPP film extrudes PP powder through a T-die to produce a primary unstretched sheet, and then stretches the sheet in the machine direction (MD) and the width direction (TD), respectively, to produce a biaxially stretched PP film.

The first BOPP film uses polypropylene alone, but is mixed with various resins or additives to secure various properties according to the application.

Republic of Korea Patent Publication No. 2006-0071687 relates to a lamination BOPP film, in order to increase the rigidity of the film, and to increase the adhesive strength and heat resistance during the lamination coating process, the petroleum resin such as C5 oil, C9 oil or polyterpene polymer A technique of using 3 to 30 parts by weight relative to 100 parts by weight of propylene is disclosed.

According to the manufacturing method of the patent, a polypropylene and petroleum resin is mixed with an extruder and then subjected to an extrusion process. In this case, polypropylene and petroleum resin have low kneading properties, resulting in uneven physical properties of the film or Problems such as deterioration of transparency occurred. In addition, fumes were generated from the petroleum resin due to the heat applied in the extrusion process at 200 to 250 ° C. A fume refers to an aerosol of solid particles produced by the condensation of combustion products in the vapor or gas phase, which is classified as a noxious gas and generates odors. Due to the fume, the work environment is deteriorated and the human hazard is increased as well as an additional problem such as environmental and ecosystem pollution is caused by the fume dispersed in the atmosphere.

Accordingly, a discharge device forcibly discharging the dust collector or the fume for removing the fume has been proposed. This approach has improved the current working environment, but with the increase in process costs, the fundamental problems of environmental and ecosystem pollution remain.

Meanwhile, various molding processes such as an extrusion process or an injection process are used in connection with processing of the polymer, and various plastic products are produced through such a molding process. When imparting color or any special function to the product to be made in the molding process, an additive of a desired function should be incorporated into the basic raw material pellets.

However, since the additives having the above functions are mostly in a powder or liquid state, it is difficult to use them in combination with pellets, and because of poor kneading property, it is difficult to manufacture a product having a desired color or a special function due to poor dispersion of the additives.

Thus, a method using masterbatch has been proposed. The master batch means a pellet prepared by primarily concentrating and dispersing the basic base polymer pellet and the additive to be added at a high concentration in order to increase the kneading property between the polymer pellet and the powder or liquid additive as a raw material. This process is carried out by mixing with the polymer pellets.

The preparation of the master batch proceeds in the order of the mixing process, the extrusion process, the cooling process, and the cutting process for mixing the materials, wherein the extrusion process depends on the T _g of the polymer, usually at 200 to 250 ° C. for polypropylene. Perform.

Therefore, even if a BOPP film is manufactured using polypropylene and petroleum resin using a master batch, since the extrusion process performed at 200 ° C. or higher is essentially performed, fume generation in the aforementioned extrusion process cannot be avoided. .

[Preceding technical literature]

[Patent Documents]

Republic of Korea Patent Publication No. 2006-0071687, 2006.06.27, resin composition for producing biaxially stretched polypropylene film having heat resistance and high rigidity, films and coatings prepared therefrom

In order to solve the above problems, the present inventors have focused on the idea that the fume generation in the extrusion process can be suppressed by improving the low thermal stability of the petroleum resin which causes the fume generation. A petroleum resin in which a linear alkyl group was introduced into was prepared, and the film was prepared by using polyolefin and molding. As a result, it was confirmed that fume generation was reduced in both the master batch process and the molding process, 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.

In addition, another object of the present invention is to provide a master batch for producing a polymer molded article comprising the thermoplastic resin blend composition.

In addition, another object of the present invention is to provide a thermoplastic molding composition comprising the resin blend, for producing a polymer molded article.

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

Wherein the petroleum resin is a hydrogenated diolefin-derived repeating unit (A); And a petroleum resin comprising at least one carbon-derived repeating unit (B) derived from hydrogenated diolefin having C1 to C18 alkyl groups.

In addition, the polyolefin resin and the petroleum resin is characterized in that the blend in a weight ratio of 1: 0.5 to 9.5: 0.5.

The present invention also provides a master batch including the thermoplastic resin blend composition, the polyolefin-based resin and a petroleum resin.

The present invention also provides a composition for forming a biaxially stretched polyolefin-based film including the thermoplastic resin blend composition and comprising a polyolefin-based resin and a petroleum resin.

At this time, the biaxially stretched polyolefin-based film is characterized in that the BOPP (Biaxially oriented polypropylene) film.

In the thermoplastic resin blend composition according to the present invention, by using a petroleum resin containing an alkyl group, the thermal stability can be greatly increased, and the compatibility can be enhanced by providing structural similarity to the repeating units of the polyolefin.

This increased thermal stability and compatibility minimize the generation of fumes in heating processes using polyolefin resins and petroleum resins, especially in master batch and film forming processes.

1 is a flow chart showing the composition added during the production of a polyolefin-based molded article subjected to the master batch process proposed in the present invention.

2 is a flow chart showing BOPP film molding according to one embodiment of the invention.

3 is a thermogravimetric analysis (TGA) graph of master batches prepared in Examples and Comparative Examples.

Figure 4 is a surface scanning microscope image of the master batch prepared in (a) Example 1 and (b) Comparative Example 1.

The thermoplastic resin blend composition according to the present invention has an effect of reducing the generation of fumes in the extrusion process, and includes a polyolefin resin and a petroleum resin for improving adhesiveness and heat resistance.

Each composition is explained in full detail below.

Polyolefin resin is what superposed | polymerized using the olefin monomer and contains polyethylene and polypropylene. The polyethylene may be high density polyethylene (HDPE, high density PE), medium density polyethylene (MDPE, middle density PE), low density polyethylene (LDPE, low density PE), linear low density polyethylene (LLDPE, linear low density PE), poly Propylene is syndiotactic polypropylene (sPP, syndiotactic PP), isotactic polypropylene (iPP, isotactic PP), atactic polypropylene (aPP, atactic PP), and regioirregular polypropylene (rir PP, regioirregular PP) Can be.

These may be homopolymers or ethylene-propylene copolymers, and if necessary, may be used by copolymerizing any one or more monomers of ethylene and propylene with comonomers such as C3-C20 alpha olefins, acetic acid or acrylates.

The alpha olefins are 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1- Linear alpha olefins such as isotoene, isobutylene, 3-methyl-1 butene, 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 Branched alpha olefins, such as -1-pentene, a mixture thereof, etc. can be used individually or in mixture, More preferably, a linear alpha olefin can be used. For example, an ethylene-butylene copolymer, an ethylene-octene copolymer, etc. are possible, and in the case of comonomers of acetic acid and acrylate, an ethylene-vinyl acetate (EVA) copolymer, an ethylene-acrylate copolymer And ethylene-methacrylate copolymers.

Most preferably, the polyolefins presented in the present invention are polypropylenes.

Extrusion process of polyolefin resin is usually carried out at 150 to 300 ℃, more specifically 200 to 250 ℃ for polypropylene, due to the low thermal stability of the petroleum resin used with the polyolefin resin at this temperature, Some chains deteriorate or ring openings and pyrolysis occur in the case of ring compounds, causing solid particles (aerosol state) in the form of fumes to float in the air. These fumes are easily volatilized into the atmosphere, worsening the working environment or affecting human health and ecosystems. Therefore, when the thermal stability of the petroleum resin is increased, the generation of the fume can be reduced.

Increasing the thermal stability can be carried out in a variety of ways, in the present invention, the petroleum resin is used in the hydrogenated form, it is prepared by copolymerizing with other comonomers, that is, olefins to increase the molecular weight and molecular size to be thermodynamically stable.

Specifically, it will be described using a dicyclopentadiene (hereinafter referred to as 'DCPD') of a typical petroleum resin. In Reaction Scheme 1, DCPD has two double bonds, is converted to polydicyclopentadiene through copolymerization with 1-hexene, one of olefins, and is present in a form in which all double bonds are removed by hydrogenation. .

Scheme 1

In this case, DCPD has a ring structure called a cyclopentyl group, and this ring structure is a strain strain caused by an increase and a decrease of a bond angle, and a strain distortion strain caused by overlapping bonds of neighboring atoms ( tortioanl strain), the steric strain, which is a strain caused by the repulsion force caused by atoms close together, has low thermal stability, and the ring is broken by heat applied during the extrusion process. Therefore, in the present invention, the cyclopentyl group has a relatively low strain alkyl group, but by adjusting the number of alkyl groups to increase the molecular weight of the petroleum resin and structural stability at the same time, to increase the thermal stability in the extrusion process to reduce the fume generation .

Specifically, the petroleum resin proposed in the present invention is a hydrogenated petroleum resin containing an alkyl group, preferably a hydrogenated diolefin-derived repeating unit (A); And a petroleum resin having a repeating unit (B) derived from hydrogenated diolefin having at least one carbon having a C1 to C18 alkyl group.

The repeating unit (A) is derived from at least one diolefin selected from the group consisting of dicyclopentadiene, piperylene, butadiene and propadiene.

The alkyl group in the repeating unit (B) is propylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, It is derived from one or more olefins selected from the group consisting of 1-octadecene.

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

Preferably, the petroleum resin includes a repeating unit represented by the following Chemical Formula 1, and a repeating unit represented by the following Chemical Formula 2.

(In Formulas 1 and 2, R1 is H or a methyl group, R2 is an alkyl group of C1 to C18, and 0≤m≤10, and 0≤n≤10)

The petroleum resin has a weight average molecular weight of 500 to 5,000 g / mol, preferably 500 to 3,000 g / mol, a softening point of 70 to 150 ℃, the color (APHA color) is characterized in that 1 to 100. If the weight average molecular weight is less than 500g / mol can not secure the effect of using the petroleum resin, if it exceeds 5000g / mol may be insufficient compatibility. If the softening point is less than 70 ℃ adhesive strength may fall, if it exceeds 150 ℃ is not preferable in terms of difficult application of the manufacturing process.

In addition, when the color (APHA color) exceeds 100 deteriorates the color may act as a disadvantage in manufacturing the adhesive.

In addition, the petroleum resin of the present invention may contain 10 to 40 mol% of components derived from olefins. When the content of the olefin is less than 10 mol%, it may be difficult to express the adhesive performance improvement effect and the heat resistance effect due to the olefin copolymerization, and when it exceeds 40 mol%, the adhesive performance may be deteriorated.

Production of the petroleum resin according to the present invention is not particularly limited in the present invention, a known method may be used. Preferably, it is prepared through a hydrogenation step after thermal polymerization. By thermally polymerizing the comonomer, it is possible to solve the problem of difficult supply of raw materials of C5 olefins used as a main raw material in conventional petroleum resins, and to solve the problem of odor that has not been solved in conventional petroleum resins. In addition, when the petroleum resin is manufactured by thermal polymerization in this way, the catalyst removal step, which is an essential step in the cationic catalyst method, which is a conventional petroleum resin manufacturing method, may not be required, and the yield may be greatly improved to 90% or more. desirable.

Specifically, S1 step of preparing a polymer through a thermal polymerization reaction of a diolefin mixed in a solvent and an olefin having 2 to 20 carbon atoms; And the polymer produced in step S1 is prepared through the step S2 to undergo a hydrogenation reaction by a hydrogenation catalyst.

Hereinafter, each step will be described in detail.

(Step S1)

First, the diolefin is dissolved in a solvent prior to the polymerization reaction with the olefin, and then made into a petroleum resin through a thermal polymerization reaction with the olefin.

In the step S1, the olefin may include one or two or more double bonds, but preferably one, more preferably an alpha olefin.

The alpha olefins are 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1- Linear alpha olefins such as isotoene, isobutylene, 3-methyl-1 butene, 2-methyl-1-butene, 3-methyl-1-butene, 4-methyl-1-butene, 3-methyl-1-pentene , Branched alpha olefins such as 4-methyl-1-pentene, 4-methyl-1-hexene, 5-methyl-1-hexene, and mixtures thereof may be used alone or in combination. More preferably, linear alpha Olefin can be used, most preferably 1-hexene, 1-octene, 1-decene and 1-dodecene in terms of price or supply and demand.

In this case, the solvent may be used without limitation as long as it is a solvent capable of dissolving the diolefin, preferably toluene, methylene chloride, hexane, xylene, trichloro benzene, alkyl benzene, and the like. In addition, the solvent may be used without particular limitation as long as the content is sufficient to dissolve the diolefin and the olefin, and in general, may be 2 to 10 moles with respect to 1 mole of the diolefin.

The thermal polymerization reaction is performed at a temperature of 200 to 320 ° C. for 0.5 to 4 hours, and when the thermal polymerization is performed at 200 ° C. or less than 0.5 hour, the yield may be low, and heat may be higher than 320 ° C. or 4 hours. When carrying out the polymerization, a gel may be formed.

(S2 step)

Next, step S2 is performed such that the polymer prepared in step S1 undergoes a hydrogenation reaction by a hydrogenation catalyst.

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

It is preferable to use 0.001-0.5 mol with respect to 1 mol of diolefins for the said hydrogenation catalyst. If the amount is less than 0.001 mole per 1 mole of diolefin, the reactivity may be insufficient, and if it exceeds 0.5 mole, there is a disadvantage that it is not economical by using a large amount of catalyst.

The S2 step may be hydrogenated at a temperature of 150 to 300 ℃ at a pressure of 50 to 150 bar. If the reaction is performed in excess of 150 bar or in excess of 300 ° C., the molecular structure may be destroyed by severe reaction conditions, and in the case of performing the reaction at less than 50 bar or less than 150 ° C., the hydrogenation reaction is sufficiently performed. This can cause problems.

The reaction product obtained from the hydrogenation reaction of step S2 may be carried out in a subsequent purification process.

The purification process is to remove and concentrate unreacted raw materials, reaction by-products, solvents, etc. present in the reaction product obtained in the above-described steps, and various methods commonly used in the process of preparing petroleum resin may be used. In one example, distillation, recrystallization, extraction, sublimation, or chromatography is carried out in one of the processes, preferably using a distillation method.

Examples of the distillation method used in the purification process may be a variety of known methods such as simple distillation, fractional distillation, azeotropic distillation, vacuum distillation, may be preferably vacuum distillation.

In this case, the petroleum resin proposed in the present invention may further perform vacuum distillation using a short path distillation after performing normal vacuum distillation in the refining process to improve thermal stability.

In this case, the short distillation unit refers to equipment used for purification and concentration of substances that are very vulnerable to heat or substances having high molecular weight and high boiling point, which are difficult to separate.There is a condenser inside the evaporator unlike the conventional distillation equipment. Due to the short distance between the evaporation zone and the condensation zone, substances with low thermal stability can be removed in a short time, thereby increasing distillation efficiency. Therefore, the petroleum resin according to the present invention can be produced by petroleum resin with improved thermal stability by effectively separating the material having a low molecular weight that causes fumes due to heat instability using the short distillation apparatus.

The single distillation unit is MYERS-VACUUM, INCON, CHEMTECH SERVICE, ASAHI, ULVAC, VTA, VTA, UIC products. Is available, but is not limited to such.

For example, the temperature of the condenser when the distillation using the single distillation apparatus is 25 to 200 ℃, the distillation temperature is 150 to 300 ℃, the vacuum may be carried out under the conditions of 0.05 to 25 torr.

As described above, the polyolefin resin and the petroleum resin may be applied to various fields, and the petroleum resin may be used in an amount of 1 to 50 parts by weight based on 100 parts by weight of the polyolefin resin. It is also changeable.

In particular, the thermoplastic resin blend composition including the polyolefin resin and the petroleum resin proposed in the present invention can be molded into various products of the polyolefin system. At this time, the polyolefin-based molded article is prepared through a step of preparing a master batch of polyolefin-based resin and petroleum resin in a predetermined ratio and then mixing and molding the polyolefin-based resin as a raw material.

The use of a master batch in the production of a polyolefin-based molded article can have the effect of further improving the quality of the molded article and increasing productivity, and by adding an additive in the master batch in advance, thereby improving flowability in the molding process.

1 is a flow chart showing the composition added during the production of a polyolefin-based molded article subjected to the master batch process proposed in the present invention.

Referring to FIG. 1, a polyolefin-based resin and a petroleum resin are mixed to perform an extrusion process, and cooled to prepare a master batch.

The content of the polyolefin resin and the petroleum resin for preparing the master batch is such that the weight ratio is 1: 0.5 to 1: 1.5, preferably 1: 1. If the content of the petroleum resin is in excess of the above range, it is not easy to mix with the polyolefin-based resin, and conversely, if the amount of the petroleum resin is less than the above range, the effect of using the petroleum resin cannot be expected.

The polyolefin-based resin for masterbatch may be a powder, pellet, plate, or flake type ground using a wet or dry ball mill grinder, and is not particularly limited in the present invention.

The mixing may be performed through an extruder during the extrusion process, or may be performed through a conventional stirrer before the extrusion process. In this case, the mixer may be a mixer equipped with a stirrer, a plasticizer (Brabender Plasticorder), a Banbury Mixer, a Kneader, a Roll Mill, a Henschel Mixer, a V Blender, a Tumbler Blender, or a Ribbon Blender. Can be.

The extrusion process is performed at a temperature of 170 to 200 ° C. using a twin-screw extruder and a single-screw extruder, and the melt obtained after melt extrusion is cooled to room temperature and then pelletized. Finish up and get a master batch.

In particular, the master batch of the present invention uses the petroleum resin as described above, so that the fumes generated when using the conventional petroleum resin are hardly generated.

The master batch may be in the form of pellets or plates, flakes, and various other shapes are possible.

The mixing or extrusion process may further add additives known in the film art, such as pigments, fillers, antioxidants, gelling agents, ultraviolet absorbers, antistatic agents, lubricants, antiblocking agents, impact modifiers, dispersants, plasticizers and the like. Can be. At this time, the selection and the content of the additives may be selected by a person having ordinary skill in the art, and preferably adjusted to be 10% by weight or less in the final resin composition.

In one example, the filler may be titanium oxide, barium sulfate, barium titanate, calcium carbonate, silica, talc, clay and mica powder, and the like, preferably silica. In addition, a lubricant such as metal stearate such as zinc stearate or calcium stearate can be used.

Next, the prepared master batch is mixed again with a polypropylene resin in a predetermined ratio to prepare a composition for thermoplastic molding, and performs a molding process for manufacturing various products thereof.

In particular, the molding composition including the petroleum resin of the present invention hardly generates fumes generated when the conventional petroleum resin is used in the molding process, and has various advantages, such as ease of processing and improvement of product quality, by using a master batch. Can be obtained.

The molding process may be any thermoforming process, and may vary depending on the application field of the polyolefin resin. For example, various molding processes such as extrusion molding, blow molding, injection molding, compression molding, vacuum molding, and mold molding may be used. Can be applied. In this case, the product form of the thermoplastic resin blend composition finally obtained may vary according to the molding process.

According to one embodiment of the present invention, by using the master batch, for example, a biaxially stretched polyol peffin-based film, in particular a biaxially oriented polypropylene (BOPP) film, may be prepared by a tenter method. Can be.

Figure 2 is a flow chart showing a manufacturing process of the BOPP film using a petroleum resin according to the present invention.

Referring to FIG. 2, a polypropylene resin and a petroleum resin in a powder state are subjected to a melt extrusion process and cooled to prepare a master batch. At this time, the polypropylene resin and the petroleum resin are mixed so as to have a weight ratio of 1: 0.5 to 1: 1.5, preferably 1: 1.

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

At this time, the composition for molding the BOPP film is blended so that the polypropylene resin and the petroleum resin in the composition is 1: 0.01 to 1: 0.5, preferably 1: 0.05 to 1: 0.2 in order to produce a BOPP film. The mixing may be performed before the melt extrusion molding process through a separate mixer similar to the master batch.

Next, the BOPP film molding composition is 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 then fixed through the stretching process, the stretching process and the cooling process, and then produced by winding and cutting.

The stretching step is performed at the time of manufacturing the stretched film, and may be excluded at the time of preparing the stretched film.

As an example, as shown in FIG. 2, when manufacturing a BOPP film which is a biaxially stretched film, MD (machine direction) stretching process and TD (width direction) stretching process are performed sequentially. In the case of a uniaxially stretched film, only one of the stretching processes is performed.

This stretching process is carried out in consideration of the T _g and T _m of the polypropylene as a raw material to be used.

Preferably, the BOPP film has an MD stretching (machine direction stretching) ratio of at least 4.0 times, preferably at least 5.0 times, and at least 4.0 times, preferably at least 5.0 times, more preferably at least 8.0 times, TD stretching (lateral direction). Stretching) ratio. The draw ratio is a ratio of the width of the first unstretched sheet to the width of the stretched sheet obtained after stretching, and corresponds to a draw ratio at which the film can be appropriately elongated without rupture of the film, and is a range used for normal commercial use of BOPP.

Subsequently, the cooling process performed is for fixing the stretched state of the film, and generally means a process of lowering the temperature to room temperature.

The stretched film is wound up using a winding roll and then cut into an appropriate size according to the shape of the product to produce a product.

The BOPP film produced through the above steps may be modified in various ways depending on the raw material and the manufacturing process used, and the thickness thereof may generally be 50 μm or less, preferably 40 μm or less.

In addition, the BOPP film can be produced in various forms, such as CPP film, IPP film, IOPP film, in addition to the BOPP film according to the process change. The polyolefin-based film thus prepared can be applied to various industrial fields.

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

Production Example  One: DCPD  / One- Hexene Copolymerized Petroleum Resin  A manufacture

30% by weight of dicyclopentadiene (DCPD) in a 1 L autoclave Dissolve to form a mixture at 50% concentration, add 20% by weight of 1-hexene to it, and after the reactor is fastened, the reaction temperature is maintained at 270 ° C. for 2 hours, followed by thermal polymerization. Terminated. After the reaction was completed, the resulting polymer was distilled at 240 ° C. for 5 minutes to prevent unreacted reaction. The oil was recovered and 55 g of remaining polymer was obtained. Toluene was added 1.5 times as a hydrogenated solvent to 55 g of the polymer obtained, completely dissolved, and 1 L autoclave was charged.

0.2 mol of a palladium catalyst was added thereto, and after the reactor was fastened, a hydrogenation reaction was performed at a hydrogen pressure of 80 bar and a temperature of 230 ° C. for 90 minutes. After the reaction was completed, the reaction product was distilled at 260 DEG C for 10 minutes in a vacuum of 10 torr to prepare 50 g of hydrogenated petroleum resin A.

Whether the polymer prepared before the hydrogenation and the petroleum resin after the hydrogenation was polymerized was measured by using a nuclear magnetic resonance spectrometer (500 NMR, Bruker 14.1 telsa). In other words, the 1H-NMR spectrum results confirming the structure of the polymer before hydrogenation showed that the peak indicating the methyl group (-CH ₃ ) derived from 1-hexene between 0.85 and 0.95 ppm was increased in the ¹ H-NMR measurement. It can be confirmed that the peak indicating the -CH ₂ -chain of 1-hexene between 1.20 and 1.30 ppm is increased, indicating that DCPD and 1-hexene are copolymerized.

In addition, the ¹ H-NMR spectrum result confirming the structure of the petroleum resin after hydrogenation shows that the peak representing the methyl group (-CH ₃ ) of 1-hexene between 0.85 and 0.95 ppm is increased in the ¹ H-NMR measurement. At the same time, the peak indicating the -CH ₂ -chain of 1-hexene between 1.20 and 1.30 ppm increases, indicating that DCPD and 1-hexene are copolymerized resins, and at the same time, the double bond peak between 4.9 and 6.5 ppm is completely removed. By confirming that the hydrogenation can be seen that complete.

At this time, in the method of measuring the ¹ H-NMR spectrum, the peak between 0.85 and 0.95 ppm is the methyl group of the olefin, and the peak between 1.20 and 1.30 ppm is the peak of the -CH ₂ -chain of the olefin and the peak between 4.9 and 6.5 ppm is As a peak of the double bond of the diolefin, by comparing the value of each peak it can be confirmed whether the DCPD and the olefin (Olefin) is copolymerized and the hydrogenation reaction proceeded.

Production Example  2: DCPD  /One- Hexene Copolymerized Petroleum Resin  B manufacturing

Hydrogenated petroleum resin B was prepared in the same manner as in Preparation Example 1, except that DCPD was used in an amount of 35% by weight and 15% by weight of 1-hexene.

Production Example  3: DCPD / One- Hexene Copolymerized Petroleum Resin  Manufacture of C

DCPD 25% by weight, the content of 1-hexene was used at 25% by weight, after the distillation was further distilled to 260 ℃ under vacuum of 10torr using a single distillation apparatus (SPD), the preparation example Hydrogenated petroleum resin C was prepared in the same manner as 1.

Production Example  4: DCPD / One- Octene Copolymerized Petroleum Resin  Manufacture of D

Hydrogenated petroleum resin D was prepared in the same manner as in Preparation Example 1, except that 15 wt% of 1-octene was used instead of 1-hexene.

Production Example  5: DCPD  Exclusive Petroleum resin  Manufacture of E

Except for using DCPD alone, the same as in Preparation Example 1 Hydrogenated Petroleum Resin E was prepared.

Experimental Example  One: Petroleum resin  Physical property analysis

After measuring the physical properties of the petroleum resin prepared in Preparation Examples 1 to 5, the results It is shown in Table 1 below.

(1) softening point

The softening point was measured by Ring and ball softening method (ASTM E 28). Melt the resin into a ring-shaped mold, place it in a beaker with glycerin, The ball was placed on the ring containing the resin, and the temperature was raised by 2.5 ° C per minute to measure the temperature (softening point) when the resin melted and the ball dropped.

(2) molecular weight

Polystyrene reduced weight average molecular weight, number average molecular weight and z-average molecular weight were measured by gel permeation chromatography (GPC) (PL GPC-220). The hydrogenated petroleum resin to be measured was dissolved in 1,2,4-trichlorobenzene so as to have a concentration of 0.34% by weight, and 288 µl was injected into GPC. The mobile phase of GPC used 1,2,4-trichlorobenzene and flowed in at a flow rate of 1 mL / min and the analysis was performed at 130 ° C. The column was connected in series with two Guard columns and one PL 5μl mixed-D. The detector was measured by increasing the temperature to 250 ° C. at 10 / min using a differential scanning calorimeter, and performing analysis under N 2 atmosphere to analyze up to 2nd scan.

In Table 1, Mn means number average molecular weight, Mw means weight average molecular weight, and PDI means Mw / Mn.

Softening point (℃) Molecular Weight (g / mol) PDI Mn Mw Mz Preparation Example 1 125 489 658 982 1.35 Preparation Example 2 125 573 757 1137 1.37 Preparation Example 3 125 561 760 1046 1.35 Preparation Example 4 125 560 781 1160 1.39 Preparation Example 5 125 254 489 952 1.93

Example  1 to 3 and Comparative example  1: master batch and so on BOPP  Film manufacturing

The master batch was produced using the petroleum resin of the manufacture examples 1-5, and process evaluation was performed. The specific method is as follows.

(1) master batch manufacturing

50 g of PP powder resin, 2 g of silica (Rhodia Korea), 3 g of zinc stearate (Shin-Won Chem), and 50 g of petroleum resin of Production Examples 1 to 4 were sequentially added to the super mixer. The input was stirred at 360 rpm for 10 minutes and then at 200 rpm for 5 minutes. The stirring temperature was 35 ° C. The compound obtained by the stirring was introduced into a plastic extruder and melt-extruded at 220 ° C., followed by cooling at room temperature. Next, it pelletized with the pellet of average diameter 5mm, and obtained the master batch.

(2) Hume visual evaluation

The VOC which generate | occur | produces in the melt-extruding process of the masterbatch manufactured by said (1) was visually observed. VOCs (olatile organic compounds) are hydrocarbons composed of carbon and hydrogen, and all organic compounds emitted in the form of gases from the atmosphere. The fumes generated by pyrolysis of petroleum resins can be included in VOCs. The degree of VOC observed with the naked eye is indicated by a grade of 0 to 5, where 0 means no VOC is generated, and the higher the number is, the higher the generation is. Described.

Used Petroleum Resin Hume visual evaluation Example 1 Petroleum resin A of Preparation Example 1 0 Example 2 Petroleum resin B of Preparation Example 2 One Example 3 Petroleum Resin C of Preparation Example 3 0 Example 4 Petroleum resin D of Preparation Example 4 One Comparative Example 1 Petroleum resin E of Preparation Example 5 5

Looking at Table 2, it can be seen that in the case of the master batch manufacturing process of Examples 1 to 4 using the hydrogenated petroleum resin according to the present invention, there is little or no fume. In comparison, the master batch of Comparative Example 1 using a petroleum resin polymerized with DCPD confirmed that the fume was serious.

(3) TGA  evaluation

In order to experimentally support the visual results evaluated in the above (2), after heating at 240 ℃ for 1 hour using a thermogravimetric analyzer, the sample reduction with time was measured, shown in Table 3 and FIG. . At this time, the higher the content of Loss in Table 3 means that the pyrolysis of the master batch occurs a lot, and as a result, the higher the amount of VOCs.

Used Petroleum Resin Loss (%), TGA Analysis Example 1 Petroleum resin A of Preparation Example 1 2.2 Example 2 Petroleum resin B of Preparation Example 2 4.30 Example 3 Petroleum Resin C of Preparation Example 3 2.0 Example 4 Petroleum resin D of Preparation Example 4 4.10 Comparative Example 1 Petroleum resin E of Preparation Example 5 14.60

Referring to Table 3 and FIG. 3, in the case of the master batch using the petroleum resin polymerized with DCPD of Comparative Example 1, it can be seen that rapid thermal decomposition occurs 10 minutes after heat application.

In comparison, the master batches of Examples 1 to 4 according to the present invention showed pyrolysis characteristics within 5% by weight, and it can be seen from the results that the petroleum resin proposed in the present invention has excellent thermal stability.

(4) compatibility evaluation

In order to confirm the compatibility between polypropylene and petroleum resin, the master batch prepared in (1) was immersed in toluene, and the surface scanning electron microscope ((Scanning Electron Microscope, SEM) image of the master batch was measured and the result was obtained. It is shown in Figure 4 below.

Poor compatibility between polypropylene and petroleum resin creates large amounts of domains consisting only of each composition in the master batch. At this time, the domain is observed in the pore (pore) state in the surface scanning microscope image, the larger the size, the larger the number means that the compatibility is poor.

Figure 4 is a surface scanning microscope image of the master batch prepared in (a) Example 1 and (b) Comparative Example 1. Referring to FIG. 4, it can be seen that the surface of the master batch of Example 1 using petroleum resin has a smooth surface and excellent compatibility with polypropylene and petroleum resin. In comparison, in the master batch of Comparative Example 1, it can be seen that a large amount of domains are generated as a plurality of pores are dispersed as a whole, and from this result, the compatibility between polypropylene and simple petroleum resin is not good. have.

Experimental Example 2: Fabrication and Evaluation of BOPP Film

BOPP using the master batch prepared in Examples 1 to 4 and Comparative Example 1 A film was produced, and at this time, it was confirmed whether or not the fume generated in the melt extrusion process.

At this time, the production of BOPP film PP powder and an extruder equipped with a T-die, Example 1 To 3 and Comparative Example 1, respectively, in a weight ratio of 8: 2, followed by mixing at 270 ° C. After extruding, the resultant was passed through a cooling roll to produce an unstretched film. MD the unstretched film Stretching (stretching ratio 3.0) and TD stretching (stretching ratio 3.0) were performed, followed by winding to prepare a BOPP film.

Master batch used Hume visual evaluation Example 5 Masterbatch of Example 1 0 Example 6 Masterbatch of Example 2 One Example 7 Masterbatch of Example 3 0 Example 8 Masterbatch of Example 4 One Comparative Example 2 Master batch of comparative example 1 5

Referring to Table 4, it can be seen that when using a conventional petroleum resin as in Comparative Example 2 in the extrusion process performed during the manufacturing process of the BOPP film, the fume is generated.

However, in Examples 5 to 8 using the master batch including the petroleum resin proposed in the present invention, it was confirmed that no or little fume occurred in the melt extrusion process.

From these results, it was found that the thermal stability of the petroleum resin having an alkyl group can be improved, and as a result, the work environment can be improved and the body and ecosystem pollution can be reduced by greatly suppressing the generation of fumes.

Thermoplastic molding compositions comprising petroleum resins according to the present invention are capable of various applications throughout the industry.

Claims (15)

Polyolefin resin, and Hydrogenated diolefin derived repeating unit (A); And a petroleum resin comprising at least one carbon-derived repeating unit (B) derived from hydrogenated diolefin having a C1 to C18 alkyl group. The method of claim 1, The polyolefin resin is a thermoplastic resin blend composition, characterized in that one selected from the group consisting of polyethylene, polypropylene, or copolymers thereof. The method of claim 1, The polyolefin resin is a thermoplastic resin blend composition, characterized in that the copolymer of any one or more monomers of ethylene and propylene and an alpha olefin comonomer. The method of claim 3, The alpha olefin is 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1- Itocene, isobutylene, 3-methyl-1 butene, 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-1-pentene and A thermoplastic resin blend composition comprising one selected from the group consisting of a combination of these. The method of claim 1, The diolefin is a thermoplastic resin blend composition comprising one selected from the group consisting of dicyclopentadiene, piperylene, butadiene, propadiene and combinations thereof. The method of claim 1, The petroleum resin has a softening point of 70 to 150 ℃, the weight average molecular weight (Mw) is a thermoplastic resin blend composition, characterized in that 500 to 5000 g / mol. The method of claim 1, The petroleum resin is prepared by copolymerizing a petroleum resin monomer and an olefin monomer in the presence of a catalyst to prepare a copolymer, and then performing a hydrogenation reaction by adding a hydrogenation catalyst. The method of claim 7, wherein The petroleum resin monomer is a thermoplastic resin blend composition, characterized in that selected from the group consisting of mixed C5 fraction, mixed C9 fraction, diolefin and mixtures thereof obtained from naphtha cracking. The method of claim 7, wherein The olefin monomer is a thermoplastic resin blend composition, characterized in that the alpha olefin. The method of claim 9, The alpha olefin is 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1- Itocene, isobutylene, 3-methyl-1 butene, 2-methyl-1-butene, 3-methyl-1-butene, 4-methyl-1-butene, 3-methyl-1-pentene, 4-methyl- A thermoplastic resin blend composition comprising one selected from the group consisting of 1-pentene, 4-methyl-1-hexene, 5-methyl-1-hexene, and combinations thereof. The method of claim 7, wherein The hydrogenation catalyst is a thermoplastic resin blend composition, characterized in that at least one selected from nickel, palladium, cobalt, platinum and rhodium-based metal catalysts. The method of claim 1, The thermoplastic resin blend composition is a thermoplastic resin blend composition comprising 1 to 50 parts by weight of petroleum resin based on 100 parts by weight of polyolefin resin. A thermoplastic resin blend composition according to any one of claims 1 to 12, Master batch characterized in that the polyolefin resin and petroleum resin is blended in a weight ratio of 1: 0.5 to 1: 1.5. A thermoplastic resin blend composition according to any one of claims 1 to 12, A composition for biaxially stretched polyolefin-based film molding, wherein the polyolefin resin and the petroleum resin are blended in a weight ratio of 1: 0.01 to 1: 0.5. The method of claim 14, The biaxially stretched polyolefin-based film is a biaxially stretched polypropylene film, the composition for forming a biaxially stretched polyolefin-based film.

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