KR101750752B1

KR101750752B1 - High-heat resistant and high-gas barrier composite resin and preparation method thereof

Info

Publication number: KR101750752B1
Application number: KR1020150143896A
Authority: KR
Inventors: 서종철; 김도완
Original assignee: 연세대학교 원주산학협력단
Priority date: 2015-10-15
Filing date: 2015-10-15
Publication date: 2017-07-11
Also published as: KR20170044336A

Abstract

More particularly, the present invention relates to a high heat resistance and high shear composite resin, and more particularly, to a method for producing a high heat resistant and high shear polyketone composite resin by adding a polyketone to a polymer resin, It can be applied to advanced packaging materials, containers, and films.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-temperature resistant and high-

The present invention relates to a high heat resistant and high shear composite resin and a method for producing the same. More specifically, the present invention relates to a method for producing a high heat resistant and high shear polyketone composite resin by adding a polyketone to a polymer resin, The present invention relates to a technique for application to an improved packaging material and container.

BACKGROUND ART Polyethylene terephthalate (PET) is a typical polyester resin and has excellent strength, heat resistance, transparency, chemical resistance, electrical insulation, and is used for various purposes such as packaging materials, films, and molded products. Particularly, polyethylene terephthalate has a high glass transition temperature of about 78 to 80 DEG C, so that when the container is made of polyethylene terephthalate, it is excellent in transparency and crystallization speed and is suitable for use as a beverage container. However, There is a problem that the heat resistance is deteriorated and the dimensional stability is lowered (Patent Document 1).

In order to solve such a problem, there has been proposed a method of imparting heat resistance without reducing the transparency by heat treating the neck of the bottle in a separate process from the process of thermally fixing the body portion of the polyethylene terephthalate container The production cost is increased and the productivity is lowered (Patent Document 2).

A method of blending a polycarbonate having excellent impact resistance and heat resistance has also been proposed. However, when simply blending polyethylene terephthalate and polycarbonate under high temperature and high pressure, there is a problem that both resins undergo ester exchange reaction to produce a copolymer. That is, the resulting copolymer is present between the interface of the polyethylene terephthalate and the polycarbonate to lower the crystallinity of the polyethylene terephthalate, thereby inhibiting the chemical resistance, electrical insulation, mechanical properties and the like inherent properties of polyethylene terephthalate (Patent Document 3).

On the other hand, the polyketone has a structure in which a half unit derived from carbon monoxide and a repeating unit derived from an ethylenically unsaturated compound are substantially alternately linked. Such a polyketone is excellent in mechanical properties and thermal properties, and is excellent in abrasion resistance and chemical resistance, and is used as a material useful as resins, fibers and films of high strength and high heat resistance (Patent Document 4).

Accordingly, the present inventors have completed the present invention by focusing on the fact that a polyketone-containing high heat-resistant and high-gas barrier polyketone composite resin can be produced, which can be applied as a packaging material and a container having improved heat resistance and gas barrier properties It came.

Patent Document 1. Korean Patent Publication No. 10-1018199 Patent Document 2. US Patent No. 4836971 Patent Document 3. Korean Patent Publication No. 10-2008-0059893 Patent Document 4: Korean Patent Publication No. 10-0668572

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a highly heat-resistant and high-shear polyketone composite resin with greatly improved heat resistance and gas barrier property, and a method of manufacturing the same.

According to an aspect of the present invention, there is provided a polyketone composite resin comprising a first polymer resin, a polyketone, and an additive mixed together, wherein the first polymer resin includes PET (polyethylene terephthalate), COC (Polyethylene terephthalate), PEI (polyetherimide), PP (polypropylene), polyvinyl alcohol (polyvinyl alcohol), polyvinyl alcohol ), PPE (polypropylene ether), PPS (polyphenylene sulfide), PVC (polyvinyl chloride), PVDF (polyvinylidene), and mixtures thereof; Wherein the polyketone further comprises 0.1 to 80% by weight based on 100% by weight of the first polymer resin; The additives may be selected from the group consisting of hydrophobic zeolites, hydrophilic zeolites, clays, graphite, calcium carbonate, titania, zinc oxide, silane surface treatment agents, thermoplastic polyurethanes, styrene block copolymers, thermoplastic polyester-polyether elastomers, PE- Wax), PE-g-MA (polyethylene grafted maleic anhydride), and mixtures thereof; Wherein the additive further comprises 0.1 to 5% by weight based on 100% by weight of the first polymer resin.

The first polymer resin is PET; Wherein the additive is a mixture of PE-WAX and PE-g-MA in a weight ratio of 1: 0.9-1.1.

And the viscosity of the first polymer is 0.6 to 0.9 dl / g.

Wherein the polyketone composite resin has a glass transition temperature of 90 to 99 占 폚.

The present invention also provides a multilayer film comprising a first PE-based polymer layer / the polyketone composite resin layer / a second PE-based polymer layer.

Wherein the first PE-based polymer and the second PE-based polymer are the same or different and each independently selected from PE (polyethylene), HDPE (high density polyethylene), LDPE (low density polyethylene) and linear low density polyethylene (LLDPE) And is characterized by being either one.

(A) drying the first polymer resin and the polyketone at 120 to 140 占 폚; (B) 0.1 to 80% by weight of the polyketone relative to 100% by weight of the first polymer resin, and 100% by weight of the first polymer resin in a twin-screw extruder, And the additive is added in an amount of from 0.1 to 5% by weight, respectively, and the sections 7 and 6 near the inlet are heated to 90 to 110 ° C and 170 to 190 ° C respectively, and from the section 5-1 to the headers close to the outlet, And heating and then melting and extruding the polyketone composite resin at 280 占 폚; Wherein the first polymer resin is any one selected from the group consisting of PET, COC, PVA, EVOH, PA, PE, PES, PEI, PP, PPE, PPS, PVC, PVDF and mixtures thereof; The additive may be selected from the group consisting of hydrophobic zeolite, hydrophilic zeolite, clay, graphite, calcium carbonate, titania, zinc oxide, silane surface treatment agent, thermoplastic polyurethane, styrene block copolymer, thermoplastic polyester-polyether elastomer, PE- g-MA, and mixtures thereof. The present invention also provides a method for producing the polyketone composite resin.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a highly heat-resistant and high-shear polyketone composite resin with greatly improved heat resistance and gas barrier properties and a method for producing the same.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a photograph showing a temperature sensor of a twin-screw extruder used in the production of a PET (polyethylene terephthalate) / POK (polyketone) composite resin according to Example 1 of the present invention and sections 1 to 7 and a header section;
2 is a graph showing a glass transition temperature measurement result using a differential scanning calorimeter of a PET (polyethylene terephthalate) / POK (polyketone) composite resin prepared from Example 1 of the present invention.
3 is a graph showing the oxygen permeability (OTR) of a multilayer film comprising HDPE (high density polyethylene) layer / COC_POK (cyclic olefin polymer_polyketone) composite resin layer / LLDPE (linear low density polyethylene) layer prepared from Example 2 of the present invention , And Oxygen transmission rate.
4 is a graph showing the results of analysis of ultraviolet barrier property of the multilayer film including the HDPE layer / COC_POK composite resin layer / LLDPE layer prepared in Example 2 of the present invention.

In the following, various aspects and various embodiments of the present invention will be described in more detail.

The present invention relates to a polyketone composite resin comprising a first polymer resin, a polyketone (POK), and an additive mixed together, wherein the first polymer resin comprises PET (polyethylene terephthalate), COC (cyclic olefin polymer) (PVA), EVOH (ethylene vinyl alcohol), PA (polyamide), PE (polyethylene), PES (polyether sulfone), PEI (polyether imide), PP (polypropylene), PPE ), PPS (polyphenylene sulfide), PVC (polyvinyl chloride), PVDF (polyvinylidene fluoride), and mixtures thereof; Wherein the polyketone further comprises 0.1 to 80% by weight based on 100% by weight of the first polymer resin; The additives may be selected from the group consisting of hydrophobic zeolites, hydrophilic zeolites, clays, graphite, calcium carbonate, titania, zinc oxide, silane surface treatment agents, thermoplastic polyurethanes, styrene block copolymers, thermoplastic polyester-polyether elastomers, PE- Wax), PE-g-MA (polyethylene grafted maleic anhydride), and mixtures thereof; Wherein the additive further comprises 0.1 to 5% by weight based on 100% by weight of the first polymer resin. Particularly, when the range of the polyketone is less than 0.1% by weight, the abrasion resistance may be deteriorated, and when it is more than 80% by weight, the glass transition temperature may be lowered sharply. The amount of the polyketone can be adjusted depending on the product group to which the polyketone is applied. When it is applied to a heat-resistant container, it is preferably 0.1 to 20%, and when it is applied to a barrier film, it is preferably 0.1 to 80%. If the range of the additive is less than 0.1% by weight, heat stability and mechanical strength are insufficient. When the additive is more than 5% by weight, A problem may arise in that the production cost may increase. It is more preferable that the additive is added in an amount of 0.5 wt% to 3 wt% in accordance with the compatibility and application.

The first polymer resin is PET; Wherein the additive is a mixture of PE-WAX and PE-g-MA in a weight ratio of 1: 0.9-1.1. Particularly, when the first polymer resin is PET, when all of the PE-WAX and PE-g-MA are added at a weight ratio of 1: 0.9-1.1, the first polymer resin and the polyketone It was confirmed that the dispersion and bonding effect can be improved during polymerization. Specifically, the dispersion and bonding effect during polymerization of the first polymer resin and the polyketone are not improved in the case where any one of the two additives is missing, the weight ratio is out of range, or the first polymer is not PET Respectively. It has also been found that addition of 1 to 3% by weight of a thermoplastic elastomer such as a thermoplastic polyurethane, a styrene block copolymer, and a thermoplastic polyester-polyether elastomer can further improve the compatibility, dispersion and bonding effect.

And the viscosity of the first polymer is 0.6 to 0.9 dl / g. If the viscosity is less than 0.6 dl / g, the molecular weight may be low and the fatigue resistance may be deteriorated. If the viscosity is more than 0.9 dl / g, the process stability and dispersibility may be deteriorated.

Wherein the polyketone composite resin has a glass transition temperature of 90 to 99 占 폚. The glass transition temperature is a value higher than 85.47 ° C, which is the glass transition temperature of a conventional PET resin, so that the polyketone composite resin can be efficiently applied to heat resistant packaging materials and containers.

The present invention also provides a multilayer film comprising a first PE-based polymer layer / the polyketone composite resin layer / a second PE-based polymer layer. When the multilayered film according to the present invention is applied to a product for ultraviolet ray shielding, POK (polyketone) is a polymer resin, whereas titanium, zinc, zirconium and iron used for ultraviolet ray blocking are inorganic substances. It is possible to improve the durability of the extruder used in the production process and the like and the economic effect of the process.

Wherein the first PE-based polymer and the second PE-based polymer are the same or different and each independently selected from PE (polyethylene), HDPE (high density polyethylene), LDPE (low density polyethylene) and linear low density polyethylene (LLDPE) Which one; Preferably, the first PE-based polymer is HDPE; The second PE-based polymer is LLDPE. It was confirmed that the first PE-based polymer was HDPE and the second PE-based polymer was LLDPE, and that the multilayered film according to the present invention was excellent in gas barrier properties. The multilayered film according to the present invention is generally used as a material for containers such as mayonnaise, kochujang, (Ethylene vinyl alcohol), and nylon (mxd6), and can be substituted therefor.

(A) drying the first polymer resin and the polyketone at 120 to 140 占 폚; (B) 0.1 to 80% by weight of the polyketone relative to 100% by weight of the first polymer resin and 0.1 to 5% by weight of an additive relative to 100% by weight of the first polymer resin, And the sections 7 and 6 close to the inlet are heated to 90 to 110 ° C and 160 to 190 ° C respectively and heated to 250 to 280 ° C from the section 5-1 to the header section close to the outlet, , And a step of melting and extruding the polyketone composite resin; The first polymer resin may be at least one selected from the group consisting of PET (polyethylene terephthalate), COC (cyclic olefin polymer), PVA (polyvinyl alcohol), EVOH (ethylene vinyl alcohol), PA (polyamide) Sulfone), PEI (polyetherimide), PP (polypropylene), PPE (polypropylene ether), PPS (polyphenylene sulfide), PVC (polyvinyl chloride), PVDF (polyvinylidene) &Lt; / RTI > The additives may be selected from the group consisting of hydrophobic zeolites, hydrophilic zeolites, clays, graphite, calcium carbonate, titania, zinc oxide, silane surface treatment agents, thermoplastic polyurethanes, styrene block copolymers, thermoplastic polyester-polyether elastomers, PE- Wax), PE-g-MA (polyethylene grafted maleic anhydride), and mixtures thereof. The present invention also provides a method for producing the polyketone composite resin. In particular, the heating temperature depending on the section of the biaxial extruder has an important influence on the production of the polyketone composite resin of the present invention. When the heating temperature is lower than the respective lower limit values, mixing of the additive and the polymer resin may not be uniformly performed, and if the heating temperature exceeds the upper limit value , The life of the equipment may be reduced. If the heating temperature is lower than the lower limit, the temperature is lowered to 250 占 폚, which is the melting point of PET, and 220 占 폚, which is the melting point of polyketone, in the case where the heating temperature is lower than the lower limit value. There may occur a problem that melting can not take place due to failure, and when the upper limit value is exceeded, the lifetime of the equipment may be reduced.

The first polymer resin is PET; Wherein the additive is a mixture of PE-WAX and PE-g-MA in a weight ratio of 1: 0.9-1.1. The PE-WAX and the PE-g-MA serve as a surface treating agent to improve the dispersion and bonding effect upon polymerization of the first polymer resin and the polyketone, and use PE-WAX and PE-g-MA alone The effect is higher when the mixture is used.

Hereinafter, production examples and embodiments according to the present invention will be described in detail with reference to the accompanying drawings.

Example One: PET ( Polyethylene terephthalate ) / POK ( Polyketone ) Preparation of composite resin

After drying at 130 占 폚 a PET resin (SK chemical, SKYPET BL) having a viscosity of 0.798 dl / g and a polyketone resin (Hyosung Corporation), 100 weight% of a PET resin having a viscosity of 0.798 dl / g, 0.1 wt.%, 0.3 wt.%, 0.5 wt.%, 1 wt.%, 3 wt.% And 5 wt.% Respectively relative to 100 wt.% Of resin) and PE-WAX and PE-g-MA as additives 3% by weight based on the total weight of the mixture. After the mixture was fed to the inlet of the twin-screw extruder, the sections 7 and 6 near the inlet were heated to 100 ° C. and 180 ° C., respectively, and heated to 280 ° C. from the section 5-1 to the header section close to the outlet. To prepare a polyketone composite resin.

The amount of the polyketone resin used in the above production process (in the order of 0.1 wt%, 0.3 wt%, 0.5 wt%, 1 wt%, 3 wt%, and 5 wt% with respect to 100 wt% 1, POK0.3, POK0.5, POK1, POK3, and POK5.

Example 2: HDPE layer/ COC _ POK The composite resin layer / LLDPE &Lt; / RTI >

A COC_POK composite resin was first prepared to prepare a multilayer film comprising an HDPE (high density polyethylene) layer / COC_POK (cyclic olefin polymer_polyketone) composite resin layer / LLDPE (linear low density polyethylene) layer. 100% by weight of a COC resin of MI 5 and 100% by weight of a different amount of a polyketone resin (100% by weight of a COC resin) after drying a COC resin (Topas, 8007F500) and a polyketone resin (Hyosung) 10 wt.%, 30 wt.%, 50 wt.%, 80 wt.% Of PE-WAX and PE-g-MA as additives, respectively. After the mixture was fed to the inlet of the twin-screw extruder, the sections 7 and 6 near the inlet were heated to 100 ° C. and 170 ° C., respectively. Heating was performed to 280 ° C. from the section 5-1 to the header section close to the outlet, To prepare a COC_POK composite resin.

COC POK10, COC POK30, COC POK50, and COC (10 wt%, 30 wt%, 50 wt% and 80 wt%, respectively) relative to the amount of the polyketone resin used in the above- Lt; / RTI >

Next, an outer layer of HDPE 20 μm thick and an inner layer of LLDPE 20 μm thick were used. As the middle layer, a COC resin which is commonly sold, COC POK 10, COC POK 30, COC POK 50 and COC POK 80 Five layers of multi-layer films with a total thickness of 100 μm were prepared according to the amount of POK added.

The multilayer film was named # 1, # 2, # 3, # 4, # 5 according to the type of COC_POK composite resin used in the above manufacturing process.

Table 1 below shows the compositions of a conventional PET resin and a PET (polyethylene terephthalate) / POK (polyketone) composite resin prepared from Example 1 of the present invention.

Sample Code PET (% by weight) Polyketone (wt%) PE-WAX (% by weight) PE-g-MA (% by weight) PET 100 0 0 0 POK0.1 100 0.1 0.3 0.3 POK0.3 100 0.3 0.3 0.3 POK0.5 100 0.5 0.3 0.3 POK1 100 One 0.3 0.3 POK3 100 3 0.3 0.3 POK5 100 5 0.3 0.3

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view showing a temperature sensor of a twin-screw extruder used in the production of a PET (polyethylene terephthalate) / POK (polyketone) composite resin in Examples 1 and 2 of the present invention, This is the picture shown. A twin-screw extruder composed of a 7-zone barrel including a header has a hot line and a temperature sensor for each section, so that the temperature can be easily adjusted for each section. In the present invention, the sections 7 and 6 near the inlet are heated to 90 to 110 DEG C and 160 to 190 DEG C, respectively, heated to 250 to 280 DEG C from the section 5-1 to the header section close to the outlet, Ketone composite resin.

2 is a graph showing a glass transition temperature measurement result of the PET (polyethylene terephthalate) / POK (polyketone) composite resin prepared in Example 1 of the present invention, wherein the glass transition temperature is measured by a differential scanning calorimeter TA instruments, Q20) at a rate of 10 ° C / min under a nitrogen atmosphere. It can be confirmed that the glass transition temperature of the PET (polyethylene terephthalate) / POK (polyketone) composite resin prepared from Example 1 of the present invention is higher than that of a conventional PET resin to which no polyketone is added.

As can be seen from the following Table 2, the PET (polyethylene terephthalate) / POK (polyketone) composite resin prepared from Example 1 of the present invention has a tendency that the glass transition temperature tends to increase as the content of polyketone increases . The glass transition temperature is due to the flexibility of the chain of molecules, so the lower the flexibility of the chain, the higher the glass transition temperature. Polyketone is added in the PET resin to increase the bond strength between PET chains. Therefore, it was confirmed that the glass transition temperature tends to increase as the content of polyketone increases. Further, it was confirmed that POK5 in which the content of polyketone was added in an amount of 5 wt% exhibited an effect of increasing the glass transition temperature by 10.57 DEG C as compared with a conventional PET resin. It is important to increase the glass transition temperature and improve the usage limit temperature in the field where heat resistance is important because the use limit temperature changes according to the glass transition temperature of the polymer resin in the packaging material and the container to which the polymer resin is applied.

PET POK0.1 POK0.3 POK0.5 POK1 POK3 POK5 Glass transition temperature (캜) 85.47 91.93 89.85 93.72 92.92 94.96 96.04

Table 3 below shows the compositions and thickness conditions of the multilayer film comprising the HDPE layer / COC_POK composite resin layer / LLDPE layer prepared in Example 2.

Sample code Outer layer (HDPE) Middle layer (COC_POK) Inner layer (LLDPE) Total thickness #One 20 μm COC 60 μm 20 μm 100 μm #2 COC POK10 # 3 COC POK30 #4 COC POK50 # 5 COC POK80

3 is a graph showing the oxygen transmittance of the multilayered film comprising the HDPE (high density polyethylene) layer / COC_POK (cyclic olefin polymer_polyethylene) composite resin layer / LLDPE (linear low density polyethylene) layer prepared in Example 2 of the present invention (OTR) transmission rate characteristics. The oxygen transmission rate was found to decrease in 320cc / m ² / day with increasing content POK to 50 cc / m ² / day. It can be concluded that POK is added to the COC polymer to increase the bonding force between the COC polymer chains and increase the density of the polymer chain per unit area, thereby decreasing the oxygen permeation.

4 is a graph showing the results of analysis of ultraviolet barrier property of the multilayered film including the HDPE layer / COC_POK composite resin layer / LLDPE layer prepared in Example 2 of the present invention. The UV transmittance of the multilayer film including the HDPE layer / COC_POK composite resin layer / LLDPE layer is greatly decreased as the POK content increases in the ultraviolet region of 200 to 380 nm. It can be confirmed that COC POK10 has a lower permeability than COC by about 50%. In particular, it can be confirmed that COC POK80 completely blocks ultraviolet rays. Therefore, POK has an ultraviolet shielding effect, and it can be confirmed that the ultraviolet shielding effect is increased with an increase of the content.

Therefore, according to the present invention, a polyketone-containing high heat-resistant and high-shear polyketone composite resin can be produced, which can be applied as a packaging material and a container having improved heat resistance and gas barrier properties.

Claims

PET resin, polyketone, and additives are mixed,
The polyketone further comprises 0.1 to 80% by weight based on 100% by weight of the PET resin;
Wherein the additive is a mixture of PE-WAX and PE-g-MA in a weight ratio of 1: 0.9-1.1;
Wherein the additive further comprises 0.1 to 5% by weight based on 100% by weight of the PET resin.

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The method according to claim 1,
Wherein the viscosity of the PET resin is 0.6 to 0.9 dl / g.

The method according to claim 1,
Wherein the polyketone composite resin has a glass transition temperature of 90 to 99 占 폚.

A first PE-based polymer layer / a polyketone composite resin layer / a second PE-based polymer layer according to the first aspect.

6. The method of claim 5,
Wherein the first PE-based polymer and the second PE-based polymer are the same or different and each independently selected from PE (polyethylene), HDPE (high density polyethylene), LDPE (low density polyethylene) and linear low density polyethylene (LLDPE) Wherein the multi-layer film is one of the two layers.

(a) drying PET resin and polyketone at 120 to 140 占 폚; And
(b) 100 parts by weight of the PET resin, 0.1 to 80 parts by weight of the polyketone relative to 100 parts by weight of the PET resin, and 0.1 to 5 parts by weight of an additive relative to 100 parts by weight of the PET resin, And heating and heating to a temperature of 250 ° C. to 280 ° C. from the section 5-1 to the header section close to the outlet, followed by melting and extruding Wherein the polyketone resin is a polyketone resin,
Wherein the additive is a mixture of PE-WAX and PE-g-MA in a weight ratio of 1: 0.9-1.1.

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