KR102119294B1 - Film, zipper - Google Patents

Abstract

In the present invention, PET-G is supplemented with TPEE resin to reduce physical properties, and it is made of vegetable oils and MBS (methyl methacrylate butadiene styrene or less MBS) resin to reduce hardness and add processing aids to extrude the composition that improves the physical properties and processability, resulting in flexibility It is a soft film made of a soft PET-G resin composition that can replace the zipper for the PVC zipper bag because it can form an excellent and soft soft film and a zipper for the zipper bag, and it is about 100 parts by weight of PET-G resin , TPEE resin 10 to 50 parts by weight of the soft PET-G resin composition and the soft film zipper bag zipper is characterized in that the extrusion.

Description

Soft film made of soft PET-G resin composition, zipper for zipper bag {FILM, ZIPPER}

The present invention relates to a soft film made of a soft PET-G resin composition, a zipper for a zipper bag, and more specifically, PET-G (Glycol modified polyethylene terephthalate, hereinafter referred to as PET-G) TPEE (Thermoplastic polyester elastomer, hereinafter) It is called TPEE) to complement the physical properties with resin, and to lower the hardness with vegetable oils and MBS (methyl methacrylate butadiene styrene) MB and resin, added processing aids, extruded a composition that improves the physical properties and processability, excellent flexibility and soft soft film And a soft film made of a soft PET-G resin composition capable of forming a zipper for a zipper bag to replace the zipper for a PVC zipper bag, and a zipper for a zipper bag.

The zipper of the plastic zipper bag is mainly made of PVC between D hardness 80 and D hardness 60 by extruding to cut the plastic fabric of suitable size and adhere to the cut fabric by high frequency adhesive method to produce the vinyl zipper bag.

The plastic fabric used for the zipper of the plastic zipper bag made of plastic, which is one of synthetic resins, is mainly used for high-frequency adhesive PVC fabric.

However, in order to replace PVC fabric due to environmental problems, some of them are replaced with polyurethane fabric made of polyurethane, but due to difficulties in secondary processing, PVC fabric cannot be completely replaced.

In addition, olefinic resins such as PE and PP cannot replace PVC fabrics due to high-frequency adhesion with the fabric for zipper bags that make zipper bags, and these resins cannot be used for the extrusion molding of zippers for zipper bags.

As a background technology of the present invention, there is a patent registration No. 1370778 "Zipper made of synthetic resin having high flexibility and good zipper engagement" (Patent Document 1). In the background art,'the fabric coil is laminated along a top surface of the coiled synthetic resin zipper coil fixing part, and a core material is introduced into the zipper coil to make the zipper head portion protrude a certain length toward the side of the fabric tape, and then fabric with a sewing thread. In a synthetic resin zipper that opens and closes the zipper head portion with a slider placed on both sides of the tape, the surface of the zipper coil is coated with a thinner looper sheet than the fabric tape in the longitudinal direction and the surface of the looper sheet. The two lines of looper yarn are coated on the cover so that the looper yarn is attached to the sewing thread. At this time, the looper yarn is inserted into the sewing thread loop made by the sewing thread to form a looper loop, and the next sewing thread loop is inserted into the looper hook to protrude. When the looper chain is first entered into the sewing thread loop through the bottom of the first sewing loop, passes through the upper surface of the sewing thread loop, passes through the next sewing loop, and when a new looper loop is formed, the next sewing loop is created into the newly created looper loop. Synthetic resin with high flexibility and good zipper chucking characteristics, characterized in that the looper yarn is compressed to form a looper yarn to be woven into a repeating structure in which is injected, and the looper yarn is pressed against the looper sheet so that the looper yarn and the looper sheet are compressed together with the zipper coil fixing portion. My zipper.'

However, the background technology is to change the composition without changing the material of the zipper itself to maintain high elasticity and ductility, but the structure is complicated and the production cost is high, and when formed of synthetic resin material, it is impossible to replace it with eco-friendly resin. There was.

Patent Registration No. 1370778 "Zipper made of synthetic resin with high flexibility and good zipper fastness"

The present invention is to provide a composition for compensating the properties and lowering the hardness with TPEE resin in PET-G and a zipper for soft film and plastic zipper bag made of the composition.

PET-G resin generally has a D hardness of 90 or more, and even if the hardness is lowered by adding a plasticizer or oil, a high quality plastic zipper bag zipper cannot be manufactured due to poor heat resistance, cold resistance, and processability, whereas the present invention overcomes this problem. In order to provide a soft PET-G resin composition capable of obtaining a composition having excellent physical properties of D hardness 70 to 60 when the hardness is lowered by mixing a low hardness TPEE resin, a soft film made of the composition and a zipper for a zipper bag are provided. .

The present invention is a soft film formed by extrusion molding a soft PET-G resin composition comprising 10 parts by weight to 140 parts by weight of TPEE resin, based on 100 parts by weight of PET-G resin, methyl methacrylate butadiene styrene (Methyl methacrylate) butadiene styrene, MBS) in a soft PET-G resin composition composed by further mixing 15 parts by weight of resin 3,

It is intended to provide a soft film formed by extruding the soft PET-G resin composition to a thickness of 0.01 mm to 0.3 mm.

It is intended to provide a zipper for a zipper bag formed by extruding the soft PET-G resin composition.

The soft PET-G resin composition of the present invention, and the soft film made of the same, the zipper for the zipper bag are mixed with the low hardness TPEE resin possible for PET-G to lower the hardness, improve heat resistance and cold resistance, and improve processability to improve PVC workability. It has the effect of replacing the zipper.

In general, PVC zippers used as zippers for vinyl zipper bags are made of PVC materials with a D hardness of 75 to 65, whereas zippers for soft vinyl zipper bags are difficult to form low-hardness compositions by mixing only PET-G and TPEE. , In the present invention, by mixing a little oil to achieve a low-hardness composition, a low-hardness composition capable of producing a zipper for a soft vinyl zipper bag can be obtained, thereby producing a soft soft film and a zipper for a zipper bag. By using it, it is possible to produce a zipper for a soft plastic zip bag, so it has a very useful effect that can replace a lot of PVC zipper bags.

Figure 1 shows a typical plastic zipper bag
Figure 1a is a perspective view of a plastic zipper bag
Figure 1b is a cross-sectional view for showing the male and female of the plastic zipper bag.
Figure 2 is a photograph of a soft film showing that the oil is leached on the surface
Figure 3 is a soft film real picture showing a state in which the oil of the present invention is not exposed

The present invention will be described in detail below with reference to the embodiments presented in the accompanying drawings, but the presented embodiments are illustrative for a clear understanding of the present invention and the invention is not limited thereto.

Hereinafter, the technical configuration of the present invention will be described in detail according to a preferred embodiment.

The present invention is a soft and flexible film and a zipper bag made by extruding a composition that improves physical properties and processability by supplementing physical properties with PET-G with TPEE resin, lowering hardness with vegetable oil, and adding a processing aid to improve flexibility. It is possible to manufacture a soft plastic zipper bag with excellent printability and good physical properties by replacing the PVC by forming a dragon zipper.

In general, plastic zipper bags are made of soft PVC, but they are avoided due to toxicity or environmental problems. Although they are intended to be replaced with olefin-based raw materials such as PP and PE, they are not successful due to poor processability, and some are replaced with polyurethane, but are difficult to process. As part of it is being replaced.

The vinyl zipper bag 100 is a vinyl zipper bag fabric 110 for producing the vinyl zipper bag 100, as shown in FIG. 1, produced by an extrusion process, and after cutting the vinyl zipper bag fabric 110 to a certain standard, a zipper for a vinyl zipper bag separately made ( 120) is a high-temperature heat-sealed adhesive to the cut-off vinyl zipper bag fabric 110 to manufacture the vinyl zipper bag 100.

The zipper 120 for the vinyl zipper bag used in the vinyl zipper bag 100 is composed of a male and female in the form of interlocking irregularities 121.

The zipper 120 for the vinyl zipper bag, which is usually used for the vinyl zipper bag 100, uses a PVC material having a D hardness of 80 to 60.

Olefin-based plastics such as PP or PE are non-toxic and environmentally-friendly plastics, but it is impossible to produce a zipper 120 for a vinyl zipper bag in a precise form due to poor extrusion processability of a molded product. It is not possible to use the zipper 120 for the vinyl zipper bag on the plastic zipper bag fabric 110 for high-frequency heat bonding, and thus it cannot be used for the zipper zipper 120 for the vinyl zipper bag used in the vinyl zipper bag 100.

Polyurethane, a plastic raw material capable of high-frequency adhesion and having a hardness of D hardness of 75 or less, is also only partially replaced due to difficulties in extrusion and post-processing.

As a means to overcome this, PET-G resin with good eco-friendliness and high-frequency processing was selected.

PET-G resin is usually D hardness of 95 or higher. If plasticizer or oil is mixed, it can be hardened to D hardness of 65 or lower.However, it is possible to precisely and precisely reduce heat resistance, cold resistance due to oils added to lower hardness, and deterioration of extrusion process. It becomes impossible to process the molded product that is combined with. As an alternative, TPEE, which has excellent compatibility with PET-G, is also manufactured with a product with a D hardness of 40 and has good high-frequency processability, but is opaque.

In general, the zipper 120 for the vinyl zipper bag is mostly transparent or translucent. Mixing 10 parts by weight to 30 parts by weight of a low-hardness TPEE resin in a PET-G resin solves these problems, and it is possible to manufacture a zipper for a vinyl zipper having good quality.

In the present invention, PET-G resin was first selected as a base resin to develop an eco-friendly material having physical properties and processability to replace soft PVC.

PET-G resin is known as an eco-friendly resin and is relatively inexpensive, so it is mainly used as a hard sheet or a product container, but it is difficult to produce a soft film or soft sheet due to the difficulty of softening.

Therefore, the properties of PET-G resin are supplemented with TPEE resin, and the advantages of PET-G, such as eco-friendliness, weatherability, and transparency, are utilized, and good physical properties and post-processing properties are combined by using good heat resistance and cold resistance of TPEE resin.

TPEE resin is a resin with good tensile strength at high temperature, low compression set (low compression permanent warping), good chemical resistance, good cold resistance, weather resistance, and processability. It is desirable to use a low hardness and low hardness TPEE resin. Do.

The soft PET-G resin composition used in the zipper and the soft film for vinyl zipper bags using the soft PET-G resin composition of the present invention includes 10 parts by weight to 140 parts by weight of TPEE resin, based on 100 parts by weight of PET-G resin.

<Experimental Example 1>

Zipper for PVC vinyl zipper bag

Zippers for PVC vinyl zipper bags generally differ somewhat depending on the type of plasticizer, but PVC with a plasticizer content of 20 to 30 parts by weight is mainly used and has a D hardness of 80 to 60.

Therefore, in Experimental Example 1, PET-G was prepared as shown in Table 1 below to prepare a raw material having a hardness suitable for the zipper 120 for the PVC vinyl zipper bag.

ingredient Unit: g Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 PET-G 1000 1000 1000 1000 1000 1000 1000 TPEE 50 100 200 300 400 500 600 Hardness (A) D hardness 90±3 86±3 79±3 75±3 69±3 68±3 68±3

※ TPEE (Thermoplastic polyester elastomer) is item number KP3340 manufactured by Cologne.

As shown in Table 1, as a result of mixing TPEE resin from 5 parts by weight to 60 parts by weight, 100 parts by weight of PET-G was added and mixed with 10 parts by weight or more of TPEE resin to improve heat resistance and replaced the zipper for PVC vinyl zipper bags. The degree of hardness to be mixed should be 20 parts by weight or more as in Example 3, and when 40 to 50 parts by weight of TPEE is mixed, the effect of improving physical properties is good, but transparency is deteriorated. As in Example 7, more than 60 parts by weight of TPEE is mixed. In the city, there is a factor of cost increase due to the large amount of TPEE resin, which is almost opaque and has a higher cost than the quality improvement effect.

Therefore, it is preferable that the zipper 120 for the PVC vinyl zipper bag includes 10 parts by weight to 50 parts by weight of the TPEE resin with respect to 100 parts by weight of the PET-G resin.

<Experimental Example 2>

In general, soft PVC films that are frequently used for plastic bags are mainly used for plastic parts with a plasticizer content of 40 parts by weight to 60 parts by weight of PVC, but 70 parts by weight of soft PVC (D hardness at 60±3 D) 85±3) may be used.

In Table 1 of Experimental Example 1, the zipper for the zipper bag should maintain a predetermined hardness, so it was possible to reduce the hardness by mixing TPEE resin with PET-G as shown in Table 1, but the low hardness TPEE resin (D hardness 40±3) Even if mixed, there is a limit to the production of low hardness compositions having a D hardness of 65±3 or less.

Therefore, in order to make a composition having a D hardness similar to that of soft PVC, an experiment was conducted as shown in Table 2 below.

ingredient Unit: g Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7
PET-G 1000 1000 1000 1000 1000 1000 1000 TPEE 200 200 200 300 300 500 600 Palm oil 50 100 200 200 300 400 500 Hardness (D) D hardness 76±3 D Hardness 70±3 D Hardness 66±3 A hardness 98±3 A hardness 96±3 A hardness 95±3 A hardness 94±3

ingredient Unit: g Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 PET-G 1000 1000 1000 1000 1000 1000 1000 TPEE 600 800 1000 1100 1200 1400 1600 Palm oil 600 700 700 900 900 900 1000 Hardness (A) 91±3 89±3 90±3 87±3 90±3 93±3 97±3 Palm oil% 37.5 38.9 35.0 42.8 40.9 37.5 38.4 TPEE% 37.5 47.0 58.8 57.9 63.2 73.7 80.0

※ 1)% of palm oil is% of mixture of PET-G and TPEE.

2)% of TPEE is% of mixture of PET-G and palm oil.

In Examples 1, 2, and 3 of Table 2, 20 parts by weight of TPEE resin was added to 100 parts by weight of PET-G, and palm oil was increased from 5 parts by weight to 20 parts by weight and mixed. It has a hardness of about ±3 to replace the zipper for PVC vinyl zipper bags, and has good physical properties such as workability, heat resistance and viscosity, but when the oil content is added to 20 parts by weight or more, the viscosity rapidly decreases and the extrusion processability and heat resistance decrease. It showed a phenomenon.

In Examples 1, 2, and 3 of Table 2, as a result of performing a test to obtain a composition suitable for the production of vinyl zippers, a composition having good processability and suitable hardness was obtained.

The vinyl zipper using the composition of Example 3 in Table 2 showed a very soft vinyl zipper among the vinyl zippers, a high-hardness soft film, and a hardness enough to produce a thin film, but showed poor heat resistance.

Example 2 of Table 2 is the result of increasing the mixing amount of TPEE from 20 parts by weight to 30 parts by weight to maintain the PET-G and palm oil of Table 2 Example 3 to compensate for the poor heat resistance, which is a disadvantage of Table 2 Example 3. There was an effect of improving the heat resistance.

Experiments were carried out to obtain compositions for soft films from Examples 5 to 14 in Tables 2 and 3.

In order to soften PVC, even if the plasticizer content added to PVC is mixed up to 100 parts by weight of PVC to 150 parts by weight, surface leaching does not occur, but PET-G or TPEE resin is used to make soft films. When the content of oil in each PET-G and TPEE resin is mixed by 40% or more, the surface leaching phenomenon of oil occurs, and the composition for making a soft film with low hardness is the amount of oil in the composition for making a soft film with high hardness. Since it is added by increasing, surface leaching of oil occurs and processability and heat resistance are deteriorated due to the participation of a large amount of oil.

Experiment for high hardness soft film (A hardness of 100 to 95±3) or thin film (0.01mm~0.05mm), as shown in Table 2, Examples 5, 6, and 7 increase the mixing amount of oil. The amount of simultaneous TPEE was also increased.

TPEE resin has better oil absorption than PET-G, excellent heat resistance, cold resistance, and workability, and excellent elasticity and compatibility with PET-G.

Therefore, when the oil content is increased, increasing the content of TPEE has a great effect of suppressing the surface leaching phenomenon, and also has an effect of improving physical properties such as heat resistance, cold resistance, processability and elasticity.

Table 3 Examples 8 to 14 are experiments by increasing the added amount of oil to 100 parts by weight of PET-G from 60 parts by weight to 100 parts by weight of oil.

The experiment was conducted in such a way that the content of the oil was maintained at 40% of the mixing amount of the PET-G, TPEE resin and oil so that the surface leaching of the oil did not occur.

Table 3 In Example 9, a composition with a hardness of about 89±3 suitable for a low hardness soft film or a thick (0.1 mm to 0.3 mm) film and no surface leaching occurred, and the heat resistance and cold resistance were superior to that of soft PVC. .

Table 3 In Example 11, the physical properties were good, with an A hardness of about 70% of PVC of 87±3. The defects of the soft PVC showed a low heat deflection temperature and a slight surface leaching as shown in FIG. 2, and the hardness of the soft PVC was slightly higher than that of the soft PVC material.

Table 3 As a result of experiments from Examples 8 to 12, a composition having good physical properties with a hardness of about 85±3 suitable for a soft film was obtained.

Table 3 Examples 10 and 11 had slight differences in glossiness, but were identical in terms of overall physical properties.

In the case of Example 10, the hardness was slightly higher than that of 70 phr PVC, but all the physical properties that the low hardness soft film had to possess, such as heat resistance, cold resistance, weather resistance, elasticity, surface strength (scratch resistance), and workability, were excellent, and Table 3 Examples 12, 13, 14 showed excellent heat resistance, cold resistance and gloss that PVC could not possess, good weatherability and cold resistance as a defect of TPU, and excellent post-processing property.

Table 3 Examples 13 and 14 did not have a significant difference in physical properties, and Example 14 increased hardness due to a large amount of TPEE resin, and cost increase caused by excessive mixing of expensive TPEE resin.

Table 3 As shown in Examples 8 and 14, when the oil content is relatively high, surface leaching occurs when exposed to a temperature of 60° C. or more for a long time. Is prevented.

Since the effect of improving physical properties is hardly exhibited when the added MBS resin is mixed in less than 3 parts by weight, the tensile strength and transparency are poor when mixed in excess of 15 parts by weight, so the MBS resin is 3 to 15. It is preferred to mix parts by weight.

MBS resins are mainly used as impact modifiers for rigid PVC or engineering plastics. MBS resin, which is mainly used as an impact modifier, has good mixing properties and compatibility with other resins, and is mainly used to improve the properties and processability of other resins.

The soft PET-G resin composition should be mixed with a large amount of oil to soften it with high hardness of the PET-G resin, and as a result of experiments as in Example 2 to prevent side effects such as surface leaching, weakening of properties, and poor processability. An excellent composition could be obtained.

As the vegetable oil, oil extracted from a plant or a seed of a plant, palm oil, coconut oil, castor oil, grape seed oil, jojoba oil, safflower oil, macadamia nut oil, olive seed oil, etc. may be used. You can use palm oil.

<Experimental Example 3>

ingredient Unit: g Example 1 Example 2 Example 3 Example 4 PET-G 1000 1000 1000 1000 TPEE 200 200 200 200 Palm oil 50 100 150 200 Processing aid 3 5 10 20 Processability Good

As in Example 2, while gradually increasing the content of the oil added to the PET-G resin while maintaining the amounts of PET-G resin and TPEE at 5 parts by weight, the viscosity decreases and processability deteriorates.

The processability deteriorates due to the addition of oil to the PET-G resin. In order to improve the deteriorated processability, as shown in Table 4, the addition amount of the processing aid was increased in proportion to the increase in the addition of oil.

Table 4 In Example 1, the processability was improved by adding at least 0.3 parts by weight of the processing aid, and when the amount of oil added was increased by 20 parts by weight or more, at least 2 parts by weight was increased to show good processability.

Accordingly, the soft PET-G resin composition is preferably composed of 0.3 to 2.0 parts by weight of a processing aid based on 100 parts by weight of the PET-G resin.

Various processing aids can be used, and it is particularly preferably made of PTFE resin. Polytetrafluoroethylene (PTFE) resin is excellent in thermal stability and chemical resistance, and has high melt strength and viscosity, so it has excellent processability.

By using the soft PET-G resin composition of the present invention, a zipper for a soft zipper bag can be produced by a method such as extrusion molding, and a soft film having a thickness of about 0.01 mm to 0.3 mm can also be produced, so it can be used as a fabric for wraps or zipper bags. You can.

The soft PET-G resin composition of the present invention as described above, and the soft film made of the same, and the zipper for the zipper bag are made by mixing TPEE resin with a low hardness as possible in PET-G to improve hardness, improve heat resistance and cold resistance, and improve processability. There is an effect that can replace the PVC zipper by producing a zipper for a zipper bag to form a zipper bag for a zipper bag by combining a soft film with a thickness of about 0.01 mm to 0.3 mm with a fabric as a fabric.

In addition, PVC zippers used as zippers used in vinyl zipper bags are usually made of PVC materials with a hardness of 80 to 60. The zippers for vinyl zipper bags 120 used for soft vinyl zipper bags are only mixed with PET-G and TPEE. While it is difficult to form a composition having a low hardness, the present invention can obtain a composition having a low hardness enough to produce a zipper 120 for a soft vinyl zipper bag by mixing a little oil to achieve a composition having a low hardness. Since it is possible to manufacture soft film and zipper for zipper bags, it is possible to produce zipper bags for soft vinyl zipper bags, which has a very useful effect that can replace many parts of PVC zippers.

Although the present invention has been described as a preferred embodiment mentioned above, it is possible to make various modifications or variations without departing from the spirit and scope of the invention. Also, the appended claims include such modifications or variations that fall within the spirit of the present invention.

100: plastic zipper bag 110: plastic zipper bag fabric
120: zipper for vinyl zipper bag

Claims (2)

With respect to 100 parts by weight of PET-G (Glycol modified polyethylene terephthalate) resin,
In the soft film formed by extruding a soft PET-G resin composition containing 10 parts by weight to 140 parts by weight of TPEE resin, 15 parts by weight of methyl methacrylate butadiene styrene (MBS) resin 3 is further mixed In the soft PET-G resin composition consisting of,
A soft film characterized in that the soft PET-G resin composition is formed by extrusion molding to a thickness of 0.01 mm to 0.3 mm. According to claim 1,
Zipper for a zipper bag, characterized in that formed by extrusion molding the soft PET-G resin composition.

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