TW202333958A - Polyester composite film and hot melt adhesive laminate comprising the same - Google Patents

Abstract

Provided is a polyester composite film, which comprises a first thermoplastic polyether ester elastomer (TPEE) film and a second TPEE film. The melting point of a second TPEE resin of the second TPEE film is higher than that of a first TPEE resin of the first TPEE film, and the absolute difference of the enthalpy of fusion between the first and second TPEE films is 5 J/g to 15 J/g. By adopting the first and second TPEE films having specific absolute difference of the enthalpy of fusion and controlling the melting points of the first and second TPEE resins, the polyester composite film can be well adhered onto the fabrics by hot pressing to obtain sufficient peel strength, and thereby the adhered fabrics can have improved water resistance. Besides, a hot melt adhesive laminate comprising the polyester composite film also exhibits the foresaid beneficial effects when it is adhered to the fabrics.

Description

Polyester composite film and hot melt adhesive laminate containing the same

This invention relates to a polymer composite film and a hot-melt adhesive laminate containing the same, in particular, a polyester composite film and a hot-melt adhesive laminate containing the same.

In response to the changes of the times, consumers have gradually increased their functional requirements for textiles. Functional fabrics with waterproof functions have become one of the key development issues in the textile industry.

The waterproofing effect of waterproof functional fabrics is evaluated by the water pressure resistance value (also called waterproof coefficient). The water pressure resistance value refers to the water pressure value that the surface of the fabric can withstand without water seepage. The unit is millimeters of water column height (mm H ₂ O). The higher the water pressure resistance value, the better the waterproof effect of the fabric. Generally speaking, a water pressure resistance value of 1000 mm H ₂ O and above represents average waterproofing effect, a water pressure resistance value of 3000 mm H ₂ O and above represents good waterproofing effect, and a water pressure resistance value of 5000 mm H ₂ O and above represents good waterproofing effect. With excellent waterproof effect, this waterproof functional fabric can be used in weather from light rain to moderate to heavy rain.

Nowadays, waterproof functional fabrics can be formed by hot-pressing a waterproof film onto the fabric, or a hot-melt adhesive film can be hot-pressed and attached to the seam between two pieces of fabric to enhance the waterproofing effect of the fabric. Most of the waterproof membranes or hot-melt adhesive membranes currently used on the market are made of polyurethane (PU) or thermoplastic polyurethane (TPU). However, the membrane layer and fabric of this material need to be hot-pressed and bonded together. Sometimes there is a problem of thermal cracking, causing the waterproof film or hot melt adhesive film to be easily peeled off the fabric, which will also deteriorate the waterproof effect of the fabric.

Therefore, waterproof membranes or hot melt adhesive membranes of different materials still need to be developed to solve the shortcomings of the existing technology.

In view of this, one of the purposes of this invention is to provide a polyester composite film that is different from the previous ones. This polyester composite film can be well adhered to fabrics and make the adhered fabrics have good waterproof properties.

In order to achieve the aforementioned objectives, the present invention provides a polyester composite film, which includes a first thermoplastic polyether ester elastomer (TPEE) film and a second thermoplastic polyether ester elastomer film; wherein, the first thermoplastic polyether ester elastomer film The material of the polyetherester elastomer film includes a first thermoplastic polyetherester elastomer resin, the material of the second thermoplastic polyetherester elastomer film includes a second thermoplastic polyetherester elastomer resin, and the second thermoplastic polyetherester elastomer resin The melting point of the polymer resin is greater than the melting point of the first thermoplastic polyether ester elastomer resin, and the enthalpy of fusion (ΔHm) of the first thermoplastic polyether ester elastomer film is the same as that of the second thermoplastic polyether ester elastomer film. The absolute difference between the melting enthalpy of the body film is 5 Joules/gram (J/g) to 15 J/g.

By combining the first and second thermoplastic polyetherester elastomer films and controlling the melting point of the second thermoplastic polyetherester elastomer resin to be greater than the melting point of the first thermoplastic polyetherester elastomer resin and the elasticity of the first thermoplastic polyetherester elastomer The absolute difference between the melting enthalpy of the body film and the melting enthalpy of the second thermoplastic polyetherester elastomer film is 5 J/g to 15 J/g. The polyester composite film of this invention can not only penetrate the first thermoplastic The polyetherester elastomer film adheres to the fabric to obtain good peel strength, and the second thermoplastic polyetherester elastomer film can still maintain its film layer quality after hot pressing and will not be affected by high temperatures. It melts due to the influence, so the fitted fabric can obtain good waterproof properties. In short, the polyester composite film of this invention can have both good peel strength and waterproofness when applied to laminated fabrics, and is suitable for development into waterproof functional clothing.

According to this invention, the absolute difference between the melting enthalpy of the first thermoplastic polyetherester elastomer film and the melting enthalpy of the second thermoplastic polyetherester elastomer film can be 5 J/g or 6 J/g. , 7 J/g, 8 J/g, 9 J/g, 10 J/g, 11 J/g, 12 J/g, 13 J/g, 14 J/g, 15 J/g; in addition, the second The absolute difference can also be within the range formed by any two of the above values. In one embodiment, the absolute difference between the melting enthalpy of the first thermoplastic polyetherester elastomer film and the melting enthalpy of the second thermoplastic polyetherester elastomer film may be 6 J/g to 15 J/g.

The melting enthalpy of the first thermoplastic polyetherester elastomer film can be 1 J/g, 2 J/g, 3 J/g, 4 J/g, 5 J/g, 6 J/g, 7 J/g , 8 J/g, 9 J/g, 10 J/g; in addition, its melting enthalpy can also be within the range of any two of the above values. In one embodiment, the melting enthalpy of the first thermoplastic polyetherester elastomer film may be 1 J/g to 10 J/g; in another embodiment, the first thermoplastic polyetherester elastomer film The melting enthalpy can be 3 J/g to 10 J/g.

The melting enthalpy of the second thermoplastic polyetherester elastomer film can be 5 J/g, 6 J/g, 7 J/g, 8 J/g, 9 J/g, 10 J/g, 11 J/g , 12 J/g, 13 J/g, 14 J/g, 15 J/g, 16 J/g, 17 J/g, 18 J/g, 19 J/g, 20 J/g, 21 J/g , 22 J/g, 23 J/g, 24 J/g, 25 J/g; in addition, its melting enthalpy can also be within the range composed of any two of the above values. In one embodiment, the melting enthalpy of the second thermoplastic polyetherester elastomer film may be 5 J/g to 25 J/g; in another embodiment, the second thermoplastic polyetherester elastomer film may have a melting enthalpy of 5 J/g to 25 J/g. The enthalpy of fusion can range from 6 J/g to 25 J/g.

According to the invention, the first thermoplastic polyether ester elastomer resin in the first thermoplastic polyether ester elastomer film and the second thermoplastic polyether ester elastomer resin in the second thermoplastic polyether ester elastomer film can be made of paraphenylene Dimethyl terephthalate (DMT), 1,4-butanediol (BDO), isophthalic acid (IPA) and polytetramethylene ether glycol (poly(tetramethylene ether) glycol, PTMEG) copolymerization and condensation, but it is not limited to this. For example, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (1,3,5 -Trimethyl-2,4,6-tris(3,5-di- tert -butyl-4-hydroxybenzyl)benzene, AO330) antioxidant or tetrabutyl titanate (titanium butoxide, TBT) catalyst participates in the reaction.

The melting point of the first thermoplastic polyetherester elastomer resin can be 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150℃, 155℃, 160℃, 164℃; in addition, its melting point can also be within the range of any two of the above values. In one embodiment, the melting point of the first thermoplastic polyetherester elastomer resin may be 90°C to 164°C; in another embodiment, the melting point of the first thermoplastic polyetherester elastomer resin may be 100°C. to 160℃.

The melting point of the second thermoplastic polyether ester elastomer resin is greater than the melting point of the first thermoplastic polyether ester elastomer resin. The melting point of the second thermoplastic polyether ester elastomer resin can be 165°C, 170°C, 175°C, 180°C. ℃, 185℃, 190℃, 195℃, 200℃, 205℃, 210℃, 215℃, 220℃; in addition, its melting point can also be within the range of any two of the above values. In one embodiment, the melting point of the second thermoplastic polyetherester elastomer resin may be 165°C to 220°C; in another embodiment, the melting point of the second thermoplastic polyetherester elastomer resin may be 165°C. to 210℃.

The specific gravity of the first or second thermoplastic polyetherester elastomer resin may be 1.00, 1.01, 1.02, 1.03, 1.04, 1.05, 1.06, 1.07, 1.08, 1.09, 1.10, 1.11, 1.12, 1.13, 1.14, 1.15; in addition , the proportions of the two can also be independently within the range composed of any two of the above numerical values. In one embodiment, the specific gravity of the first or second thermoplastic polyetherester elastomer resin can be independently from 1.00 to 1.15.

The Shore hardness of the first or second thermoplastic polyetherester elastomer resin may be 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28 , 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45; in addition, the Shore hardness of the two can also be independently introduced Within the range formed by any two of the above values. In one embodiment, the first or second thermoplastic polyetherester elastomer resin may have a Shore hardness of 15 to 45 independently. In another embodiment, the Shore hardness of the first thermoplastic polyetherester elastomer resin can independently range from 15 to 30. In yet another embodiment, the Shore hardness of the second thermoplastic polyetherester elastomer resin can be independently 25 to 45. In yet another embodiment, the Shore hardness of the second thermoplastic polyetherester elastomer resin may be greater than the Shore hardness of the first thermoplastic polyetherester elastomer resin.

In addition, another purpose of this invention is to provide a hot-melt adhesive laminate that can be hot-pressed and bonded together with fabrics to obtain sufficient peel strength, and to enable the bonded fabrics to obtain good waterproof properties.

In order to achieve the above purpose, the present invention also provides a hot melt adhesive laminate, which includes a polyester composite film and a release film as described above. The second thermoplastic polyetherester elastomer film of the polyester composite film is sandwiched between between the first thermoplastic polyetherester elastomer film of the polyester composite film and the release film.

When using the hot melt adhesive laminate of the present invention to adhere to fabrics, the first thermoplastic polyether ester elastomer film of the hot melt adhesive laminate can be placed on the fabric. Since the first thermoplastic polyether ester elastomer film has The melting point of the first thermoplastic polyether ester elastomer resin is lower than the melting point of the second thermoplastic polyether ester elastomer resin in the second thermoplastic polyether ester elastomer film. Therefore, the hot pressing process only needs to be between the first and second thermoplastic polyether ester elastomer resins. , the temperature of the melting point of the second thermoplastic polyetherester elastomer resin can melt the first thermoplastic polyetherester elastomer film and fit it well on the fabric, and this hot pressing temperature will not destroy the second thermoplastic polyetherester elastomer. The quality of the elastomer film layer ensures the waterproofing effect of the fitted fabric at the same time.

According to this invention, the release film is, for example: polyethylene (PE) release film, polyethylene terephthalate (PET) release film, oriented polypropylene film (oriented polypropylene, OPP) ) release film, but it is not limited to this.

There are no special restrictions on the fabrics that this creation can be applied to. Any general knitted fabric, woven fabric or non-woven fabric can be applied. In addition, the hot-melt adhesive laminate can be hot-pressed and bonded to a large area of fabric to form a whole piece of waterproof fabric; or the hot-melt adhesive laminate can also be hot-pressed and bonded to the seams of the fabric locally to form a waterproof fabric. This improves the waterproofness of the sewn fabric and avoids the problem of water seepage from the seams.

Below, several preparation examples and examples are enumerated to illustrate the embodiments of polyester composite films and hot melt adhesive laminates containing them, and several comparative examples are provided as controls. Those with ordinary knowledge in the technical field can refer to the following examples It is easy to understand the advantages and effects that this creation can achieve with the contents of comparative examples. It should be understood that the embodiments listed in this specification are only used to illustrate the implementation of the present invention, and are not used to limit the scope of the present invention. Those with ordinary knowledge in the technical field can make decisions based on common knowledge without departing from the present invention. Various modifications and changes may be made in the spirit of this work to implement or apply the contents of this creation.

"Thermoplastic polyetherester elastomer resin"

Preparation example 1 : TPEE resin pellets

First, according to the weights shown in Table 1 below, weigh 10 kg of dimethyl terephthalate (DMT), 10 kg of 1,4-butanediol (BDO), and 3.43 kg of isophthalic acid ( IPA), 22 kilograms of polytetramethylene ether glycol (PTMEG, whose number average molecular weight is 1000, shown as "PTMEG1000" in Table 1 below), 70 grams of 1,3,5-trimethyl- 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (AO330) was added to a 3-liter reaction kettle, and 70 grams of tetrabutyl titanate was added (TBT). Thereafter, the temperature of the heating plate of the reaction kettle is set at 210°C to 230°C to carry out the esterification reaction.

During the esterification reaction, the by-products methanol (MeOH, boiling point 64.7°C) and water (H ₂ O, boiling point 100°C) will be produced. Methanol and water will boil in the reaction kettle at 220°C to 225°C, and will react with the reaction kettle. It condenses again in the connected condensation tube and is collected in the condensation collection tank. When the temperature at the top of the condenser tube drops below 40°C, the esterification reaction is deemed to be completed and the polycondensation stage is immediately entered.

During the polycondensation stage, raise the temperature of the reactor to 240°C to 250°C, and turn on the vacuum pump to bring the internal pressure of the reactor to less than 1 millibar (mbar). Then maintain the temperature and pressure of the reactor for about 200 minutes, and wait for the reaction. When the melt index of the copolymer in the kettle reaches 15 grams/10 minutes (g/10 min) to 20 g/10 min, the reaction is deemed to be complete, and the bottom valve of the kettle can be unscrewed to proceed with the subsequent drawing and pelletizing processes. Here, the melt index refers to the weight of the copolymer passing through a standard die with a diameter of about 2.095 mm within 10 minutes under the test conditions of 190°C and a load of 2.16 kg.

Finally, prepare water pelletizing equipment at the outlet of the kettle bottom valve. The cutter speed is set to 2000 revolutions per minute (rpm), the die temperature is set to 230°C, and the pelletizing water temperature is set to 10°C, and the gear pump is used to pump out the water. The material quantity is set to 50 kilograms/hour (kg/hr) for pelletizing. After pelletizing, the particles form round pellets with a diameter of about 3 millimeters (mm). They are cooled and crystallized in the cooling water channel, and then removed from the water through a dehydrator. product (i.e., TPEE resin particles).

Preparation example 2 to 12 : TPEE resin pellets

The manufacturing process of TPEE resin particles in Preparation Examples 2 to 12 is roughly the same as Preparation Example 1. The only difference lies in the weight of DMT, BDO, IPA, AO300, TBT and other raw materials as shown in Table 1 below, and the number average molecular weight and weight of PTMEG. .

Here, the number average molecular weight of the polytetramethylene ether glycol selected in each preparation example is slightly different. As mentioned above, polytetramethylene ether glycol with a number average molecular weight of 1000 is shown as "PTMEG1000" in Table 1 below, and polytetramethylene ether glycol with a number average molecular weight of 2000 is shown as "PTMEG2000" ” Show it.

The theoretical product weight (W _theor ) of the TPEE resin particles of the above-mentioned Preparation Examples 1 to 12 can be obtained by the following calculation formula: In the above formula, W _theor : theoretical product weight; W _DMT : DMT weight; W _PTMEG : PTMEG weight; W _IPA : IPA weight; W _TBT : TBT weight; W _AO300 : AO300 weight; M _DMT : DMT molecular weight: 194 g /mol; M _IPA : IPA molecular weight: 166 g/mol; M _PTMEG : PTMEG molecular weight; M _BDO : BDO molecular weight: 90 g/mol; M _MeOH : MeOH molecular weight: 32 g/mol; M _H2O : H ₂ O molecular weight: 18 g/mol.

In addition, the weight ratio of PTMEG and IPA can be obtained by the following formula:

The theoretical product weight of the TPEE resin particles of Preparation Examples 1 to 12, the weight ratio of PTMEG, and the weight ratio of IPA calculated according to the above calculation formula are as shown in Table 1 below.

In addition to the embodiments illustrated in the foregoing preparation examples, those with ordinary skill in the art can adjust, modify, and change the above process without departing from the spirit of the present invention to obtain TPEE resin particles applicable to the present invention. For example, the weight of various raw materials can be adjusted according to the needs, or the timing of adding the catalyst can be adjusted according to the needs during the manufacturing process; for example, an additional catalyst can be added during the polycondensation stage to accelerate the reaction, that is, the timing of adding the catalyst It is not limited to being added only during the initial esterification reaction stage.

Test example 1 : melting point

In this test example, the TPEE resin particles of the above-mentioned Preparation Examples 1 to 12 are used as the sample to be tested. 10 mg of the sample to be tested is placed in an aluminum pan, and together with the blank aluminum pan, is placed into a Differential Scanner (DSC) (Manufacturer: TA Instrument, model: Q-2000), heated from room temperature at a temperature rise rate of 10°C per minute until a melting peak appeared, and recorded the melting point of the TPEE resin particles in each preparation example. The results are shown in Table 1.

Test example 2 :proportion

In this test example, the TPEE resin particles of the aforementioned Preparation Examples 1 to 12 are used as samples to be tested, and their specific gravity is measured according to the standard method of ISO1183.

Specifically, use a balance to weigh the weight of each sample to be measured (a, unit: grams) in the air to the fourth decimal place; hang a small steel wire on the balance and immerse it in the filled beaker. The weight of the small steel wire in the water is returned to zero; then, hook the sample to be measured with the small steel wire, immerse it from the hook on the balance into the beaker filled with water, completely immerse the sample to be measured in the water, and carefully remove the bubbles in the sample; weigh the weight of the sample immersed in water (b, unit: grams) to the fourth decimal place; finally, calculate the specific gravity of each sample to be tested based on a/(ab). As shown in Table 1 below, the specific gravity of the TPEE resin particles in Preparation Examples 1 to 12 is 1.00 to 1.15. Table 1: Weight of raw materials, theoretical product weight, and weight ratio of PTMEG to IPA used to produce TPEE resin particles of Preparation Examples 1 to 12 (PE1 to PE12) PE1 PE2 PE3 PE4 PE5 PE6 PE7 PE8 PE9 PE10 PE11 PE12 DMT weight (kg) 10 17.08 7.75 10 11 12 15.75 7.6 8.75 9.65 10.5 7.95 BDO weight (kg) 10 11.9 5.5 6 8.2 7.5 10.25 7.6 10 8.5 8.5 6.5 IPA weight (kg) 3.43 0 0 0 0 0 0 3.45 4.5 2.4 1.75 0 PTMEG1000 weight (kg) twenty two 33.6 0 0 0 0 0 twenty three 19 twenty two twenty two 0 PTMEG2000 weight (kg) 0 0 28 27 20.6 19.6 17.5 0 0 0 0 25 AO 330 weight(g) 70 100 72 75 65 65 70 70 67.5 70 70 67.5 TBT weight(g) 70 100 72 75 65 65 70 70 67.5 70 70 67.5 Theoretical product weight (kg) 36.05 50.15 35.68 37.28 32.29 32.46 34.72 34.25 33.3 34.25 34.35 33 PTMEG weight ratio (%) 61 67 78.5 72.4 63.8 60.3 50.4 67 57 64 64 75.7 IPA weight proportion (%) 9.5 0 0 0 0 0 0 10 13.5 7 5 0 Table 2: Melting point, specific gravity and Shore hardness of TPEE resin particles of Preparation Examples 1 to 12 PE1 PE2 PE3 PE4 PE5 PE6 PE7 PE8 PE9 PE10 PE11 PE12 Melting point(℃) 110 140 152 167 185 190 207 94 101 118 126 160 proportion 1.1023 1.0921 1.0443 1.0686 1.0825 1.1078 1.1335 1.0804 1.1133 1.0939 1.1016 1.0581 Shore hardness 20 28 twenty three 26 30 33 40 18 19 19 twenty one 20

Test example 3 : Shore hardness

This test example uses the TPEE resin particles of the aforementioned Preparation Examples 1 to 12 as the analysis object. According to the standard method of ISO868, a hardness tester (brand: Bareiss, Germany, model: digi test II) is used to measure the Shore hardness.

Specifically, the TPEE resin particles of each preparation example were injection molded to obtain a test piece with a thickness of at least 4 mm; turn on the hardness tester and confirm that the weight and probe have been installed and positioned; enter the FUNC page and select Std.PV mode; then place the test piece on the platform, and the target measurement point must be at least 9 mm away from the edge of the test piece; press the start button to measure, and wait for 3 seconds. The value displayed on the instrument is the Shore value of the TPEE resin particles. hardness. As shown in Table 1 above, the Shore hardness of the TPEE resin particles of Preparation Examples 1 to 12 is 15 to 45.

"Polyester composite film and hot melt adhesive lamination"

Please refer to Figure 1. This invention mixes two types of TPEE resins (first and second TPEE resins) with different characteristics to form two types of TPEE films (first and second TPEE resin films) with different characteristics. By controlling The melting point between the two TPEE resins and the absolute difference in the melting enthalpy between the two TPEE films are controlled to obtain the desired polyester composite film and hot melt adhesive laminate. The embodiments of the polyester composite film and hot melt adhesive laminate are described below.

Example 1

Example 1 uses the TPEE resin particles of the aforementioned Preparation Example 1 as the first TPEE resin, and uses the TPEE resin particles of the aforementioned Preparation Example 6 as the second TPEE resin, and prepares the first TPEE film and the second TPEE film through the following method. , you can get polyester composite film and hot melt adhesive laminate.

As shown in Figure 1, take 20 kilograms to 25 kilograms of the second TPEE resin (high melting point TPEE resin pellets) and place it in the crystallization drying tank. Set the temperature at 100°C to 120°C and crystallize and dry for at least 4 to 8 hours. The dry air transports the high melting point TPEE resin pellets to the metering extruder; the extruder speed is set to 10 rpm to 50 rpm, and the temperature of each zone of the extrusion screw is set to 150°C to 230°C, so that the high melting point TPEE resin pellets are The heating temperature of the extruder and the screw friction shear heat melt into a high-melting point TPEE molten slurry, which is then extruded and cast into a high-melting TPEE molten slurry by setting the temperature in each zone of the extrusion die at a constant temperature of 190°C to 230°C.

At this time, a continuous PET release film is placed on one side of the injection molding machine, with a release force of 250 g to 1500 g. When the high melting point TPEE molten slurry is cast out through the extrusion die, the release film passes through Between the pressure roller and the cooling roller, the pressing area is located below the mold to accept the high melting point TPEE molten slurry and press it to form a high melting point TPEE film. The high melting point TPEE film is then extended through one to several sets of ripening rollers. The temperature of the ripening rollers The temperature is 5℃ to 30℃, the speed is 1 rpm to 10 rpm, and finally the release film and the high melting point TPEE film (i.e., the second TPEE film) on it are rolled up through the winding roller at a speed of 1 rpm to 10 rpm. Roll forming.

Take 20 kilograms to 25 kilograms of the first TPEE resin (low melting point TPEE resin pellets) and place it into a crystallization drying tank. Set the temperature at 60°C to 120°C to crystallize and dry for at least 4 to 8 hours. Use dry air to dry the low melting point TPEE. The resin pellets are transported to the metering extruder; the extruder speed is set to 10 rpm to 50 rpm, and the temperature of each zone of the extrusion screw is set to 100°C to 210°C, so that the low melting point TPEE resin pellets are heated by the extruder. It melts with the friction and heat of screw agitation and shear to form a low melting point TPEE molten slurry, which is then extruded and cast into molding by setting the temperature in each zone of the extrusion die at a temperature of 140°C to 210°C.

At this time, the aforementioned continuous release film and high melting point TPEE film are placed on one side of the injection molding machine. When the low melting point TPEE molten slurry is cast out through the extrusion die, the aforementioned release film and high melting point TPEE film pass through Between the pressure roller and the cooling roller, the pressing area is located below the mold to receive the low-melting TPEE molten slurry and press it into a low-melting TPEE film (i.e., the first TPEE film). This low-melting TPEE film is then passed through one to several sets of ripening rollers. The wheel set is extended, the temperature of the ripening roller is 5℃ to 30℃, and the speed is 1 rpm to 10 rpm. Finally, the release film, high melting point TPEE film, and low melting point TPEE are rolled out by the winding roller at a speed of 1 rpm to 10 rpm. The films are rolled together to form a polyester composite film formed on the release film. The release film and polyester composite film constitute a hot melt adhesive laminate.

As shown in Figure 2, the polyester composite film 20 includes a first thermoplastic polyether ester elastomer film 21 and a second thermoplastic polyether ester elastomer film 22 disposed on the first thermoplastic polyether ester elastomer film 21; The material of the first thermoplastic polyetherester elastomer film 21 includes a first thermoplastic polyetherester elastomer resin, and the material of the second thermoplastic polyetherester elastomer film 22 includes a second thermoplastic polyetherester elastomer resin.

As shown in Figure 3, the hot melt adhesive laminate 30 includes the aforementioned polyester composite film 20 and a release film 31. The polyester composite film 20 is disposed on the release film 31. Specifically, the polyester composite film 20 has The second thermoplastic polyetherester elastomer film 22 is sandwiched between the first thermoplastic polyetherester elastomer film 21 of the polyester composite film 20 and the release film 31 .

Example 2 to 7 , comparative example 1 to 3

Examples 2 to 7 and Comparative Examples 1 to 3 adopt the same method as Example 1 to prepare polyester composite films and hot melt adhesive laminates. The difference lies in the first TPEE resin used in each Example and Comparative Example. The source and melting point of the second TPEE resin are different, and their data are shown in Tables 2 to 4.

As mentioned above, the structures of the polyester composite films of Examples 2 to 7 and Comparative Examples 1 to 3 are also shown in Figure 2, and the structures of the hot melt adhesive laminates of Examples 2 to 7 and Comparative Examples 1 to 3 are also shown in Figure 2. As shown in Figure 3. Depending on the sources of the first and second TPEE resins used, the differences between Examples 2 to 7 and Comparative Examples 1 to 3 and Example 1 will be further described later.

Test example 4 : melting enthalpy

In this test example, the polyester composite films of the aforementioned Examples 1 to 7 and Comparative Examples 1 to 3 are used as the analysis objects. Each analysis object is divided into two samples to be tested according to the following method, and then the melting enthalpy of each sample is measured respectively. .

First, take a polyester composite film with a length of 10 cm and a width of 4 cm, fill a 25 ml sample bottle with 15 ml of acetone, and then soak the polyester composite film of the specific size in the sample bottle for up to 1 day. Take out the soaked polyester composite film and use scissors or a utility knife to separate the first TPEE film and the second TPEE film in the polyester composite film to obtain two samples to be tested (the first TPEE film and the second TPEE film). ).

Then, take 10 mg of the sample to be tested and place it in an aluminum pan, and place it together with the blank aluminum pan into a differential scanning card meter (DSC) (manufacturer: TA Instrument, model: Q-2000), at a temperature of 10°C per minute. The heating rate is from room temperature until the melting peak appears, and then it is cooled to room temperature at a cooling rate of 10°C per minute. The area enclosed by the line connecting the melting peak and the starting and ending points of the melting is calculated to obtain each test item. The melting enthalpy of the sample is shown in Table 3 below. For each polyester composite film, the melting enthalpy of the first TPEE film is represented by "△H _1st " in Table 3 below, and the melting enthalpy of the second TPEE film is represented by "△H _2nd " in Table 3 below. means; the absolute difference between the melting enthalpy of the first TPEE film and the melting enthalpy of the second TPEE film in each polyester composite film is represented by " "express.

As shown in Table 3 and Table 4, the melting point of the second TPEE resin in the polyester composite films of Examples 1 to 7 is greater than the melting point of the first TPEE resin, and its is 5 J/g to 15 J/g. Looking back at the polyester composite films of Comparative Examples 1 to 3, although the melting point of the second TPEE resin is greater than the melting point of the first TPEE resin, All exceed the range of 5 J/g to 15 J/g. Specifically, the melting enthalpies of the first and second TPEE films in the polyester composite films of Comparative Examples 1 and 3 are very close. are both lower than 5 J/g; while the difference in melting enthalpy between the first and second TPEE films in the polyester composite film of Comparative Example 2 is too large. More than 15 J/g. Table 3: Source and melting point of the first and second TPEE resins of Examples 1 to 7 and Comparative Examples 1 to 3, melting enthalpy (ΔH _1st ) of the first TPEE resin film, and both of the second TPEE resin film The melting enthalpy (ΔH _2nd ) and the absolute difference in the melting enthalpy of the first and second TPEE resin films ( ) The first TPEE membrane Second TPEE membrane The first source of TPEE resin Melting point of the first TPEE resin △H _1st Source of second TPEE resin Melting point of the second TPEE resin △H _2nd Example 1 Preparation Example 1 110℃ 3.04 J/g Preparation Example 6 190℃ 15.39 J/g 12.35 J/g Example 2 Preparation Example 2 140℃ 7.77 J/g Preparation Example 6 190℃ 15.39 J/g 7.62 J/g Example 3 Preparation Example 8 94℃ 1.4 J/g Preparation Example 4 167℃ 7.67 J/g 6.27 J/g Example 4 Preparation Example 9 101℃ 5.1 J/g Preparation Example 6 190℃ 15.39 J/g 10.29 J/g Example 5 Preparation Example 10 118℃ 4.9 J/g Preparation Example 6 190℃ 15.39 J/g 10.49 J/g Example 6 Preparation Example 11 126℃ 6.0 J/g Preparation Example 7 207℃ 20.51 J/g 14.51 J/g Example 7 Preparation Example 12 160℃ 3.6 J/g Preparation Example 6 190℃ 15.39 J/g 11.79 J/g Comparative example 1 Preparation Example 2 140℃ 7.77 J/g Preparation Example 4 167℃ 7.67 J/g 0.1 J/g Comparative example 2 Preparation Example 3 152℃ 3.79 J/g Preparation Example 7 207℃ 20.51 J/g 16.72 J/g Comparative example 3 Preparation Example 5 185℃ 16.73 J/g Preparation Example 7 207℃ 20.51 J/g 3.78 J/g

"Application of Polyester Composite Film and Hot Melt Adhesive Lamination"

The polyester composite film and hot melt adhesive laminate of this invention can have sufficient peel strength when attached to the fabric, so it can be well attached to the fabric and make the fabric have good waterproof properties. In order to verify the effect of the polyester composite film or hot melt adhesive laminate of this invention applied to fabrics, the peel strength and waterproofness are evaluated through Test Example 5 and Test Example 6 below. The test results are combined and explained below.

Test example 5 : Peel strength

This test example uses the hot melt adhesive laminates of the aforementioned Examples 1 to 7 and Comparative Examples 1 to 3. The release film of the hot melt adhesive laminate is peeled off and placed on a woven cloth, and then heated as follows. After pressing, washing, standing and other processing steps, the sample to be tested is obtained; then according to the standard method of ISO2411, a tensile testing machine (manufacturer: INSTRON, model: 3345) is used to measure the peeling between the polyester composite film and the woven fabric. intensity. Detailed preparation methods for each sample to be tested are described below.

First, prepare 9 pieces of test woven fabrics. The length of each woven fabric is at least 200 mm and the width is at least 75 mm. Its surface is covered with a waterproof film made of TPU; another polyester composite film with a length of at least 200 mm (width is not limited) ), place it on the woven fabric, with the first TPEE film of the polyester composite film facing the waterproof film on the woven fabric; then set the single-sided hot pressing temperature of the hot press at 175°C, and press The pressure is set at 3.0 kilograms per square centimeter (kg/cm ² ), and the polyester composite film and woven fabric are continuously hot-pressed with a hot press for a period of time to obtain a hot-pressed laminate. Here, among the aforementioned 9 pieces of test woven fabrics, 3 pieces were each hot-pressed with the polyester composite film for 20 seconds, and another 3 pieces of test woven fabrics were each hot-pressed with the polyester composite film for 30 seconds. Another 3 pieces of test woven fabrics were hot-pressed with the polyester composite film for 30 seconds. The fabrics were each heat-pressed with the polyester composite film for 40 seconds. A 100 mm length of the polyester composite film is left to be hot-pressed and laminated to the woven fabric, and the unattached end is left for clamping by the clamp of the tensile testing machine. Then, the hot-pressed laminate is left to stand for 24 hours to allow the polyester composite film to mature.

As shown in Figure 4, the hot-pressed laminate includes a woven fabric 41, a waterproof film 42 and the aforementioned polyester composite film 20. The waterproof film 42 is formed on the woven fabric 41, and the polyester composite film 20 passes through the third A thermoplastic polyether ester elastomer film 21 is attached to the waterproof film 42 , that is, the first thermoplastic polyether ester elastomer film 21 is sandwiched between the waterproof film 42 and the second thermoplastic polyether ester elastomer film 22 .

Afterwards, place each hot-pressed laminate into a washing test machine, add a standard cleaning cloth to bring the total weight to 1.8 kg ± 0.1 kg, and then add 66.0 g ± 1 g of 1993AATCC standard detergent dissolved in 18.0 gallons ±0.5 gallons of water, wash with water at a water temperature of 60℃±3℃ and a stirring speed of 179 rpm±2 rpm for 12 minutes, then spin dry at a dehydration speed of 645 rpm±15 rpm for 6 minutes, and repeat the washing and After being dehydrated 50 times and left to stand for 24 hours, the sample to be tested is obtained.

Finally, use the upper clamp of the tensile testing machine to clamp the woven fabric end of the sample to be tested, and the lower clamp to clamp the polyester composite film end of the sample to be tested (the clamps of the upper and lower clamps can be interchanged). The size is 6 inches * 2 inches, and the clamping distance between the upper and lower clamps is set at 50 mm; then the tensile speed of the peeling clamp in the tensile testing machine is set at 100 mm/min (mm/min) ± 10 mm/ min, and select an appropriate stress load range, and stretch at a constant speed until the polyester composite film and the woven fabric are peeled off. The maximum stress value detected during peeling is the peel strength between the polyester composite film and the woven fabric, unit : Kilogram weight/centimeter (kgf/cm). The peel strengths measured on the three samples to be tested were averaged after hot pressing for 20 seconds, and the results are shown in Table 4. In the same way, the peel strengths of the three samples to be tested that were hot pressed for 30 seconds and the three samples to be tested that were hot pressed for 40 seconds were averaged. The results are also shown in Table 4.

As shown in Table 4, whether the polyester composite film undergoes a hot pressing time of 20 seconds, 30 seconds or 40 seconds, the peel strength between the polyester composite film and the fabric of Examples 1 to 7 is significantly greater than that of Comparative Examples 1 to 7. The peeling strength between the polyester composite film of Example 3 and the fabric shows that the polyester composite film of Examples 1 to 7 can adhere well to the fabric and avoid unexpected peeling.

After a hot pressing time of 20 seconds, the peel strength between the polyester composite films of Examples 1 to 7 and the fabric exceeds 0.65 kgf/cm; specifically, the peel strength between the polyester composite films of Examples 1 to 7 and the fabric The peel strength is 0.68 kgf/cm to 1.50 kgf/cm. After a hot pressing time of 30 seconds, the peel strength between the polyester composite films of Examples 1 to 7 and the fabric exceeds 0.68 kgf/cm; specifically, the peel strength between the polyester composite films of Examples 1 to 7 and the fabric The peel strength is 0.70 kgf/cm to 1.75 kgf/cm. After a hot pressing time of 40 seconds, the peel strength between the polyester composite films of Examples 1 to 7 and the fabric exceeds 0.72 kgf/cm; specifically, the peel strength between the polyester composite films of Examples 1 to 7 and the fabric The peel strength is 0.85 kgf/cm to 2.00 kgf/cm.

Test example 6 : Waterproof

This test example uses the hot melt adhesive laminates of the aforementioned Examples 1 to 7 and Comparative Examples 1 to 3. The release film of the hot melt adhesive laminate is peeled off and placed on two pieces of woven fabric that have been sewn. After the following processing steps of hot pressing, water washing, and standing, the sample to be tested is obtained; then, according to the standard method of ISO811, a water-resistant press machine (manufacturer: HEZO, model: 322AD) is used to measure the lamination of the polyester composite film. The water pressure resistance of woven fabrics. Detailed preparation methods for each sample to be tested are described below.

First, take two pieces of test woven fabrics with a length of 200 mm to 225 mm and a width of 200 mm to 225 mm, and sew them in a flat seam manner. The sewing lines are folded and pressed so that the seams can be evenly connected. Paste so that the seam allowance does not appear as a triangular convex surface when viewed from the side. In addition, the surface of the woven fabric above is covered with a waterproof membrane made of TPU.

After that, peel off the release film of the hot melt adhesive laminate, and then place the polyester composite film on the seam of the two woven fabrics, with the first TPEE film of the polyester composite film facing the woven fabric. Waterproof membrane: Set the single-sided hot pressing temperature of the hot press machine at 175°C and the hot pressing pressure at 3.0 kg/cm ^2. Use the hot press machine to continue hot pressing the polyester composite film and the two-woven fabric for 20 seconds. 30 seconds or 40 seconds to obtain a heat-pressed laminate.

As shown in Figure 5, the hot-pressed laminate in this test example includes a first woven fabric 51, a second woven fabric 52, a waterproof film 53 and a polyester composite film. The first woven fabric 51 and the second woven fabric 52 are The two woven fabrics 52 are formed into one body by sewing; the waterproof membrane 53 is formed on the first woven fabric 51 and the second woven fabric 52; and the polyester composite film is arranged on the seam (as shown by the dotted line in the figure) , that is, the polyester composite film is attached to the waterproof film 53 through the first thermoplastic polyether ester elastomer film 21, and the first thermoplastic polyether ester elastomer film 21 of the polyester composite film is sandwiched between the waterproof film 53 and the second between the thermoplastic polyetherester elastomer films 22 .

After that, put the hot-pressed laminate into the washing test machine, add standard cleaning cloth to bring the total weight to 1.8 kg ± 0.1 kg, and then add 66.0 g ± 1 g of 1993 AATCC standard detergent dissolved in 18.0 gallons ± 0.5 gallons In water, wash with water at a temperature of 60°C ± 3°C and a stirring speed of 179 rpm ± 2 rpm for 12 minutes, and then spin-dry at a dehydration speed of 645 rpm ± 15 rpm for 6 minutes. Repeat this method for washing and drying for 50 minutes. After several times, let it stand for 24 hours to obtain the sample to be tested.

Finally, the water column water pressure of the hydraulic pressure machine is increased at 100±0.5 mm water column height/minute (mm H ₂ O/min), and the area on the sample to be tested with the polyester composite film is observed to bear the hydrostatic head (hydrostatic head). ), until three penetrating water droplets appear on the cloth surface, stop pressurizing and record the current water pressure value, which is the water pressure resistance value of the polyester composite membrane. The results are shown in Table 4. Alternatively, set the water column pressure of the hydraulic press to a fixed value, for example, set the hydrostatic pressure to 5,000 mmH ₂ O and hold the pressure for 120 seconds. Observe that the area on the sample to be tested where the polyester composite film is attached bears the hydrostatic head. In the case of water seepage, if there are less than 3 water droplets leaking, record the set value as the water pressure resistance value of the polyester composite membrane.

As shown in Table 4, the polyester composite films of Examples 1 to 7 can achieve a water pressure resistance of more than 5,000 mmH ₂ O regardless of whether they are attached to the fabric through a hot pressing time of 20 seconds, 30 seconds or 40 seconds. It shows that The polyester composite membranes of Examples 1 to 7 can make the fabrics have good waterproof properties and can be used to withstand rainwater from light rain to moderate heavy rain. However, the polyester composite membrane of Comparative Example 3 cannot obtain sufficient contact with the fabric. The peel strength caused the polyester composite film of Comparative Example 3 to be unable to support the weight of water during the water pressure resistance test, so the water pressure resistance results of Comparative Example 3 could not be measured. Table 4: The melting points of the first and second TPEE resins of Examples 1 to 7 and Comparative Examples 1 to 3, and the absolute difference in melting enthalpy of the first and second TPEE resin films ( ), and the peel strength and water pressure resistance test results of Examples 1 to 7 and Comparative Examples 1 to 3 applied to fabrics after hot pressing for 20 seconds, 30 seconds and 40 seconds. Melting point of the first TPEE resin Melting point of the second TPEE resin Peel strength (kgf/cm) Water pressure resistance value (mmH ₂ O) 20 seconds 30 seconds 40 seconds Example 1 110℃ 190℃ 12.35 J/g 1.06 1.03 1.09 ≧5,000 Example 2 140℃ 190℃ 7.62 J/g 0.88 0.88 0.90 ≧5,000 Example 3 94℃ 167℃ 6.27 J/g 0.7 0.85 0.88 ≧5,000 Example 4 101℃ 190℃ 10.29 J/g 1.12 1.39 1.33 ≧5,000 Example 5 118℃ 190℃ 10.49 J/g 1.05 1.01 1.15 ≧5,000 Example 6 126℃ 207℃ 14.51 J/g 0.68 0.7 0.92 ≧5,000 Example 7 160℃ 190℃ 11.79 J/g 1.32 1.38 1.61 ≧5,000 Comparative example 1 140℃ 167℃ 0.1 J/g 0.65 0.61 0.60 ≧5,000 Comparative example 2 152℃ 207℃ 16.72 J/g 0.48 0.68 0.72 ≧5,000 Comparative example 3 185℃ 207℃ 3.78 J/g 0.08 0.14 0.15 Unmeasurable

Discussion of experimental results

As shown in Table 4, the polyester composite films of Examples 1 to 7 adopt the first and second TPEE films, and the polyester composite films have the melting point of the second TPEE resin being greater than the melting point of the first TPEE resin, and the second TPEE resin. The absolute difference between the melting enthalpy of one TPEE film and the melting enthalpy of the second TPEE film is 5 J/g to 15 J/g, so the polyester composite film heat treatment method of Examples 1 to 7 is used. When pressed onto the fabric, not only can the first TPEE film be bonded to the fabric to obtain good peel strength, but the second TPEE film above it can still maintain its film quality after hot pressing and will not be affected by the high temperature of hot pressing. Therefore, it can ensure that the adhered fabric obtains a water pressure resistance value of up to 5,000 mmH ₂ O and above, so that the fabric coated with the polyester composite film of Examples 1 to 7 can obtain good waterproof properties.

Looking back at Comparative Examples 1 to 3, the peel strengths of the polyester composite films of Comparative Examples 1 and 2 that are hot pressed and bonded to the fabric are lower than those of Examples 1 to 7, and there is a risk of the polyester composite film peeling off from the fabric; In particular, the peel strength of the polyester composite film of Comparative Example 3 that was hot-pressed onto the fabric was not even sufficient to withstand the weight of water applied in the water pressure test, resulting in the polyester composite film of Comparative Example 3 being unable to adhere well to the fabric. Provides the required water resistance.

In addition, since the melting point of the second TPEE resin is greater than the melting point of the first TPEE resin, when the polyester composite films of Examples 1 to 7 are hot-pressed and bonded to the fabric through the first TPEE film, only a relatively low heat-pressing time is required. temperature (that is, a temperature between the melting point of the first TPEE resin and the melting point of the second TPEE resin) can melt the first TPEE film of the polyester composite film and adhere well to the fabric, and the second TPEE The membrane will not be melted by the influence of hot pressure and high temperature, so the fabric can obtain good waterproof properties.

In summary, by combining the first TPEE film and the second TPEE film, and controlling the melting point of the second TPEE resin in the polyester composite film to be greater than the melting point of the first TPEE resin and the melting enthalpy of the first TPEE film and the The absolute difference between the melting enthalpy of the second TPEE film and the other technical means is 5 J/g to 15 J/g. The polyester composite film of this invention can be well hot-pressed and bonded to the fabric to obtain sufficient peel strength. , and make the fitted fabric obtain good waterproof properties. In the same way, the hot melt adhesive laminate containing the aforementioned polyester composite film can also be used for fabric lamination, so that it can obtain sufficient peel strength between it and the fabric, and the laminate fabric can obtain good waterproofness.

20:Polyester composite film 21: First thermoplastic polyetherester elastomer film 22: Second thermoplastic polyetherester elastomer film 30: Hot melt adhesive lamination 31: Release film 41:Woven fabric 42:Waterproof membrane 51:First woven fabric 52:Second woven fabric 53:Waterproof membrane

Figure 1 is a schematic flow chart for preparing a polyester composite film and hot melt adhesive laminate. Figure 2 is a schematic side view of a polyester composite film. Figure 3 is a schematic side view of a hot melt adhesive laminate. Figure 4 is a schematic side view of the hot-pressed laminate in Test Example 5. FIG. 5 is a schematic side view of the hot-pressed laminate in Test Example 6.

without

20:Polyester composite film

21: First thermoplastic polyetherester elastomer film

22: Second thermoplastic polyetherester elastomer film

Claims (14)

A polyester composite film, which includes a first thermoplastic polyetherester elastomer film and a second thermoplastic polyetherester elastomer film; wherein the material of the first thermoplastic polyetherester elastomer film includes a first thermoplastic polyetherester elastomer film The second thermoplastic polyether ester elastomer film is made of a second thermoplastic polyether ester elastomer resin, and the second thermoplastic polyether ester elastomer resin has a melting point greater than that of the first thermoplastic polyether ester elastomer resin. melting point, and the absolute difference between the melting enthalpy of the first thermoplastic polyetherester elastomer film and the melting enthalpy of the second thermoplastic polyetherester elastomer film is 5 J/g to 15 J/g. The polyester composite film of claim 1, wherein the melting enthalpy of the first thermoplastic polyetherester elastomer film is 1 J/g to 10 J/g. The polyester composite film of claim 1, wherein the melting enthalpy of the first thermoplastic polyetherester elastomer film is 3 J/g to 10 J/g. The polyester composite film of claim 1, wherein the melting enthalpy of the second thermoplastic polyetherester elastomer film is 5 J/g to 25 J/g. The polyester composite film of claim 4, wherein the melting enthalpy of the second thermoplastic polyetherester elastomer film is 6 J/g to 25 J/g. The polyester composite film of claim 1, wherein the melting point of the first thermoplastic polyetherester elastomer resin is 90°C to 164°C. The polyester composite film of claim 6, wherein the melting point of the first thermoplastic polyetherester elastomer resin is 100°C to 160°C. The polyester composite film of claim 1, wherein the melting point of the second thermoplastic polyetherester elastomer resin is 165°C to 220°C. The polyester composite film according to any one of claims 1 to 8, wherein the specific gravity of the first thermoplastic polyetherester elastomer resin or the second thermoplastic polyetherester elastomer resin is 1.00 to 1.15. The polyester composite film of any one of claims 1 to 8, wherein the first thermoplastic polyetherester elastomer resin or the second thermoplastic polyetherester elastomer resin has a Shore hardness of 15 to 45. The polyester composite film of claim 10, wherein the first thermoplastic polyetherester elastomer resin has a Shore hardness of 15 to 30. The polyester composite film of claim 10, wherein the second thermoplastic polyetherester elastomer resin has a Shore hardness of 25 to 45. The polyester composite film of claim 10, wherein the Shore hardness of the second thermoplastic polyetherester elastomer resin is greater than the Shore hardness of the first thermoplastic polyetherester elastomer resin. A hot melt adhesive laminate, which includes the polyester composite film and a release film as described in any one of claims 1 to 13, and the second thermoplastic polyetherester elastomer film of the polyester composite film is sandwiched between the The polyester composite film is between the first thermoplastic polyetherester elastomer film and the release film.

Images