KR20200035386A - Recyclable laminated fabric - Google Patents

Abstract

The present invention relates to a recyclable laminated fabric. The present invention relates to a laminated fabric, which is made of a polybutylene terephthalate (PBT) elastomer resin by laminating PBT elastomers on a polyester fabric to a certain thickness, and which is recyclable and has excellent heat resistance, cold resistance, weather resistance, printability, and adhesiveness.

Description

Recyclable laminated fabric {RECYCLABLE LAMINATED FABRIC}

The present invention relates to a laminated fabric that can be recycled, and more particularly, to a laminated fabric of a PBT elastomer resin that is recyclable and has excellent heat resistance, cold resistance, weather resistance, printability, and adhesiveness.

Currently, generally, the textile materials of laminated fabrics are cotton, nylon, and polyester, and PVC resin, polyurethane, PP, PE, and PVC are mainly used as the resin. PVC resin has excellent physical properties such as processability, printability, adhesiveness, weatherability and tensile strength and elongation, but it has been used as a main raw material for laminated fabrics, but it is often replaced with other types of resins such as polyurethane, PP, and PE due to toxicity or environmental problems. However, PVC due to poor processability of polyurethane resin, deterioration of physical properties due to hydrolysis, poor printability, adhesion of PP or PE or olefin-based elastomers, poor adhesion, weatherability, and oil resistance of styrene-based fluoropolymers The resin laminated fabric has not been completely replaced, and recycling is almost impossible, so it is disposed of by incineration.

The fiber material of the laminated fabric is generally cotton, nylon, and polyester fiber materials, and the resin is mainly PVC, polyurethane, PE, and PP. Of these, laminated fabrics made of polyester fiber materials and PVC resins have been replaced by other resins due to the toxicity and environmental problems of PVC resins, but they are still used in many parts due to the excellent properties of PVC resins, and are made of eco-friendly resins such as polyurethane, PE, and PP. Laminated fabrics, such as synthetic leather or tarpaulin, can be recycled in a very small amount, but they are almost impossible to recycle, so the environmental problems of laminated fabrics, such as vinyl leather and tarpaulin, are serious. PBT elastomer is an eco-friendly resin composed of materials such as PET-G, TPEE, styrene-based fluoropolymer, vegetable oil, and eco-friendly plasticizer, using PBT resin as the main raw material.The laminated fabric composed of PBT elastomer and polyester-based fiber material is It is 100% recyclable and it is thought that it is possible to replace laminated fabrics made of PVC resin with excellent properties.

As a background technology of the present invention, there is a patent registration No. 1004614 "PET-based molding deco sheet having similar moldability to PCC" (Patent Document 1). In the background art, 'the polyethylene terephthalate glycol (PETG) resin contains a PETG alloy resin in which an elastomer resin is melt-mixed (alloy), and the elastomer resin is a polybutylene terephthalate (PBT) resin and a polyether glycol. (Polyether Glycol) is an elastomer resin copolymerized.

However, the background technology has a moldability similar to that of PPC, but it is mainly used as a hard sheet, a product container, etc., but it is difficult to produce a soft film or soft sheet due to difficulty in softening.

Patent registration No. 1004614 "PET-type molding deco sheet with similar moldability to PC"

The present invention is to solve the above problems, as well as general use, such as furniture and bags, PBT elastomer resin and polyester fiber having excellent processability, adhesiveness, printability, weather resistance and better heat resistance and cold resistance than PVC of PBT elastomer. The laminated fabric composed of ash is intended to provide a recyclable laminated fabric capable of replacing the laminated fabric composed of polyurethane, PP, PE or olefin-based elastomers and various fibrous materials to the place where the PVC resin laminated fabric cannot be replaced. There is this.

In addition, in general, air boats or air tubes are made of rubber or PVC tarpaulin, and excellent water resistance and adhesion are required. These resins cannot be used due to the hydrolysis of polyurethane and poor adhesion of PP, PE, and olefin elastomers. , Air boats or air tubes made of rubber and textile materials have a heavy weight, and air boats or air tubes made of PVC resin tarpaulin have poor cold resistance, making it difficult to use in winter and tarpaulin used as a billboard for printing is also partly PP or Although PE is used in combination with an olefinic elastomer, it is used only partially due to poor adhesion and printability, and most of it is PVC tarpaulin. The fiber material of laminated fabrics composed of resins possessing excellent physical properties such as PVC or polyurethane is composed of cotton or polyester-based fiber materials, and cannot be recycled due to the heterogeneity of the fiber materials and resins, but can be recycled in the present invention. The purpose of the fabric is to provide a 100% recyclable laminated fabric.

The present invention is to provide a recyclable laminated fabric, characterized in that it is composed of a polyester fiber (polyester fabric) PBT (polybutylene terephthalate) elastomer is laminated to a certain thickness.

In addition, the PBT elastomer is a recyclable laminated fabric, characterized by mixing 10 to 120 parts by weight of an eco-friendly plasticizer and 10 to 120 parts by weight of a TPEE (Thermoplastic copolyester elastomer) resin with respect to 100 parts by weight of the PBT resin. Want to provide.

In addition, the PBT resin is to provide a recyclable laminated fabric, characterized in that 20% to 100% by weight of the PET-G (Glycol modified polyethylene terephthalate) resin.

In addition, with respect to 100 parts by weight of the PBT resin, a recyclable laminated fabric characterized by further mixing 5 parts to 100 parts by weight of a styrene-based block copolymer and 5 parts to 100 parts by weight of a paraffin oil. Want to provide

In addition, it is intended to provide a recyclable laminated fabric characterized by selectively mixing 10 parts by weight to 100 parts by weight of an acrylic rubber or an acrylic rubber-based copolymer or a butadiene rubber or a butadiene rubber-based copolymer based on 100 parts by weight of the PBT resin.

In addition, with respect to 100 parts by weight of the PBT resin, it is intended to provide a recyclable laminated fabric characterized by further mixing 10 parts by weight to 120 parts by weight of vegetable oil.

The recyclable laminated fabric of the present invention is a laminate composed of a PBT elastomer resin and a polyester fiber material having not only general use such as furniture or bags, but also excellent workability, adhesiveness, printability, weatherability and better heat resistance and cold resistance than PVC of the PBT elastomer. The fabric has the effect that the laminated fabric composed of polyurethane, PP, PE or olefin-based elastomer and various fiber materials can be replaced even where the PVC resin laminated fabric cannot be replaced.

In addition, in general, air boats or air tubes are made of rubber or PVC tarpaulin, and excellent water resistance and adhesion are required. These resins cannot be used due to the hydrolysis of polyurethane and poor adhesion of PP, PE, and olefin elastomers. , Air boats or air tubes made of rubber and textile materials have a heavy weight, and air boats or air tubes made of PVC resin tarpaulin have poor cold resistance, making it difficult to use in winter and tarpaulin used as a billboard for printing is also partly PP or Although PE is used in combination with an olefinic elastomer, it is used only partially due to poor adhesion and printability, and most of it is PVC tarpaulin. The fiber material of laminated fabrics composed of resins possessing excellent physical properties such as PVC or polyurethane is composed of cotton or polyester-based fiber materials, and cannot be recycled due to the heterogeneity of the fiber materials and resins, but can be recycled in the present invention. The fabric has a very useful effect, 100% recyclable.

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

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

Generally, a laminated fabric refers to synthetic leather (vinyl leather), tarpaulin, etc. as two or more layers of fabric bonded to a fibrous material with a resin made of a film. Therefore, the adhesiveness and printability of the fiber material and the resin are important elements of the laminated fabric. Constituting a resin composition having these properties, and using low PBT resin as the main raw material, and other additives such as PET-G, TPEE, styrene-based fluoropolymer, eco-friendly plasticizer, vegetable oil, processing aid, flame retardant, filler, weathering reinforcing agent, compatibilizer Provided is a composition.

The recyclable laminated fabric of the present invention is constructed by laminating a polybutylene terephthalate (PBT) elastomer with a certain thickness on a polyester fabric.

<Experimental Example 1>

The present invention relates to the production of a laminated fabric formed by bonding two or more layers of a polyester fiber and a film made of a PBT resin elastomer. In general, the PVC resin used in PVC laminated fabric is a soft PVC with a plasticizer content of 40 to 60 parts by weight mixed with 100 parts by weight of PVC. A film with an A hardness of 9585 is mainly used. In this experiment, the physical properties of PVC, LDPE, and LLDPE resins and PBT elastomers mainly used in laminated fabrics were compared and examined.

Resin type A hardness importance Tensile strength kgf / ㎟ Elongation (%) Example 1: PVC 95 ± 3 1.25 2.06 327 Example 2: PVC 88 ± 3 1.23 1.78 356 Example 3: PVC 85 ± 3 1.21 1.60 354 Example 4: PBT elastomer 95 ± 3 1.14 2.14 349 Example 5: PBT elastomer 88 ± 3 1.14 1.52 430 Example 6: PBT elastomer 85 ± 3 1.12 1.33 419 Example 7: LDPE 94 ± 3 0.92 1.14 290 Example 8: LLDPE (Hanhwa; 3120) 96 ± 3 0.94 1.34 184 Example 9: Olefin-based elastomer 85 ± 3 0.99 1.46 710

LDPE; 722 (Hanhwa Petrochemical Item Number) LLDPE; 3120 (Hanhwa Petrochemical Item Number)

As in Examples 1 to 9, physical properties of resins mainly used in the manufacture of laminated fabrics were comparatively reviewed. In general, if the thickness of the film is thick, a soft resin having low hardness is selected.

From Example 1 to Example 6, as compared with PVC and PBT elastomers, A hardness of 95 was better than that of PBT elastomers, but PVC resin was superior to PBT elastomers at low hardness such as A hardness 88 and 85, and LDPE or LLDPE. Rather, PVC resin or PBT elastomer was superior. Olefin-based elastomers are mainly used for manufacturing low-hardness products and exhibit excellent properties at low hardness. Mainly, the tensile strength of laminated fabrics tends to be determined by the tensile strength of the fibrous material.

As shown in the experiment in Table 1, it is determined that the physical properties of the laminated fabric composed of PBT elastomer are similar to that of the PVC resin laminated fabric.

<Experimental Example 2>

In this experiment, a polyester-based nonwoven faric was selected from the fiber materials, and a physical property test of the laminated fabric was conducted.

Polyester fiber materials used for laminated fabrics are mainly woven fabrics and non-woven fabrics, and non-woven fabrics are mainly made of polyester resin and PP resin, and due to the nature of the resin, polyester non-woven fabrics have a thinner thickness and higher tensile strength than fabrics. It was also low and the adhesive strength with the PBT elastomer was good, and the physical properties test of the laminated fabric composed of the polyester nonwoven fabric was made as in the Examples.

Practical example Thickness (mm) Tensile strength (kg / 5cm) PBT elastomer 171 1.Non-woven fabric 30g / ㎡ 0.14   Upper adhesive 0.38 208kgf / ㎠   Upper and lower adhesive 0.57 286 2.Non-woven fabric 70g / ㎡   Upper adhesive 0.39 360   Upper and lower adhesive 0.66 520 3.Non-woven fabric 100g / ㎡   Upper adhesive 0.42 574   Upper and lower adhesive 0.7 776

As shown in Table 2, the tensile strength of the laminated fabric bonded with the PBT elastomer and the nonwoven fabric was compared. In Example 1, the thickness of the nonwoven fabric was 0.14 mm, and there was no obvious improvement effect. However, as in Examples 2 and 3, the PBT elastomer laminated fabric reinforced with a thick nonwoven fabric has a large property-reinforcing effect so that it is made of a resin such as PVC or polyurethane. It is thought that it is possible to replace the fabric and contribute greatly to the environment improvement by recycling effect.

<Experimental Example 3>

In this experiment, a recycling test was conducted.

Recycling of resins generally involves crushing resin wastes to produce products by injection or extrusion, and injection products are mainly produced rather than extruded products. Extrusion processing has a high incidence of defective products due to foreign substances mixed in recycled resin.

In this experiment, recycling of laminated fabrics composed of polyester fiber materials and PBT elastomers must be made in the form of pellets through a compound process before being recycled. Due to the large difference between the processing temperature of the polyester fiber material and the processing temperature of the PBT elastomer, it is impossible to process the product with simple crushed products.

PVC laminated fabrics cannot be mixed due to the incompatibility and melting point difference between cotton or polyester fiber material used as fiber material and PVC resin. In general, the processing temperature of PVC and polyurethane is 200 ℃ or less, and the processing temperature of polyester fiber is 250 ℃ ~ 300 ℃.

The processing temperature of the fibers constituting the woven fabric is 280 to 300 ° C, and the fibers for the nonwoven fabric are 250 to 280 ° C, and the processing temperature of the nonwoven fabric is low. The processing temperature of the PBT elastomer used in the present invention is 200 ~ 280 ℃, the processing temperature is wide, and even when it becomes 300 ℃, there is no carbonization phenomenon, and it is also excellent in usability with polyester fiber, so it can be recycled and the physical properties of PBT elastomer with excellent physical properties. It is possible to manufacture excellent recycled products with little degradation. Even if PVC resin is recycled, there is no change in physical properties, but polyurethane resin has a severe property deterioration.

division        Compound Processing Temperature (℃) Heater 1 and 2 3,4,5,6 heater 7,8 heater Heater 9 and 10 Adapter, Dice Polyester fabric 250 300 280 250 230 Polyester non-woven fabric 250 280 250 230 200

In Experimental Example 3, as a result of experimenting with the waste laminated fabric, as a result of performing the temperature setting as shown in Table 3 through the compound processing of the waste laminated fabric adhered to the top of the PBT elastomer film on the fabric and the nonwoven fabric, a good recycled compound in pellet form was formed and the nonwoven fabric The silver was in a good regenerated state so that extrusion was possible. Until now, fabric fiber materials were almost impossible to recycle alone, but it is possible to recycle laminated fabrics made of PBT elastomer film and polyester fiber material, so it is possible to replace non-recyclable laminated fabric products made of PVC resin or polyurethane resin. I think that. The method of processing the laminated fabric composed of polyester fiber material and PBT elastomer is possible in the same way as the laminated fabric composed of fiber material and PVC resin, but the processing method using T-dies is preferred over the calendar processing method. The properties of the processed products are also good in the way using Tidys and easy to process. This is considered to be due to the processing temperature of the PBT elastomer higher than the processing temperature of the PVC resin and the melting viscosity lower than that of the PVC resin.

Particularly, the PBT elastomer in the present invention may be made by mixing 10 to 120 parts by weight of an eco-friendly plasticizer and 10 to 120 parts by weight of a TPEE (Thermoplastic copolyester elastomer) resin with respect to 100 parts by weight of the PBT resin.

In the PBT elastomer composition, PBT resin having excellent cold resistance, heat resistance, and weather resistance is used as a base resin, and an eco-friendly plasticizer is mixed to reduce hardness, and heat resistance, weather resistance, and cold resistance are good, and TPEE resin excellent in mixability and compatibility with other resins is mixed and stretched. Complement physical properties such as strength and elongation.

PBT (Polybutylene Terehpthalate) resin is made by reacting terephthalic acid with 1,4-butanediol. It is a crystalline resin that has excellent heat resistance, chemical resistance, and electrical properties among various engineering plastics. It has excellent abrasion resistance, abrasion resistance and dimensional stability, and is mainly used in electrical, electronic, and automotive parts. In particular, it is a resin with excellent heat resistance and has a narrow range of deterioration in physical properties even at high temperatures. It can be used for a long time even at 120 to 130 ° C and does not deform at high temperatures and high loads. Melting point is 220 ~ 225 ℃. TPEE (Thermoplastic copolyester elastomer) resin is a block copolymer composed of hard and soft segments, which has all the characteristics of rubber and engineering plastics, and has excellent heat resistance, cold resistance, and mechanical properties.

 When mixing with less than 10 parts by weight of TPEE (Thermoplastic copolyester elastomer) resin, the effect of enhancing the physical properties of tensile strength and elongation does not appear, and when mixing more than 120 parts by weight, the economic efficiency is poor, so mixing 10 parts by weight to 120 parts by weight It is preferred.

It is preferable to mix 10 to 120 parts by weight since the eco-friendly plasticizer does not have an effect of lowering the hardness when mixing less than 10 parts by weight, and weakens the durability when mixing more than 120 parts by weight.

Particularly, the PBT resin may be replaced with a PET-G (Glycol modified polyethylene terephthalate) resin having good compatibility and processability to improve processability.

When the PBT resin is replaced with less than 20 parts by weight of the PET-G resin, it is preferable to replace the PBT resin with 20 to 100% by weight of the PET-G (Glycol modified polyethylene terephthalate) resin because the processability improvement effect does not appear.

PET-G resin is a glycol-modified polyethylene terephthalate (glycol-modified polyethylene terephthalate) .It is a copolymerized amorphous resin added with CHDM (1,4-cyclohexanedimethanol) as a comonomer to improve the properties and processability of the PET resin. It is excellent in printability, impact resistance and chemical resistance, has a wide range of processability, does not contain environmental hormones, does not contain harmful substances, and does not generate harmful substances. It is an eco-friendly resin, relatively low in price, and is used as a rigid sheet, food container, etc. Also, the processing temperature is as low as 190 ~ 200 ℃. In general, a suitable high-frequency processing temperature is 160 to 180 ° C, and a foaming agent having a foaming temperature of 160 to 190 ° C is suitable.

In addition, 10 parts by weight to 120 parts by weight of vegetable oil may be further mixed with respect to 100 parts by weight of the PBT resin.

Vegetable oil is less than 10 parts by weight, when mixing does not have the effect of lowering the hardness, when mixing more than 120 parts by weight, it is preferable to mix 10 to 120 parts by weight because the durability is weakened.

In addition, with respect to 100 parts by weight of the PBT resin, a styrene-based block copolymer may be further mixed with 5 parts by weight to 100 parts by weight and 5 parts by weight to 100 parts by weight of paraffin oil.

In order to form a composition excellent in cold resistance, heat resistance, and oil resistance as well as weatherability, it is also possible to mix PBT resin and paraffin oil with relatively good compatibility and good blendability in a polystyrene-elastomer block copolymer (TPR). .

When the block copolymer is mixed with less than 5 parts by weight, the synergistic effect of compatibility and mixing does not appear, and when it exceeds 100 parts by weight, the economic efficiency decreases.

In order to improve processability and reduce the hardness, paraffin-based oil is used instead of an eco-friendly plasticizer or vegetable oil, and it is possible to mix more than 100 parts by weight, but since durability and economy are poor, it is preferable to mix from 10 parts by weight to 100 parts by weight.

In addition, 10 parts by weight to 100 parts by weight of the acrylic rubber or acrylic rubber-based copolymer or butadiene rubber or butadiene rubber-based copolymer can be selectively mixed with respect to 100 parts by weight of the PBT resin.

 The core-shell type copolymer is mainly used as a PVC impact modifier and consists of a double structure of the shell part and the core part, and the cell part is mainly made of acrylic or SAN resin. It is a resin and the core part is composed of rubbers such as acrylic rubber, butadiene rubber, and silicone rubber.

Butadiene copolymers are widely used due to their excellent compatibility with other resins, and acrylic or silicone copolymers are mainly used as impact modifiers for improving weather resistance. These copolymers are spherical (round) powders with good oil or plasticizer absorption and good compatibility with PBT, PET-G and TPEE resins. When mixing less than 10 parts by weight, the synergistic effect of compatibility and mixing does not appear, and if it exceeds 100 parts by weight, the economic efficiency is poor.

The recyclable laminated fabric of the present invention as described above is not only for general use such as furniture or bags, but also PBT elastomer resins and polyester fiber materials having excellent processability, adhesiveness, printability, weather resistance and better heat resistance and cold resistance than PVC. Laminated fabrics made of polyurethane, PP, PE or olefin-based elastomers and laminated fabrics composed of various fibrous materials have the effect of being able to replace even the parts that cannot replace PVC resin laminated fabrics.

In addition, in general, air boats or air tubes are made of rubber or PVC tarpaulin, and excellent water resistance and adhesion are required. These resins cannot be used due to the hydrolysis of polyurethane and poor adhesion of PP, PE, and olefin elastomers. , Air boats or air tubes made of rubber and textile materials have a heavy weight, and air boats or air tubes made of PVC resin tarpaulin have poor cold resistance, making it difficult to use in winter and tarpaulin used as a billboard for printing is also partly PP or Although PE is used in combination with an olefinic elastomer, it is used only partially due to poor adhesion and printability, and most of it is PVC tarpaulin. The fiber material of laminated fabrics composed of resins possessing excellent physical properties such as PVC or polyurethane is composed of cotton or polyester-based fiber materials, and cannot be recycled due to the heterogeneity of the fiber materials and resins, but can be recycled in the present invention. The fabric has a very useful effect, 100% recyclable.

The present invention has been described in detail with reference to the presented embodiments, but those skilled in the art can make various modifications and modified inventions without departing from the technical spirit of the present invention with reference to the presented embodiments. will be. The present invention is not limited by such modified and modified inventions, but is limited by the appended claims.

Claims (5)

It is made by laminating PBT (polybutylene terephthalate) elastomer to a polyester fiber material to a certain thickness,
PBT elastomers,
It is made by mixing 10 to 120 parts by weight of an eco-friendly plasticizer and 10 to 120 parts by weight of a TPEE (Thermoplastic copolyester elastomer) resin with respect to 100 parts by weight of the PBT resin,
PBT resin replaces 20% to 100% by weight of PET-G (Glycol modified polyethylene terephthalate) resin,
With respect to 100 parts by weight of the PBT resin, styrene-based block copolymer is further mixed with 5 parts by weight to 100 parts by weight, and 5 parts by weight to 100 parts by weight of paraffin oil,
In 100 parts by weight of the PBT resin, in the laminated fabric recyclable of the above-described known technology to further mix 10 parts by weight to 120 parts by weight of vegetable oil,
Recyclable laminated fabric, characterized in that the laminated fabric is eco-friendly. The method according to claim 1,
A recyclable laminated fabric, characterized in that the laminated fabric is part of a product designed to contact water. The method according to claim 2,
A recyclable laminated fabric characterized in that the product is an air boat or air tube. The method according to claim 1, Recyclable laminated fabric, characterized in that the laminated fabric is a printing fabric or a part thereof. The method according to claim 4,
Recyclable laminated fabric, characterized in that the laminated fabric is a fabric for printing billboards.