KR101307184B1 - Thermoplastic elastomer composition - Google Patents

Abstract

The present invention relates to a thermoplastic elastomer resin composition comprising a modified polyester, a soft polyester thermoplastic elastomer, a polyolefin copolymer, a non-halogen flame retardant, a non-halogen flame retardant adjuvant, and nanoclays.
According to the present invention, it is possible to provide a thermoplastic elastomer resin composition having a low hardness and weight, excellent flexibility, flame retardancy, mechanical strength and workability, and excellent surface feel, which is very suitable for the production of an insulating material for covering an electric wire used in a device or an apparatus. have.

Description

Thermoplastic elastomer composition

The present invention relates to a thermoplastic elastomer resin composition, and more particularly to a flame retardant thermoplastic elastomer comprising a modified polyester, a flexible polyester thermoplastic elastomer, a polyolefin copolymer, a non-halogen flame retardant, a flame retardant aid, and a nano clay. It relates to a resin composition.

Generally, flexible plastic materials such as polyvinyl chloride (PVC) and polypropylene (PP) are widely used for vibration absorbers or wire insulation. Flame retardant use is a very important factor. The most common inexpensive flame retardants are bromine or halogen-based. In recent years, halogen-based flame retardants have been greatly restricted in use due to environmental problems.

Researchers have been working on flame retardants. However, halogen phosphate compounds in flame retardants also adversely affect the environment. In addition, metal phosphate in the flame retardant is an insufficient supply of resources, the price is expensive, there is some limitation in use.

Aluminum hydroxide and magnesium hydroxide are also widely used as a practical flame retardant, but the flexibility and softness of the thermoplastic material is reduced by 60% or more, thereby limiting its use for wire cables.

Polyvinyl chloride (PVC) resins are widely used in the wire industry for wire insulation. However, polyvinyl chloride (PVC) resins have been controversial in that they adversely affect the environment as halogen-based materials. Polyethylene or crosslinked polyethylene compounds have been successful as non-halogen wire insulators, but are limited in practical applications due to mechanical strength and surface hardness problems. In addition, it has been pointed out that it is difficult to reduce the thickness of the crosslinked polyethylene compound so that it can be actually used as the wire insulation material.

GE Plastics discloses a wire compound including polyaryl ether and polyolefin containing a functional group selected from the group consisting of epoxy, carbonyl anhydride and magnesium hydroxide as an inorganic flame retardant filler. (US 7453044 B2, US 2010/0276488 A1). Meanwhile, BPADP has also disclosed inventions for flame retardants (US 2010/0276180 A1, US 2006/0131052 A1). However, since the price of the product is very expensive, there is a continuous need for research and development of inexpensive materials.

United States Patent US 7453044 B2 United States Patent Application Publication US 2010/0276488 A1 United States Patent Application Publication No. 2010/0276180 A1 United States Patent Application Publication US 2006/0131052 A1

The problem to be solved by the present invention is a modified polyester, a flexible polyester-based thermoplastic elastomer, a polyolefin copolymer, a non-halogen flame retardant, a flame retardant aid and nano clay, and has a low hardness and weight, flexibility, flame retardancy, mechanical It is to provide a flame retardant thermoplastic elastomer resin composition excellent in strength and workability.

The present invention provides 5 to 50 parts by weight of at least one modified polyester selected from the group consisting of polyethylene terephthalate glycol, polycyclohexane terephthalate and polycyclohexylenedimethylene cyclohexanedicarboxylate, 15 to 80 parts by weight of a flexible polyester thermoplastic elastomer, 0.5 to 30 parts by weight of a polyolefin copolymer for promoting miscibility and suppressing phase separation, 10 to 30 parts by weight of a non-halogen flame retardant to impart flame retardancy, and It provides a thermoplastic elastomer resin composition comprising 1 to 10 parts by weight of a non-halogen metal oxide for imparting and 0.05 to 5 parts by weight of nanoclay for improving flame retardancy and processability.

The present invention also provides 5 to 50 parts by weight of at least one modified polyester selected from the group consisting of polyethylene terephthalate glycol, polycyclohexane terephthalate and polycyclohexylenedimethylene cyclohexanedicarboxylate, and provides flexibility 15 to 80 parts by weight of a flexible polyester thermoplastic elastomer for use, 0.5 to 30 parts by weight of a polyolefin copolymer for promoting admixture and suppressing phase separation, 10 to 30 parts by weight of a non-halogen flame retardant to impart flame retardancy, It provides a thermoplastic elastomer resin composition comprising 1 to 10 parts by weight of non-halogen organic phosphate for imparting flame retardancy and 0.05 to 5 parts by weight of nano clay for improving flame retardancy and processability.

The non-halogen metal oxide is one from the group consisting of antimony oxide (Sb ₂ O ₃ ), molybdenum oxide, aluminum trihydride, amine molybdate, copper oxalate, zinc sulfide, magnesium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide and alumina It may be a non-halogen metal oxide selected above.

The non-halogen organic phosphate is from the group consisting of melamine phosphate, melamine pyrophosphate phosphate, boron phosphate, organophosphate ester, diammonium phosphate, tricresyl phosphate, thiamine pyrophosphate, ammonium polyphosphate, aromatic polyphosphate and trimetal phosphate At least one non-halogen organic phosphate selected.

The thermoplastic elastomer resin composition is based on 100 parts by weight of the thermoplastic elastomer resin composition. It may further comprise 0.1 to 2 parts by weight of epoxy soybean oil or epoxide seed oil.

The thermoplastic elastomer resin composition may further include 0.1 to 5 parts by weight of polyolefin based on 100 parts by weight of the thermoplastic elastomer resin composition.

The thermoplastic elastomer resin composition may include 0.1 to 1 material selected from the group consisting of di2-ethylhexyl phthalate, diisononyl phthalate, diisodecyl phthalate, and trioctyl trimeryltate based on 100 parts by weight of the thermoplastic elastomer resin composition. 5 parts by weight may be further included.

The polyethylene terephthalate glycol is an amorphous copolyester formed by a reaction between terephthalic acid and ethylene glycol, and a part of ethylene glycol may be substituted with cyclohexane dimethanol.

The flexible polyester-based thermoplastic elastomer may be a polyester copolymer having a Shore hardness A of 60 to 95.

The flexible polyester thermoplastic elastomers include thermoplastic polyester, thermoplastic polyetherester copolymer, thermoplastic polyetherester glycol copolymer, thermoplastic polyesterurethane copolymer, thermoplastic polyesteramide copolymer, thermoplastic polyesterimide copolymer and thermoplastic poly It may be at least one soft polyester-based thermoplastic elastomer selected from the group consisting of ester methyl methacrylate copolymer.

The non-halogen flame retardant may be melamine cyanurate.

In addition, the non-halogen flame retardant may be at least one non-halogen flame retardant selected from the group consisting of magnesium hydroxide, bentonite modified antimony, sodium ammonium, aluminum hydroxide and zinc borate.

It is preferable that the nanoclay has a size of 20 to 100 nm in diameter.

In addition, the nanoclay may be at least one nanoclay selected from organic compound modified clay whose surface is modified by a flame retardant organic compound or inorganic compound modified clay whose surface is modified by a flame retardant inorganic compound.

The polyolefin-based copolymer may be made of one or more materials selected from polyethylene propylene copolymer, polystyrene propylene copolymer, and polyethylene butadiene copolymer.

According to the present invention, there is provided an environment-friendly thermoplastic elastomer resin composition having a low hardness and weight, excellent flexibility, flame retardancy, mechanical strength and workability, and excellent surface feel, which is very suitable for the production of an insulating material for covering an electric wire used in a device or an apparatus. can do.

Hereinafter, preferred embodiments according to the present invention will be described in detail. However, it should be understood that the following embodiments are provided so that those skilled in the art will be able to fully understand the present invention, and that various modifications may be made without departing from the scope of the present invention. It is not.

In the thermoplastic elastomer resin composition of the present invention, a modified polyester is first used together with a soft polyester-based thermoplastic elastomer. Modified polyesters are characterized by flame retardancy itself and have excellent compatibility with soft polyester-based thermoplastic elastomers and other components.

Nano clay improves flame retardancy and processability. The use of nano clays with modified polyesters, soft polyester-based thermoplastic elastomers should be considered first.

As a result, a thermoplastic elastomer resin composition having a low hardness and weight, excellent flexibility, flame retardancy, mechanical strength and workability, and excellent surface feel, which is very suitable for the production of an insulating material for covering an electric wire used in a device or an apparatus is provided.

EMBODIMENT OF THE INVENTION Below, the thermoplastic elastomer resin composition of this invention is demonstrated in detail.

Polyethylene terephthalate glycol (PETG), polycyclohexane terephthalate (PCTG), and polycyclohexylenedimethylene cyclohexanedicarboxylate (poly (1), which are main components of the thermoplastic elastomer resin composition of the present invention , 4-cyclohexylenedimethylene) 1,4-cyclohexanedicarboxylate (PCCD) is a modified polyester copolymer with molding properties suitable for sheet extrusion, injection molding and blow molding. Polyethylene terephthalate glycol (PETG), polycyclohexane terephthalate (PCTG) and polycyclohexylenedimethylene cyclohexanedicarboxylate (poly (1,4-cyclohexylenedimethylene) 1,4-cyclohexanedicarboxylate The processing conditions of PCCD) are similar to those of polyesters, with only some differences in chemical structure to improve optical or chemical properties.

Formula 1 below is a structural formula of polyethylene terephthalate glycol (PETG), polyethylene terephthalate glycol (PETG) is an amorphous form formed by the reaction between terephthalic acid (TPA) and ethylene glycol (EG) Copolyester. In this embodiment, polyethylene terephthalate glycol (PETG) is used in which a part of ethylene glycol (EG) is substituted with cyclohexane dimethanol (CHDM). By the substitution of the cyclohexane dimethanol (CHDM) as described above, the crystallization of polyethylene terephthalate glycol (PETG) is suppressed and the workability is improved while improving the strength, transparency, and chemical resistance. In general, cyclohexane dimethanol (CHDM) is formed by hydrogenation of dimethyl terephthalate (DMT).

Polyethylene terephthalate glycol (PETG) is a granule with high density and excellent extruding properties, excellent chemical resistance, excellent cold formability, printing property and heat processability, and is widely used as a window material after polycarbonate. have. The polyethylene terephthalate glycol (PETG) has a physical property of 0.75 dl / g density and 150% elongation and has flame retardant properties of V-2 grade.

Formula 2 is a structural formula of polycyclohexylenedimethylene cyclohexanedicarboxylate (PCCD), wherein polycyclohexylenedimethylene cyclohexanedicarboxylate (PCCD) is the first to sixth of the cyclohexane of the polyester A linear cycloaliphatic polyester in which an aliphatic functional group is substituted for a carbon atom. Such polycyclohexylenedimethylene cyclohexanedicarboxylate (PCCD) is an esterification reaction of dimethyl transcyclohexanedicarboxylate (Dimethyl trans-1,4-cyclohexanedicarboxylate (DMCD), cyclohexane dimethanol (1,4 It is formed by the esterification of -cyclohexanedimethanol (CHDM). Polycyclohexylenedimethylene cyclohexanedicarboxylate (PCCD) has excellent crystallization properties and has a viscosity of 2000 to 22000 poise, and has the property of uniformly dispersing a non-halogen flame retardant. The polycyclohexylenedimethylene cyclohexanedicarboxylate (PCCD) has a melting point of 225 to 240 ° C and is excellent in thermal properties and workability.

Formula 3 is a structural formula of polycyclohexane terephthalate (PCTG), except that the chemical structure of polycyclohexane terephthalate (PCTG) is increased in that the content of cyclohexane dimethanol (CHDM) is substituted with hydroxyl group (OH). And similar to polyethylene terephthalate glycol (PETG).

One or more modified polyesters selected from the group consisting of polyethylene terephthalate glycol (PETG), polycyclohexane terephthalate (PCTG) and polycyclohexylenedimethylene cyclohexanedicarboxylate (PCCD) as described above An elastomer resin composition is made. The at least one modified polyester selected from the group consisting of polyethylene terephthalate glycol, polycyclohexane terephthalate and polycyclohexylenedimethylene cyclohexanedicarboxylate is preferably contained 5 to 50 parts by weight in the thermoplastic elastomer resin composition. .

In addition, a soft polyester-based thermoplastic elastomer is included to impart flexibility to the thermoplastic elastomer resin composition of the present invention.

Due to the nature of the wires, the compositions used for wire insulation applications are indispensable for flexibility. In order to meet these demands, in the present invention, a flexible polyester-based thermoplastic elastomer having excellent flexibility and having some flame retardancy is included to constitute a thermoplastic elastomer resin composition.

By soft polyester thermoplastic elastomer is meant a thermoplastic soft polyester copolymer based on a thermoplastic soft polyester polymer or ester group.

The soft polyester thermoplastic elastomer is preferably a polyester copolymer having a Shore hardness A of 60 to 95.

The flexible polyester thermoplastic elastomers include thermoplastic polyester, thermoplastic polyetherester copolymer, thermoplastic polyetherester glycol copolymer, thermoplastic polyesterurethane copolymer, thermoplastic polyesteramide copolymer, thermoplastic polyesterimide copolymer and thermoplastic poly Ester methylmethacrylate copolymers may be used alone or in combination. For example, the thermoplastic polyether ester copolymer, which is one of the soft polyester thermoplastic elastomers described above, has an aromatic polyester mainly made of polybutylene terephthalate (PBT) as a hard segment, and an aliphatic polyether is used. A polyether ester block copolymer made of soft segments, which is a soft polyester thermoplastic elastomer having low glass transition temperature and flexibility.

In the thermoplastic elastomer resin composition of the present invention, a thermoplastic polyester, a thermoplastic polyether ester copolymer, a thermoplastic polyether ester glycol copolymer, a thermoplastic polyester urethane copolymer, a thermoplastic polyesteramide copolymer, a thermoplastic, as an elastomer having high elasticity It is preferable to use one or more soft polyester-based thermoplastic elastomers selected from the group consisting of polyesterimide copolymers and thermoplastic polyestermethyl methacrylate copolymers, but is not necessarily limited thereto, and ethylene vinyl acrylate Elastomers such as acrylate (EVA) may be used to form the thermoplastic elastomer resin composition. Products commercialized as the above high elastic elastomers include DuPont's thermoplastic elastomers (trade name: Hytrel, Elvaloy), Samyang's thermoplastic polyester elastomers (trade name: TRIPET, Triel), and SK Chemicals' thermoplastic polyester elastomers (trade name: SKYVIVA). ), And a thermoplastic polyester elastomer (trade name: Keyflex) of LG Chem. More specifically, for example, Keyflex BT 1028D, EG8100, SEBS, etc. are commercially available as thermoplastic elastomers.

It is preferable that 15-80 weight part of flexible polyester thermoplastic elastomers are contained in a thermoplastic elastomer resin composition. If the content of the flexible polyester-based thermoplastic elastomer in the thermoplastic elastomer resin composition is less than 15 parts by weight, the flexibility of the thermoplastic elastomer resin composition may be lowered. If the content of the flexible polyester-based thermoplastic elastomer exceeds 80 parts by weight, the thermoplastic elastomer resin Mechanical properties such as strength of the composition may be lowered.

Also included are polyolefin copolymers for promoting the admixture of the respective components of the thermoplastic elastomer resin composition of the present invention and for inhibiting phase separation.

Specifically, the modified polyester and the flexible polyester-based thermoplastic elastomer are commercialized, as well as the modified polyester and the flexible polyester-based thermoplastic elastomer, which are polymer components, and the non-halogen flame-retardant, flame-retardant aid, and nanopolymer component. The thermoplastic elastomer resin composition is formed by including a polyolefin-based copolymer which promotes the mixing of the clay and prevents phase separation.

The polyolefin copolymer included in the thermoplastic elastomer resin composition is preferably a polyolefin copolymer such as polyethylene propylene copolymer, polystyrene propylene copolymer, polyethylene butadiene copolymer, or the like.

The thermoplastic elastomer resin composition preferably includes a polyolefin copolymer having excellent miscibility, but is not limited thereto. Commercially available products as polyolefin copolymers include copolymers of Asahi Chemical (product name: Tufmer or Tuftec), copolymers of Kurary Chemical (product name: SEPTON), and olefin elastomers (product name of Dow Corporation). Engage).

The polyolefin copolymer as described above is preferably contained in the thermoplastic elastomer resin composition 0.5 to 30 parts by weight to form a thermoplastic elastomer resin composition. If the content of the polyolefin copolymer in the thermoplastic elastomer resin composition is less than 0.5 parts by weight, the components of the thermoplastic elastomer resin composition may not be properly mixed. If the content of the polyolefin copolymer exceeds 30 parts by weight, the thermoplastic elastomer resin composition The flame retardant properties of may be lowered.

In addition, a non-halogen flame retardant is included to impart flame retardance to the thermoplastic elastomer resin composition of the present invention.

The non-halogen flame retardant included to impart flame retardancy to the thermoplastic elastomer resin composition is preferably melamine cyanurate, which is excellent in flame retardant effect, but is not limited thereto. And non-halogen flame retardants selected from the group consisting of zinc borate may be used alone or in combination of two or more thereof. Non-halogen flame retardants include commercially available products such as melamine cyanurate (product name: MC-315), KSS flame retardant, BDDP flame retardant, BPADP flame retardant, and the like.

It is preferable that the non-halogen flame retardant, preferably non-halogen flame retardant, which is melamine cyanurate, is contained in the thermoplastic elastomer resin composition in an amount of 10 to 30 parts by weight to form the thermoplastic elastomer resin composition. If the content of the non-halogen flame retardant in the thermoplastic elastomer resin composition is less than 10 parts by weight, the flame retardancy of the thermoplastic elastomer resin composition may be lowered. If the content of the non-halogen flame retardant exceeds 30 parts by weight, mechanical properties such as strength of the thermoplastic elastomer resin composition may be reduced. Physical properties may be reduced.

In addition, the non-halogen metal oxide or non-halogen organic phosphate is contained in the thermoplastic elastomer resin composition of this invention.

A flame retardant aid is included to promote the flame retardancy of the non-halogen flame retardant contained in the thermoplastic elastomer resin composition, wherein the flame retardant aid is preferably a non-halogen metal oxide or a non-halogen organic phosphate. The non-halogen metal oxide is preferably antimony oxide (Sb ₂ O ₃ ) excellent in the flame retardant promoting effect, but is not limited to this, in addition to antimony oxide (Sb ₂ O ₃ ) molybdenum oxide, aluminum trihydride, amine molybdate acid, oxalic acid Other types of non-halogen metal oxides such as copper, zinc bead, magnesium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, alumina and the like can be used to form the thermoplastic elastomer resin composition. In addition, the non-halogen organic phosphate is melamine phosphate, melamine pyrophosphate phosphate, boron phosphate, organophosphate ester, diammonium phosphate, tricresyl phosphate, thiamine pyrophosphate, ammonium polyphosphate, aromatic polyphosphate, trimetal phosphate alone It may be used as or mixed with two or more kinds. Phosphite-FR is a commercially available product as a non-halogen organic phosphate.

The non-halogen metal oxide-based or non-halogen organic phosphate as described above is preferably included in the thermoplastic elastomer resin composition to form a thermoplastic elastomer resin composition. When the content of the flame retardant aid in the thermoplastic elastomer resin composition is less than 1 part by weight, the action of promoting the flame retardancy of the flame retardant may be insufficient in the thermoplastic elastomer resin composition. Due to this, the manufacturing cost of the thermoplastic elastomer resin composition may increase. Of course, non-halogen metal oxides and non-halogen organic phosphates may be used together as flame retardant aids.

The thermoplastic elastomer resin composition of the present invention also includes nano clay, which is clay of 1 to 1000 nm in diameter.

Nano clay is included to improve the flame retardancy and processability of the thermoplastic elastomer resin composition, and the inorganic material together with the modified polyester and the soft polyester thermoplastic elastomer, which are high molecular materials in the constituent components of the thermoplastic elastomer resin composition. The use of phosphorus nano clays should be considered first. Hereinafter, the term "nano clay" is used to mean clay having a particle diameter of 1 to 1000 nm in nanometer units.

In the present invention, the thermoplastic elastomer resin composition may be formed using nano clay, which is a clay having a diameter of 1 to 1000 nm, but among the nano clays having the same size, the diameter of 20 to 100 nm It is preferable to form a thermoplastic elastomer resin composition using nano clay in view of providing a thermoplastic elastomer resin composition having a uniform composition in which a balance between flame retardancy and processability, flexibility and surface feel is provided.

The nano clay has a plurality of polar groups on the surface and is located at the interface between the particles and the particles to prevent the polymer from agglomeration by the plate-like structure to prevent phase separation. Such nano clays may use organic nanoclays prepared by exchanging sodium plus charges with organic ammonium compatibilizers in order to enhance affinity with other components and thereby inhibit phase separation. Nano clays have a large number of negative charges on their surface, and nano clays included in the thermoplastic elastomer resin composition of the present invention are organic ammonium. Organic clays are preferably used as compatibilizers, and organic nanoclays are preferable in terms of improving affinity between nano clays and other components to prevent phase separation.

In the present invention, the nano-clay may be used as it is to form the thermoplastic elastomer resin composition, but the organic compound modified clay or the flame-retardant inorganic material whose surface is modified by the flame-retardant organic compound to further increase the flame retardancy of the thermoplastic elastomer resin composition The thermoplastic elastomer resin composition may be formed by using one or more nano clays selected from inorganic compound-modified clays whose surface is modified by a compound. It is preferable that such a nano clay is contained in the thermoplastic elastomer resin composition in an amount of 0.05 to 5 parts by weight to form the thermoplastic elastomer resin composition. When the content of nano clay in the thermoplastic elastomer resin composition is less than 0.05 part by weight, the flame retardancy and processability improvement effect of the thermoplastic elastomer resin composition may be weak due to the lack of the content of the nano clay, and the nano clay ( When the content of the nano clay is greater than 5 parts by weight, the flexibility and surface feel of the thermoplastic elastomer resin composition may be reduced.

The thermoplastic elastomer resin composition is based on 100 parts by weight of the thermoplastic elastomer resin composition It may further comprise 0.1 to 2 parts by weight of epoxy soybean oil or epoxide seed oil. The thermoplastic elastomer resin composition of the present invention may further include a heat stabilizer to improve the thermal stability.

In order to improve the thermal stability of the thermoplastic elastomer resin composition, it is preferable to include 0.1 to 2 parts by weight of a heat stabilizer such as epoxy soybean oil (ESO) and epoxide seed oil in the thermoplastic elastomer resin composition to form the thermoplastic elastomer resin composition. . When the content of the thermal stabilizer in the thermoplastic elastomer resin composition is less than 0.1 part by weight, it is not possible to expect an improvement in the thermal stability of the thermoplastic elastomer resin composition, and when the content of the thermal stabilizer exceeds 2 parts by weight, mechanical properties such as strength of the thermoplastic elastomer resin composition This can lower the manufacturing cost.

The thermoplastic elastomer resin composition may further include 0.1 to 5 parts by weight of polyolefin based on 100 parts by weight of the thermoplastic elastomer resin composition. Polyolefin may be further included to reduce specific gravity and hardness of the thermoplastic elastomer resin composition of the present invention.

In order to reduce the specific gravity and hardness of the thermoplastic elastomer resin composition, 0.1 to 5 parts by weight of polyolefin, such as polyethylene and polypropylene, is included to provide a lightweight flexible wire insulation material, thereby forming the thermoplastic elastomer resin composition. When the content of the polyolefin in the thermoplastic elastomer resin composition is less than 0.1 part by weight, the specific gravity and hardness of the thermoplastic elastomer resin composition may not be reduced, and when the content of the polyolefin exceeds 5 parts by weight, the flame retardancy of the thermoplastic elastomer resin composition may be reduced. .

The thermoplastic elastomer resin composition may be selected from the group consisting of di2-ethylhexyl phthalate, diisononyl phthalate, diisodecyl phthalate, and trioctyl trimeryltate based on 100 parts by weight of the thermoplastic elastomer resin composition. It may further include parts by weight. The thermoplastic elastomer resin composition of the present invention may further include a plasticizer for improving flexibility.

In order to improve the flexibility of the thermoplastic elastomer resin composition, in the group consisting of di2-ethylhexyl phthalate (DEHP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP) and trioctyl trimeryl tate (TOTM) It is preferable that the thermoplastic elastomer resin composition is comprised by containing 0.1-5 weight part of at least 1 plasticizer selected. When the content of the plasticizer in the thermoplastic elastomer resin composition is less than 0.1 part by weight, it is not expected to improve the flexibility of the thermoplastic elastomer resin composition, and when the content of the plasticizer exceeds 5 parts by weight, mechanical properties such as strength of the thermoplastic elastomer resin composition may be degraded. Can be.

Since the thermoplastic elastomer resin composition composed of the above constituent components has excellent molding processing characteristics, it is possible to form a thin wire insulation material.

In addition, the thermoplastic elastomer resin composition composed of the above constituent components has a flame retardancy based on UL94, and in particular, may have a flame retardancy of UL94 V-0 grade.

In addition, the wire insulation material having a thickness of 1.5 to 3.5 mm manufactured by the thermoplastic elastomer resin composition of the present invention may also have flame retardancy of UL94 V-0 grade.

Hereinafter, the method of manufacturing the thermoplastic elastomer resin composition of this invention is demonstrated.

Polyethylene terephthalate glycol (PETG), polycyclohexane terephthalate (PCTG) and polycyclohexylenedimethylene cyclohexanedicarboxylate (PCCD) to prepare a thermoplastic elastomer resin composition according to a preferred embodiment of the present invention 5 to 50 parts by weight of one or more modified polyesters selected from the group, 15 to 80 parts by weight of a flexible polyester thermoplastic elastomer, 0.5 to 30 parts by weight of a polyolefin copolymer, 10 to 30 parts by weight of a non-halogen flame retardant, and a non-halogen metal oxide A raw material mixture containing 1 to 10 parts by weight of the system-based or non-halogen organic phosphate and 0.05 to 5 parts by weight of nano clay is introduced into a hopper of a continuous flow twin screw extruder and melted. After extrusion, it is cooled and cut in a water bath to form a thermoplastic elastomer resin in pellet form. The form. In order to improve the light weight and flexibility of the thermoplastic elastomer resin composition, a thermal stabilizer, a polyolefin or a plasticizer may be added together when the raw material mixture described above is introduced into a continuous twin screw extruder.

In addition, after feeding a masterbatch including a modified polyester, a flexible polyester thermoplastic elastomer, and a polyolefin copolymer into a continuous twin screw extruder, side feeding is performed through an injection hole provided in the melting and compression region of the continuous twin screw extruder. A non-halogen flame retardant and a flame retardant aid may be added by side feeding, and nano clay may be added by side feeding through an injection hole provided in a dispersion region.

The continuous twin screw extruder includes a hopper for feeding raw materials, two shafts rotatably installed, a cylinder surrounding the two shafts, and driving means for rotating the shafts. And a heating means for heating the cylinder, a control means for controlling a heating temperature of the heating means, a discharge die for discharging the composition, and a composition in a process in which the raw material melted and kneaded is dispersed. And a side feeding inlet for injecting secondary raw material into the side feeding method. The two shafts rotate in a constant direction (eg clockwise) to apply shear stress to the molten mixture, and the rotation speed of the shafts is on the order of 150-300 rpm.

The continuous twin-screw extruder can be divided into three zones according to its function, including a melting and compression zone for mixing and melting and compressing a raw material mixture, and a melted and compressed raw material. The mixture may be divided into a dispersing region for discontinuously dispersing the mixture by the shear stress caused by the rotation of the shaft and moving toward the discharging region, and an ejecting zone for discharging the dispersed thermoplastic elastomer resin composition to the outside.

The dispersion zone is a region in which the molten raw material mixture having passed through the melting and compression regions is sufficiently kneaded and dispersed while being maintained at a predetermined temperature and pressure to flow into the discharge region. The constituent components of the raw material mixture are discontinuously dispersed by the shear stress caused by the rotation of the shaft, thereby forming a uniform composition.

In the dispersion region, a side feeding inlet for injecting the secondary raw material into the cylinder by side feeding method is formed in the composition in which the molten and kneaded raw material is dispersed. Nano clay is injected into the melt through a side feeding hole to obtain a thermoplastic elastomer resin composition including nano clay. When the nano clay is introduced into the hopper, phase separation may occur due to the difference in the master arrangement, chemical structure, polarity, and interfacial tension, but the modified polyester and the soft polyester type are provided through the side feeding inlet. This phenomenon can be suppressed by injecting a masterbatch comprising a thermoplastic elastomer and a polyolefin-based copolymer, a non-halogen flame retardant and a flame retardant aid into the molten melt. In addition, there is an advantage that can improve the mechanical properties and the like of the thermoplastic elastomer resin composition by injecting nano clay through the side-feeding inlet. The plurality of side feeding inlets may be provided in a dispersion region.

The discharge region is in the form of a spiral screw for supplying to the discharge die while compressing the thermoplastic elastomer resin composition dispersed in the dispersion region. The ratio of the length of the helical screw to the diameter of the helical screw in the discharge region is appropriately determined in consideration of the viscosity, discharge speed, etc. of the melt, and is about 20 to 40.

The thermoplastic elastomer resin composition pressed in the discharge region is continuously discharged through the discharge die. The composition passed through the discharge die may be quenched through a cooling apparatus such as a water bath, cut into pellets of a desired size, and dried to obtain a desired thermoplastic elastomer resin composition.

The flow rate in the cylinder can be controlled by appropriately adjusting the viscosity of the melted and compressed raw material mixture, the shaft size of the continuous twin screw extruder, the separation distance between the cylinder and the shaft, the separation distance between the shafts, etc. have. It is preferable that the internal temperature of a continuous twin screw extruder is about 190-270 degreeC. More specifically, in the melting and compression region of the extruder, it is maintained at a temperature of 240 to 260 ° C. (temperature of the cylinder) higher than the melting temperature of the modified polyester, the soft polyester thermoplastic elastomer, and the polyolefin copolymer injected through the hopper. , After the melting and compression of the raw material injected through the hopper is completed, the temperature of the cylinder is set to 190 ~ 240 ℃ according to the dispersion zone of the extruder, the discharge temperature of the extruder in the discharge zone of the cylinder is 240 ~ higher than the temperature in the dispersion zone The temperature is maintained at 270 ° C. The thermoplastic elastomer resin composition discharged from the continuous twin screw extruder may be quenched in a water bath, cut into pellets of a desired size, and dried to obtain a final thermoplastic elastomer resin composition. The temperature of the water bath is maintained at a temperature of 40 ℃ or less lower than the glass transition temperature of the modified polyester, flexible polyester thermoplastic elastomer. The drying may be carried out at a temperature of about 80 ℃.

The thermoplastic elastomer resin composition is melted and stretched to form a wire insulation material.

The physical properties of the thermoplastic elastomer resin composition thus obtained were measured by the following method.

(1) heat distortion temperature (HDT)

According to ASTM D648, when the specimen was subjected to a load of 18.6 kgf / cm ² and the ambient fluid temperature was increased at a rate of 2 ° C./min, the temperature when the deformation of the specimen reached 0.254 mm was measured.

(2) flexual strength (FS) and flexual modulus (FM)

Cross head speed was measured at a test speed of 5 mm / min according to ASTM D790.

(3) tensile strength

According to ASTM D638, it was measured at a tensile rate of 5 mm / min under conditions of temperature 23 ± 2 ° C., relative humidity 50%, and atmospheric pressure. The elongation was recorded at the breaking point, and the average value was measured at least five times.

(4) impact strength

According to ASTM D256, the energy at break of a specimen divided by the unit thickness corresponds to the impact strength. Impact strength was measured using a specimen having a thickness of 1/8 inch, measured at least five times as an average value, was measured by the Izod notch method at room temperature.

(5) flame out time

After ignition of one point of the specimen, the time to natural digestion was measured.

Hereinafter, the embodiments of the thermoplastic elastomer resin composition according to the present invention are presented in more detail, and the present invention is not limited to the following examples. In addition, the comparative examples presented below are merely shown to be compared with the examples, it should be noted that the prior art of the present invention.

≪ Comparative Example 1 &

1. Raw material 26 parts by weight of high density polyethylene (HDPE), 32 parts by weight of thermoplastic elastomer 1 (product name: Keyflex BT 1028D, LG Chemical), 20 parts by weight of thermoplastic elastomer 2 (product name: EG8100), non-halogen flame retardant (product name: MC- 315) 22 parts by weight, 0.5 parts by weight of nano clay was charged to a continuous twin screw extruder.

2. The raw material mixture was melted and compressed in a continuous twin screw extruder at 240-250 ° C. higher than the melting temperature of high density polyethylene (HDPE) and thermoplastic elastomers 1, 2.

3. The shafts of the continuous twin screw extruder were rotated at 200 rpm to disperse the melt discontinuously and uniformly.

4. The thermoplastic elastomer resin composition was discharged in a continuous twin screw extruder while heating the dispersed melt to 270 ° C.

5. The discharged thermoplastic elastomer resin composition was cooled in a water bath, and then dried and cut to form a thermoplastic elastomer resin composition in pellet form.

6. The pellet of the thermoplastic elastomer resin composition was injection molded to form a wire insulation specimen.

Comparative Example 2

Raw material 25 parts by weight of high density polyethylene (HDPE), 30 parts by weight of thermoplastic elastomer 1 (product name: Keyflex BT 1028D), 20 parts by weight of thermoplastic elastomer 2 (product name: EG8100), 22 parts by weight of non-halogen flame retardant (product name: MC-315) , 3 parts by weight of antimony oxide (Sb ₂ O ₃ ), a flame retardant adjuvant, and 0.5 parts by weight of nano clay (nano clay) is the same as in Comparative Example 1 except that.

≪ Comparative Example 3 &

Raw material 21 parts by weight of high density polyethylene (HDPE), 32 parts by weight of thermoplastic elastomer 1 (product name: Keyflex BT 1028D), 20 parts by weight of thermoplastic elastomer 2 (product name: EG8100), 22 parts by weight of non-halogen flame retardant (product name: MC-315) , 5 parts by weight of antimony oxide (Sb ₂ O ₃ ), a flame retardant adjuvant, and 0.5 parts by weight of nano clay (nano clay) is the same as in Comparative Example 1 except that.

≪ Comparative Example 4 &

Raw material 19 parts by weight of high density polyethylene (HDPE), 34 parts by weight of thermoplastic elastomer 1 (product name: Keyflex BT 1028D), 20 parts by weight of thermoplastic elastomer 2 (product name: EG8100), 20 parts by weight of non-halogen flame retardant (product name: MC-315) , 7 parts by weight of antimony oxide (Sb ₂ O ₃ ), a flame retardant adjuvant, and 0.5 parts by weight of nano clay are added to a continuous twin screw extruder, the same as in Comparative Example 1.

≪ Comparative Example 5 &

Raw material 19 parts by weight of high density polyethylene (HDPE), 32 parts by weight of thermoplastic elastomer 1 (product name: Keyflex BT 1028D), 20 parts by weight of thermoplastic elastomer 2 (product name: EG8100), 22 parts by weight of non-halogen flame retardant (product name: MC-315) , 7 parts by weight of antimony oxide (Sb ₂ O ₃ ), a flame retardant adjuvant, and 0.5 parts by weight of nano clay are added to a continuous twin screw extruder, the same as in Comparative Example 1.

Various physical property measurement experiments were carried out on the specimens prepared according to Comparative Examples 1 to 5, and the results are shown in Table 1 below.

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Flexural Strength (㎏ / ㎠) 220 225 230 235 232 Flexural modulus (㎏ / ㎠) 3820 3950 4020 4120 4210 Tensile Strength (㎏ / ㎠) 215 195 220 227 230 Elongation (%) 650 550 400 340 296 Impact strength (kg.cm/cm) 65 55 45 37 32 HDT 1.8㎏f 40 45 48 49 52 Burning time (sec) - - - 165 135 Surface tactile coarseness coarseness coarseness coarseness coarseness

Referring to Table 1, the specimens of Comparative Examples 1 to 5 made of high density polyethylene (HDPE) includes a non-halogen flame retardant and a flame retardant auxiliary antimony oxide (Sb ₂ O ₃ ), nano clay (nano clay) Although the flame retardant properties were not provided, in particular, the specimens of Comparative Examples 1 to 3 were not completely extinguished and completely burned. In addition, the surface feel of each specimen also appeared to be rough, which is judged not to be suitable for wire insulation.

≪ Comparative Example 6 >

1. 51 parts by weight of polypropylene 1 (product name: HA5029), 5 parts by weight of thermoplastic elastomer (product name: KEPA), 19 parts by weight of ethylene vinyl acrylate (EVA), non-halogen flame retardant (product name: MC- 315) 20 parts by weight, 5 parts by weight of antimony oxide (Sb ₂ O ₃ ) as a flame retardant aid was introduced into a continuous twin screw extruder.

2. The raw material mixture was melted and compressed in a continuous twin screw extruder at 250-260 ° C. above the melting temperature of polypropylene 1 and thermoplastic elastomer, ethylene vinyl acrylate.

3. The shafts of the continuous twin screw extruder were rotated at 200 rpm to disperse the melt discontinuously and uniformly.

4. The thermoplastic elastomer resin composition was discharged in a continuous twin screw extruder while heating the dispersed melt to 270 ° C.

5. The discharged thermoplastic elastomer resin composition was cooled in a water bath, and then dried and cut to form a thermoplastic elastomer resin composition in pellet form.

6. The pellet of the thermoplastic elastomer resin composition was injection molded to form a wire insulation specimen.

≪ Comparative Example 7 &

47 parts by weight of polypropylene 1 (product name: HA5029), 11 parts by weight of thermoplastic elastomer (product name: KEPA), 16 parts by weight of ethylene vinyl acrylate, 22 parts by weight of non-halogen flame retardant (product name: MC-315) Parts, 4 parts by weight of antimony oxide (Sb ₂ O ₃ ), a flame retardant auxiliary, 0.5 parts by weight of nano clay (nano clay) is the same as in Comparative Example 6 except that the input.

≪ Comparative Example 8 >

Raw material Polypropylene 1 (product name: HA5029) 45 parts by weight, thermoplastic elastomer (product name: KEPA) 15 parts by weight, 14 parts by weight of ethylene vinyl acrylate, non-halogen flame retardant (product name: MC-315) 23 parts by weight In addition, 3 parts by weight of antimony oxide (Sb ₂ O ₃ ), a flame retardant aid, and 0.5 parts by weight of nano clay are added to a continuous twin screw extruder, and the same as in Comparative Example 6 above.

≪ Comparative Example 9 &

51 parts by weight of polypropylene 2 (product name: 733W), 5 parts by weight of thermoplastic elastomer (product name: KEPA), 19 parts by weight of ethylene vinyl acrylate, 20 parts by weight of non-halogen flame retardant (product name: MC-315) In addition, 5 parts by weight of antimony oxide (Sb ₂ O ₃ ), a flame retardant aid, and 0.5 parts by weight of nano clay are added to a continuous twin screw extruder, and the same as in Comparative Example 6 above.

≪ Comparative Example 10 &

47 parts by weight of polypropylene 2 (product name: 733W), 11 parts by weight of thermoplastic elastomer (product name: KEPA), 16 parts by weight of ethylene vinyl acrylate, 22 parts by weight of non-halogen flame retardant (product name: MC-315) Parts, 4 parts by weight of antimony oxide (Sb ₂ O ₃ ), a flame retardant auxiliary, 0.5 parts by weight of nano clay (nano clay) is the same as in Comparative Example 6 except that the input.

Various physical property measurement experiments were carried out on the specimens prepared by Comparative Examples 6 to 10, and the results are shown in Table 2 below.

division Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Flexural Strength (㎏ / ㎠) 120 110 101 177 152 Flexural modulus (㎏ / ㎠) 3220 2960 2940 5428 5232 Tensile Strength (㎏ / ㎠) 210 190 192 232 220 Elongation (%) 750 900 962 755 850 Impact strength (kg.cm/cm) 70 82 - 40 55 HDT 1.8㎏f 51 43 40 80 74 Burning time (sec) 110 102 97 75 82 Surface tactile coarseness coarseness coarseness coarseness coarseness

Referring to Table 2, the specimens of Comparative Examples 6 to 10 made of polypropylene, although the non-halogen flame retardant and flame retardant aids include antimony oxide (Sb ₂ O ₃ ), nano clay (nano clay) The flame retardant properties were insufficient. In addition, the surface feel of each specimen also appeared to be rough, which is judged not to be suitable for wire insulation.

≪ Example 1 >

1.20 parts by weight of polyethylene terephthalate glycol (PETG), 34 parts by weight of polyethylene, 10 parts by weight of polyolefin copolymer (product name: Tufmer), 10 parts by weight of thermoplastic elastomer (product name: SEBS), non-halogen flame retardant (product name: MC-315) 20 parts by weight, 5 parts by weight of antimony oxide (Sb ₂ O ₃ ), a flame retardant aid, and 1 part by weight of nano clay were introduced into a continuous twin screw extruder.

2. The raw material mixture was melted and compressed in a continuous twin screw extruder at 250-260 ° C. above the melting temperatures of polyethylene terephthalate glycol (PETG), polyethylene and thermoplastic elastomers 1 and 2.

3. The shafts of the continuous twin screw extruder were rotated at 200 rpm to disperse the melt discontinuously and uniformly.

4. The thermoplastic elastomer resin composition was discharged in a continuous twin screw extruder while heating the dispersed melt to 270 ° C.

5. The discharged thermoplastic elastomer resin composition was cooled in a water bath, and then dried and cut to form a thermoplastic elastomer resin composition in pellet form.

6. The pellet of the thermoplastic elastomer resin composition was injection molded to form a wire insulation specimen.

<Example 2>

Raw material polyethylene terephthalate glycol (PETG) 20 parts by weight, polyethylene 18 parts by weight, polyolefin copolymer (product name: Tufmer) 15 parts by weight, 19 parts by weight of ethylene vinyl acrylate, non-halogen flame retardant (product name: MC-315) 22 parts by weight, flame retardant auxiliary antimony oxide (Sb ₂ O ₃ ) 5 parts by weight, and 1 part by weight of nano clay (nano clay) is the same as in Example 1 except the input to a continuous twin screw extruder.

<Example 3>

Raw material polyethylene terephthalate glycol (PETG) 15 parts by weight, polyethylene 25 parts by weight, polyolefin copolymer (product name: Tufmer) 14 parts by weight, ethylene vinyl acrylate 19 parts by weight, non-halogen flame retardant (product name: MC-315) 23 parts by weight, flame retardant auxiliary antimony oxide (Sb ₂ O ₃ ) 3 parts by weight, and 1 part by weight of nano clay (nano clay) is the same as in Example 1 except that the continuous twin-screw extruder.

<Example 4>

Raw material polyethylene terephthalate glycol (PETG) 20 parts by weight, polyethylene 20 parts by weight, polyolefin copolymer (product name: Tufmer) 25 parts by weight, thermoplastic elastomer (product name: SEBS) 6 parts by weight, non-halogen flame retardant (product name: MC- 315) 25 parts by weight, 3 parts by weight of antimony oxide (Sb ₂ O ₃ ) as a flame retardant aid, 1 part by weight of nano clay (nano clay) is the same as in Example 1 except the input.

<Example 5>

20 parts by weight of polyethylene terephthalate glycol (PETG), 26 parts by weight of thermoplastic elastomer 2 (product name: SEBS), 25 parts by weight of ethylene vinyl acrylate, 25 parts by weight of non-halogen flame retardant (product name: MC-315) In addition, 3 parts by weight of antimony oxide (Sb ₂ O ₃ ), a flame retardant aid, and 1 part by weight of nano clay were added to a continuous twin screw extruder, except that the same procedure as in Example 1 was carried out.

Various physical property measurement experiments were carried out on the specimens prepared according to Examples 1 to 5, and the results are shown in Table 3 below.

division Example 1 Example 2 Example 3 Example 4 Example 5 Flexural Strength (㎏ / ㎠) 110 190 170 120 190 Flexural modulus (㎏ / ㎠) 3200 3500 2960 3020 3020 Tensile Strength (㎏ / ㎠) 125 210 190 205 220 Elongation (%) 250 195 370 520 640 Impact strength (kg.cm/cm) 22 95 91 - - HDT 1.8㎏f 45 55 47 45 40 Burning time (sec) 77 53D 51D 87D 92D Surface tactile Great Great Great Great Great

Referring to Table 3, polyethylene terephthalate glycol (PETG) is used as the modified polyester, and the specimens of Examples 1 to 5 in which polyethylene is additionally used are anti-halogen flame retardants and flame retardant aids of antimony oxide ( Sb ₂ O ₃ ), nanoclays were included, but the flame retardant properties were insufficient. However, the surface of each specimen was found to be smooth and the surface feel was good.

<Example 6>

1.10 parts by weight of polyethylene terephthalate glycol (PETG) as a raw material, 61 parts by weight of a soft polyester thermoplastic elastomer (product name: Keyflex BT 1028D, LG Chemical), 22 parts by weight of non-halogen flame retardant (product name: MC-315), flame retardant 7 parts by weight of an antimony oxide (Sb ₂ O ₃ ) as a supplement and 0.5 parts by weight of nano clay were introduced into a continuous twin screw extruder.

2. The raw material mixture was melted and compressed in a continuous twin screw extruder at 250-260 ° C. above the melting temperature of polyethylene terephthalate glycol (PETG) and soft polyester-based thermoplastic elastomer.

3. The shafts of the continuous twin screw extruder were rotated at 200 rpm to disperse the melt discontinuously and uniformly.

4. The thermoplastic elastomer resin composition was discharged in a continuous twin screw extruder while heating the dispersed melt to 270 ° C.

5. The discharged thermoplastic elastomer resin composition was cooled in a water bath, and then dried and cut to form a thermoplastic elastomer resin composition in pellet form.

6. The pellet of the thermoplastic elastomer resin composition was injection molded to form a wire insulation specimen.

&Lt; Example 7 >

Raw material polyethylene terephthalate glycol (PETG) 25 parts by weight, soft polyester-based thermoplastic elastomer (product name: Keyflex BT 1028D) 49 parts by weight, non-halogen flame retardant (product name: MC-315) 20 parts by weight, antimony flame retardant auxiliary antimony ( 5 parts by weight of Sb ₂ O ₃ ) and 1 part by weight of nanoclay are the same as those in Example 6 except that the continuous twin screw extruder is added.

&Lt; Example 8 >

35 parts by weight of polyethylene terephthalate glycol (PETG) as a raw material, 39 parts by weight of a soft polyester thermoplastic elastomer (product name: Keyflex BT 1028D), 20 parts by weight of a non-halogen flame retardant (product name: MC-315), and antimony oxide as a flame retardant ( 5 parts by weight of Sb ₂ O ₃ ) and 1 part by weight of nanoclay are the same as those in Example 6 except that the continuous twin screw extruder is added.

&Lt; Example 9 >

45 parts by weight of polyethylene terephthalate glycol (PETG) as a raw material, 29 parts by weight of a soft polyester thermoplastic elastomer (product name: Keyflex BT 1028D), 20 parts by weight of a non-halogen flame retardant (product name: MC-315), and antimony oxide as a flame retardant ( 5 parts by weight of Sb ₂ O ₃ ) and 1 part by weight of nanoclay are the same as those in Example 6 except that the continuous twin screw extruder is added.

&Lt; Example 10 >

35 parts by weight of polyethylene terephthalate glycol (PETG) as a raw material, 35 parts by weight of a soft polyester thermoplastic elastomer (product name: Keyflex BT 1028D), 22 parts by weight of non-halogen flame retardant (product name: MC-315), and antimony oxide as a flame retardant ( Sb ₂ O ₃ ) 7 parts by weight, and 1 part by weight of nano clay (nano clay) is the same as in Example 6 except that the continuous twin-screw extruder.

<Example 11>

35 parts by weight of polyethylene terephthalate glycol (PETG) as a raw material, 41 parts by weight of a soft polyester thermoplastic elastomer (product name: Keyflex BT 1028D), 20 parts by weight of a non-halogen flame retardant (product name: MC-315), and antimony oxide as a flame retardant ( Sb ₂ O ₃ ) 3 parts by weight, and 1 part by weight of nano clay (nano clay) is the same as in Example 6 except for feeding into a continuous twin screw extruder.

Various physical properties measurement experiments were carried out on the specimens prepared according to Examples 6 to 11, and the results are shown in Table 4 below.

division Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Flexural Strength (㎏ / ㎠) 104 42 96 201 68 32 Flexural modulus (㎏ / ㎠) 1300 1038 3031 8751 3778 1822 Tensile Strength (㎏ / ㎠) 130 92 115 160 120 112 Elongation (%) 170 240 82 41 80 134 Impact strength
(Kg.cm/cm) 21 19 21 23 20 21 HDT 1.8㎏f 47 41 49 63 67 32 Burning time (sec) 65 D 50D 42D 25D 51D 50D Surface tactile Great Great Great Great Great Great

Referring to Table 4, the specimens of Examples 6 to 11 in which polyethylene terephthalate glycol (PETG) is used as the modified polyester according to the present invention had relatively good flame retardant properties, and were used as wire insulation materials. It can be seen that it has sufficient mechanical properties. In addition, the surface of each specimen was found to be smooth and excellent in surface feel.

&Lt; Example 12 >

1.20 parts by weight of polyethylene terephthalate glycol (PETG) as a raw material, 49 parts by weight of a soft polyester-based thermoplastic elastomer (product name: Keyflex BT 1028D), 25 parts by weight of a non-halogen flame retardant (product name: MC-315), a flame retardant aid (product name) : 5 parts by weight of Phosphite-FR and 1 part by weight of nano clay were charged to a continuous twin screw extruder.

2. The raw material mixture was melted and compressed in a continuous twin screw extruder at 250-260 ° C. above the melting temperature of polyethylene terephthalate glycol (PETG) and soft polyester-based thermoplastic elastomer.

3. The shafts of the continuous twin screw extruder were rotated at 200 rpm to disperse the melt discontinuously and uniformly.

4. The thermoplastic elastomer resin composition was discharged in a continuous twin screw extruder while heating the dispersed melt to 270 ° C.

5. The discharged thermoplastic elastomer resin composition was cooled in a water bath, and then dried and cut to form a thermoplastic elastomer resin composition in pellet form.

6. The pellet of the thermoplastic elastomer resin composition was injection molded to form a wire insulation specimen.

&Lt; Example 13 >

Raw material polyethylene terephthalate glycol (PETG) 25 parts by weight, soft polyester-based thermoplastic elastomer (product name: Keyflex BT 1028D) 43 parts by weight, non-halogen flame retardant (product name: MC-315) 25 parts by weight, flame retardant auxiliary (product name: Phosphite -FR) 5 parts by weight, 1 part by weight of nano clay (nano clay) is the same as in Example 12 except that the continuous twin screw extruder.

&Lt; Example 14 >

Raw material polyethylene terephthalate glycol (PETG) 30 parts by weight, soft polyester-based thermoplastic elastomer (product name: Keyflex BT 1028D) 39 parts by weight, non-halogen flame retardant (product name: MC-315) 26 parts by weight, flame retardant auxiliary (product name: Phosphite -FR) 5 parts by weight, 1 part by weight of nano clay (nano clay) is the same as in Example 12 except that the continuous twin screw extruder.

&Lt; Example 15 >

Polyethylene terephthalate glycol (PETG) 45 parts by weight, soft polyester-based thermoplastic elastomer (product name: Keyflex BT 1028D) 25 parts by weight, non-halogen flame retardant (product name: MC-315) 22 parts by weight, flame retardant aid (product name: Phosphite-FR 7 parts by weight and 1 part by weight of nano clay are the same as in Example 12 except that the continuous twin screw extruder is added.

&Lt; Example 16 >

Raw material polyethylene terephthalate glycol (PETG) 45 parts by weight, soft polyester thermoplastic elastomer (product name: Keyflex BT 1028D) 30 parts by weight, non-halogen flame retardant (product name: MC-315) 19 parts by weight, flame retardant auxiliary (product name: Phosphite -FR) 5 parts by weight, 1 part by weight of nano clay (nano clay) is the same as in Example 12 except that the continuous twin screw extruder.

Various physical properties measurement experiments were carried out on the specimens prepared according to Examples 12 to 16, and the results are shown in Table 5 below.

division Example 12 Example 13 Example 14 Example 15 Example 16 Flexural Strength (㎏ / ㎠) 70 85 115 190 165 Flexural modulus (㎏ / ㎠) 2400 2640 3520 7520 6580 Tensile Strength (㎏ / ㎠) 80 105 120 140 145 Elongation (%) 105 85 65 50 75 Impact strength (kg.cm/cm) 16 18 21 23 28 HDT 1.8㎏f 57 62 63 65 56 Burning time (sec) 0 0 0 0 2 Surface tactile eminence eminence eminence eminence eminence

Referring to Table 5 above, the specimens of Examples 12 to 16 in which polyethylene terephthalate glycol (PETG) is used as the modified polyester according to the present invention are excellent in flame retardant properties, in particular Examples 12 to Example 15 specimens were substantially not burned at all. In addition, the surface of each specimen was smooth and the surface feel was also excellent. It can be seen that the mechanical properties sufficient for use as the wire insulation material.

&Lt; Example 17 >

1.20 parts by weight of polycyclohexane terephthalate (PCTG) as a raw material, 49 parts by weight of a soft polyester thermoplastic elastomer (product name: Keyflex BT 1028D), 25 parts by weight of a non-halogen flame retardant (product name: MC-315), a flame retardant aid ( Product Name: 5 parts by weight of Phosphite-FR) and 1 part by weight of nano clay were introduced into a continuous twin screw extruder.

2. The raw material mixture was melted and compressed in a continuous twin screw extruder at 250-260 ° C. above the melting temperature of polycyclohexane terephthalate (PCTG) and soft polyester-based thermoplastic elastomer.

3. The shafts of the continuous twin screw extruder were rotated at 200 rpm to disperse the melt discontinuously and uniformly.

4. The thermoplastic elastomer resin composition was discharged in a continuous twin screw extruder while heating the dispersed melt to 270 ° C.

5. The discharged thermoplastic elastomer resin composition was cooled in a water bath, and then dried and cut to form a thermoplastic elastomer resin composition in pellet form.

6. The pellet of the thermoplastic elastomer resin composition was injection molded to form a wire insulation specimen.

&Lt; Example 18 >

25 parts by weight of polycyclohexane terephthalate (PCTG) as a raw material, 43 parts by weight of a soft polyester thermoplastic elastomer (product name: Keyflex BT 1028D), 25 parts by weight of non-halogen flame retardant (product name: MC-315), and a flame retardant aid (product name: Except for 5 parts by weight of Phosphite-FR), 1 part by weight of nano clay (nano clay) in the continuous twin-screw extruder was the same as in Example 17.

&Lt; Example 19 >

Raw material of polycyclohexane terephthalate (PCTG) 30 parts by weight, soft polyester thermoplastic elastomer (product name: Keyflex BT 1028D) 39 parts by weight, non-halogen flame retardant (product name: MC-315) 26 parts by weight, flame retardant auxiliary (product name: Except for 5 parts by weight of Phosphite-FR), 1 part by weight of nano clay (nano clay) in the continuous twin-screw extruder was the same as in Example 17.

&Lt; Example 20 >

Raw material of polycyclohexane terephthalate (PCTG) 35 parts by weight, soft polyester thermoplastic elastomer (product name: Keyflex BT 1028D) 25 parts by weight, non-halogen flame retardant (product name: MC-315) 22 parts by weight, flame retardant auxiliary (product name: Except for adding 7 parts by weight of Phosphite-FR) and 1 part by weight of nanoclay to a continuous twin screw extruder, the same procedure as in Example 17 was carried out.

&Lt; Example 21 >

45 parts by weight of polycyclohexane terephthalate (PCTG) as a raw material, 30 parts by weight of a soft polyester thermoplastic elastomer (product name: Keyflex BT 1028D), 19 parts by weight of a non-halogen flame retardant (product name: MC-315), a flame retardant aid (product name: Except for 5 parts by weight of Phosphite-FR), 1 part by weight of nano clay (nano clay) in the continuous twin-screw extruder was the same as in Example 17.

Various physical property measurement experiments were carried out on the specimens prepared according to Examples 17 to 21, and the results are shown in Table 6 below.

division Example 17 Example 18 Example 19 Example 20 Example 21 Flexural Strength (㎏ / ㎠) 85 95 103 110 115 Flexural modulus (㎏ / ㎠) 2470 2770 3220 4520 5570 Tensile Strength (㎏ / ㎠) 90 105 110 113 115 Elongation (%) 115 117 95 80 75 Impact strength (kg.cm/cm) 20 22 21 23 20 HDT 1.8㎏f 58 60 63 65 63 Burning time (sec) 0 2 2 2 2 Surface tactile eminence eminence eminence eminence eminence

Referring to Table 6, the specimens of Examples 17 to 21 in which polycyclohexane terephthalate (PCTG) is used as the modified polyester according to the present invention are excellent in flame retardant properties, in particular, the specimen of Example 17 Was virtually not burnt at all. In addition, the surface of each specimen was smooth and the surface feel was also excellent. It can be seen that the mechanical properties sufficient for use as the wire insulation material.

&Lt; Example 22 >

1.20 parts by weight of polycyclohexylenedimethylene cyclohexanedicarboxylate (PCCD) as a raw material, 49 parts by weight of a soft polyester thermoplastic elastomer (product name: Keyflex BT 1028D), a non-halogen flame retardant (product name: MC-315) 25 parts by weight, 5 parts by weight of a flame retardant aid (product name: Phosphite-FR) and 1 part by weight of nano clay were fed to a continuous twin screw extruder.

2. The raw material mixture was melted and compressed in a continuous twin screw extruder at 250-260 ° C. above the melting temperature of polycyclohexylenedimethylene cyclohexanedicarboxylate (PCCD) and soft polyester-based thermoplastic elastomer.

3. The shafts of the continuous twin screw extruder were rotated at 200 rpm to disperse the melt discontinuously and uniformly.

4. The thermoplastic elastomer resin composition was discharged in a continuous twin screw extruder while heating the dispersed melt to 270 ° C.

5. The discharged thermoplastic elastomer resin composition was cooled in a water bath, and then dried and cut to form a thermoplastic elastomer resin composition in pellet form.

6. The pellet of the thermoplastic elastomer resin composition was injection molded to form a wire insulation specimen.

<Example 23>

25 parts by weight of polycyclohexylenedimethylene cyclohexanedicarboxylate (PCCD) as a raw material, 43 parts by weight of a flexible polyester thermoplastic elastomer (product name: Keyflex BT 1028D), 25 parts by weight of non-halogen flame retardant (product name: MC-315) Parts, flame retardant auxiliary (product name: Phosphite-FR) 5 parts by weight, 1 part by weight of nano clay (nano clay) is the same as in Example 22 except that the continuous twin-screw extruder.

&Lt; Example 24 >

30 parts by weight of polycyclohexylenedimethylene cyclohexanedicarboxylate (PCCD) as a raw material, 39 parts by weight of a flexible polyester thermoplastic elastomer (product name: Keyflex BT 1028D), 26 parts by weight of non-halogen flame retardant (product name: MC-315) Parts, flame retardant auxiliary (product name: Phosphite-FR) 5 parts by weight, 1 part by weight of nano clay (nano clay) is the same as in Example 22 except that the continuous twin-screw extruder.

&Lt; Example 25 >

35 parts by weight of polycyclohexylenedimethylene cyclohexanedicarboxylate (PCCD) as a raw material, 25 parts by weight of a soft polyester thermoplastic elastomer (product name: Keyflex BT 1028D), 22 parts by weight of non-halogen flame retardant (product name: MC-315) Parts, flame retardant auxiliary (product name: Phosphite-FR) 7 parts by weight, 1 part by weight of nano clay (nano clay) is the same as in Example 22 except that the continuous twin-screw extruder.

&Lt; Example 26 >

45 parts by weight of polycyclohexylenedimethylene cyclohexanedicarboxylate (PCCD) as a raw material, 30 parts by weight of a flexible polyester thermoplastic elastomer (product name: Keyflex BT 1028D), 19 parts by weight of non-halogen flame retardant (product name: MC-315) Parts, flame retardant aid (product name: te-FR) 5 parts by weight, and 1 part by weight of nano clay (nano clay) is the same as in Example 22 except that the continuous twin-screw extruder.

Various physical property measurement experiments were performed on the specimens prepared according to Examples 22 to 26, and the results are shown in Table 7 below.

division Example 22 Example 23 Example 24 Example 25 Example 26 Flexural Strength (㎏ / ㎠) 55 65 77 84 86 Flexural modulus (㎏ / ㎠) 1870 2075 2220 2520 2658 Tensile Strength (㎏ / ㎠) 90 95 100 113 115 Elongation (%) 85 80 77 70 65 Impact strength (kg.cm/cm) 14 18 20 20 20 HDT 1.8㎏f 52 55 57 58 63 Burning time (sec) 0 0 0 0 5 Surface tactile eminence eminence eminence eminence eminence

Referring to Table 7, the specimens of Examples 22 to 26, in which polycyclohexylenedimethylene cyclohexanedicarboxylate (PCCD) is used as the modified polyester according to the present invention, have excellent flame retardant properties. In particular, the specimens of Examples 22-25 did not burn substantially at all. In addition, the surface of each specimen was smooth and the surface feel was also excellent. It can be seen that the mechanical properties sufficient for use as the wire insulation material.

As mentioned above, although preferred embodiment of this invention was described in detail, this invention is not limited to the said embodiment, A various deformation | transformation by a person of ordinary skill in the art within the scope of the technical idea of this invention is carried out. This is possible.

Claims (15)

5 to 50 parts by weight of at least one modified polyester selected from the group consisting of polyethylene terephthalate glycol, polycyclohexane terephthalate and polycyclohexylenedimethylene cyclohexanedicarboxylate;
15 to 80 parts by weight of the soft polyester-based thermoplastic elastomer for imparting flexibility;
0.5 to 30 parts by weight of a polyolefin copolymer for promoting miscibility and suppressing phase separation;
10 to 30 parts by weight of a non-halogen flame retardant for imparting flame retardancy;
1 to 10 parts by weight of non-halogen metal oxide for imparting flame retardancy; And
Including 0.05 to 5 parts by weight of nano clay for improving the flame retardancy and processability,
The flexible polyester thermoplastic elastomers include thermoplastic polyester, thermoplastic polyetherester copolymer, thermoplastic polyetherester glycol copolymer, thermoplastic polyesterurethane copolymer, thermoplastic polyesteramide copolymer, thermoplastic polyesterimide copolymer and thermoplastic poly At least one soft polyester-based thermoplastic elastomer selected from the group consisting of ester methyl methacrylate copolymers,
The polyolefin-based copolymer is made of at least one material selected from polyethylene propylene copolymer, polystyrene propylene copolymer and polyethylene butadiene copolymer,
The non-halogen metal oxide is one from the group consisting of antimony oxide (Sb ₂ O ₃ ), molybdenum oxide, aluminum trihydride, amine molybdate, copper oxalate, zinc sulfide, magnesium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide and alumina The non-halogen metal oxide selected above,
The non-halogen flame retardant is a thermoplastic elastomer resin composition, characterized in that at least one non-halogen flame retardant selected from the group consisting of magnesium hydroxide, bentonite modified antimony, sodium ammonium, aluminum hydroxide and zinc borate or melamine cyanurate.
5 to 50 parts by weight of at least one modified polyester selected from the group consisting of polyethylene terephthalate glycol, polycyclohexane terephthalate and polycyclohexylenedimethylene cyclohexanedicarboxylate;
15 to 80 parts by weight of the soft polyester-based thermoplastic elastomer for imparting flexibility;
0.5 to 30 parts by weight of a polyolefin copolymer for promoting miscibility and suppressing phase separation;
10 to 30 parts by weight of a non-halogen flame retardant for imparting flame retardancy;
1 to 10 parts by weight of non-halogen organic phosphate for imparting flame retardancy; And
Including 0.05 to 5 parts by weight of nano clay for improving the flame retardancy and processability,
The flexible polyester thermoplastic elastomers include thermoplastic polyester, thermoplastic polyetherester copolymer, thermoplastic polyetherester glycol copolymer, thermoplastic polyesterurethane copolymer, thermoplastic polyesteramide copolymer, thermoplastic polyesterimide copolymer and thermoplastic poly At least one soft polyester-based thermoplastic elastomer selected from the group consisting of ester methyl methacrylate copolymers,
The polyolefin-based copolymer is made of at least one material selected from polyethylene propylene copolymer, polystyrene propylene copolymer and polyethylene butadiene copolymer,
The non-halogen organic phosphate is from the group consisting of melamine phosphate, melamine pyrophosphate, boron phosphate, organophosphate esters, diammonium phosphate, tricresyl phosphate, thiamine pyrophosphate, ammonium polyphosphate, aromatic polyphosphate and trimetal phosphate At least one non-halogen organic phosphate selected,
The non-halogen flame retardant is a thermoplastic elastomer resin composition, characterized in that at least one non-halogen flame retardant selected from the group consisting of magnesium hydroxide, bentonite modified antimony, sodium ammonium, aluminum hydroxide and zinc borate or melamine cyanurate.
delete delete The method of claim 1 or 2, wherein the thermoplastic elastomer resin composition is based on 100 parts by weight of the thermoplastic elastomer resin composition The thermoplastic elastomer resin composition further comprises 0.1 to 2 parts by weight of epoxy soybean oil or epoxide seed oil.
The thermoplastic elastomer resin composition according to claim 1 or 2, wherein the thermoplastic elastomer resin composition further comprises 0.1 to 5 parts by weight of polyolefin based on 100 parts by weight of the thermoplastic elastomer resin composition.
The method of claim 1 or 2, wherein the thermoplastic elastomer resin composition is di2-ethylhexyl phthalate, diisononyl phthalate, diisodecyl phthalate and trioctyltrimeryltate based on 100 parts by weight of the thermoplastic elastomer resin composition. The thermoplastic elastomer resin composition further comprises 0.1 to 5 parts by weight of at least one material selected from the group consisting of:
The polyethylene terephthalate glycol is an amorphous copolyester formed by a reaction between terephthalic acid and ethylene glycol, wherein a part of ethylene glycol is substituted with cyclohexane dimethanol. Thermoplastic elastomer resin composition.
The thermoplastic elastomer resin composition according to claim 1 or 2, wherein the flexible polyester thermoplastic elastomer is a polyester copolymer having a Shore hardness A of 60 to 95.
delete delete delete The thermoplastic elastomer resin composition according to claim 1 or 2, wherein the nanoclay has a size of 20 to 100 nm in diameter.
The nanoclay of claim 1 or 2, wherein the nanoclay is at least one nanoclay selected from an organic compound modified clay whose surface is modified by a flame retardant organic compound or an inorganic compound modified clay whose surface is modified by a flame retardant inorganic compound. The thermoplastic elastomer resin composition characterized by the above-mentioned.
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