JP2014148656A - Method for manufacturing polyester/carbon copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite of a polyester resin and reinforcing glass fiber or carbon fiber, which is expected to increase its application as an aerospace material and other advanced materials when its intensity and conductivity, etc., are further improved, and whose composition conventionally has enhanced intermolecular affinity between the fiber material and polyester by surface-treating on the fiber material to improve adhesion therebetween.SOLUTION: A polyester/carbon copolymer obtained by chemically bonding a terminal carboxyl group of polyester and a carboxyl group of a carbon fine body with an epoxy resin and a catalyst improves the strength thereof. Improved are various physical properties, such as intensity and conductivity, etc., of a fiber reinforced composite obtained by mixing the copolymer with glass fiber or carbon fiber, and 0.1-5 pts.wt. of the carbon fine body having a carboxyl group, such as carbon black, artificial graphite, a carbon nanotube, a nano diamond is reacted by a reaction extrusion method.

Description

  In the present invention, first, an aromatic saturated polyester and a carbon microparticle having a carboxyl group are bonded and reacted in the presence of a catalyst through a multifunctional epoxy resin binder as a medium. It is related with providing the manufacturing method of the polyester carbon copolymer which improved various physical properties, such as. Second, fiber-reinforced polyester / carbon copolymer with improved physical properties such as strength and conductivity by mixing glass fiber or carbon fiber with the polyester / carbon copolymer having improved properties. The present invention relates to providing a method for manufacturing a composite composite.

Conventional aromatic saturated polyesters include, for example, polyethylene terephthalate (hereinafter referred to as PET or PET), polybutylene terephthalate (PBT), polyethylene-2,6-naphthalenedicarboxylate (PEN), polycarbonate (PC). Etc. These have excellent physical properties such as transparency, strength and rigidity as thermoplastic resins, and are widely used as fibers, films, plastics and the like. In particular, in the plastic field, molded products are widely used in bottles, sheets, containers, daily necessities, automobiles, machine parts, electrical / electronic materials, building materials, various industrial products, and the like.
In addition, these polyesters have been used for higher-grade applications by further improving various properties such as strength and heat resistance by mixing glass fibers or carbon fibers into thermoplastic composites. Yes.

  In recent years, in the advanced industries such as the automobile industry, Shinkansen vehicle industry, aerospace industry, linear motor car, etc., we have reduced the weight and energy saving by improving the strength of the constituent materials, as well as conductivity, heat resistance, heat dissipation, etc. There is a need for improved performance. Synthetic resins generally have improved physical properties and moldability when their molecular weight is increased. However, polyester is difficult to obtain a high molecular weight product due to the polycondensation method of its production method, and the solid layer polymerization method for increasing the molecular weight of its medium molecular weight requires several hours and is low in productivity.

As shown in Patent Document 1 and Patent Document 2, the present inventors adopt a reactive extrusion method for the medium molecular weight of these polyesters in a few minutes depending on the epoxy resin binder (chain extender) and catalyst. A high-productivity manufacturing method with high molecular weight was provided. However, although remarkable progress has been made in the molding processability of polyester, the effect expected in the present invention has not been seen in improving physical properties.
It is known to increase the electrical conductivity of the composition by mechanically mixing polyester with carbon black as fine carbon particles and artificial graphite fine powder. However, since these carbon micro objects are manufactured by a high-temperature firing method, they have a carboxyl group on the surface and are dispersed macroscopically in affinity with the resin. However, since it is a foreign material that does not melt into the resin, the interface between the two peels off due to the stress, and generally makes the mixture composition brittle and reduces the strength.
On the other hand, in Patent Document 3, vapor-grown carbon fibers (2 to 12 parts by weight) containing carbon nanotubes (CNT) are mechanically mixed with polycarbonate using a twin-screw extruder, and the conductivity of the mixture composition and Improves thermal conductivity. In addition, the description about intensity | strength is not seen.
There are three types of nano-sized diamond as carbon micro-particles: polycrystalline diamond by impact compression method, single crystal diamond by static pressure method, and cluster diamond by explosion method. A group is present. In recent years, cluster diamonds produced by the explosion method using idle gunpowder have begun to be produced at low cost in the USSR and China. According to Patent Document 4, there is a method of repeatedly pulverizing and centrifuging explosive diamond so that the primary particle diameter is 50 nm or less and a method of introducing a carboxyl group, a hydroxyl group, an amino group, an acetyl group or the like on the surface by chemical treatment. Proposed. The purpose was to complete the aqueous solvent slurry by preventing secondary aggregation of nano-sized diamonds with these hydrophilic groups.

Notice No. 3503952 International Publication WO2009 / 004745 A1 JP 2006-225648 A (page 25, Table 2) International Publication WO2008 / 096854A1

“High Pressure Science and Technology Vol.13, No.1 (2003)” (p. 34, FIG. 6)

  The present invention includes light weight and energy saving by improving the strength of components in advanced industries such as the automobile industry, the Shinkansen vehicle industry, the space aircraft industry, and linear motor cars, as well as conductivity, heat resistance, heat dissipation, etc. The purpose is to improve performance. In particular, in the aircraft industry, there is an urgent need in the global market for weight reduction and energy saving by improving the strength of component materials by 5% or more.

Means to try to solve the problem

The idea of the present invention will be described. First, the carboxyl group present on the surface of the carbon microparticles and the carboxyl group at the molecular end of the polyester are converted into the epoxy ring of the multifunctional epoxy resin as a binder in the presence of a catalyst as shown in the following chemical formula (1). A chemical reaction involving cleavage is caused to form a new ester bond containing a hydroxy group to obtain a macromolecular polyester / carbon copolymer. However, PES indicates a polyester skeleton, and ● indicates a carbon microbody. The hydroxyl group does not react. Further, this bonding reaction can be performed at a high speed by the reaction mechanism shown in FIG. 1 according to the reactive extrusion method using a twin-screw extruder. Since this polyester / carbon copolymer has a large molecular weight and is a long-chain branched structure, its tensile strength is increased by the “entanglement” effect of the molecular chains. Since the bond strength of the ester chain of the present polyester / carbon copolymer is overwhelmingly greater than the intermolecular affinity of the conventional polyester / carbon microparticle composition, the toughness is improved. In addition, the introduction of carbon microparticles further improves other performance such as conductivity and heat dissipation.
Next, using this polyester / carbon copolymer with improved toughness, conductivity, etc. as a base material, using a twin screw extruder, carbon fiber or glass fiber is supplied and kneaded in a side surface supply method, CFRTP (carbon fiber reinforced polyester / carbon copolymer composite) and GFRTP (glass fiber reinforced polyester / carbon copolymer composite) pellets as “supercomposites” are manufactured at high speed.

FIG.

  It is a principle figure of the reaction mechanism of a carbon micro object and polyester. A blank inverted triangle indicates an epoxy ring, a black inverted triangle indicates an ester bond containing hydroxy in which it reacts with a carboxyl group, and a black circle indicates a carbon body. R is a residue of the epoxy resin.

More specifically, the present invention provides the following production method.
In the present invention, first, 100 parts by weight of the saturated polyester of the component (A), 0.1 to 30 parts by weight of a carbon-based fine body having a carboxyl group of the component (B), the molecule as a binder of the component (C) 0.1 to 5 parts by weight of a polyfunctional epoxy compound containing two or more epoxy groups therein, 0.01 to 1 part by weight of a binding reaction catalyst of component (D), 0.01 of a spreading agent for component (E) The present invention provides a method for producing a polyester-carbon copolymer characterized by reacting a mixture composed of ˜1 part by weight at a temperature equal to or higher than the melting point of the polyester to form an ester bond.

  Secondly, the present invention is characterized in that the polyester of component (A) contains one or more of polyethylene terephthalate, polybutylene terephthalate, polycarbonate, or a recycled product of these recovered cedar products. A method for producing a polyester / carbon copolymer is provided.

  The third aspect of the present invention is that the carbon microparticles having a carboxyl group as the component (B) contain at least one member selected from the group consisting of carbon black, acetylene black and Ketchen black having a carboxyl group. A feature of the present invention is to provide a method for producing a polyester-carbon copolymer.

  The fourth aspect of the present invention is the polyester / carbon, wherein the carbon microparticles having a carboxyl group as the component (B) contain at least one of the group consisting of graphite or graphene having a carboxyl group. A method for producing a copolymer is provided.

  Fifthly, the present invention is characterized in that the carbon microparticle having a carboxyl group as the component (B) contains at least one of the group consisting of carbon nanotubes having a carboxyl group or diamond-like carbon. A method for producing a polyester / carbon copolymer is provided.

  The present invention sixthly provides a method for producing a polyester-carbon copolymer, wherein the carbon microparticles having a carboxyl group as component (B) are nano-sized diamonds having a carboxyl group. Is.

  7thly, the binder of (C) component uses the polyfunctional epoxy compound which has 2 or more of epoxy groups in this molecule individually or in mixture of 2 or more types. A method for producing a carbon copolymer is provided.

  The ninth aspect of the present invention is that the binding reaction catalyst of component (D) is an alkali metal carboxylate, an alkaline earth metal carboxylate, an alkali metal carbonate or an alkaline earth metal carbonate. The present invention provides a method for producing a polyester / carbon copolymer characterized by containing at least one of them.

  The present invention provides, in a tenth aspect, a method for producing a polyester-carbon copolymer, wherein the spreading agent of component (E) contains liquid paraffin.

In the present invention, 100 parts by weight of the polyester as the component (A), 0.1 to 30 parts by weight of carbon-based fine particles having a carboxyl group as the component (B), and a binder as the component (C) 0.1 to 5 parts by weight of a polyfunctional epoxy compound containing two or more epoxy groups, 0.01 to 1 part by weight of a binding reaction catalyst of component (D), 0.01 to 1 of a spreading agent for component (E) A mixture composed of parts by weight is reacted at a temperature equal to or higher than the melting point of the polyester to form an ester bond, and then 5 to 30 parts by weight of (F) component glass fibers or (G) component carbon fibers are mixed. The present invention provides a method for producing a fiber-reinforced polyester / carbon copolymer composite.

Effect of the invention

  According to the present invention, the aromatic saturated polyester is copolymerized with a carbon microparticle to form a polyester / carbon copolymer, and its strength, conductivity, heat transfer, heat resistance, oil resistance, weather resistance, etc. Various physical properties can be improved. Since the product of the present invention is a copolymer with chemical bonds, it can be mixed uniformly without using a special mixing device compared to conventional compositions, and the performance changes due to phase separation in long-term use of molded products. Less is. In addition, by mixing glass fiber or carbon fiber with this improved polyester / carbon copolymer, various physical properties such as strength, conductivity, heat resistance, oil resistance and weather resistance have been improved. A fiber-reinforced polyester / carbon copolymer composite can be obtained.

Hereinafter, the present invention will be described in detail.
[Polyester of component (A)]
The polyester of component (A) as the main raw material in the present invention is an aromatic saturated polyester, and a series of compounds synthesized from a dicarboxylic acid component and a glycol component can be used. Examples of the dicarboxylic acid component include aromatic and alicyclic dicarboxylic acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and cyclohexanedicarboxylic acid. Of these, aromatic dicarboxylic acids, particularly terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid are preferred.
Examples of the glycol component include ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, and cyclohexanedimethanol. Of these, ethylene glycol and tetramethylene glycol (1,4-butanediol) are particularly preferred.
Specific examples of this series of polyesters include polyethylene terephthalate (PET), low melting point PET copolymerized with a small amount of isophthalic acid, a copolymer of ethylene glycol, cyclohexanedimethanol and terephthalic acid (PETG), polytetramethylene terephthalate (poly Butylene terephthalate (PBT), polyethylene-2,6-naphthalate (PEN), and the like. Polybutylene terephthalate (PBT) is preferred. Polyethylene terephthalate (PET) that is mass-produced and extremely inexpensive is particularly preferred.
In the present invention, the polyester of component (A) as the main raw material may be polycarbonate (PBT; poly-4,4′-isopropylene diphenyl carbonate) having bisphenol A as the main raw material as another series.

  PET as a representative polyester that can be used in the present invention has an intrinsic viscosity of 0.50 dl / g or more measured at 25 ° C. by dissolving in a 1,1,2,2-tetrachloroethane / phenol (1: 1) mixed solvent. (For fibers) is preferred, 0.70 dl / g or more (for sheets) is more preferred, and 0.80 dl / g or more (for bottles) is even more preferred. When the intrinsic viscosity is less than 0.50 dl / g, the bonding reaction is difficult even according to the present invention, and the obtained polyester / carbon copolymer may not always have excellent mechanical strength. The upper limit of the intrinsic viscosity is not particularly limited, but is usually 1.1 dl / g or less, preferably about 0.80 dl / g, which is relatively inexpensive. The upper limit for the availability of commercially available PET is an intrinsic viscosity of 1.25 dl / g. However, since the moldability deteriorates when used alone, the intrinsic viscosity is 0.60-0.80 dl / g in the present invention. It is preferable to use a mixture.

[Carbon microparticles having a carboxyl group as component (B)]
In the present invention, the carbon microparticles having a carboxyl group of the component (B) can use carbon black, acetylene black and Ketchen black having a carboxyl group as the first series. In particular, carbon black is preferable because it is produced in large quantities and is extremely inexpensive. For example, HCF series for high-grade colors (particle diameter 13-15 nm, volatile matter 1.8-8%, PH value 2.5-8), MCF series for intermediate colors (particle diameter 16-22 nm, Mitsubishi Chemical Corporation) Volatile content 1-3.5%, PH value 3.5-8), RCF series for general-purpose color (particle size 23-40nm, volatile content 0.6-1.1%, PH value 7-8), good flow Commercial LFF series (particle size 23-55 nm, volatile matter 1.5-3%, PH value 2.5-3.5) and the like can be used. In particular, an acidic substance having a low volatile content and a PH value of 7 or less has a carboxyl group, which is preferable.

  The carbon microparticles having a carboxyl group of the component (B) of the present invention can use graphite or graphene having a carboxyl group as the second series. For example, artificial graphite fine powders UF-G05 (average particle size 3.0 μm), UF-G10 (average particle size 4.5 μm), UF-G30 (average particle size 10.5 μm) manufactured by Showa Denko KK Can be used.

  The carbon microparticles having a carboxyl group of the component (B) of the present invention can use carbon nanotubes or diamond-like carbon (DLC) having a carboxyl group as the third series. For example, VGCF (bulk density 0.04, consolidation specific resistance value 0.01 ohm cm), VGCF-H (bulk density 0.08, as a multi-walled carbon nanotube (gas phase carbon fiber) manufactured by Showa Denko KK (Consolidation specific resistance value 0.02 Ωcm) can be used. As the carbon nanotubes, single-walled, cup-stacked and other shaped carbon nanotubes can be used.

  The nano-sized diamond having a carboxyl group can be used as the fourth series for the carbon microparticle having a carboxyl group of the component (B) of the present invention. Polycrystalline diamond by impact compression method, single crystal diamond by static pressure method, and cluster diamond by explosion method can be used. If there are few carboxyl groups on the surface, it can be improved with chemicals. For example, ultra fine powder (nano) diamond of Sumiishi Materials Co., Ltd .: polycrystalline die (sintered body with primary particle diameter of 5 to 20 nm, secondary particle diameter of 50 nm or more), single crystal diamond by static pressure method (single Particles, with corners, 100 nm or more), and aggregates with cluster primary particle diameters of 3 to 8 nm (about 100 nm) can be used. Further, as fine diamonds, gray fine powder (primary particle diameter of 3.5 to 7.5 nm) from Nanocarbon Laboratory Co., Ltd. can be used.

[Binder for component (C)]
The binder of the component (C) of the present invention preferably has a weight average molecular weight of 1,000 to 300,000, and a polymer type polyfunctional epoxy compound containing 2 to 100 epoxy groups in the molecule. Can be used alone or as a mixture of two or more. Commercially available products in which a glycidyl group containing an epoxy ring is suspended in a resin that forms a high molecular weight skeleton in a pendant form or in which an epoxy group is contained in the molecule, such as “Mafproof” series of NOF Corporation, BASF Japan "Jonkrill ADR" series of Co., Ltd. can be used. As the skeleton resin, an acrylic resin system or a styrene acrylic resin system is more preferable than a polyolefin system (PP, PS, PE). This is because the solubility parameters of the resin are: raw material PET 10.7, epoxy resin 10.8, polymethyl acrylate 10.2, polyethyl acrylate 9.4, polypropylene (PP) 9.3, polyethyl methacrylate 9 This is because the dispersion is 0.0, the polyspillage (PS) is 8.9, and the polyethylene (PE) is 8.0. In addition, even if the polyolefin type is mixed at 1-2%, the PET resin film / sheet is clouded, so it is not suitable when the molded product requires transparency. However, since the foam and pipe or the 220 ° C. heat and oil resistant container are white, they can be used for applications that do not require transparency.

  (C) The compounding quantity of the polyfunctional epoxy compound of a component is 0.1-5 weight part with respect to 100 weight part of polyester of (A) component. This greatly depends on the type of component (C) and the type and amount of carbon microparticles (B). In general, if the amount is less than 0.1 parts by weight, the effect of increasing the molecular weight and melt viscosity is insufficient, so that the moldability is insufficient and the basic physical properties and mechanical properties of the molded product are inferior. On the other hand, if it exceeds 5 parts by weight, the moldability deteriorates, and the resin is yellowed and colored, and gel and FE are by-produced.

[(D) Component Binding Reaction Catalyst]
The coupling reaction catalyst as component (D) in the present invention is composed of (1) alkali metal organic acid salt, carbonate and bicarbonate, (2) alkaline earth metal organic acid salt, carbonate and bicarbonate. A catalyst containing at least one selected from the group consisting of: As the organic acid salt, carboxylate, acetate and the like can be used, but stearates are particularly preferable among the carboxylates. The metal that forms the metal salt of the carboxylic acid can be an alkali metal such as lithium, sodium and potassium; an alkaline earth metal such as magnesium, calcium, strontium and barium.
The compounding amount of the carboxylate as the binding reaction catalyst is 0.01 to 1 part by weight with respect to 100 parts by weight of the polyester (A). In particular, the amount is preferably 0.1 to 0.5 part by weight. If the amount is less than 0.01 parts by weight, the catalytic effect is small, the copolymerization reaction is not achieved, and the molecular weight may not be sufficiently increased. If the amount exceeds 1 part by weight, problems such as gel generation due to local reactions and troubles in the extruder due to rapid increase in melt viscosity due to acceleration of hydrolysis are caused.

[(E) Component spreading agent]
As the spreading agent of the present invention, paraffin oil, liquid paraffin, trimethylsilane, or the like can be used. Liquid paraffin is particularly preferred because it is nonpolar, has a high boiling point and is a moderately viscous fluid. These spreading agents are necessary for uniformly adhering the (B) component carbon microparticles to the (A) component polyester pellets or powders, and the carbon microparticles soar into the atmosphere to human bodies and equipment. It is an indispensable auxiliary agent necessary to prevent adverse effects on the skin.

[(F) Component Glass Fiber and (G) Component Carbon Fiber]
The glass fiber of the component (F) of the present invention uses a short fiber for thermoplastic resin. For example, Nippon Electric Glass Co., Ltd. chopped strand for functional resin: ARG and ACS series (cut length: 6 to 13 mm) can be applied.

  (G) The carbon fiber of a component uses the short fiber for thermoplastic resins. For example, Toray Industries, Inc. trading card cut fibers T008 to T010 and TS12 series (cut length 3 to 1 mm) can be applied. A fiber surface treated with an epoxy resin is preferable for improving dispersibility and adhesion with the polyester / carbon copolymer of the present invention.

[Formulation method, reactive extrusion method]
Next, a method for blending the polyester resin of the present invention will be described. As the polyester (A), those having an arbitrary shape such as ordinary virgin pellets, recovered flakes, granules, powders and chips can be used. In general, it is preferable to dry the main component polyester. Each component is mixed with a mixer such as a tumbler or a Henschel mixer, and then supplied to the extrusion apparatus. It is desirable from the viewpoint of the reactive extrusion method that the temperature for melting by heating is 250 degrees or more and 300 degrees or less of the melting point of the polyester. In particular, it is preferably 280 ° C. or lower, particularly preferably 265 ° C. If it exceeds 300 ° C, the polyester may be discolored or thermally decomposed. In addition to the method of mixing each component at the same time, the polyester of component (A) is wetted with the spreading agent of component (E), the carbon microparticles of component (B) are mixed, and then the binding of component (C) It is also possible to add an agent and a catalyst of component (D).

  As the reactive extrusion apparatus, a single screw extruder, a twin screw extruder, a two-stage extruder of a combination thereof, or the like can be used. When injection molding, pipe, sheet or board molding, hollow molding, foam molding, or the like is molded by an off-line method, pellets manufactured in advance by a reactive extrusion apparatus can be used. On the other hand, the raw material mixture obtained by dry blending the above five components can be directly supplied to the hopper of the reactive extrusion apparatus and immediately molded by the in-line method. However, in the case of a single screw extruder, a pearl structure screw with good mixing properties and a vacuum line where the resin does not vent up are required. It is important to select an optimum blending composition in consideration of the number of stages of the screw kneading process and heating conditions. In the case of a twin screw extruder, a screw structure with good mixing properties and a vacuum line where the resin does not vent up are required.

Examples 1-2

[Production and properties of polyester / carbon copolymer pellets P1 and P2 based on PET resin, carbon black (40% MB) and polyfunctional epoxy resin]

: PET polyester pellets as unit A polyester (NEH2050 manufactured by Unitika: IV value 0.78, for potable water bottles) 80 parts by weight (400 g, moisture content after drying with hot air at 120 ° C. for 12 hours, 150 ppm), B 20 parts by weight (100 g) of carbon black masterbatch (BS1005: 40% product of polyethylene base manufactured by Toho Jiki Kogyo Co., Ltd.) as a carbon micro-component of the component, polyfunctional epoxy compound (NOF) Marproof G-0130S manufactured by Co., Ltd .: weight average molecular weight Mw 9,000, number average molecular weight Mn 5,500, epoxy equivalent WPE 530 g / eq., Functional group: weight average reference 17 / molecule, number average reference 10 / Molecule) 1 part by weight (5 g), calcium stearate / sodium stearate / su 0.2 parts by weight (1 g) of lithium allate (50/25/25 weight ratio) composite and 0.1 part by weight of liquid paraffin (0.5 g) of E component spreader are manually placed in a polyethylene bag. And mixed.
Using the same-direction twin screw extruder (KZW15-30MG: Screw diameter 15 mm, L / D = 30, rotation speed 200 rpm, 1 vent type) manufactured by Technobel, the set temperature of the screw and die of this extruder While the temperature was set to 240 to 280 ° C., the flake mixture was put into a hopper while being evacuated with a dry system pump, and the reaction extrusion was performed by supplying the flake mixture at a predetermined speed with a rotary feeder. The strand was continuously extruded into water at a speed of about 2 m / min from a nozzle having a diameter of 3 mm, and cut with a rotary cutter to produce black resin pellets P1 (about 450 g). The warm resin pellets were immediately dried with hot air at 140 ° C. for 4 hours and then stored in an aluminum / polyethylene laminated moisture-proof bag.
The black strand of this example has a thickness of 2.3 mm, has a good gloss, does not break when bent 180 degrees, and exhibits permanent plastic deformability (Dead Hold property) like a wire. That is, with the binder and the catalyst of the present invention, the carbon blacks having carboxyl groups do not react with each other and aggregate, and no gel or fish eye is produced as a by-product. Indicated.

The glossy black pellets P1 of this example (raw material ratio: PET / carbon black-polyethylene / binder-catalyst / spreading agent = 100 / 10-15 / 1.25-0.25 / 0.125 parts by weight) It was formed into a sheet at 280 ° C. according to the pressing method. The tensile strength at break according to the tensile test was 47.0 MPa (479 Kg / cm ² ). Compared to the composition (simple blended product) extruded and mixed under the same conditions without the binder, catalyst and spreading agent of Comparative Example 1, this example improved the tensile strength at break to 113%. Moreover, the electrical resistance value of the sheet was 4.3 × 10 ¹³ Ωcm, which was slightly improved compared to the electrical resistance value of 1 × 10 ¹⁵ Ωcm of the molded sheet of the raw material PET of Comparative Example 2.

: High molecular weight type epoxy compound as binder for component C (Mafproof G-0130S manufactured by NOF Corporation: weight average molecular weight Mw 9,000, number average molecular weight Mn 5,500, epoxy equivalent WPE 530 g / eq., Functional group : Weight average basis 17 pieces / molecule, number average basis 10 pieces / molecule) was increased to 2 parts by weight (10 g), and the reactive extrusion method was carried out under substantially the same conditions as in Example 1. Black resin pellets P2 (about 450 g) were produced. The warm resin pellets were immediately dried with hot air at 140 ° C. for 4 hours and then stored in an aluminum / polyethylene laminated moisture-proof bag.
The black strand of this example was about 2.3 mm in thickness and slightly reduced in gloss, but was not broken by bending at 180 ° and showed permanent plasticity (Dead Hold) like a wire. That is, the binder and the catalyst of the present invention showed that the carbon blacks having carboxyl groups did not react with each other and aggregated, and neither gel nor fish eye was produced as a by-product.

Glossy black resin pellet P2 of this example (Raw material ratio: PET / carbon black-polyethylene / binder-catalyst / spreader = 100 / 10-15 / 2.5-0.25 / 0.125 parts by weight) Was formed into a sheet at 280 ° C. by a pressing method, and a tensile test was performed. The tensile strength at break was 47.8 MPa (488 Kg / cm ² ). Compared to the composition (simple blended product) extruded and mixed under the same conditions without the binder, catalyst and spreading agent of Comparative Example 1, the tensile strength at break was improved to 115%. Moreover, the electrical resistance value of the sheet was 1 × 10 ¹⁵ Ωcm.

Comparative Example 1

80 parts by weight of PET resin pellets (made by Unitika, NEH2050, IV value 0.78, for bottles) as component A polyester (400 g, hot-air dried product), carbon black masterbatch 20 weights as component B carbon-based microparticles A simple blend composition pellet R1 was produced with an extruder under substantially the same conditions as in Example 1 except that only a part (100 g) was used and a C component binder and a D component coupling reaction catalyst were not used. .
The tensile strength at break of the sheet formed from this glossy black pellet R1 (raw material ratio: PET / carbon black-polyethylene = 100 / 10-15 parts by weight) was 41.7 MPa (425 Kg / cm ² ). Moreover, the electrical resistance value of the sheet was 1 × 10 ¹⁵ Ωcm.

Comparative Example 2

Extruded under almost the same conditions as in Example 1 using only 100 parts by weight (400 g, hot-air dried product) of PET resin pellets (manufactured by Unitika, NEH2050, IV value 0.78, for bottles) as component A polyester A pellet R2 (raw material ratio: PET = 100 parts by weight) was produced using a machine. The tensile strength at break of the sheet formed from the white pellet R2 after drying was 55.5 MPa (566 Kg / cm ² ). Moreover, the electrical resistance value of the press sheet was 1 × 10 ¹⁵ Ωcm.

[Production and properties of polyester resin / carbon copolymer pellets P3 based on PET resin, carbon black fine particles, fine powder and polyfunctional epoxy]
A component PET resin pellet (Unitika NEH2050: IV value 0.78, for bottles) 90 parts by weight (450 g, dried in hot air), carbon black fine powder (manufactured by Mitsubishi Chemical Co., Ltd.) as the carbon component of component B MA100: particle size 24 nm, volatile matter 1.5%, PH value 3.5; strong acidity) 10 parts by weight (50 g), multifunctional epoxy compound as binder for component C (Malproof G manufactured by NOF Corporation) -0130S: weight average molecular weight Mw 9,000, number average molecular weight Mn 5,500, epoxy equivalent WPE 530 g / eq., Functional group: weight average reference 17 / molecule, number average reference 10 / molecule) 1 part by weight (5 g) , 0.2 parts by weight of a calcium stearate / sodium stearate / lithium stearate (50/25/25 weight ratio) composite as a coupling reaction catalyst for component D ( g) and liquid paraffin 0.2 parts by weight of component E of spreading agent (1 g) were mixed manually in a polyethylene bag.
Using the same direction twin screw extruder (KZW15-30MG) manufactured by Technobel Co., Ltd., reactive extrusion was performed in the same manner as in Example 1 to produce black resin pellets P3 (about 450 g). The warm resin pellets were immediately dried with hot air at 140 ° C. for 4 hours and then stored in an aluminum / polyethylene laminated moisture-proof bag.
The black strand of this example has a thickness of 2.3 mm, is glossy, and exhibits permanent plastic deformability (Dead Hold property) like a wire without being broken by bending at 180 degrees. That is, with the binder and the catalyst of the present invention, the carbon blacks having carboxyl groups do not react with each other and aggregate, and no gel or fish eye is produced as a by-product. Indicated.

Glossy black pellets P3 in this example (raw material ratio: PET / carbon black fine powder / binder-catalyst / spreading agent = 100 / 11.1 / 1.11-0.22 / 0.22 parts by weight) are pressed. According to the method, it was formed into a sheet at 280 ° C. The tensile strength at break according to the tensile test was 57.6 MPa (588 Kg / cm ² ). The tensile strength at break was improved by 20% compared to the composition (simple blended product) extruded and mixed under the same conditions as the binder of Comparative Example 3 and no catalyst. Further, the tensile strength at break was improved to only 104% as compared with the raw material PET of Comparative Example 2 alone.
On the other hand, the electrical resistance value of this sheet was 5.5 × 10 ¹³ Ωcm, which was slightly improved compared to the sheet 1 × 10 ¹⁵ Ωcm formed from the pellet R2 made of only the raw material PET of Comparative Example 2.

Comparative Example 3

90 parts by weight of A component PET resin pellets (manufactured by Unitika, NEH2050) (450 g, hot air dried product), 10 parts by weight of carbon black fine powder (50 g) as component B fine carbon, 0.2 parts by weight of E component spreading agent The composition pellet R3 of a simple blend was used in an extruder under substantially the same conditions as in Example 1 except that only a part (0.99 g) was used, and a binder for the C component and a coupling reaction catalyst for the D component were not used. Manufactured.
The tensile breaking strength of the sheet formed from this glossy black pellet R3 (raw material ratio: PET / carbon black fine powder / spreading agent = 100 / 11.1 / 0.22 parts by weight) is 48.2 MPa (492 Kg / cm ² ). Compared to the pellet R2 containing only the PET resin of component A in Comparative Example 2, it was 13% lower. On the other hand, the electrical resistance value of the sheet was 1.4 × 10 ⁷ Ωcm, and the conductivity was improved to the semiconductor level.

Examples 4-5

[Production and properties of polyester / carbon copolymer pellets P4 to P5 based on PET resin, artificial graphite fine powder and polyfunctional epoxy]

: A component PET resin pellet (Unitika NEH2050: IV value 0.78, for bottles) 90 parts by weight (450 g, hot-air dried product), artificial graphite fine powder (manufactured by Showa Denko KK) as the B component carbon fine body UF-05: average particle size 3 μm, volatile content 1%, specific gravity 2.2) 10 parts by weight (50 g), multifunctional epoxy compound as binder for component C (Malproof G-manufactured by NOF Corporation) 0130S: weight average molecular weight Mw 9,000, number average molecular weight Mn 5,500, epoxy equivalent WPE 530 g / eq., Functional group: weight average reference 17 / molecule, number average reference 10 / molecule) 1 part by weight (5 g) 0.2 parts by weight (1 g) of a calcium stearate / sodium stearate / lithium stearate (50/25/25 weight ratio) composite as a binding reaction catalyst for component D and component E Liquid paraffin 0.2 parts by weight of a spreading agent (1 g) were mixed manually in a polyethylene bag.
The reactive extrusion method was carried out under substantially the same conditions as in Example 1 using the same direction twin screw extruder (KZW15-30MG) manufactured by Technobel. Black resin pellets P4 (about 450 g) were produced. The warm resin pellets were immediately dried with hot air at 140 ° C. for 4 hours and then stored in an aluminum / polyethylene laminated moisture-proof bag.
The black strand of this example has a thickness of about 2.3 mm, is a glossy black color, and shows permanent plasticity (Dead Hold property) like a wire without being broken by bending 180 degrees. That is, the binder and the catalyst of the present invention showed that the carbon blacks having a carboxyl group did not react with each other and aggregated, and did not by-produce gel or fish eye.
The black resin pellet P4 (raw material ratio: PET / artificial graphite fine powder / binder-catalyst / spreading agent = 100 / 11.1 / 1.11-0.22 / 0.22 parts by weight) of this example was used as a press method. Therefore, it was molded into a sheet at 280 ° C. and subjected to a tensile test. The tensile strength at break was 55.7 MPa (568 Kg / cm ² ). Compared to the sheet from pellet R2 extruded under the same conditions of only the raw material PET of Comparative Example 2, there was no decrease in tensile break strength. Moreover, the electric resistance value of the sheet was 1.3 × 10 ¹³ Ωcm, which was slightly improved.

: A component PET resin pellets (NEH2050 manufactured by Unitika) 80 parts by weight (400 g, hot air dried product), artificial graphite fine powder (UF-05 manufactured by Showa Denko KK) 20 parts by weight as the B component carbon fines ( Except for doubling to 50 g), reactive extrusion was carried out in the same manner as in Example 4 to produce black resin pellets P5 (about 450 g).
The black strand of this example has a thickness of about 2.3 mm, is a glossy black color, and shows permanent plasticity (Dead Hold property) like a wire without being broken by bending 180 degrees. That is, the binder and the catalyst of the present invention showed that the carbon blacks having a carboxyl group did not react with each other and aggregated, and did not by-produce gel or fish eye.
The black resin pellet P5 of this example (raw material ratio: PET / artificial graphite fine powder / binder-catalyst / spreading agent = 100/25 / 1.25-0.25 / 0.25 parts by weight) is 280 depending on the pressing method. Molded into a sheet at 0 ° C. and subjected to a tensile test. The tensile strength at break was 61.1 MPa (623 Kg / cm ² ). Compared to the sheet from pellet R2 extruded under the same conditions of only the raw material PET of Comparative Example 2, the tensile strength at break was improved to 110%. Moreover, the electrical resistance value of the sheet was 9.3 × 10 ⁶ Ωcm, which was improved to the semiconductor level.

Examples 6-8

[Production and Physical Properties of Polyester / Carbon Copolymer Pellets P6 to P8 Based on Gas Phase Processed Carbon Fiber Microparticles Made of PET Resin and Carbon Nanotubes (CNT) and Multifunctional Epoxy]

: A component PET resin pellet (NEH2050 made by Unitika) 95 parts by weight (570 g, hot-air dried product), vapor-grown carbon fiber fine powder composed of carbon nanotubes (CNT) as the B component carbon microparticles (Showa Denko K.K.) VGCF-H manufactured: Fiber thickness estimated 150 nm, bulk specific gravity 0.08, consolidation specific resistance 0.02 Ωcm) 5 parts by weight (30 g), polyfunctional epoxy compound (manufactured by NOF Corporation) as binder for component C Proof G-0130S: weight average molecular weight Mw 9,000, number average molecular weight Mn 5,500, epoxy equivalent WPE 530 g / eq., Functional group: weight average reference 17 / molecule, number average reference 10 / molecule) 1.25 weight Part (7.5 g), calcium stearate / sodium stearate / lithium stearate (50/25/2) 0.1 parts by weight ratio) composite (0.6 g) and liquid paraffin 0.15 parts by weight of component E of spreading agent (0.9 g) were mixed manually in a polyethylene bag.
The reactive extrusion method was carried out under substantially the same conditions as in Example 1 using the same direction twin screw extruder (KZW15-30MG) manufactured by Technobel. Black resin pellets P6 (about 500 g) were produced. The warm resin pellets were immediately dried with hot air at 140 ° C. for 4 hours and then stored in an aluminum / polyethylene laminated moisture-proof bag.
The black strand of this example has a thickness of about 2.3 mm, is a glossy black color, and shows permanent plasticity (Dead Hold property) like a wire without being broken by bending 180 degrees. That is, the binder and the catalyst of the present invention showed that the carbon blacks having a carboxyl group did not react with each other and aggregated, and did not by-produce gel or fish eye.
Black resin pellet P6 of this example (raw material ratio: PET / gas phase method carbon fiber fine powder / binder-catalyst / spreading agent = 100 / 5.26 / 1.32-0.11 / 0.16 parts by weight) A sheet was molded at 280 ° C. according to the pressing method and subjected to a tensile test. The tensile strength at break was 61.7 MPa (629 Kg / cm ² ). Compared to the sheet from pellet R2 extruded under the same conditions of only the raw material PET of Comparative Example 2, the tensile strength at break was improved to 111%. Moreover, the electrical resistance value of the sheet was 1 × 10 ¹⁵ Ωcm.

: A component PET resin pellet (NEH2050 manufactured by Unitika) 90 parts by weight (450 g, hot-air dried product), vapor-grown carbon fiber fine powder composed of carbon nanotubes (CNT) as the B component carbon microparticles (Showa Denko K.K.) 10 parts by weight (50 g) manufactured by VGCF-H), 2.5 parts by weight (12.5 g) of a polyfunctional epoxy compound (Marproof G-0130S manufactured by NOF Corporation) as a binder for component C, component D The reaction extrusion was carried out in the same manner as in Example 6 except that 0.2 parts by weight (1.0 g) of the combined reaction catalyst composite and 0.3 parts by weight of liquid paraffin (1.5 g) as the E component spreading agent were used. The black resin pellet P7 (about 450 g) was manufactured.
The black strand of this example has a thickness of about 3 mm, is a slightly thin black, is strong without bending when bent by 180 degrees, and exhibits permanent hold (Dead Hold property) like a wire. That is, the binder and catalyst of the present invention showed that carbon blacks having carboxyl groups did not react with each other and aggregated, and gels and fish eyes were hardly produced as by-products.
Slightly grayish black resin pellet P7 of this example (raw material ratio: PET / gas phase method carbon fiber fine powder / binder-catalyst / spreading agent = 100 / 11.1 / 2.78-0.22 / 0.33 parts by weight) was formed into a sheet at 280 ° C. by a pressing method and subjected to a tensile test. The tensile strength at break was 64.0 MPa (653 Kg / cm ² ). Compared to the sheet from pellet R2 extruded under the same conditions of only the raw material PET of Comparative Example 2, the tensile strength at break was improved to 16%. Moreover, the electrical resistance value of the sheet was 1 × 10 ¹⁵ Ωcm.

: A component PET resin powder (TJ-2 manufactured by Toho Juki Kogyo Co., Ltd .: Pulverized fine powder of pellets with an IV value of 0.92, dry product) 90 parts by weight, carbon nanotubes (CNT) as carbon component microparticles of B component Gas phase method carbon fiber fine powder (VGCF manufactured by Showa Denko KK: fiber thickness estimated 70 nm, bulk specific gravity 0.04, consolidation specific resistance 0.01 Ωcm) 10 parts by weight, polyfunctional as a binder for C component 1.5 parts by weight of an epoxy compound (Mafproof G-0130S manufactured by NOF Corporation), 0.2 parts by weight of a D component binding reaction catalyst composite, and 0.5 parts by weight of liquid paraffin as a spreading agent for E component Except for the above, reactive extrusion was carried out under substantially the same conditions as in Example 7 to produce black resin pellets P8 (about 10 kg).
The black strand of this example has a thickness of about 3 mm, is a glossy black color, is strong without bending when bent 180 degrees, and exhibits permanent plasticity (Dead Hold property) like a wire. That is, the binder and the catalyst of the present invention showed that the carbon blacks having carboxyl groups did not react with each other and aggregated, and neither gel nor fish eye was produced as a by-product.
Grayish black resin pellet P8 of this example (Raw material ratio: PET / gas phase method carbon fiber fine powder / binder-catalyst / spreading agent = 100 / 11.1 / 1.67-0.22 / 0.56 Part by weight) was formed into a sheet at 280 ° C. by a pressing method, and a tensile test was performed. The tensile strength at break was 66.6 MPa (679 Kg / cm ² ). Compared to the sheet from pellet R2 extruded under the same conditions of only the raw material PET of Comparative Example 2, the tensile strength at break was improved to 120%. Moreover, the electrical resistance value of the sheet was 2.6 × 10 ⁴ Ωcm, which was improved to a level below the semiconductor level.

[Production of polyester / carbon copolymer pellet P9 based on PET resin and carbon micro-particles as nano-sized diamond and polyfunctional epoxy]
PET resin pellet of component A (3802 manufactured by Nanya Plastic Technology Co., Ltd., IV value 0.80, melting point 245 ° C., carboxyl group 20 × 10 ⁻⁶ equ / g, for general-purpose bottles) 100 parts by weight (600 g, hot air drying Product), B-component carbon micro-particles, nano-sized diamond (SCM Nanodiamond manufactured by Sumiishi Materials Co., Ltd .: polycrystalline type, primary particle diameter 5 to 20 nm) 2 parts by weight (12 g), C component binder As a polyfunctional epoxy compound (Mafproof G-0150M manufactured by NOF Corporation: weight average molecular weight Mw 10,000, number average molecular weight Mn 4,000, epoxy equivalent WPE 310 g / eq., Functional group: weight average reference 32 / 1.0 part by weight (6 g) of molecule, number average reference 13 molecules / molecule), calcium stearate / sodium stearate as a coupling reaction catalyst for component D A polyethylene bag containing 0.2 parts by weight (1.2 g) of a composite of lithium / lithium stearate (50/25/25 weight ratio) and 0.15 parts by weight (0.9 g) of liquid paraffin as an E component spreading agent. Manually mixed in.
The reactive extrusion method was carried out under substantially the same conditions as in Example 1 using the same direction twin screw extruder (KZW15-30MG) manufactured by Technobel. Gray resin pellet P9 (about 500 g) was produced. The warm resin pellets were immediately dried with hot air at 140 ° C. for 4 hours and then stored in an aluminum / polyethylene laminated moisture-proof bag.

[Production of Composite P10 by Mixing Glass Fiber Chops with Vapor Phase Carbon Fiber Microparticles Made of PET Resin and Carbon Nanotubes (CNT) and Polyester / Carbon Copolymer Pellets P8 Based on Multifunctional Epoxy]
Grayish black pet resin pellets P8 of Example 8 (Raw material ratio: PET / gas phase method carbon fiber fine powder / binder-catalyst / spreading agent = 100 / 11.1 / 1.67-0.22 / 0 .56 parts by weight) using the same direction twin screw extruder (screw diameter 25 mm, L / D = 40, rotation speed 100 rpm, side feed type) manufactured by Soken Co., Ltd. The temperature is set to 240 to 280 ° C., charged into a hopper, supplied at a speed of 6 kg / h with a rotary feeder, and 3 mm long glass fiber chop (manufactured by Nippon Electric Glass, chopped strand T351 for functional resin) Was side fed at a rate of 1.2 kg / h. Two strands were continuously extruded into water from a nozzle with a diameter of 3 mm at a speed of about 2 m / min, and cut with a rotary cutter to obtain gray glass fiber chopped composite (GFRTP) pellets P10 (composition ratio: polyester / carbon). Copolymer pellet P8 / glass fiber chop = 100/20 parts by weight) About 4 kg was produced. The warm resin pellets were immediately dried with hot air at 140 ° C. for 4 hours and then stored in an aluminum / polyethylene laminated moisture-proof bag.

[Production of Composite P11 by Mixing Carbon Fiber Chops with Polyester / Carbon Copolymer Pellet P8 Based on Gas Phase Process Carbon Fiber Microparticles Made of PET Resin and Carbon Nanotubes (CNT) and Multifunctional Epoxy]
Grayish black pet resin pellets P8 of Example 8 (Raw material ratio: PET / gas phase method carbon fiber fine powder / binder-catalyst / spreading agent = 100 / 11.1 / 1.67-0.22 / 0 .56 parts by weight) using the same direction twin screw extruder (screw diameter 25 mm, L / D = 40, rotation speed 100 rpm, side feed type) manufactured by Souken Co., Ltd. Set the temperature to 240-280 ° C., put it in a hopper and feed it at a speed of 6 Kg / h with a rotary feeder. Side feed was performed at a speed of 1.2 kg / h. Two strands were continuously extruded into water from a nozzle with a diameter of 3 mm at a speed of about 2 m / min, cut with a rotary cutter, and black carbon fiber reinforced composite (CFRTP) pellets P11 (composition ratio: polyester / carbon) Copolymer pellet P8 / carbon fiber chop = 100/20 parts by weight) About 4 kg was produced. The warm resin pellets were immediately dried with hot air at 140 ° C. for 4 hours and then stored in an aluminum / polyethylene laminated moisture-proof bag.

According to the present invention, the aromatic saturated polyester is copolymerized with a carbon microparticle to form a polyester / carbon copolymer, and its strength, conductivity, heat transfer, heat resistance, oil resistance, weather resistance, etc. It was possible to improve various physical properties. In addition, by mixing glass fiber or carbon fiber with this improved polyester / carbon copolymer, various physical properties such as strength, conductivity, heat resistance, oil resistance and weather resistance have been improved. A fiber-reinforced polyester / carbon copolymer composite material could be obtained.
The present invention includes light weight and energy saving by improving the strength of components in advanced industries such as the automobile industry, the Shinkansen vehicle industry, the space aircraft industry, and linear motor cars, as well as conductivity, heat resistance, heat dissipation, etc. As a result, the applicability in this field is great. In particular, in the aircraft industry, there is an urgent need in the global market for weight reduction and energy saving by improving strength by 5% or more for constituent materials.

Claims (10)

(A) 100 parts by weight of polyester as component, (B) 0.1 to 30 parts by weight of carbon microparticles having a carboxyl group as component, (C) 2 or more epoxy groups in the molecule as a binder for component A mixture composed of 0.1 to 5 parts by weight of a polyfunctional epoxy compound contained, 0.01 to 1 part by weight of a binding reaction catalyst for component (D), and 0.01 to 1 part by weight of a spreading agent for component (E) Is produced at a temperature equal to or higher than the melting point of the polyester to form an ester bond. 2. The polyester according to claim 1, wherein the polyester as the component (A) contains at least one of polyethylene terephthalate, polybutylene terephthalate, polycarbonate, or a recycled product of these recovered cedar products. A method for producing a carbon copolymer. The carbon microparticle having a carboxyl group as component (B) contains at least one member selected from the group consisting of carbon black having a carboxyl group, acetylene black, and Ketchen black. A method for producing the polyester / carbon copolymer as described. The polyester / carbon copolymer according to claim 1, wherein the carbon microparticle having a carboxyl group as component (B) contains at least one of the group consisting of graphite or graphene having a carboxyl group. A method for producing a polymer. 2. The polyester according to claim 1, wherein the carbon microparticles having a carboxyl group as component (B) contain at least one member selected from the group consisting of carbon nanotubes having a carboxyl group or diamond-like carbon. A method for producing a carbon copolymer. The method for producing a polyester-carbon copolymer according to claim 1, wherein the carbon microparticles having a carboxyl group as component (B) are nano-sized diamonds having a carboxyl group. 2. The polyester / polyester according to claim 1, wherein the binder of component (C) is a polyfunctional epoxy compound having two or more epoxy groups in the molecule, alone or in combination of two or more. A method for producing a carbon copolymer. The component (D) binding reaction catalyst contains at least one of the group consisting of an alkali metal carboxylate, an alkaline earth metal carboxylate, an alkali metal carbonate, or an alkaline earth metal carbonate. The method for producing a polyester / carbon copolymer according to claim 1, wherein: (E) Component spreading agent contains liquid paraffin, The manufacturing method of the polyester carbon copolymer of Claim 1 characterized by the above-mentioned. (A) 100 parts by weight of polyester as component, (B) 0.1 to 30 parts by weight of carbon microparticles having a carboxyl group as component, (C) 2 or more epoxy groups in the molecule as a binder for component A mixture composed of 0.1 to 5 parts by weight of a polyfunctional epoxy compound to be contained, 0.01 to 1 part by weight of a binding reaction catalyst of component (D), and 0.01 to 1 part by weight of a spreading agent for component E, It is characterized by reacting at a temperature equal to or higher than the melting point of the polyester to form an ester bond, and then mixing 5 to 30 parts by weight of glass fiber of component (F) or 5 to 30 parts by weight of carbon fiber of component (G). To produce a fiber reinforced polyester / carbon copolymer composite.

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