JP5268797B2 - High hardness polyester elastomer composition and resin-coated wire rope - Google Patents

Description

  The present invention relates to a high-hardness polyester elastomer composition suitable for a wire rope coating resin and a resin-coated wire rope using the same.

  In addition to resin-coated electric wires, the drive wire rope used as a moving cable has the purpose of improving the life and function of the wire rope, such as reducing contact friction, protecting against dust, chemicals, and preventing the wire rope twisting oil from escaping. Thus, resin-coated wire ropes are widely used.

  Resins used in all cable coverings, including electric wires and drive wire ropes, are polyolefin resins such as vinyl chloride resin, polyethylene, and polypropylene, nylons 6, 11, and 12 and soft segments such as polyether. Nylon resins of block copolymers (polyamide elastomers), polyester resins, fluorine resins such as PVDF, ETFE, and PFA are widely used when high weather resistance and chemical resistance are required.

  However, the drive wire rope used especially in cold regions and in summer greenhouses under agricultural heat is handled in a very wide temperature environment from 100 ° C to -50 ° C and from extremely low temperatures. In the temperature range, adhesion, wear resistance, and bending fatigue resistance are first required, and the resin that has been put to practical use as a drive wire rope coating resin is a polyolefin resin such as polyethylene and polypropylene in the case of light loads. However, in the case of a high load, nylon 11, 12 and coating with a block copolymer (polyamide elastomer) of them and polyether occupy most of the market.

  The bending fatigue resistance of the resin used to coat electric wires and cables has been evaluated based on the reference axis based on the static bending elastic modulus and degree of polymerization (molecular weight) for the bending fatigue test. The bending fatigue resistance required for the wire rope coating resin for driving that is always in a dynamic environment is largely dependent on the dynamic storage elastic modulus (E ′), although there is a difference depending on the resin type. When the rate (E ′) exceeds 1000 MPa, the bending fatigue resistance tends to decrease, and it has been found that about 2500 MPa is practically the limit of repeated bending. On the other hand, if the dynamic storage elastic modulus (E ′) or the bending elastic modulus is low, the bending fatigue resistance is enhanced. However, if the coating resin is too flexible, the coating resin will bend by the compressive stress caused by a high load, and the related resin may be plastically deformed. Excessive wear due to contact with the wire, bending when a power transmission part is attached to a wire rope, bending to a tensile stress, and the holding power of the power transmission part (adhesion between the wire rope and the coating resin) tends to decrease, and dynamic storage elasticity When the rate (E ′) is less than 200 MPa, the amount of compression set at the time of high load starts to increase, and the dynamic storage elastic modulus (E ′) is required to be as high as possible while ensuring the bending fatigue resistance. Because the drive wire rope coating resin is hardened at low temperatures, or because it is easily crushed by high loads, the load on the coating resin is not reduced, and the entire load of the wire rope is applied to the coating resin, especially Driving wire ropes used outdoors in cold regions and in summer greenhouses for agricultural use are exposed to a very wide temperature environment from 100 ° C to -50 ° C and have a dynamic storage modulus (E '). 320 MPa to 2500 MPa at -50 ° C, 320 MPa to 1800 MPa at -25 ° C, 320 MPa to 1250 MPa at 0 ° C in the normal range, 320 MPa to 1000 MPa at 25 ° C in the normal range, 250 MPa to 1000 MPa at 50 ° C in the normal range. , 190 MPa or more and 1000 MPa or less at 75 ° C., and at 100 ° C. It is required in the first to the driving wire rope coating resin having a high hardness resin is 50MPa or more 1000MPa or less.

  In addition, the dynamic storage elastic modulus (E ′) and the adhesion between the wire rope and the wire rope are considered to have a certain proportional relationship. Specifically, as an example, a 1.5 mm diameter 7 × 7 wire rope at room temperature is used. In addition, a coating resin adhesion force (restraint force in the wire rope axial direction per 1 cm of resin coating) when the resin is coated to a diameter of 2.8 mm is desired to be 10 kgf or more.

  The nylon 11, 12 coated on the driving wire rope in the case of a high load and a block copolymer (polyamide elastomer) of them with polyether greatly change the water absorption rate of the resin, and accordingly, the normal temperature range The dynamic storage elastic modulus (E ′) at the same temperature varies greatly, but generally it is about 2000 MPa at −50 ° C., about 1000 MPa at 0 ° C. in the normal range, about 500 MPa at 50 ° C. in the normal range, and at 100 ° C. Although it is about 200 MPa, it has excellent adhesion to wire rope, wear resistance and bending fatigue resistance under high load environment, but weather resistance under sunlight even if it contains a considerable amount of weathering agent etc. In addition, the chemical resistance in an acidic environment is not sufficient, and even if it is used as a wire rope coating resin for high load driving in such an environment, even a black colored product containing a light heat resistant agent will be coated in a few years Deterioration to occur a crack.

  ETFE, which is considered to have extremely high weather resistance, chemical resistance, and bending fatigue resistance as a wire coating resin, is a coating of a driving wire rope that constantly receives a combination of high tensile, bending, and compressive stresses. As a resin, in a bending durability test under a high load environment, the resin was plastically deformed at an early stage, and the adhesion with the wire rope was poor.

  Therefore, various polyester copolymer compositions including a blend composition of polyester elastomers are widely known as coating resins having a balance of weather resistance, chemical resistance, abrasion resistance, and bending fatigue resistance, and patent documents. Various compositions have been developed specifically for injection molding and extrusion molding as described in 1 to 18 or for cable coating, and some are used for coating cables such as electric wires. Is a polyester elastomer composition mainly intended for low hardness, and it is 100 ° C to -50 ° C as a wire rope coating resin for driving, which has high flexibility, weather resistance, heat resistance and chemical resistance, but has a high load on the coating resin. The required dynamic storage modulus (E ′) in the entire temperature range from the high temperature range to the low temperature range is not sufficient, and the bending fatigue resistance in the low temperature range is Considering that it is too soft at high temperatures and poor in wear resistance and adhesion, and considering bending fatigue resistance at high temperatures, it is too hard and poor in fatigue resistance at low temperatures, and the application range is limited. Therefore, the current situation is that it is not widely used as a high load driving wire rope coating resin.

JP 2005-511886 A Japanese Patent Publication No. 6-53841 Japanese Patent Publication No. 63-23225 Japanese Patent Publication No. 63-48899 JP-A-5-239198 JP 2001-254006 A Japanese Patent No. 2849011 JP 11-66959 A JP 2003-192880 A Japanese Patent No. 3674722 Japanese Patent Laid-Open No. 11-172531 JP 2002-253306 A Japanese Patent No. 3678867 JP 2001-240663 A JP 2001-253032 A Japanese Patent No. 3083136 International Publication No. 2007/0297768 Pamphlet Japanese Patent Publication No. 3-80170

  The present invention mainly provides adhesion, weather resistance, and resistance to use as a coating resin for resin-coated wire ropes that are continuously used at high loads from a low temperature range to a high temperature range in a solar environment in and outside agricultural greenhouses. It is an object of the present invention to provide a high hardness thermoplastic polyester elastomer composition having excellent chemical properties and excellent bending characteristics in a low temperature range, and a resin-coated wire rope coated with the thermoplastic polyester elastomer composition. To do.

Actually, when the present inventor conducted a test, the main composition was a polyester having terephthalic acid and 1,4-butanediol as constituent components, having a hardness comparable to that of the unplasticized polyamides 11 and 12 in the normal temperature range. Polybutylene terephthalate resin NOVADURAN ^TM 5010R8M manufactured by Mitsubishi Engineering Plastics Co., Ltd., which has been softened by copolymerizing other constituents as follows (Comparative Example 1, bending elastic modulus 1500 MPa, conforming to ASTM D790; notched Charpy impact strength 5 kJ / m ² , conforming to ISO 179 (23 ° C.), the static bending property was good. However, when the bending fatigue resistance was confirmed by covering the driving wire rope, the bending fatigue resistance was already too hard in the normal temperature range. It was bad (1800 times until crack generation) and could not be applied as a wire rope coating resin for driving. A similar phenomenon was also confirmed in flexible polyamide 6 (Reference Example 3, bending elastic modulus 600 MPa, conforming to ASTM D790; notched Charpy impact strength NB (not breaking), conforming to ISO179).

In addition, polyester (PBN) using naphthalene-2,6-dicarboxylic acid and 1,4-butanediol as a crystalline hard segment, which has good heat resistance and weather resistance, and polytetra Polyether polyester elastomer composition using methylene glycol (Perprene ^TM EN7000 manufactured by Toyobo Co., Ltd. (Comparative Example 2, flexural modulus 700 MPa, conforming to ASTM D790) has good adhesion and weather resistance in the normal temperature range. However, since the glass transition temperature is as high as 49 ° C, the amount of change in hardness in the normal temperature range is large (hardens suddenly), and the bending fatigue resistance is poor (6000 times until crack generation). Considering the dynamic storage elastic modulus (E ') in the polymer, the soft segment polymerization amount is slightly higher (the glass transition temperature of PBN) The degree of polymerization of polytetramethylene glycol as an amorphous soft segment component is estimated to be 30 to 35% by weight from the difference between the degree of 76 ° C. and the glass transition temperature of 49 ° C. at 27 ° C. The storage elastic modulus (E ′) decreased and was too soft to be applied as a drive wire rope coating resin.

Furthermore, polyester using terephthalic acid and 1,4-butanediol as the crystalline hard segment, which has the best balance of elastic properties from low temperature to high temperature, and polytetramethylene glycol as the amorphous soft segment are used. Hytrel ^TM 5577 manufactured by Toray DuPont Co., Ltd. (flexural modulus 210 MPa, conforming to ASTM D790) has good bending fatigue resistance at low temperatures, but its absolute hardness is too low and soft at room temperature and high temperatures. In the case of Hytrel ^TM 7277 (Comparative Example 3, flexural modulus 539 MPa, conforming to ASTM D790) manufactured by Toray DuPont, which is hard, the adhesion from room temperature to high temperature is good, but it is too hard and resistant at low temperatures. Bending fatigue resistance is slightly worse (fine cracks occur at 16000 times), intermediate product of Toray DuPont High Trel ^TM 6377 (Comparative Example 4, bending elastic modulus 353 MPa, conforming to ASTM D790) is also slightly harder than the dynamic storage elastic modulus (E ′) in the cryogenic region and slightly softer in the normal temperature region, resulting in poor adhesion (coating) Adhesion force per 1 cm 6 kgf) It was not sufficient as a wire rope coating resin for driving.

  Therefore, as a result of diligent research by the inventor, the blending of two or more specific polyester elastomer block copolymers minimizes the increase in the amount of soft segments that affect the weather resistance and over-softening at high temperatures. As a wire rope coating resin, it was discovered that the dynamic storage elastic modulus (E ′) in the high temperature range can be increased as much as possible while the dynamic storage elastic modulus (E ′) in the low temperature range can be reduced as much as possible. Is an index of flexural fatigue resistance at −50 ° C. from 320 MPa to 2500 MPa, −25 ° C. from 320 MPa to 1800 MPa, normal range from 0 ° C. to 320 MPa to 1250 MPa, normal range from 25 ° C. to 320 MPa to 1000 MPa, normal use 250 MPa to 1000 MPa at 50 ° C., 190 MPa to 1000 MPa at 75 ° C. Under a low temperature, and can achieve a dynamic storage modulus (E ′) of 150 MPa or more and 1000 MPa or less at 100 ° C. The inventors have found that a thermoplastic polyester elastomer composition having high hardness can be obtained, and have completed the present invention.

That is, the gist of the present invention is as follows.
(1) (a) a block copolymer of a crystalline hard segment composed of a polyester formed from an aromatic dicarboxylic acid or an ester-forming derivative thereof and a diol and an amorphous soft segment formed from a polyether and / or polyester A polyester elastomer block having a dynamic loss tangent (tan δ) maximum temperature measured by dynamic viscoelasticity measurement at 1 Hz according to JIS K 7244-4 or a glass transition temperature measured by DSC of 0 ° C. or higher. A crystalline polyester comprising a copolymer A-1 and a polyester formed from an aromatic dicarboxylic acid or its ester-forming derivative and a diol, and measured by dynamic viscoelasticity measurement at 1 Hz according to JIS K 7244-4. Dynamic loss tangent (tan δ) maximum temperature or DSC Constant glass transition temperature of 0 ℃ or more crystalline polyester A-2
At least one polymer selected from the group consisting of the dynamic loss tangent (tan δ) maximum temperature or the glass transition temperature of each polymer multiplied by the weight fraction of the polymer as a whole. A polymer A having a total of 10% by weight to 30% by weight of a total value obtained by multiplying the amorphous soft segment copolymerization amount of each polymer by a weight fraction with respect to the whole polymer,
(B) a block copolymer of a crystalline hard segment composed of a polyester formed from an aromatic dicarboxylic acid or an ester-forming derivative thereof and a diol, and an amorphous soft segment formed from a polyether and / or polyester, Polyester elastomer block copolymer having a dynamic loss tangent (tan δ) maximum temperature measured by dynamic viscoelasticity measurement at 1 Hz according to JIS K 7244-4 or a glass transition temperature measured by DSC of less than 0 ° C. At least one polymer selected from the group consisting of the dynamic loss tangent (tan δ) maximum temperature or the glass transition temperature of each polymer multiplied by the weight fraction of the whole polymer, − 70 ° C. or more and less than 0 ° C., and the amorphous soft segment copolymerization amount of each polymer and the weight A polymer B sum less 80 wt% 33.5 wt% or more of a value obtained by multiplying the weight fraction for the entire body,
The weight ratio of the polymer A and the polymer B is 75:25 to 97.5: 2.5.
And the difference of the said dynamic loss tangent (tan (delta)) maximum temperature or the said glass transition temperature of the said polymer A and the said polymer B is 20 degreeC or more, Amorphous soft segment copolymerization amount is 17.5 weight% or more 27.5 wt% or less of a thermoplastic polyester elastomer composition,
The dynamic storage elastic modulus (E ′) is 320 MPa to 2500 MPa at −50 ° C., 320 MPa to 1800 MPa at −25 ° C., 320 MPa to 1250 MPa at 0 ° C. in the normal range, 320 MPa to 1000 MPa at 25 ° C. in the normal range, A thermoplastic polyester elastomer composition that is 250 MPa to 1000 MPa at 50 ° C., 190 MPa to 1000 MPa at 75 ° C., and 150 MPa to 1000 MPa at 100 ° C.

(2) The polymer A and the polymer B are block copolymers in which crystalline hard segments made of polybutylene terephthalate and amorphous soft segments made of terephthalic acid ester of polyalkylene ether glycol are alternately bonded ( The thermoplastic polyester elastomer composition as described in 1).

(3) A thermoplastic polyester elastomer composition obtained by melt-mixing the thermoplastic polyester elastomer composition according to (1) or (2).

(4) The thermoplastic polyester elastomer composition according to any one of (1) to (3), which is used for coating a driving wire rope.

(5) A wire rope formed by coating the thermoplastic polyester elastomer composition according to (1) or (2).

(6) The wire rope according to the above (5) for driving an operation member mainly installed in the facility horticulture equipment.

  The thermoplastic polyester elastomer composition of the present invention is excellent in adhesion, weather resistance and chemical resistance, which can be used as a coating resin for wire ropes used mainly under high temperatures, high loads and sunlight environments, and at low temperatures. It has excellent bending characteristics, is relatively high in hardness, and has excellent characteristics as a coating resin for a driving wire rope.

FIG. 1 is a reference diagram for explaining a bending fatigue endurance test.

Although the mechanism of physical properties of the polyester elastomer composition of the present invention has not been fully elucidated, various literatures relating to known polymer blends describe blend compositions of polyester elastomer compositions having greatly different hardness and composition in a transmission electron microscope. Although (TEM) observation confirmed an incompatible dispersion structure and it could not be said that the affinity (solubility, reactivity) was good (in the examples, the tensile break elongation was a single composition before mixing (Comparative Example 3 and Significantly reduced compared to Hytrel ^TM 4047)), but still not too bad than being of the same type of polyester, and consequently moderate, the dynamic storage modulus (E ') of the blend composition is While exhibiting semi-compatible behavior, it is possible to achieve stabilization that is not possible with existing synthetic compositions, and wire ropes that are subject to high loads. Excellent flexible properties can be used as a covering resin is assumed obtained.

(Polymer A)
The polymer A used in the present invention is a block of a crystalline hard segment composed of a polyester formed from an aromatic dicarboxylic acid or an ester-forming derivative thereof and a diol, and an amorphous soft segment formed from a polyether and / or polyester. It is selected from polyester elastomer block copolymer A-1 which is a copolymer and crystalline polyester A-2 comprising a polyester formed from an aromatic dicarboxylic acid or an ester-forming derivative thereof and a diol.

  The polyester elastomer block copolymer A-1 used in the present invention is a glass measured by dynamic loss tangent (tan δ) maximum temperature measured by dynamic viscoelasticity measurement at 1 Hz or DSC according to JIS K 7244-4. The transition temperature is 0 ° C. or higher, preferably 0 ° C. or higher and 48 ° C. or lower, more preferably 7.5 ° C. or higher and 24 ° C. or lower.

  The dynamic loss tangent (tan δ) maximum temperature measured by dynamic viscoelasticity measurement at 1 Hz according to JIS K 7244-4 and the glass transition temperature measured by DSC (differential scanning calorimetry) are almost equal. Accordingly, in the present invention, any one may satisfy the requirements of the present invention.

  The polyester elastomer block copolymer A-1 used in the present invention preferably has a polyether and / or polyester copolymerization amount as an amorphous soft segment of less than 33.5% by weight, more preferably 10% by weight or more and 25% by weight. % Or less, Shore D hardness (conforming to JIS K7215) is preferably 59D or more, more preferably 67.5D or more and 75D or less, and a relatively high rigidity (plastic) polyester elastomer block copolymer.

  The flexural modulus (based on ASTM D790) of the polyester elastomer block copolymer A-1 is preferably 500 MPa to 1000 MPa, more preferably 525 MPa to 750 MPa.

  The polyester elastomer block copolymer A may be used alone or in combination of two or more.

  The crystalline polyester A-2 used in the present invention has a dynamic loss tangent (tan δ) maximum temperature measured by dynamic viscoelasticity measurement at 1 Hz according to JIS K 7244-4 or a glass transition temperature measured by DSC. 0 ° C. or higher, preferably 0 ° C. or higher and 78 ° C. or lower, more preferably 0 ° C. or higher and 48 ° C. or lower. Flexural modulus (according to ASTM D790) is preferably 1000 MPa or higher and 2500 MPa or lower, more preferably 1000 MPa or higher and 1500 MPa or lower. is there.

  Examples of the crystalline polyester A-2 include an aromatic dicarboxylic acid or an ester-forming derivative thereof described later as “crystalline hard segment aromatic dicarboxylic acid or an ester-forming derivative thereof” and an “crystalline hard-segment diol” described below. Polyesters formed from diols, preferably polybutylene terephthalate, polytrimethylene terephthalate, polybutylene naphthalate, more preferably polybutylene terephthalate.

  Crystalline polyester A-2 may be individual or may combine 2 or more types.

  As the polymer A used for this invention, the said polyester elastomer block copolymer A-1 and the said crystalline polyester A-2 may be used independently, and 2 or more types may be combined.

  The polymer A used in the present invention is a sum of values obtained by multiplying the dynamic loss tangent (tan δ) maximum temperature or the glass transition temperature of each polymer constituting the polymer A by the weight fraction of the whole polymer A. Is 0 ° C. or higher and 48 ° C. or lower, preferably 7.5 ° C. or higher and 24 ° C. or lower, and the sum of values obtained by multiplying the amorphous soft segment copolymerization amount of each polymer and the weight fraction of the whole polymer A is It is 10 to 30% by weight, preferably 10 to 25% by weight.

(Polyester elastomer block copolymer B)
Polymer B used in the present invention has a dynamic loss tangent (tan δ) maximum temperature measured by dynamic viscoelasticity measurement at 1 Hz according to JIS K 7244-4 or a glass transition temperature measured by DSC of less than 0 ° C. It is.

  In order to improve the dynamic storage elastic modulus (E ′) in a small amount and suppress the stickiness of the resin, the dynamic loss tangent (tan δ) maximum temperature or the glass transition temperature is preferably −60 ° C. or more and −12. It is .5 ° C or lower, more preferably -60 ° C or higher and -35 ° C or lower.

  The polymer B used in the present invention preferably has a polyester copolymerization amount of 33.5% by weight or more and less than 80% by weight, more preferably 50% by weight or more and 70% by weight or less, and a Shore D hardness (based on JIS K7215). Is a highly flexible (rubbery) polyester elastomer block copolymer of 27D to less than 59D, more preferably 38D to 55D.

  The flexural modulus (based on ASTM D790) of the polymer B used in the present invention is preferably 25 MPa or more and 300 MPa or less, more preferably 50 MPa or more and 210 MPa or less.

  The polymer B used for this invention may be individual, or may combine 2 or more types.

  The polymer B used in the present invention is a sum of values obtained by multiplying the dynamic loss tangent (tan δ) maximum temperature or the glass transition temperature of each polymer constituting the polymer B by the weight fraction of the whole polymer B. Is −70 ° C. or higher and lower than 0 ° C., preferably −60 ° C. or higher and −12.5 ° C. or lower, more preferably −60 ° C. or higher and −35 ° C. or lower, and the amorphous soft segment copolymerization amount and weight of each polymer The sum of the values obtained by multiplying the weight fraction with respect to the entire combined B is 33.5 wt% or more and 80 wt% or less, preferably 35 wt% or more and 65 wt% or less.

  When the amount of the soft segment copolymer of the polymer B is less than 33.5% by weight, the dynamic loss tangent (tan δ) maximum temperature or the glass transition temperature exists in a high temperature range (the plastic property becomes strong). The temperature-dependent form of the dynamic storage elastic modulus (E ′) of the polymer B itself in the low temperature region is similar to the polymer A, and the dynamic storage elastic modulus (E in the low temperature region of the mixed composition) ′) Cannot be reduced as required. Further, a polyester elastomer block copolymer in which the dynamic loss tangent (tan δ) maximum temperature or the glass transition temperature is less than −70 ° C., or the soft segment copolymerization amount exceeds 80% by weight. When used, it becomes a composition in which an unnecessarily low melting point soft segment copolymer is mixed, and even if it is blended in a small amount in the polymer A, the dynamic storage elastic modulus (E ′) in the high temperature range is reduced more than necessary. Resin stickiness is undesirable.

(Crystalline hard segment aromatic dicarboxylic acid or ester-forming derivative thereof)
The aromatic dicarboxylic acid or ester-forming derivative thereof used in the polymer A and the polymer B is terephthalic acid, dimethyl terephthalate, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7. -Dynamic loss tangent (tan δ) that is advantageous for low-temperature characteristics, such as dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sulfoisophthalic acid, or ester-forming derivatives thereof. Most preferably, terephthalic acid and / or dimethyl terephthalate, which can lower the maximum temperature or the glass transition temperature, are used.

(Crystalline hard segment diol)
Diols used in the polymer A and the polymer B are ethylene glycol, trimethylene glycol, tetramethylene glycol (1,4-butanediol), pentamethylene glycol, hexamethylene glycol, neopentyl glycol having a molecular weight of 300 or less, Aliphatic diols such as decamethylene glycol, alicyclic diols such as 1,4-cyclohexanedimethanol and tricyclodecane dimethylol, xylylene glycol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxy Phenyl) propane, 2,2-bis [4- (2-hydroxyethoxy) phenyl] propane, bis (4-hydroxyphenyl) sulfone, bis (2-hydroxyphenyl) sulfone, bis [4- (2-hydroxyethoxy) Phenyl] Aromatic diols such as luphone, 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane, 4,4'-dihydroxy-p-terphenyl, 4,4'-dihydroxy-p-quaterphenyl However, it is most preferable to use 1,4-butanediol which can lower the dynamic loss tangent (tan δ) maximum temperature or the glass transition temperature, which is advantageous for low temperature characteristics.

  The aromatic dicarboxylic acid or its ester-forming derivative and diol used in the polymer A and the polymer B may be a copolyester in which two or more types are used in combination for softening the crystalline hard segment. . Moreover, the polyester which copolymerized the trifunctional or more polyfunctional carboxylic acid component, the polyfunctional oxyacid component, the polyfunctional hydroxy component, etc. may be sufficient.

(Amorphous soft segment)
Polyethers (polyoxyalkylenes) of amorphous soft segments used in the polyester elastomer block copolymer A-1 and the polymer B are poly (ethylene oxide) glycol having a number average molecular weight of about 300 to 6000, Propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, ethylene oxide propylene oxide copolymer, poly (propylene oxide) glycol ethylene oxide addition polymer, ethylene oxide tetrahydrofuran copolymer, etc. Poly (propylene oxide) glycol and poly (tetramethylene oxide) glycol are most preferred because of their overall properties such as water resistance, water resistance, low temperature properties, elastic recovery, and mechanical strength. .

  The polyester elastomer block copolymer A-1 and the non-crystalline soft segment polyester used in the polymer B are ring-opening polymers (for example, poly (ε-caprolactone), polyenanthlactone, polycaprylolactone, etc. ), Derivatives of aliphatic dicarboxylic acids and aliphatic diols having about 2 to 12 carbon atoms (for example, polybutylene adipate, polyethylene adipate, polyhexylene sebacate), aromatic dicarboxylic acids such as phthalic acid and isophthalic acid And an aromatic polyester (for example, polyhexylene isophthalate, polyhexylene phthalate, etc.) composed of an aliphatic diol having 5 or more carbon atoms. Among amorphous polyesters, poly (ε- Caprolactone), polybutylene adipate, polyethylene It is preferable to use dipate, polyhexylene sebacate, or polyhexylene isophthalate.

  The amorphous soft segment used in the polyester elastomer block copolymer A-1 and the polymer B is 2 within the range of the dynamic loss tangent (tan δ) maximum temperature or the glass transition temperature and the soft segment amount, respectively. A polyester elastomer block copolymer that is used in combination (copolymerization or melt mixing) may be used.

(Production of polymer A and polymer B)
The production method of the polyester elastomer block copolymer A-1, the crystalline polyester A-2 and the polymer B used in the present invention is not particularly limited and can be produced by a known method. For example, as a method for producing crystalline polyester A-2, a method of transesterifying a dicarboxylic alcohol diester with glycol and polyoxyalkylene glycol in the presence of a catalyst and polycondensing the reaction product, dicarboxylic acid with glycol and polyoxy Examples include a method in which an alkylene glycol is ester-reacted in the presence of a catalyst and a reaction product is polycondensed. As a method for producing the polyester elastomer block copolymer A-1 and the polymer B, dicarboxylic acid or dicarboxylic acid alcohol diester is used. A method in which a crystalline segment is prepared by ester reaction or transesterification of glycol with glycol, and polyoxyalkylene glycol is added to effect transesterification to copolymerize the amorphous soft segment; Method of addition reaction of instrument, a scheme of the method or the respective reaction product is coupled with a chain linking agent is melt-mixed and the like.

(Preferable polyester elastomer block copolymer)
The polyester elastomer block copolymer used in the present invention is preferably a block copolymer in which crystalline hard segments made of polybutylene terephthalate and amorphous soft segments made of terephthalic acid ester of polyalkylene ether glycol are alternately bonded. .

The preferable polyester elastomer block copolymer has a crystalline hard segment represented by the following formula (I):
[—COC ₆ H ₄ CO—O (CH ₂ ) ₄ O—] _n
(In the formula, —COC ₆ H ₄ CO— represents a terephthaloyl group.)
The amorphous soft segment is represented by the following formula (II):
[—COC ₆ H ₄ CO—O {(CH ₂ ) _p 0} _q −] _m
(In the formula, —COC ₆ H ₄ CO— represents a terephthaloyl group.)
Indicated by

As the preferable polyester elastomer block copolymer, for example, Hytrel ^TM series (manufactured by Toray DuPont) is commercially available, and the commercially available product can be used.

For example, Hytrel ^TM 7277 has a glass transition temperature (DSC) of 12 ° C., a Shore D hardness (according to JIS K7215) 72, a flexural modulus (according to ASTM D790) of 539 MPa, and is suitable as a polyester elastomer block copolymer A. Can be used. Hytrel ^TM 4047 has a glass transition temperature (DSC) of −40 ° C., a Shore D hardness (in accordance with JIS K7215) 40, a flexural modulus (in accordance with ASTM D790) of 70.6 MPa, and Hytrel ^TM 5557 has a glass transition temperature. (DSC) -20 ° C., Shore D hardness (conforming to JIS K7215) 55, flexural modulus (conforming to ASTM D790) 210 MPa, Hytrel ^TM 3046 has a glass transition temperature (DSC) of −69 ° C., Shore D hardness ( JIS K7215) 27, flexural modulus (according to ASTM D790) 23.5 MPa, and can be suitably used as the polyester elastomer block copolymer B.

(Mixing of polymer A and polymer B)
The combination of the polymer A and the polymer B to be mixed has a difference of the dynamic loss tangent (tan δ) maximum temperature or the glass transition temperature of 20 ° C. or more, preferably 20 ° C. or more and 118 ° C. or less, more preferably Is set to 20 ° C. or higher and 84 ° C. or lower. If the difference between the dynamic loss tangent (tan δ) maximum temperature or the glass transition temperature is less than 20 ° C., the temperature-dependent form of the dynamic storage elastic modulus (E ′) is similar. The dynamic storage elastic modulus (E ′) suddenly decreases and becomes too soft or sticky, so that the effect of improving the dynamic storage elastic modulus (E ′) by mixing cannot be satisfied.

  The weight ratio of the polymer A and the polymer B is 75:25 to 97.5: 2.5. When the mixing ratio of the polymer B is less than the lower limit, the dynamic storage elastic modulus (E ′) in a low temperature range cannot be reduced as required, and when the mixing ratio of the polymer B exceeds the upper limit, The amount of copolymerization of the crystalline soft segment itself increases, and the dynamic storage elastic modulus (E ′) at a high temperature range is too low and too soft. In order to further smooth the temperature dependence of the dynamic storage elastic modulus (E ′), it is preferable to blend a small amount of an appropriate low-hardness polymer B, and considering resin preparation and workability in actual production The weight ratio of the polymer A and the polymer B is preferably 92: 8 to 97.5: 2.5, so that the polyether and / or polyester copolymer as an amorphous soft segment after mixing. The polymerization amount is preferably 17.5 wt% or more and 27.5 wt% or less, more preferably 20 wt% or more and 25 wt% or less (the theoretically possible combination range is 10.5 wt% or more and 42.5 wt% The composition of the polymer A and the polymer B is selected so that

The composition of the present invention is not limited to the examples described below (Hytrel ^TM 7277: 94: 6 wt% Hytrel ^TM 4047). When the blending ratio of the polymer A is close to the upper limit, the following (i) may be mentioned, and when close to the lower limit, the following (ii) may be mentioned, and the crystalline polyester A-2 is used. In such cases, the following (iii) may be mentioned.

(i) Hytrel ^TM 7277: In the case of Hytrel ^TM 3046, 97.5: 2.5% by weight (soft segment amount 21.5% by weight) to 92: 8% by weight (soft segment amount 24.8% by weight) is preferable. .

(ii) Hytrel ^TM 7277: In the case of Hytrel ^TM 5557, it is preferably 92: 8% by weight (soft segment amount 21.4% by weight) to 75: 25% by weight (soft segment amount 24.5% by weight).

(iii) Polybutylene terephthalate (hereinafter referred to as “PBT”): Hytrel ^TM 7277: In the case of Hytrel ^TM 3046, 24: 72: 4 wt% (soft segment amount 17.6 wt%) to 37.5: 37.5 : 25% by weight (soft segment amount 27.5% by weight) is preferable.

  A known method can be used for mixing the polymer A and the polymer B used in the present invention. A method in which the polymer A and the polymer B are dry blended with a mixer such as a mixer or a blender, and supplied to an extruder, a Banbury mixer, a kneader, or a roll machine, and melt-kneaded. For example, a method of adding a viscosity adjusting step may be used, but simple mixing may be mixing that also serves as kneading by an extruder at the time of wire rope coating.

  The mixed composition of the polymer A and the polymer B used in the present invention is a known hindered phenol-based, phosphite-based, thioether-based, aromatic amine-based oxidized material within the range not impairing the object of the present invention. Inhibitor, benzophenone-based, triazine-based, benzotriazole-based, hindered amine-based light-proofing agent, crystallization accelerator, crystal nucleating agent, plasticizer, lubricant, antistatic agent, conductivity improver, hydrolysis resistance improver, An appropriate amount of various additives such as a polyfunctional crosslinking agent, a metal deterioration inhibitor, a flame retardant, a colorant, a reinforcing material such as silica, talc, and calcium carbonate can be blended.

  In the mixed composition of the polymer A and the polymer B used in the present invention, a known epoxy compound, polycarbodiimide compound, etc. within the range not impairing the object of the present invention for the purpose of improving moldability and creep elasticity Can be blended in an appropriate amount.

  In the mixed composition of the polymer A and the polymer B used in the present invention, various other resins such as polyamides, polyolefins, polyurethanes, etc., which are known for the purpose of improving impact resistance and the like, as long as the object of the present invention is not impaired. Can be blended in an appropriate amount.

  The total amount of optional components such as the above-mentioned additives is preferably 10% by weight or less, more preferably 5% by weight or less.

  In order to describe the present invention more specifically and in detail, examples and comparative examples are shown below, but the present invention is not limited to the following examples.

Example 1
As a polyester elastomer block copolymer A Hytrel ^TM 7277 (glass transition temperature (DSC) 12 ° C., Shore D hardness (according to JIS K7215) 72, flexural modulus (according to ASTM D790) 539 MPa, amorphous 94% by weight copolymer soft segment copolymerization amount), and polyester elastomer block copolymer B Hytrel ^TM 4047 manufactured by Toray DuPont (glass transition temperature (DSC) -40 ° C., Shore D hardness (according to JIS K7215) ) 40, flexural modulus (according to ASTM D790) 70.6 MPa, amorphous soft segment copolymerization amount 63 wt%) 6 wt% was premixed with a mixer at the time of wire rope coating, and at a barrel temperature of 225 ° C by an extruder Add kneading, die temperature 230 ° C, outer diameter 1.5m It was coated so that the outer diameter 2.8mm to steel wire made 7 × 7 wire rope. The Shore D hardness measured according to JIS K7215 was 68.

Comparative Example 1
Mitsubishi engineering plastics polybutylene terephthalate resin Novaduran ^TM 5010R8M (glass transition temperature (DSC) 51 ° C., Shore D hardness (according to JIS K7215) 74, flexural modulus (according to ASTM D790) 1500 MPa, amorphous soft segment Copolymerization amount 0% by weight) was coated on a steel wire 7 × 7 wire rope having an outer diameter of 1.5 mm so as to have an outer diameter of 2.8 mm. The Shore D hardness measured according to JIS K7215 was 74.

Comparative Example 2
Toyobo Co., Ltd. Perprene ^TM EN7000 (Glass transition temperature (DSC) 49 ° C., Shore D hardness (conforming to JIS K7215) 71, flexural modulus (conforming to ASTM D790) 700 MPa) as a polyester elastomer block copolymer in an extruder Then, a 7 × 7 wire rope made of steel wire having an outer diameter of 1.5 mm was coated to an outer diameter of 2.8 mm. The Shore D hardness measured according to JIS K7215 was 71.

Comparative Example 3
Hytrel ^TM 7277 manufactured by Toray DuPont as a polyester elastomer block copolymer (glass transition temperature (DSC) 12 ° C., Shore D hardness (according to JIS K7215) 72, flexural modulus (according to ASTM D790) 539 MPa, amorphous The amount of the soft segment copolymer (20% by weight) was coated on a steel wire 7 × 7 wire rope having an outer diameter of 1.5 mm so as to have an outer diameter of 2.8 mm.

Comparative Example 4
Hytrel ^TM 6377 manufactured by Toray DuPont as a polyester elastomer block copolymer (glass transition temperature (DSC) 3 ° C., Shore D hardness (according to JIS K7215) 63, flexural modulus (according to ASTM D790) 353 MPa, amorphous The amount of soft segment copolymer (29% by weight) was coated on a steel wire 7 × 7 wire rope having an outer diameter of 1.5 mm so as to have an outer diameter of 2.8 mm.

Reference example 1
PA11 manufactured by Arkema Co., Ltd. and Rilsan ^TM BESN O TL were coated on a 7 × 7 wire rope made of steel wire having an outer diameter of 1.5 mm so as to have an outer diameter of 2.8 mm using an extruder.

Reference example 2
PA12 manufactured by Arkema Co., Ltd. and Rilsan ^TM AESN Bk P40 TL were coated on a 7 × 7 wire rope made of steel wire having an outer diameter of 1.5 mm so as to have an outer diameter of 2.8 mm using an extruder.

Reference example 3
Unit 6 PA6 and EX-1030 were coated on a steel wire 7 × 7 wire rope having an outer diameter of 1.5 mm so as to have an outer diameter of 2.8 mm using an extruder.

Reference example 4
An Arkema PVDF-HFP copolymer, Kynerflex ^™ 3120 was coated on a 7 × 7 wire rope made of steel wire having an outer diameter of 1.5 mm to an outer diameter of 2.8 mm using an extruder.

Reference Example 5
Asahi Glass Co., Ltd. ETFE and Fullon ^TM C88AXP were coated on a steel wire 7 × 7 wire rope having an outer diameter of 1.5 mm so as to have an outer diameter of 2.8 mm using an extruder.

Table 1 shows the basic properties of the resins and polyester elastomers used in Examples, Comparative Examples and Reference Examples (values extracted or estimated from the technical data of the material manufacturer).

Test example (1) Measurement test of dynamic storage elastic modulus (E ′) According to JIS K 7244-4, dynamic in tensile deformation mode, sinusoidal vibration 1 Hz using viscoelasticity measuring device DMS6100 manufactured by SII Nanotechnology Inc. The storage elastic modulus (E ′) was measured. 320 MPa to 2500 MPa at -50 ° C, 320 MPa to 1800 MPa at -25 ° C, 320 MPa to 1250 MPa at 0 ° C in the normal range, 320 MPa to 1000 MPa at 25 ° C in the normal range, 250 MPa to 1000 MPa at 50 ° C in the normal range. Those that deviate from 190 MPa to 1000 MPa at 75 ° C. and from 150 MPa to 1000 MPa at 100 ° C. were regarded as unfit. The results are shown in Table 2.

(2) Wire rope coating resin adhesion test Measurement of the coating resin is cut out with the wire rope core wire left and right so that the length of the coating resin is 1 cm, and one end of the resin is passed through a perforated clamp of about 2 mm. The adhesion strength of the wire rope coating resin was measured by fixing to Tensilon RTC-1210 and measuring the tensile strength at a speed of 100 mm / min. The room temperature at the time of measurement was not strictly regulated, but was about 20 ° C., and the measurement sample was a coated resin wire rope that was left in the measurement chamber for several days or more. Those less than 10 kgf were regarded as nonconforming. The results are shown in Table 3.

(3) Bending fatigue endurance test with wire rope covered FIG. 1 shows a reference diagram for explaining this test. As shown in FIG. 1, both ends of a resin-coated wire rope with an overall length of about 18 m (inner rope diameter 1.5 mm, 7 × 7 configuration, outer diameter after outer resin coating of about 2.8 mm) are grooved with the same axis 90 mm in diameter. It is wound around the drum in different directions. The wire rope goes out from the drum in parallel in the same direction, turns 180 ° through a 50 mm diameter single pulley located 3 m from the drum, and goes out in parallel in the same direction. They are connected via a triple pulley (triple pulley) with a diameter of 36.5 mm at a position of 5 m, and this is the turning point. A 55 kg load (weight) is continuously applied to the triple pulley, and tension is applied to the wire rope. The load is applied in the middle of a series of wire ropes, and the load substantially applied to the wire ropes is 27.5 kg. If the drum fixed on the same shaft is rotated, the wire rope moves linearly, the reciprocating stroke is 2.9 m, the reciprocating speed is 7.5 minutes / reciprocating (2.5 minutes rest time) Included). The bending fatigue condition of the coating resin was confirmed by visual observation of the presence or absence of cracks and the resin adhesion. The bending fatigue endurance test equipment is installed outdoors where it is not exposed to direct sunlight due to its size. Is considered to have been carried out each time at an arbitrary fluctuating temperature due to the daily difference repeated within the range from the extreme value of -6 ° C of the minimum temperature to the extreme value of 31 ° C of the maximum temperature as recorded by the nearest Japan Meteorological Agency Oyama Meteorological Observatory . Those with cracks and poor adhesion at less than 20000 times were regarded as unsuitable. The results are shown in Table 4.

(4) Weather resistance test of wire rope coating resin The weather resistance test of the wire rope coating resin is a resin coated wire rope (steel wire having an outer diameter of 1.25 to 1.5 mm) for a resin having a relatively good bending fatigue durability test. Each wire-coated wire rope is coated to have an outer diameter of 2.8 mm, and each colored resin-coated wire rope is cut to about 20 cm and attached to a stainless steel plate with an aluminum thin adhesive tape. Super UV tester SUV-W151 was installed in an accelerated weathering tester. Irradiance was 750 W / m ² , black panel temperature was 83 ° C., and rainfall was carried out for 240 hours in 30 seconds during 60 minutes of irradiation. Confirmation was also made at 144 and 192 hours. Evaluation of weather resistance is performed by bending the resin-coated wire rope after the weather resistance test so that the irradiated surface becomes a bent surface, and cutting the thickness of the crack generated with a cutter while observing the generated crack with a microscope. The outer diameter was measured and calculated as the deteriorated layer thickness. A deterioration layer thickness of 0.225 mm or more after 240 hours was regarded as nonconforming. The results are shown in Table 5.

Claims (5)

(A) A block copolymer in which a crystalline hard segment made of polybutylene terephthalate and an amorphous soft segment made of a terephthalic acid ester of polyalkylene ether glycol are alternately bonded, at 1 Hz according to JIS K 7244-4 Polyester elastomer block copolymer A-1 having a dynamic loss tangent (tan δ) maximum temperature measured by dynamic viscoelasticity measurement or a glass transition temperature measured by DSC of 7.5 ° C. or more and 24 ° C. or less , Or
Crystalline polyester comprising the polyester elastomer block copolymer A-1 and polybutylene terephthalate, and a dynamic loss tangent (tan δ) maximum measured by dynamic viscoelasticity measurement at 1 Hz according to JIS K 7244-4 A mixture with crystalline polyester A-2 having a glass transition temperature of 0 ° C. or higher and 48 ° C. or lower as measured by DSC or DSC, wherein the dynamic loss tangent (tan δ) of each polymer is The sum of values obtained by multiplying the maximum temperature or the glass transition temperature and the weight fraction of the whole polymer is 7.5 ° C. or more and 24 ° C. or less , and the amorphous soft segment copolymerization amount of each polymer and the polymer A polymer A having a sum of values obtained by multiplying the weight fraction with respect to the whole of 10% by weight to 30% by weight;
(B) A block copolymer in which a crystalline hard segment composed of polybutylene terephthalate and an amorphous soft segment composed of a terephthalic acid ester of polyalkylene ether glycol are alternately bonded, at 1 Hz according to JIS K 7244-4 At least one polymer selected from polyester elastomer block copolymers having a dynamic loss tangent (tan δ) maximum temperature measured by dynamic viscoelasticity measurement or a glass transition temperature measured by DSC of less than 0 ° C. And the sum of the dynamic loss tangent (tan δ) maximum temperature or the glass transition temperature of each polymer multiplied by the weight fraction of the whole polymer is −70 ° C. or more and less than 0 ° C., and The amount of amorphous soft segment copolymerization of the polymer and the weight fraction of the polymer as a whole Flip was a polymer B sum less 80 wt% 33.5 wt% or more values,
The weight ratio of the polymer A and the polymer B is 92: 8 to 97.5: 2.5.
And the difference of the said dynamic loss tangent (tan (delta)) maximum temperature or the said glass transition temperature of the said polymer A and the said polymer B is 20 degreeC or more, Amorphous soft segment copolymerization amount is 17.5 weight% or more 27.5 wt% or less of a thermoplastic polyester elastomer composition,
The dynamic storage elastic modulus (E ′) is 320 MPa to 2500 MPa at −50 ° C., 320 MPa to 1800 MPa at −25 ° C., 320 MPa to 1250 MPa at 0 ° C. in the normal range, 320 MPa to 1000 MPa at 25 ° C. in the normal range, A thermoplastic polyester elastomer composition having a pressure of 250 MPa to 1000 MPa at 50 ° C., 190 MPa to 1000 MPa at 75 ° C., and 150 MPa to 1000 MPa at 100 ° C., which is used to coat a driving wire rope Thermoplastic polyester elastomer composition . The thermoplastic polyester elastomer according to claim 1, wherein the polymer A is a block copolymer in which a crystalline hard segment composed of polybutylene terephthalate and an amorphous soft segment composed of a terephthalic acid ester of polyalkylene ether glycol are alternately bonded. Composition.   A thermoplastic polyester elastomer composition obtained by melt-mixing the thermoplastic polyester elastomer composition according to claim 1 or 2.   A wire rope formed by coating the thermoplastic polyester elastomer composition according to claim 1 or 2. The wire rope according to claim 4 for driving an operation member mainly installed in a facility horticulture facility.

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