JP2006316262A - Polyetherester block copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyetherester block copolymer which has surface hardness capable of being utilized for structural members and has an excellent silencing property and an excellent sliding property. <P>SOLUTION: This polyetherester block copolymer comprising (a) aromatic dicarboxylic acid units, (b) 1,3-propanediol and/or 1,4-butanediol units, and (c) long chain diol units consisting mainly of polyoxytrimethylene glycol, is characterized in that durometer hardness (type D) measured in accordance with JIS K6253 is 40 to 78. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a polyetherester block copolymer, a sound deadening structural member, an automobile part and an electric / electronic device part using the same. Specifically, the present invention relates to a polyetherester block copolymer having characteristics of both an engineering plastic and a rubber elastic body, and a silencing structure member, an automobile part and an electric / electronic device part using the same.

  The polyether ester block copolymer is composed of a hard segment and a soft segment. Mainly polybutylene terephthalate is used as a hard segment, and polyoxyalkylene glycol ester is used as a soft segment. A polyetherester block copolymer can be produced by copolymerizing these hard segments and soft segments. This copolymer has properties of engineering plastics (durability, heat resistance, oil resistance, chemical resistance, ozone resistance, molding processability, etc.) and rubber elastic properties (silence, impact resistance, impact resilience, The material has both low temperature resistance and bending fatigue resistance, and is widely used in, for example, automobile parts, industrial parts, precision machine parts, electric / electronic parts, fibers, films, daily necessities, and the like. Among them, in particular, the use as structural members such as automobile parts, industrial parts, precision machine parts, electric / electronic parts is progressing.

  Generally, polyoxytetramethylene glycol (hereinafter sometimes abbreviated as “PTMG”) is widely used as the polyoxyalkylene glycol used in the polyether ester block copolymer. The heat resistance and low temperature resistance were not always satisfactory. In order to improve these problems, by selecting and combining each segment, polyoxytetramethylene glycol as a soft segment, which has excellent properties of returning to its original state as an elastic body when it is pulled, that is, “elastic recovery” A polyether ester block copolymer using an ester is disclosed (see Patent Document 1).

Furthermore, in order to overcome these problems, polybutylene terephthalate is used as the hard segment, polyoxytrimethylene glycol ester is used as the soft segment, and a polyether ester block copolymer containing 60 to 90% by weight of the soft segment is obtained. Accordingly, it is disclosed that the above-mentioned elastic recovery is very excellent (see Patent Document 2).
Japanese Patent No. 3164168 US Pat. No. 6,562,457

  According to the study by the present inventors, the polyether ester block copolymer disclosed in Patent Document 2 has a soft surface hardness and a silencing property, and the polyether ester block copolymer using polyoxytetramethylene glycol ester as a soft segment. Since there is no effect compared with a polymer, it was difficult to use it for a structural member.

  The present invention has been made to overcome these problems, and is a polyetherester block copolymer excellent in surface hardness, sound deadening property and sliding property, and a sound deadening structural member, an automobile part and an electric device using the same.・ The purpose is to provide electronic equipment parts.

  As a result of intensive studies to solve the above problems, the present inventors have adjusted each component of the polyetherester block copolymer comprising a dicarboxylic acid unit, a short-chain diol unit, and a long-chain diol unit, The present inventors have found that the above problems can be solved and have completed the present invention.

  That is, the gist of the present invention is mainly composed of (a) an aromatic dicarboxylic acid unit, (b) 1,3-propanediol and / or 1,4-butanediol unit, and (c) polyoxytrimethylene glycol. Polyether ester block copolymer comprising a long-chain diol unit, wherein the durometer hardness (type D) measured in accordance with JIS K6253 is 40 or more and 78 or less. It exists in coalescence. The durometer hardness (type D) is an index for representing the surface hardness of the copolymer molded product by a numerical value.

  Another gist of the present invention is a silencing structure member characterized by using the above-mentioned polyether ester block copolymer, and an automobile part and an electric device characterized by using this silencing structure member.・ It exists in electronic equipment parts.

  ADVANTAGE OF THE INVENTION According to this invention, the polyether ester block copolymer which has the surface hardness which can be utilized for a structural member, and is excellent in silencing property and sliding property, and a silencing structural member using the same, an automotive component, and electricity・ Electronic equipment parts are provided.

  Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.

  The polyetherester block copolymer of the present invention comprises (a) an aromatic dicarboxylic acid unit, (b) 1,3-propanediol and / or 1,4-butanediol unit, and (c) polyoxytrimethylene glycol. (Hereinafter sometimes abbreviated as “PO3G”).

[I. Polyetherester block copolymer]
The polyether ester block copolymer is composed of a hard segment having crystallinity and a soft segment rich in molecular mobility compared to the hard segment. In the present invention, in order to more clearly distinguish the hard segment and the soft segment, the unit represented by the following formula (1) is a hard segment, and the unit represented by the following formula (2) is a soft segment. did.

In the above formulas (1) and (2),
Each R ¹ independently represents a chemical structure derived from a carbocyclic compound having a benzene nucleus and / or a non-benzenoid aromatic compound;
R ² represents a trimethylene group and / or a tetramethylene group;
n represents an integer of 1 to 1000.
Here, the “benzene nucleus” represents a carbon six-membered ring having aromaticity, and the “non-benzenoid aromatic compound” refers to a benzene nucleus such as azulene or a heterocyclic compound exhibiting aromaticity. A compound which does not have, but exhibits aromaticity.

  The hard segment represented by the above formula (1) is a polyester comprising (a) an aromatic dicarboxylic acid unit and (b) 1,3-propanediol and / or 1,4-butanediol unit. The soft segment represented by the above formula (2) is a polyether ester composed of (a) an aromatic dicarboxylic acid unit and (c) a long-chain diol unit mainly composed of polyoxytrimethylene glycol. In addition, in some known documents, a soft segment is represented only by a long-chain diol unit that is a main component.

  The content of the soft segment in the polyetherester block copolymer of the present invention, that is, the polyetherester portion comprising (a) an aromatic dicarboxylic acid unit and (c) a long-chain diol unit mainly composed of polyoxytrimethylene glycol. The content based on the total polyetherester block copolymer is usually 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, most preferably 23% by weight or more, usually less than 60% by weight, preferably Is 59% by weight or less, more preferably 57% by weight or less, and still more preferably 54% by weight or less. Under the present circumstances, when the content rate of the said soft segment is less than a minimum, the property as an elastic body originating in the soft segment of a copolymer may become small. On the other hand, if the content of the soft segment exceeds the upper limit, the surface hardness of the copolymer becomes soft, making it difficult to utilize the structural member.

  In general, the monomer charge weight ratio at the time of production of the copolymer is substantially equal to the monomer component weight ratio in the resulting copolymer. Therefore, the weight content of the soft segment in the copolymer can be usually calculated from the charged weight ratio of the monomer raw materials.

(1) (a) Aromatic dicarboxylic acid unit:
The raw material for the aromatic dicarboxylic acid unit (a) (hereinafter referred to as “(a ′) aromatic dicarboxylic acid component”) of the present invention is generally used as a raw material for polyester, particularly as a raw material for a polyether ester block copolymer. For example, terephthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, isophthalic acid, phthalic acid, diphenoxy Examples include ethanedicarboxylic acid and 5-sulfoisophthalic acid. Among these, terephthalic acid and 2,6-naphthalenedicarboxylic acid are preferable, and terephthalic acid is more preferable. These aromatic dicarboxylic acids are usually used alone or in combination of two or more in any combination and ratio. Moreover, when using the alkyl ester of aromatic dicarboxylic acid, dimethyl ester, diethyl ester, etc. of said aromatic dicarboxylic acid are used, for example. Among these, dimethyl terephthalate and 2,6-dimethyl naphthalene dicarboxylate are preferable.

(2) (b) 1,3-propanediol and / or 1,4-butanediol unit:
The raw material of the (b) 1,3-propanediol and / or 1,4-butanediol unit of the present invention (hereinafter referred to as “(b ′) 1,3-propanediol and / or 1,4-butanediol component”) ), It is usual to use 1,3-propanediol or 1,4-butanediol alone, but these may be used in any ratio. Among these, it is preferable to use 1,4-butanediol alone.

(3) (c) Long chain diol unit:
As a raw material of the long chain diol unit (hereinafter referred to as “(c ′) long chain diol component”) which is a part of the structural unit of the soft segment in the polyether ester block copolymer of the present invention, the following formula Polyoxytrimethylene glycol having a structure represented by (3) is used.

（上記式（３）中、ｎは、１以上１０００以下の整数を表わす。）

(In the above formula (3), n represents an integer of 1 to 1000)

  The number average molecular weight (Mn) of the polyoxytrimethylene glycol used in the present invention is usually 400 or more, preferably 600 or more, more preferably 800 or more, usually 6000 or less, preferably 4000 or less, more preferably 3000 or less, Most preferably, it is 2000 or less. If the number average molecular weight is too small, the melting point drop becomes severe and the heat resistance may be adversely affected. On the other hand, if the number average molecular weight is too large, the viscosity of the polyoxytrimethylene glycol increases, so that phase separation in the polyetherester block copolymer using the polyoxytrimethylene glycol becomes remarkable, and the physical properties of the copolymer molded product deteriorate. There is a case.

  The “number average molecular weight (Mn)” used herein means that the hydroxyl group at the end of polyoxyalkylene glycol such as polyoxytrimethylene glycol is esterified with phthalic anhydride and unreacted phthalic anhydride is decomposed into phthalic acid. The hydroxyl value was determined by reverse titration (terminal group titration method) with an alkali such as an aqueous sodium hydroxide solution, and was calculated from the value.

  The polyoxytrimethylene glycol can be synthesized by dehydrating condensation polymerization of 1,3-propanediol or ring-opening polymerization of trimethylene oxide, but the latter method is expensive because trimethylene oxide as a raw material is expensive. Therefore, it is preferable to synthesize by the dehydration condensation polymerization of 1,3-propanediol in the former method. The dehydration condensation polymerization product of 1,3-propanediol is, for example, a dehydration condensation reaction of 1,3-propanediol in the presence of a catalyst comprising an acid and a base, as disclosed in JP-A-2004-182974. It can synthesize | combine by well-known methods, such as making it.

  The long-chain diol component (c ′) of the present invention is mainly composed of the polyoxytrimethylene glycol, but may be partially substituted with other polyoxyalkylene glycol as necessary. Examples of the polyoxyalkylene glycol used for the substitution include polyoxyethylene glycol, polyoxy (1,2-propylene) glycol, polyoxytetramethylene glycol, a block or random copolymer of ethylene oxide and propylene oxide, ethylene oxide and THF ( Tetrahydrofuran) block or random copolymer, polyoxy (2-methyl-1,3-propylene) glycol, polyoxypropylene diimide diacid and the like. However, in the present invention, since the polyoxytrimethylene glycol is mainly used as the (c ′) long-chain diol component, the polyoxytrimethylene glycol is included in the total weight of the (c ′) long-chain diol component. The lower limit of the trimethylene glycol content is usually 60% by weight or more, preferably 70% by weight or more, more preferably 80% by weight or more, and the upper limit is usually 100% by weight or less. If the content of the polyoxytrimethylene glycol is too small, the effects of the present invention, such as silencing, may not be exhibited.

[II. Method for producing polyetherester block copolymer]
Below, the method to manufacture the polyetherester copolymer of this invention is demonstrated in detail.

  The method for producing the polyetherester block copolymer of the present invention is not particularly limited, and any conventionally known method for producing a copolyester can be employed. Specific examples include (a ′) aromatic dicarboxylic acid component, excess (b ′) 1,3-propanediol and / or 1,4-butanediol component and (c ′) long-chain diol component. A method of transesterifying in the presence and then polycondensing the obtained reaction product under reduced pressure, or (a ′) an aromatic dicarboxylic acid component and (b ′) 1,3-propanediol and / or 1 , 4-butanediol component and (c ′) long chain diol component are esterified in the presence of a catalyst, followed by polycondensation of the resulting reaction product under reduced pressure, short chain polyester (for example, polybutylene) Terephthalate), add other aromatic dicarboxylic acid component and (c ') long chain diol component and polycondensate, add other copolymer polyester using twin screw extruder etc. ester How to conversion, and the like. Any of these methods may be selected.

  As a catalyst common to the transesterification reaction or the esterification reaction and the copolymerization reaction, particularly preferred examples include tetra (isopropoxy) titanate, tetraalkyl titanates represented by tetra (n-butoxy) titanate, and these tetraalkyl titanates and Ti-based catalysts such as reaction products with alkylene glycols, partial hydrolysates of tetraalkyl titanates, metal salts of titanium hexaalkoxides, carboxylates of titanium, and titanyl compounds. Other examples include mono-n-butyl monohydroxytin oxide, mono-n-butyltin triacetate, mono-n-butyltin monooctylate, monoalkyltin compounds such as mono-n-butyltin monoacetate, di- Examples thereof include dialkyl (or diaryl) tin compounds such as n-butyltin oxide, di-n-butyltin diacetate, diphenyltin oxide, diphenyltin diacetate, and di-n-butyltin dioctylate. In addition, metal compounds such as Mg, Pb, Zr, Zn, Sb, Ge, and P are useful. Any one of these catalysts may be used alone, or two or more thereof may be used in any combination and ratio. In particular, when used alone, tetraalkyl titanate is preferred. Moreover, when using in combination of 2 or more types, it is preferable to use tetraalkyl titanate and magnesium acetate.

  The amount of the catalyst used is usually 0.001% by weight or more, preferably 0.003% by weight or more, and the upper limit is usually 0.5% by weight or less, based on the polyetherester block copolymer to be produced. Preferably it is 0.2 weight% or less. At this time, if the amount of the catalyst to be added is less than the above lower limit, the reaction may not easily proceed and the productivity may be deteriorated. If the amount exceeds the above upper limit, the produced polyetherester block copolymer may be colored or co-polymerized. The surface appearance of the polymer molded product may be deteriorated by bumps or the like.

  These catalysts are added to the reaction system at the start of transesterification or esterification reaction. Thereafter, the catalyst may be added again to the reaction system during the copolymerization reaction, but may not be added.

  Moreover, polyfunctional components, such as polycarboxylic acid, a polyfunctional hydroxy compound, and oxy acid, may be copolymerized as a part of dicarboxylic acid or diol. The polyfunctional component effectively acts as a thickening component, and the content in the copolymer is preferably 0 mol% or more and 3 mol% or less. When there is too much content of a polyfunctional component, the polyether ester block copolymer to produce | generate may gelatinize and is unpreferable. Examples of such polyfunctional components include trimellitic acid, trimesic acid, pyromellitic acid, benzophenonetetracarboxylic acid, butanetetracarboxylic acid, glycerin, trimethylolpropane, pentaerythritol and esters thereof, acid An anhydride etc. can be mentioned. Any one of these may be used alone, or two or more may be used in any combination and ratio.

  Further, an antioxidant can be added at any time during or after the production of the polyetherester block copolymer. In particular, when polyoxytrimethylene glycol is exposed to high temperatures, for example, when it enters a copolymerization reaction, in order to prevent oxidative degradation of polyoxyalkylene glycol, the copolymerization reaction is not inhibited and the function of the catalyst is impaired. Unless otherwise, it is desirable to add an antioxidant. These antioxidants include, for example, phosphoric acid, phosphorous acid aliphatic, aromatic or alkyl group-substituted aromatic esters, hypophosphorous acid derivatives, phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonate, dialkyl. Sulfur such as phosphorus compounds such as pentaerythritol diphosphite and dialkylbisphenol A diphosphite, phenol derivatives such as hindered phenol compounds, thioethers, dithiosates, mercaptobenzimidazoles, thiocarbanilides, thiodipropionates, etc. Including compounds, tin compounds such as tin malate and dibutyltin monoxide, and the like can be used. Any one of these may be used alone, or two or more may be used in any combination and ratio.

  The amount of these antioxidants used is usually 0.001 part by weight or more, preferably 0.01 part by weight or more, usually 3 parts by weight or less, preferably 2 parts per 100 parts by weight of the polyetherester block copolymer. Less than parts by weight. At this time, if the amount of the antioxidant used is less than the lower limit, the effect of the antioxidant may be difficult to be exhibited. If the amount exceeds the upper limit, the produced polyetherester block copolymer is colored. In some cases, the surface appearance of the copolymer molded product may be deteriorated due to irregularities.

  Moreover, well-known usual conditions can be used for the reaction conditions at the time of manufacturing a polyetherester block copolymer. For example, a transesterification reaction is performed in the presence of a catalyst, and the resulting reaction product is polycondensed under reduced pressure, or an esterification reaction is performed in the presence of a catalyst, and the resulting reaction product is subsequently reduced under reduced pressure. The polycondensation method is as follows.

  That is, the transesterification reaction or esterification reaction in the former stage is usually 120 ° C. or higher, preferably 140 ° C. or higher, and usually 250 ° C. or lower, preferably 240 ° C. or lower, and usually 1 hour or longer and 5 hours or shorter. It is done over. At this time, when the temperature falls below the lower limit reaction temperature, the reaction may not proceed easily, and the productivity may deteriorate. When the temperature exceeds the upper limit reaction temperature, the produced polyether ester block copolymer may be colored. If the reaction time is too short, the transesterification reaction or esterification reaction may not proceed sufficiently, and the subsequent polycondensation reaction may not proceed. Since the exchange reaction or esterification reaction proceeds sufficiently, the production efficiency may deteriorate.

  The latter polycondensation reaction is usually performed at a reaction temperature of 200 ° C. or higher, preferably 220 ° C. or higher, and usually 280 ° C. or lower, preferably 270 ° C. or lower, under a reduced pressure of 10 torr or lower. For less than an hour. At this time, when the temperature falls below the lower limit reaction temperature, the reaction may not proceed easily, and the productivity may deteriorate. When the temperature exceeds the upper limit reaction temperature, the produced polyether ester block copolymer may be colored. Also, if the reaction time is too short, the degree of polymerization of the copolymer produced may be extremely low because the polycondensation reaction does not proceed sufficiently. If the reaction time is too long, the polymer produced will be colored. Or a depolymerization reaction may occur and the degree of polymerization of the polymer may decrease.

  Usually, the polyether ester block copolymer of the present invention obtained by melt-condensation polymerization as described above is maintained at a temperature equal to or higher than its melting point, and is sequentially discharged from a reactor such as a reaction can, and pelletized. Is done. In addition, you may further solid-phase-polymerize the pellet obtained here as needed.

  When producing the polyetherester block copolymer of the present invention, the above-mentioned (a ′) aromatic dicarboxylic acid component, (b ′) 1,3-propanediol and / or 1,4-butanediol component, And (c ′) In addition to the long-chain diol component mainly composed of polyoxytrimethylene glycol, the purpose and effect of the present invention are impaired as necessary for the finally obtained polyetherester block copolymer. Arbitrary components can be blended as long as there is no range. Specifically, for example, silica, talc, mica, titanium dioxide, alumina, calcium carbonate, calcium silicate, clay, kaolin, diatomaceous earth, asbestos, barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, disulfide Fillers and reinforcing materials such as molybdenum, graphite, glass fiber, carbon fiber; mold release agents or lubricants such as zinc stearate and bisamide, stearate; carbon black, ultramarine, titanium oxide, zinc white, red rose, bitumen for coloring Dyes such as azo pigments, nitro pigments, lake pigments and phthalocyanine pigments; flame retardants such as octabromodiphenyl and tetrabromobisphenol polycarbonate; light stabilizers such as hindered amine compounds; ultraviolet absorbers such as benzotriazole compounds; Sodium carbonate, etc. Foaming agents such as inorganic salts and organic salts such as sodium citrate; crosslinking agents such as epoxy compounds and isocyanate compounds; viscosity modifiers such as mineral oils, vegetable oils, silicone oils, silicone resins; substituted amide compounds, fatty acid amide compounds, etc. Sliding property improving agents: Various known additives such as various conductive materials for imparting conductivity can be used. Any one of these may be used alone, or two or more may be used in any combination and ratio.

[III. Physical properties of polyetherester block copolymer]
The polyether ester block copolymer of the present invention has the following physical properties.

(1) Surface hardness:
The durometer hardness (type D) measured in accordance with JIS K6253 is one index that expresses the surface hardness of a molded product as a numerical value. This measurement item is generally known to change its measurement value due to the difference in molecular orientation due to the difference in the molding method of the measurement test piece. In the present invention, a thermal test piece having a thickness of 2 mm is used as the measurement test piece. The measurement value using the press sheet is described in detail below as a reference.

  The polyether ester block copolymer of the present invention has a durometer hardness (type D) measured according to JIS K6253, usually having a lower limit of 40 or more, preferably 42 or more, more preferably 44 or more, and usually having an upper limit. 78 or less, preferably 76 or less, more preferably 74 or less, and most preferably 65 or less. At this time, if the durometer hardness is lower than the lower limit, the surface hardness of the copolymer is soft, making it difficult to use for structural members. In addition, in terms of noise reduction, polyoxytetramethylene glycol ester is used as a soft segment. The superiority of the copolymer compared to the polyether ester block copolymer or the like is reduced. On the other hand, if the upper limit of the durometer hardness is exceeded, the surface hardness of the copolymer becomes so hard that the properties as an elastic body may be reduced.

(2) Viscosity:
The inherent viscosity (η _inh ) of the solution of the polyetherester block copolymer of the present invention is usually 0.30 dl / g or more, preferably 0.40 dl / g or more, and usually 2.50 dl / g or less, preferably 2.40 dl / g or less, more preferably 2.30 dl / g or less. At this time, if the inherent viscosity is lower than the lower limit, the physical properties of the copolymer molded product as the structural member may be significantly lowered. On the other hand, if the inherent viscosity exceeds the upper limit, the fluidity of the copolymer is lowered, so that it may be difficult to form the structural member.
The inherent viscosity (η _inh ) of the polyetherester block copolymer solution is such that the copolymer is dissolved in a solvent in which phenol and 1,1,2,2-tetrachloroethane are mixed at a weight ratio of 1: 1. The relative viscosity (η _rel ) at 30 ° C. of the obtained solution was measured, and the natural logarithm of the relative viscosity (η _rel ) was divided by the solution concentration (C) as shown in the following formula (I). Can be obtained as a value.

但し、上記式（Ｉ）において、η_relは相対粘度を表わし、Ｃは溶液濃度（ｇ／ｄｌ）を表わす。

In the above formula (I), η _rel represents the relative viscosity, and C represents the solution concentration (g / dl).

(3) Amount of terminal carboxyl group:
The terminal carboxyl group amount (AV) of the polyetherester block copolymer of the present invention is usually 70 eq / ton or less, preferably 65 eq / ton or less, more preferably 60 eq / ton or less. At this time, if AV exceeds the upper limit, long-term stability such as hydrolysis resistance may be remarkably reduced.

(4) Density:
The density of the polyether ester block copolymer of the present invention is usually 1.155 g / cm ³ or more, preferably 1.160 g / cm ³ or more, more preferably 1.165 g / cm ³ or more, and further preferably 1.170 g. / cm ³ or more, most preferably 1.175G / cm ³ or more and usually 1.290G / cm ³ or less, preferably 1.280G / cm ³ or less, more preferably 1.270G / cm ³ or less, and most preferably Is 1.260 g / cm ³ or less. At this time, when the density is lower than the lower limit of the density, the surface hardness of the copolymer becomes soft, making it difficult to use the structural member. On the other hand, if the density exceeds the upper limit, the surface hardness of the copolymer becomes hard, and the properties as an elastic body may be reduced.

(5) Silence:
In the present invention, the muffling property is described by dividing it into the following two types of characteristics (i) and (ii).
(I) A characteristic that reduces the noise level of collision sound generated when an object collides.
(Ii) A characteristic that attenuates the collision sound generated when an object collides in a short time.

  These two types of characteristics (i) and (ii) can be simultaneously evaluated using, for example, an apparatus having the configuration shown in FIGS. Here, FIGS. 1A and 1B show an apparatus for measuring characteristics that reduce the noise level of collision sound generated when an object collides, and characteristics that attenuate the collision sound in a short time. It is a figure for demonstrating an example of a structure of. Specifically, FIG. 1 (a) is a view of the main part of the apparatus as viewed from the side. Reference numerals 1 and 2 represent a raising base (square bar), reference numeral 3 represents a steel plate, and reference numeral 4 represents This represents a hot press sheet of a polyether ester block copolymer to be measured (hereinafter sometimes referred to as “specimen”), symbol 5 represents an iron ball, symbol 6 represents an electromagnetic separation device, Reference numeral 7 represents a sound level meter. Moreover, FIG.1 (b) is the figure which looked at the steel plate 3 and the test body 4 from upper direction. The distance from the upper surface of the steel plate 3 to the separation part of the iron ball 5 in the electromagnetic separating device 6 (distance represented by the symbol x in FIG. 1A) is 660 mm. The distance to the measurement part (the distance represented by the symbol y in FIG. 1A) is 1000 mm.

At the center of a steel plate 3 (made of SUS304, 30 cm × 10 cm × 1 cm thick) installed by placing a 5 mm high square on the floor as a raised base 1, a hot press sheet of a polyetherester block copolymer (75 mm) When the specimen 4 (× 75 mm × 2 mm thick) is placed and the iron ball 5 (weight 5.4 g) is freely dropped from a position 660 mm higher than the specimen 4 using the electromagnetic separation device 6 and collides with it. The generated noise is measured by the sound level meter 7. Then, the maximum noise level (L) of the measured noise is obtained, and the attenuation of the noise level in 0.2 seconds from the time of occurrence of the maximum noise level is obtained as a time-dependent change curve of the noise level. A straight line is approximated and the absolute value (D) of the slope of the straight line is obtained. The maximum noise level (L) and the absolute value (D) of the slope of the attenuation line (approximate straight line) of the noise level are used as the maximum noise when the ball 5 directly collides with the steel plate 3 without placing the specimen 4. The level (L ₀ ) and the absolute value (D ₀ ) of the slope of the attenuation line of the noise level obtained by the same method as described above are compared.

When the value of the maximum noise level (L ₀ -L), which is reduced as compared with the case where the specimen 4 is not placed by placing the specimen 4 on the steel plate 3, is defined as “ΔL”, the above characteristic ( i) (Characteristic for reducing the noise level of collision sound generated when an object collides) can be evaluated based on the magnitude of ΔL, and the greater the value of ΔL, the better the silence. The value of ΔL is preferably 0.5 dB or more, more preferably 1 dB or more, and most preferably 2 dB or more. If ΔL is less than the lower limit, the amount of reduction in the noise level of the collision sound is too small, and the silencing effect may be small.

In addition, the absolute value (D−D ₀ ) of the slope of the attenuation line of the noise level increased by placing the specimen 4 on the steel plate 3 as compared with the case where the specimen 4 is not placed is “ΔD”. If defined, the characteristic (ii) (characteristic for attenuating the collision sound generated when an object collides in a short time) can be evaluated by the magnitude of ΔD, and the larger the value of ΔD, the more the noise reduction. Excellent in properties. The value of ΔD is preferably 1 dB / sec or more, more preferably 2 dB / sec or more, and most preferably 3 dB / sec or more. When ΔD is below the lower limit, the noise level attenuation amount of the collision sound is too small, and thus the silencing effect may be small.

(6) Sliding property:
In general, the slidability of a structural member is considered to be better as the friction coefficient on the member surface is lower. The value of the static friction coefficient when the structural members using the polyetherester block copolymer of the present invention are rubbed together is preferably 0.6 or less, more preferably 0.5 or less, and the value of the dynamic friction coefficient is preferably Is 0.5 or less, more preferably 0.4 or less. If the respective friction coefficients are larger than these ranges, abnormal noise may be caused by stick-slip or the like when the structural members are rubbed against each other, which is not preferable.

[IV. Use of polyetherester block copolymer]
The polyether ester block copolymer of the present invention has a surface hardness that can be used for a structural member, and also has excellent properties such as sound deadening and sliding properties. Utilizing such characteristics, the polyether ester block copolymer of the present invention is used as a material for various sound-absorbing structural members that reduce noise and abnormal noise generated from engines, motors, cooling fans, etc. it can.

  Specifically, the polyether ester block copolymer of the present invention includes, for example, a constant velocity joint boot, a suspension boot, a rack and pinion boot, a steering rod cover, a cable inner liner, a cable outer jacket, an AT slide cover, and a seat belt component. , Emblems, door latch strikers, reband stoppers, safety belt ratchets, leaf spring bushes and other automotive parts; hydraulic hoses, pneumatic hoses and other hoses, various seals and packings, flexible couplings, conveyor belts, timing belts, compression Industrial parts such as springs; precision mechanical parts such as gears; mobile phone housings, damping materials, vibration-proofing materials, keyboard pads, conductive pads, OA rolls, telephone curl cords, optical fiber coatings, gears, etc. Electronic parts; daily goods such as hair brushes, hot curlers, ski soles, shoe inner soles; textile products such as clothing fibers, nonwoven fabrics and various filters; suitable as film products such as biaxially stretched films and conductive films Can be used for

  Among these, the polyether ester block copolymer of the present invention is an automotive part, such as a constant velocity joint boot, a suspension boot, a rack & pinion boot, etc., which is required to be soundproof and slidable, a motor, a cooling fan, etc. It can be used particularly suitably as an electrical / electronic component in which noise countermeasures are important.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples unless it exceeds the gist.

[Method for evaluating physical properties]
First, evaluation methods for various physical properties of the polyetherester block copolymers obtained in each of Examples and Comparative Examples described later will be described together.

<Inherent viscosity (η _inh )>
Polyether ester block copolymer pellets (0.2 g) were dissolved in 40 ml of a solvent in which phenol and 1,1,2,2-tetrachloroethane were mixed at a ratio of 1: 1 with stirring at 110 ° C. over 15 minutes. The relative viscosity (η _rel ) of the solution at 30 ° C. was measured using an Ubbelohde viscometer (Sentec fully automatic viscometer DT610). Then, based on the following formula (I), a value obtained by dividing the natural logarithm of the relative viscosity (η _rel ) by the solution concentration (C), that is, the inherent viscosity (η _inh ) of the solution was calculated.

但し、上記式（Ｉ）において、η_relは相対粘度を表わし、Ｃは溶液濃度（ｇ／ｄｌ）を表わす。

In the above formula (I), η _rel represents the relative viscosity, and C represents the solution concentration (g / dl).

<Amount of terminal carboxyl group>
Collect 0.5 g of the polyether ester block copolymer pellets in a test tube, add 25 ml of benzyl alcohol, dissolve the mixture with stirring at 150 ° C. for 15 minutes, and dissolve the resulting solution with an automatic titrator (manufactured by Toa DKK). AUT-501) was titrated with 0.01N sodium hydroxide / benzyl alcohol solution using a composite pH electrode. The 0.01N sodium hydroxide / benzyl alcohol solution was prepared and standardized according to JIS K8006, and the factor was calculated. Titration amount was calculated | required from the inflection point of the obtained titration curve, and AV was computed based on following formula (II).

上記式（II）において、ＡＶは末端カルボキシル基量（ｅｑ／ｔｏｎ）を表わし、Ａは測定滴定量（ｍｌ）を表わし、Ｂはブランク滴定量（ｍｌ）を表わし、Ｆは０．０１Ｎ水酸化ナトリウム・ベンジルアルコール溶液の力価を表わし、Ｗはポリエーテルエステルブロック共重合体重量（ｇ）を表わす。

In the above formula (II), AV represents the amount of terminal carboxyl group (eq / ton), A represents the measured titer (ml), B represents the blank titer (ml), and F represents 0.01N hydroxylation. This represents the titer of the sodium benzyl alcohol solution, and W represents the weight (g) of the polyetherester block copolymer.

<Density>
Using a hot press molding machine and a pressurizing cooling water circulation type cooling device, a 2 mm thick hot press sheet of polyetherester block copolymer is produced under the following molding conditions, and then conforms to JIS K7112 (Method A) The density was measured.

  A hot-pressed sheet having a thickness of 2 mm was prepared by performing hot pressing and cooling using pellets of the polyether ester block copolymer. As a condition of the hot press process at this time, using a hot press molding machine, the set temperature of the hot press molding machine is the case of the copolymers described in Examples 1, 2 and 6, and Comparative Examples 1 to 4 and 8. Was 240 ° C., 250 ° C. for the copolymers described in Examples 3 and 4, and Comparative Examples 5 and 6, and 260 ° C. for the copolymers described in Example 5, Comparative Examples 7 and 9. The preheating time was 7 minutes, the hot pressing pressure was 4.4 MPa, and the hot pressing time was 2 minutes. The cooling process was performed using a cooling water circulation type cooling device, with a cooling pressure of 14.7 MPa and a cooling time of 3 minutes.

<Tensile breaking strength>
The tensile strength at break was measured in accordance with JIS K6251 (No. 3 dumbbell) using a hot-pressed sheet of a polyetherester block copolymer molded in the same manner by the method described in the <Density> column as a sample. .

<Tensile break elongation>
The tensile elongation at break was measured in accordance with JIS K6251 (No. 3 dumbbell) using as a sample a hot-pressed sheet of a polyetherester block copolymer molded in the same manner as described in the section <Density> above. .

<Durometer hardness>
A durometer hardness (D type) was measured in accordance with JIS K6253 using as a sample a hot-pressed sheet of a polyetherester block copolymer molded in the same manner as described above in the section of <Density>.

<Sound muffling evaluation>
In order to evaluate the silencing performance, the characteristics of reducing the noise level of the collision sound generated when the object collides using the apparatus configured as shown in FIGS. 1A and 1B, and the collision sound The characteristics of attenuating in a short time were evaluated by the following procedure.

  That is, the method described in the above <Density> column at the center of a steel plate 3 (made of SUS304, 30 cm × 10 cm × 1 cm thick) installed on a floor with square members 1 and 2 having a height of 5 mm as a raised base. The specimen 4 of the polyether ester block copolymer hot press sheet (75 mm × 75 mm × 2 mm thickness) formed in the same manner as above was placed, and the electromagnetic separation device 6 was used from a position 660 mm higher than the specimen 4. The maximum noise level (L) generated when an iron ball 5 (weight 5.4 g) was freely dropped and collided was measured with a precision sound level meter 7 (NL-14 manufactured by Lion). . The target position of the iron ball 5 is the center of the specimen 4, and the iron ball 5 before being dropped is attached to the electromagnetic separation device 6 in order to make the drop position and speed of the iron ball 5 constant. The mechanism is such that the iron ball 5 falls freely at the moment when the electromagnetic force applied to the separating device 6 is cut off. Also, in order to respond to instantaneous events, the noise level was analyzed using a time constant of 0.8 ms. The attenuation of the noise level in 0.2 seconds from the time of occurrence of the maximum noise level is obtained as a time-dependent change curve of the noise level, the obtained time-dependent change curve is linearly approximated, and the absolute value (D) of the obtained straight line slope is obtained. Asked.

Further, in the same manner as described above, the maximum noise level (L ₀ ) when the iron ball 5 directly collides with the steel plate 3 without placing the specimen 4 of the hot press sheet, and the noise level attenuation straight line (approximate curve). ) The absolute value (D ₀ ) of the slope was determined. The maximum noise level (L ₀ ) corrected for the A characteristic is 97.6 dB (A), and the absolute value (D ₀ ) of the slope of the noise level attenuation line is the values of Examples 1-3 and Comparative Examples 1-5. Was 126.6 dB / sec, and Examples 4 to 6 and Comparative Examples 6 to 9 were 146.3 dB / sec. The characteristic correction was performed by the characteristic correction function of the sound level meter. This function is a function set so that a sound volume close to the volume of sound felt by a person can be measured, and the “A characteristic” is a correction characteristic based on when the noise is 40 phones.

Next, by placing the specimen 4 of the hot press sheet on the steel plate 3, the value of the maximum noise level (L ₀ -L) decreased compared with the case where the specimen 4 is not placed is “ΔL”, and, the absolute value of the slope of the increased noise level attenuation straight line than when not place the specimen 4 _{(D-D 0) "△} D" and defined to evaluate the sound deadening qualities the magnitude of the value. In addition, each measurement was performed 3 times and the average value was used as each measurement value.

<Slidability evaluation>
In order to evaluate the slidability of the polyether ester block copolymer, the static friction coefficient and the dynamic friction coefficient were measured using HEIDON tribogear TYPE = 14DR (manufactured by Shinto Kagaku). Measurement is performed by stacking two hot-pressed sheets formed in the same manner by the method described in the above density, and moving the upper sheet at a speed of 100 mm / min with a 50 g weight applied. The coefficient of static friction and the coefficient of dynamic friction were determined.

[Synthesis Example 1]
Polyoxytrimethylene glycol (Mn = 1163) was synthesized as the (c ′) long chain diol component of the polyether ester block copolymer by the following procedure. In the following description, this polyoxytrimethylene glycol may be represented by the symbol “A”.

  That is, 50 g of 1,3-propanediol purified by distillation was charged into a 100 ml four-necked flask equipped with a distillation tube, a nitrogen introduction tube, a thermometer and a stirrer while supplying nitrogen at 100 Nml / min. To this was added 0.0348 g of sodium carbonate, and then 0.678 g of concentrated sulfuric acid (95%) was slowly added with stirring. The flask was immersed in an oil bath and heated to 162 ° C. After the liquid temperature was adjusted to 162 ° C. ± 2 ° C. and held for 11 hours for reaction, the flask was taken out of the oil bath and allowed to cool to room temperature. Water produced during the reaction was distilled off accompanying nitrogen. The reaction liquid cooled to room temperature was transferred to a 300 ml eggplant type flask using 50 g of tetrahydrofuran, 50 g of demineralized water was added thereto, and the mixture was gently refluxed for 1 hour to hydrolyze the sulfate ester. After cooling to room temperature and cooling, the lower layer (water layer) separated into two layers was removed. After adding 0.5 g of calcium hydroxide to the upper layer (oil layer) and stirring at room temperature for 1 hour, 50 g of toluene was added and heated to 60 ° C., and tetrahydrofuran, water and toluene were distilled off under reduced pressure. The obtained oil layer was dissolved in 100 g of toluene and filtered through a 0.45 μm filter to remove insoluble matters. The filtrate was heated to 60 ° C. and vacuum dried for 6 hours.

[Example 1]
In a reactor equipped with a stirrer, a distillation tube and a pressure reducing device, 68.7 g of dimethyl terephthalate (manufactured by Tokyo Chemical Industry), 39.8 g of 1,4-butanediol (manufactured by Tokyo Chemical Industry), polyoxy prepared in Synthesis Example 1 above. Trimethylene glycol (A) (78.0 g) was charged, and after substitution with nitrogen, the mixture was heated and melted at 150 ° C. for 30 minutes in a nitrogen atmosphere. Next, 4.4 ml of a solution prepared by dissolving tetrabutyl titanate (manufactured by Kishida Chemical Co., Ltd.) in 1-butanol at 6% by weight (0.02% by weight of catalyst with respect to the produced polyetherester block copolymer in terms of Ti atoms) The mixture was held at 150 ° C. for 60 minutes with stirring at a rotational speed of 150 rpm, heated to 230 ° C. over 2 hours, and held at 230 ° C. for 15 minutes to conduct a transesterification reaction. In the obtained melt, 5.4 g of slurry in which Irganox 1330 (manufactured by Ciba Specialty Chemicals) was dispersed in 1,4-butanediol at 5% by weight, and 1.1 ml of the tetrabutyl titanate solution (Ti atom) (Corresponding to a catalyst amount of 0.005% by weight with respect to the produced polyetherester block copolymer), and the pressure is further reduced to 1 torr over 85 minutes while raising the temperature to 245 ° C. over 45 minutes. Then, the polycondensation reaction was carried out until the copolymer having the desired inherent viscosity was obtained while decreasing the stirring rotational speed sequentially under the reduced pressure condition. Stirring was stopped, the inside of the reactor was restored to normal pressure with nitrogen, and the polycondensation reaction was stopped. Then, the obtained polyether ester block copolymer strands were pelletized with a pelletizer, and the obtained pellets were converted into the aforementioned pellets. It used for various physical-property evaluation as described in the column of [Method of evaluating physical properties]. The results are shown in Table 1 below. In this polymerization, 1,4-butanediol was added excessively in order to accelerate the transesterification reaction, and the ratio of the number of hydroxyl groups and the number of carboxylic acid groups in the reactor before the start of the transesterification reaction (number of hydroxyl groups / carboxyl group). The number of acid groups) is 1.6 calculated from the charged weight of the raw material. Taking it into account, the content of the soft segment in the polyetherester block copolymer produced, that is, the total of the polyetherester moiety composed of (a) aromatic dicarboxylic acid units and (c) long-chain diol units The content with respect to the polyetherester block copolymer is 57.9% by weight calculated from the charged weight of the raw material.

[Example 2]
In Example 1, the raw material composition was changed to 89.5 g of dimethyl terephthalate, 57.2 g of 1,4-butanediol, and 52.5 g of polyoxytrimethylene glycol (A). A condensation reaction was performed. The same applies to the types and blending ratios of additives. The content of the soft segment in the polyether ester block copolymer produced by this blending is 38.9% by weight calculated from the charged weight of the raw material. The obtained polyetherester block copolymer was similarly pelletized and subjected to the above-described various physical property evaluations. The results are shown in Table 1 below.

[Example 3]
In Example 1, the raw material composition was changed to 107.8 g of dimethyl terephthalate, 72.6 g of 1,4-butanediol, and 30.0 g of polyoxytrimethylene glycol (A). A condensation reaction was performed. The same applies to the types and blending ratios of additives. The content of the soft segment in the polyether ester block copolymer produced by this blending is 22.2% by weight when calculated from the charged weight of the raw material. The obtained polyetherester block copolymer was similarly pelletized and subjected to the above-described various physical property evaluations. The results are shown in Table 1 below.

[Example 4]
In Example 4 and Example 5 described later, polyoxytrimethylene glycol (Mn = 1963) synthesized according to the synthesis method described in Synthesis Example 1 was used. In the following description, this polyoxytrimethylene glycol may be represented by the symbol “C”.

  In Example 1, the raw material composition was changed to 66.6 g of dimethyl terephthalate, 40.7 g of 1,4-butanediol, and 78.0 g of polyoxytrimethylene glycol (C). A condensation reaction was performed. The same applies to the types and blending ratios of additives. The content of the soft segment in the polyether ester block copolymer produced by this blending is 55.5% by weight calculated from the charged weight of the raw material. The obtained polyetherester block copolymer was similarly pelletized and subjected to the above-described various physical property evaluations. The results are shown in Table 1 below.

[Example 5]
In Example 1, the raw material composition was changed to 88.1 g of dimethyl terephthalate, 57.9 g of 1,4-butanediol, and 52.5 g of polyoxytrimethylene glycol (C). A condensation reaction was performed. The same applies to the types and blending ratios of additives. The content of the soft segment in the polyether ester block copolymer produced by this blending is 37.3 wt% when calculated from the charged weight of the raw material. The obtained polyetherester block copolymer was similarly pelletized and subjected to the above-described various physical property evaluations. The results are shown in Table 1 below.

[Example 6]
In Example 1, the raw material composition was changed to 72.5 g of dimethyl terephthalate, 35.2 g of 1,3-propanediol, and 78.0 g of polyoxytrimethylene glycol (A). A condensation reaction was performed. Although the kind and preparation ratio of the additive were the same, Irganox 1330 was a slurry dispersed with 1,3-propanediol. The content of the soft segment in the polyether ester block copolymer produced by this blending is 57.9% by weight calculated from the charged weight of the raw material. The obtained polyetherester block copolymer was similarly pelletized and subjected to the above-described various physical property evaluations. The results are shown in Table 1 below.

[Comparative Example 1]
In Example 1, the raw material composition was changed to 52.8 g of dimethyl terephthalate, 26.5 g of 1,4-butanediol, and 97.5 g of polyoxytrimethylene glycol (A). A condensation reaction was performed. The same applies to the types and blending ratios of additives. The content of the soft segment in the polyether ester block copolymer produced by this blending is 72.4% by weight calculated from the charged weight of the raw material. The obtained polyetherester block copolymer was similarly pelletized and subjected to the above-described various physical property evaluations. The results are shown in Table 2 below.

[Comparative Example 2]
In Example 1, the raw material composition was 53.8 g of dimethyl terephthalate, 26.1 g of 1,4-butanediol, polyoxytetramethylene glycol (PTMG1000, Mn = 1011 manufactured by Mitsubishi Chemical. In the following description, this polyoxy Tetramethylene glycol may be represented by the symbol “B”.) A transesterification reaction and a polycondensation reaction were carried out in the same manner except that the amount was changed to 97.5 g. The same applies to the types and blending ratios of additives. The content of the soft segment in the polyether ester block copolymer produced by this blending is 73.5% by weight when calculated from the raw material charge weight. The obtained polyetherester block copolymer was similarly pelletized and subjected to the above-described various physical property evaluations. The results are shown in Table 2 below.

[Comparative Example 3]
In Example 1, the raw material composition was changed to 69.5 g of dimethyl terephthalate, 39.5 g of 1,4-butanediol, and 78.0 g of polyoxytetramethylene glycol (B). A condensation reaction was performed. The same applies to the types and blending ratios of additives. The content of the soft segment in the polyether ester block copolymer produced by this blending is 58.8% by weight calculated from the charged weight of the raw material. The obtained polyetherester block copolymer was similarly pelletized and subjected to the above-described various physical property evaluations. The results are shown in Table 2 below.

[Comparative Example 4]
In Example 1, the raw material composition was changed to 90.0 g of dimethyl terephthalate, 57.0 g of 1,4-butanediol, and 52.5 g of polyoxytetramethylene glycol (B). A condensation reaction was performed. The same applies to the types and blending ratios of additives. The content of the soft segment in the polyether ester block copolymer produced by this blending is 39.5% by weight calculated from the charged weight of the raw material. The obtained polyetherester block copolymer was similarly pelletized and subjected to the above-described various physical property evaluations. The results are shown in Table 2 below.

[Comparative Example 5]
In Example 1, the raw material composition was changed to 108.1 g of dimethyl terephthalate, 72.5 g of 1,4-butanediol, and 30.0 g of polyoxytetramethylene glycol (B). A condensation reaction was performed. The same applies to the types and blending ratios of additives. The content of the soft segment in the polyether ester block copolymer produced by this blending is 22.6% by weight calculated from the charged weight of the raw material. The obtained polyetherester block copolymer was similarly pelletized and subjected to the above-described various physical property evaluations. The results are shown in Table 2 below.

[Comparative Example 6]
In Example 1, the raw material composition was 66.5 g of dimethyl terephthalate, 40.7 g of 1,4-butanediol, polyoxytetramethylene glycol (PTMG2000 manufactured by Mitsubishi Chemical, Mn = 1968. In the following description, this polyoxy Tetramethylene glycol may be represented by the symbol “D”.) A transesterification reaction and a polycondensation reaction were carried out in the same manner except that the amount was changed to 78.0 g. The same applies to the types and blending ratios of additives. The content of the soft segment in the polyether ester block copolymer produced by this blending is 22.6% by weight calculated from the charged weight of the raw material. The obtained polyetherester block copolymer was similarly pelletized and subjected to the above-described various physical property evaluations. The results are shown in Table 2 below.

[Comparative Example 7]
In Example 1, the raw material composition was changed to 88.0 g of dimethyl terephthalate, 57.8 g of 1,4-butanediol, and 52.5 g of polyoxytetramethylene glycol (D). A condensation reaction was performed. The same applies to the types and blending ratios of additives. The content of the soft segment in the polyether ester block copolymer produced by this blending is 37.3 wt% when calculated from the charged weight of the raw material. The obtained polyetherester block copolymer was similarly pelletized and subjected to the above-described various physical property evaluations. The results are shown in Table 2 below.

[Comparative Example 8]
In Example 1, the raw material composition was changed to 73.2 g of dimethyl terephthalate, 34.9 g of 1,3-propanediol, and 78.0 g of polyoxytetramethylene glycol (B). A condensation reaction was performed. Although the kind and preparation ratio of the additive were the same, Irganox 1330 was a slurry dispersed with 1,3-propanediol. The content of the soft segment in the polyether ester block copolymer produced by this blending is 58.8% by weight calculated from the charged weight of the raw material. The obtained polyetherester block copolymer was similarly pelletized and subjected to the above-described various physical property evaluations. The results are shown in Table 2 below.

[Comparative Example 9]
Mitsubishi Engineering Plastics Novaduran 5010R5 was used as the PBT resin containing only the hard segment and not including the soft segment, and was subjected to the above-described various physical property evaluations. The results are shown in Table 2 below.

[Evaluation results]
The evaluation results of various physical properties of the polyether ester block copolymers obtained in Examples 1 to 6 and Comparative Examples 1 to 9 are shown in Tables 1 and 2 below. In Tables 1 and 2, “DMT” represents dimethyl terephthalate, “1,4-BG” represents 1,4-butanediol, and “1,3-PDO” represents 1,3-propanediol. Represent. The polyoxytrimethylene glycol and polyoxytetramethylene glycol used as the long-chain diol component are indicated by the symbols A to D defined above (A and C represent polyoxytrimethylene glycol (PO3G)). , B and D represent polyoxytetramethylene glycol (PTMG)).

From the results of Tables 1 and 2, the following is clear.
That is, in each comparison of Example 1 and Comparative Example 3, Example 2 and Comparative Example 4, and Example 3 and Comparative Example 5, the surface hardness of the hot press sheet used for measuring various physical properties is almost the same. The polyether ester block copolymer described in the Examples using polyoxytrimethylene glycol having an average molecular weight of 1163 as a long-chain diol component has polyoxytetramethylene glycol having a number-average molecular weight of 1011 as a long-chain diol component. It is superior in sound deadening and sliding properties than the polyether ester block copolymer described in the comparative example used.

  Moreover, in each comparison of Example 4 and Comparative Example 6 and Example 5 and Comparative Example 7 in which the surface hardness of the hot press sheet is almost equal, polyoxytrimethylene glycol having a number average molecular weight of 1962 is changed to a long-chain diol. The polyether ester block copolymer described in Examples used as a component is more than the polyether ester block copolymer described in Comparative Example using polyoxytetramethylene glycol having a number average molecular weight of 1968 as a long-chain diol component. Also, it is excellent in silence and slidability.

  Furthermore, in the comparison between Example 6 and Comparative Example 8 in which the hard segment is not polybutylene terephthalate but polytrimethylene terephthalate, the polyether ester block copolymer described in the examples using polyoxytrimethylene glycol as the long-chain diol component is also used. The polymer is more excellent in silence than the polyether ester block copolymer described in the comparative example using polyoxytetramethylene glycol as the long-chain diol component.

  On the other hand, in Comparative Example 1 and Comparative Example 2, since the surface hardness of the hot-pressed sheet of the copolymer is soft, it is difficult to use it as a structural member. The advantage when using polyoxytrimethylene glycol is very small compared to when using glycol.

  Lastly, Comparative Example 9 using a PBT resin containing only hard segments and not including soft segments has a low surface hardness of the copolymer and thus has a low elastic property.

  The polyether ester block copolymer of the present invention can be used as a material for various silencing structural members. Specifically, for example, it can be suitably used for applications such as automobile parts, industrial parts, precision machine parts, electric / electronic parts, daily necessities, textile products, and film products. Among them, it can be particularly suitably used as an automobile part that is required to have both slidability and slidability and an electric / electronic part in which noise countermeasures are important.

Each of (a) and (b) is a configuration of an apparatus for measuring a characteristic for reducing the noise level of a collision sound generated when an object collides, and a characteristic for attenuating the collision sound in a short time. It is a figure for demonstrating an example.

Explanation of symbols

1, 2 Raised base (Square)
3 Steel plate 4 Specimen 5 Iron ball 6 Electromagnetic separation device 7 Sound level meter

Claims (6)

  (A) A polyether comprising an aromatic dicarboxylic acid unit, (b) a 1,3-propanediol and / or 1,4-butanediol unit, and (c) a long-chain diol unit mainly composed of polyoxytrimethylene glycol. A polyether ester block copolymer which is an ester block copolymer and has a durometer hardness (type D) measured in accordance with JIS K6253 of 40 or more and 78 or less.   (C) The polyether ester block copolymer according to claim 1, wherein the long-chain diol unit mainly composed of polyoxytrimethylene glycol is a condensate of 1,3-propanediol.   The polyether ester block according to claim 1 or 2, wherein the (b) 1,3-propanediol and / or 1,4-butanediol unit is a 1,4-butanediol unit. Copolymer.   A silencer structural member, wherein the polyetherester block copolymer according to any one of claims 1 to 3 is used.   An automobile part comprising the silencer structural member according to claim 4.   An electric / electronic device component comprising the sound-absorbing structural member according to claim 4.

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