JP2008155450A - Hose - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hose having simultaneously excellent heat resistance, heat aging resistance, water resistance, light resistance, low temperature characteristics and the like, and excellent in stability at severe environments, flexibility and the like. <P>SOLUTION: A thermoplastic polyester elastomer is a polyester elastomer prepared by binding a hard segment consisting of a polyester composed of an aromatic dicarboxylic acid and an aliphatic or alicyclic diol and a soft segment mainly consisting of an aliphatic polycarbonate, and has a melting point difference (Tm1-Tm3) of 0-50°C, when a cycle in which temperature of the thermoplastic polyester elastomer is elevated at a temperature elevating speed of 20°C/min from the room temperature to 300°C, is kept at 300°C for 3 min and is lowered at a temperature lowering speed of 100°C/min to the room temperature is repeated three times, and the melting point difference (Tm1-Tm3) is a difference between the melting point (Tm1) obtained by the first measurement by using a differential scanning calorimeter and the melting point (Tm3) obtained by the third measurement, and has tensile strength at break of 15-100 MPa. The hose uses the thermoplastic polyester elastomer as at least one tube-constituting element. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a hose using a thermoplastic elastomer composition, and includes at least one polyester elastomer having a specific structure excellent in heat aging resistance, oil resistance, and flexibility up to a high temperature region of 120 ° C. or higher. It relates to the hose used above.

  The hose of the present invention is a tube formed by laminating in a tubular shape composed of an inner tube, a reinforcing layer, an outer tube, or the like, or a tube composed of a single layer. Further, a tube whose one end is closed, a donut-shaped tube, or the like Can also be used.

  Single-layer or laminated tubular hoses and tubes are known. These inner pipes, outer pipes, or single layers are made of vulcanized rubber or resin, and the reinforcing layer is braided with fibers such as fibers, steel, or stainless steel braided or spiraled, and rubber as necessary. The thing etc. which gave adhesion processing, such as drawing, are used. However, when rubber is used for the inner and outer pipes, a vulcanization process is required and the manufacturing process becomes complicated. In addition, when a thermoplastic resin is used, there is a problem that flexibility is poor, and depending on the resin, the melting point is low and the heat resistance is poor. As a proposal for solving such a problem, a hose using a thermoplastic elastomer in which a vulcanized rubber is dispersed in a thermoplastic resin such as a polyolefin resin, a polyvinyl chloride resin, a polyamide resin, or a polyester resin (Patent Document 1). In addition, there are known hydraulic pipe hoses composed of polyamide elastomer and polyester elastomer inner tube / reinforcing material / urethane elastomer appearance.

However, conventional polyester elastomers have poor water resistance and heat aging resistance, polyamide elastomers have poor flexibility, and swelling with high temperature oil and chemicals is remarkable. Although it is slightly lower than that of the conventional thermoplastic elastomer, the softening temperature is low, and there is a problem that the demand of the market in recent years cannot be satisfied.
JP-A-6-64102

  An object of the present invention is to provide a hose which is flexible and has excellent water resistance and heat aging resistance comprising a polyester elastomer having excellent heat resistance, heat aging resistance, water resistance, light resistance, low temperature characteristics, and the like. .

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a specific hard segment and a specific soft segment in the polyester elastomer, and complete the present invention. It reached. That is, the present invention relates to a hose using a polyester elastomer composition as at least one of the tube constituents, a hard segment comprising a polyester in which the polyester elastomer is composed of an aromatic dicarboxylic acid and an aliphatic or alicyclic diol, and A polyester elastomer in which soft segments mainly composed of aliphatic polycarbonate are bonded, and the temperature is raised from room temperature to 300 ° C. at a temperature rising rate of 20 ° C./min using a differential scanning calorimeter of the thermoplastic polyester elastomer, The melting point (Tm1) obtained by the first measurement and the melting point (Tm3) obtained by the third measurement when the cycle of lowering to room temperature at a temperature lowering rate of 100 ° C / min after being held at 3 ° C for 3 minutes and repeated three times Melting point difference (Tm1-Tm3) is 0 to 50 ° C. and at the time of cutting A hose and a tensile strength is a thermoplastic polyester elastomer, which is a 15～100MPa.
In this case, it is preferable that the hard segment is composed of a polybutylene terephthalate unit, and the melting point of the obtained elastomer is 200 to 225 ° C.
Moreover, in this case, it is preferable that the hard segment is composed of a polybutylene naphthalate unit, and the melting point of the obtained elastomer is 215 to 240 ° C.
In this case, when the average chain length (x) of the hard segment and the average chain length (y) of the soft segment calculated using the nuclear magnetic resonance method (NMR method) are used, the average chain length of the hard segment (x ) Is 5 to 20, and the block property (B) calculated by the following formula (1) is preferably 0.11 to 0.45.
B = 1 / x + 1 / y (1)
Further, in this case, it is preferable that the polyester is made by reacting a polyester composed of an aromatic dicarboxylic acid and an aliphatic or alicyclic diol with an aliphatic polycarbonate diol having a molecular weight of 5000 to 80000 in a molten state.

  The hose using the thermoplastic polyester elastomer of the present invention as at least one of the tube constituents has good heat resistance and is excellent in heat aging resistance, water resistance, low temperature characteristics, etc. In addition, the block property and the block property retention are improved. Due to the high block property, a decrease in heat resistance due to a decrease in melting point is suppressed, and mechanical properties such as hardness, tensile strength and elastic modulus are improved. In addition, the improvement of the block property holding property suppresses the fluctuation of the block property during the molding process, so that the uniformity of the quality of the molded product can be enhanced. In addition, recyclability is enhanced by the characteristics, which can lead to environmental load and cost reduction.

  Hereinafter, the present invention will be described in detail. In the thermoplastic polyester elastomer used in the present invention, a normal aromatic dicarboxylic acid is widely used as the aromatic dicarboxylic acid constituting the hard segment polyester, and the main aromatic dicarboxylic acid is terephthalic acid or naphthalene. A dicarboxylic acid is desirable. Other acid components include diphenyl dicarboxylic acid, isophthalic acid, aromatic dicarboxylic acid such as 5-sodium sulfoisophthalic acid, cycloaliphatic dicarboxylic acid, alicyclic dicarboxylic acid such as tetrahydrophthalic anhydride, succinic acid, glutaric acid, adipine Examples thereof include aliphatic dicarboxylic acids such as acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid, and hydrogenated dimer acid. These are used within a range that does not significantly lower the melting point of the resin, and the amount thereof is less than 30 mol%, preferably less than 20 mol% of the total acid component.

  Further, in the thermoplastic polyester elastomer used in the present invention, the aliphatic or alicyclic diol constituting the hard segment polyester is widely used as a general aliphatic or alicyclic diol, and is not particularly limited. It is desirable to be an alkylene glycol having a number of 2 to 8. Specific examples include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol and the like. Most preferred are 1,4-butanediol and 1,4-cyclohexanedimethanol.

  The component constituting the hard segment polyester is preferably a butylene terephthalate unit or a butylene naphthalate unit from the viewpoint of physical properties, moldability, and cost performance.

  Moreover, the aromatic polyester suitable as polyester which comprises the hard segment in the thermoplastic polyester elastomer used for this invention can be easily obtained according to the manufacturing method of a normal polyester. Moreover, what has the number average molecular weight 10000-40000 is desirable for this polyester.

  Moreover, it is preferable that the aliphatic polycarbonate which comprises the soft segment in the thermoplastic polyester elastomer used for this invention mainly consists of a C2-C12 aliphatic diol residue. Examples of these aliphatic diols include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 2, 2-dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,9-nonanediol, 2-methyl-1,8- Examples include octanediol. In particular, aliphatic diols having 5 to 12 carbon atoms are preferable from the viewpoint of flexibility and low temperature characteristics of the obtained thermoplastic polyester elastomer. These components may be used alone or in combination of two or more as required, based on the case described below.

  As the aliphatic polycarbonate diol having a low temperature characteristic and constituting the soft segment of the thermoplastic polyester elastomer used in the present invention, those having a low melting point (for example, 70 ° C. or less) and a low glass transition temperature are preferable. In general, an aliphatic polycarbonate diol composed of 1,6-hexanediol used to form a soft segment of a thermoplastic polyester elastomer has a low glass transition temperature of around -60 ° C and a melting point of around 50 ° C. Good low temperature characteristics. In addition, an aliphatic polycarbonate diol obtained by copolymerizing an appropriate amount of, for example, 3-methyl-1,5-pentanediol with the above aliphatic polycarbonate diol has a glass transition point with respect to the original aliphatic polycarbonate diol. Although the melting point is slightly increased, the melting point is lowered or becomes amorphous, so that it corresponds to an aliphatic polycarbonate diol having good low-temperature characteristics. Moreover, for example, an aliphatic polycarbonate diol composed of 1,9-nonanediol and 2-methyl-1,8-octanediol has a melting point of about 30 ° C. and a glass transition temperature of about −70 ° C., which is sufficiently low. Corresponds to aliphatic polycarbonate diol with good low-temperature properties.

  The above-mentioned aliphatic polycarbonate diol is not necessarily composed of only the polycarbonate component, and may be obtained by copolymerizing a small amount of other glycol, dicarboxylic acid, ester compound or ether compound. Examples of copolymer components include, for example, dimer diols, hydrogenated dimer diols and glycols such as modified products thereof, dicarboxylic acids such as dimer acid and hydrogenated dimer acid, aliphatic, aromatic, and alicyclic dicarboxylic acids Examples thereof include polyesters or oligoesters composed of glycol, polyesters or oligoesters composed of ε-caprolactone, polyalkylene glycol such as polytetramethylene glycol, polyoxyethylene glycol, or oligoalkylene glycol.

  The copolymer component can be used to such an extent that the effect of the aliphatic polycarbonate segment is not substantially lost. Specifically, it is 40 parts by mass or less, preferably 30 parts by mass or less, more preferably 20 parts by mass or less with respect to 100 parts by mass of the aliphatic polycarbonate segment. When the amount of copolymerization is too large, the resulting thermoplastic polyester elastomer has poor heat aging resistance and water resistance.

  As long as the thermoplastic polyester elastomer used in the present invention does not lose the effect of the invention, as a soft segment, for example, polyalkylene glycol such as polyethylene glycol and polyoxytetramethylene glycol, polyester such as polycaprolactone and polybutylene adipate, etc. The copolymer component may be introduced. The content of the copolymer component is usually 40 parts by mass or less, preferably 30 parts by mass or less, and more preferably 20 parts by mass or less with respect to 100 parts by mass of the soft segment.

  In the thermoplastic polyester elastomer used in the present invention, the mass part ratio of the polyester constituting the hard segment to the aliphatic polycarbonate and copolymer component constituting the soft segment is generally hard segment: soft segment = 30: 70 to 95: 5, preferably 40:60 to 90:10, more preferably 45:55 to 87:13, and most preferably 50:50 to 85:15.

The thermoplastic polyester elastomer used in the present invention is composed of a hard segment composed of a polyester composed of the above aromatic dicarboxylic acid and an aliphatic or alicyclic diol and a soft segment composed mainly of an aliphatic polycarbonate. A polyester elastomer. Here, the term “bonded” means that the hard segment and the soft segment are not bonded by a chain extender such as an isocyanate compound, but the units constituting the hard segment and the soft segment are directly bonded by an ester bond or a carbonate bond. The state is preferable.
For example, it is preferable to obtain the polyester constituting the hard segment, the polycarbonate constituting the soft segment, and if necessary, various copolymerization components while melting and repeating the transesterification reaction and depolymerization reaction for a certain period of time (hereinafter referred to as blocking reaction). Sometimes called).

  The blocking reaction is preferably performed at a temperature within the range of the melting point of the polyester constituting the hard segment to the melting point + 30 ° C. In this reaction, the concentration of the active catalyst in the system is arbitrarily set according to the temperature at which the reaction is carried out. That is, since the transesterification and depolymerization proceed rapidly at higher reaction temperatures, it is desirable that the active catalyst concentration in the system be low, and that there is some concentration of active catalyst at lower reaction temperatures. It is desirable that

  The catalyst may be an ordinary catalyst such as titanium compounds such as titanium tetrabutoxide and potassium oxalate titanate, or one or more tin compounds such as dibutyltin oxide and monohydroxybutyltin oxide. The catalyst may be pre-existing in the polyester or polycarbonate, in which case it need not be added anew. Furthermore, the catalyst in the polyester or polycarbonate may be partially or substantially completely deactivated in advance by any method. For example, when titanium tetrabutoxide is used as a catalyst, for example, phosphorous acid, phosphoric acid, triphenyl phosphate, tristriethylene glycol phosphate, orthophosphoric acid, carbethoxydimethyl diethyl phosphonate, triphenyl phosphite, trimethyl phosphate, trimethyl phosphite, etc. The deactivation is performed by adding a phosphorus compound or the like, but is not limited thereto.

  The above reaction can be carried out by arbitrarily determining a combination of reaction temperature, catalyst concentration, and reaction time. That is, the appropriate values of the reaction conditions vary depending on various factors such as the types and amount ratios of the hard segments and soft segments to be used, the shape of the apparatus to be used, and the stirring conditions.

  The optimum value of the reaction conditions is, for example, when the melting point of the obtained chain extension polymer and the melting point of the polyester used as the hard segment are compared, and the difference is 2 ° C to 60 ° C. When the melting point difference is less than 2 ° C., both segments are not mixed or / and reacted, and the resulting polymer exhibits poor elastic performance. On the other hand, when the difference between the melting points exceeds 60 ° C., the progress of the transesterification reaction is remarkable, so that the block property of the obtained polymer is lowered, and crystallinity, elastic performance and the like are lowered.

  It is desirable that the remaining catalyst in the molten mixture obtained by the above reaction is deactivated as completely as possible by any method. When the catalyst remains more than necessary, it is considered that the transesterification further proceeds during compounding or molding, and the physical properties of the obtained polymer fluctuate.

  This deactivation reaction can be performed, for example, in the manner described above, i.e., phosphorous acid, phosphoric acid, triphenyl phosphate, tristriethylene glycol phosphate, orthophosphoric acid, carbethoxydimethyl phosphonate, triphenyl phosphite, trimethyl phosphate, trimethyl phosphite, Although it is carried out by adding a phosphorus compound or the like, it is not limited to this.

  The thermoplastic polyester elastomer used in the present invention may contain a trifunctional or higher polycarboxylic acid or polyol only in a small amount. For example, trimellitic anhydride, benzophenone tetracarboxylic acid, trimethylolpropane, glycerin and the like can be used.

  Furthermore, the thermoplastic polyester elastomer used in the present invention can be blended with various additives depending on the purpose to obtain a composition. Additives include known hindered phenol-based, sulfur-based, phosphorus-based, amine-based antioxidants, hindered amine-based, triazole-based, benzophenone-based, benzoate-based, nickel-based, salicyl-based light stabilizers, antistatic agents, etc. Agents, lubricants, molecular modifiers such as peroxides, epoxy compounds, isocyanate compounds, compounds having reactive groups such as carbodiimide compounds, metal deactivators, organic and inorganic nucleating agents, neutralizing agents, control agents Acid agents, antibacterial agents, fluorescent brighteners, fillers, flame retardants, flame retardant aids, organic and inorganic pigments, and the like can be added.

  Examples of hindered phenolic antioxidants that can be incorporated into the thermoplastic polyester elastomer used in the present invention include 3,5-di-t-butyl-4-hydroxy-toluene, n-octadecyl-β- (4 ′ -Hydroxy-3 ', 5'-di-t-butylphenyl) propionate, tetrakis [methylene-3- (3', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, 1,3 , 5-Trimethyl-2,4,6′-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, calcium (3,5-di-tert-butyl-4-hydroxy-benzyl-monoethyl) -Phosphate), triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], pentaerythris Til-tetrakis [3- (3,5-di-t-butylanilino) -1,3,5-triazine, 3,9-bis [1,1-dimethyl-2- {β- (3-t-butyl- 4-hydroxy-5-methylphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, bis [3,3-bis (4'-hydroxy-3'-t- Butylphenyl) butyric acid] glycol ester, triphenol, 2,2′-ethylidenebis (4,6-di-t-butylphenol), N, N′-bis [3- (3,5-di-t-butyl-) 4-hydroxyphenyl) propionyl] hydrazine, 2,2′-oxamidobis [ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,1,3-tris (3 ′, 5'-di-t- Til-4′-hydroxybenzyl) -S-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6- Dimethylbenzyl) isocyanurate, 3,5-di-t-butyl-4-hydroxyhydrocinnamic ahydrtriester with-1,3,5-tris (2-hydroxyethyl) -S-triazine-2,4 6 (1H, 3H, 5H), N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,9-bis [2- {3- (3- and t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane.

  Examples of the sulfur-based antioxidant that can be blended in the thermoplastic polyester elastomer used in the present invention include dilauryl-3,3′-thiodipropionic acid ester, dimyristyl-3,3′-thiodiuropionic acid ester, distearyl- 3,3′-thiodipropionic acid ester, lauryl stearyl-3,3′-thiodipropionic acid ester, dilauryl thiodipropionate, dioctadecyl sulfide, pentaerythritol tetra (β-lauryl-thiopropio) Nate) esters and the like.

  Phosphorus antioxidants that can be incorporated into the thermoplastic polyester elastomer used in the present invention include tris (mixed, mono and dinolylphenyl) phosphite, tris (2,3-di-t-butylphenyl). Phosphite, 4,4'-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-di-tridecyl phosphite) -5-t-butylphenyl) butane, tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, tetrakis (2 , 4-Di-t-butylphenyl) -4,4′-biphenylenephosphanite, bis (2,6-di-t-butyl-4-methyl) Phenyl) pentaerythritol-di-phosphite, tetrakis (2,4-di-t-butylphenyl) 4,4′-biphenylenediphosphonite, triphenyl phosphite, diphenyldecyl phosphite, tridecyl phosphite, Examples include trioctyl phosphite, tridodecyl phosphite, trioctadecyl phosphite, trinonylphenyl phosphite, tridodecyl trithiophosphite, and the like.

  Examples of amine-based antioxidants that can be incorporated into the thermoplastic polyester elastomer used in the present invention include N, N-diphenylethylenediamine, N, N-diphenylacetamidine, N, N-diphenylfluamidine, and N-phenylpiperidine. , Dibenzylethylenediamine, triethanolamine, phenothiazine, N, N′-di-sec-butyl-p-phenylenediamine, 4,4′-tetramethyl-diaminodiphenylmethane, P, P′-dioctyl-diphenylamine, N, N '-Bis (1,4-dimethyl-pentyl) -p-phenylenediamine, phenyl-α-naphthylamine, phenyl-β-naphthylamine, 4,4'-bis (4-α, α-dimethyl-benzyl) diphenylamine, etc. Amines and their derivatives and amines and alde Reaction products of de, mention may be made from the reaction product of an amine with a ketone.

  As a hindered amine light stabilizer that can be blended in the thermoplastic polyester elastomer used in the present invention, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethyl oxalate is used. Polycondensate with piperidine, poly [[6- (1,1,3,3-tetrabutyl) imino-1,3,5-triazine-2,4-diyl] hexamethylene [(2,2,6,6 -Tetramethyl-4-piperidyl) imyl]], bis (1,2,2,6,6-pentamethyl-4-piperidyl) ester of 2-n-butylmalonic acid, tetrakis (2,2,6,6- Tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N′-bis (2 , 2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 1,2-dibromoethane, poly [(N, N′-bis (2,2,6,6-tetramethyl) -4-piperidyl) hexamethylenediamine)-(4-monophorino-1,3,5-triazine-2,6-diyl) -bis (3,3,5,5-tetramitylpiperazinone)], tris ( 2,2,6,6-tetramethyl-4-piperidyl) -dodecyl-1,2,3,4-butanetetracarboxylate, tris (1,2,2,6,6-pentamethyl-4-piperidyl)- Dodecyl-1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1,6,11-tris [{4,6-bis ( N-butyl-N- (1, 2,2,6,6-pentamethylpiperidin-4-yl) amino-1,3,5-triazin-2-yl) amino} undecane, 1- [2- (3,5-di-t-butyl- 4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetromethylpiperidine, 8-benzyl-7,7,9,9-tetramethyl-3-octyl-1,3,8-triazaspiro [4 5] Undecane-2,4-dione, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, N, N′-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl And -N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate.

  The benzophenone-based, benzotriazole-based, triazole-based, nickel-based, and salicyl-based light stabilizers that can be blended in the thermoplastic polyester elastomer used in the present invention include 2,2′-dihydroxy-4-methoxybenzophenone, 2- Hydroxy-4-n-octoxybenzophenone, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, 2- (2′- Hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amyl-phenyl) benzotriazole, 2- [2'-hydroxy-3', 5'- Bis (α, α-dimethylbenzylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-me Tilphenyl) -5-chlorobenzazotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzothiazole, 2,5-bis- [5′-t -Butylbenzoxazolyl- (2)]-thiophene, bis (3,5-di-tert-butyl-4-hydroxybenzylphosphoric acid monoethyl ester) nickel salt, 2-ethoxy-5-tert-butyl-2 ' A mixture of 85-90% ethyl oxalic acid-bis-anilide and 10-15% 2-ethoxy-5-t-butyl-2'-ethyl-4'-t-butyl oxalic acid-bis-anilide, 2 -[2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2-ethoxy-2'-ethyloxazalic acid bisanilide, 2- [ '-Hydroxy-5'-methyl-3'-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimido-methyl) phenyl] benzotriazole, bis (5-benzoyl-4-hydroxy-2 -Methoxyphenyl) methane, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2-hydroxy-4-i-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy Examples include light stabilizers such as -4-octadecyloxybenzophenone and phenyl salicylate.

  Hydrocarbon, fatty acid, fatty acid amide, ester, alcohol, metal soap, natural wax, silicone, and fluorine compounds as lubricants that can be incorporated into the thermoplastic polyester elastomer used in the present invention Is mentioned. Specifically, liquid paraffin, synthetic paraffin, synthetic hard paraffin, synthetic isoparaffin petroleum hydrocarbon, chlorinated paraffin, paraffin wax, micro wax, low-polymerized polyethylene, fluorocarboxylic oil, lauric acid having 12 or more carbon atoms, myristic acid, Fatty acid compounds such as palmitic acid, stearic acid, arachidic acid, behenic acid, hexylamide, octylamide, stearylamide, palmitylamide, oleylamide, erucylamide, ethylenebisstearylamide, laurylamide, behenylamide, methylenebisstearylamide, C3-C30 saturated or unsaturated aliphatic amides and derivatives thereof such as ricinolamide, fatty acid lower alcohol esters, fatty acid polyhydric alcohol esters, fatty acid polyglycols Steal, butyl stearate, fatty alcohol ester of fatty acid, hydrogenated castor oil, ethylene glycol monostearate, etc., cetyl alcohol, stearyl alcohol, ethylene glycol, polyethylene glycol having a molecular weight of 200 to 10,000 or more, polyglycerol, carnauba wax, candelilla wax, montan wax And lubricants such as dimethyl silicone, silicon gum, and ethylene tetrafluoride. Also, a metal salt composed of a compound having a linear saturated fatty acid, a side chain acid, and cinnolic acid, wherein the metal is selected from (Li, Mg, Ca, Sr, Ba, Zn, Cd, Al, Sn, Pb) Can also be mentioned.

  Fillers that can be incorporated into the thermoplastic polyester elastomer used in the present invention include magnesium oxide, aluminum oxide, silicon oxide, calcium oxide, titanium oxide (rutile type, anatase type), chromium oxide (trivalent), and oxidation. Iron, zinc oxide, silica, diatomaceous earth, alumina fiber, antimony oxide, barium ferrite, strontium ferrite, beryllium oxide, pumice, pumice balloon and other oxides and basic substances such as manesium hydroxide, aluminum hydroxide and basic magnesium carbonate Or hydroxides, carbonates such as magnesium carbonate, calcium carbonate, barium carbonate, ammonium carbonate, calcium sulfite, dolomite, and dawsonite, or calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, basic magnesium sulfate (Nitrous) sulfates such as nesium or silicates such as sodium silicate, magnesium silicate, aluminum silicate, potassium silicate, calcium silicate, talc, clay, mica, asbestos, glass fiber, montmorillonite, glass balloon, glass beads, pentonite Or kaolin (ceramic clay), perlite, iron powder, copper powder, lead powder, aluminum powder, tungsten powder, molybdenum sulfide, carbon black, boron fiber, silicon carbide fiber, brass fiber, potassium titanate, lead zirconate titanate, Examples thereof include zinc borate, aluminum borate, barium metaborate, calcium borate, and sodium borate.

  Flame retardant aids that can be blended in the thermoplastic polyester elastomer used in the present invention include antimony trioxide, antimony tetroxide, antimony pentoxide, sodium pyroantimonate, tin dioxide, zinc metaborate, aluminum hydroxide, Examples thereof include magnesium hydroxide, zirconium oxide, molybdenum oxide, red phosphorus compound, ammonium polyphosphate, melamine cyanurate, and ethylene tetrafluoride.

  Examples of the compound having a triazine group and / or a derivative thereof that can be blended in the thermoplastic polyester elastomer used in the present invention include melamine, melamine cyanurate, melamine phosphate, and guanidine sulfamate.

  Examples of the inorganic phosphorus compound of the phosphorus compound that can be blended in the thermoplastic polyester elastomer used in the present invention include red phosphorus compounds and ammonium polyphosphate. Examples of red phosphorus compounds include red phosphorus coated with a resin, and composite compounds with aluminum. Examples of organic phosphorus compounds include phosphate esters and melamine phosphate. Phosphate esters include phosphates, phosphonates, trimethyl phosphates of phosphinates, triethyl phosphate, tributyl phosphate, trioctyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, octyl diphenyl phosphate, tricresyl phosphate, Cresyl diphenyl phosphate, triphenyl phosphate, trixylenyl phosphate, tris-isopropylphenyl phosphate, diethyl-N, N-bis (2-hydroxyethyl) aminomethylphosphonate, bis (1,3-phenylenediphenyl) Phosphate, aromatic condensed phosphate ester 1,3- [bis (2,6-dimethylphenoxy) phosphenyloxy] benzene, 1,4- [bis 2,6-dimethyl-phenoxy) such as phosphorylase phenyloxy] benzene hydrolysis and heat stability, preferably a flame retardant.

  As a method for blending these additives, they can be blended using a kneader such as a heating roll, an extruder, or a Banbury mixer. Moreover, it can add and mix in the oligomer before the transesterification reaction or polycondensation reaction at the time of manufacturing a thermoplastic polyester elastomer resin composition.

  The thermoplastic polyester elastomer used in the present invention was heated from room temperature to 300 ° C. at a heating rate of 20 ° C./min using a differential scanning calorimeter of the thermoplastic polyester elastomer, and held at 300 ° C. for 3 minutes. The melting point difference (Tm1−Tm3) between the melting point (Tm1) obtained by the first measurement and the melting point (Tm3) obtained by the third measurement when the cycle of lowering the temperature to room temperature at a temperature lowering rate of 100 ° C./min is repeated three times. ) Is 0 to 50 ° C. The melting point difference is more preferably 0 to 40 ° C, further preferably 0 to 30 ° C. The melting point difference is a measure of the blockability retention of the thermoplastic polyester elastomer. The smaller the temperature difference, the better the blockability retention. When the difference in melting point exceeds 50 ° C., the blockability retention is deteriorated, the quality fluctuation at the time of molding is increased, and the uniformity of the quality of the molded product is deteriorated and the recyclability is deteriorated.

  By satisfy | filling the said characteristic, the outstanding block effect which the thermoplastic polyester elastomer used for this invention mentioned later has can be utilized effectively.

  In the thermoplastic polyester elastomer used in the present invention, it is preferable that the hard segment is composed of a polybutylene terephthalate unit and the melting point of the obtained thermoplastic polyester elastomer is 200 to 225 ° C. 205-225 degreeC is more preferable.

  Moreover, in this invention, it is preferable that a hard segment consists of a polybutylene naphthalate unit and melting | fusing point of the thermoplastic polyester elastomer obtained is 215-240 degreeC. 220-240 degreeC is more preferable.

  When the hard segment is a polybutylene terephthalate unit or a polybutylene naphthalate unit, a commercially available polyester such as polybutylene terephthalate or polybutylene naphthalate can be used, which is advantageous in terms of economy.

  Moreover, when the melting point of the thermoplastic polyester elastomer is less than the lower limit, the block property is lowered, and the heat resistance and mechanical properties of the thermoplastic polyester elastomer are deteriorated, which is not preferable. On the other hand, when the above upper limit is exceeded, the compatibility between the hard segment and the soft segment is lowered, and the workability and mechanical properties of the hose using the thermoplastic polyester elastomer are deteriorated.

  The thermoplastic polyester elastomer used in the present invention has a polyester unit as a hard segment and an aliphatic polycarbonate unit as a ft segment. The average value of the number of repeating units constituting one homopolymer structural unit is an average chain. In the present specification, unless otherwise indicated, values calculated using a nuclear magnetic resonance method (NMR method) are shown.

When the average chain length (x) of the hard segment and the average chain length (y) of the soft segment calculated using the nuclear magnetic resonance method (NMR method) are used, the average chain length (x) of the hard segment is 5 to 20 It is preferable that the block property (B) calculated by the following formula (1) is 0.11 to 0.45.
B = 1 / x + 1 / y (1)

  As for the thermoplastic polyester elastomer used for this invention, the average chain length of the polyester unit which is a hard segment structural component has 5-20 preferable. More preferably, it is 7-18, More preferably, it is the range of 9-16.

  In the thermoplastic polyester elastomer used in the present invention, the average chain length (x) of the polyester unit of the hard segment is an important factor that determines the block property of the thermoplastic polyester elastomer, and the melting point of the thermoplastic polyester elastomer is It has a big impact. Generally, as the average chain length (x) of the polyester units increases, the melting point of the thermoplastic polyester elastomer also increases. Further, the average chain length (x) of the polyester units of the hard segment is a factor that affects the mechanical properties of the thermoplastic polyester elastomer. When the average chain length (x) of the polyester unit of the hard segment is less than 5, it means that randomization has progressed, and the mechanical properties such as the decrease in heat resistance due to the decrease in melting point, hardness, tensile strength, elastic modulus, etc. Degradation of properties is large. When the average chain length (x) of the polyester unit of the hard segment is large, the compatibility with the aliphatic carbonate diol constituting the soft segment is lowered, causing phase separation, greatly affecting the mechanical properties, and its strength. , Reduce the elongation.

Moreover, it is preferable that block property (B) is 0.11-0.45. 0.13-0.40 is more preferable and 0.15-0.35 is still more preferable. As the value increases, the block property decreases. When the block property exceeds 0.4, the polymer properties such as the melting point of the thermoplastic polyester elastomer being lowered due to the block property decline are not preferable. On the other hand, if it is less than 0.10, the compatibility between the hard segment and the soft segment is lowered, causing deterioration of mechanical properties such as strong elongation and bending resistance of the thermoplastic polyester elastomer and an increase in fluctuation of the properties. Therefore, it is not preferable.
Here, the block property is calculated by the following equation (1).
B = 1 / x + 1 / y (1)

From the above relationship, the average chain length (y) of the soft segment is preferably 4-15.
Only when the above block property is satisfied, it is possible to achieve both high heat resistance and mechanical properties.

In the present invention, the method for bringing the above-mentioned blockability retention and blockability into the above ranges is not limited, but it is preferable to optimize the molecular weight of the polycarbonate diol as a raw material. That is, it is preferably produced by reacting the polyester constituting the hard segment in the thermoplastic polyester elastomer used in the present invention with an aliphatic polycarbonate diol having a molecular weight of 5000 to 80000 in a molten state. The larger the molecular weight of the aliphatic polycarbonate diol, the higher the block property retention and the block property. The polycarbonate diol has a number average molecular weight of preferably 5000 or more, more preferably 7000 or more, and still more preferably 10,000 or more. The upper limit of the molecular weight of the polycarbonate diol is preferably 80000 or less, more preferably 70000 or less, and even more preferably 60000 or less, from the viewpoint of compatibility between the hard segment and the soft segment. If the molecular weight of the polycarbonate diol is too large, the compatibility is lowered, phase separation occurs, the mechanical properties are greatly affected, and the strength and elongation are lowered.
The tensile strength at the time of cutting of the thermoplastic polyester elastomer of the present invention is 15 to 100 MPa, preferably 20 to 60 MPa.

  The thermoplastic polyester elastomer of the present invention preferably has a flexural modulus of 1000 MPa or less. The flexural modulus is more preferably 800 MPa or less, and further preferably 600 MPa or less. When the flexural modulus exceeds 1000 MPa, the flexibility of the thermoplastic polyester elastomer is insufficient, which is not preferable. The lower limit is preferably 50 MPa or more, more preferably 80 MPa or more, and further preferably 100 MPa or more. If the pressure is less than 50 MPa, the thermoplastic polyester elastomer is too soft to ensure the strength of the product.

  Further, the thermoplastic polyester elastomer used in the present invention has an elongation retention ratio at break after the heat aging test and after the water aging test of the thermoplastic polyester elastomer composition evaluated by the method described in the measurement method section of 50%. The above is preferable.

  In addition, what has the number average molecular weight 10000-40000 for the aromatic polyester suitable as a polyester used as a raw material which comprises a hard segment at the time of the synthesis | combination of the thermoplastic polyester elastomer used for this invention is desirable.

  The method for optimizing the molecular weight of the polycarbonate diol is not limited. An optimal molecular weight may be purchased or prepared, or a molecular weight adjusted by increasing the molecular weight in advance with a low molecular weight polycarbonate diol and a chain extender such as diphenyl carbonate or diisocyanate may be used. .

  For example, as a method for producing the above high molecular weight aliphatic polycarbonate diol, the above-mentioned aliphatic diol and the following carbonates, that is, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, dimethyl carbonate, diphenyl carbonate It can obtain by making it react.

  Another method for producing a high molecular weight aliphatic polycarbonate diol is to react a low molecular weight aliphatic polycarbonate diol with dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, dimethyl carbonate, diphenyl carbonate, etc. This is also possible.

  The polyester elastomer composition described above is not particularly problematic when used in the hose of the present invention in any of an inner tube, an outer tube or a single layer, and is a polyolefin resin, a polyvinyl chloride resin, a polyamide resin, a polyester resin. A combination of a resin, a thermoplastic elastomer resin, or the like and the polyester elastomer composition described above can be arbitrarily selected. The polyester elastomers having different hardnesses according to the present invention may be used as the inner tube and the outer tube. There is no problem even if an adhesive such as an alloy material, an isocyanate, a phenol resin, an epoxy resin, or a urethane is used to improve the adhesion between the inner tube and the outer tube. Moreover, when making the dimensional precision of a hose strict, a mandrel may be used and it does not specifically limit even if it does not use it.

  In the hose of the present invention, the presence or absence of the reinforcing material is not particularly limited. The reinforcing agent may be either a blade shape or a spiral shape, and the material used may be a thread or a wire. Examples of the reinforcing yarn include yarns made of vinylon fiber, rayon fiber, polyester fiber, nylon fiber, aromatic polyamide fiber and the like. Examples of the reinforcing wire include a hard steel wire, and more specifically, a steel wire plated with brass, zinc, or the like for rust prevention and adhesion. For the purpose of improving the adhesion to these reinforcing materials, there is no particular problem even if an adhesive is used, and examples of the adhesive include isocyanate-based, phenolic resin-based, epoxy resin-based, urethane-based adhesives.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but is not limited thereto. In this specification, each measurement was performed according to the following method.
(1) Reduced viscosity of thermoplastic polyester elastomer 0.05 g of thermoplastic polyester elastomer was dissolved in 25 mL of a mixed solvent (phenol / tetrachloroethane = 60/40) and measured at 30 ° C. using an Ostwald viscometer.

(2) Melting point (Tm) of thermoplastic polyester elastomer
Thermoplastic polyester elastomer dried under reduced pressure at 50 ° C. for 15 hours was measured by using a differential scanning calorimeter DSC-50 (manufactured by Shimadzu Corporation) at a rate of 20 ° C./min from the room temperature. did.
In addition, 10 mg of a measurement sample was weighed in an aluminum pan (TA Instruments, product number 900793.901), sealed with an aluminum lid (TA Instruments, product number 900794.901), and measured in an argon atmosphere. .

(3) Tensile strength and elongation during cutting of the thermoplastic polyester elastomer The tensile strength and elongation during cutting of the thermoplastic polyester elastomer were measured in accordance with JIS K6251. The test piece was injection-molded into a flat plate of 100 mm x 100 mm x 2 mm at a cylinder temperature (Tm + 20 ° C) and a mold temperature of 30 ° C using an injection molding machine (model-SAV, manufactured by Yamashiro Seiki Co., Ltd.), and then a dumbbell shape. A JIS No. 3 type test piece was punched from a flat plate.

(4) Flexural modulus Measured according to ASTM D790.

(5) Heat aging resistance (Elongation retention at cutting after heat aging test)
<Preparation of test piece>
A polyfunctional epoxy compound (0.35 parts by mass), a catalyst (0.2 parts by mass) and a stabilizer (1.2 parts by mass) are placed in a drum tumbler at 100 parts by mass of a thermoplastic polyester elastomer pellet dried at 100 ° C. for 8 hours under reduced pressure. For 30 minutes. The mixture was melt-kneaded at a temperature of (Tm + 20 ° C.) using a 40 mmφ same-direction twin screw extruder with a vent hole and extruded into a strand shape, and the strand was cut into chips by cooling with water. The chip was dried under reduced pressure at 100 ° C. to obtain a chip of a thermoplastic polyester elastomer composition.
After injection molding the thermoplastic polyester elastomer into a flat plate of 100 mm × 100 mm × 2 mm at a cylinder temperature (Tm + 20 ° C.) and a mold temperature of 30 ° C. using an injection molding machine (model-SAV manufactured by Yamashiro Seiki Co., Ltd.) A dumbbell-shaped JIS No. 3 test piece was punched from the flat plate.
<Evaluation of elongation retention during dry heat treatment and cutting>
The test piece obtained by the above method was treated at 180 ° C. for 1000 hours in a gear type hot air dryer, and then elongation at break was measured according to JIS K6251. For the test pieces not subjected to the dry heat treatment, the elongation at break was measured by the same method, and the retention rate of the elongation at break after the dry heat treatment was calculated.

(6) Water aging resistance (Elongation retention at cutting after water aging test)
<Preparation of test piece>
It was produced by the same method as described in the above heat aging resistance measurement method.
<Evaluation of boiling water treatment, elongation retention during cutting>
After treating the test piece in boiling water at 100 ° C. for 2 weeks, the elongation at break was measured according to JIS K6251. For the test pieces not treated in boiling water, the elongation at break was measured in the same manner, and the retention of elongation at break after the boiling water treatment was calculated.

(7) Average chain length and block property of hard segment and soft segment (when the glycol component of the polyester is butanediol and the glycol in the aliphatic polycarbonate diol is an aliphatic diol having 5 to 12 carbon atoms)
[NMR measurement]
Apparatus: Fourier transform nuclear magnetic resonance apparatus (AVANCE500 manufactured by BRUKER)
Measuring solvent: Deuterated chloroform Sample solution concentration: 3-5 vol%
¹ H resonance frequency: 500.13 MHz
Detection pulse flip angle: 45 °
Data acquisition time: 4 seconds Delay time: 1 second Integration count: 50-200 times Measurement temperature: Room temperature

〔Method of calculation〕
The H-NMR integrated value (in arbitrary units) of the methylene peak adjacent to oxygen in the aromatic dicarboxylic acid-butanediol-butanediol of the aromatic dicarboxylic acid chain is defined as A.
The H-NMR integrated value (unit is arbitrary) of the peak of the methylene adjacent to oxygen closer to carbonic acid of butanediol of the aromatic dicarboxylic acid-butanediol-carbonic acid chain is defined as C.
H-NMR integrated value (unit is arbitrary) of the peak of methylene adjacent to oxygen closer to the aromatic dicarboxylic acid of aromatic dicarboxylic acid-C5-C12 aliphatic diol-carbonic acid chain hexanediol And
The H-NMR integrated value (unit is arbitrary) of the methylene peak adjacent to oxygen of the carbonic acid-aliphatic diol having 5 to 12 carbon atoms-aliphatic diol having 5 to 12 carbon atoms in the carbonic acid chain is defined as D.
Hard segment average chain length (x) is
x = ((((A / 4) + (C / 2)) / ((B / 2) + (C / 2)))) × 2.
Soft segment average chain length (y) is
y = (((D / 4) + (B / 2)) / ((B / 2) + (C / 2)))) × 2.
The block property (B) was calculated by the following equation (1) from the values of x and y obtained by the above method. The smaller the value of B, the higher the block property.
B = 1 / x + 1 / y (1)

(8) Blockability retention 10 mg of the thermoplastic polyester elastomer dried under reduced pressure at 50 ° C. for 15 hours is weighed in an aluminum pan (TA Instruments, product number 900793.901), and an aluminum lid (TA Instruments, product number). After preparing the measurement sample in a sealed state in 90079.901), a differential scanning calorimeter DSC-50 (manufactured by Shimadzu Corporation) was used, and the temperature was increased from room temperature to 300 ° C. at a temperature rising rate of 20 ° C./min under a nitrogen atmosphere. The sample was taken out of the sample pan, held at 300 ° C. for 3 minutes, and immersed in liquid nitrogen to be rapidly cooled. Thereafter, the sample was taken out from the liquid nitrogen and left at room temperature for 30 minutes. The measurement sample pan is set on a differential scanning calorimeter and allowed to stand at room temperature for 30 minutes, and then the temperature is raised again from room temperature to 300 ° C. at a temperature rising rate of 20 ° C./min. The melting point difference (Tm1−Tm3) between the melting point (Tm1) obtained by the first measurement when this cycle is repeated three times and the melting point (Tm3) obtained by the third measurement is obtained, and the melting point difference is determined as a block property. Retainability. The smaller the temperature difference, the better the blockability retention.
Based on the melting point difference evaluated by the above method, the blockability retention was determined and displayed according to the following criteria.
A: Melting point difference 0 to 30 ° C.
○: Melting point difference 30-40 ° C
Δ: Melting point difference 40-50 ° C
X: Melting point difference 50 ° C. or more

(9) Molecular weight of aliphatic polycarbonate diol A terminal group was determined by dissolving an aliphatic polycarbonate diol sample in deuterated chloroform (CDCl ₃ ) and measuring H-NMR in the same manner as described in (7) above. It calculated and calculated | required with the following formula.
Molecular weight = 1000000 / ((Terminal group weight (equivalent / ton)) / 2)

(10) Number average molecular weight (Mn) of aromatic polyester
The value was calculated according to the following formula using the value of reduced viscosity (ηsp / c) determined by the same method as that for measuring the reduced viscosity of the thermoplastic polyester elastomer.
ηsp / c = 1.919 × 10 ⁻⁴ × Mn ^0.8929 −0.0167

(11) Heat aging resistance / water aging resistance of hose <Preparation of test piece>
A polyfunctional epoxy compound 0.5 mass part, a catalyst 0.2 mass part, and a stabilizer 1.2 mass part are put in a drum tumbler in 100 mass parts of a thermoplastic polyester elastomer pellet dried under reduced pressure at 100 ° C. for 8 hours. For 30 minutes. The mixture was melt-kneaded at a temperature of (Tm + 20 ° C.) using a 40 mmφ same-direction twin screw extruder with a vent hole and extruded into a strand shape, and the strand was cut into chips by cooling with water.
The chip was dried under reduced pressure at 100 ° C. to obtain a chip of a thermoplastic polyester elastomer composition having a moisture content of 0.05% or less. Polyester elastomer composition obtained as a resin for producing hose outer pipes, polyamide elastomer (Pebax 5533 (Toray Industries, Inc.)) as resin for producing inner pipes, and polyester yarn (1500d, thickness 1 mm) as a reinforcing material. A resin hose having an outer diameter of 17.5 mm was manufactured.
Heat aging resistance: A 200 mm long hose was heat-treated for 30 days with a gear-type aging tester at 140 ° C. to conduct an aging test. Thereafter, a bending test with a diameter of 80 mm was performed, and the presence or absence of cracks or breaks was observed.
Water aging resistance: A 200 mm long hose was immersed in boiling water at 100 ° C. for 20 days, then taken out and subjected to a bending test with a diameter of 80 mm to observe the presence or absence of cracks and breaks.

[Method for producing aliphatic polycarbonate diol]
Method for producing aliphatic polycarbonate diol (molecular weight 10,000):
Aliphatic polycarbonate diol (Ube Industries, Ltd. carbonate diol UH-CARB200, molecular weight 2000, 1,6-hexanediol type) 100 parts by mass and diphenyl carbonate 8.6 parts by mass were respectively charged and reacted at a temperature of 205 ° C. and 130 Pa. It was. After 2 hours, the contents were cooled and the polymer was removed. The molecular weight was 10,000.

Method for producing aliphatic polycarbonate diol (molecular weight 20000):
Aliphatic polycarbonate diol (Ube Industries, Ltd. carbonate diol UH-CARB200, molecular weight 2000, 1,6-hexanediol type) 100 parts by mass and diphenyl carbonate 9.6 parts by mass were respectively charged and reacted at a temperature of 205 ° C. and 130 Pa. It was. After 2 hours, the contents were cooled and the polymer was removed. The molecular weight was 20000.

Method for producing aliphatic copolymer polycarbonate diol (molecular weight 10,000):
Aliphatic copolymer polycarbonate diol (Asahi Kasei Chemicals carbonate diol T5652, molecular weight 2000, copolymer of 1,6-hexanediol and 1,5-pentanediol, amorphous) 100 parts by mass and diphenyl carbonate 8.6 Each mass part was charged and reacted at a temperature of 205 ° C. and 130 Pa. After 2 hours, the contents were cooled and the polymer was removed. The molecular weight was 10,000.

Production method of aliphatic polycarbonate diol (molecular weight 85000) Aliphatic polycarbonate diol (Ube Industries, Ltd. carbonate diol UH-CARB200, molecular weight 2000, 1,6-hexanediol type) and diphenyl carbonate were each 100 parts by mass and 10.7. Polymerization was advanced at a temperature of 205 ° C. and 130 Pa by charging a mass part. After 2 hours and 45 minutes, the contents were cooled and the polymer was removed. The molecular weight was 85000.

[Example 1]
100 parts by mass of polybutylene terephthalate (PBT) having a number average molecular weight of 30000 and 43 parts by mass of a polycarbonate diol having a number average molecular weight of 10000 prepared by the above method were stirred at 230 ° C. to 245 ° C. under 130 Pa for 1 hour, After confirming that it became transparent, the contents were taken out and cooled to obtain a polymer. Each physical property of the obtained polymer was measured, and the result is shown in Table 1. The polymer (thermoplastic polyester elastomer) obtained in this example had good properties and high quality. Moreover, although the resin hose was shape | molded for evaluation for the obtained polyester elastomer and heat aging resistance and water aging resistance were evaluated, it had the resin characteristic for hose excellent.

[Example 2]
100 parts by weight of polybutylene terephthalate (PBT) having a number average molecular weight of 30000 and 43 parts by weight of a polycarbonate diol having a number average molecular weight of 20000 prepared by the above method were stirred at 230 ° C. to 245 ° C. under 130 Pa for 1.5 hours, After confirming that the resin became transparent, the contents were taken out and cooled to obtain a polymer. Each physical property of the obtained polymer was measured, and the result is shown in Table 1. The polymer (thermoplastic polyester elastomer) obtained in this example had the same quality as the thermoplastic polyester elastomer obtained in Example 1 and was of high quality. Further, a resin hose was molded for evaluation of the obtained polyester elastomer, and the heat aging resistance and water aging resistance were evaluated. However, they had excellent hose resin characteristics.

Example 3
100 parts by mass of polybutylene terephthalate (PBT) having a number average molecular weight of 30,000 and 43 parts by mass of an aliphatic copolymer polycarbonate diol having a number average molecular weight of 10,000 prepared by the above method are stirred at 230 ° C. to 245 ° C. under 130 Pa for 1 hour. After confirming that the resin became transparent, the contents were taken out and cooled to obtain a polymer. Each physical property of the obtained polymer was measured, and the result is shown in Table 1.
The polymer (thermoplastic polyester elastomer) obtained in this example had the same quality as the thermoplastic polyester elastomer obtained in Example 1 and was of high quality. Moreover, compared with the case where the polycarbonate diol which consists of 1, 6- hexanediol is used as a soft segment, it is excellent in the low temperature characteristic. Further, a resin hose was molded for evaluation of the obtained polyester elastomer, and the heat aging resistance and water aging resistance were evaluated. However, they had excellent hose resin characteristics.

Example 4
100 parts by weight of polybutylene naphthalate (PBN) having a number average molecular weight of 30,000 and 43 parts by weight of a polycarbonate diol having a number average molecular weight of 10,000 prepared by the above method are stirred at 245 ° C. to 260 ° C. under 130 Pa for 1 hour, and resin Was confirmed to be transparent, and the contents were taken out and cooled to obtain a polymer. The physical properties of the obtained polymer were measured, and the results are shown in Table 1. The polymer (thermoplastic polyester elastomer) obtained in this example was a block equivalent to the thermoplastic polyester elastomer obtained in Example 1. The thermoplastic polyester elastomer obtained in Example 1 had a higher melting point and higher quality than the thermoplastic polyester elastomer obtained in Example 1. Further, a resin hose was molded for evaluation of the obtained polyester elastomer, and the heat aging resistance and water aging resistance were evaluated. However, they had excellent hose resin characteristics.

[Comparative Example 1]
100 parts by mass of polybutylene terephthalate (PBT) having a number average molecular weight of 30000 and 43 parts by mass of polycarbonate diol C (carbonate diol UH-CARB200, molecular weight 2000) manufactured by Ube Industries, Ltd. are stirred at 230 ° C. to 245 ° C. and 130 Pa for 10 minutes. After confirming that the resin became transparent, the contents were taken out and cooled to obtain a polymer. Each physical property of the obtained polymer was measured, and the result is shown in Table 1. The polymer (thermoplastic polyester elastomer) obtained in this comparative example was inferior in block property and block property retention. Furthermore, the reduced viscosity was low, the heat aging resistance was inferior, and the quality was low. Moreover, since the molecular weight was low, the flexural modulus could not be measured. Further, a resin hose was molded for evaluation of the obtained polyester elastomer, and the heat aging resistance and water aging resistance were evaluated. However, they had excellent hose resin characteristics.

[Comparative Example 2]
100 parts by weight of polybutylene terephthalate (PBT) having a number average molecular weight of 30000 and 43 parts by weight of a polycarbonate diol having a number average molecular weight of 85000 prepared by the above method were stirred at 230 ° C. to 245 ° C. under 130 Pa for 5 hours. Remained cloudy. The contents were taken out and cooled to obtain a polymer. Each physical property of the obtained polymer was measured and shown in result 1. The polymer (thermoplastic polyester elastomer) obtained in this comparative example has excellent blockability and blockability retention, but the compatibility between the hard segment and the soft segment is poor, so mechanical properties such as tensile strength are inferior. The characteristic variation was large and the quality was low. Further, a resin hose was molded for evaluation of the obtained polyester elastomer, and the heat aging resistance and water aging resistance were evaluated. However, they had excellent hose resin characteristics.

[Comparative Example 3]
100 parts by weight of polybutylene terephthalate (PBT) having a number average molecular weight of 2000 and aliphatic copolymer polycarbonate diol (carbonate diol T5652 manufactured by Asahi Kasei Chemicals Co., Ltd., molecular weight 2000, 1,6-hexanediol and 1,5-pentanediol Polymer, amorphous) and 43 parts by mass were stirred at 230 ° C. to 245 ° C. and 130 Pa for 10 minutes to confirm that the resin became transparent, and the contents were taken out and cooled to obtain a polymer. Each physical property of the obtained polymer was measured, and the result is shown in Table 1. The polymer (thermoplastic polyester elastomer) obtained in this comparative example was inferior in blockability and blockability retention and was of lower quality than the thermoplastic polyester elastomer obtained in Example 4. Moreover, since the molecular weight was low, the flexural modulus could not be measured. Further, a resin hose was molded for evaluation of the obtained polyester elastomer, and the heat aging resistance and water aging resistance were evaluated. However, they had excellent hose resin characteristics.

[Comparative Example 4]
Regarding the thermoplastic polyester elastomer (polybutylene terephthalate unit / polyoxytetramethylene glycol unit = 63.5 / 36.5 (mass ratio)) composed of polybutylene terephthalate and polyoxytetramethylene glycol, the physical properties were measured and the results As shown in Table 1, it is clear that the heat aging resistance is inferior. Moreover, although the resin hose was shape | molded for evaluation for the obtained polyester elastomer and heat aging resistance and water aging resistance were evaluated, it had the resin characteristic for hose excellent.

[Comparative Example 5]
Various properties of a thermoplastic polyester elastomer (polybutylene terephthalate unit / polycaprolactone unit = 70/30 (mass ratio)) composed of polybutylene terephthalate and polycaprolactone were measured and the results are shown in Table 1, but the water resistance is poor. It is clear. Further, a slight odor was felt when remelted. Further, a resin hose was molded for evaluation of the obtained polyester elastomer, and the heat aging resistance and water aging resistance were evaluated. However, they had excellent hose resin characteristics.

As mentioned above, although the hose characterized by using the thermoplastic thermoplastic polyester elastomer of the present invention for at least one of the tube components has been described based on a plurality of examples, the present invention is described in the above examples. The present invention is not limited to the configuration, and the configuration can be changed as appropriate without departing from the spirit of the invention, for example, by appropriately combining the configurations described in the embodiments.

  As described above, a polyester elastomer in which a hard segment composed of a polyester composed of an aromatic dicarboxylic acid and an aliphatic or alicyclic diol and a soft segment composed mainly of an aliphatic polycarbonate are bonded, and the thermoplastic polyester elastomer Using a differential scanning calorimeter, the temperature was increased from room temperature to 300 ° C. at a temperature increase rate of 20 ° C./min, held at 300 ° C. for 3 minutes, and then the temperature decrease rate to 100 ° C./min to room temperature was repeated three times. The melting point difference (Tm1−Tm3) between the melting point (Tm1) obtained by the first measurement and the melting point (Tm3) obtained by the third measurement is 0 to 50 ° C., and the tensile strength at the time of cutting is 15 Design using a thermoplastic polyester elastomer of ~ 100 MPa for at least one of the tube components of the hose Ukoto by, good heat resistance and heat aging resistance is good in water resistance, it is possible to provide a hose tube stability in harsh environments, such as flexibility is excellent.

Claims (5)

  A polyester elastomer in which a hard segment composed of a polyester composed of an aromatic dicarboxylic acid and an aliphatic or alicyclic diol and a soft segment composed mainly of an aliphatic polycarbonate are bonded, and the differential scanning of the thermoplastic polyester elastomer Using a calorimeter, the temperature was raised from room temperature to 300 ° C. at a temperature rising rate of 20 ° C./min, held at 300 ° C. for 3 minutes, and then the cycle of cooling to room temperature at a temperature lowering rate of 100 ° C./min was repeated three times. The melting point difference (Tm1−Tm3) between the melting point (Tm1) obtained by the first measurement and the melting point (Tm3) obtained by the third measurement is 0 to 50 ° C., and the tensile strength at the time of cutting is 15 to 100 MPa. A hose characterized by using a thermoplastic polyester elastomer as at least one of the tube components. When the average chain length (x) of the hard segment and the average chain length (y) of the soft segment calculated using the nuclear magnetic resonance method (NMR method) are used, the average chain length (x) of the hard segment is 5 to 20 And the block property (B) calculated by the following formula (1) is 0.11 to 0.45, characterized in that the thermoplastic polyester elastomer according to claim 1 is used for at least one of the tube components. And hose.
B = 1 / x + 1 / y (1)   The thermoplastic polyester elastomer according to claim 1, wherein the hard segment comprises a polybutylene terephthalate unit, and the obtained thermoplastic polyester elastomer has a melting point of 200 to 225 ° C. And hose.   The thermoplastic polyester elastomer according to claim 1, wherein the hard segment comprises polybutylene naphthalate units, and the melting point of the obtained thermoplastic polyester elastomer is 215 to 240 ° C. A hose characterized by being used above.   The polyester comprising an aromatic dicarboxylic acid and an aliphatic or alicyclic diol and an aliphatic polycarbonate diol having a molecular weight of 5000 to 80000 are produced by reacting in a molten state. A hose comprising: a thermoplastic polyester elastomer of at least one of the tube components.