JP2001240663A - Thermoplastic polyester elastomer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic polyester elastomer formula capable of being used as various kinds of forming materials for an article exemplified by a fiber, a film and a sheet, especially suitable for an elastic yarn, a wire- covering material and also the forming material such as boots, a gear, a tube and a packing, and excellent in heat aging resistance, water resistance and low-temperature characteristics. SOLUTION: This thermoplastic polyester elastomer is characterized by <1,000 MPa flexural modulus, >50% retention of breaking elongation after a heat aging test, >50% retention of breaking elongation after a water-resisting aging test, and <-15 deg.C temperature exhibiting the maximum value of loss tangent (tan δ).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic polyester elastomer.
Thermoplastic polyester elastomer with excellent low temperature properties,
In particular, thermoplastic polyester elastomer which can be used for various molding materials including fibers, films, sheets, etc., and more particularly, suitable for molding materials such as elastic yarns, boots, gears, tubes, packings, etc. The present invention relates to a thermoplastic polyester elastomer useful for applications requiring heat aging resistance, water resistance, and low-temperature properties, such as joint boots and wire covering materials.

[0002]

2. Description of the Related Art As a thermoplastic polyester elastomer, polybutylene terephthalate (PB) has been used.
T), crystalline polyesters such as polybutylene naphthalate (PBN) as hard segments, and polyoxyalkylenes such as polytetramethylene glycol (PTMG) and / or polycaprolactone (PC)
L) and polyesters having soft segments such as polybutylene adipate (PBA) are known and have been put to practical use.

[0003] However, polyester polyether type elastomers using polyoxyalkylenes for the soft segment are excellent in water resistance and low temperature characteristics, but are inferior in heat aging resistance. Elastomers are known to be excellent in heat aging resistance, but inferior in water resistance and low-temperature properties.

For the purpose of solving the above-mentioned drawbacks, a polyester polycarbonate type elastomer using polycarbonate for the soft segment has been proposed, but for example, the one disclosed in Japanese Patent Publication No. 7-39480 (Toray) has poor mechanical properties, It only shows a slight improvement in hydrolysis resistance. Japanese Unexamined Patent Publication (Kokai) No. 5-295094 (Teijin) discloses that since a block copolymer is obtained only by transesterification, the polymerization takes a long time, but its polymerization degree is low (inherent viscosity is about 1). Moreover, it is practically difficult to control the manufacturing process. In addition, heat aging resistance is hardly mentioned.
In addition, the elastomer disclosed in JP-A-10-182782 (DSM) has very excellent heat aging resistance and excellent water resistance, but uses a highly crystalline polycarbonate for the soft segment, so that it has a low temperature. Poor characteristics.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a thermoplastic polyester elastomer having excellent heat aging resistance, water resistance and low-temperature properties.

[0006]

Means for Solving the Problems The present inventors have found that the above problems can be solved by using specific hard segments and soft segments and performing a chain extension reaction, and have completed the present invention. That is, the polyester elastomer of the present invention is as follows. 1. Flexural modulus <1000 MPa, elongation retention at break after heat aging test> 50%, elongation retention at break after water aging test> 50%, and loss tangent ta
A thermoplastic polyester elastomer, wherein the temperature at which nδ has a maximum value is <−15 ° C. (Here, the flexural modulus is a value measured based on ASTM D790, and the elongation at break is a value measured based on ASTM D638. The heat aging test is 150 ° C. using a gear hot air dryer. , 125 days, and the water aging test is equivalent to two weeks of treatment in boiling water at 100 ° C. Further, the loss tangent tan δ is measured by a dynamic viscoelasticity measuring device of a tensile forced vibration type (for example, manufactured by UBM Co., Ltd.). R
HEOGEL-E4000) and -100 ° C to 2
It shall be measured at 11 Hz while heating at a rate of ° C./min. ) 2. The temperature at which the loss tangent tan δ has a maximum value is <−20 ° C.
2. The polyester elastomer according to the above item 1, wherein 3. A hard segment mainly composed of an aromatic dicarboxylic acid and an aliphatic or alicyclic diol, and a soft segment mainly composed of an aliphatic polycarbonate, wherein the segments are substantially bonded by a chain extender. 3. The polyester elastomer according to the above 1 or 2. 4. The soft segment is an aliphatic polycarbonate essentially containing a hydrogenated dimer diol, and the copolymerization amount of the hydrogenated dimer diol is 30 mol% or less of all glycol components of the segment.
4. The polyester elastomer according to any one of items 1 to 3. 5. The hard segment is a polyester which is required to contain a hydrogenated dimer diol, and the copolymerization amount of the hydrogenated dimer diol is 15 mol% or less of all glycol components in the segment. The polyester elastomer according to any one of the above. 6. The hard segment is a polyester which is essential to contain a hydrogenated dimer diol, and the copolymerization amount of the hydrogenated dimer diol is one of the total glycol components in the segment.
0 mol% or less, and the soft segment is an aliphatic polycarbonate which must contain a hydrogenated dimer diol, and the copolymerization amount of the hydrogenated dimer diol is 30 mol% or less of the total glycol component in the segment. 4. The polyester elastomer according to any one of the above items 1 to 3, wherein 7. 7. The polyester elastomer according to any one of the above items 1 to 6, wherein the aromatic dicarboxylic acid constituting the hard segment is mainly terephthalic acid or 2,6-naphthalenedicarboxylic acid. 8. The hard segment is polybutylene terephthalate,
The above-mentioned item 1, which is any one of polybutylene naphthalate, polycyclohexylene dimethylene terephthalate and a hydrogenated dimer diol copolymer thereof.
8. The polyester elastomer according to any one of items 1 to 7, above. 9. Wherein each segment is linked by an ester bond and / or a bond derived from a chain extender.
9. The polyester elastomer according to any one of items 1 to 8, above. 10. 10. The polyester elastomer according to claim 1, wherein the chain extender is an isocyanate compound or a carbodiimidated compound thereof. 11. 10. The polyester elastomer according to any one of the above items 1 to 9, wherein the chain extender is a phenyl carbonate compound or a phenyl ester compound. 12. 10. The polyester elastomer according to any one of the above items 1 to 9, wherein the chain extender is an oxazoline compound.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. In the thermoplastic elastomer of the present invention, the aromatic dicarboxylic acid constituting the hard segment is preferably mainly terephthalic acid or 2,6-naphthalenedicarboxylic acid. Other acid components include diphenyldicarboxylic acid, isophthalic acid, aromatic dicarboxylic acids such as 5-sodium sulfoisophthalic acid, cyclohexanedicarboxylic acid, alicyclic dicarboxylic acids such as tetrahydrophthalic anhydride, succinic acid, glutaric acid, adipine acid,
Examples thereof include aliphatic dicarboxylic acids such as azelaic acid, sebacic acid, dodecane diacid, dimer acid, and hydrogenated dimer acid. These are used in 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.

The aliphatic or alicyclic diol constituting the hard segment is mainly an alkylene glycol having 2 to 8 carbon atoms. Specifically, ethylene glycol,
Examples thereof include 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, and 1,4-cyclohexanedimethanol. 1,4-butanediol and 1,4-cyclohexanedimethanol are most preferred.

When the hydrogenated dimer diol is copolymerized with the hard segment, the copolymerization amount must be 15 mol% or less, more preferably 10 mol% or less of all glycol components in the segment. Desirably. If the copolymerization amount of the hydrogenated dimer diol is more than 15 mol%, the melting point of the finally obtained polyester elastomer is lowered, and the crystallinity is also unfavorably lowered.

The aromatic polyester comprising the above-mentioned components and a copolymer thereof can be easily obtained according to a usual polyester production method. In addition, this polyester,
Generally, those having a number average molecular weight of 5,000 to 35,000 are desirable.

The hydrogenated dimer diol used as a copolymer component in the present invention is, of course, not limited to its production method. For example, dimer acid which is a dimer of unsaturated fatty acid (15 to 21 carbon atoms) is converted to hydrogen. A compound containing the compound represented by the following general formula (1) as a main component (50% by weight or more), or a compound represented by the following general formula (1) and a compound represented by the following general formula (2) Corresponds to a mixture of

[0012]

Embedded image (In the above formula, R ¹ , R ² , R ³ , and R ⁴ are substantially free from unsaturated groups and are substantially linear, and among them, R ¹ , R ²
Alkyl group, R ^3, R ⁴ is an alkylene group, R ¹ ~
The total number of carbon atoms of R ⁴ is 22 to 34. )

[0013]

Embedded image(R in the above formula^Five, R⁶, R⁷, R⁸Contains a substantially unsaturated group.
First, it is also substantially linear, of which R^Five, R⁶Is
Alkyl group, R⁷, R⁸Is an alkylene group; ^Five~ R⁸
Is 25 to 37. )

The aliphatic polycarbonate constituting the soft segment mainly comprises an aliphatic diol residue having 2 to 12 carbon atoms. Examples of these aliphatic diol residues 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-octanediol and the like. These components may be used alone or in combination of two or more as necessary based on the case briefly described below.

When the hydrogenated dimer diol is copolymerized with the soft segment, the copolymerization amount must be 30 mol% or less of the total glycol component in the segment. If the content is 30 mol% or more, the compatibility between the soft segment and the hard segment decreases, which is not preferable.

The above-mentioned aliphatic polycarbonate and its copolymer can be obtained by any known method. For example, a method of reacting a dialkyl carbonate, a diaryl carbonate or an alkylene carbonate with various glycols in the presence of a titanium catalyst, a method of removing methanol from dimethyl carbonate and various glycols without using a catalyst, a method of hydrogenating an aliphatic polycarbonate with a dimer diol or a carbonate. Examples thereof include a method of adding a compound and obtaining a copolymer by transesterification, but are not limited thereto.

The polycarbonate comprising the above diol preferably has a molecular weight of about 500 to 5,000, and more preferably has a molecular weight of 800 to 3,000. Further, it is desirable to use a material having good low-temperature characteristics.

A polycarbonate having good low-temperature properties is
This corresponds to a material having a low melting point (for example, 50 ° C. or lower) and a low glass transition temperature. Generally, a polycarbonate made of hexanediol used as a soft segment of an elastomer has a low glass transition temperature of about −60 ° C., but has a relatively high melting point of about 60 ° C., and thus corresponds to a polycarbonate having inferior low-temperature characteristics. On the other hand, a polycarbonate obtained by copolymerizing the above polycarbonate with, for example, an appropriate amount of 3-methyl-1,5-pentanediol has a slightly higher glass transition point than that of the original polycarbonate, but has a lowered melting point or an amorphous property. Therefore, it corresponds to a polycarbonate having good low-temperature characteristics.
Further, for example, 1,9-nonanediol and 2-methyl-
Polycarbonate composed of 1,8-octanediol has a sufficiently low melting point of about 50 ° C. and a glass transition temperature of about −60 ° C., and thus also corresponds to a polycarbonate having good low-temperature characteristics. Note that the polycarbonate obtained by copolymerizing the hydrogenated dimer diol also has a lower melting point or becomes amorphous compared to the original polycarbonate, and thus corresponds to a polycarbonate having good low-temperature characteristics.

The above polycarbonate may be obtained by copolymerizing a small amount of other glycol, dicarboxylic acid, ester compound or ether compound. Examples of copolymerization components include, for example, glycols such as modified hydrogenated dimer diols, dimer acids, dicarboxylic acids such as hydrogenated dimer acids, aliphatic or aromatic, poly or oligos composed of glycols and alicyclic dicarboxylic acids. Examples thereof include poly- or oligoesters such as esters and ε-caprolactone, and poly- or oligoalkylene glycols such as polytetramethylene glycol and polyoxyethylene glycol.

The above copolymer component can be used to such an extent that the effects of the present invention are not substantially lost. Specifically, 4
0 parts by weight or less, preferably 30 parts by weight or less, more preferably 20 parts by weight or less. If the copolymerization amount is too large,
The heat aging resistance and water resistance of the obtained elastomer are reduced.

The polyester elastomer of the present invention may contain, as a soft segment, a polyalkylene oxide such as polyethylene oxide or polyoxytetramethylene glycol, as long as the effects of the invention are not lost.
A copolymer component such as polyester such as polycaprolactone and polybutylene adipate may be introduced. The content of the copolymer component is 0 based on the polyester elastomer.
-40% by weight, preferably 0-30% by weight, more preferably 0-20% by weight.

The above-mentioned polycarbonate and / or modified polycarbonate segment may be used after previously being treated with any acid anhydride. This treatment is performed by heating and mixing an arbitrary acid anhydride and polycarbonate to make the polycarbonate uniform. This reaction does not necessarily need to be completed, and its end point can be arbitrarily determined.

In the polyester elastomer of the present invention, the weight ratio of the polyester constituting the hard segment to the polycarbonate constituting the soft segment and the copolymer component is generally in the range of 20:80 to 95: 5.

The chain extender used for chain extension is not particularly limited as long as it has a bifunctional or higher functional group. Examples thereof include an isocyanate compound, an oxazoline compound, a phenyl carbonate compound or a phenyl ester compound, Lactam compounds, epoxy compounds, aromatic tetracarboxylic anhydrides and the like can be mentioned. Preferred are isocyanate compounds, oxazoline compounds, and phenyl carbonate compounds. These may be used alone or, if necessary, two or more kinds may be used.

As the isocyanate compound used for chain extension or its carbodiimidated compound, for example,
4,4′-diphenylmethane diisocyanate, toluene diisocyanate, xylene diisocyanate, xylylene diisocyanate, tetramethyl xylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, naphthalene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4- Examples include, but are not limited to, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, norbornene diisocyanate, and the like. Also,
The carbodiimidated compounds of the isocyanate compounds may also be used. In addition, these are 2
More than one species may be used in combination. Preferably, 4,4'-
Examples include diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.

The oxazoline compound used for chain extension is a compound having two or more oxazoline rings in one molecule, such as 2,2-bis (2-oxazoline),
1,3-bis (4,5-dihydro-2-oxazoyl)
Benzene, 1,4-bis (4,5-dihydro-2-oxazoyl) benzene, 2,2-bis (4-methyl-2-oxazoline), 2,2-bis (4,4-dimethyl-2-oxazoline) ), 2,2-bis (4-ethyl-2-oxazoline), 2,2-bis (4,4-diethyl-2-oxazoline), 2,2-bis (4-propyl-2-oxazoline),
2,2-bis (4-butyl-2-oxazoline), 2,2-
Bis (4-hexyl-2-oxazoline), 2,2-bis (4-phenyl-2-oxazoline), 2,2-bis (4-
Cyclohexyl-2-oxazoline), 2,2-bis (4-
Benzyl-2-oxazoline), 2,2-ethylenebis (2-oxazoline), 2,2-tetramethylenebis (2
-Oxazoline), 2,2-hexamethylenebis (2-oxazoline), 2,2-octamethylenebis (2-oxazoline), 2,2-ethylenebis (4-ethyl-2-oxazoline), 2,2- Tetraethylenebis (4-ethyl-2-
Examples thereof include bisoxazoline compounds such as oxazoline) and 2,2-cyclohexylenebis (4-ethyl-2-oxazoline), and preferably include 2,2-bis (2-oxazoline).

Examples of the phenyl carbonate compound or phenyl ester compound used for chain extension include diphenyl carbonate, diphenyl terephthalate, diphenyl isophthalate, diphenyl phthalate,
Diphenyl 2,6-naphthalenedicarboxylate, 1,5-
Examples include, but are not limited to, diphenyl naphthalenedicarboxylate, diphenyl 2,7-naphthalenedicarboxylate, diphenyl 4,4-biphenyldicarboxylate. Preferably, diphenyl carbonate, diphenyl terephthalate, and diphenyl phthalate can be used alone or in combination of two or more.

The lactam compound used for chain extension is
For example, a compound represented by the following general formula (3), wherein Ar is an arylene group having 6 to 20 carbon atoms, specifically p-
Phenylene, m-phenylene, o-phenylene, 2,6
-Naphthylene, 1,5-naphthylene, 2,7-naphthylene, and 4,4'-biphenylene, but are not limited thereto.

Embedded image

Examples of the epoxy compound used for chain extension include diglycidyl esters of various aromatic dicarboxylic acids such as diglycidyl terephthalate, diglycidyl isophthalate, and diglycidyl phthalate, and p-phenylenediglycidyl ether. Including aromatic diglycidyl ethers, diglycidyl esters of various aliphatic dicarboxylic acids, diethylene glycol diglycidyl ether, and the like,
It is not limited to this.

As the aromatic tetracarboxylic anhydride used for chain extension, for example, pyromellitic dianhydride, 3,
Examples include, but are not limited to, 3 ', 4,4'-biphenyltetracarboxylic anhydride.

The above-mentioned various chain extenders are usually used in an equivalent amount to 1.5 times the molar number of the polymer in the reaction system.
The optimum value of the addition amount varies depending on the type of the chain extender used, the reaction temperature, and the like. When the addition amount is small, the chain extension reaction is insufficient and a desired block copolymer may not be obtained.

The thermoplastic polyester elastomer of the present invention is obtained by subjecting a polyester constituting a hard segment, a polycarbonate constituting a soft segment and, if necessary, various copolymerization components to a transesterification reaction for a certain period of time under melting, followed by a chain reaction. It can be obtained by performing an extension reaction.

The transesterification reaction under the above-mentioned melting condition is preferably carried out at a temperature within the range from 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 performed. That is, since the transesterification reaction proceeds rapidly at a higher reaction temperature, it is desirable that the concentration of the active catalyst in the system be low, and that at a lower reaction temperature, a certain concentration of the active catalyst is present. Is desirable.

As the catalyst, one or more conventional compounds, for example, titanium compounds such as titanium tetrabutoxide and potassium oxalate, and tin compounds such as dibutyltin oxide and monohydroxybutyltin oxide may be used. The catalyst may already be present in the polyester or polycarbonate segment, in which case it need not be added again. Further, the catalyst in the polyester or polycarbonate segment may be partially or substantially completely deactivated in advance by any method. For example, when using titanium tetrabutoxide as a catalyst, for example, phosphorous acid, phosphoric acid, triphenyl phosphate, tristriethylene glycol phosphate,
Orthophosphoric acid, carbethoxy dimethyl diethyl phosphonate,
Deactivation is carried out by adding a phosphorus compound such as triphenyl phosphite, trimethyl phosphate, trimethyl phosphite and the like, but is not limited thereto.

The above reaction can be carried out by arbitrarily determining the combination of the reaction temperature, the catalyst concentration and the reaction time. That is, the reaction conditions include the types and amount ratios of the hard segments and soft segments used, the shape of the device used,
The appropriate value changes depending on various factors such as the stirring state.

The optimum value of the above reaction conditions is determined, for example, by comparing the melting point of the obtained chain-extended polymer and the melting point of the polyester used as the hard segment.
° C. If the melting point difference is less than 2 ° C., both segments are not mixed or / and reacted, and the resulting polymer shows poor elastic performance. On the other hand, the melting point difference is 60
If the temperature is higher than or equal to ℃, the transesterification reaction proceeds remarkably, resulting in a decrease in the blockability of the obtained polymer,
The elastic performance and the like decrease.

It is desirable that the residual catalyst in the molten mixture obtained by the above reaction be completely deactivated by an arbitrary method. When the catalyst remains more than necessary, it is considered that the transesterification reaction further proceeds at the time of compounding, molding and the like, including the chain extension reaction performed later, and the physical properties of the obtained polymer may fluctuate.

The deactivation reaction is carried out, for example, in the manner described above, ie, phosphorous acid, phosphoric acid, triphenyl phosphate, tristriethylene glycol phosphate, orthophosphoric acid, carbethoxy dimethyldiethyl phosphonate, triphenyl phosphite, trimethyl phosphate, phosphorous acid This is performed by adding a phosphorus compound such as trimethyl, but is not limited thereto.

The chain extension reaction is carried out by adding a chain extender to the above melt. The amount of chain extender added is usually approximately equal to the total number of polymer ends. The progress of the chain extension reaction can be known by measuring the melt viscosity of the melt, for example, by tracking the torque change of a device for stirring the chain extender and the polymer. That is, the point in time when the increase in the torque substantially stops and reaches a certain value can be regarded as the end point of the reaction. The volatile component can be removed under reduced pressure during and / or after the chain extension reaction if necessary.

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

Further, the thermoplastic polyester elastomer of the present invention can be blended with various additives according to the purpose to obtain a composition. Examples of additives include known hindered phenol, sulfur, phosphorus, and amine antioxidants, hindered amine, triazole, benzophenone, benzoate, nickel, and salicyl light stabilizers, and antistatic agents. Agents, lubricants, molecular regulators such as peroxides, compounds having reactive groups such as epoxy compounds, isocyanate compounds, carbodiimide compounds, metal deactivators, organic and inorganic nucleating agents, neutralizing agents, Acid agents, antibacterial agents, optical brighteners, fillers, flame retardants, flame retardant aids, organic and inorganic pigments, and the like can be added.

The hindered phenolic antioxidants which can be incorporated 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-tert-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-t-butyl-4-hydroxy-benzyl-monoethyl-phosphate), triethylene glycol-
Bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3,5-di-tert-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-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 2,2'-oxamidobis [ethyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] , 1,1,3-tris (3 ′, 5′-di-tert-butyl-4′-hydroxybenzyl) -S-triazine-2,4,6 (1H, 3
H, 5H) -trione, 1,3,5-tris (4-t-
Butyl-3-hydroxy-2,6-dimethylbenzyl)
Isocyanurate, 3,5-di-t-butyl-4-hydroxyhydrocinnamic acid triester wizz-
1,3,5-tris (2-hydroxyethyl) -S-triazine-2,4,6 (1H, 3H, 5H), N, N-
Hexamethylene bis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 3,9-bis [2-
{3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.
5] Undecane and the like.

The sulfur-based antioxidants that can be added in the present invention include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodiuropionate, distearyl-3,3'-thiodithioate. Propionate, lauryl stearyl-3,3'-thiodipropionate, dilauryl thiodipropionate, dioctadecyl sulfide, pentaerythryl-tetra (β-lauryl-thiopropionate) ester and the like. Can be.

Examples of the phosphorus-based antioxidants that can be added in the present invention include tris (mixed, mono- and dinolylphenyl) phosphite, tris (2,3-di-t-butylphenyl) phosphite, and 4,4 ′. -Butylidene-
Bis (3-methyl-6-t-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-di-tridecylphosphite-5-t-butylphenyl) butane, Tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butyl)
Butylphenyl) pentaerythritol-diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenephosphanite, bis (2,6-di-t-butyl-4-methyl) Phenyl) pentaeristol-di-phosphite, tetrakis (2,4-di-t-butylphenyl) 4,4′-biphenylenediphosphonite, triphenylphosphite,
Examples thereof include diphenyldecyl phosphite, tridecyl phosphite, trioctyl phosphite, tridodecyl phosphite, trioctadecyl phosphite, trinonyl phenyl phosphite, and tridodecyl trithiophosphite.

The amine-based antioxidants that can be added to the present invention include N, N-diphenylethylenediamine, N, N
-Diphenylacetamidine, N, N-diphenylfluamidine, N-phenylpiperidine, dibenzylethylenediamine, triethanolamine, phenothiazine, N, N'-di-sec-butyl-p-phenylenediamine, 4,4'-tetra Methyl-diaminodiphenylmethane, P, P′-dioctyl-diphenylamine,
N, N'-bis (1,4-dimethyl-pentyl) -p-
Phenylenediamine, phenyl-α-naphthylamine,
Phenyl-β-naphthylamine, 4,4′-bis (4-
Examples thereof include amines such as (α, α-dimethyl-benzyl) diphenylamine and derivatives thereof, reaction products of amine and aldehyde, and reaction products of amine and ketone.

The hindered amine light stabilizer which can be blended in the present invention includes dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-succinate.
Polycondensate with tetramethylpiperidine, 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 (1,2,2,2-n-butylmalonic acid)
2,6,6-pentamethyl-4-piperidyl) ester, 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,
Polycondensate of 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-1,2,2
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-triazine-
2-yl) amino @ undecane, 1- [2- (3,5-
Di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 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-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-
1,3,5-triazine condensate and the like can be mentioned.

The benzophenone-based, benzotriazole-based, triazole-based, nickel-based and salicyl-based light stabilizers that can be blended 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′-t-butyl-5′-methylphenyl) -5-chlorobenazotriazole, 2-
(2'-Hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzothiazole, 2,5-bis- [5'-t-butylbenzoxazolyl- (2)]- Thiophene, bis (3,5-di-t-butyl-4-hydroxybenzylphosphoric acid monoethyl ester) nickel salt, 2
-Ethoxy-5-t-butyl-2'-ethyl oxalic acid-85-90% of bis-anilide and 2-ethoxy-5-t-butyl-2'-ethyl-4'-t-butyl oxalic acid- Bis-anilide 10-15% mixture, 2- [2-hydroxy-3,5-bis (α, α
-Dimethylbenzyl) phenyl] -2H-benzotriazole, 2-ethoxy-2'-ethyloxazalic acid bisanilide, 2- [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- Light stabilizers such as 4-i-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone and phenyl salicylate can be mentioned.

Examples of the lubricant which can be blended in the present invention include hydrocarbon compounds, fatty acid compounds, fatty acid amide compounds, ester compounds, alcohol compounds, metal soap compounds, natural wax compounds, silicone compounds and fluorine compounds. Specifically, liquid paraffin, synthetic paraffin, synthetic hard paraffin, synthetic isoparaffin petroleum hydrocarbon, chlorinated paraffin, paraffin wax, microwax, 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, and behenic acid, hexylamide, octylamide, stearylamide, palmitylamide, oleylamide, erucylamide, ethylenebisstearylamide, laurylamide, behenylamide,
C3-30 saturated or unsaturated aliphatic amides such as methylenebisstearylamide and ricinolamide and derivatives thereof, lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids, polyglycol esters of fatty acids, fatty alcohol esters of fatty acids Butyl stearate, hydrogenated castor oil, ethylene glycol monostearate, etc., cetyl alcohol, stearyl alcohol, ethylene glycol, molecular weight 200 to 1000
0 or more polyethylene glycol, polyglycerol,
Lubricants such as carnauba wax, candelilla wax, montan wax, dimethyl silicone, silicone gum, and ethylene tetrafluoride. Also, linear saturated fatty acids, side chain acids,
A metal salt comprising a compound having cinoleic acid, wherein the metal is (L
i, Mg, Ca, Sr, Ba, Zn, Cd, Al, S
n, Pb) can also be mentioned.

The fillers that can be added in the present invention include magnesium oxide, aluminum oxide, silicon oxide,
Calcium oxide, titanium oxide (rutile type, anatase type), chromium oxide (trivalent), iron oxide, zinc oxide, silica, diatomaceous earth, alumina fiber, antimony oxide, barium ferrite, strontium ferrite, beryllium oxide, pumice, pumice balloon, etc. Oxides or magnesium hydroxide, aluminum hydroxide, basic substances such as magnesium carbonate or hydroxides, or magnesium carbonate, calcium carbonate, barium carbonate, ammonium carbonate, calcium sulfite, dolomite, carbonates such as dawsonite or (Sulfite) such as calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, basic magnesium sulfate or sodium silicate, magnesium silicate, aluminum silicate, potassium silicate, calcium silicate, talc, clay, mica, a Best, glass fiber, montmorillonite, glass balloon, glass beads,
Silicates such as pentonite or kaolin (porcelain), perlite, iron powder, copper powder, lead powder, aluminum powder, tungsten powder, molybdenum sulfide, carbon black, boron fiber, silicon carbide fiber, brass fiber, potassium titanate, Examples thereof include lead zirconate titanate, zinc borate, aluminum borate, barium metaborate, calcium borate, and sodium borate.

Examples of the compound having an epoxy group which can be blended in the present invention include polyepoxy compounds such as sorbiol-polyglycidyl-ether, polyglycerol-polyglycidyl-ether, triglycidyl-tris (2-hydroxyethyl) isocyanurate, and diethylene glycol. Diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, diglycidyl hexahydrophthalate, A condensate of bisphenol A and epichlorohydrin,
Condensates of bisphenol F and epichlorohydrin, diepoxy compounds such as condensates of bisphenol F and epichlorohydrin, higher alcohol glycidyl ether, butyl glycidyl ether, allyl glycidyl ether, stearyl glycidyl ether, methyl glycidyl ether, phenyl glycidyl ether, glycidyl methacrylate, p- Monoepoxy compounds such as t-butylphenyl glycidyl ether and the like can be mentioned.

Compounds having a halogen-substituted phenyl group which can be blended in the present invention include tetrabromobisphenol A (TBA) and tetrabromobisphenol S
(TBS), bis (dibromopropyl) tetrabromobisphenol A ether, TBA epoxy, TBA ethyl ether oligomer, TBA bis (2,3-dibromopropyl ether), TBA (allyl ether), TB
A bis (2-hydroxyethyl ether), TBA carbonate oligomer, TBS bis (2,3-dibromopropyl ether), hexabromobenzene, tetrabromophthalic anhydride, decabromodiphenine oxide, tris (tribromophenoxy) triazine, Bis (pentabromophenyl) ethane, bis (tribromophenoxy) ethane, bis (pentabromophenoxy) ethane,
Brominated phenoxy, ethylene bis (tetrabromophthal) imide, brominated diphenyl oxide, brominated polystyrene and the like can be mentioned.

The flame retardant aid which can be blended in the present invention includes antimony trioxide, antimony tetroxide, antimony pentoxide, sodium pyroantimonate, tin dioxide, zinc metaborate, aluminum hydroxide, magnesium hydroxide, zirconium oxide, Molybdenum oxide, red phosphorus compounds, ammonium polyphosphate, melamine cyanurate, ethylene tetrafluoride and the like can be mentioned.

Examples of the compound having a triazine group and / or a derivative thereof which can be blended in the present invention include melamine, melamine cyanurate, melamine phosphate, guanidine sulfamate and the like.

Examples of the inorganic phosphorus compound of the phosphorus compound that can be blended in the present invention include a red phosphorus compound and an ammonium polyphosphate. Examples of the red phosphorus compound include red phosphorus coated with a resin, a composite compound with aluminum, and the like. Examples of the organic phosphorus compound include a phosphoric ester and a melamine phosphate. Phosphates include phosphates, phosphonates, phosphinates such as trimethyl phosphate, 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, 1,3- [bis (2,6-dimethylphenoxy) of aromatic condensed phosphate
Phosphenyloxy] benzene, 1,4- [bis (2,
6-dimethylphenoxy) phosphenyloxy] benzene and the like are preferable from the viewpoint of hydrolysis resistance, heat stability, and flame retardancy.

These additives can be compounded using a kneader such as a heating roll, an extruder, or a Banbury mixer. Further, it can be added and mixed into the oligomer before the transesterification reaction or before the polycondensation reaction when producing the thermoplastic polyester elastomer resin composition.

The polyester elastomer of the present invention is molded from a melt by a usual molding technique, for example, injection molding, flat film extrusion, extrusion blow molding, and coextrusion.

[0057]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but is not limited thereto. In these examples, each measurement was performed according to the following method. (1) Reduced viscosity: 25 g of a mixed solvent of 0.05 g of polymer (phenol / tetrachloroethane = 60/40)
And measured at 30 ° C. using an Ostwald viscometer. (2) Melting point: Measured at a rate of 20 ° C./min from room temperature using DSC. (3) Flexural modulus: Measured based on ASTM D790. (4) Heat aging resistance: 150 using a gear hot air dryer.
At 125 ° C. for 125 days, and elongation retention at break
It was measured based on MD638. (5) Water resistance: The elongation retention at break after treatment at 100 ° C. for 2 weeks was measured based on ASTM D638. (6) Low temperature characteristics: using a tensile forced vibration type dynamic viscoelasticity measuring device (Rheogel-E4000 manufactured by UBM)
Evaluation was made based on the temperature at which the loss tangent (tan δ) measured at 11 Hz while increasing the temperature at a rate of 2 ° C./min from −100 ° C. showed the maximum.

Polycarbonate diol A: Polycarbonate diol N980 manufactured by Nippon Polyurethane Co., Ltd.
Polycarbonate diol B: polycarbonate diol PNOC-2000 manufactured by Kuraray Co., Ltd., molecular weight 2000, melting point 62 ° C.
0, melting point 50 ° C

Reference Example 1 Preparation of polycarbonate diol C (hydrogenated dimer diol-modified polycarbonate) Polycarbonate diol (C manufactured by Daicel Chemical Industries, Ltd.)
D220PL, molecular weight 2000) 144 g, high-purity hydrogenated dimer diol (PELPOL manufactured by Toagosei Co., Ltd.)
HP1000) 59.1 g, diphenyl carbonate (manufactured by Nacalai Tesque, Inc.) 21.4 g, and tetra-n-butyl titanate 0.01 g were charged into a 1 L glass flask,
The mixture was stirred and heated under a nitrogen stream. Decompression was started when the system reached 225 ° C, and 245 ° C and 1 mm in 30 minutes.
The temperature was raised to Hg and the pressure was reduced. After the system was returned to normal pressure with nitrogen, 0.01 g of trimethylphosphoric acid was added and stirred for 10 minutes to obtain a viscous polymer. Molecular weight about 230
It was 0.

Example 1 100 parts by weight of polybutylene terephthalate having a number average molecular weight of 17,500 was polymerized in a reaction vessel by a conventional method. Next, 67 parts by weight of polycarbonate diol C was added, and the mixture was stirred at 225 to 245 ° C. for 20 minutes. Then, 1 part by weight of TMPA (trimethyl phosphoric acid) was added to the reaction melt, and the mixture was further stirred for 10 minutes. Thereafter, 8.4 parts by weight of dicyclohexylmethane diisocyanate were added and stirring was continued until the torque on the stirrer reached a maximum. After degassing the reaction vessel, the contents were taken out and cooled to obtain a polymer. Each physical property of the obtained polymer was measured, and the results are shown in Table 1.

Example 2 100 parts by weight of polybutylene naphthalate obtained by copolymerizing hydrogenated dimer diol with 5 mol% of all glycol components was polymerized in a reaction vessel by a conventional method. Next, 67 parts by weight of polycarbonate diol B was added, and the mixture was heated at 245 to 255 ° C for 2 hours.
After stirring for 0 minutes, 1 part by weight of TMPA (trimethyl phosphoric acid) was added to the reaction melt, and the mixture was further stirred for 10 minutes.
Thereafter, 8.4 parts by weight of 4,4'-diphenylmethane diisocyanate were added and stirring was continued until the torque on the stirring device reached a maximum. After degassing the reaction vessel, the contents were taken out and cooled to obtain a polymer. Each physical property of the obtained polymer was measured, and the results are shown in Table 1.

Example 3 100 parts by weight of polybutylene terephthalate obtained by copolymerizing hydrogenated dimer diol with 5 mol% of all glycol components was
Polymerization was carried out in a reaction vessel by a conventional method. Then, 67 parts by weight of polycarbonate diol C was added,
After stirring for 20 minutes, 1 part by weight of phosphorous acid was added to the reaction melt, and the mixture was further stirred for 10 minutes. Thereafter, 8.4 parts by weight of dicyclohexylmethane diisocyanate were added and stirring was continued until the torque on the stirrer reached a maximum. After degassing the reaction vessel, the contents were taken out and cooled to obtain a polymer. Each physical property of the obtained polymer was measured, and the results are shown in Table 1.

Example 4 To 100 parts by weight of PBT polymerized by a conventional method, 53.8 parts by weight of polycarbonate diol C was added, and
Stirred at 45 ° C. for 20 minutes. 22 parts by weight of diphenyl carbonate was added, and dephenol was removed under reduced pressure. When the distillation of phenol was completed and the stirring torque reached the maximum, the polymer was taken out. Each physical property of the obtained polymer was measured, and the results are shown in Table 1.

Comparative Example 1 A polymer was obtained in the same manner as in Example 1 except that the polycarbonate diol C was changed to the polycarbonate diol A. The physical properties of the obtained polymer were measured, and the results are shown in Table 1. It can be seen that the obtained polymer has a high temperature at which tan δ has the maximum value and is inferior in low-temperature characteristics.

Comparative Example 2 A polymer was obtained in the same manner as in Example 1 except that 4,4′-diphenylmethane diisocyanate as a chain extender was not used. The physical properties of the obtained polymer were measured, and the results are shown in Table 1. The obtained polymer had a reduced reduced viscosity of about 1 and was therefore inferior in heat aging resistance (retention rate <50%). I understand.

Comparative Example 3 The properties of perprene P90B (polyester elastomer composed of polybutylene terephthalate and polyoxytetramethylene glycol) manufactured by Toyobo Co., Ltd. were measured, and the results are shown in Table 1. It is clear that it is inferior.

Comparative Example 4 For perprene S2002 (polyester elastomer composed of polybutylene terephthalate and polycaprolactone) manufactured by Toyobo Co., Ltd., various physical properties were measured, and the results are shown in Table 1. The water resistance is clearly poor. It is.

[0068]

[Table 1]

[0069]

As is clear from Table 1, the thermoplastic polyester elastomer of the present invention has an elongation retention of 50% or more after a heat aging test and an elongation retention of 50% or more after a water resistance test. It is. Furthermore, it is clear that the low temperature characteristic is excellent because the temperature at which the loss tangent has the maximum value is low. Therefore, it is understood that the thermoplastic polyester elastomer of the present invention is excellent in heat aging resistance, water resistance and low-temperature properties. That is, the present invention provides heat aging resistance,
Since it has excellent water resistance and low-temperature properties, it can be used for various molding materials such as fibers, films and sheets.
It is also suitable for molding materials such as elastic yarns and boots, gears, tubes, and packings.For example, applications requiring heat aging resistance, water resistance, and low-temperature properties of automobiles and home appliances,
Specifically, it is useful for joint boots, wire covering materials, and the like, and greatly contributes to the industry.

Continued on the front page F-term (reference) 4J029 AA08 AB01 AC03 AD10 AE01 AE02 AE03 BA02 BA03 BA04 BA05 BA07 BA08 BA10 BD05C BD07A BF25 CA02 CA04 CA05 CA06 CB05A CB06A CB10A CC06A CD03 CD04 CH07 EG09 FC03 FC01 FC03 FC03 FC01 HC05A JA253 JB131 JB171 JC142 JC152 JC242 JC302 JC483 JC583 JC593 JC751 JE152 JF041 JF321 JF371 KB02 KE02 4J034 BA03 DA01 DB03 DB07 DF03 DF16 DF20 DF21 DF22 DQ28 HA01 HA07 HA18 HCB HC HC HC HC HC HC HC HC HC HC HC HC HC HC HC HC HC HC HC HC HC HC HC HC HC HC RA12 RA14

Claims (12)

[Claims] The flexural modulus is less than 1000 MPa, the elongation retention at break after heat aging test is more than 50%, the elongation retention at break after water aging test is more than 50%, and the loss tangent tan δ is maximum. A thermoplastic polyester elastomer, wherein the temperature showing the value is <-15 ° C.
(Here, the flexural modulus is a value measured based on ASTM D790, and the elongation at break is a value measured based on ASTM D638. The heat aging test is 150 ° C. using a gear hot air dryer. , 125 days, and the water aging test is equivalent to 2 weeks of treatment in boiling water at 100 ° C. Further, the loss tangent tan δ is determined by a tensile forced vibration type dynamic viscoelasticity measuring apparatus (for example, UB).
M company Rheogel-E4000) and -100
The measurement shall be performed at 11 Hz while the temperature is raised at a rate of 2 ° C./min from the temperature. ) 2. The polyester elastomer according to claim 1, wherein the temperature at which the loss tangent tan δ has a maximum value is <−20 ° C. 3. A hard segment mainly composed of an aromatic dicarboxylic acid and an aliphatic or alicyclic diol, and a soft segment mainly composed of an aliphatic polycarbonate, wherein the segments are substantially bound by a chain extender. The polyester elastomer according to claim 1 or 2, wherein: 4. An aliphatic polycarbonate essentially containing a hydrogenated dimer diol as a soft segment, wherein a copolymerization amount of the hydrogenated dimer diol is 30 mol% or less of all glycol components of the segment. The polyester elastomer according to any one of claims 1 to 3, wherein 5. A polyester in which a hard segment contains a hydrogenated dimer diol, wherein the copolymerization amount of the hydrogenated dimer diol is not more than 15 mol% of all glycol components in the segment. The polyester elastomer according to any one of claims 1 to 3, wherein 6. A polyester in which a hard segment contains a hydrogenated dimer diol, wherein the copolymerization amount of the hydrogenated dimer diol is 10 mol% or less of all glycol components in the segment. The segment is an aliphatic polycarbonate essentially containing a hydrogenated dimer diol, and the copolymerization amount of the hydrogenated dimer diol is 30% of the total glycol component in the segment.
The polyester elastomer according to any one of claims 1 to 3, wherein the amount is at most mol%. 7. The aromatic dicarboxylic acid constituting the hard segment is mainly terephthalic acid or 2,6-
The polyester elastomer according to any one of claims 1 to 6, which is naphthalenedicarboxylic acid. 8. The method according to claim 1, wherein the hard segment is any one of polybutylene terephthalate, polybutylene naphthalate, polycyclohexylene dimethylene terephthalate and a hydrogenated dimer diol copolymer thereof. C. The polyester elastomer described in C. 9. The polyester elastomer according to claim 1, wherein each segment is linked by an ester bond and / or a bond derived from a chain extender. 10. The polyester elastomer according to claim 1, wherein the chain extender is an isocyanate compound or a carbodiimidated compound thereof. 11. The polyester elastomer according to claim 1, wherein the chain extender is a phenyl carbonate compound or a phenyl ester compound. 12. The polyester elastomer according to claim 1, wherein the chain extender is an oxazoline compound.