JP6273882B2 - Polyamide elastomer and molded article produced using the same - Google Patents

Description

  The present invention relates to a polyamide elastomer and a molded article produced using the polyamide elastomer.

  Polyamide elastomers are generally used for aliphatic polyamides in hard segments and aliphatic polyethers in soft segments, and have high elasticity, transparency, stretch recovery, and melt moldability. It is used for various purposes.

JP 2000-7780 A Japanese Patent No. 3199797 JP 2004-161964 A US4119615

  Polyether polyamide elastomers have high elasticity, transparency, stretch recovery, and melt moldability, so they may be used for automobile parts, electronic device peripheral parts, battery materials, packing, sealing materials, etc. Low and needs improvement.

  In order to obtain a highly heat-resistant polyether polyamide elastomer, it is effective to use a high melting point polyamide for the hard segment, but since the decomposition temperature of the soft segment polyether is low, using a high melting point polyamide, The polyether of the soft segment decomposes and it is difficult to obtain a highly heat-resistant polyether polyamide elastomer. Patent Documents 1 to 3 disclose polyether polyamide elastomers having various polyamide units in the hard segment, A polyether polyamide elastomer having a melting point of 200 ° C. or higher and having a high elongation recovery rate and excellent elastomer properties, that is, a polyether polyamide elastomer having both heat resistance and elastomer properties is not disclosed.

  On the other hand, in Patent Document 4, an aliphatic polyamide resin using a oxalic acid compound as a dicarboxylic acid component called a polyoxamide resin is used for the hard segment, and a polyether having a melting point of 206 ° C. at the maximum using polypropylene oxide for the polyether unit of the soft segment. Polyamide elastomers are disclosed, but elastomeric properties such as elongation recovery rate are not sufficient.

  An object of the present invention is to provide a polyether polyamide elastomer having a high elongation recovery rate and a high melting point of 200 ° C. or more, which is excellent in elastomer properties and heat resistance at the same time.

  The inventors of the present invention provide a polyamide elastomer containing a polyamide unit (A) and a polyetherdiamine unit (B), wherein the polyamide unit (A) is a unit represented by the general formula (1) and the general formula (2). It has been found that a polyamide elastomer containing a unit represented by general formula (3) includes a unit represented by general formula (3) solves the above problems.

（ここで、Ｒ１は炭素数１〜２０の炭化水素の分子鎖又は炭素原子１〜２０を有するアルキレン基を示す。）

(Here, R1 represents a hydrocarbon molecular chain having 1 to 20 carbon atoms or an alkylene group having 1 to 20 carbon atoms.)

（ここで、ｘ及びｚは１〜２０であり、ｙは４〜５０を示す。）

(Here, x and z are 1-20, and y is 4-50.)

The polyamide elastomer of the present invention has a high elongation recovery rate and a high melting point of 200 ° C. or more, and is excellent in both elastomeric properties and heat resistance. Therefore, it can be used in various applications such as automobile parts, electronic device peripheral parts, battery materials, packing, sealing materials, etc. that require high heat resistance and elastomeric properties at the same time.
Moreover, since the polyamide elastomer of the present invention is excellent in high elasticity, transparency and melt moldability, in addition to the use of the conventional polyamide elastomer and the above-mentioned use, elastomer properties, heat resistance, high elasticity, transparency, melting It can also be used for applications that require formability at the same time.

  The polyamide elastomer of the present invention includes a polyamide unit (A) and a polyetherdiamine unit (B), and the polyamide unit (A) is a unit represented by the general formula (1) and a unit represented by the general formula (2). The polyether diamine unit (B) contains a unit represented by the general formula (3).

[Polyamide unit (A)]
The polyamide unit (A) includes a unit represented by the general formula (1) and a unit represented by the general formula (2).

The ratio of the polyamide unit (A) in the total amount of the polyamide elastomer is a function that does not lower the crystallinity of the polyamide component that affects mechanical properties such as strength and elastic modulus, and functions as an elastomer such as rubber elasticity and flexibility. From the viewpoint of performance, it is preferably 10 to 95% by weight, more preferably 20 to 95% by weight, still more preferably 25 to 85% by weight, and particularly preferably 30 to 80% by weight.
Examples of the compound providing the unit represented by the general formula (1) include oxalic acid or a salt thereof, oxalic acid monoester or a salt thereof, or oxalic acid diester. (These compounds may hereinafter be referred to as oxalic acid compounds.)
The oxalic acid compound can be used as a raw material for the polyamide elastomer of the present invention, and oxalic acid diester is preferably used from the viewpoint of suppressing side reactions in the polycondensation reaction.
As the oxalic acid diester, an oxalic acid diester having an alkoxy group having 1 to 6 carbon atoms, an oxalic acid diester having a cycloalkoxy group having 2 to 6 carbon atoms, and / or an oxalic acid diaryl ester are preferable.
Examples of the oxalic acid diester having an alkoxy group having 1 to 6 carbon atoms include dimethyl oxalate, diethyl oxalate, di (n or iso) propyl oxalate, di (n, iso, sec or tert) butyl oxalate, and dihexyl oxalate. It is done.
Examples of the oxalic acid diester having a cycloalkoxy group having 2 to 6 carbon atoms include dicyclohexyl oxalate.
Examples of the succinic acid diaryl ester include diphenyl succinate.
Among these, dibutyl oxalate and / or diphenyl oxalate are preferable, and dibutyl oxalate is more preferable.
The proportion of the unit represented by the general formula (1) in the total amount of the polyamide unit (A) is preferably 18 to 50% by weight, more preferably 20 to 45% by weight, and still more preferably from the viewpoint of heat resistance. 22 to 40% by weight.

The compound that provides the unit represented by the general formula (2) contained in the polyamide unit (A) may be any compound that can form an amide bond with an oxalic acid compound. Examples include diamines.
Aliphatic diamines include ethylene diamine, propylene diamine, 1,4-butane diamine, 1,5-pentane diamine, 2-methyl-1,5-pentane diamine, 1,6-hexane diamine, 1,9-nonane diamine, 2 -Methyl-1,8-octanediamine, 1,8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14- Tetradecanediamine, 1,15-pentadecanediamine, 1,16-hexadecanediamine, 1,18-octadecanediamine, 3-methyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl-1,9-no Njiamin, and the like.
Examples of the alicyclic diamine include cyclohexane diamine, methyl cyclohexane diamine, and isophorone diamine.
As aromatic diamines, p-phenylenediamine, m-phenylenediamine, p-xylenediamine, m-xylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylether Etc.
One or two or more of these diamines can be used.

Among these diamines, 1,5-pentanediamine, 2-methyl-1,5-pentanediamine, 1,6-hexanediamine, 1,9-nonanediamine, 2 which can be polymerized below the decomposition temperature of the polyamide elastomer of the present invention, 2 One or more diamines selected from the group consisting of -methyl-1,8-octanediamine, 1,8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine and 1,12-dodecanediamine are preferred. More preferably one or more diamines selected from the group consisting of 2-methyl-1,5-pentanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine and 1,12-dodecanediamine, 1,12-dodecanediamine is more preferred.
The proportion of the unit represented by the general formula (2) in the total amount of the polyamide unit (A) is preferably 50 to 90% by weight, more preferably 55 to 85% by weight, and still more preferably from the viewpoint of heat resistance. 60 to 80% by weight.

The polyamide unit (A) of the present invention may contain units other than the unit represented by the general formula (1) and the unit represented by the general formula (2) as long as the effects of the present invention are not impaired. Examples of the compound providing such a unit include linear aliphatic dicarboxylic acid, dimer acid, alicyclic dicarboxylic acid, and aromatic dicarboxylic acid.
Examples of linear aliphatic dicarboxylic acids include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3- Examples include diethyl succinic acid, azelaic acid, sebacic acid, dodecanedioic acid, and suberic acid.
Dimer acid refers to a dimerized aliphatic dicarboxylic acid obtained by dimerizing an unsaturated fatty acid obtained by fractional distillation of triglycerides.
Hydrogenated dimer acid refers to a hydrogenated product of dimer acid.
As the dimer acid and hydrogenated dimer acid, “Prepol 1004”, “Prepol 1006”, “Prepol 1009”, “Prepol 1013” and the like can be used.
Examples of the alicyclic dicarboxylic acid include 1,3-cyclopentane dicarboxylic acid and 1,4-cyclohexane dicarboxylic acid.
Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3 -Phenylenedioxydiacetic acid, dibenzoic acid, 4,4'-oxydibenzoic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, etc. Can be mentioned. One or more of these compounds can be added and added during the polycondensation reaction. Furthermore, in addition to the above compounds, polycarboxylic acids such as trimellitic acid, trimesic acid and pyromellitic acid can be represented by the general formula (1) contained in the polyamide unit (A) within the range in which melt molding is possible. It can also be used as a compound (raw material) that provides a unit other than the unit represented by formula (2) and the unit represented by formula (2).

[Polyetherdiamine unit (B)]
The polyether diamine unit (B) includes a unit represented by the general formula (3).
As a compound providing the unit represented by the general formula (3), polypropylene glycol is obtained by adding propylene oxide to both ends of poly (oxytetramethylene) glycol and the like, and then ammonia or the like is added to the end of the polypropylene glycol. Polyether diamine etc. manufactured by making it react can be used.

  In the unit represented by the general formula (3), x and z are 1 to 20, preferably 1 to 18, more preferably 1 to 16, still more preferably 1 to 14, particularly preferably 1 to 12, y is 4 to 50, preferably 5 to 45, more preferably 6 to 40, still more preferably 7 to 35, and particularly preferably 8 to 30.

  In the unit represented by the general formula (3), when x and z are smaller than the above range, it is not preferable because the transparency of the obtained elastomer is particularly poor, and when y is smaller than the above range. The rubber elasticity is low, which is not preferable. Moreover, when x and z are larger than the above range and when y is larger than the above range, the compatibility with the polyamide component is lowered and it is difficult to obtain a tough elastomer.

  As a commercial product of a compound that provides the unit represented by the general formula (3), XTJ-533 manufactured by HUNTSMAN (USA) (in formula (1), x is approximately 12, y is approximately 11, and z is approximately 11), XTJ -536 (in formula (1), x is about 8.5, y is about 17, and z is about 7.5), XTJ-542 (in formula (1), x is about 3, y is about 9, z Is approximately 2), and XTJ-559 (in formula (3), x is approximately 3, y is approximately 14, z is approximately 2), and the like can be used.

  Further, examples of the compound that provides the unit represented by the general formula (3) include XYX type triblock polyether diamine. For example, XYX-1 (in the formula (1), x is approximately 3, y is approximately 14, z is approximately 2), XYX-2 (in formula (1), x is approximately 5, y is approximately 14, z is approximately 2), and XYX-3 (in formula (1), x is approximately 3, y is It is also possible to use about 19, z is about 2), or the like.

The proportion of the polyetherdiamine unit (B) in the total amount of the polyamide elastomer is preferably 2 to 87 wt. From the viewpoint of expressing characteristics as an elastomer such as bending fatigue and excellent mechanical strength characteristic of polyamide. %, Particularly preferably 7 to 78% by weight.
The proportion of the unit represented by the general formula (1) contained in the total amount of the polyetherdiamine unit (B) is preferably 50 to 100% by weight, more preferably 60 to 100% by weight from the viewpoint of developing the properties as an elastomer. %, More preferably 70 to 100% by weight.

[Polyamide elastomer]
From the viewpoint of sufficiently increasing the molecular weight of the polyamide elastomer of the present invention, it is preferable that the number of acid terminal groups and the number of amino terminal groups of the compound (raw material) to be used be the same as the whole compound. That is, the total number of moles of amino end groups of the compound providing the polyamide unit (A) and the compound providing the polyetherdiamine unit (B) is the number of moles of acid end groups of the compound providing the polyamide unit (A) It is preferable to be the same.

(1) Properties of Polyamide Elastomer The polyamide elastomer of the present invention preferably has a relative viscosity (ηr) measured at 25 ° C. using a 1.0 g / dl trifluoroacetic acid solution from the viewpoint of the development of elastomer properties and moldability. Is 1.0 to 4.0, more preferably 1.2 to 3.0.

  From the viewpoint of heat resistance, the polyamide elastomer of the present invention preferably has a melting point (Tm) of 180 ° C. or higher, more preferably 200 ° C. or higher.

  The polyamide elastomer of the present invention has an elastic modulus of preferably 900 MPa or less, more preferably 800 MPa or less, from the viewpoint of developing elastomeric properties.

  The polyamide elastomer of the present invention has an elongation recovery rate of preferably 45% or more, more preferably 55% or more, measured from a 20% elongation condition from the viewpoint of developing elastomeric properties.

[Production method of polyamide elastomer]
As a method for producing the polyamide elastomer of the present invention, any known method can be used. From the viewpoint of high molecular weight and productivity, the general formulas (1), (2), It can be obtained by subjecting the compound providing the unit represented by (3) to a polycondensation reaction batchwise or continuously.
Specifically, it can be obtained by (i) a two-stage polymerization method, (ii) a one-stage polymerization method, or (iii) a prepolymer method comprising a pre-polycondensation step and a post-polycondensation step.

(I-1) Two-stage polymerization method: pre-polycondensation step First, the inside of the reactor is purged with nitrogen, and then a compound that provides units represented by the general formulas (1), (2), and (3) is mixed. When mixing, a solvent in which the above three components are both soluble may be used. Solvents in which the three components are both soluble include aromatic hydrocarbon solvents such as toluene and xylene, halogenated hydrocarbon solvents such as trichlorobenzene, phenol solvents such as phenol and cresol, 2,2,2-tri A halogenated alcohol solvent such as fluoroethanol can be exemplified, and a preferable solvent is toluene. The temperature in the reactor charged in this way is increased under normal pressure while stirring and / or nitrogen bubbling. The reaction temperature is preferably controlled so that the final temperature reaches 80 to 150 ° C., preferably 100 to 140 ° C. The reaction time at the final temperature reached is 3-6 hours.

(I-2) Two-stage polymerization method: post-polycondensation step In order to further increase the molecular weight, the polymer produced in the pre-polycondensation step is gradually heated in the reactor under normal pressure. In the temperature rising process, the temperature finally reaches the final polycondensation step, that is, preferably 80 to 150 ° C., and finally reaches a temperature range of preferably 220 ° C. or higher and 280 ° C. or lower, more preferably 230 ° C. or higher and 270 ° C. or lower. It is preferable to carry out the reaction preferably for 1 to 8 hours, more preferably 2 to 6 hours including the temperature rising time. Furthermore, in the post-polymerization step, polymerization can be performed under reduced pressure as necessary. The preferable final pressure in the case of carrying out the vacuum polymerization is less than 0.1 MPaG to 13.3 PaG.

(Ii) One-stage polymerization method First, a compound that provides the units represented by the general formulas (2) and (3) is placed in a reaction vessel and purged with nitrogen, and then the temperature is raised to the primary reaction temperature under normal pressure or pressurized conditions. The primary reaction temperature is preferably 100 ° C. to 200 ° C., more preferably 120 ° C. to 180 ° C., from the viewpoint of preventing thermal decomposition of the compound that provides the unit represented by the general formula (1). Thereafter, at the primary reaction temperature, a compound that provides a unit represented by the general formula (1) is injected into the reaction vessel under normal pressure or pressurized conditions, and a polycondensation reaction is started.

  After starting the polycondensation reaction, the temperature is raised to the secondary reaction temperature while maintaining normal pressure or pressurized conditions. The secondary reaction temperature is preferably 160 ° C. or higher and 270 ° C. or lower, more preferably 180 ° C. or higher and 260 ° C. or lower, from the viewpoint of uniformly melting and kneading the product. The pressure in the reaction vessel until reaching the secondary reaction temperature is adjusted to 0.1 to 1 MPaG. After reaching the secondary reaction temperature, the pressure is released and the temperature is raised to the tertiary reaction temperature. The tertiary reaction temperature is preferably 200 ° C. or higher and 280 ° C. or lower, more preferably 220 ° C. or higher and 270 ° C. or lower, from the viewpoint of preventing thermal decomposition of the compound providing the unit represented by the general formula (3). After reaching the tertiary reaction temperature, the polycondensation reaction is continued for 0.5 to 30 hours under a normal pressure nitrogen stream or reduced pressure as necessary. A preferable final pressure in the case of carrying out the vacuum polymerization is 0.1 MPaG to 13.3 PaG.

(Iii) Prepolymer method The compound which provides the unit represented by General formula (1), (2) by the procedure of said (i-1) two-stage polymerization method: a pre-polycondensation process or (ii) one-stage polymerization method. React to obtain a prepolymer. Next, a compound providing a unit represented by the general formula (3) and a prepolymer produced by the procedure of the above (i-1) two-stage polymerization method: post-polycondensation step or (ii-1) one-stage polymerization method React.

  In the production of the polyamide elastomer of the present invention, the method of charging the raw material (compound) is not particularly limited, but from the viewpoint of not reducing the crystallinity of the polyamide component and the function and performance of the elastomer, from the raw material charging ratio The calculated polyamide unit (A) is preferably 10 to 95% by weight, more preferably 30 to 80% by weight, based on the total amount of the polyamide elastomer, and the polyether diamine unit (B) calculated from the raw material charge ratio is The total amount of polyamide elastomer is preferably 2 to 87% by weight, more preferably 7 to 78% by weight. Further, the total number of moles of amino terminal groups in the total amount of the compound that provides the polyamide unit (A) and the polyetherdiamine unit (B) is the same as the total number of moles of the acid end groups of the compound that provides the polyamide unit (A). It is desirable to do.

  The production of the polyamide elastomer of the present invention can be carried out batchwise or continuously. A batch reactor, a single- or multi-tank continuous reactor, a tubular continuous reactor, etc. can be used alone or as appropriate. They can be used in combination.

  In the production of the polyamide elastomer of the present invention, a monoamine such as laurylamine, stearylamine, hexamethylenediamine, and metaxylylenediamine, or a diamine, acetic acid, Monocarboxylic acids such as benzoic acid, stearic acid, adipic acid, sebacic acid and dodecanedioic acid, or dicarboxylic acids can be added. The amount used is appropriately added so that the relative viscosity (ηr) of the finally obtained elastomer is in the range of 1.0 to 4.0 (1.0 g / dl trifluoroacetic acid solution, 25 ° C.). Is preferred.

  In the production of the polyamide elastomer of the present invention, the addition amount of the monoamine and diamine, monocarboxylic acid, dicarboxylic acid and the like is preferably within a range in which the properties of the obtained polyamide elastomer are not inhibited.

  In the production of the polyamide elastomer of the present invention, phosphoric acid, pyrophosphoric acid, polyphosphoric acid, etc. are used as a catalyst as necessary, and phosphorous acid, hypophosphorous acid, and these are aimed at the effects of both the catalyst and the heat-resistant agent. Inorganic phosphorus compounds such as alkali metal salts and alkaline earth metal salts can be added. The addition amount is usually 50 to 3000 ppm with respect to the charged amount.

  The polyamide elastomer of the present invention has a heat resistance agent, an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a lubricant, a slip agent, a crystal nucleating agent, a tackifier, and a sealing property as long as the properties are not hindered. An improving agent, an antifogging agent, a release agent, a plasticizer, a pigment, a dye, a fragrance, a flame retardant, a reinforcing material, and the like can be added.

[Molding and molded products]
With the polyamide elastomer of the present invention, a molded product can be obtained by a known molding method such as injection molding, extrusion molding, blow molding, vacuum molding or pressure molding. Each molded product can be used in various applications such as automobile parts, electronic device peripheral parts, battery materials, packings, sealing materials, etc. that require heat resistance.

  The polyamide elastomer of the present invention has good compatibility with thermoplastic resins such as polyamide, polyvinyl chloride, thermoplastic polyurethane and ABS resin excluding the polyamide elastomer of the present invention, and can be used by blending with these thermoplastic resins. Is possible.

[Physical property measurement, molding, evaluation method]
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, the relative viscosity, melting | fusing point, elasticity modulus, the expansion | restoration recovery rate, and the saturated water absorption rate in an Example and evaluation of chemical resistance were performed with the following method.

(1) Relative viscosity (ηr)
The relative viscosity was measured at 25 ° C. with an Ostwald viscometer using a trifluoroacetic acid solution having a polyamide elastomer concentration of 1.0 g / dl.

(2) Melting point (Tm)
The melting point was measured under a nitrogen atmosphere using a PYRIS Diamond DSC manufactured by PerkinELmer.
The obtained polyamide elastomer is heated from 30 ° C. to 280 ° C. at a rate of 10 ° C./min (referred to as a temperature rising first run), held at 280 ° C. for 3 minutes, and then up to 30 ° C. at a rate of 10 ° C./min. The temperature was lowered (referred to as a first temperature-decreasing run), and then the temperature was raised to 280 ° C. at a rate of 10 ° C./min (referred to as a temperature-rising second run). The endothermic peak temperature of the elevated temperature second run was defined as the melting point (Tm).

(3) Film formation Polyamide elastomer film formation was performed by the following method using Toho Machinery's vacuum press TMB-10.
The obtained polyamide elastomer was heated and melted at 240 to 270 ° C. for 3 minutes in a reduced pressure atmosphere of 500 to 700 PaG, then pressed at 10 MPaG for 1 minute, and then the reduced pressure atmosphere was returned to normal pressure. And cooled for 3 minutes to obtain a film having a thickness of 0.25 mm and 1 mm.

(4) Elastic modulus From the film of 0.25 mm thickness obtained in the above (3), a JIS tensile No. 8 dumbbell was punched out to produce a dumbbell specimen. The dumbbell test piece was subjected to a tensile test using TENSILON RTA-500 manufactured by ORIENTEC. In a 23 ° C. environment, a tensile test was performed under the conditions of a distance between chucks of 30 mm and a tensile speed of 30 mm / min, and the elastic modulus was calculated from the slope of the stress-strain line between elongations of 0.5% and 2%.

(5) Extension recovery rate Dumbbell test pieces were prepared in the same manner as in (4) above, and the extension recovery rate was measured with a tester of TENSILON RTA-500 manufactured by ORIENTEC. Residual strain A when the stress becomes zero when the distance between chucks is 30 mm and the tensile speed is 100 mm / min, and the tension is returned to the original speed at the same speed when stretched by 3.2 mm in a 23 ° C. environment. (Mm) was determined. The elongation recovery rate was calculated by substituting the obtained residual strain A into the following formula (1).

(6) Durability test for each liquid The 1 mm-thick film formed in (3) above was cut into a square with a side of 40 mm, and the cut-out film was each liquid at 23 ° C. (ion-exchanged water, methanol, 10% by weight). (Nitric acid, 10% by weight hydrochloric acid), the film was taken out every predetermined time, and the weight of the film was measured. When the rate of increase in the film weight lasts three times in the range of 0.2%, it is judged that the absorption of the liquid into the polyamide resin film has reached saturation, and when the film reaches the weight and saturation before immersion. The weight change rate (%) was calculated from the weight of the film.

(7) Preparation of Test Specimens for Adhesive Strength Test Adhesive strength test between the polyamide elastomer of the present invention, polyether-based thermoplastic polyurethane (ELASTOLLAN ET890 manufactured by BASF) and polyester-based thermoplastic polyurethane (ELASTOLLAN ET690 manufactured by BASF) is performed. Therefore, a test piece was prepared by the following method.
The temperature of the upper die of the vacuum press TMB-10 manufactured by Toho Machinery Co., Ltd. is stacked with the 1 mm thick polyamide elastomer film formed in (3) above and the 1 mm thick polyurethane film on the upper side. Was set to 200 ° C., the temperature of the lower mold was set to 260 ° C., and welding press was performed at 20 MPa for 1 minute.
The film subjected to welding press was cut with a cutter knife to obtain a test piece for an adhesive strength test having a width of 10 mm and a length of 15 cm.

(8) Adhesive strength test The test piece of (7) above was subjected to a T-type peel test under the condition of a tensile speed of 30 mm / min in a 23 ° C environment using a TENSILON RTA-500 tester manufactured by ORIENTEC Co., Ltd. The strength (N / mm) was measured.

[Example 1]
The inside of a 2 L separable flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, and raw material inlet was replaced with nitrogen gas, 1150 ml of dehydrated toluene, 156 g of 1,12-dodecanediamine (0.78 Mol), 91 g (0.087 mol) of XYX type triblock polyether diamine (XTJ-542 manufactured by HUNTSMAN) was charged. After this separable flask was placed in an oil bath and heated to 50 ° C., 175 g (0.87 mol) of dibutyl oxalate was charged. Next, the temperature of the oil bath was raised to 130 ° C., and the reaction was carried out for 5 hours under reflux. Note that all operations from preparation of raw materials to completion of the reaction were performed under a nitrogen stream of 50 ml / min.

  10 g of the polymer obtained by the above operation and 0.02 g of sodium hypophosphite monohydrate were charged into a glass reaction tube having a diameter of about 35 mmφ equipped with a stirrer, an air cooling tube, and a nitrogen introduction tube. The operation of maintaining the pressure under a pressure of 3 PaG or less and then introducing nitrogen gas to normal pressure was repeated five times, and then transferred to a salt bath maintained at 250 ° C. under a nitrogen stream of 50 ml / min and reacted for 4 hours. Subsequently, after introducing nitrogen gas to normal pressure, the polyamide elastomer was taken out from the salt bath and cooled to room temperature under a nitrogen stream of 50 ml / min.

[Example 2]
5L equipped with a stirrer, thermometer, torque meter, pressure gauge, nitrogen gas inlet, pressure outlet, polymer outlet, and raw material inlet with a raw material feed pump directly connected by SUS316 piping of 1/8 inch diameter In a pressure vessel, 347 g (1.7 mol) of 1,12-dodecanediamine, 457 g (0.43 mol) of XYX type triblock polyether diamine (XTJ-542 manufactured by HUNTSMAN), sodium hypophosphite monohydrate 2.50 g of the product was charged and the inside of the pressure vessel was pressurized to 3.0 MPaG with nitrogen gas, and then the nitrogen gas was released to normal pressure to perform nitrogen substitution, and the system was heated under sealed pressure. After the primary reaction temperature (150 ° C.), 438 g (2.2 mol) of dibutyl oxalate was injected into the reaction vessel at a flow rate of 65 ml / min by a raw material feed pump. The internal pressure in the pressure vessel immediately after injection of the entire amount increased to 0.65 MPaG by 1-butanol generated by the polycondensation reaction, and the internal temperature increased to 155 ° C.
Distillation of butanol produced immediately after the injection was started, and the temperature was raised to the secondary reaction temperature (230 ° C.) while maintaining the internal pressure at 0.50 MPaG. Immediately after the internal temperature reached 230 ° C., 1-butanol produced by the polycondensation reaction was extracted from the pressure relief port. After releasing the pressure, the temperature was raised under a nitrogen stream of 260 ml / min, the temperature was raised to the tertiary reaction temperature (245 ° C.), and the temperature was maintained at 245 ° C. for 3 hours. Thereafter, the stirring was stopped, the inside of the system was pressurized to 3 MPaG with nitrogen and allowed to stand for 10 minutes, then the pressure was released to an internal pressure of 0.5 MPaG, and the polymer was extracted from the lower part of the pressure vessel. The extracted polymer was immediately cooled with water and recovered.

[Example 3]
Polymerization was conducted in the same manner as in Example 2 using 264 g (1.3 mol) of 1,12-dodecanediamine and 380 g (1.9 mol) of dibutyl oxalate, and the prepolymer was recovered.
Subsequently, the total amount of the obtained prepolymer, 595 g (0.56 mol) of XYX type triblock polyether diamine (XTJ-542, manufactured by HUNTSMAN), and 2.42 g of sodium hypophosphite monohydrate were used in Examples In the same manner as in 2, a 5 L pressure vessel was charged and nitrogen substitution was performed. Next, the temperature in the tank was raised to 200 ° C. under a nitrogen stream, held at 200 ° C. for 1 hour, further heated to 245 ° C. and held at 245 ° C. for 3 hours. Thereafter, the polymer was extracted from the lower part of the pressure vessel, and immediately cooled with water and collected.

[Comparative Example 1]
Polymerization was carried out in the same manner as in Example 2 using 649 g (3.2 mol) of 1,12-dodecanediamine and 655 g (3.2 mol) of dibutyl oxalate.

[Comparative Example 2]
840 g (3.9 mol) of 12-aminododecanoic acid, 45 g (0.31 mol) of adipic acid, 321 g (0.30 mol) of XYX type triblock polyetherdiamine (XTJ-542 manufactured by HUNTSMAN), hypophosphorous acid In the same manner as in Example 2, 2.41 g of sodium acid monohydrate was charged into a 5 L pressure vessel, and nitrogen substitution was performed. Next, the inside of a tank was heated up to 180 degreeC under nitrogen stream, and after hold | maintaining at 180 degreeC for 1 hour, it heated up further to 200 degreeC and hold | maintained at 200 degreeC for 3 hours. Thereafter, the polymer was extracted from the lower part of the pressure vessel, and immediately cooled with water and collected.

[Comparative Example 3]
480 g (2.3 mol) of 12-aminododecanoic acid, 89 g (0.61 mol) of adipic acid, 645 g (0.61 mol) of XYX type triblock polyether diamine (XTJ-542 manufactured by HUNTSMAN), hypophosphorous acid Polymerization was carried out in the same manner as in Comparative Example 2 using 2.43 g of sodium acid monohydrate.

[Comparative Example 4]
378 g (1.8 mol) of 12-aminododecanoic acid, 102 g (0.70 mol) of adipic acid, 737 g (0.70 mol) of XYX type triblock polyetherdiamine (XTJ-542 manufactured by HUNTSMAN), hypophosphorous acid Polymerization was carried out in the same manner as in Comparative Example 2 using 2.43 g of sodium acid monohydrate.

[Comparative Example 5]
Conducted was 1042 g (4.8 mol) of 12-aminododecanoic acid, 38 g (0.26 mol) of adipic acid, 257 g (0.26 mol) of polytetramethylene glycol having a number average molecular weight Mn = 989, and 4.10 g of tetrabutyl titanate. In the same manner as in Example 2, a 5 L pressure vessel was charged and nitrogen substitution was performed. Next, the temperature in the tank was raised to 200 ° C. under a nitrogen stream, held at 200 ° C. for 4 hours, further heated to 240 ° C., depressurized, and held at 240 ° C. and 10 Pa for 3 hours. Thereafter, the pressure was restored, and the polymer was extracted from the lower part of the pressure vessel, and immediately cooled with water and collected.

  Table 1 shows the measurement results of the relative viscosity ηr, melting point Tm, elastic modulus, and elongation recovery rate of the polyamide elastomers obtained in Examples 1 to 3 and Comparative Examples 1 to 4. Each unit of the structural units in Table 1 indicates a value calculated from the raw material charge ratio. In Table 1, HS is an abbreviation for hard segment and refers to a polyamide unit, and SS is an abbreviation for soft segment and refers to a polyether diamine unit (B). HS / SS in Table 1 refers to the weight ratio of the polyamide unit (A) and the polyetherdiamine unit (B). Further, Comparative Example 1 did not dissolve in trifluoroacetic acid, and the relative viscosity was not measurable.

  Table 2 shows the results of durability tests on the liquids of the films obtained from the polyamide elastomers of Examples 1 to 3 and Comparative Examples 2 and 3.

  Table 3 shows the results of the adhesive strength tests of Example 3, Comparative Example 2 and Comparative Example 5. Example 3 and Comparative Example 2 were strongly bonded to the polyether-based thermoplastic polyurethane, and the polyether-based thermoplastic polyurethane film itself broke before the adhesive surface peeled off.

  From Table 1, it can be seen that the polyamide elastomers of the present invention (Examples 1 to 3) have a higher melting point than conventional polyamide elastomers while having a sufficient elongation recovery rate. Table 3 also shows that the polyamide elastomer of the present invention (Example 3) has an adhesive strength equal to or higher than that of a conventional polyamide elastomer with respect to thermoplastic polyurethane.

  Since the polyamide elastomer of the present invention is excellent in high elasticity, transparency, elongation recovery property, and melt moldability, it is not only used for conventional polyamide elastomers, but also automotive parts, electronic device peripheral parts, and batteries that require heat resistance. It can be used for various uses such as materials, packing, and sealing materials.

Claims (6)

A polyamide elastomer comprising a polyamide unit (A) and a polyetherdiamine unit (B),
The polyamide unit (A) includes a unit represented by the general formula (1) and a unit represented by the general formula (2),
A polyamide elastomer in which the polyetherdiamine unit (B) contains a unit represented by the general formula (3).

(Here, R1 represents a hydrocarbon molecular chain having 1 to 20 carbon atoms or an alkylene group having 1 to 20 carbon atoms.)

(Here, x and z are 1-20, and y is 4-50.)   2. The polyamide elastomer according to claim 1, wherein the elongation recovery rate is 55% or more and the melting point is 200 ° C. or more.   The polyamide elastomer according to claim 1 or 2, wherein the unit derived from the diamine component represented by the general formula (2) includes a unit derived from an aliphatic diamine component having 5 to 18 carbon atoms.   The polyamide elastomer according to any one of claims 1 to 3, which has a relative viscosity of 1.2 to 3.0 (1.0 g / dl trifluoroacetic acid solution, 25 ° C).   The molded article manufactured using the polyamide elastomer of any one of Claims 1-4.   The molded object formed by welding the polyamide elastomer in any one of Claims 1-4, and another thermoplastic resin.