JP2016204499A - Polyamide elastomer and molded article manufactured by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyether polyamide elastomer having high elongation recovery rate and high melting point of 200°C or more and excellent in elastomer property and heat resistance at same time.SOLUTION: There is provided a polyamide elastomer containing a polyamide unit (A) and a polyether diamine unit (B), where the polyamide unit (A) contains a structural unit having neighboring two carbonyl groups and at least two kinds of a unit represented by the formula (2) and the polyether diamine unit (B) contains a unit represented by the formula (3). (2), R1 is a molecule chain of C1 to 20 hydrocarbon or a C1 to 20 alkylene group. (3), where x and z are 1 to 20 and y is 4 to 50.SELECTED DRAWING: None

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 present inventors provide a polyamide elastomer comprising a polyamide unit (A) and a polyetherdiamine unit (B), wherein the polyamide unit (A) comprises a unit represented by the general formula (1), and further comprises a general formula It has been found that a polyamide elastomer (X) containing at least two units represented by (2) and having a polyetherdiamine unit (B) containing a unit represented by the 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 (X) of the present invention has a high elongation recovery rate and a high melting point of 200 ° C. or higher, and is excellent in elastomeric properties and heat resistance at the same time. 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.
In addition, since the polyamide elastomer (X) 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, it is elastomeric, heat resistant, high elasticity, transparent. It can also be used for applications that simultaneously require the properties and melt moldability.

  The polyamide elastomer (X) of the present invention includes a polyamide unit (A) and a polyetherdiamine unit (B), the polyamide unit (A) includes a unit represented by the general formula (1), and further includes a general formula The unit represented by (2) includes at least two types, and the polyetherdiamine unit (B) includes 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 includes at least two units represented by the general formula (2).

The proportion of the polyamide unit (A) in the total amount of the polyamide elastomer (X) is not limited to the crystallinity of the polyamide component affecting the mechanical properties such as strength and elastic modulus, and the elastomer such as rubber elasticity and flexibility. From the viewpoint of manifesting the function and performance, the content 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 (X) 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, and may be an aliphatic diamine, alicyclic diamine, aromatic. 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.
At least two of these diamines are used.

Among these diamines, 1,5-pentanediamine, 2-methyl-1,5-pentanediamine, 1,6-hexanediamine, 1,9-, which can be polymerized below the decomposition temperature of the polyamide elastomer (X) of the present invention. One or more selected from the group consisting of nonanediamine, 2-methyl-1,8-octanediamine, 1,8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine, and 1,12-dodecanediamine. Diamine is preferred, and at least one diamine selected from the group consisting of 2-methyl-1,5-pentanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine and 1,12-dodecanediamine is used. More preferred is 1,12-dodecanediamine.
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 (X) is preferably 2 from the viewpoint of expressing the properties as an elastomer such as bending fatigue and the excellent mechanical strength characteristic of the polyamide. It is -87 weight%, Most preferably, it is 7-78 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 (X)]
From the viewpoint of making the polyamide elastomer (X) of the present invention sufficiently high in molecular weight, 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 are 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 (X) The polyamide elastomer (X) of the present invention has a relative viscosity measured at 25 ° C. using a 1.0 g / dl trifluoroacetic acid solution from the viewpoint of the development of elastomer properties and moldability. (Ηr) is preferably 1.0 to 4.0, more preferably 1.2 to 3.0.

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

  The polyamide elastomer (X) 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 (X) of the present invention has an elongation recovery rate measured under a 20% elongation condition, preferably 45% or more, more preferably 55% or more, from the viewpoint of the development of elastomer properties.

[Production Method of Polyamide Elastomer (X)]
As the method for producing the polyamide elastomer (X) of the present invention, any known method can be used. From the viewpoints of increasing the molecular weight and productivity, the general formula (1), ( It can be obtained by subjecting the compound providing the unit represented by 2) or (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 more and 280 ° C. or less, more preferably 230 ° C. or more and 270 ° C. or less 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 (X) of the present invention, there is no particular limitation on the method of charging the raw material (compound), but from the viewpoint of not reducing the crystallinity of the polyamide component and the function and performance as an elastomer, The polyamide unit (A) calculated from the charging ratio is preferably 10 to 95% by weight, more preferably 30 to 80% by weight, based on the total amount of the polyamide elastomer (X). The diamine unit (B) is preferably 2 to 87% by weight, more preferably 7 to 78% by weight, based on the total amount of the polyamide elastomer (X). 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 (X) of the present invention can be carried out either batchwise or continuously, and a batch reactor, a single- or multi-tank continuous reactor, a tubular continuous reactor, etc. can be used alone. Or can be used in appropriate combination.

  In the production of the polyamide elastomer (X) of the present invention, monoamines such as laurylamine, stearylamine, hexamethylenediamine, and metaxylylenediamine, or diamines are used for adjusting the molecular weight and stabilizing the melt viscosity at the time of molding as necessary. Acetic acid, benzoic acid, stearic acid, adipic acid, sebacic acid, monocarboxylic acid such as dodecanedioic acid, or dicarboxylic acid 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 (X) of the present invention, the addition amount of the monoamine, diamine, monocarboxylic acid, dicarboxylic acid and the like is preferably in a range in which the properties of the obtained polyamide elastomer (X) are not inhibited.

  In the production of the polyamide elastomer (X) of the present invention, phosphoric acid, pyrophosphoric acid, polyphosphoric acid or the like is used as a catalyst, if necessary, and phosphorous acid or hypophosphorous acid for the effect of both the catalyst and the heat-resistant agent. And inorganic phosphorus compounds such as alkali metal salts and alkaline earth metal salts thereof can be added. The addition amount is usually 50 to 3000 ppm with respect to the charged amount.

  The polyamide elastomer (X) 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, and a tackifier as long as the properties are not inhibited. Sealing property improvers, antifogging agents, mold release agents, plasticizers, pigments, dyes, fragrances, flame retardants, and the like can be added.

[Composition]
The polyamide elastomer (X) of the present invention preferably contains a component (Y) other than the polyamide elastomer (X).

  Component (Y) is preferably at least one selected from the group consisting of a flame retardant, glass fiber, talc, carbon fiber, mica, kaolin, plasticizer, magnetic powder, and thermoplastic resin excluding polyamide elastomer (X), At least one selected from the group consisting of a flame retardant, a plasticizer, a magnetic powder and a thermoplastic resin excluding the polyamide elastomer (X) is preferable. In addition, component (Y) is a heat-resistant agent, an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a lubricant, a slip agent, a crystal nucleating agent, a tackifier, a sealing property improving agent, an antifogging agent, It is not a release agent, pigment, dye, or fragrance.

  The melting point of the thermoplastic resin excluding the polyamide elastomer (X) is preferably 300 ° C. or less, more preferably 290 ° C. or less, and particularly preferably 280 ° C. or less.

  The polyamide has an acid amide bond (—CONH—) in the main chain, and is obtained from a polymer obtained from at least one component selected from aliphatic and alicyclic groups, or obtained from at least two components. An aliphatic or alicyclic polyamide such as a polymer is preferable, and an aliphatic polyamide is more preferable.

  Examples of the aliphatic polyamide include polycaproamide (nylon-6), polyaminoundecanoic acid (nylon-11), polylauryllactam (nylon-12), polyhexamethylenediaminoadipic acid (nylon-66), polyhexamethylene Polymers such as diamino sebacic acid (nylon-610), polyhexamethylene diaminododecanedioic acid (nylon-612), caprolactam / lauryl lactam copolymer (nylon-6 / 12), caprolactam / aminoundecanoic acid copolymer ( Nylon-6 / 11), caprolactam / hexamethylenediaminoadipic acid copolymer (nylon-6 / 66), caprolactam / hexamethylenediaminoadipic acid / aminododecanedioic acid (nylon-6 / 66/12), caprolactam / hexa Tylenediaminoadipic acid / lauryllactam (nylon-6 / 66/12), caprolactam / hexamethylenediaminoadipic acid / hexamethylenediaminosebacic acid (nylon-6 / 66/610), caprolactam / hexamethylenediaminoadipic acid / hexamethylene Examples thereof include aliphatic polyamides such as (co) polymers such as diaminododecanedioic acid (nylon-6 / 66/612). These polyamide resins can be used alone or in combination of two or more. Among these, at least one aliphatic polyamide selected from the group consisting of nylon 6, nylon 66, nylon 610, nylon 11, nylon 12 and nylon 612 is preferable.

  Polyamides can be made from lactams, aminocarboxylic acids, or combinations of diamines and dicarboxylic acids.

Examples of the lactam include ε-caprolactam, ω-enantolactam, ω-laurolactam, α-pyrrolidone, α-piperidone and the like.
Examples of aminocarboxylic acids include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid.

Examples of diamines include ethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, peptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecane methylene diamine, tridecane diamine, and tetradecane diamine. , Pentadecanediamine, hexadecanediamine, heptadecanediamine, octadecanediamine, nonadecanediamine, eicosanediamine, 2-methyl-1,8-octanediamine, 2,2,4 / 2,4,4-trimethylhexamethylenediamine, etc. Aliphatic diamine, 1,3 / 1,4-cyclohexyldiamine, bis (4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) propane, bis (3 Methyl-4-aminocyclohexyl) methane, (3-methyl-4-aminocyclohexyl) propane, 1,3 / 1,4-bisaminomethylcyclohexane, 5-amino-2,2,4-trimethyl-1-cyclopentane Cycloaliphatic diamines such as methylamine, 5-amino-1,3,3-trimethylcyclohexanemethylamine, bis (aminopropyl) piperazine, bis (aminoethyl) piperazine, norbornanedimethyleneamine, p-xylylenediamine, m -Aromatic diamines such as xylylenediamine can be mentioned.

  Dicarboxylic acids include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedionate, eico Aliphatic dicarboxylic acids such as Sandioic acid, 1,3 / 1,4-cyclohexanedicarboxylic acid, dicyclohexanemethane-4,4′-dicarboxylic acid, norbornanedicarboxylic acid, isophthalic acid, terephthalic acid And aromatic dicarboxylic acids such as 1,4 / 1,8 / 2,6 / 2,7-naphthalenedicarboxylic acid.

  The thermoplastic resin other than the polyamide elastomer is preferably mainly composed of polyamide. Other thermoplastic resins excluding polyamide, polyvinyl chloride, polyurethane, polyester, ABS resin, acid-modified polyethylene, polyolefin such as acid-modified polypropylene, etc. It is preferable to include a thermoplastic resin.

  As the flame retardant, a brominated flame retardant and a triazine flame retardant can be used.

  As the brominated flame retardant, brominated phenoxy resin, brominated polycarbonate, brominated polystyrene, polybrominated styrene, brominated polyphenylene ether and the like can be used.

  As the triazine flame retardant, cyanuric acid, isocyanuric acid, melamine, melamine cyanurate, or the like can be used.

  5-40 mass% is preferable with respect to the composition whole quantity, and, as for the addition amount of a flame retardant, 10-30 mass% is more preferable.

As the flame retardant aid, a compound containing antimony can be used. Examples of the compound containing antimony include antimony trioxide, antimony pentoxide, antimony tetroxide, and sodium antimonate.

0.1-12 mass% is preferable with respect to the composition whole quantity, and, as for the addition amount of the compound containing antimony, 1-10 mass% is more preferable. By using these together with a brominated flame retardant, flame retardancy is improved.

  The plasticizer is one or more compounds selected from esters and alkylamides.

  Examples of the esters include phthalic acid esters, fatty acid esters, polyhydric alcohol esters, phosphoric acid esters, trimellitic acid esters, and hydroxybenzoic acid esters.

  Phthalate esters include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, diisodecyl phthalate, ditridecyl phthalate, dicyclohexyl phthalate, phthalate Examples thereof include butyl benzyl acid, diisononyl phthalate, ethyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, diundecyl phthalate, and di-2-ethylhexyl tetrahydrophthalate.

  Examples of fatty acid esters include dimethyl adipate, dibutyl adipate, diisobutyl adipate, dibutyl diglycol adipate, di-2-ethylhexyl adipate, di-n-octyl adipate, diisodecyl adipate, diisononyl adipate, din adipate -Dibasic saturated carboxylic acids such as mixed alkyl esters, dimethyl sebacate, dibutyl sebacate, di-2-ethylhexyl sebacate, di-2-ethylhexyl azelate, di-2-ethylhexyl mixed acid, bis-2-ethylhexyl dodecamate Dibasic ester, dibutyl fumarate, bis-2-methylpropyl fumarate, bis-2-ethylhexyl fumarate, dimethyl maleate, diethyl maleate, dibutyl maleate, bis-2-ethylhexyl maleate, etc. Saturated carboxylic acid esters, butyl oleate, Izobuchiru oleate, acetyl butyl ricinoleate, and the like acetyl tributyl citrate and 2-ethylhexyl acetate.

  Examples of polyhydric alcohol esters include 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, diethylene glycol dibenzoate, triethylene glycol Examples thereof include ethylene glycol di-2-ethylbutyrate, pentaerythritol monooleate, pentaerythritol monostearate, pentaerythritol trialkyl ester, behenic acid monoglyceride, 2-ethylhexyl triglyceride, glycerin triacetate, and glycerin tributyrate.

  Examples of phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, n-octyl diphenyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, trixylenyl phosphate and 2-hydroxyphosphate 2-phosphate. Examples include ethylhexyl diphenyl.

  Examples of trimellitic acid esters include tributyl trimellitic acid, tri-2-ethylhexyl trimellitic acid, tri-n-octyl trimellitic acid, triisononyl trimellitic acid, triisodecyl trimellitic acid, and trimellitic acid tri-mixed alcohol ester. .

  Hydroxybenzoic acid esters include ethyl hexyl o- or p-hydroxybenzoate, hexyl decyl o- or p-hydroxybenzoate, ethyl decyl o- or p-hydroxybenzoate, octyloctyl o- or p-hydroxybenzoate, o- or p-hydroxybenzoic acid decyldodecyl, o- or p-hydroxybenzoic acid methyl, o- or p-hydroxybenzoic acid butyl, o- or p-hydroxybenzoic acid hexyl, o- or p-hydroxybenzoic acid n -Octyl, o- or p-hydroxybenzoic acid decyl and o- or p-hydroxybenzoic acid dodecyl.

  Examples of the alkylamides include toluenesulfonic acid alkylamides and benzenesulfonic acid alkylamides.

  Examples of toluenesulfonic acid alkylamides include N-ethyl-o-toluenesulfonic acid butyramide, N-ethyl-p-toluenesulfonic acid butyramide, N-ethyl-o-toluenesulfonic acid 2-ethylhexylamide, N-ethyl-p. -Toluenesulfonic acid 2-ethylhexylamide and the like.

  Examples of benzenesulfonic acid alkylamides include benzenesulfonic acid propylamide, benzenesulfonic acid butyramide, and benzenesulfonic acid 2-ethylhexylamide.

  The plasticizers mentioned above may be used alone or in combination of two or more.

Among these plasticizers, phthalates such as dibutyl phthalate, diisodecyl phthalate, di-2-ethylhexyl phthalate, ethyl hexyl p-hydroxybenzoate, p-
Hydroxybenzoic acid esters such as hexyldecyl hydroxybenzoate, and alkylamides such as benzenesulfonic acid butyramide and benzenesulfonic acid 2-ethylhexylamide are preferably used.

It is preferable to contain 5-95 mass% of components (Y) with respect to the composition whole quantity.
The polyamide elastomer (X) and the other components (Y) are preferably contained in an amount of 80% by mass, more preferably 90% by mass or more, and more preferably 95% by mass or more based on the total amount of the composition. Preferably, it is particularly preferably 98% by mass or more.

  However, from the viewpoint of increasing the magnetic properties, the magnetic powder preferably contains 80% by mass or more, and more preferably 80-95% by mass of the magnetic powder with respect to the total amount of the composition.

  As the magnetic powder, known magnetic powder can be used. For example, ferrite magnetic powders such as barium ferrite and strontium ferrite, and rare earth magnetic powders such as samarium-cobalt and neodymium-iron-boron can be used.

  In order to improve the miscibility with the resin component, the magnetic powder can be used after surface treatment with a silane coupling agent, a titanate coupling agent, a zircoaluminate coupling agent, an aluminum coupling agent or the like.

The method for obtaining the composition of the present invention is not particularly limited, and various known methods can be used. For example, after using a low-speed rotary mixer such as a V-type blender or tumbler or a constrained rotary mixer such as a Henschel mixer, the polyamide elastomer (X) and magnetic powder are mixed in advance, and then a single-screw extruder or twin-screw extruder is used. Examples thereof include a melt-kneading method and a method of previously mixing the polyamide elastomer (X) and the magnetic powder using a constrained rotary mixer such as a low-speed rotary mixer or a Henschel mixer.

The composition of the present invention comprises a heat-resistant agent, an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a lubricant, a slip agent, a crystal nucleating agent, a tackifier, a sealing property improving agent, an antifogging agent, a release agent. Molding agents, pigments, dyes, fragrances and the like can be added.

  The method for obtaining the composition of the present invention is not particularly limited, and various known methods can be used. For example, using a low-speed rotary mixer such as a V-type blender or tumbler or a constrained rotary mixer such as a Henschel mixer, the polyamide elastomer (X) and the other components (Y) are mixed in advance, Examples thereof include a method of melt-kneading with a shaft extruder or the like, and a method of preliminarily mixing the polyamide elastomer (X) and the other component (Y) using a constrained rotary mixer such as a low-speed rotary mixer or a Henschel mixer.

[Molding]
The polyamide elastomer (X) and the composition of the present invention can be molded by a known molding method such as injection molding, extrusion molding, blow molding, vacuum molding or pressure molding. In addition, each molded product includes automotive parts, electronic device peripheral parts, battery materials, packing, sealing materials, plastic magnets, sports shoe materials, ski surface materials, automotive malls, automotive mirror boots that require heat resistance. It can be used for various applications such as coating materials.

  The composition of the present invention containing magnetic powder can produce a plastic magnet part with a metal part inserted by insert molding or the like.

  The molded product of the present invention containing magnetic powder has no degradation of the binder resin due to hydrolysis even after being immersed in pressurized hot water at 100 ° C. for 24 hours. It can withstand use.

  The polyamide elastomer (X) and the composition of the present invention can be made into a laminate with another thermoplastic resin as well as a laminate with the polyamide elastomer (X) of the present invention.

Other thermoplastic resins include polycaproamide (polyamide 6), polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polyethylene adipamide (polyamide 26), polytetramethylene succinamide (polyamide 44). ), Polytetramethylene glutamide (polyamide 45), polytetramethylene adipamide (polyamide 46), polytetramethylene suberamide (polyamide 48), polytetramethylene azelamide (polyamide 49), polytetramethylene sebacamide ( Polyamide 410), polytetramethylene dodecamide (polyamide 412), polypentamethylene succinamide (polyamide 54), polypentamethylene glutamide (polyamide 55), polypentamethylene adipamide (polyamide 56). Polypentamethylene suberamide (polyamide 58), polypentamethylene azelamide (polyamide 59), polypentamethylene sebamide (polyamide 510), polypentamethylene dodecamide (polyamide 512), polyhexamethylene succinamide (polyamide 64) ), Polyhexamethylene glutamide (polyamide 65), polyhexamethylene adipamide (polyamide 66), polyhexamethylene suberamide (polyamide 68), polyhexamethylene azelamide (polyamide 69), polyhexamethylene sebacamide ( Polyamide 610), polyhexamethylene dodecamide (polyamide 612), polyhexamethylene tetradecanamide (polyamide 614), polyhexamethylene hexadecanamide (polyamide 616), polyhexamethylene Kutadecamide (Polyamide 618), Polynonamethylene adipamide (Polyamide 96), Polynonamethylene suberamide (Polyamide 98), Polynonamethylene azelamide (Polyamide 99), Polynonamethylene sebacamide (Polyamide 910), Polynona Methylene dodecamide (polyamide 912), polydecamethylene adipamide (polyamide 106), polydecamethylene suberamide (polyamide 108), polydecamethylene azelamide (polyamide 109), polydecamethylene sebacamide (polyamide 1010), Polydecamethylene dodecamide (polyamide 1012), polydodecamethylene adipamide (polyamide 126), polydodecamethylene suberamide (polyamide 128), polydodecamethylene azelamide (polyamide 129), poly Dodecamethylene sebamide (polyamide 1210), polydodecamethylene dodecamide (polyamide 1212), polymetaxylylene adipamide (polyamide MXD6), polymetaxylylene beramide (polyamide MXD8), polymetaxylylene azelamide (polyamide MXD9) ), Polymetaxylylene sebacamide (polyamide MXD10), polymetaxylylene dodecamide (polyamide MXD12), polymetaxylylene terephthalamide (polyamide MXDT), polymetaxylylene isophthalamide (polyamide MXDI), polymetaxylylene hexahydro Terephthalamide (polyamide MXDT (H)), polymetaxylylene naphthalamide (polyamide MXDN), polyparaxylylene adipamide (polyamide PXD6), polyparax Rylensberamide (Polyamide PXD8), Polyparaxylylene Azelamide (Polyamide PXD9), Polyparaxylylene Sebamide (Polyamide PXD10), Polyparaxylylene Dodecamide (Polyamide PXD12), Polyparaxylylene Terephthalamide (Polyamide PXDT) ), Polyparaxylylene isophthalamide (polyamide PXDI), polyparaxylylene hexahydroterephthalamide (polyamide PXDT (H)), polyparaxylylene naphthalamide (polyamide PXDN), polyparaphenylene terephthalamide (PPTA) ), Polyparaphenylene isophthalamide (PPIA), polymetaphenylene terephthalamide (PMTA), polymetaphenylene isophthalamide (PMIA), poly (2,6-naphthalene dimethylene adipa) ) (Polyamide 2,6-BAN6), poly (2,6-naphthalene dimethylene suberamide) (polyamide 2,6-BAN8), poly (2,6-naphthalene dimethylene azelamide) (polyamide 2,6- BAN9), poly (2,6-naphthalene dimethylene sebacamide) (polyamide 2,6-BAN10), poly (2,6-naphthalene dimethylene dodecamide) (polyamide 2,6-BAN12), poly (2, 6-naphthalene dimethylene terephthalamide) (polyamide 2,6-BANT), poly (2,6-naphthalene dimethylene isophthalamide) (polyamide 2,6-BANI), poly (2,6-naphthalene dimethylene hexa) Hydroterephthalamide) (polyamide 2,6-BANT (H)), poly (2,6-naphthalenedimethylmethylene naphthalamide) ( Polyamide 2,6-BANN), poly (1,3-cyclohexanedimethylene adipamide) (polyamide 1,3-BAC6), poly (1,3-cyclohexanedimethylene suberamide (polyamide 1,3-BAC8), Poly (1,3-cyclohexanedimethylene azelamide) (polyamide 1,3-BAC9), poly (1,3-cyclohexanedimethylene sebacamide) (polyamide 1,3-BAC10), poly (1,3-cyclohexane Dimethylene dodecamide) (polyamide 1,3-BAC12), poly (1,3-cyclohexanedimethylene terephthalamide) (polyamide 1,3-BACT), poly (1,3-cyclohexanedimethylene isophthalamide) ( Polyamide 1,3-BACI), poly (1,3-cyclohexanedimethylene hexahydrote) Phthalamide) (polyamide 1,3-BACT (H)), poly (1,3-cyclohexanedimethylene naphthalamide) (polyamide 1,3-BACN), poly (1,4-cyclohexanedimethylene adipamide) (polyamide) 1,4-BAC6), poly (1,4-cyclohexanedimethylenesberamide) (polyamide 1,4-BAC8), poly (1,4-cyclohexanedimethylene azelamide) (polyamide 1,4-BAC9), poly (1,4-cyclohexanedimethylene sebacamide) (polyamide 1,4-BAD10), poly (1,4-cyclohexanedimethylene dodecamide) (polyamide 1,4-BAD12), poly (1,4-cyclohexanedi) Methylene terephthalamide) (polyamide 1,4-BACT), poly (1,4-cyclohexanedi) Tylene isophthalamide) (polyamide 1,4-BACI), poly (1,4-cyclohexanedimethylene hexahydroterephthalamide) (polyamide 1,4-BACT (H)), poly (1,4-cyclohexanedimethylene) Naphthalamide) (polyamide 1,4-BACN), poly (4,4′-methylenebiscyclohexylene adipamide) (polyamide PACM6), poly (4,4′-methylenebiscyclohexylene suberamide) (polyamide PACM8) Poly (4,4′-methylenebiscyclohexylene azelamide) (polyamide PACM9), poly (4,4′-methylenebiscyclohexylene sebamide) (polyamide PACM10), poly (4,4′-methylenebiscyclohexylhexamide) Silendecamide) (polyamide PACM12), poly (4,4'-me Tylene biscyclohexylene tetradecanamide) (polyamide PACM14), poly (4,4′-methylenebiscyclohexylene hexadecanamide) (polyamide PACM16), poly (4,4′-methylenebiscyclohexylene octadecanamide) (polyamide) PACM18), poly (4,4′-methylenebiscyclohexylene terephthalamide) (polyamide PACMT), poly (4,4′-methylenebiscyclohexylene isophthalamide) (polyamide PACMI), poly (4,4′- Methylenebiscyclohexylenehexahydroterephthalamide) (polyamide PACMT (H)), poly (4,4′-methylenebiscyclohexylenenaphthalamide) (polyamide PACMN), poly (4,4′-methylenebis (2-methyl-) (Cyclohexylene) adipamide ) (Polyamide MACM6), poly (4,4′-methylenebis (2-methyl-cyclohexylene) suberamide) (polyamide MACM8), poly (4,4′-methylenebis (2-methyl-cyclohexylene) azeramide) (polyamide MACM9) ), Poly (4,4′-methylenebis (2-methyl-cyclohexylene) sebacamide) (polyamide MACM10), poly (4,4′-methylenebis (2-methyl-cyclohexylene) dodecamide) (polyamide MACM12), poly ( 4,4′-methylenebis (2-methyl-cyclohexylene) tetradecamide) (polyamide MACM14), poly (4,4′-methylenebis (2-methyl-cyclohexylene) hexadecamide) (polyamide MACM16), poly (4,4 ′ -Methylenebis (2-methyl-silane Chloroxylene) octadecamide) (polyamide MACM18), poly (4,4′-methylenebis (2-methyl-cyclohexylene) terephthalamide) (polyamide MACMT), poly (4,4′-methylenebis (2-methyl-cyclohexylene) isophthalamide) (Polyamide MACMI), poly (4,4′-methylenebis (2-methyl-cyclohexylene) hexahydroterephthalamide) (polyamide MACMT (H)), poly (4,4′-methylenebis (2-methyl-cyclohexylene) ) Naphthalamide) (polyamide MACMN), poly (4,4′-propylene biscyclohexylene adipamide) (polyamide PACP6), poly (4,4′-propylene biscyclohexylene suberamide) (polyamide PACP8), poly (4 , 4'-propire Biscyclohexylene azelamide) (polyamide PACP9), poly (4,4′-propylene biscyclohexylene sebacamide) (polyamide PACP10), poly (4,4′-propylene biscyclohexylene dodecamide) (polyamide PACP12) , Poly (4,4′-propylene biscyclohexylene tetradecanamide) (polyamide PACP14), poly (4,4′-propylene biscyclohexylene hexadecanamide) (polyamide PACP16), poly (4,4′-propylene bis Cyclohexylene octadecanamide) (polyamide PACP18), poly (4,4′-propylene biscyclohexylene terephthalamide) (polyamide PACPT), poly (4,4′-propylene biscyclohexylene isophthalamide) (polyamide PACPI) , Poly (4,4′-propylene biscyclohexylene hexahydroterephthalamide) (polyamide PACPT (H)), poly (4,4′-propylene biscyclohexylene naphthalamide) (polyamide PACPN), polyisophorone adipamide (Polyamide IPD6), polyisophorone beramide (polyamide IPD8), polyisophorone azeramide (polyamide IPD9), polyisophorone sebamide (polyamide IPD10), polyisophorondecamide (polyamide IPD12), polyisophorone terephthalamide (polyamide IPDT) ), Polyisophorone isophthalamide (polyamide IPDI), polyisophorone hexahydroterephthalamide (polyamide IPDT (H)), polyisophorone naphthalamide (polyamide IPDN), polyte Lamethylene terephthalamide (polyamide 4T), polytetramethylene isophthalamide (polyamide 4I), polytetramethylene hexahydroterephthalamide (polyamide 4T (H)), polytetramethylene naphthalamide (polyamide 4N), polypentamethylene Terephthalamide (polyamide 5T), polypentamethylene isophthalamide (polyamide 5I), polypentamethylene hexahydroterephthalamide (polyamide 5T (H)), polypentamethylene naphthalamide (polyamide 5N), polyhexamethylene terephthalate Ramide (polyamide 6T), polyhexamethylene isophthalamide (polyamide 6I), polyhexamethylene hexahydroterephthalamide (polyamide 6T (H)), polyhexamethylene naphthalamide (polyamide 6N), poly Li (2-methylpentamethylene terephthalamide) (polyamide M5T), poly (2-methylpentamethylene isophthalamide) (polyamide M5I), poly (2-methylpentamethylene hexahydroterephthalamide)
(Polyamide M5T (H)), poly (2-methylpentamethylene naphthalamide (polyamide M5N), polynonamethylene terephthalamide (polyamide 9T), polynonamethylene isophthalamide (polyamide 9I), polynonamethylene hexahydrotere Phthalamide (polyamide 9T (H)), polynonamethylene naphthalamide (polyamide 9N), poly (2-methyloctamethylene terephthalamide) (polyamide M8T), poly (2-methyloctamethylene isophthalamide) (polyamide M81) ), Poly (2-methyloctamethylenehexahydroterephthalamide) (polyamide M8T (H)), poly (2-methyloctamethylenenaphthalamide) (polyamide M8N), polytrimethylhexamethylene terephthalamide (polyamide TMHT), Poly Limethylhexamethylene isophthalamide (polyamide TMHI), polytrimethylhexamethylenehexahydroterephthalamide (polyamide TMHT (H)), polytrimethylhexamethylene naphthalamide (polyamide TMHN), polydecamethylene terephthalamide (polyamide 10T) Polydecamethylene isophthalamide (polyamide 10I), polydecamethylene hexahydroterephthalamide (polyamide 10T (H)), polydecamethylene naphthalamide (polyamide 10N), polyundecamethylene terephthalamide (polyamide 11T), Polyundecamethylene isophthalamide (Polyamide 11I), Polyundecamethylene hexahydroterephthalamide (Polyamide 11T (H)), Polyundecamethylene naphthalamide (Polyamide 1) N), polydodecamethylene terephthalamide (polyamide 12T), polydodecamethylene isophthalamide (polyamide 12I), polydodecamethylene hexahydroterephthalamide (polyamide 12T (H)), polydodecamethylene naphthalamide (polyamide 12N) And polyamide resins such as copolymers using several types of raw material monomers of these polyamides,

  Polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer (PFA), tetrafluoro Ethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / perfluoro (alkyl vinyl ether) / hexafluoropropylene copolymer, ethylene / tetrafluoroethylene copolymer (ETFE), ethylene / tetrafluoroethylene / hexafluoro Propylene copolymer (EFEP), vinylidene fluoride / tetrafluoroethylene copolymer, vinylidene fluoride / hexafluoropropylene copolymer, vinylidene fluoride / perfluoro (A) Kill vinyl ether) copolymer, tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (THV), vinylidene fluoride / perfluoro (alkyl vinyl ether) / tetrafluoroethylene copolymer, tetrafluoroethylene / hexafluoropropylene / Vinylidene fluoride / perfluoro (alkyl vinyl ether) copolymer, ethylene / chlorotrifluoroethylene copolymer (ECTFE), chlorotrifluoroethylene / tetrafluoroethylene copolymer, vinylidene fluoride / chlorotrifluoroethylene copolymer Chlorotrifluoroethylene / perfluoro (alkyl vinyl ether) copolymer, chlorotrifluoroethylene / hexafluoropropylene copolymer, chlorotrifluoroethylene / te Lafluoroethylene / hexafluoropropylene copolymer, chlorotrifluoroethylene / tetrafluoroethylene / vinylidene fluoride copolymer, chlorotrifluoroethylene / perfluoro (alkyl vinyl ether) / tetrafluoroethylene copolymer (CPT), chloro Trifluoroethylene / perfluoro (alkyl vinyl ether) / hexafluoropropylene copolymer, chlorotrifluoroethylene / tetrafluoroethylene / hexafluoropropylene / perfluoro (alkyl vinyl ether) copolymer, chlorotrifluoroethylene / tetrafluoroethylene / Vinylidene fluoride / perfluoro (alkyl vinyl ether) copolymer, chlorotrifluoroethylene / tetrafluoroethylene / vinylidene fluoride / hexaf Functional groups having reactivity with fluororesins such as fluoropropylene copolymer, chlorotrifluoroethylene / tetrafluoroethylene / vinylidene fluoride / perfluoro (alkyl vinyl ether) / hexafluoropropylene copolymer, and amino groups Containing the fluororesin,

  High density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ultra high molecular weight polyethylene (UHMWPE), polypropylene (PP), polybutene (PB), poly Methylpentene (TPX), ethylene / propylene copolymer (EPR), ethylene / butene copolymer (EBR), ethylene / vinyl acetate copolymer (EVA), ethylene / acrylic acid copolymer (EAA), ethylene / Polyolefin resins such as methacrylic acid copolymer (EMAA), ethylene / methyl acrylate copolymer (EMA), ethylene / methyl methacrylate copolymer (EMMA), ethylene / ethyl acrylate copolymer (EEA), Polystyrene (PS), syndiotactic polystyrene (SPS), methyl methacrylate / styrene copolymer (MS), methyl methacrylate / styrene / butadiene copolymer (MBS), styrene / butadiene copolymer (SBR), styrene / isoprene copolymer (SIR), Styrene / isoprene / butadiene copolymer (SIBR), styrene / butadiene / styrene copolymer (SBS), styrene / isoprene / styrene copolymer (SIS), styrene / ethylene / butylene / styrene copolymer (SEBS), Polystyrene resins such as styrene / ethylene / propylene / styrene copolymer (SEPS), acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, mesaconic acid, citraconic acid, glutaconic acid, cis-4- Cyclohexene-1,2-dicarboxylic acid, endobi Carboxyl group such as chloro- [2.2.1] -5-heptene-2,3-dicarboxylic acid, and metal salts thereof (Na, Zn, K, Ca, Mg), maleic anhydride, itaconic anhydride, anhydrous Acid anhydride groups such as citraconic acid and endobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic acid anhydride, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, citracone Polyolefin resins and polystyrene resins containing functional groups such as epoxy groups such as glycidyl acid, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), poly (ethylene terephthalate / ethylene iso Phthalate) copolymer (PET / PEI), polytrimethyle Terephthalate (PTT), polycyclohexanedimethylene terephthalate (PCT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyarylate (PAR), liquid crystalline polyester (LCP), polylactic acid (PLA), polyglycol Polyester resins such as polyester resins such as acid (PGA), polyether resins such as polyacetal (POM) and polyphenylene ether (PPO), polysulfones such as polysulfone (PSU), polyethersulfone (PESU), and polyphenylsulfone (PPSU) Resins, polythioether resins such as polyphenylene sulfide (PPS), polythioethersulfone (PTES), polyketone (PK), polyetherketone (PEK), polyetheretherketone (PEEK), polyethylene Polyketone resins such as ether ketone ketone (PEKK), polyether ether ether ketone (PEEEK), polyether ether ketone ketone (PEEEKK), polyether ketone ketone ketone (PEKKK), polyether ketone ether ketone ketone (PEKEKK), poly Acrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer (ABS), acrylonitrile / butadiene copolymer (NBR) Polynitrile resins such as polymethyl methacrylate (PMMA), polymethacrylate resins such as polyethyl methacrylate (PEMA), and polyvinyl s such as polyvinyl acetate (PVAc) Resin, polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), polyvinyl chloride / vinylidene chloride copolymer, polyvinylidene chloride / methyl acrylate copolymer, etc., cellulose acetate, cellulose butyrate, etc. Cellulose resins, polycarbonate resins such as polycarbonate (PC), thermoplastic polyimide (TPI), polyetherimide, polyesterimide, polyamideimide (PAI), polyesteramideimide, and other polyimide resins, thermoplastic polyurethane resins, Examples include polyamide elastomers, polyurethane elastomers, and polyester elastomers other than the polyamide elastomer (X) of the present invention.

  As other thermoplastic resins used in the laminate, polyurethane and / or diene rubber can be preferably used.

  The adhesive strength of the laminate of the present invention is preferably 5 N / mm or more, more preferably 8 N / mm or more.

[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 measurement, shaping | molding, and evaluation in an Example 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 at 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) Retention rate of elastic modulus after immersion in 10% by mass hydrochloric acid After creating a dumbbell test piece similar to the above (4) and dipping in ion exchange water at 23 ° C., the weight of the test piece reached saturation, The elastic modulus was measured by the same method as in (4) above. The elastic modulus retention was determined from the elastic modulus before and after immersion by the following formula.
Elastic modulus retention rate (%) = 100 × (elastic modulus after immersion) / (elastic modulus before immersion)

(8) Laminate with polyurethane resin The following polyurethane 1 mm thick films were prepared.
-BASF polyether-based thermoplastic polyurethane ELASTOLLAN ET890
・ BASF polyester-based thermoplastic polyurethane ELASTOLLAN ET690
The 1 mm thick film obtained in the above (3) is placed on the lower side and the prepared polyurethane film is placed on the upper side, and the temperature of the upper die of the vacuum press TMB-10 manufactured by Toho Machinery Co., Ltd. is 200 ° C. The temperature of the lower mold was set to 260 ° C. and pressed under conditions of 20 MPa for 1 minute to obtain a laminate with a polyurethane resin.
The obtained laminate was cut to a width of 10 mm and a length of 15 cm to obtain a test piece for an adhesive strength test.

(9) Laminate with diene rubber The rubber compounding ingredients shown in Table 1 were kneaded at 90 ° C. for 4.5 minutes using a Banbury mixer at the ratio shown in Table 1.
The kneaded product was adjusted to 1 mm in thickness with a press at 165 ° C., 10 MPa, and 8 minutes.

The 1 mm film obtained in the above (3) is placed on the lower side, and the obtained diene rubber molded product is placed on the upper side, and the temperature of the upper mold is set to 200 with a vacuum press TMB-10 manufactured by Toho Machinery Co., Ltd. C., the temperature of the lower mold was set to 260.degree. C., and pressed under conditions of 20 MPa for 1 minute to obtain a laminate with a diene rubber.
The obtained laminate was cut to a width of 10 mm and a length of 15 cm to obtain a test piece for an adhesive strength test.

(10) Adhesive strength test The test piece obtained in (8) and (9) above was subjected to a T-type peel test under the conditions of a tensile speed of 30 mm / min in a 23 ° C environment using a TENSILON RTA-500 testing machine manufactured by ORIENTEC. The first maximum adhesive strength (N / mm) was measured.

(11) Flexural modulus Based on ASTM D790, the flexural modulus of a test piece of 6.35 mm × 12.7 mm × 127 mm was measured at 23 ° C.

(12) Izod impact strength (notched)
In accordance with ASTM D256, the Izod impact strength of a 3.18 mm × 12.7 mm × 127 mm notched test piece was measured at 23 ° C.

(13) Hydrolysis resistance Cut out from a 100 mm x 300 mm x 2 mm plate formed by injection molding using a JIS No. 3 dumbbell (test piece), and put the cut out test pieces in a stainless steel container with a capacity of 5 liters so as not to overlap. After putting 2 liters of distilled water and sealing it with a lid, it was put in an 80 ° C. hot water bath. After 2000 hours, the test piece (hydrolyzed test piece) was taken out, the moisture on the surface of the test piece was removed, and sandwiched at a distance between chucks of 50 mm using a tensile tester, and a tensile test at a speed of 500 mm / min. And tensile elongation at break was measured. The tensile break elongation of a test piece not hydrolyzed (not put in a stainless steel container) was measured, and the retention of tensile break elongation was calculated from the following formula.
Tensile elongation at break (%) = 100 × (tensile elongation at break of test piece subjected to hydrolysis treatment) / (tensile elongation at break of test piece not subjected to hydrolysis treatment)

(14) Hydrolysis resistance of plastic magnet A cylindrical plastic magnet with a diameter of 30 mm and a thickness of 30 mm as a central axis and a plastic product of a cylindrical shape with a thickness of 40 mm and a thickness of 30 mm were molded. . The obtained molded product was immersed in pressurized hot water at 100 ° C., taken out after 24 hours, and the occurrence of cracks was confirmed.

[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, dehydrated toluene 1150 ml, 1,12-dodecanediamine 140.7 g (0 702 mol), 1,9-nonanediamine 10.5 g (0.066 mol), 2-methyl-1,8-octanediamine 1.9 g (0.012 mol) and XYX type triblock polyether diamine (HUNTSMAN) XTJ-542) (91 g, 0.087 mol) 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 the polyamide elastomer (hereinafter sometimes referred to as PAE1) was 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, 306.6 g (1.53 mol) of 1,12-dodecanediamine, 22.9 g (0.145 mol) of 1,9-nonanediamine, 4.0 g of 2-methyl-1,8-octanediamine (0. 026 mol) and 457 g (0.43 mol) of XYX type triblock polyether diamine (XTJ-542 manufactured by HUNTSMAN) and 2.50 g of sodium hypophosphite monohydrate were charged with nitrogen gas in the pressure vessel After pressurizing to 3.0 MPaG, nitrogen gas was then released to normal pressure to perform nitrogen substitution, and the system was heated under a sealing 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 (hereinafter sometimes referred to as PAE2) was immediately cooled with water and recovered.

[Example 3]
234.4 g (1.17 mol) of 1,12-dodecanediamine, 17.5 g (0.111 mol) of 1,9-nonanediamine, and 3.1 g (0.020 mol) of 2-methyl-1,8-octanediamine Polymerization was conducted in the same manner as in Example 2 using 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 No. 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, a polymer (hereinafter sometimes referred to as PAE3) was extracted from the lower part of the pressure vessel, and immediately cooled and recovered with water.

[Example 4]
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, dehydrated toluene 1150 ml, 1,12-dodecanediamine 140.7 g (0 702 mol), 9.1 g (0.078 mol) of 1,6-hexanediamine and 91 g (0.087 mol) of XYX type triblock polyether diamine (XTJ-542 manufactured by HUNTSMAN). 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 the polyamide elastomer (hereinafter sometimes referred to as PAE4) was cooled to room temperature under a nitrogen stream of 50 ml / min.

[Example 5]
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, 306.6 g (1.53 mol) of 1,12-dodecanediamine, 19.8 g (0.17 mol) of 1,6-hexanediamine and XYX type triblock polyetherdiamine (XTJ-manufactured by HUNTSMAN) 542) 457 g (0.43 mol) and sodium hypophosphite monohydrate 2.50 g were charged, 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. Then, nitrogen replacement was performed, and the system was heated under a sealing 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 (hereinafter sometimes referred to as PAE5) was immediately cooled with water and recovered.

[Example 6]
In the same manner as in Example 2, using 234.4 g (1.17 mol) of 1,12-dodecanediamine, 15.1 g (0.13 mol) of 1,6-hexanediamine, and 380 g (1.9 mol) of dibutyl oxalate. Polymerization was performed 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 No. 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, a polymer (hereinafter sometimes referred to as PAE6) was extracted from the lower part of the pressure vessel, and immediately cooled and recovered with water.

[Reference example]
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.

[Comparative Example 1]
1,12-dodecanediamine 577.1 g (2.88 mol), 1,9-nonanediamine 43.1 g (0.272 mol), 2-methyl-1,8-octanediamine 7.6 g (0.048 mol), Polymerization was carried out in the same manner as in Example 2 using 655 g (3.2 mol) of dibutyl oxalate. (Hereinafter, the obtained polyamide elastomer may be referred to as PAE7.)

[Comparative Example 2]
In the same manner as in Example 2, using 577.1 g (2.88 mol) of 1,12-dodecanediamine, 37.2 g (0.32 mol) of 1,6-hexanediamine, and 655 g (3.2 mol) of dibutyl oxalate. Polymerization was performed. (Hereinafter, the obtained polyamide elastomer may be referred to as PAE8.)

[Comparative Example 3]
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 holding 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. (Hereinafter, the obtained polyamide elastomer may be referred to as PAE9.)

[Comparative Example 4]
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 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. (Hereinafter, the obtained polyamide elastomer may be referred to as PAE10.)

[Comparative Example 5]
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. (Hereinafter, the obtained polyamide elastomer may be referred to as PAE11.)

[Comparative Example 6]
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. (Hereinafter, the obtained polyamide elastomer may be referred to as PAE12.)

  Table 2 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 6, Reference Examples and Comparative Examples 1 to 6. Each unit of the structural units in Table 2 indicates a value calculated from the raw material charge ratio. In Table 2, HS is an abbreviation for hard segment and indicates a polyamide unit, and SS is an abbreviation for soft segment and indicates a polyetherdiamine unit (B). HS / SS in Table 2 refers to the weight ratio of the polyamide unit (A) and the polyetherdiamine unit (B). Further, Comparative Examples 1 and 2 did not dissolve in trifluoroacetic acid, and the relative viscosity was not measurable.

  Table 3 shows the results of durability tests on the liquids of the films obtained from the polyamide elastomers of Examples 1 to 6, Reference Examples and Comparative Examples 3 and 4.

  Table 4 shows the results of the elastic modulus retention after immersion in 10% by mass hydrochloric acid of the films obtained from the polyamide elastomers of Examples 2 and 5 and Reference Example.

  Table 5 shows the results of the adhesive strength tests of Examples 2 and 5, Comparative Example 3 and Comparative Example 6. Examples 2 and 5 and Comparative Example 3 were strongly bonded to the polyether-based thermoplastic polyurethane, and the polyether-based thermoplastic polyurethane film itself broke before the adhesive surface peeled off.

[Examples 7 to 18, Comparative Example 7]
Polyamide elastomer and 3020U, which is nylon 12 manufactured by Ube Industries, Ltd., are melt-kneaded at 240 ° C. using a twin-screw kneader with a cylinder diameter of 40 mm at the ratio shown in Table 2, extruded into a strand, and in a water tank After cooling, it was pelletized using a pelletizer. The resulting composition was measured for flexural modulus, Izod impact value, and elongation at break after hydrolysis treatment, and the results are shown in Table 6.

［実施例１９〜２８、比較例８］
難燃剤Aは、東都化成製のYPB-43C（臭素化フェノキシ樹脂）を用いた。
難燃剤Bは、グレートレークス製のBC-58（臭素化ポリカーボネート）を用いた。
難燃剤Cは、メラミンイソシアヌレートを用いた。
表７に示す割合で、ポリアミドエラストマー、難燃剤と難燃助剤を、シリンダー径４０ｍｍの二軸混練機を用い、２４０℃で溶融混練して、ストランド状に押出、水槽で冷却した後ペレタイザーを用いペレットにした。得られた組成物の曲げ弾性率、アイゾット衝撃値、加水分解処理後の破断伸び保持率を測定し、その結果を表３に示す。

[Examples 19 to 28, Comparative Example 8]
As flame retardant A, YPB-43C (brominated phenoxy resin) manufactured by Toto Kasei was used.
As flame retardant B, BC-58 (brominated polycarbonate) manufactured by Great Lakes was used.
As flame retardant C, melamine isocyanurate was used.
Polyamide elastomer, flame retardant and flame retardant aid in the proportions shown in Table 7 were melt kneaded at 240 ° C. using a twin screw kneader with a cylinder diameter of 40 mm, extruded into a strand, cooled in a water tank, and then pelletized. Used as pellets. The resulting composition was measured for flexural modulus, Izod impact value, and elongation at break after hydrolysis treatment, and the results are shown in Table 3.

［実施例２９〜３６、比較例９、１０］
表８に示す割合で、宇部興産株式会社製のナイロン１２である３０２０Ｕとポリアミドエラストマーと可塑剤を、シリンダー径４０ｍｍの二軸混練機を用い、２４０℃で溶融混練して、ストランド状に押出、水槽で冷却した後ペレタイザーを用いペレットにした。得られた組成物の曲げ弾性率、アイゾット衝撃値、加水分解処理後の破断伸び保持率を測定し、その結果を表８に示す。

[Examples 29 to 36, Comparative Examples 9 and 10]
In the ratio shown in Table 8, 3020U which is nylon 12 manufactured by Ube Industries, Ltd., polyamide elastomer and plasticizer are melt-kneaded at 240 ° C. using a biaxial kneader with a cylinder diameter of 40 mm, and extruded into a strand shape. After cooling in a water bath, it was pelletized using a pelletizer. The resulting composition was measured for flexural modulus, Izod impact value, and elongation at break after hydrolysis, and the results are shown in Table 8.

[Examples 37 to 42, Comparative Examples 11 to 14]
10% by mass of the polyamide elastomer shown in Table 9 and 90% by mass of ferrite powder treated with an aminosilane coupling agent were mixed by a mixer and then melt-kneaded using a kneader to obtain pellets. The resulting composition was evaluated for hydrolysis resistance of the plastic magnet. The results are shown in Table 9. The obtained molded product could be used as a magnet.

Claims (7)

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),
Furthermore, it contains at least two units 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.)   The polyamide elastomer according to claim 1, wherein R1 is at least two selected from the group consisting of hexamethylene, nonamethylene, 2-methyloctamethylene and dodecamethylene.   The polyamide elastomer according to claim 1 or 2, wherein the elongation recovery rate is 55% or more and the melting point is 200 ° C or more.   The polyamide elastomer according to any one of claims 1 to 3, having 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 in any one of Claims 1-4.   A laminate formed by welding the polyamide elastomer according to any one of claims 1 to 4 and another thermoplastic resin.   A laminate comprising the polyamide elastomer layer according to any one of claims 1 to 4 and a diene rubber layer.