JP5024550B2 - Laminated body - Google Patents

Description

  The present invention relates to a laminate having a structure in which a thermoplastic resin such as polyamide and a layer containing a thermoplastic resin such as thermoplastic polyurethane are laminated.

  As described in Patent Document 1, a laminate obtained by laminating a polyamide resin and a polyurethane resin has been proposed so far. However, the adhesive is insufficient and easily peels off, and cannot be practically used. There was a case.

  On the other hand, as described in Patent Document 2, a laminate obtained by laminating a polyamide-based elastomer and a polyurethane resin has been proposed so far.

Patent Document 3 describes a polyamide-based elastomer, and Patent Document 4 describes a resin composition containing a thermoplastic resin and a polyamide-based elastomer.
JP-A-56-8257 JP 2005-119207 A JP 2004-161964 A JP 2004-352789 A

  However, conventionally, a laminate in which a layer mainly composed of polyamide resin and a layer of polyurethane resin are laminated with high peel strength has not been known.

  In view of such problems, the present invention provides a laminate obtained by laminating a layer containing a polyamide resin and a layer containing a polyurethane resin, and having improved properties such as peel strength. With the goal.

The present invention includes an X layer containing a first thermoplastic resin mainly composed of a polyamide resin and a polyetheramide elastomer (X);
A structure in which a Y layer containing a second thermoplastic resin mainly composed of a polyurethane resin is laminated;
The polyetheramide elastomer (X) is
A diamine compound (A) containing a triblock polyether diamine compound (A1) represented by the following formula (1);
A polyamide-forming monomer (B);
The present invention relates to a laminate obtained by polymerizing a component containing a dicarboxylic acid compound (C).

ただし、ｘは１〜２０の整数、ｙは４〜５０の整数、およびｚは１〜２０の整数をそれぞれ表わす。

However, x represents an integer of 1 to 20, y represents an integer of 4 to 50, and z represents an integer of 1 to 20, respectively.

  The diamine compound (A) is at least one diamine compound (A2) selected from the group consisting of branched saturated diamines having 6 to 22 carbon atoms, branched alicyclic diamines having 6 to 16 carbon atoms, and norbornane diamines. It is preferable that it is further included.

  Preferred embodiments of the present invention are listed below.

  1: The polyamide resin is an aliphatic polyamide.

  2: The polyamide resin is at least one aliphatic polyamide selected from the group consisting of nylon 6, nylon 66, nylon 610, nylon 11, nylon 12 and nylon 612.

  3: X layer contains 95-50 mass% of 1st thermoplastic resins, and 5-50 mass% of polyetheramide elastomer (X).

  4: The dicarboxylic acid compound (C) is represented by the following formula (2).

（ただし、Ｒ^１は炭化水素鎖を含む連結基を表し、ｍは０または１を表す。）

(However, R ¹ represents a linking group containing a hydrocarbon chain, and m represents 0 or 1.)

  5: The polyamide-forming monomer (B) is an aminocarboxylic acid compound, a lactam compound, a compound synthesized from a diamine and a dicarboxylic acid, and at least one aliphatic, alicyclic group selected from the group consisting of salts thereof And / or aromatics.

  6: Polyamide-forming monomer (B) comprises at least one of an aminocarboxylic acid compound (B1) represented by the following formula (3) and a lactam compound (B2) represented by the following formula (4) Including.

（ただし、Ｒ^２は炭化水素鎖を含む連結基を表わす。）

(However, R ² represents a linking group containing a hydrocarbon chain.)

（ただし、Ｒ^３は炭化水素鎖を含む連結基を表わす。）

(However, R ³ represents a linking group containing a hydrocarbon chain.)

  7: The dicarboxylic acid compound (C) is an aliphatic dicarboxylic acid compound and / or an alicyclic dicarboxylic acid compound.

  8: The ratio of the polyamide-forming monomer (B) is 10 to 95% by mass with respect to the total amount of the diamine compound (A), the polyamide-forming monomer (B) and the dicarboxylic acid compound (C).

  9: The ratio of the polyamide-forming monomer (B) to the total amount of the diamine compound (A), the polyamide-forming monomer (B) and the dicarboxylic acid compound (C) is 15 to 80% by mass, and the diamine compound (A ) And the dicarboxylic acid compound (C) is 20 to 85% by mass.

10: R ^{2 of the} formula (3) includes an alkylene group having 2 to 20 carbon atoms.

11: The alkylene group whose carbon atom number of R < ³ > of Formula (4) is 2-20 is included.

  12: x in Formula (1) represents an integer of 2 to 6, y represents an integer of 6 to 12, and z represents an integer of 1 to 5, respectively.

  13: x in Formula (1) represents an integer of 2 to 10, y represents an integer of 13 to 28, and z represents an integer of 1 to 9, respectively.

  14: The ratio of the diamine compound (A2) is 0.5 to 10% by mass with respect to the total amount of the diamine compound (A), the polyamide-forming monomer (B), and the dicarboxylic acid compound (C).

  15: a branched saturated diamine having 6 to 22 carbon atoms is 2,2,4-trimethyl-1,6-diaminohexane, 2,4,4-trimethyl-1,6-diaminohexane, 1,2-diaminopropane, It is a diamine selected from 1,3-diaminopentane, 2-methyl-1,5-diaminopentane, 2-methyl-1,8-diaminooctane or a mixture thereof.

  16: The branched alicyclic diamine having 6 to 16 carbon atoms is 5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine, 5-amino-1,3,3-trimethylcyclohexanemethylamine, or these A diamine selected from a mixture.

  17: The norbornanediamine is a diamine selected from 2,5-norbornanedimethylamine, 2,6-norbornanedimethylamine, or a mixture thereof.

18: m in Formula (2) is 1, and R ¹ represents an alkylene group having 1 to 20 carbon atoms.

  19: The polyurethane resin is a thermoplastic polyurethane.

  20: The thermoplastic polyurethane has at least one unit selected from the group consisting of polyester diol, polyether diol, polycarbonate diol and polycaprolactone diol as a soft segment.

  21: The X layer contains a plasticizer.

  In the laminate of the present invention, the X layer and the Y layer are firmly bonded to achieve a laminate with little warpage. Therefore, this laminate can be used for sports shoe soles, ski boots, etc., and has toughness such as bending strength and bending elastic modulus, and elasticity of rubber such as bending fatigue resistance, low temperature impact resistance, and low temperature flexibility. This material is excellent in balance and suitable for low warpage.

<< X layer >>
The X layer of the present invention is a resin composition layer containing a first thermoplastic resin mainly composed of a polyamide resin and a polyetheramide elastomer (X).

  The X layer is 95 to 50% by mass of the first thermoplastic resin and 5 to 50% by mass of the polyetheramide elastomer (X) based on the total of the first thermoplastic resin and the polyetheramide elastomer (X). %, Preferably 90 to 60% by mass of the first thermoplastic resin and 10 to 40% by mass of the polyetheramide elastomer (X), and particularly 85 to 70% by mass of the first thermoplastic resin. % And the polyetheramide elastomer (X) are preferably contained in an amount of 15 to 30% by mass.

<First thermoplastic resin>
The first thermoplastic resin is mainly composed of a polyamide resin, and is generally 70% or more, preferably 80% or more, more preferably 90%, most preferably 95% or more of the polyamide resin on a mass basis. Yes, it may be substantially composed only of a polyamide resin. Here, examples of the component other than the polyamide resin include thermoplastic resins having good compatibility such as polyvinyl chloride, thermoplastic polyurethane, and ABS resin. The first thermoplastic resin has a molding temperature of preferably 300 ° C. or lower, more preferably 290 ° C. or lower, particularly preferably 280 ° C. or lower.

  The X layer may contain other resins and the like as long as the characteristics are not impaired. However, when these satisfy the conditions of the first thermoplastic resin together with the polyamide resin, the first thermoplastic resin It can be regarded as a component constituting. When it is not regarded as a component constituting the first thermoplastic resin, as the other component, it is preferably 70% by mass or less, more preferably 20% by mass or less, more preferably 10% by mass or less, particularly in the X layer. Preferably, it may be contained in an amount of 5% by mass or less (may be 0%).

  The polyamide resin has an acid amide bond (—CONH—) in the main chain, and is an aliphatic polyamide, an alicyclic polyamide, an aromatic polyamide, and a (co) polymer corresponding to a combination or combination thereof. Examples thereof include polyamide resins containing at least one selected resin. The monomer unit constituting the polyamide resin may be one type or two or more types.

  As the polyamide resin, an aliphatic polyamide is preferable.

  Polyamide resins include aliphatic, alicyclic and / or aromatic polyamides derived 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 aminocarboxylic acids include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, Examples thereof include 11-aminoundecanoic acid and 12-aminododecanoic acid.

  Examples of diamines that can be used as raw materials for polyamides derived from diamines and dicarboxylic acids include ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, peptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecacene. Methylene diamine, dodecane methylene diamine, tridecane diamine, tetradecane diamine, pentadecane diamine, hexadecane diamine, heptadecane diamine, octadecane diamine, nonadecane diamine, eicosane diamine, 2-methyl-1,8-octane diamine, 2,2, Aliphatic diamine such as 4 / 2,4,4-trimethylhexamethylenediamine, 1,3 / 1,4-cyclohexyldiamine, bis (4-aminocyclohexyl) Tan, 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-cyclopentanemethylamine, 5-amino-1,3,3-trimethylcyclohexanemethylamine, bis (aminopropyl) piperazine, bis (aminoethyl) piperazine, norbornane dimethylene Examples thereof include alicyclic diamines such as amines, aromatic diamines such as p-xylylenediamine and m-xylylenediamine.

  Examples of the dicarboxylic acid used as a raw material for polyamide derived from diamine and dicarboxylic acid include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, Aliphatic dicarboxylic acids such as pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosandioic acid, 1,3 / 1,4-cyclohexanedicarboxylic acid, dicyclohexanemethane-4,4′-dicarboxylic acid, norbornane dicarboxylic acid And alicyclic dicarboxylic acids such as isophthalic acid, terephthalic acid, and aromatic dicarboxylic acids such as 1,4 / 1,8 / 2,6 / 2,7-naphthalenedicarboxylic acid.

  As the polyamide resin, these polyamides can be used alone or in combination of two or more. Furthermore, a copolyamide composed of a combination of two or more types can be used.

  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), and caprolactam / hexamethylenediaminoadipic acid / hexa And (co) polymers such as methylene diaminododecanedioic acid (nylon-6 / 66/612). These polyamide resins can be used alone or in combination of two or more.

  The polyamide resin is preferably at least one aliphatic polyamide selected from nylon 6, nylon 66, nylon 610, nylon 11, nylon 12 and nylon 612, particularly preferably nylon 11 and nylon 12, most preferably nylon 12. It is.

<Polyetheramide elastomer (X)>
The polyetheramide elastomer (X) comprises a diamine compound (A) containing at least a triblock polyetherdiamine compound (A1) represented by the following formula (1), a polyamide-forming monomer (B), a dicarboxylic acid compound ( C) and a polymer obtained by polymerization.

  However, x represents an integer of 1 to 20, y represents an integer of 4 to 50, and z represents an integer of 1 to 20, respectively.

  The diamine compound (A) is preferably at least one diamine compound (A2) selected from the group consisting of a branched saturated diamine having 6 to 22 carbon atoms, a branched alicyclic diamine having 6 to 16 carbon atoms and a norbornane diamine. Containing.

One particularly preferred embodiment of the polyetheramide elastomer (X) is an XYX-type triblock polyetherdiamine (A1) represented by the formula (1) (Y is polyoxybutylene), preferably a diamine (A1). A diamine compound (A) containing at least one diamine compound (A2) selected from a branched saturated diamine having 6 to 22 carbon atoms, a branched alicyclic diamine having 6 to 16 carbon atoms and a norbornane diamine,
A polyamide-forming monomer (B) selected from an aminocarboxylic acid compound (B1) represented by formula (3) and a lactam compound (B2) represented by formula (4), and a dicarboxylic acid represented by formula (2) Acid compound (C)
Is a polyetheramide elastomer (X) obtained by polymerizing.

  In the polyetheramide elastomer (X), the terminal carboxylic acid or carboxyl group contained in the diamine compound (A), the polyamide-forming monomer (B), and the dicarboxylic acid compound (C) is almost equal to the terminal amino group. A proportion such that it is a mole is preferred.

  In particular, when one end of the polyamide-forming monomer (B) is an amino group and the other end is a carboxylic acid or a carboxyl group, the amino group of the diamine compound (A) and the carboxyl group of the dicarboxylic acid compound (C) are almost The ratio is preferably equimolar.

  The XYX-type triblock polyether diamine compound (A1) represented by the formula (1) is converted to polypropylene glycol by adding propylene oxide to both ends of poly (oxytetramethylene) glycol and the like, and then the polypropylene glycol. The polyether diamine etc. which are manufactured by making ammonia etc. react with the terminal of can be used.

  In the XYX type triblock polyether diamine compound (A1), x and z are 1 to 20, preferably 1 to 18, more preferably 1 to 16, more preferably 1 to 14, and particularly preferably 1 to 12. , Y is 4 to 50, preferably 5 to 45, more preferably 6 to 40, more preferably 7 to 35, and particularly preferably 8 to 30.

  When x and z are too small, the transparency of the properties of the obtained elastomer is particularly lowered, and when y is too small, the rubber elasticity is lowered. Moreover, when x and z are too large, or when y is too large, compatibility with a polyamide component becomes low and it is difficult to obtain a tough elastomer. Therefore, it is preferably selected from the above range.

  Specific examples of the XYX-type triblock polyether diamine compound (A1) include XTJ-533 (manufactured by HUNTSMBN, 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, and z is about 2), and XTJ-559 (in formula (1), x is about 3, y is about 14, and z is about 2).

  Further, as the XYX type triblock polyether diamine compound (A1), XYX-1 (in formula (1), x is about 3, y is about 14, z is about 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 approximately 19, z is approximately 2), and the like can also be used.

  The proportion of the XYX-type triblock polyether diamine compound (A1) is preferably 2 to 87% by mass, particularly with respect to the total amount of the diamine compound (A), the polyamide-forming monomer (B) and the dicarboxylic acid compound (C). Preferably it is 7-78 mass%. When the ratio of the XYX type triblock polyether diamine compound (A1) is less than the above range, characteristics as an elastomer such as bending fatigue may not be sufficiently exhibited, which may be undesirable. When the ratio of the XYX type triblock polyether diamine compound (A1) is larger than the above range, there are few polyamide components, so that the excellent mechanical strength characteristic of polyamide may not be expressed, which may be undesirable.

  Examples of the branched saturated diamine having 6 to 22 carbon atoms of the diamine compound (A2) used in a preferred embodiment include 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4- Examples include trimethyl-1,6-hexanediamine, 1,2-diaminopropane, 1,3-diaminopentane, 2-methyl-1,5-diaminopentane, and 2-methyl-1,8-diaminooctane. These may be used alone, or may be used by mixing two or more kinds in an appropriate ratio.

  Examples of the branched alicyclic diamine having 6 to 16 carbon atoms of the diamine compound (A2) used in a preferred embodiment include 5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine and 5-amino. -1,3,3-trimethylcyclohexanemethylamine (also referred to as “isophoronediamine”) and the like. These diamines may be either cis- or trans-isomers or a mixture of these isomers. Further, these diamines may be used alone, or two or more kinds may be mixed and used in an appropriate ratio.

Examples of the norbornane diamine of the diamine compound (A2) used in a preferred embodiment include 2,5-norbonane dimethylamine, 2,6-norbonane dimethylamine, and mixtures thereof. These may be used alone, or may be used by mixing two kinds in an appropriate ratio. In a preferred embodiment, the ratio of the diamine compound (A2) is the diamine compound (A), the polyamide-forming monomer ( Preferably it is 0.5-10 mass% with respect to the total amount of B) and the dicarboxylic acid compound (C), More preferably, it is 1-5 mass%. When the ratio of a diamine compound (A2) is less than the said range, transparency may not fully be expressed and it may be unpreferable. When the ratio of the diamine compound (A2) is larger than the above range, the crystallinity derived from the polyamide-forming monomer is lowered, and sufficient mechanical strength is not expressed, which is not preferable.

  Moreover, as a diamine compound (A), you may include other diamine compounds (A3) other than a triblock polyether diamine compound (A1) and a diamine compound (A2).

  Other diamine compounds (A3) include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2 , 2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, aliphatic diamine such as 3-methylpentanemethylenediamine, bis (4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) propane , Cycloaliphatic diamines such as 1,3-bisaminomethylcyclohexane and 1,4-bisaminomethylcyclohexane, aromatic diamines such as metaxylylenediamine and paraxylylenediamine The recited, these diamines may be used alone, or two or more may be used in combination as appropriate.

  Next, the aminocarboxylic acid compound (B1) and the lactam compound (B2) in the polyamide-forming monomer (B) will be described.

In the aminocarboxylic acid compound (B1), R ² is preferably a hydrocarbon molecular chain having 2 to 20 carbon atoms, particularly an alkylene group having 2 to 20 carbon atoms, more preferably a carbon atom having 3 to 18 carbon atoms. Hydrogen molecular chain, particularly an alkylene group having 3 to 18 carbon atoms, more preferably a hydrocarbon molecular chain having 4 to 15 carbon atoms, particularly an alkylene group having 4 to 15 carbon atoms, particularly preferably carbon. A hydrocarbon molecular chain having several to 15 to 15 carbon atoms, particularly an alkylene group having 4 to 15 carbon atoms, particularly preferably a hydrocarbon molecular chain having 10 to 15 carbon atoms, particularly an alkylene group having 10 to 15 carbon atoms. Show.

In the lactam compound (B2), R ³ is preferably a hydrocarbon molecular chain having 3 to 20 carbon atoms, particularly an alkylene group having 3 to 20 carbon atoms, and more preferably a hydrocarbon group having 3 to 18 carbon atoms. A molecular chain, particularly an alkylene group having 3 to 18 carbon atoms, more preferably a hydrocarbon molecular chain having 4 to 15 carbon atoms, particularly an alkylene group having 4 to 15 carbon atoms, particularly preferably 10 carbon atoms. An alkylene group having 4 to 15 carbon atoms, particularly an alkylene group having 4 to 15 carbon atoms, particularly preferably an alkylene group having 10 to 15 carbon atoms or an alkylene group having 10 to 15 carbon atoms.

  Examples of the aminocarboxylic acid compound (B1) include 5-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 10-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like having 5 to 5 carbon atoms. There may be mentioned 20 aliphatic ω-aminocarboxylic acids.

  Examples of the lactam compound (B2) include aliphatic lactams having 5 to 20 carbon atoms such as ε-caprolactam, ω-enantolactam, ω-undecalactam, ω-dodecalactam, and 2-pyrrolidone.

  The ratio of the polyamide-forming monomer (B) with respect to all the components of the polyetheramide elastomer (X) is preferably 10 to 95% by mass, more preferably 15 to 95% by mass, more preferably 15 to 85% by mass, and particularly preferably. 15-80 mass% is preferable. When the ratio of the polyamide-forming monomer (B) with respect to all the components of the polyetheramide elastomer (X) is too small, the crystallinity of the polyamide component is lowered, and mechanical properties such as strength and elastic modulus are lowered. When the ratio of the polyamide-forming monomer (B) to all the components of the polyetheramide elastomer (X) is too large, the function and performance as an elastomer such as rubber elasticity and flexibility are hardly exhibited.

  In particular, when forming the laminate of the present invention in which the X layer and the Y layer are laminated, the ratio of the polyamide-forming monomer (B) is particularly excellent in the adhesion between the X layer and the Y layer within the above range. It is preferable because of its excellent mechanical properties as an elastomer such as strength, elastic modulus and flexibility. When the proportion of the polyamide-forming monomer (B) is less than the above range, the adhesive strength between the X layer and the Y layer may be insufficient, which is not preferable because mechanical properties such as strength and elastic modulus are lowered. There is. When the ratio of the polyamide-forming monomer (B) is more than the above range, it may be unfavorable because functions and performance as an elastomer such as rubber elasticity and flexibility are hardly exhibited. It can be presumed that the intermolecular hydrogen bond between the amide bond of the polyetheramide elastomer (X) and the urethane bond of the polyurethane has an influence on the adhesive strength between the X layer and the Y layer.

In the dicarboxylic acid compound (C), R ¹ is preferably a molecular chain having 1 to 20 carbon atoms, particularly an alkylene group having 1 to 20 carbon atoms, more preferably a hydrocarbon molecular chain having 1 to 15 carbon atoms. In particular, an alkylene group having 1 to 15 carbon atoms, more preferably a hydrocarbon molecular chain having 2 to 12 carbon atoms, particularly an alkylene group having 2 to 12 carbon atoms, and particularly preferably 4 to 10 carbon atoms. Represents a hydrocarbon molecular chain, particularly an alkylene group having 4 to 10 carbon atoms. m represents 0 or 1;

  As the dicarboxylic acid compound (C), at least one dicarboxylic acid selected from aliphatic, alicyclic and aromatic dicarboxylic acids or derivatives thereof can be used.

  Specific examples of the dicarboxylic acid compound (C) include linear fatty acids having 2 to 25 carbon atoms such as oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid. 14-48 dimerized aliphatic dicarboxylic acids (dimer acids) obtained by dimerizing unsaturated fatty acids obtained by fractional distillation of triglycerides, or hydrogenated products thereof (hydrogenated dimer acids), etc. Mention may be made of aliphatic dicarboxylic acids, alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, and aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid. As the dimer acid and hydrogenated dimer acid, “Prepol 1004”, “Prepol 1006”, “Prepol 1009”, “Prepol 1013” and the like can be used.

  As an example of the method for producing the polyetheramide elastomer (X), a polyamide-forming monomer (B), a diamine compound (A) {XYX-type triblock polyetherdiamine compound (A1) and, if necessary, a diamine compound (A2) including. } And the four components of the dicarboxylic acid compound (C) can be used by a method comprising melt polymerization under pressure and / or normal pressure, and further melt polymerization under reduced pressure, if necessary. A method in which the two components of the polyamide-forming monomer (B) and the dicarboxylic acid compound (C) are polymerized first, and then the diamine compound (A) is polymerized can also be used.

  In the production of the polyetheramide elastomer (X), there is no particular limitation on the method of charging the raw materials, but the charging ratio of the polyamide-forming monomer (B), the diamine compound (A), and the dicarboxylic acid compound (C) The polyamide-forming monomer (B) is preferably 10 to 95% by mass, particularly preferably in the range of 15 to 80% by mass, and the XYX type triblock polyether diamine compound (A1) is preferably 2 to 87% by mass. The diamine compound (A2) contained in a preferable form, particularly preferably 7 to 78% by mass, is preferably 0.5 to 10% by mass, particularly preferably 1 to 5% by mass. In the diamine compound (A) and the dicarboxylic acid compound (C), the amino group of the diamine compound (A) (including the amino group when other diamine compounds are included) and the carboxyl group of the dicarboxylic acid compound (C) are almost the same. It is preferable to charge so that it may become equimolar.

  The production of the polyetheramide elastomer (X) can be carried out at a polymerization temperature of preferably 150 to 300 ° C, more preferably 160 to 280 ° C, particularly preferably 170 to 250 ° C. When the polymerization temperature is lower than the above temperature, the polymerization reaction is slow. When the polymerization temperature is higher than the above temperature, thermal decomposition tends to occur, and a polymer having good physical properties may not be obtained.

  The polyetheramide elastomer (X) is produced by a method comprising steps of normal pressure melt polymerization or normal pressure melt polymerization followed by low pressure melt polymerization when ω-aminocarboxylic acid is used as the polyamide-forming monomer (B). can do.

  On the other hand, when lactam is used as the polyamide-forming monomer (B), an appropriate amount of water is allowed to coexist, and melt polymerization under pressure of 0.1 to 5 MPB, followed by normal pressure melt polymerization and / or reduced pressure melt polymerization. Can be manufactured by the following method.

  The polyetheramide elastomer (X) can be produced with a polymerization time of usually 0.5 to 30 hours. When the polymerization time is shorter than the above range, the molecular weight is not sufficiently increased, and when the polymerization time is long, coloring due to thermal decomposition occurs, and in any case, the polyetheramide elastomer (X) having desired physical properties may not be obtained. .

  The production of the polyetheramide elastomer (X) 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 it can use combining suitably.

  The polyetheramide elastomer (X) preferably has a relative viscosity (ηr) in the range of 1.2 to 3.5 (0.5 mass / volume% metacresol solution, 25 ° C.).

  In the production of the polyetheramide elastomer (X), a monoamine such as laurylamine, stearylamine, hexamethylenediamine, metaxylylenediamine, or a diamine for adjusting the molecular weight and stabilizing the melt viscosity at the time of molding as required. Acetic acid, benzoic acid, stearic acid, adipic acid, sebacic acid, monocarboxylic acid such as dodecanedioic acid, or dicarboxylic acid can be added. These used amounts are appropriately added so that the relative viscosity (ηr) of the finally obtained elastomer is in the range of 1.2 to 3.5 (0.5 mass / volume% metacresol solution, 25 ° C.). It is preferable.

  In the production of the polyetheramide elastomer (X), the addition amount of the monoamine and diamine, monocarboxylic acid, dicarboxylic acid and the like is preferably in a range where the properties of the resulting polyetheramide elastomer (X) are not inhibited.

  In the production of the polyetheramide elastomer (X), phosphoric acid, pyrophosphoric acid, polyphosphoric acid, etc. are used as a catalyst as necessary, and phosphorous acid, hypophosphorous acid, And inorganic phosphorus compounds, such as these 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.

  In the X layer, additives such as 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, as long as the properties are not hindered, Sealing property improvers, antifogging agents, mold release agents, plasticizers, pigments, dyes, fragrances, flame retardants, reinforcing materials, and the like can be added.

  Furthermore, in addition to the polyetheramide elastomer (X), other known polyamide elastomers may be contained in the X layer. Other polyamide elastomers include at least one polyamide block composed of at least one aliphatic nylon selected from nylon 6, nylon 66, nylon 11 and nylon 12, and at least selected from polyoxyethylene, polyoxypropylene and polyoxybutylene. An elastomer composed of one kind of polyether block is exemplified. These other polyamide-based elastomers are generally 30% by weight or less, preferably 10% by weight or less (or 0% by weight) based on the total amount with the polyetheramide elastomer (X).

<Plasticizer>
A plasticizer may be added to the X layer. The plasticizer is one or more kinds of compounds selected from esters and alkylamides. The esters referred to in the present invention are phthalic acid esters, fatty acid esters, polyhydric alcohol esters, phosphoric acid esters, trimellitic acid esters and hydroxybenzoic acid esters. Specific examples of phthalates include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, diisodecyl phthalate, ditridecyl phthalate, phthalate Examples include dicyclohexyl acid, butyl benzyl phthalate, diisononyl phthalate, ethyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, diundecyl phthalate, and di-2-ethylhexyl tetrahydrophthalate.

  Specific 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, Adipic acid di-n-mixed alkyl ester, dimethyl sebacate, dibutyl sebacate, di-2-ethylhexyl sebacate, di-2-ethylhexyl azelate, di-2-ethylhexyl mixed acid ester, bis-2-ethylhexyl dodecamate Dibasic saturated carboxylic acid esters such as dibutyl fumarate, bis-2-methylpropyl fumarate, bis-2-ethylhexyl fumarate, dimethyl maleate, diethyl maleate, dibutyl maleate, bis-2-ethyl maleate Dibasic unsaturated carboxylic acid esters such as hexyl, butyl oleate, Izobuchiru oleate, acetyl butyl ricinoleate, and the like acetyl tributyl citrate and acetate-2-ethylhexyl.

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

  Specific examples of phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, n-octyldiphenyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, trixylenyl phosphate And 2-ethylhexyldiphenyl phosphate.

  Specific 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 Etc.

  Specific examples of hydroxybenzoic acid esters include ethylhexyl o- or p-hydroxybenzoate, o- or p-hydroxybenzoic acid-2-hexyldecyl (HDPB), o- or ethyldecyl hydroxybenzoate, o- Or octyloctyl p-hydroxybenzoate, o- or decyldodecyl p-hydroxybenzoate, methyl o- or p-hydroxybenzoate, o- or butyl p-hydroxybenzoate, o- or hexyl p-hydroxybenzoate, Examples include n-octyl o- or p-hydroxybenzoate, decyl o- or p-hydroxybenzoate, and dodecyl o- or p-hydroxybenzoate.

  The alkylamides are toluenesulfonic acid alkylamides and benzenesulfonic acid alkylamides. Specific 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. Specific examples of the benzenesulfonic acid alkylamides include benzenesulfonic acid propylamide, N-butylbenzenesulfonic acid amide (BBSA), benzenesulfonic acid butyramide, benzenesulfonic acid-2-ethylhexylamide, and the like. 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, hydroxy benzoates such as ethyl hexyl p-hydroxybenzoate, hexyl decyl p-hydroxybenzoate Alkylamides such as benzenesulfonic acid butyramide and benzenesulfonic acid-2-ethylhexylamide are preferably used.

<< resin composition for X layer >>
The method for obtaining the resin composition constituting the X layer is not particularly limited, and various known methods can be used. For example, the first thermoplastic resin and the polyetheramide elastomer (X) are mixed with a predetermined amount of various additives as needed, and a high-speed rotary mixer such as a V-type blender or tumbler or a Henschel mixer. There is a method in which the mixture is preliminarily mixed using a machine, and then melt-kneaded and pelletized with a single-screw extruder, a twin-screw extruder, or the like. This pellet is used in a molding process for forming an X layer in the laminate. Further, the first thermoplastic resin and the polyetheramide elastomer (X) are mixed in advance together with predetermined amounts of various additives as required using a high-speed rotary mixer such as a low-speed rotary mixer or a Henschel mixer. Thereafter, a method of directly forming the X layer in a molding process for forming the X layer can be applied.

  The resin composition for the X layer has excellent melt moldability, excellent moldability, excellent toughness, excellent impact resistance, and excellent hydrolysis resistance.

<< Y layer and second thermoplastic resin >>
The Y layer is composed of a second thermoplastic resin mainly composed of a polyurethane resin. The second thermoplastic resin usually contains 70% or more, preferably 80% or more, more preferably 90%, most preferably 95% or more of a polyurethane resin on a mass basis. It may consist essentially of a polyurethane resin. Here, examples of the component other than the polyurethane resin include thermoplastic polymers, elastomers, rubbers, and the like, which can be blended with the polyurethane resin.

  The Y layer may contain other resins other than polyurethane as long as the characteristics are not impaired. However, when the second thermoplastic resin is constituted together with these polyurethane resins, the second thermoplastic resin. In the case where the second thermoplastic resin is not constituted, the other components are preferably 70% by mass or less, more preferably 20% by mass or less, more preferably 10% by mass or less, particularly preferably. Is contained in an amount of 5% by mass or less (may be 0%).

  The polyurethane resin is preferably a thermoplastic polyurethane. The above-mentioned resin composition for the X layer can be advantageously used for forming a laminate with a thermoplastic polyurethane, and is particularly preferably used in sports shoe soles, ski boots and the like. In particular, the present invention is advantageous in providing a laminate directly laminated with a thermoplastic polyurethane.

  As the polyurethane resin, polyurethane obtained by reacting polyol and diisocyanate, polyurethane obtained by reacting chain extender and diisocyanate, polyurethane obtained by reacting polyol, diisocyanate and chain extender, and the like are used. Can do. In particular, it is preferable to use thermoplastic polyurethane as the polyurethane.

  In the Y layer, as the polyurethane, a thermoplastic polyurethane having a polyester diol and / or a polyether diol as a soft segment can be preferably used.

  As the polyol, condensed polyester polyols, lactone polyester polyols, polycarbonate polyols, polyether polyols, and the like are used. As the condensed polyester polyol, a polyester diol obtained by using one or more of dicarboxylic acid and diol is preferably used.

  Examples of the dicarboxylic acid include glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid and other aliphatic dicarboxylic acids; cyclohexanedicarboxylic acid and other alicyclic dicarboxylic acids; terephthalic acid, isophthalic acid, An aromatic dicarboxylic acid such as orthophthalic acid, or a lower alkyl ester thereof can be mentioned, and one or more of them can be used. Among these, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, and sebacic acid, or lower alkyl esters thereof are preferable.

  Examples of the diol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6- Hexanediol, 1,7-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1 Aliphatic diols such as 1,12-dodecanediol; cycloaliphatic diols such as cyclohexanedimethanol and cyclohexanediol, and one or more of these can be used. Among these, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,12 It is preferred to use an aliphatic diol such as dodecanediol.

  Lactone-based polyester polyols include short-chain lactone compounds such as β-propiolactone, pivalolactone, δ-valerolactone, ε-caprolactone, methyl-ε-caprolactone, dimethyl-ε-caprolactone, and trimethyl-ε-caprolactone. What reacted with hydroxy compounds, such as a polyol, is mentioned.

  The polycarbonate diol can be obtained, for example, by a reaction between a low molecular diol and a carbonate compound such as an alkyl carbonate, alkylene carbonate, or diaryl carbonate. As the low molecular diol which is a raw material for producing polycarbonate diol, the low molecular diols exemplified above as the raw material for producing polyester diol can be used. Examples of the dialkyl carbonate include dimethyl carbonate and diethyl carbonate, examples of the alkylene carbonate include ethylene carbonate, and examples of the diaryl carbonate include diphenyl carbonate.

  Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxypropylene glycol, and glycerin-based polyalkylene ether glycol. In addition to the above, various known polyols for polyurethane can also be used.

  The type of polyisocyanate used for polyurethane is not particularly limited, and any of the polyisocyanates conventionally used for producing polyurethane, preferably thermoplastic polyurethane, can be used.

  Examples of polyisocyanates include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, cyclohexylmethane diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate, and isopropylidenebis (4-cyclohexylisocyanate). ), Aliphatic or cycloaliphatic diisocyanates such as isophorone diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 3-methyldiphenylmethane-4,4'-diisocyanate, m- or p-phenylene diisocyanate, chlorophenylene 2,4-diisocyanate, naphthalene-1,5-diisocyanate, xylylene diene Isocyanate, may be used an aromatic diisocyanate, such as tetramethyl xylylene diisocyanate can be used alone or in combination of two or more polyisocyanates of these. Of these, 4,4'-diphenylmethane diisocyanate is preferably used.

  The type of chain extender used in the production of the polyurethane is not particularly limited, and any of the chain extenders conventionally used in the production of ordinary polyurethane can be used, but an active hydrogen atom capable of reacting with an isocyanate group is used. It is preferable to use a low molecular weight compound having a molecular weight of 300 or less having two or more in the molecule.

  Chain extenders include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-cyclohexanediol, bis- (β -Hydroxyethyl) terephthalate, xylylene glycol and other diols; hydrazine, ethylenediamine, propylenediamine, xylylenediamine, isophoronediamine, piperazine and derivatives thereof, phenylenediamine, tolylenediamine, xylenediamine, adipic acid dihydrazide, isophthalic acid dihydrazide Diamines such as: alcohols such as aminoethyl alcohol and aminopropyl alcohol, and the like, and one or more of these can be used. Preferably, zero aliphatic diol is used, and 1,4-butanediol is preferably used.

  As the chain extender, polyhydric alcohol, polyhydric amine and the like can be used. Specific commercial names on the market include “Pandex” (manufactured by Dainippon Ink & Chemicals, Inc.), “Kuramylon” (manufactured by Kuraray Co., Ltd.), “Milactolan” (manufactured by Nihon Miractolan)

  As thermoplastic polyurethanes (TPU etc.), trade names “Elastollan ET195”, “Elastollan ET690”, “Elastollan ET890” manufactured by BASF Japan, and trade names “Pandex T-8190U” manufactured by Dainippon Ink & Chemicals, Inc. "Milactolan E190", "Milactolane E390", "Milactolane E490", "Milactolane E590", "Milactolane E990", etc. manufactured by Nippon Polyurethane Industry Co., Ltd. can be used.

<< Laminate >>
The X layer and / or the Y layer can be obtained by a molding method such as injection molding, extrusion molding, blow molding, or calendar molding using the above-described resin.

  The laminated body is (1) a method of simultaneously forming each layer including the X layer and the Y layer, (2) a method of forming and bonding the layers, and (3) a method of stacking layers while forming further layers (tandem) Method) or a combination thereof.

  The laminate has one or more X layers and Y layers. The thickness of each layer is not particularly limited, and can be adjusted according to the type of polymer constituting each layer, the total number of layers in the laminate, the application, and the like. Moreover, although the number of layers of a laminated body is two or more layers, the whole number of layers in a laminated body is not restrict | limited in particular, Any may be sufficient. Judging from the mechanism of the laminate manufacturing apparatus, it is 7 layers or less, preferably 2 to 5 layers.

  Furthermore, an adhesive layer may be provided for the purpose of improving the adhesion between the layers. It is also possible to laminate any substrate other than thermoplastic resin, such as paper, metal-based materials, non-stretched, uniaxially or biaxially stretched plastic film or sheet, woven fabric, non-woven fabric, metallic cotton, wood, etc. It is. Examples of the metal-based material include aluminum, iron, copper, nickel, gold, silver, titanium, molybdenum, magnesium, manganese, lead, tin, chromium, beryllium, tungsten, cobalt, and other metals and metal compounds, and two or more of these. Examples include alloy steels such as stainless steel, aluminum alloys, rigid alloys such as brass and bronze, and alloys such as nickel alloys.

  Examples of the laminated structure of the laminate of the present invention include X layer / Y layer, X layer / Y layer / X layer, Y layer / X layer / Y layer, X layer / Y layer / base material layer, base material layer / X layer / Y layer, X layer / Y layer / X layer / base material layer, Y layer / X layer / Y layer / base material layer, Y layer / X layer / adhesive layer / base material layer, X layer / Y Layer / adhesive layer / base material layer, base material layer / adhesive layer / X layer / Y layer / X layer / adhesive layer / base material layer, base material layer / adhesive layer / Y layer / X layer / Y layer / adhesive layer / Substrate layer. The base layer is obtained from inorganic fibers made from natural / synthetic fibers, glass / ceramics, etc .; films, sheets, membranes and molded articles obtained from other polymer materials, excluding the polymers of the X layer and Y layer Woven fabrics, knitted fabrics, braided fabrics, and non-woven fabrics; glass, metals, ceramics, coating films, paper, etc .; leathers and the like can be used.

  When the adhesive layer is used, it is possible to use known adhesive components, adhesive sheets or films, and those that do not impair the characteristics of the present invention are preferably used.

The laminate of the present invention can be used for automobile parts, industrial materials, industrial materials, electrical and electronic parts, machine parts, office equipment parts, household goods, sporting goods, shoe parts, containers, sheets, films, fibers, and other arbitrary uses. And used as various shaped products. More specifically, an industrial tube or hose, a pneumatic tube or hose, a hydraulic tube or hose, a paint spray hose or tube, a tube or hose for automobile piping, and the like can be mentioned. Among them, it is useful as an industrial hose or tube.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated, this invention is not limited to these Examples. In the following examples, comparative examples, and production examples, the polyetheramide elastomer (X) and other polyamide-based elastomers may be collectively referred to as polyamide-based elastomers.

  The physical property values were measured as follows.

(1) Relative viscosity (ηr) (0.5 wt / vol% metacresol solution, 25 ° C.):
Using reagent-grade m-cresol as a solvent, it was measured at 25 ° C. using an Ostwald viscometer at a concentration of 5 g / dm ³ .

<Measurement method of adhesive strength>
The peel strength was measured at a tensile rate of 50 mm / min using Tensilon 2500 manufactured by Orientec Co., Ltd. as a T peel test apparatus.

<Production Example 1: Production of PAE1>
In a 70 liter pressure vessel equipped with a stirrer, thermometer, torque meter, pressure gauge, nitrogen gas inlet, pressure regulator and polymer outlet, 12.231 kg of 12-aminododecanoic acid manufactured by Ube Industries, Ltd., adipic acid 1 0.089 kg, XYX type triblock polyether diamine (XTJ-542 manufactured by HUNTSMAN, amine value: 1.94 meq / g) 7.680 kg, 6 g of sodium hypophosphite monohydrate and heat-resistant agent Minox 917) 60 g was charged. After sufficiently replacing the inside of the container with nitrogen, the temperature inside the container was raised from room temperature to 230 ° C. over 3.5 hours while the pressure inside the container was adjusted to 0.05 MPa while supplying nitrogen gas at 186 liters / hour. Polymerization was carried out at 230 ° C. for 4 hours while adjusting the internal pressure to 0.05 MPa to obtain a polymer. After completion of the polymerization, stirring was stopped, and the colorless and transparent polymer in a molten state was drawn out from the polymer outlet in a string shape, cooled with water, and pelletized to obtain about 15 kg of pellets. The obtained pellet was a colorless and translucent tough polymer rich in rubber elasticity, and ηr = 1.98.

<Production Example 2: Production of PAE2>
A 70-liter pressure vessel equipped with a stirrer, thermometer, torque meter, pressure gauge, nitrogen gas inlet, pressure regulator and polymer outlet, 12-aminododecanoic acid manufactured by Ube Industries, Ltd., 10.725 kg, adipic acid 1 390 kg, XYX type triblock polyether diamine (XTJ-542 manufactured by HUNTSMAN, amine value: 1.94 meq / g) 7.505 kg, isophorone diamine (trade name: VESTAMIN IPD manufactured by Degussa) 0.380 kg, hypochlorous 6 g of sodium phosphate monohydrate and 60 g of heat-resistant agent (Tominox 917 manufactured by Yoshitomi Pharmaceutical) were charged. After sufficiently replacing the inside of the container with nitrogen, the temperature inside the container was raised from room temperature to 230 ° C. over 3.5 hours while the pressure inside the container was adjusted to 0.05 MPa while supplying nitrogen gas at 186 liter / hour, Polymerization was carried out at 230 ° C. for 4 hours while adjusting the internal pressure to 0.05 MPa to obtain a polymer. After completion of the polymerization, stirring was stopped, and the colorless and transparent polymer in a molten state was drawn out from the polymer outlet in a string shape, cooled with water, and pelletized to obtain about 15 kg of pellets. The obtained pellet was a colorless and translucent tough polymer rich in rubber elasticity, and ηr = 1.99.

<Production Example 3: Production of PAE3>
In a 70 liter pressure vessel equipped with a stirrer, thermometer, torque meter, pressure gauge, nitrogen gas inlet, pressure regulator and polymer outlet, 12.985 kg of 12-aminododecanoic acid manufactured by Ube Industries, Ltd., adipic acid 1 115 kg, XYX-type triblock polyether diamine (XTJ-559 manufactured by HUNTSMAN, amine value: 1.40 meq / g), 10.900 kg, sodium hypophosphite monohydrate 6 g and heat-resistant agent Minox 917) 60 g was charged. After sufficiently replacing the inside of the container with nitrogen, the temperature inside the container was raised from room temperature to 230 ° C. over 3.5 hours while the pressure inside the container was adjusted to 0.05 MPa while supplying nitrogen gas at 186 liters / hour. Polymerization was carried out at 230 ° C. for 4 hours while adjusting the internal pressure to 0.05 MPa to obtain a polymer. After completion of the polymerization, stirring was stopped, and the colorless and transparent polymer in a molten state was drawn out from the polymer outlet in a string shape, cooled with water, and pelletized to obtain about 15 kg of pellets. The obtained pellet was a colorless and translucent tough polymer rich in rubber elasticity, and ηr = 1.98.

<Production Example 4: Production of PAE4>
12-aminododecanoic acid (manufactured by Ube Industries, Ltd.) 12.897 kg and adipine in a 70 liter pressure vessel equipped with a stirrer, thermometer, torque meter, pressure gauge, nitrogen gas inlet, pressure regulator and polymer outlet 0.906 kg of acid (special grade reagent) was charged. After sufficiently replacing the container with nitrogen, the container was gradually heated while supplying nitrogen gas at a flow rate of 300 liters / hour. Stirring was performed at a speed of 20 rpm. The temperature was raised from room temperature to 240 ° C. over 3 hours, and polymerization was carried out at 230 ° C. for 4 hours to synthesize nylon 12 oligomers.

  To this oligomer, 6.197 kg of polytetramethylene glycol (manufactured by BASF, PolyTHF1000), 0.020 kg of tetrabutylzirconate and 0.050 kg of an antioxidant (trade name: Tominox 917, manufactured by Yoshitomi Pharmaceutical) were charged. After sufficiently replacing the inside of the container with nitrogen, heating was performed gradually while supplying nitrogen gas at a flow rate of 300 liters / hour. Stirring was performed at a speed of 20 rpm. The temperature was raised from room temperature to 210 ° C. over 3 hours, heated at 210 ° C. for 3 hours, then gradually reduced in pressure to 50 Pa over 1 hour, polymerized for 2 hours, and then increased over 30 minutes. The temperature and pressure were reduced, and polymerization was completed at 230 ° C. and about 30 Pa for 3 hours. Next, stirring was stopped, nitrogen gas was supplied into the polymerization layer, and the pressure was returned to normal pressure. Next, a colorless and transparent polymer in a molten state was drawn out from the polymer outlet, cooled with water, and pelletized to obtain about 13 kg of pellets.

  The obtained polymer was polyether ester amide, and the pellets were white tough and flexible polymer rich in rubber elasticity, and ηr = 2.01.

<Example 1>
A polyamide resin molding material was prepared by melting and kneading 100 parts by mass of nylon 12 (trade name: 3020U) manufactured by Ube Industries, Ltd. and 11.1 parts by mass of polyamide elastomer (Production Example 1: PAE1).

  On the other hand, BASF Japan Co., Ltd. product name: Elastollan ET890 was used as the ether-based TPU (thermoplastic polyurethane), and BASF Japan Ltd. product name: Elastollan ET690 was used as the ester-based TPU.

  Using the above polyamide and TPU, a polyamide molded body and a TPU molded body are thermally welded according to the following method to produce a test laminate having a width of 25 mm, a length of 120 mm, and a thickness of 3.5 mm, and measuring the adhesive strength. did. The results are shown in Table 1.

<Production of laminate>
(1) Preparation of polyamide sheet About 25 g of the polymerized PA pellets were set in a spacer (120 mm × 120 mm, thickness 1.5 mm). Next, the spacer, metal plate, and Teflon sheet are set to have a layer structure of metal plate / Teflon (registered trademark, the same applies hereinafter) sheet / spacer / Teflon sheet / metal plate, and this is set in a press molding machine. The sample was preheated at 190 ° C. for 2 minutes without pressure, then pressed and pressed at 190 ° C. for 2 minutes at 10 kg / cm ² , taken out, cooled and molded for 2 minutes.

(2) Production of TPU (thermoplastic polyurethane) sheet About 45 g of TPU pellets were set in a spacer (120 mm × 120 mm, thickness 2 mm). Next, the spacer, metal plate, and Teflon sheet are set so as to have a layer structure of metal plate / Teflon sheet / spacer / Teflon sheet / metal plate, and this is set in a press molding machine. The sample was preheated at 190 ° C. for 1 minute, then pressed and pressed at 190 ° C. for 2 minutes at 10 kg / cm ² , taken out, cooled and molded for 2 minutes.

(3) Production of Laminate Sheet The polyamide sheet and TPU sheet produced in (1) and (2) above were stacked in two layers and set in a spacer of 120 mm × 120 mm and a thickness of 3.5 mm.

Next, the spacer, the metal plate layer, and the Teflon sheet were set so that the layer configuration was metal plate / Teflon sheet / spacer / Teflon sheet / metal plate, and this was set on a press molding machine. Next, it was preheated at 210 ° C. for 1 minute without pressure, then pressed and pressed at 210 ° C. for 1 minute at 10 kg / cm ² , taken out, cooled and molded for 2 minutes. The sample was cut out with a width of 25 mm and used for a T peel test as a test sample.

<Comparative Example 1>
A test laminate was prepared in the same manner as in Example 1 except that PAE1 was not added, and the adhesive strength was measured. The results are shown in Table 1.

<Example 2>
In the preparation of the polyamide resin molding material in Example 1, a test laminate was prepared in the same manner as in Example 1 except that PAE2 was used instead of PAE1, and the adhesive strength was measured. The results are shown in Table 1.

<Example 3>
In the preparation of the polyamide resin molding material in Example 1, a test laminate was prepared in the same manner as in Example 1 except that PAE3 was used instead of PAE1, and the adhesive strength was measured. The results are shown in Table 1.

<Comparative example 2>
In the preparation of the polyamide resin molding material in Example 1, a test laminate was prepared in the same manner as in Example 1 except that PAE4 was used instead of PAE1, and the adhesive strength was measured. The results are shown in Table 1.

<Example 4>
100 parts by mass of nylon 12 (trade name: 3020U) manufactured by Ube Industries, Ltd., 20.0 parts by mass of 2-hexyldecyl p-hydroxybenzoate (hereinafter referred to as “HDPB”), and polyamide elastomer (Production Example 1: PAE1) ) A test laminate was prepared in the same manner as in Example 1 except that 13.3 parts by mass was melt-kneaded to prepare a polyamide resin molding material, and the adhesive strength was measured. The results are shown in Table 1.

<Example 5>
In the preparation of the polyamide resin molding material in Example 3, the test laminate was prepared in the same manner as in Example 3 except that N-butylbenzenesulfonic acid amide (hereinafter referred to as “BBSA”) was used instead of HDB. Prepared and measured the adhesive strength. The results are shown in Table 1.

<Comparative Example 3>
A test laminate was prepared in the same manner as in Example 4 except that PAE1 was not added, and the adhesive strength was measured. The results are shown in Table 1.

<Comparative example 4>
A test laminate was prepared in the same manner as in Example 5 except that PAE1 was not added, and the adhesive strength was measured. The results are shown in Table 1.

<Example 6>
In the preparation of the polyamide resin molding material in Example 1, a test laminate was prepared in the same manner as in Example 1 except that nylon 6 (trade name: 1024B) manufactured by Ube Industries, Ltd. was used instead of 3030U. Prepared and measured the adhesive strength. The results are shown in Table 1.

<Comparative Example 5>
A test laminate was prepared in the same manner as in Example 6 except that PAE1 was not added, and the adhesive strength was measured. The results are shown in Table 1.

Claims (8)

An X layer containing a first thermoplastic resin mainly composed of a polyamide resin and a polyetheramide elastomer (X);
A structure in which a Y layer containing a second thermoplastic resin mainly composed of a polyurethane resin is laminated,
The polyetheramide elastomer (X) is
A diamine compound (A) containing a triblock polyether diamine compound (A1) represented by the following formula (1);
A polyamide-forming monomer (B) containing at least one of an aminocarboxylic acid compound (B1) represented by the following formula (3) and a lactam compound (B2) represented by the following formula (4) ;
A laminate obtained by polymerizing a component containing a dicarboxylic acid compound (C).

(However, x represents an integer of 1 to 20, y represents an integer of 4 to 50, and z represents an integer of 1 to 20, respectively.)

(However, R ² represents a linking group containing a hydrocarbon chain.)

(However, R ³ represents a linking group containing a hydrocarbon chain.)   The diamine compound (A) further includes at least one diamine compound (A2) selected from the group consisting of branched saturated diamines having 6 to 22 carbon atoms, branched alicyclic diamines having 6 to 16 carbon atoms, and norbornane diamines. The laminate according to claim 1, comprising:   The laminate according to claim 1 or 2, wherein the X layer contains 95 to 50% by mass of the first thermoplastic resin and 5 to 50% by mass of the polyetheramide elastomer (X). . The said dicarboxylic acid compound (C) is represented by following formula (2), The laminated body in any one of Claims 1-3 characterized by the above-mentioned.

(However, R ¹ represents a linking group containing a hydrocarbon chain, and m represents 0 or 1.) The laminate according to any one of claims 1 to 4 , wherein the dicarboxylic acid compound (C) contains at least one of an aliphatic dicarboxylic acid compound and an alicyclic dicarboxylic acid compound. The laminate according to any one of claims 1 to 5 , wherein the X layer contains a plasticizer. The laminate according to claim 6 , wherein the polyurethane resin is a thermoplastic polyurethane. The laminate according to claim 7, wherein the thermoplastic polyurethane has at least one unit selected from the group consisting of polyester diol, polyether diol, polycarbonate diol, and polycaprolactone diol as a soft segment.