WO2018088495A1

WO2018088495A1 - Polyamide resin, molded body, laminate, medical device, and polyamide resin production method

Info

Publication number: WO2018088495A1
Application number: PCT/JP2017/040477
Authority: WO
Inventors: 加藤　隆之
Original assignee: 株式会社カネカ
Priority date: 2016-11-10
Filing date: 2017-11-09
Publication date: 2018-05-17
Also published as: JPWO2018088495A1; JP7118891B2

Abstract

A polyamide resin with excellent balance of mechanical characteristics such as breaking strength and breaking elongation in a solid state, a molded body containing said polyamide resin, a laminate provided with a film or sheet containing said polyamide resin, a medical device provided with the aforementioned molded body and or the aforementioned laminate, and a production method of the aforementioned polyamide resin are provided. A polyamide resin is used which contains a linear aliphatic dicarbonyl unit with a carbon number of 10-20 as unit (a), a linear aliphatic diamino unit with a carbon number of 10-20 as unit (b), and an aliphatic unit of a prescribed structure other than those of unit (a) and unit (b).

Description

POLYAMIDE RESIN, MOLDED BODY, LAMINATE, MEDICAL DEVICE, AND METHOD FOR PRODUCING POLYAMIDE RESIN

The present invention includes at least one of a polyamide-based resin, a molded body including the polyamide-based resin, a laminate including a film or sheet including the polyamide-based resin, the above-described molded body, and the above-described stacked body. The present invention relates to a medical device and a method for producing the aforementioned polyamide-based resin.

Polyamide-based resins such as polyamide elastomers are resin compounds that are widely used in various fields such as packaging materials for foods, medical device members, electrical / mechanical precision device members, automobile members, and the like. Among these, as a member for medical equipment, it is used as constituent materials, such as a medical tube and a balloon for catheters, for example. When used as a medical device member, the polyamide elastomer has an extrudability that can be precisely molded into a desired shape, a moldability such as blow moldability, a flexibility that can withstand breakage due to pressure and bending during use, and fracture Mechanical properties such as elongation and breaking strength are required.

Patent Document 1 discloses a block polyether amide obtained by polycondensing a polyamide having a carboxy group at both ends, an aminopolyoxyalkylene at both ends having an alkylene group having 3 or more carbon atoms, and a predetermined diamine. Has been. Patent Document 2 discloses a polyether amide obtained by polycondensation of a polyamide-forming monomer, an aminopolyoxyalkylene at both ends having an alkylene group having 3 or more carbon atoms, a predetermined diamine and a specific amount of dicarboxylic acid. It is disclosed. The polyether amides described in Patent Document 1 and Patent Document 2 are considered to have a certain degree of flexibility and impact resistance.
However, in the polyteramide having the component structure described in Patent Documents 1 and 2, even when a polyether having an alkylene group having 3 or more carbon atoms is used, the mechanical strength such as flexibility, elongation at break and strength at break is high. It was insufficient and further improvement was required.

Patent Document 3 includes (A) a polyamide-forming monomer selected from a predetermined aminocarboxylic acid compound and a predetermined lactam compound, (B) a polyether diamine having a PTMO (polytetramethylene oxide) skeleton, a branched diamine, and a branched diamine. A polyamide elastomer obtained by polymerizing at least one diamine compound selected from alicyclic diamine and norbornanediamine and (C) a predetermined dicarboxylic acid compound is disclosed. However, these diamine compounds used in the invention described in Patent Document 3 are poor in reactivity and require a long polymerization time. Therefore, there is a problem that a part of the polymer is thermally decomposed during the polymerization, and the resulting elastomer is colored or the strength such as breaking elongation and breaking strength of the obtained elastomer is not sufficient. .

Patent Document 4 discloses a copolymer polyether polyamide resin for coating or impregnation on a flexible woven or knitted fabric having a breaking elongation of 1000% or more and an elastic modulus of 15 MPa or less. Further, as a specific configuration, a soft segment composed of a polyether polyamide composed of a polyetherdiamine compound having an alkylene group having 2 to 3 carbon atoms and a predetermined dicarboxylic acid compound, and a predetermined aminocarboxylic acid and / or Alternatively, a polyether polyamide resin is disclosed in which hard segments made of polyamide composed of a predetermined lactam compound are bonded. However, the polyether polyamide resin described in Patent Document 4 has a problem that the reactivity of the polyether component is low and the breaking strength of the resin is not sufficient.

JP 59-193923 A JP 59-131628 A International Publication No. 2007/145324 International Publication No. 2009/139087

In view of the above problems, an object of the present invention is to provide a polyamide-based resin excellent in the balance of mechanical properties such as breaking strength and elongation at break in a solid state, a molded body including the polyamide-based resin, and the polyamide-based resin. It is providing the laminated body provided with the film or sheet | seat containing resin, the medical device provided with at least 1 of the above-mentioned molded object, and the above-mentioned laminated body, and the manufacturing method of the above-mentioned polyamide-type resin.

As a result of intensive studies for solving the above-mentioned problems, the present inventors have completed the present invention. That is, the present invention provides the following polyamide resins [1] to [7], [8] to [9] molded articles, [10] laminates, [11] medical devices, [12] to [14]. The present invention relates to a method for producing a polyamide-based resin.

[1] selected from the group consisting of unit (a) and unit (b), and further comprising unit (cI), unit (c-II), unit (dI), and unit (d-II) A polyamide-based resin comprising at least one of the following:
The unit (a) is represented by the following formula (A):
—CO—R ¹ —CO— (A)
(In Formula (A), R ¹ is a linear aliphatic group having 8 to 20 carbon atoms.)
Is a unit represented by
The unit (b) is represented by the following formula (B):
—NH—R ² —NH— (B)
(In the formula (B), R ² is a linear aliphatic having 10 to 20 carbon atoms.)
A unit (b) represented by:
The unit (cI) is represented by the following formula (CI):
—CO—R ³ (—O—R ⁴ ) _m —CO— (CI)
(In the formula (CI), R ³ and R ⁴ are each independently a chain aliphatic group having 1 to 6 carbon atoms, and m is an integer of 1 to 30.)
Is a unit represented by
The unit (c-II) is represented by the following formula (C-II):
—NH—R ⁵ (—O—R ⁶ ) _n —NH— (C-II)
(In Formula (C-II), R ⁵ and R ⁶ are each independently a chain aliphatic group having 1 to 3 carbon atoms, and n is an integer of 1 to 30.)
Is a unit represented by
The unit (dI) is represented by the following formula (DI):
—CO—R ⁷ —CO— (DI)
(In the formula (DI), R ⁷ is a linear or branched aliphatic group having 1 to 20 carbon atoms, but in a linear aliphatic group having 8 to 20 carbon atoms, Absent.)
Is a unit represented by
The unit (d-II) is represented by the following formula (D-II):
—NH—R ⁸ —NH— (D-II)
(In the formula (D-II), R ⁸ is a linear or branched aliphatic group having 1 to 20 carbon atoms, but in a linear aliphatic group having 10 to 20 carbon atoms, Absent.)
Is a unit represented by
In the polyamide-based resin, the content of the unit (a) and the content of the unit (b) are 1% by mass or more and 50% by mass or less,
When the polyamide-based resin contains at least one selected from the unit (cI) and the unit (c-II), the content of the unit (cI) in the polyamide-based resin and the unit (c-II) And the total content is 1 mass% or more and 50 mass% or less,
When the polyamide-based resin includes at least one selected from the unit (dI) and the unit (d-II), the content of the unit (dI) in the polyamide-based resin and the unit (d-II) And the total content is 1 mass% or more and 50 mass% or less,
The total content of the unit (a), the unit (b), the unit (c1), the unit (c2), the unit (d1), and the unit (d2) in the polyamide resin is 90% by mass or more.
Polyamide resin in which the ratio of carbonyl end group molar amount (Ac) to amino (Aa) end group molar amount is 80/100 to 100/80 as Ac / Aa in all units constituting the polyamide resin .

[2] The polyamide resin according to [1], comprising unit (a), unit (b), and at least one selected from unit (cI) and unit (c-II).

[3] The polyamide resin according to [1] or [2], wherein the unit (c-II) is a unit represented by the following general formula (1).
—NH— (CH (CH ₃ ) CH ₂ O—) _x — (CH ₂ CH ₂ O—) _y — (CH (CH ₃ ) CH ₂ O—) _z —CH ₂ CH (CH ₃ ) —NH— (1)
(In the formula (1), x, y and z are x + z is a real number from 1 to 6, and y is a real number from 1 to 20.)

[4] The polyamide resin according to any one of [1] to [3], comprising a unit (a), a unit (b), a unit (c-II), and a unit (d-II).

[5] The unit (a) is a dodecandioyl unit, the unit (b) is a 1,12-diaminododecane unit, and the unit (c-II) is an amino group (—NH at both ends of the triblock polyether. The polyamide resin according to any one of [1] to [4], which is a diamino unit having-).

[6] The polyamide resin according to any one of [1] to [5], wherein the content of the unit (a) is 1% by mass or more and less than 50% by mass.

[7] The polyamide resin according to any one of [1] to [6], wherein the content of the unit (b) is 1% by mass or more and less than 50% by mass.

[8] A molded body made of a material containing the polyamide-based resin according to any one of [1] to [7].

[9] The molded article according to [8], which is a film, sheet, tube, powder, fiber, woven fabric, nonwoven fabric, or catheter balloon.

[10] A laminate comprising the film or sheet according to [9].

[11] A medical device comprising at least one selected from the group consisting of the molded body according to [9] and the laminate according to [10].

[12]
Formula (C-1) below:
HOOC-R ³ (—O—R ⁴ ) _m —COOH (C-1)
(In formula (C-1), R ³ and R ⁴ are each independently a chain aliphatic group having 1 to 6 carbon atoms, and m is an integer of 1 to 30.)
A dicarboxylic acid (c-1) represented by: or an amide-forming derivative thereof,
Formula (C-2) below:
H ₂ N—R ⁵ (—O—R ⁶ ) _n —NH ₂ (C-2)
(In Formula (C-2), R ⁵ and R ⁶ are each independently a chain aliphatic group having 1 to 3 carbon atoms, and n is an integer of 1 to 30.)
Diamine (c-2) represented by
Formula (D-1) below:
HOOC-R ⁷ -COOH (D-1)
(In the formula (D-1), R ⁷ is a linear or branched aliphatic group having 1 to 20 carbon atoms, but in a linear aliphatic group having 8 to 20 carbon atoms, Absent.)
A dicarboxylic acid (d-1) represented by: or an amide-forming derivative thereof, and
The following formula (D-2):
H ₂ N—R ⁸ —NH ₂ (D-2)
(In the formula (D-2), R ⁸ is a linear or branched aliphatic group having 1 to 20 carbon atoms, but in a linear aliphatic group having 10 to 20 carbon atoms, Absent.)
One or more selected from the group consisting of diamines (d-2) represented by:
The following formula (A1):
HOOC-R ¹ -COOH (A1)
(In Formula (A), R ¹ is a linear aliphatic group having 8 to 20 carbon atoms.)
A dicarboxylic acid (a1) represented by the formula:
The following formula (B1):
H ₂ N—R ² —NH ₂ (B1)
(In the formula (B), R ² is a linear aliphatic having 10 to 20 carbon atoms.)
A diamine (b1) represented by:
To produce a polyamide-based resin, and producing the polyamide-based resin according to [1].

[13] reacting dicarboxylic acid (a1) or its amide-forming derivative with diamine (b1) to obtain a prepolymer;
A prepolymer is obtained by dicarboxylic acid (c-1) or its amide-forming derivative, diamine (c-2), dicarboxylic acid (d-1) or its amide-forming derivative, and diamine (d-2). Reacting with at least one selected from the group consisting of: and [12].

[14] The method according to [13], wherein the reaction for generating the prepolymer and the reaction for generating the polyamide resin are performed by a melt-kneading method.

According to the present invention, in a solid state, a polyamide-based resin having an excellent balance of mechanical properties such as breaking strength and elongation at break, a molded body including the polyamide-based resin, and a film or sheet including the polyamide-based resin are provided. There can be provided a laminate, a medical device including at least one of the above-described molded body, and the above-described laminate, and a method for producing the above-described polyamide-based resin.

≪Polyamide resin≫
The polyamide-based resin includes a unit (a) and a unit (b), and further includes a unit (cI), a unit (c-II), a unit (dI), and a unit (d-II). It contains at least one selected from more. Each unit will be described in detail later.
The content of the unit (a) and the content of the unit (b) in the polyamide resin are 1% by mass or more and 50% by mass or less, respectively.
When the polyamide-based resin contains at least one selected from the unit (cI) and the unit (c-II), the content of the unit (cI) in the polyamide-based resin and the unit (c-II) The total content of is 1% by mass or more and 50% by mass or less.
When the polyamide-based resin includes at least one selected from the unit (d1-I) and the unit (d-II), the content of the unit (dI) in the polyamide-based resin and the unit (d-II) The total content of is 1% by mass or more and 50% by mass or less.

The total content of units (a), units (b), units (c-I), units (c-II), units (d-I), and units (d-II) in the polyamide resin is 90 mass% or more, preferably 95 mass% or more, more preferably 98 mass% or more, and particularly preferably 100 mass%.
If the polyamide-based resin contains a predetermined amount of a predetermined type of unit (a), an ester bond (—CO—O—), a urethane bond (—NH—CO—O—), and a carbonate bond (—O—) It may contain a small amount of bonds such as O—CO—.

Since the polyamide-based resin has various mechanical properties, it includes the unit (a), the unit (b), the unit (c-II), and the unit (d-II). The unit (a), the unit (b), the unit (c-II), and the unit (d-II) are preferable.

The ratio of the carbonyl end group molar amount (Ac) to the amino (Aa) end group molar amount in all units constituting the polyamide-based resin is 80/100 to 100/80 as Ac / Aa. To 100/90 is preferable, 95/100 to 100/95 is more preferable, and 100/100 is particularly preferable.

Each of the polyamide-based resins has a predetermined structure, unit (a), unit (b), unit (cI), unit (c-II), unit (dI), and unit (d- By containing at least one selected from II) in a predetermined ratio, the polyamide-based resin is excellent in the balance of mechanical properties such as breaking strength and breaking elongation.

The polyamide-based resin that satisfies the above predetermined requirements exhibits elastomeric characteristics and is preferably used as a polyamide elastomer.

Hereinafter, each unit contained in the polyamide-based resin will be described.

<Unit (a)>
The unit (a) is represented by the following formula (A):
—CO—R ¹ —CO— (A)
(In Formula (A), R ¹ is a linear aliphatic group having 8 to 20 carbon atoms.)
It is a unit represented by.

R ¹ is a linear aliphatic group having 8 to 20 carbon atoms. The upper limit of the number of carbon atoms of R ¹ is 20, 18 is preferable, and 16 is more preferable in terms of the availability of the monomer that gives the unit (a) and the mechanical properties of the polyamide-based resin. 14 is more preferable, and 12 is particularly preferable.
R ¹ may be a saturated aliphatic group or an unsaturated aliphatic group, but is preferably a saturated aliphatic group.

Specifically, R ¹ is octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12. -Diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane-1,17-diyl group, octadecane -1,18-diyl group, nonadecane-1,19-diyl group, and eicosane-1,20-diyl group.

Unit (a) has a carbonyl group at both ends. The method for introducing the unit (a) into the polyamide resin is not particularly limited, but the unit (a) is usually introduced into the polyamide resin using a monomer such as alkanedicarboxylic acid or alkanedicarboxylic acid dihalide. The
The carbonyl group in the unit (a) is derived from the carboxy group of the monomer or the carbonyl group in the halocarbonyl group.

The unit (a) is preferably an octane oil unit, a nonane oil unit, a decane oil unit, an undecane oil unit, or a dodecane oil unit, more preferably a decane oil unit, an undecane oil unit, or a dodecane oil unit. Preferably, dodecanedioyl units are particularly preferred.

When the unit (a) is a dodecanedioyl unit, the unit (b) described later is preferably a 1,12-diaminododecane unit. In this case, the polyamide resin preferably contains diamino units having amino groups (—NH—) at both ends of the triblock polyether as the unit (c-II) described later.
Polyamide resins containing a combination of the above structural units are particularly excellent in the balance of mechanical properties such as breaking strength and breaking elongation.

The unit (a) described above constitutes a hard segment in the polyamide resin together with the unit (b) described later. Such a hard segment contributes to a good balance of mechanical properties such as breaking strength and breaking elongation of the polyamide-based resin.

Specific examples of the monomer that gives the unit (a) include decanedioic acid (sebacic acid), undecanedioic acid, dodecanedioic acid decane, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid. Acids, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, helicosyldioic acid, and docosanedioic acid. These acid halides such as acid chlorides or acid bromides can also be used as monomers.

The content of the unit (a) in the polyamide resin is 1% by mass or more and less than 50% by mass, preferably 10% by mass or more and less than 50% by mass, more preferably 20% by mass or more and less than 50% by mass, and 30% by mass. % Or more and less than 50% by mass is particularly preferable.

<Unit (b)>
The unit (b) is represented by the following formula (B):
—NH—R ² —NH— (B)
(In the formula (B), R ² is a linear aliphatic having 10 to 20 carbon atoms.)
It is a unit represented by.

R ² is a linear aliphatic group having 10 to 20 carbon atoms. The upper limit of the number of carbon atoms of R ² is 20, 18 is preferable, and 16 is more preferable in terms of the availability of the monomer that gives the unit (b) and the mechanical properties of the polyamide-based resin. 14 is more preferable, and 12 is particularly preferable.
R ² may be a saturated aliphatic group or an unsaturated aliphatic group, but is preferably a saturated aliphatic group.

Specifically, R ² is decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14. A diyl group, a pentadecane-1,15-diyl group, a hexadecane-1,16-diyl group, a heptadecane-1,17-diyl group, an octadecane-1,18-diyl group, a nonadecane-1,19-diyl group, and Eicosane-1,20-diyl group.

The unit (b) has an amino group (—NH—) at both ends. The method for introducing the unit (b) into the polyamide resin is not particularly limited, but the unit (b) is usually introduced into the polyamide resin using a monomer such as a linear aliphatic diamine.
The amino group (—NH—) in the unit (b) is derived from the amino group (—NH ₂ —) of the monomer.

As the unit (b), 1,10-diaminodecane unit, 1,11-diaminoundecane unit, 1,12-diaminododecane unit, 1,13-diaminotridecane unit and 1,14-diaminotetradecane unit are preferable. 1,10-diaminodecane units and 1,12-diaminododecane units are more preferred, and 1,12-diaminododecane units are particularly preferred.

As a combination of the unit (a) and the unit (b), a combination of a dodecandioyl unit as the unit (a) and a 1,12-diaminododecane unit as the unit (b) is preferable.
When the polyamide-based resin contains a combination of a dodecanedioyl unit as the unit (a) and a 1,12-diaminododecane unit as the unit (b), the polyamide-based resin is a unit (c-II) described later. The triblock polyether preferably contains diamino units having amino groups (—NH—) at both ends.
Polyamide resins containing a combination of the above structural units are particularly excellent in the balance of mechanical properties such as breaking strength and breaking elongation.

The unit (b) described above constitutes a hard segment in the polyamide resin together with the unit (a) described later. Such a hard segment contributes to a good balance of mechanical properties such as breaking strength and breaking elongation of the polyamide-based resin.

Specific examples of the monomer that gives the unit (b) include decane-1,10-diamine, undecane-1,11-diamine, dodecane-1,12-diamine, tridecane-1,13-diamine, and tetradecane-1. , 14-diamine, pentadecane-1,15-diamine, hexadecane-1,16-diamine, heptadecane-1,17-diamine, octadecane-1,18-diamine, nonadecane-1,19-diamine, and eicosane-1, 20-diamine.

The content of the unit (b) in the polyamide-based resin is 1% by mass or more and less than 50% by mass, preferably 10% by mass or more and less than 50% by mass, more preferably 20% by mass or more and less than 50% by mass, and 30% by mass. % Or more and less than 50% by mass is particularly preferable.

<Unit (cI), Unit (c-II), Unit (dI), and Unit (d-II)>
The polyamide-based resin essentially contains at least one unit selected from the group consisting of units (c-I), units (c-II), units (d-I), and units (d-II). .
By adjusting the type and content of the unit (c-I), unit (c-II), unit (d-I), and unit (d-II), various physical properties of the polyamide resin can be adjusted. The
Hereinafter, the unit (cI), the unit (c-II), the unit (dI), and the unit (d-II) will be described.

[Unit (cI)]
The unit (cI) is represented by the following formula (CI):
—CO—R ³ (—O—R ⁴ ) _m —CO— (CI)
(In the formula (CI), R ³ and R ⁴ are each independently a chain aliphatic group having 1 to 6 carbon atoms, m is an integer of 1 to 30 and m is When it is an integer of 2 or more, the plurality of R ⁴ may be the same or different.)
It is a unit represented by.

R ³ and R ⁴ may be a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, or a saturated aliphatic hydrocarbon group.
R ³ and R ⁴ may be a linear aliphatic group or a branched aliphatic group.

Preferable specific examples of R ³ and R ⁴ include methylene group, ethane-1,2-diyl group, ethane-1,1-diyl group, propane-1,3-diyl group, propane-1,2- And diyl group, propane-1,1-diyl group, propane-2,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, and hexane-1,6-diyl group. It is done.
Of these, ethane-1,2-diyl group, propane-1,3-diyl group, propane-1,2-diyl group, and butane-1,4-diyl group are preferable, and ethane-1,2- A diyl group and a propane-1,2-diyl group are more preferable.

In the formula (CI), the upper limit of m is, for example, 30 and 20 is preferable.

[Unit (c-II)]
The unit (c-II) is represented by the following formula (C-II):
—NH—R ⁵ (—O—R ⁶ ) _n —NH— (C-II)
(In the formula (C-II), R ⁵ and R ⁶ are each independently a chain aliphatic group having 1 to 3 carbon atoms, n is an integer of 1 to 30 and n is When it is an integer of 2 or more, the plurality of R ⁶ may be the same or different.)
It is a unit represented by.

Preferable specific examples of R ⁵ and R ⁶ include methylene group, ethane-1,2-diyl group, ethane-1,1-diyl group, propane-1,3-diyl group, propane-1,2- Examples include a diyl group, a propane-1,1-diyl group, and a propane-2,2-diyl group.
Among these, ethane-1,2-diyl group, propane-1,3-diyl group, and propane-1,2-diyl group are preferable, and ethane-1,2-diyl group and propane-1,2 -Diyl groups are more preferred.

The unit (c-II) is preferably a diamino unit having amino groups (—NH—) at both ends of the triblock polyether. Such a diamino unit is preferably a diamino unit represented by the following general formula (1).
—NH— (CH (CH ₃ ) CH ₂ O—) _x — (CH ₂ CH ₂ O—) _y — (CH (CH ₃ ) CH ₂ O—) _z —CH ₂ CH (CH ₃ ) —NH— (1)

In the formula (1), x, y and z are x + z is a real number from 1 to 6, and y is a real number from 1 to 20. Thereby, the suitable balance of polymerization reactivity and a softness | flexibility can be taken. x + z is preferably 1 or more and 5 or less, more preferably 1 or more and 3.8 or less. Moreover, y is preferably 1 or more and 15 or less, more preferably 1 or more and 9.2 or less. Furthermore, x + z is preferably a real number of 1 to 6, and y is preferably a real number of 1 to 15. Here, x, y, and z can be determined by GPC measurement, for example, as in the examples described later.

Examples of the monomer compound that gives the diamino unit represented by the formula (1) include polyoxyethylene, 1,2-polyoxypropylene, 1,3-polyoxypropylene, and polyoxyethylene that is a copolymer thereof. Examples include polyether diamine compounds such as amino-modified products of alkylene. Specifically, Jeffamine ED series manufactured by HUNTSMAN, USA can be preferably used. In the Jeffermin ED series, in formula (1), x + z is 1 or more and 6 or less, and y is 1 or more and 20 or less, which are ED600 and ED900. Of these, ED900 is used when x + z is 1 or more and 6 or less, ED600 is used when x + z is 1 or more and 3.8 or less, and ED900 is used when y is 1 or more and 15 or less, and y is 1 or more and 9.2. The following is ED600. Further, within such a range of x + z and y, the number average molecular weight of ED600 is preferably 500 to 700, and the number average molecular weight of ED900 is preferably 800 to 1,000. The number average molecular weight in this case is a numerical value calculated by a proton ratio by a nuclear magnetic resonance method using a deuterated chloroform solvent.

The total of the content of the unit (cI) and the content of the unit (c-II) in the polyamide resin is 1% by mass or more and less than 50% by mass, and 1% by mass or more and less than 40% by mass. It is preferably 1% by mass or more and less than 30% by mass, more preferably 1% by mass or more and less than 20% by mass.

[Unit (d-1)]
The unit (dI) is represented by the following formula (DI):
—CO—R ⁷ —CO— (DI)
(In the formula (DI), R ⁷ is a linear or branched aliphatic group having 1 to 20 carbon atoms, but in a linear aliphatic group having 8 to 20 carbon atoms, Absent.)
It is a unit represented by.

R ⁷ is a linear or branched aliphatic group having 1 to 20 carbon atoms. However, R ⁷ is not a linear aliphatic group having 8 to 20 carbon atoms. That is, R ⁷ is a branched aliphatic group having 8 to 20 carbon atoms, or a linear or branched aliphatic group having 7 or less carbon atoms.
The upper limit of the number of carbon atoms of R ⁷ is 20 in terms of the availability of the monomer giving the unit (dI) and the mechanical properties of the polyamide-based resin, preferably 18 and more preferably 16 14 is more preferable, and 12 is particularly preferable.
R ⁷ may be a saturated aliphatic group or an unsaturated aliphatic group, but is preferably a saturated aliphatic group.

R ⁷ is preferably a linear or branched aliphatic group having 7 or less carbon atoms. Specific examples of such aliphatic groups include methylene group, ethane-1,2-diyl group, ethane-1,1-diyl group, propane-1,3-diyl group, propane-1,2-diyl group, propane -1,1-diyl group, propane-2,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, and heptane-1,7 A diyl group.

Preferable specific examples of the monomer that gives the unit (dI) include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid.

[Unit (d-II)]
The unit (d-II) is represented by the following formula (D-II):
—NH—R ⁸ —NH— (D-II)
(In the formula (D-II), R ⁸ is a linear or branched aliphatic group having 1 to 20 carbon atoms, but in a linear aliphatic group having 10 to 20 carbon atoms, Absent.)
It is a unit represented by.

R ⁸ is a linear or branched aliphatic group having 1 to 20 carbon atoms. However, R ⁸ is not a linear aliphatic group having 10 to 20 carbon atoms. That is, R ⁸ is a branched aliphatic group having 10 to 20 carbon atoms, or a linear or branched aliphatic group having 9 or less carbon atoms.
The upper limit of the number of carbon atoms of R ⁸ is 20 in view of the availability of the monomer that gives the unit (d-II) and the mechanical properties of the polyamide-based resin, 18 is preferable, and 16 is more 14 is more preferable, and 12 is particularly preferable.
R ⁸ may be a saturated aliphatic group or an unsaturated aliphatic group, but is preferably a saturated aliphatic group.

R ⁸ is preferably a linear or branched aliphatic group having 9 or less carbon atoms. Specific examples of such aliphatic groups include methylene group, ethane-1,2-diyl group, ethane-1,1-diyl group, propane-1,3-diyl group, propane-1,2-diyl group, propane -1,1-diyl group, propane-2,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7- Examples thereof include a diyl group, an octane-1,8-diyl group, and a nonane-1,9-diyl group.

Preferable specific examples of the monomer that gives the unit (dI) include diaminomethane, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, and nona. And methylene diamine.

The total content of the unit (dI) and the content of the unit (d-II) in the polyamide resin is 1% by mass or more and less than 50% by mass, and 1% by mass or more and less than 40% by mass. It is preferably 1% by mass or more and less than 30% by mass, more preferably 1% by mass or more and less than 20% by mass.

<Other ingredients>
The polyamide-based resin described above may contain a phosphorus compound. Thereby, the breaking elongation and breaking stress of the molded object containing a polyamide-type resin can be improved more. Therefore, the polyamide resin composition containing a phosphorus compound is suitable for medical balloons, for example.
Further, as will be described later, in the production process of the polyamide-based resin, it is possible to prevent coloration due to stabilization of the polymerization reaction or oxidation.
Examples of such phosphorus compounds include phosphoric acid, pyrophosphoric acid, polyphosphoric acid, phosphorous acid, hypophosphorous acid, and alkali metal salts and alkaline earth metal salts thereof. Among these, phosphorous acid, hypophosphorous acid, and alkali metal salts thereof are used from the viewpoint of improving the stability of the polymerization reaction, imparting heat stability to the polyamide-based resin, and improving the mechanical properties of the molded body. Alkaline earth metal salts are preferred.
The content of the phosphorus compound is preferably 5 mass ppm or more and 5000 mass ppm or less, more preferably 20 mass ppm or more and 4000 mass ppm or less, and more preferably 30 mass ppm or more and 3000 mass ppm or less as the phosphorus element with respect to the mass of the polyamide-based resin. Further preferred.

In addition to the above-mentioned phosphorus compounds, various additives can be blended with the polyamide-based resin in accordance with the purpose within a range that does not impair the characteristics. Specifically, heat-resistant agents, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, lubricants, slip agents, crystal nucleating agents, tackifiers, mold release agents, plasticizers, pigments, dyes, Flame retardants, reinforcing materials, inorganic fillers, fine fibers, radiopaque agents and the like can be added.

The polyamide-based resin can be prepared by polycondensing the monomer giving the above units in a desired ratio according to a known method.

The melt viscosity (melt flow rate, MFR) of the polyamide-based resin is preferably 0.1 to 20 (g / 10 min) at 230 ° C. and 2.16 kgf (21.2 N). Thereby, extrusion moldability becomes favorable. In order to make the melt viscosity in such a range, the reaction temperature, the reaction time, the solution concentration, etc. at the time of polymerization may be appropriately adjusted.

The Shore D hardness of the polyamide resin is preferably 50 to 100, more preferably 60 to 80. Thereby, the softness | flexibility of a molded object is obtained. For example, the Shore D hardness can be adjusted by appropriately changing the composition ratio of the monomer giving each unit.

The number average molecular weight of the polyamide-based resin is preferably 10,000 to 150,000, more preferably 20,000 to 100,000. By setting the number average molecular weight in such a range, the processability and mechanical properties are excellent.

In the polyamide-based resin, the elongation at break in the tensile test of the molded product is preferably from 100% to 600%, more preferably from 200% to 600%. The breaking stress is preferably 20 MPa or more and 100 MPa or less, and more preferably 30 MPa or more and 90 MPa or less. Note that the tensile test is performed, for example, by a method described later.

Since the polyamide-based resin described above has an excellent balance of mechanical properties such as breaking strength and breaking elongation, it is suitably used in various applications.

≪Method for producing polyamide resin≫
The polyamide-based resin described above is
Formula (C-1) below:
HOOC-R ³ (—O—R ⁴ ) _m —COOH (C-1)
(In Formula (C-1), R ³ and R ⁴ are each independently a chain aliphatic group having 1 to 6 carbon atoms, m is an integer of 1 to 30 and m is When it is an integer of 2 or more, the plurality of R ⁴ may be the same or different.)
A dicarboxylic acid (c-1) represented by: or an amide-forming derivative thereof,
Formula (C-2) below:
H ₂ N—R ⁵ (—O—R ⁶ ) _n —NH ₂ (C-2)
(In Formula (C-2), R ⁵ and R ⁶ are each independently a chain aliphatic group having 1 to 3 carbon atoms, n is an integer of 1 to 30 and n is When it is an integer of 2 or more, the plurality of R ⁶ may be the same or different.)
Diamine (c-2) represented by
Formula (D-1) below:
HOOC-R ⁷ -COOH (D-1)
(In the formula (D-1), R ⁷ is a linear or branched aliphatic group having 1 to 20 carbon atoms, but in a linear aliphatic group having 8 to 20 carbon atoms, Absent.)
A dicarboxylic acid (d-1) represented by: or an amide-forming derivative thereof, and
The following formula (D-2):
H ₂ N—R ⁸ —NH ₂ (D-2)
(In the formula (D-2), R ⁸ is a linear or branched aliphatic group having 1 to 20 carbon atoms, but in a linear aliphatic group having 10 to 20 carbon atoms, Absent.)
One or more selected from the group consisting of diamines (d-2) represented by:
The following formula (A1):
HOOC-R ¹ -COOH (A1)
(In Formula (A), R ¹ is a linear aliphatic group having 8 to 20 carbon atoms.)
A dicarboxylic acid (a1) represented by the formula:
The following formula (B1):
H ₂ N—R ² —NH ₂ (B1)
(In the formula (B), R ² is a linear aliphatic having 10 to 20 carbon atoms.)
It is manufactured by making diamine (b1) represented by these react.

The dicarboxylic acid (a1) or an amide-forming derivative thereof is a monomer that gives the unit (a).
Diamine (b1) is a monomer that provides the above-mentioned unit (b).
The dicarboxylic acid (c-1) or its amide-forming derivative is a monomer that gives the unit (cI) described above.
Diamine (c-2) is a monomer that provides the aforementioned unit (c-II).
The dicarboxylic acid (d-1) or its amide-forming derivative is a monomer that gives the unit (dI).
Diamine (d-2) is a monomer that provides the aforementioned unit (d-II).
As for the dicarboxylic acid, examples of the amide-forming derivative include an acid halide. Examples of the acid halide include acid chlorides and acid bromides, and acid chlorides are preferable.

The polyamide-based resin is obtained by reacting dicarboxylic acid (a1) or its amide-forming derivative with diamine (b1) to obtain a prepolymer,
The obtained prepolymer was mixed with dicarboxylic acid (c-1) or its amide-forming derivative, diamine (c-2), dicarboxylic acid (d-1) or its amide-forming derivative, and diamine (d -2), it is also preferable to produce by reacting with one or more selected from the group consisting of.

In synthesizing the polyamide-based resin, the amount of each monomer used is appropriately adjusted so that the content of each unit is a desired value.
In the production of a polyamide-based resin, it is desirable that the monomer that can cause the equimolarity of the amino group and the carboxylic acid group to be added to an extent that does not deteriorate the desired physical properties.

In the method for producing a polyamide-based resin, the monomer polycondensation reaction can be performed in a solvent or in the absence of a solvent without using a solvent. It is preferable to carry out the reaction without using a solvent without using a solvent, because no purification or the like is required and the desired polyamide-based resin can be easily obtained. Such a solvent-free reaction can be performed by a melt-kneading method.
Therefore, when synthesizing the prepolymer or synthesizing the polyamide-based resin, it is preferable to react the monomers by a melt-kneading method.

In the method for producing a polyamide-based resin, as the polycondensation reaction, an atmospheric pressure melt polycondensation reaction, a reduced pressure melt polycondensation reaction, or a combination thereof can be employed. In the case of reduced pressure melt polycondensation, the pressure in the reaction vessel is preferably set to 0.1 to 0.01 (MPa) in a nitrogen gas atmosphere from the viewpoint of polymerization reactivity. These melt polycondensation reactions can be performed by a melt-kneading method in a solvent-free state.

In the method for producing a polyamide-based resin, the temperature at which the monomer is reacted is not particularly limited as long as a polycondensation reaction occurs, but is preferably 160 to 300 ° C., and preferably 200 to 280 ° C. from the balance of reaction rate and suppression of thermal decomposition. More preferably.

The polycondensation reaction time in the method for producing a polyamide-based resin is preferably 3 to 10 hours from the viewpoint of increasing the molecular weight and suppressing coloring. When producing the prepolymer, the reaction time for producing the prepolymer and the reaction time for producing the polyamide resin by reacting the prepolymer with other monomers are also 3 to 10 hours as described above. It is preferable.

The production method of the polyamide-based resin may be a batch type or a continuous type. For example, a batch type using a batch type reaction kettle or the like, or a continuous type using a single tank type or multi tank type continuous reaction apparatus, a tubular continuous reaction apparatus or the like alone or in combination may be used.

In the production of the polyamide-based resin, a phosphorus compound can be used as a catalyst as necessary. Examples of such phosphorus compounds include phosphoric acid, pyrophosphoric acid, polyphosphoric acid, phosphorous acid, hypophosphorous acid, and alkali metal salts and alkaline earth metal salts thereof. Among these, from the viewpoint of improving the stability of the polymerization reaction, imparting heat stability to the polyamide resin, and improving the mechanical properties of the molded article, phosphorous acid, hypophosphorous acid, and alkali metal salts thereof, Inorganic phosphorus compounds such as alkaline earth metal salts are preferably used.
The weight when such a phosphorus compound is charged is preferably 10 mass ppm or more and 10000 mass ppm or less, more preferably 100 mass ppm or more and 5000 mass ppm or less with respect to the total weight of the monomers.
In addition, since a phosphorus compound may be discharged | emitted out of a reaction system by the by-product generate | occur | produced by reaction, the preparation weight and phosphorus element content in a polyamide-type resin may not be the same. The amount of phosphorus element in the obtained polyamide-based resin is preferably 5 mass ppm or more and 5000 mass ppm or less, more preferably 20 mass ppm or more and 4000 mass ppm or less, and 30 mass ppm or more and 3000 mass ppm or less. Is more preferable.

After reacting each monomer or reacting the prepolymer and another monomer, for example, a molten polyamide resin is drawn out in a string shape and cooled, and if necessary, obtained as pellets or the like be able to.

≪Molded body≫
As described above, the above polyamide-based resin is excellent in the balance of mechanical properties such as breaking strength and breaking elongation. For this reason, the molded object which consists of a polyamide-type resin or the polyamide-type resin which mix | blended various additives with the polyamide-type resin is used suitably in various uses.

Other shapes of the molded body are not particularly limited. What are polyamide-based resins and polyamide-based resin compositions? By various known molding methods, spinning methods, fabric manufacturing methods, etc., they are processed into molded products of various forms. As the molding method, for example, extrusion molding, blow molding, injection molding or the like can be applied.
Suitable shapes of the molded body include films, sheets, tubes, powders, fibers, woven fabrics, nonwoven fabrics, balloons for catheters, and the like.

Since the polyamide-based resin and the polyamide-based resin composition are excellent in breaking strength and elongation at break, the molded body made of the polyamide-based resin and the polyamide-based resin composition is, for example, a film, a sheet, or a tube. Is preferred.
When a film or sheet made of a polyamide-based resin and a polyamide-based resin composition is included in the laminate, good rupture strength and elongation at break are also imparted to the laminate.
For this reason, the laminated body containing the film or sheet | seat which consists of a polyamide-type resin and a polyamide-type resin composition is also preferable.

The above-mentioned polyamide-based resin is excellent in extrusion moldability and take-off moldability due to the melting characteristics of the resin, excellent in blow moldability, and excellent in toughness. Therefore, it can be used for manufacturing molded articles in various fields. For example, a member such as a tube, a hose, or a medical tube can be manufactured by extrusion molding using a polyamide-based resin. Moreover, members such as bottles, containers, catheter balloons and the like can be produced by blow molding a polyamide-based resin.
In particular, the polyamide-based resin is suitable as a constituent material for medical members used in medical devices. Examples of medical members include catheter balloons, medical tubes, and laminates.

Hereinafter, the case where the medical member is a catheter balloon will be described as an example of the medical member manufactured using the polyamide-based resin, but the molded body used as the medical member is not limited thereto.

For a balloon for a catheter (hereinafter simply referred to as “balloon”), first, a tube (hereinafter sometimes referred to as “parison”) is manufactured using a polyamide-based resin, and then the obtained parison is further produced. It can be manufactured by processing.
As a method for producing a parison using a polyamide-based resin, a general known molding method can be used. For example, extrusion molding, injection molding, melt spinning molding and the like can be mentioned. The parison generally has a cylindrical shape whose diameter is constant in the major axis direction.
As a method for producing a balloon from a parison, a general known molding method can be used. For example, a balloon having a desired shape can be produced by biaxial stretching by blow molding such as air blowing or die blowing, vacuum molding, or the like. The molding temperature is generally 95 to 165 ° C.
The inner diameter expansion rate of the balloon from the parison is preferably 400% to 900%, more preferably 500% to 800%. The inner diameter expansion rate in the present invention is a value calculated by the following equation.
Inner diameter expansion rate (%) = (inner diameter during balloon expansion during molding / parison inner diameter) × 100
Appearance inspection or the like is performed on the balloon obtained as described above, and only those that pass the inspection can be used as medical members of medical devices such as balloon catheters. In the appearance inspection, diamond-shaped scratches, fish eyes, and cracks observed on the surface of the balloon are regarded as defective.

As described above, polyamide-based resins have an excellent balance of mechanical properties such as elongation at break and strength at break. Therefore, in addition to medical device components, packaging materials such as food, and electrical / mechanical precision devices Of course, it can be used for various applications such as members, automobile members and the like.

Hereinafter, in order to further clarify the present invention, specific examples will be described. However, the present invention is not limited to these examples.

Hereinafter, with respect to the evaluation of the polyamide resins of Examples and Comparative Examples, a tensile test method and a Shore D hardness measurement method will be described.

(Tensile test)
In the tensile test, a test piece conforming to ASTM-D638 (TYPE 5) was used. The test piece was obtained by pressing the polyamide resin pellets obtained in Examples and Comparative Examples at 190 ° C. using a small press machine (product name: MP-2FH, manufactured by Toyo Seiki Seisakusho Co., Ltd.), and cooling the thickness 1 A (mm) film was prepared and punched with a punching blade of the above standard. And the drying process of the test piece was 80 degreeC and 4 hours. The tensile test was performed at a speed of 200 (mm / min).

(Measurement of Shore D hardness)
The Shore D hardness was measured according to ASTM-D2240 using a 6 mm thick sheet in a 23 ° C. constant temperature room. A sheet having a thickness of 6 mm was produced by using the above-described press machine using the polyamide resin pellets of Examples and Comparative Examples. As a measuring device, a rubber hardness meter load tester D type manufactured by Kobunshi Keiki Co., Ltd. was used.

[Example 1]
749 g (3.26 mol) of dodecanedioic acid (carbon number 12) as a dicarboxylic acid (a1) was added to a 3 L reaction vessel equipped with a stirrer, temperature controller, pressure gauge, nitrogen gas inlet and condensed water outlet. As a diamine (b1), 600 g (3 mol) of dodecamethylenediamine (carbon number 12) and 0.6 g of hypophosphorous acid were charged. After sufficiently purging the inside of the container with nitrogen, in order to melt the reaction product, the temperature was raised to 280 ° C. over 1 hour, and then polymerization was carried out at 260 ° C. About 1 hour later, a dicarboxylic acid polyamide (prepolymer) having a molecular weight of about 5000 was obtained.
There, polyether diamine (diamine represented by the following formula (2) as diamine (c-2). In formula (4), y = 9 and x + z = 3.6. Jeffamine, manufactured by HUNTSMAN 78 g (0.13 mol) of ED600 (ED600)) and 15 g (0.13 mol) of hexamethylenediamine (HMD) as diamine (d-2) were added, followed by polymerization at the same temperature for about 4 hours to obtain a polyamide resin. Got.

H ₂ N— (CH (CH ₃ ) CH ₂ O—) _x — (CH ₂ CH ₂ O—) _y — (CH (CH ₃ ) CH ₂ O—) _z —CH ₂ CH (CH ₃ ) —NH ₂ ... (2)

After completion of the polymerization, stirring was stopped, and a colorless and transparent polyamide-based resin in a molten state was drawn out from the takeout port in a string shape, cooled with water, and pelletized to obtain about 1 kg of pellets. The number average molecular weight Mn was measured about the obtained pellet. Mn is shown in Table 2.
Moreover, the tensile test and the measurement of Shore D hardness were performed according to the above-mentioned method using the obtained pellet. The evaluation results are shown in Table 2.

[Example 2]
In a 3 L reaction vessel equipped with a stirrer, temperature controller, pressure gauge, nitrogen gas inlet, and condensed water outlet, 655 g (3.24 mol) of sebacic acid (carbon number 10) as dicarboxylic acid (a1), As diamine (b1), 600 g (3 mol) of dodecamethylenediamine (carbon number 12) and 0.6 g of hypophosphorous acid were charged. After sufficiently purging the inside of the container with nitrogen, in order to melt the reaction product, the temperature was raised to 280 ° C. over 1 hour, and then polymerization was carried out at 260 ° C. About 1 hour later, a dicarboxylic acid polyamide (prepolymer) having a molecular weight of about 5000 was obtained.
Thereto, 75 g (0.125 mol) of polyetherdiamine (JEFAMINE ED600 (ED600) manufactured by HUNTSMAN) as diamine (c-2) and 14.5 g of hexamethylenediamine (HMD) as diamine (d-2) (0.125 mol) was further added, and polymerization was carried out at the same temperature for about 4 hours to obtain a polyamide resin.

After the polymerization, about 1 kg of pellets was obtained in the same manner as in Example 1. The number average molecular weight Mn was measured about the obtained pellet. Mn is shown in Table 2.
Moreover, the tensile test and the measurement of Shore D hardness were performed according to the above-mentioned method using the obtained pellet. The evaluation results are shown in Table 2.

Example 3
869 g (3.78 mol) of dodecanedioic acid (12 carbon atoms) as dicarboxylic acid (a1) in a 3 L reaction vessel equipped with a stirrer, temperature controller, pressure gauge, nitrogen gas inlet and condensed water outlet As a diamine (b1), 600 g (3.5 mol) of decamethylenediamine (carbon number 10) and 0.6 g of hypophosphorous acid were charged. After sufficiently purging the inside of the container with nitrogen, in order to melt the reaction product, the temperature was raised to 280 ° C. over 1 hour, and then polymerization was carried out at 260 ° C. About 1 hour later, a dicarboxylic acid polyamide (prepolymer) having a molecular weight of about 5000 was obtained.
Thereto, 87 g (0.145 mol) of polyetherdiamine (Jephamine ED600 (ED600) manufactured by HUNTSMAN) as diamine (c-2) and 16.8 g of hexamethylenediamine (HMD) as diamine (d-2) (0.145 mol) was further added, and polymerization was carried out at the same temperature for about 4 hours to obtain a polyamide resin.

Example 4
In a reaction vessel having a volume of 3 L equipped with a stirrer, a temperature controller, a pressure gauge, a nitrogen gas inlet, and a condensed water outlet, 760 g (3.76 mol) of sebacic acid (carbon number 10) as dicarboxylic acid (a1), As the diamine (b1), 600 g (3.5 mol) of decamethylenediamine (10 carbon atoms) and 0.6 g of hypophosphorous acid were charged. After sufficiently purging the inside of the container with nitrogen, in order to melt the reaction product, the temperature was raised to 280 ° C. over 1 hour, and then polymerization was carried out at 260 ° C. About 1 hour later, a dicarboxylic acid polyamide (prepolymer) having a molecular weight of about 5000 was obtained.
Thereto, 81 g (0.135 mol) of polyetherdiamine (JEFAMINE ED600 (ED600) manufactured by HUNTSMAN) as diamine (c-2) and 15.7 g of hexamethylenediamine (HMD) as diamine (d-2) (0.135 mol) was further added, and polymerization was carried out at the same temperature for about 4 hours to obtain a polyamide resin.

Example 5
749 g (3.26 mol) of dodecanedioic acid (carbon number 12) as a dicarboxylic acid (a1) was added to a 3 L reaction vessel equipped with a stirrer, temperature controller, pressure gauge, nitrogen gas inlet and condensed water outlet. As a diamine (b1), 600 g (3 mol) of dodecamethylenediamine (carbon number 12) and 0.6 g of hypophosphorous acid were charged. After sufficiently purging the inside of the container with nitrogen, in order to melt the reaction product, the temperature was raised to 280 ° C. over 1 hour, and then polymerization was carried out at 260 ° C. About 1 hour later, a dicarboxylic acid polyamide (prepolymer) having a molecular weight of about 5000 was obtained.
There, polyether diamine (diamine represented by the following formula (3) as diamine (c-2). In formula (3), y = 12.5 and x + z = 6. Jeffamine, manufactured by HUNTSMAN 117 g (0.13 mol) of ED900 (ED900)) and 15 g (0.13 mol) of hexamethylenediamine (HMD) as diamine (d-2) were added, and polymerization was performed at the same temperature for about 5 hours to obtain a polyamide resin. Got.

H ₂ N— (CH (CH ₃ ) CH ₂ O—) _x — (CH ₂ CH ₂ O—) _y — (CH (CH ₃ ) CH ₂ O—) _z —CH ₂ CH (CH ₃ ) —NH ₂ ... (3)

[Comparative Example 1]
Charged 1200 g of 12 aminododecanoic acid (12 carbon atoms) and 0.6 g of hypophosphorous acid into a 3 L reaction vessel equipped with a stirrer, temperature controller, pressure gauge, nitrogen gas inlet, and condensed water outlet. The inside of the container was sufficiently replaced with nitrogen and heated at 280 ° C. for 1 hour in order to melt it, and polymerized until the number average molecular weight reached 5000 to obtain a hard segment.
Then, 35 g (0.24 mol) of adipic acid (AA, carbon number 8) equivalent to the molar amount of the terminal amine group of the hard segment was added and reacted at 220 ° C. for 1 hour to carry out dicarboxylic oxidation of the hard segment ( Step (i)).
Hexamethylenediamine (HMD, carbon number 6) 13.9 g (0.12 mol) and polyether diamine (JEFARMIN manufactured by HUNTSMAN) so as to be equimolar with the both-terminal carboxylic acid groups of the obtained dicarboxylic acid oxidation hard segment ED600 (ED600)) was charged in 72 g (0.12 mol), heated to 260 ° C., and further polymerized for 4 hours to obtain a polymer (step (ii)).

[Comparative Example 2]
Into a reaction vessel having a volume of 3 L equipped with a stirrer, temperature controller, pressure gauge, nitrogen gas inlet, and condensed water outlet, was charged 1200 g of 10 aminodecanoic acid (10 carbon atoms) and 0.6 g of hypophosphorous acid, In order to sufficiently replace the inside of the container with nitrogen and melt it, the temperature was raised at 280 ° C. for 1 hour, and polymerization was performed until the number average molecular weight reached 5000, thereby obtaining a hard segment.
Then, 35 g (0.24 mol) of adipic acid (AA, carbon number 8) equivalent to the molar amount of the terminal amine group of the hard segment was added and reacted at 220 ° C. for 1 hour to carry out dicarboxylic oxidation of the hard segment ( Step (i)).
Hexamethylenediamine (HMD, carbon number 6) 13.9 g (0.12 mol) and polyether diamine (JEFARMIN manufactured by HUNTSMAN) so as to be equimolar with the both-terminal carboxylic acid groups of the obtained dicarboxylic acid oxidation hard segment 72 g (0.12 mol) of ED600 (ED600) was charged, the temperature was raised to 260 ° C., and polymerization was further performed for 4 hours to obtain a polymer (step (ii)).

[Comparative Example 3]
749 g (3.26 mol) of dodecanedioic acid (carbon number 12) as a dicarboxylic acid (a1) was added to a 3 L reaction vessel equipped with a stirrer, temperature controller, pressure gauge, nitrogen gas inlet and condensed water outlet. As a diamine (b1), 600 g (3 mol) of dodecamethylenediamine (carbon number 12) and 0.6 g of hypophosphorous acid were charged. After sufficiently purging the inside of the container with nitrogen, in order to melt the reaction product, the temperature was raised to 280 ° C. over 1 hour, and then polymerization was carried out at 260 ° C. About 1 hour later, a dicarboxylic acid polyamide (prepolymer) having a molecular weight of about 5000 was obtained.
Thereto, 130 g (0. 1) of diamine (c-2), a polyether diamine (Jefamine THF 100 manufactured by HUNTSMAN, PTMEG [poly (tetramethyl ether ether)] and PPG (polypropylene glycol), a molecular weight of about 1000). 13 mol), 15 g (0.13 mol) of hexamethylenediamine (HMD) was added as the diamine (d-2), and polymerization was carried out at the same temperature for about 6 hours to obtain a polyamide resin.

After completion of the polymerization, stirring was stopped, and a colorless and transparent polyamide-based resin in a molten state was drawn out from the takeout port in a string shape, cooled with water, and pelletized to obtain about 1 kg of pellets. The number average molecular weight Mn was measured about the obtained pellet. Mn is shown in Table 2.
Moreover, the tensile test and the measurement of Shore D hardness were performed according to the above-mentioned method using the obtained pellet. The evaluation results are shown in Table 2.
A tensile test and a measurement of Shore D hardness were performed according to the method described above. The evaluation results are shown in Table 2.

According to Table 1 and Table 2, respectively obtained by polycondensation of dicarboxylic acid (a1), diamine (b1), diamine (c-2), and diamine (d-2) having a predetermined structure. The polyamide-based resin containing units (a), units (b), units (c-II), and units (d-II) having the same structure has the same Shore D hardness, but the units (a), Compared with polyamide resin not containing unit (b) and at least one selected from unit (c-I), unit (c-II), unit (d-I), and unit (d-II) And it turns out that breaking elongation and breaking strength are excellent.
The polyamide-based resin of this example can be particularly suitably used for the production of medical tubes and balloons.

Claims

At least selected from the group consisting of unit (a) and unit (b), further comprising unit (c-I), unit (c-II), unit (d-I), and unit (d-II) A polyamide-based resin containing one kind,
The unit (a) is represented by the following formula (A):
—CO—R 1 —CO— (A)
(In Formula (A), R 1 is a linear aliphatic group having 8 to 20 carbon atoms.)
Is a unit represented by
The unit (b) is represented by the following formula (B):
—NH—R 2 —NH— (B)
(In the formula (B), R 2 is a linear aliphatic having 10 to 20 carbon atoms.)
A unit (b) represented by:
The unit (cI) is represented by the following formula (CI):
—CO—R 3 (—O—R 4 ) m —CO— (CI)
(In the formula (CI), R 3 and R 4 are each independently a chain aliphatic group having 1 to 6 carbon atoms, and m is an integer of 1 to 30.)
Is a unit represented by
The unit (c-II) is represented by the following formula (C-II):
—NH—R 5 (—O—R 6 ) n —NH— (C-II)
(In Formula (C-II), R 5 and R 6 are each independently a chain aliphatic group having 1 to 3 carbon atoms, and n is an integer of 1 to 30.)
Is a unit represented by
The unit (dI) is represented by the following formula (DI):
—CO—R 7 —CO— (DI)
(In the formula (DI), R 7 is a linear or branched aliphatic group having 1 to 20 carbon atoms, but in a linear aliphatic group having 8 to 20 carbon atoms, Absent.)
Is a unit represented by
The unit (d-II) is represented by the following formula (D-II):
—NH—R 8 —NH— (D-II)
(In the formula (D-II), R 8 is a linear or branched aliphatic group having 1 to 20 carbon atoms, but in a linear aliphatic group having 10 to 20 carbon atoms, Absent.)
Is a unit represented by
In the polyamide-based resin, the content of the unit (a) and the content of the unit (b) are 1% by mass or more and 50% by mass or less, respectively.
When the polyamide-based resin contains at least one selected from the units (cI) and the units (c-II), the content of the units (cI) in the polyamide-based resin, The total of the content of the unit (c-II) is 1% by mass or more and 50% by mass or less,
When the polyamide-based resin contains at least one selected from the unit (d1-I) and the unit (d-II), the content of the unit (dI) in the polyamide-based resin, The total of the content of the unit (d-II) is 1% by mass or more and 50% by mass or less,
The total content of the unit (a), the unit (b), the unit (c1), the unit (c2), the unit (d1), and the unit (d2) in the polyamide resin is as follows. 90% by mass or more,
The polyamide system wherein the ratio of the carbonyl end group molar amount (Ac) to the amino (Aa) end group molar amount is 80/100 to 100/80 as Ac / Aa in all units constituting the polyamide resin. resin.
The polyamide-based resin according to claim 1, comprising the unit (a), the unit (b), and at least one selected from the unit (cI) and the unit (c-II). .
The polyamide resin according to claim 1 or 2, wherein the unit (c-II) is a unit represented by the following general formula (1).
—NH— (CH (CH 3 ) CH 2 O—) x — (CH 2 CH 2 O—) y — (CH (CH 3 ) CH 2 O—) z —CH 2 CH (CH 3 ) —NH— (1)
(In the formula (1), x, y and z are x + z is a real number from 1 to 6, and y is a real number from 1 to 20.)
The polyamide resin according to any one of claims 1 to 3, comprising the unit (a), the unit (b), the unit (c-II), and the unit (d-II).
The unit (a) is a dodecanedioyl unit, the unit (b) is a 1,12-diaminododecane unit, and the unit (c-II) is an amino group (—NH at both ends of the triblock polyether. The polyamide resin according to any one of claims 1 to 4, which is a diamino unit having-).
The polyamide resin according to any one of claims 1 to 5, wherein the content of the unit (a) is 1% by mass or more and less than 50% by mass.
The polyamide resin according to any one of claims 1 to 6, wherein the content of the unit (b) is 1% by mass or more and less than 50% by mass.
A molded body made of a material containing the polyamide-based resin according to any one of claims 1 to 7.
The molded article according to claim 8, which is a film, sheet, tube, powder, fiber, woven fabric, nonwoven fabric, or balloon for catheter.
A laminate comprising the film or the sheet according to claim 9.
A medical device comprising at least one selected from the group consisting of the molded body according to claim 9 and the laminate according to claim 10.
Formula (C-1) below:
HOOC-R 3 (—O—R 4 ) m —COOH (C-1)
(In formula (C-1), R 3 and R 4 are each independently a chain aliphatic group having 1 to 6 carbon atoms, and m is an integer of 1 to 30.)
A dicarboxylic acid (c-1) represented by: or an amide-forming derivative thereof,
Formula (C-2) below:
H 2 N—R 5 (—O—R 6 ) n —NH 2 (C-2)
(In Formula (C-2), R 5 and R 6 are each independently a chain aliphatic group having 1 to 3 carbon atoms, and n is an integer of 1 to 30.)
Diamine (c-2) represented by
Formula (D-1) below:
HOOC-R 7 -COOH (D-1)
(In the formula (D-1), R 7 is a linear or branched aliphatic group having 1 to 20 carbon atoms, but in a linear aliphatic group having 8 to 20 carbon atoms, Absent.)
A dicarboxylic acid (d-1) represented by: or an amide-forming derivative thereof, and
The following formula (D-2):
H 2 N—R 8 —NH 2 (D-2)
(In the formula (D-2), R 8 is a linear or branched aliphatic group having 1 to 20 carbon atoms, but in a linear aliphatic group having 10 to 20 carbon atoms, Absent.)
One or more selected from the group consisting of diamines (d-2) represented by:
The following formula (A1):
HOOC-R 1 -COOH (A1)
(In the formula (A), R 1 is a linear aliphatic group having 8 or more carbon atoms.)
A dicarboxylic acid (a1) represented by the formula:
The following formula (B1):
H 2 N—R 2 —NH 2 (B1)
(In the formula (B), R 2 is a linear aliphatic having 10 or more carbon atoms.)
A diamine (b1) represented by:
The method for producing a polyamide resin according to claim 1, comprising: reacting a compound to produce a polyamide resin.
Reacting the dicarboxylic acid (a1) or its amide-forming derivative with the diamine (b1) to obtain a prepolymer;
The prepolymer comprises a dicarboxylic acid (c-1) or an amide-forming derivative thereof, the diamine (c-2), the dicarboxylic acid (d-1) or an amide-forming derivative thereof, and the diamine ( reacting with one or more selected from the group consisting of: d-2).
The method according to claim 13, wherein the reaction for generating the prepolymer and the reaction for generating the polyamide-based resin are performed by a melt-kneading method.