JP6905327B2 - Polyamide-based resin, molded product, laminate, medical device, and method for manufacturing polyamide-based resin - Google Patents

Description

The present invention comprises at least one of a polyamide resin, a molded product containing the polyamide resin, a laminate having a film or sheet containing the polyamide resin, the above-mentioned molded product, and the above-mentioned laminate. The present invention relates to a medical device and the above-mentioned method for producing a polyamide resin.

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

As such polyamide-based resins, for example, Patent Document 1 describes linear aliphatic aminocarbonyl units derived from lactam such as lauryl lactam and dicarbonyl units derived from aromatic dicarboxylic acids such as isophthalic acid and terephthalic acid. A resin composed of a diamino unit derived from an alicyclic diamine such as bis (4-aminocyclohexyl) methane is disclosed.
However, the polyamide resin described in Patent Document 1 has a good balance of mechanical properties such as shore hardness and yield strength, which are required for molded articles such as medical tubes and balloons that require appropriate rigidity and strength. There was a problem lacking.

Japanese Unexamined Patent Publication No. 1-135834

In view of the above problems, an object of the present invention is to provide a polyamide resin having an excellent balance of mechanical properties such as shore hardness and yield strength in a solid state, a molded product containing the polyamide resin, and the polyamide resin. An object of the present invention is to provide a laminate including a film or sheet containing a resin, a medical device including at least one of the above-mentioned molded product and the above-mentioned laminate, and the above-mentioned method for producing a polyamide-based resin.

The present inventor has completed the present invention as a result of diligent studies for solving the above-mentioned problems. That is, the present invention relates to the following polyamide resins [1] to [6], molded articles [7] to [9], laminates [10], medical devices [11], and [12] to [15]. The present invention relates to a method for producing a polyamide-based resin.

[1] and the unit (a), the unit (b), a poly amide resin containing the units (c),
The unit (a) is the following formula (A):
-CO-R ¹ (-NH-CO-R ¹ ) _m -NH-... (A)
(In the formula (A), R ¹ is independently a linear saturated hydrocarbon group having 10 or more and 12 or less carbon atoms, m is an integer of 1 or more and 14 or less, and a plurality of R ^1s are the same. It may be different.)
It is a unit represented by
The unit (b) is the following formula (B):
-CO-R ² -CO-... (B)
(In the formula (B), R ² is an organic group containing one or more cyclic groups selected from an aromatic ring and an aliphatic ring.)
It is a unit represented by
The unit (c) is the following formula (C):
-NH-R ³ -NH-... (C)
(In formula (C), R ³ is an organic group containing an aromatic ring.)
It is a unit represented by
The total content of the unit (a), the unit (b), and the unit (c) in the polyamide resin is 90% by mass or more.
A polyamide resin in which the ratio of the molar amount of carbonyl terminal groups (Ac) to the molar amount of amino (Aa) terminal groups in all the units constituting the polyamide resin is 80/100 to 100/80 as Ac / Aa. ..

[2] The amount of the unit (a) with respect to the total content of the unit (a), the unit (b), and the unit (c) in the polyamide resin is 50% by mass or more and 99% by mass or less [1]. ] The polyamide resin described in.

[3] The polyamide resin according to [1] or [2], wherein the unit (b) is at least one selected from a terephthaloyl unit, an isophthaloyl unit, and a phthaloyl unit.

で表される単位から選択される１種以上である、［１］〜［３］のいずれか１つに記載のポリアミド系樹脂。 [4] The unit (c) is the following formula (c-1) to (c-3):

The polyamide resin according to any one of [1] to [3], which is one or more selected from the units represented by.

[5] The polyamide resin according to any one of [1] to [4], wherein the unit (c) is derived from a diamine having a melting point of less than 200 ° C. and a boiling point of 200 ° C. or higher.

[6] The polyamide resin according to any one of [1] to [5], which has a melting point of 50 ° C. or higher and 410 ° C. or lower.

[7] A molded product made of a material containing the polyamide resin according to any one of [1] to [6].

[8] The molded product according to [7], which is a film, sheet, tube, powder, fiber, woven fabric, or non-woven fabric.

[9] The molded product according to [7], which is a balloon for a catheter or a medical tube.

[10] A laminate containing the film or sheet according to [8].

[11] A medical device comprising at least one selected from the group consisting of the molded article according to [8] or [9] and the laminate according to [10].

[12] The following formula (A1):
HOOC-R ¹ (-NH-CO-R ¹ ) _m- NH ₂ ... (A1)
(In the formula (A1), R ¹ is independently a linear saturated hydrocarbon group having 10 or more and 12 or less carbon atoms, m is an integer of 1 or more and 14 or less, and a plurality of R ^1s are the same. It may be different.)
Aminocarboxylic acid (a1) represented by, or an amide-forming derivative thereof, and
The following formula (B1):
HOOC-R ^2- COOH ... (B1)
(In formula (B1), R ² is an organic group containing one or more cyclic groups selected from an aromatic ring and an aliphatic ring.)
Dicarboxylic acid (b1) represented by, or an amide-forming derivative thereof, and
The following formula (C1):
H ₂ N-R ^3- NH ₂ ... (C1)
(In formula (C1), R ³ is an organic group containing an aromatic ring.)
The method for producing a polyamide resin according to [1], which comprises reacting with a diamine (c1) represented by (1) to produce a polyamide resin.

[13]
(I) Reacting an aminocarboxylic acid (a1) or an amide-forming derivative thereof with a dicarboxylic acid (b1) or an amide-forming derivative thereof to obtain a prepolymer.
(Ii) The method according to [12], comprising reacting a prepolymer with a diamine (c1) to produce a polyamide resin.

[14] The method according to [12] or [13], wherein the diamine (c1) has a melting point of less than 200 ° C. and a boiling point of 200 ° C. or higher.

[15] The method according to [13], wherein the reaction for producing a prepolymer and the reaction for producing a polyamide resin are carried out by a melt-kneading method.

According to the present invention, a polyamide resin having an excellent balance of mechanical properties such as shore hardness and yield strength in a solid state, a molded product containing the polyamide resin, and a film or sheet containing the polyamide resin are provided. It is possible to provide a medical device including at least one of the laminate, the above-mentioned molded product, and the above-mentioned laminate, and the above-mentioned method for producing a polyamide-based resin.

≪Polyamide resin≫
The polyamide resin contains a unit (a), a unit (b), and a unit (c). Each unit will be described in detail later.

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

The ratio of the molar amount of carbonyl terminal groups (Ac) to the molar amount of amino (Aa) terminal groups in all the units constituting the polyamide resin is 80/100 to 100/80 as Ac / Aa, which is 90/100. ~ 100/90 is preferable, 95/100 to 100/95 is more preferable, and 100/100 is particularly preferable.

Polyamide-based resins that satisfy the above-mentioned predetermined requirements have good mechanical properties and thermoplasticity, and are suitably used in applications in which various thermoplastic resins have been conventionally used.

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

<Unit (a)>
The unit (a) is the following formula (A):
-CO-R ¹ (-NH-CO-R ¹ ) _m -NH-... (A)
(In the formula (A), R ¹ is independently a linear saturated hydrocarbon group having 10 or more and 12 or less carbon atoms, m is an integer of 1 or more and 14 or less, and a plurality of R ^1s are the same. It may be different.)
It is a unit represented by.
The unit (a) functions as a hard segment in the polyamide resin. The larger the number of carbon atoms in R ^1, the more the toughness of the polyamide resin tends to improve.

Specific examples of R ¹ are a decane-1,10-diyl group, an undecane-1,11-diyl group, and a dodecane-1,12-diyl group.

m is an integer of 1 or more and 14 or less. The unit (a) usually includes various units having different values of m. The average value of m can be determined by the number average molecular weight obtained by gel permeation chromatography (GPC).

Specific examples of suitable monomers giving the unit (a) include one or more condensates selected from 11-aminoundecanoic acid, 12-aminododecanoic acid, and 13-aminotridecanoic acid.
As the monomer giving the unit (a), a condensate of 11-aminoundecanoic acid, a condensate of 12-aminododecanoic acid, and a condensate of 13-aminotridecanoic acid are preferable, and a condensation of 12-aminododecanoic acid. The thing is more preferable.

The amount of the unit (a) with respect to the total content of the unit (a), the unit (b), and the unit (c) in the polyamide resin is preferably 50% by mass or more and 99% by mass or less, preferably 60% by mass. % Or more and 99% by mass or less are more preferable, 70% by mass or more and 90% by mass or less are particularly preferable, and 80% by mass or more and 90% by mass or less are most preferable.

When the number of moles of the unit (a) is Ma and the number of moles of the unit (b) is Mb in all the units constituting the polyamide resin, the ratio Ma / Mb is 95/100 to 100/95. Is preferable.
The polyamide resin preferably contains a dicarbonyl unit derived from a prepolymer composed of a composite unit in which the unit (b) is bonded to the amino group terminal of the unit (a). When the ratio Ma / Mb is within the above range, dicarbonyl units derived from the prepolymer having the desired structure are satisfactorily produced.

<Unit (b)>
The unit (b) is the following formula (B):
-CO-R ² -CO-... (B)
(In the formula (B), R ² is an organic group containing one or more cyclic groups selected from an aromatic ring and an aliphatic ring.)
It is a unit represented by.

R ² is an organic group containing one or more cyclic groups selected from an aromatic ring and an aliphatic ring.
The aromatic ring contained in the organic group may be an aromatic heterocycle or an aromatic hydrocarbon ring, and an aromatic hydrocarbon ring is preferable, and a benzene ring is more preferable.
The aliphatic ring contained in the organic group may be an aliphatic heterocycle or an aliphatic hydrocarbon ring, and an aliphatic hydrocarbon ring is preferable.
The aliphatic hydrocarbon ring may be monocyclic or polycyclic. Examples of the single ring include a cycloalkane ring having 3 to 10 carbon atoms. Examples of the polycycle include a norbornane ring, a tricyclononane ring, a tricyclodecane ring (for example, an adamantane ring), and a tetracyclododecane ring (for example, a decahydro-1,4: 5,8-dimethanonaphthalene ring).

When ^{the organic group as R 2} contains two or more cyclic groups, the two or more cyclic groups may be bonded by a single bond or via a linking group, or may be condensed with each other. ..
In the organic group as R ^2, the total number of ring members in cyclic groups contained in the organic group is preferably 50 or less, more preferably 20 or less, particularly preferably 12 or less.

When the aromatic ring and the aliphatic ring have a substituent, the type of the substituent is not particularly limited as long as the object of the present invention is not impaired.
Typical examples of substituents are an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkyl halide group having 1 to 6 carbon atoms, and a fat having 2 to 6 carbon atoms. Examples thereof include a group acyl group, an aliphatic acyloxy group having 2 to 6 carbon atoms, a halogen atom, a nitro group, a cyano group and the like. Among these substituents, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a nitro group, and a cyano group are preferable, and an alkyl group having 1 to 6 carbon atoms, Alkoxy groups having 1 to 6 carbon atoms and halogen atomic groups are more preferable.

When R ² is an organic group containing an aromatic ring, preferred examples of the organic group include groups represented by the following formulas (1) to (4).

In the above formulas (1) to (4), R ¹¹ is independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen atom. It is one kind to be done. R ¹¹ is preferably a hydrogen atom.
Wherein (4), Q has the _{formula: -C 6 H 4 -, -} O-C 6 H 4 -CO-C 6 H 4 -O -, - OCO-C 6 H 4 -COO -, - OCO- C ₆ H _4- C ₆ H _4- COO-, -OCO-, -O-, -S-, -CO-, -SO _2- , -C (CF ₃ ) _2- , -C (CH ₃ ) _{2 -, - CH 2 -, -} O-C 6 H 4 -C (CH 3) 2 -C 6 H 4 -O -, - O-C 6 H 4 -C (CF 3) 2 -C 6 H 4 - _{O -, - O-C 6} H 4 -SO 2 -C 6 H 4 -O -, - C (CH 3) 2 -C 6 H 4 -C (CH 3) 2 -, - O-C 10 H 6 _{-O -, - O-C 6} H 4 -C 6 H 4 -O-, and represents one selected from the group consisting of groups represented by _{-O-C 6} H 4 -O-.
Q in the illustrated, _-C 6 _{H 4} - is a phenylene group, preferably a m- phenylene group, and p- phenylene, p- phenylene group is more preferable. _{Further, -C} 10 _{H 6} - is a naphthalene-diyl group, a naphthalene-1,2-diyl group, a naphthalene-1,4-diyl group, a naphthalene-2,3-diyl group, naphthalene-2,6-diyl A group and a naphthalene-2,7-diyl group are preferable, and a naphthalene-1,4-diyl group and a naphthalene-2,6-diyl group are more preferable.

Or Among the organic group as R ² described, p- phenylene, m- phenylene group, and o- phenylene group is preferred.
That is, the polyamide-based resin preferably contains, as the unit (b), one or more selected from a terephthaloyl unit, an isophthaloyl unit, and a phthaloyl unit.

Preferable examples of the monomer giving the unit (b) are 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2 , 7-Naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 4,4'-dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether and the like.
Of these, terephthalic acid, isophthalic acid, and phthalic acid are preferred.

Further, the ratio of the total content of the unit (b) and the unit (c) to the total content of the unit (a), the unit (b), and the unit (c) in the polyamide resin is 1 mass. % Or more and 50% by mass or less is preferable, 1% by mass or more and 30% by mass or less is more preferable, and 10% by mass or more and 30% by mass or less is particularly preferable.
When the number of moles of the unit (b) is Mb and the number of moles of the unit (c) is Mc in all the units constituting the polyamide resin, the ratio Mb / Mc is 95/100 to 100/95. Is preferable. When the ratio of the unit (b) to the unit (c) is within the above range, it is easy to obtain a polyamide resin having excellent mechanical properties .

<Unit (c)>
The unit (c) is the following formula (C):
-NH-R ³ -NH-... (C)
(In formula (C), R ³ is an organic group containing an aromatic ring.)
It is a unit represented by.

^{The organic group as R 3} in the formula (C) is the same as the organic group as ^{R 2} except that it does not contain an aliphatic ring.

Preferable examples of the organic group as R ³ include an o-xylylene group, an m-xylylene group, a p-xylylene group, and a group represented by the above formulas (1) to (4).
Among the groups represented by the formulas (1) to (4), preferred groups are p-phenylene group, m-phenylene group, o-phenylene group, 1-methylbenzene-2,4-diyl group, 1 -Methylbenzene-2,5-diyl group, 1-methylbenzene-2,6-diyl group, 1-methylbenzene-3,4-diyl group, naphthalene-1,2-diyl group, naphthalene-1,4- Diyl group, naphthalene-2,3-diyl group, naphthalene-2,6-diyl group, naphthalene-2,7-diyl group, biphenyl-4,4'-diyl group, biphenyl-3,4'-diyl group, Biphenyl-3,3'-diyl group, diphenylmethane-4,4'-diyl group, diphenylmethane-3,4'-diyl group, diphenylmethane-3,3'-diyl group, 1,2-diphenylethane-4', 4 "-diyl group, 1,2-diphenylethane-3', 4" -diyl group, 1,2-diphenylethane-3', 3 "-diyl group, 2,2-diphenylpropane-4', 4" -Diyl group, 2,2-diphenylpropane-3', 4 "-diyl group, 2,2-diphenylpropane-3', 3"-diyl group, diphenyl ether-4,4'-diyl group, diphenyl ether-3, 4'-diyl group, diphenyl ether-3,3'-diyl group, benzophenone-4,4'-diyl group, benzophenone-3,4'-diyl group, benzophenone-3,3'-diyl group, diphenylsulfon-4 , 4'-diyl group, diphenylsulfon-3,4'-diyl group, and diphenylsulfon-3,3'-diyl group.

で表される単位から選択される１種以上が好ましい。 Particularly preferable groups as the organic group as R ³ include a diphenyl ether-4,4'-diyl group, a diphenyl ether-3,4'-diyl group, and a diphenyl ether-3,3'-diyl group.
That is, as the unit (c), the following equations (c-1) to (c-3):

One or more selected from the units represented by is preferable.

Preferable examples of the monomer giving the unit (c) are p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diamino. Toluene, 3,4-diaminotoluene, 1,2-diaminonaphthalene, 1,4-diaminonaphthalene, 2,3-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 4,4'-diamino Biphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4', 4 "-diamino- 1,2-diphenylethane, 3', 4 "-diamino-1,2-diphenylethane, 3', 3"-diamino-1,2-diphenylethane, 4', 4 "-diamino-2,2-diphenyl Propane, 3', 4 "-diamino-2,2-diphenylpropane, 3', 3"-diamino-2,2-diphenylpropane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3, 3'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, and 3 , 3'-diphenylsulfone.
Among these, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, and 3,3'-diaminodiphenyl ether are preferable.

The unit (c) is preferably derived from a diamine having a melting point of less than 200 ° C. and a boiling point of 200 ° C. or higher. By using such a diamine, the polycondensation reaction of the monomer is carried out satisfactorily by carrying out the polycondensation reaction at an appropriate temperature, and the diamine giving the unit (c) is distilled from the polycondensation reaction apparatus. Easy to suppress.
The diamine giving the unit (c) preferably has a melting point of less than 230 ° C. and a boiling point of 230 ° C. or higher, and more preferably a melting point of less than 260 ° C. and a boiling point of 260 ° C. or higher.
The boiling point is the boiling point under atmospheric pressure.

From the viewpoint of the melting point, boiling point, and availability, the monomers giving the unit (c) include 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, and 3,4-. Diaminotoluene, 2,3-diaminonaphthalene, p-xylylene diamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, and 3,3'-diaminodiphenyl ether

<Other ingredients>
The polyamide resin described above may contain a phosphorus compound. This makes it possible to further improve the breaking elongation and breaking stress of the molded product containing the polyamide resin. Therefore, the polyamide-based resin composition containing a phosphorus compound is suitable for, for example, a medical balloon.
Further, as will be described later, in the manufacturing process of the polyamide resin, it is possible to stabilize the polymerization reaction and prevent coloring due to 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. Of these, from the viewpoints of improving the stability of the polymerization reaction, imparting heat-resistant stability to the polyamide resin, and improving the mechanical properties of the molded product, phosphorous acid, hypophosphorous acid, and alkali metal salts thereof. , 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 30 mass ppm or more and 3000 mass ppm or less as the phosphorus element with respect to the mass of the polyamide resin. More preferred.

In addition to the above-mentioned phosphorus compounds, various additives can be added to the polyamide-based resin depending on the purpose as long as the properties are not impaired. Specifically, heat resistant agents, ultraviolet absorbers, light stabilizers, antioxidants, antioxidants, fillers, slip agents, crystal nucleating agents, tackifiers, mold release agents, plasticizers, pigments, dyes, Flame retardants, reinforcing materials, inorganic fillers, fine fibers, X-ray impermeable agents and the like can be added.

The polyamide resin can be prepared by polycondensing the monomers giving the above units at a desired ratio according to a known method.

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

The Shore D hardness of the polyamide resin is preferably 70 to 85, more preferably 74 to 80. As a result, the flexibility of the molded product can be obtained.
The yield stress (bending) of the polyamide resin is preferably 0.1 to 5N, more preferably 0.5 to 2.0N. For example, the shore D hardness and the yield stress can be adjusted by appropriately changing the composition ratio of the monomer giving each unit.

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

In the polyamide resin, the elongation at break in the tensile test of the molded product is preferably 100% or more and 600% or less, and more preferably 200% or more and 600% or less. 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. The tensile test is performed, for example, by the method described later.

The polyamide-based resin described above is suitably used in various applications because it has an excellent balance of mechanical properties such as shore D hardness and yield stress.

≪Manufacturing method of polyamide resin≫
The polyamide-based resin described above can be produced by reacting a monomer giving the unit (a), a monomer giving the unit (b), and a monomer giving the unit (c).
That is, the polyamide resin described above is (A1) :.
HOOC-R ¹ (-NH-CO-R ¹ ) _m- NH ₂ ... (A1)
(In the formula (A1), R ¹ is independently a linear saturated hydrocarbon group having 10 or more and 12 or less carbon atoms, m is an integer of 1 or more and 14 or less, and a plurality of R ^1s are the same. It may be different.)
Aminocarboxylic acid (a1) represented by, or an amide-forming derivative thereof, and
The following formula (B1):
HOOC-R ^2- COOH ... (B1)
(In formula (B1), R ² is an organic group containing one or more cyclic groups selected from an aromatic ring and an aliphatic ring.)
Dicarboxylic acid (b1) represented by, or an amide-forming derivative thereof, and
The following formula (C1):
H ₂ N-R ^3- NH ₂ ... (C1)
(In formula (C1), R ³ is an organic group containing an aromatic ring.)
It is obtained by reacting with the diamine (c1) represented by.

The aminocarboxylic acid (a1), or an amide-forming derivative thereof, is a monomer that gives the above-mentioned unit (a).
The dicarboxylic acid (b1) or an amide-forming derivative thereof is a monomer that gives the above-mentioned unit (b).
The diamine (c1) is a monomer that gives the above-mentioned unit (c).
Examples of the amide-forming derivative include acid halides and lactams. Examples of the acid halide include acid chlorides and acid bromides, and acid chlorides are preferable.

As a specific reaction method, a method of simultaneously mixing and reacting an aminocarboxylic acid (a1) or an amide-forming derivative thereof, a dicarboxylic acid (b1) or an amide-forming derivative thereof, and a diamine (c1). Or, a method of reacting an aminocarboxylic acid (a1) or an amide-forming derivative thereof with a dicarboxylic acid (b1) or an amide-forming derivative thereof, and then adding the remaining monomer to cause the reaction. Can be mentioned.

Among the above reaction methods, from the viewpoint of efficiently synthesizing a polyamide resin as a block copolymer having a desired hard segment and soft segment, (i) aminocarboxylic acid (a1) or an amide-forming derivative thereof. And a dicarboxylic acid (b1) or an amide-forming derivative thereof are mixed and reacted to obtain a prepolymer (hereinafter referred to as "step (i)"), and the pre obtained in the step (i). A method including a step of mixing the diamine (c1) with the polymer and reacting the polymer (hereinafter referred to as "step (ii)") is preferable.

In synthesizing the polyamide resin, the amount of each monomer used is appropriately adjusted so that the content of each unit is a desired value.
When producing a polyamide resin, it is desirable that the addition of a monomer that can be a factor that destroys the equimolarity of the amino group and the carboxylic acid group is such that the desired physical properties are not deteriorated.

In the method for producing a polyamide resin, the polycondensation reaction of the monomers in steps (i) and (ii) can be carried out in a solvent or in a solvent-free state without using a solvent. It is preferable to carry out the reaction without using a solvent because the desired polyamide resin can be easily obtained without the need for purification or the like. Such a solvent-free reaction can be carried out by a melt-kneading method.
Therefore, when synthesizing the prepolymer in the step (i) or when synthesizing the polyamide resin in the step (ii), it is preferable to react the monomers by a melt-kneading method.

In the method for producing a polyamide resin, as the polycondensation reaction, a normal pressure melt polycondensation reaction, a reduced pressure melt polycondensation reaction, or a combination thereof can be adopted. In the case of reduced pressure melt polycondensation, the pressure in the reaction vessel is preferably 0.1 to 0.01 (MPa) in a nitrogen gas atmosphere in terms of polymerization reactivity. These melt polycondensation reactions can be carried out by a melt kneading method in a solvent-free state.
Depending on the reaction temperature, the pressure in the reaction vessel, the type of monomer, etc., a part of the monomer may be distilled out of the reaction apparatus. In this case, the reaction may be carried out while adding an amount of monomer equivalent to the amount of distillate to the reactor.

In the method for producing a polyamide resin, the temperature at which the monomer is reacted in the step (i) and the step (ii) is not particularly limited as long as the polycondensation reaction occurs, but is 160 to 160 to the balance between the reaction rate and the suppression of thermal decomposition. The temperature is preferably 300 ° C, more preferably 200 to 280 ° C. The reaction temperatures in steps (i) and (ii) may be the same or different.

Since the polycondensation reaction is preferably carried out at the above temperature, the diamine (c1) preferably has a melting point of less than 200 ° C. and a boiling point of 200 ° C. or higher, a melting point of less than 230 ° C. and a boiling point of 230 ° C. or higher. It is more preferable that the melting point is less than 260 ° C. and the boiling point is more preferably 260 ° C. or higher.
When the melting point and boiling point of the diamine (c1) are within the above ranges, the diamine (c1) during the polycondensation reaction is suppressed from being distilled out of the reaction apparatus, and the diamine (c1) is satisfactorily at a preferable polycondensation reaction temperature. It is easy to proceed with the polycondensation reaction.

The polycondensation reaction time of steps (i) and (ii) in the method for producing a polyamide resin is preferably 3 to 10 hours from the viewpoint of increasing the molecular weight and suppressing coloring. The polycondensation reaction times in steps (i) and (ii) may be the same or different.

The method for producing the polyamide resin may be a batch method or a continuous method. For example, it may be 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 device, a tubular continuous reaction device, or the like alone or in combination.

In the production of the polyamide resin, a phosphorus compound can be used as a catalyst, if 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. Of these, from the viewpoints of improving the stability of the polymerization reaction, imparting heat-resistant stability to the polyamide resin, and improving the mechanical properties of the molded product, phosphorous acid, hypophosphorous acid, and alkali metal salts thereof. It is preferable to use an inorganic phosphorus compound such as an alkaline earth metal salt.
The weight of such a phosphorus compound at the time of charging is preferably 10% by mass or more and 10000% by mass or less with respect to the total weight of the monomers in at least one of the step (i) and the step (ii). , More preferably 100 mass ppm or more and 5000 mass ppm or less.
Since the phosphorus compound may be discharged from the reaction system due to the by-products generated in the reaction, the charged weight and the phosphorus element content in the polyamide resin do not have to be the same. The amount of phosphorus element in the obtained polyamide 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 even more preferable.

After reacting each component in the step (ii), for example, the polymer in a molten state can be drawn out in a string shape and cooled to obtain pellets or the like, if necessary.

≪Molded body≫
As described above, the above-mentioned polyamide resin has an excellent balance of mechanical properties such as shore D hardness and yield stress. Therefore, a polyamide-based resin or a molded product made of a polyamide-based resin in which various additives are mixed with the polyamide-based resin is suitably used in various applications.

The shape of the molded body and others is not particularly limited. Polyamide-based resin and polyamide-based resin composition. It is processed into various forms of molded products by various known molding methods, spinning methods, fabric manufacturing methods, and the like. As the molding method, for example, extrusion molding, blow molding, injection molding and the like can be applied.
Suitable shapes of the molded product include films, sheets, tubes, powders, fibers, woven fabrics, non-woven fabrics and the like.

Since the polyamide-based resin and the polyamide-based resin composition are excellent in shore D hardness and yield stress, examples of the molded product made of the polyamide-based resin and the polyamide-based resin composition are films, sheets, and tubes. Is preferable.
When a film or sheet made of a polyamide resin and a polyamide resin composition is included in the laminate, good shore D hardness and yield stress are also imparted to the laminate.
Therefore, a film or a laminate containing a polyamide-based resin and a polyamide-based resin composition is also preferable.

The above-mentioned polyamide-based resin is excellent in extrusion moldability and take-up moldability due to the melting characteristics of the resin, is excellent in blow moldability, and is excellent in toughness. Therefore, it can be used for manufacturing molded products in various fields. For example, members such as tubes, hoses, and medical tubes can be manufactured by extrusion molding using a polyamide resin. In addition, a polyamide resin can be blow-molded to manufacture members such as bottles, containers, and balloons for catheters.
In particular, polyamide-based resins are suitable as constituent materials for medical members used in medical devices. Examples of the medical member include a balloon for a catheter, a medical tube, a laminate, and the like.

Hereinafter, the medical member manufactured by using the polyamide resin will be described by taking the case where the medical member is a balloon for a catheter as an example, but the molded body used as the medical member is not limited to this.

For a balloon for catheter (hereinafter, simply referred to as "balloon"), a tube (hereinafter, may be referred to as "parison") is first manufactured using a polyamide resin, and then the obtained parison is further added. It can be manufactured by processing.
As a method for producing a parison using a polyamide resin, a generally known molding method can be used. For example, extrusion molding, injection molding, melt spinning molding and the like can be mentioned. The shape of the parison generally has a cylindrical shape with a constant diameter in the major axis direction.
As a method for producing a balloon from a parison, a generally known molding method can be used. For example, a balloon having a desired shape can be produced by biaxial stretching molding by blow molding such as air blowing method or die blowing method, vacuum forming 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% or more and 900% or less, and more preferably 500% or more and 800% or less. The inner diameter expansion rate in the present invention is a value calculated by the following formula.
Inner diameter expansion rate (%) = (inner diameter when expanding balloon during molding / inner diameter of parison) x 100
A visual inspection or the like is performed on the balloon obtained as described above, and only those that have passed the inspection can be used as a medical member of a medical device such as a balloon catheter. If a diamond-shaped scratch, fisheye, or crack is observed on the surface of the balloon by visual inspection, it is considered to be defective.

As described above, the polyamide resin has an excellent balance of mechanical properties such as shore D hardness and yield stress. Therefore, in addition to medical device members, packaging materials such as foods, and electrical / mechanical precision devices. Of course, it can be used for various purposes such as members and automobile members.

Hereinafter, the present invention will be described with reference to specific examples in order to further clarify the present invention, but the present invention is not limited thereto.

Hereinafter, the method for measuring the shore D hardness and the method for measuring the yield stress will be described with respect to the evaluation of the polyamide resin of Examples and Comparative Examples.

(Measurement of Shore D hardness)
The shore D hardness was measured in accordance with ASTM-D2240 using a sheet having a thickness of 6 mm in a constant temperature room at 23 ° C. A sheet having a thickness of 6 mm was produced by the above-mentioned press using pellets of the polyamide resin of Examples and Comparative Examples. As a measuring device, a rubber hardness tester load tester D type manufactured by Polymer Instruments Co., Ltd. was used.

(Measurement of yield stress)
The yield stress was measured using an extruded tube with an outer diameter of 0.95 mm and an inner diameter of 0.63 mm, and was measured by a three-point indentation bending test using Shimadzu EZ-SX and a 5N load cell with a distance between fulcrums of 16 mm. did. The highest bending stress value at that time was calculated as the yield stress (N).

[Example 1]
1200 g of 12-aminododecanoic acid and 0.6 g of hypophosphorous acid were charged into 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 discharge port. After sufficient nitrogen substitution in the container, in order to melt the monomer, the temperature is raised to 280 ° C. in 1 hour, and polymerization is carried out until the number average molecular weight reaches 3000, and amino becomes a hard segment composed of the component (a). Carboxylic acid (a1) was obtained.

Next, 66.4 g of terephthalic acid (TA) as a dicarboxylic acid (b1) was added to the reaction vessel. Aminocarboxylic acid (a1) and dicarboxylic acid (b1) were reacted at 220 ° C. for 1 hour to obtain a prepolymer (step (i)).

The reaction vessel was charged with 84.4 g of 4,4'-diaminodiphenyl ether (ODA) as diamine (c1). The prepolymer and diamine (c1) were polycondensed at 260 for 4 hours to obtain a polyamide resin (step (ii)).
In addition, terephthalic acid and 4,4'-diaminodiphenyl ether (ODA) are the amount of the unit derived from terephthalic acid in the polyamide resin and the unit derived from 4,4'-diaminodiphenyl ether (ODA). An amount having a total of 11% by mass with the amount was used.

After completion of the polymerization, stirring was stopped, a colorless and transparent polyamide resin in a molten state was extracted in a string shape from an outlet, cooled with water, and then pelletized to obtain about 1 kg of pellets.
Further, using the obtained pellets, a tensile test and a shore D hardness measurement were carried out according to the above-mentioned method. The results of these evaluations are shown in Table 1.

[Example 2]
The same as in Example 1 except that the amount of terephthalic acid (TA) used is changed to 132.6 g and the amount of 4,4'-diaminodiphenyl ether (ODA) used is changed to 160 g. A pellet of about 1 kg of polyamide resin was obtained.
Further, using the obtained pellets, a tensile test and a shore D hardness measurement were carried out according to the above-mentioned method. The results of these evaluations are shown in Table 1.
In addition, terephthalic acid and 4,4'-diaminodiphenyl ether (ODA) are the amount of the unit derived from terephthalic acid in the polyamide resin and the unit derived from 4,4'-diaminodiphenyl ether (ODA). An amount having a total of 20% by mass with the amount was used.

[Example 3]
The amount of terephthalic acid (TA) used was changed to 265 g, the amount of 4,4'-diaminodiphenyl ether (ODA) used was changed to 319 g, and the others were about 1 kg in the same manner as in Example 1. , Polyamide-based resin pellets were obtained.
Further, using the obtained pellets, a tensile test and a shore D hardness measurement were carried out according to the above-mentioned method. The results of these evaluations are shown in Table 1.
In addition, terephthalic acid and 4,4'-diaminodiphenyl ether (ODA) are the amount of the unit derived from terephthalic acid in the polyamide resin and the unit derived from 4,4'-diaminodiphenyl ether (ODA). An amount having a total of 33% by mass with the amount was used.

[Comparative Examples 1 and 2]
The following commercially available polyamide-based resins were used as the polyamide-based resins of Comparative Examples 1 and 2. For each polyamide resin, a tensile test and a shore D hardness measurement were carried out according to the above-mentioned method. The results of these evaluations are shown in Table 1.
Comparative Example 1: PEBAX 72 (Arkema, aliphatic polyamide)
Comparative Example 2: Rilsamide PA12 (Arkema, 12 nylon)

From Table 1, the polyamide-based resins of Examples 1 to 3 comprising the above-mentioned unit (a), unit (b), and unit (c) yielded good yields within the range of 0.7 to 1.1N. It can be seen that it has both stress (bending) and good Shore D hardness in the range of 74-80.
On the other hand, from Table 1, the commercially available polyamide resin of the comparative example, which does not contain the unit (a), the unit (b), and the unit (c) in combination, has low shore D hardness and yield stress. I understand.

Claims (15)

A polyamide resin containing the unit (a), the unit (b), and the unit (c).
The unit (a) is the following formula (A):
-CO-R ¹ (-NH-CO-R ¹ ) _m -NH-... (A)
(In the formula (A), R ¹ is independently a linear saturated hydrocarbon group having 10 or more and 12 or less carbon atoms, m is an integer of 1 or more and 14 or less, and a plurality of R ^1s are the same. It may be different.)
It is a unit represented by
The unit (b) is the following formula (B):
-CO-R ² -CO-... (B)
(In the formula (B), R ² is an organic group containing one or more cyclic groups selected from an aromatic ring and an aliphatic ring.)
It is a unit represented by
The unit (c) is the following formula (C):
-NH-R ³ -NH-... (C)
(In the formula (C), R ³ is the following formula (4):

It is an organic group containing an aromatic ring represented by, and R ¹¹ is independently composed of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen atom. It is one selected from the group, and Q is −O−. )
It is a unit represented by
The total content of the unit (a), the unit (b), and the unit (c) in the polyamide resin is 90% by mass or more.
The ratio of the molar amount of carbonyl terminal groups (Ac) to the molar amount of amino (Aa) terminal groups in all the units constituting the polyamide resin is 80/100 to 100/80 as Ac / Aa. resin. The amount of the unit (a) with respect to the total content of the unit (a), the unit (b), and the unit (c) in the polyamide resin is 50% by mass or more and 99% by mass or less. The polyamide resin according to claim 1. The polyamide-based resin according to claim 1 or 2, wherein the unit (b) is at least one selected from a terephthaloyl unit, an isophthaloyl unit, and a phthaloyl unit. The unit (c) is the following formula (c-1) to (c-3):

The polyamide resin according to any one of claims 1 to 3, which is one or more selected from the units represented by. The polyamide resin according to any one of claims 1 to 4, wherein the unit (c) is derived from a diamine having a melting point of less than 200 ° C. and a boiling point of 200 ° C. or higher. The polyamide resin according to any one of claims 1 to 5, which has a melting point of 50 ° C. or higher and 410 ° C. or lower. A molded product made of a material containing the polyamide resin according to any one of claims 1 to 6. The molded product according to claim 7, which is a film, a sheet, a tube, a powder, a fiber, a woven fabric, or a non-woven fabric. The molded product according to claim 7, which is a balloon for a catheter or a medical tube. A laminate comprising the film or the sheet according to claim 8. A medical device comprising at least one selected from the group consisting of the molded article according to claim 8 or 9 and the laminate according to claim 10. The following formula (A1):
HOOC-R ¹ (-NH-CO-R ¹ ) _m- NH ₂ ... (A1)
(In the formula (A1), R ¹ is independently a linear saturated hydrocarbon group having 10 or more and 12 or less carbon atoms, m is an integer of 1 or more and 14 or less, and a plurality of R ^1s are the same. It may be different.)
Aminocarboxylic acid (a1) represented by, or an amide-forming derivative thereof, and
The following formula (B1):
HOOC-R ^2- COOH ... (B1)
(In formula (B1), R ² is an organic group containing one or more cyclic groups selected from an aromatic ring and an aliphatic ring.)
Dicarboxylic acid (b1) represented by, or an amide-forming derivative thereof, and
The following formula (C1):
H ₂ N-R ^3- NH ₂ ... (C1)
(In the formula (C1), R ³ is the following formula (4):

It is an organic group containing an aromatic ring represented by, and R ¹¹ is independently composed of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen atom. It is one selected from the group, and Q is −O−. )
The method for producing a polyamide-based resin according to claim 1, which comprises reacting the diamine (c1) represented by (1) with (c1) to produce a polyamide-based resin. (I) Reacting the aminocarboxylic acid (a1) or an amide-forming derivative thereof with the dicarboxylic acid (b1) or an amide-forming derivative thereof to obtain a prepolymer.
(Ii) The method according to claim 12, wherein the prepolymer is reacted with the diamine (c1) to produce the polyamide resin. The method according to claim 12 or 13, wherein the diamine (c1) has a melting point of less than 200 ° C. and a boiling point of 200 ° C. or higher. The method according to claim 13, wherein the reaction for producing the prepolymer and the reaction for producing the polyamide resin are carried out by a melt-kneading method.