WO2018101054A1 - 末端変性ポリアミド樹脂 - Google Patents
末端変性ポリアミド樹脂 Download PDFInfo
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- WO2018101054A1 WO2018101054A1 PCT/JP2017/041196 JP2017041196W WO2018101054A1 WO 2018101054 A1 WO2018101054 A1 WO 2018101054A1 JP 2017041196 W JP2017041196 W JP 2017041196W WO 2018101054 A1 WO2018101054 A1 WO 2018101054A1
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- Prior art keywords
- terminal
- polyamide resin
- general formula
- modified polyamide
- structure represented
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- 0 CCC(C)(C(C)COC(C)(CC)C(*)CCOC(C)C)NC Chemical compound CCC(C)(C(C)COC(C)(CC)C(*)CCOC(C)C)NC 0.000 description 2
- QUSUSWYTQASYBY-UHFFFAOYSA-N CCCC(C)(CCOC(C)(C)CC)C(CC)(C=C)OCC(C)C(C)(C=C)N Chemical compound CCCC(C)(CCOC(C)(C)CC)C(CC)(C=C)OCC(C)C(C)(C=C)N QUSUSWYTQASYBY-UHFFFAOYSA-N 0.000 description 1
- GWIDQKWZSRPDQO-UHFFFAOYSA-N C[NH+](c1ccccc1)[O-] Chemical compound C[NH+](c1ccccc1)[O-] GWIDQKWZSRPDQO-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/40—Polyamides containing oxygen in the form of ether groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
- C08G69/50—Polymers modified by chemical after-treatment with aldehydes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
Definitions
- the present invention relates to a terminal-modified polyamide resin having a specific terminal structure, a low melt viscosity, and excellent molding processability and mechanical strength of a molded product.
- Polyamide resins have excellent mechanical and thermal properties and are widely used as materials for various molded products such as fibers, various containers, films, electrical equipment parts, electronic equipment parts, automotive parts, and mechanical parts. .
- a polyamide resin having excellent mechanical properties and fluidity a polyamide resin having a hydrocarbon group having 6 to 22 carbon atoms and a relative viscosity of 2 or more and less than 2.5 has been proposed (see Patent Document 1). ).
- a high molecular weight terminal-modified polyamide resin having excellent moldability and excellent crystallinity it contains 0.5 to 4.5% by mass of a specific terminal structure and has a relative viscosity ⁇ r of 2.1 to 10.
- a certain terminal-modified polyamide resin has been proposed (see Patent Document 2).
- Non-Patent Document 1 Although the thermal stability of the polyamide resin can be improved and the molding processing temperature can be increased, the melt viscosity is still high, and the recent miniaturization and complexity of the molded product has been increased. There is a problem that molding processability is insufficient in response to demands for reduction in thickness, thickness, and weight.
- the polyamide resin described in the above-mentioned Patent Document 1 still has a high melt viscosity, and there is a problem that molding processability is insufficient in response to the recent demands for downsizing, complexity, thinning, and weight reduction of molded products. is there.
- the terminal-modified polyamide resin proposed in Patent Document 2 has a melt viscosity that is lowered by introducing a polyalkylene oxide structure into the polyamide resin only at the terminal.
- further reduction in melt viscosity, improvement in mechanical strength, and improvement in molding processability are required.
- an object of the present invention is to provide a terminal-modified polyamide resin having a low melt viscosity and excellent molding processability and mechanical strength of a molded product.
- the ratio of the weight average molecular weight Mw and the terminal structure content [mass%] represented by the following general formula (I) (weight average molecular weight / terminal structure content represented by the following general formula (I) The ratio of 6,000 to 20,000, the melting point is 60 ° C., and the melt viscosity is 0.1 Pa ⁇ s to 8 Pa ⁇ s at a shear rate of 9728 sec ⁇ 1.
- R 1 represents a divalent hydrocarbon group having 2 to 10 carbon atoms
- R 2 represents H or a monovalent organic group.
- —X— represents —NH—, —N (CH 3 ) —, — (C ⁇ O) —, or —CH 2 —CH (OH) —CH 2 —O—, which is included in formula (I).
- M R 1 groups may be the same or different.
- the main chain of the terminal-modified polyamide resin and the terminal-modified polyamide resin are represented by the general formula (I).
- terminal-modified polyamide resin of the present invention and the production method thereof will be described in detail.
- the terminal-modified polyamide resin of the present invention is a terminal-modified polyamide resin having a terminal structure represented by the following general formula (I), and is represented by the following general formula (I) in 100% by mass of the terminal-modified polyamide resin.
- —X— (R 1 —O) m —R 2 (I) (In the general formula (I), m represents a range of 2 to 100. R 1 represents a divalent hydrocarbon group having 2 to 10 carbon atoms, and R 2 represents H or a monovalent organic group.
- —X— represents —NH—, —N (CH 3 ) —, — (C ⁇ O) —, or —CH 2 —CH (OH) —CH 2 —O—.
- the terminal-modified polyamide resin of the present invention is a polyamide resin that can be obtained by using one or more selected from amino acids, lactams, and “mixtures of diamines and dicarboxylic acids” as a main raw material. It has the terminal structure represented.
- the terminal-modified polyamide resin in the present invention is a polyamide resin that can be obtained as a main raw material at least one selected from the group consisting of a combination consisting of a diamine and a dicarboxylic acid, an amino acid, and a lactam. It has a terminal structure represented by (I).
- the chemical structure constituting the main structural unit of the polyamide resin when amino acid or lactam is used as a raw material, those having 4 to 20 carbon atoms are preferably used.
- the diamine and dicarboxylic acid are used as raw materials, the diamine preferably has 2 to 20 carbon atoms, and the dicarboxylic acid preferably has 2 to 20 carbon atoms. The following are mentioned as a typical example of a raw material.
- amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and paraaminomethylbenzoic acid
- lactams such as ⁇ -caprolactam, ⁇ -undecanactam and ⁇ -laurolactam
- ethylenediamine, trimethylene Diamine tetramethylenediamine
- octamethylenediamine nonamethylenediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine
- pentadecanediamine hexadecanediamine, heptadecane Diamine
- octadecanediamine nonadecanediamine, eicosanediamine, 2-methyl-1,5-diaminopentane, 2-methyl-1 Aliphatic diamines such as 8-d
- polyamide homopolymers or copolymers derived from these raw materials can be used. It is acceptable that two or more polyamides are mixed to form a polyamide resin.
- the structural unit derived from the raw materials exemplified above is represented by the terminal structure represented by the general formula (I), or In 100 mol% of all structural units constituting the polyamide resin excluding the terminal structure represented by formula (I) and general formula (II) described later, it is preferable to have 80 mol% or more, and to have 90 mol% or more. More preferably, having 100 mol% is a further preferred embodiment. Moreover, it is preferable that the polymerization structure derived from the raw material illustrated above is linear.
- polyamide homopolymers or copolymers obtained using the above raw materials examples include polycaproamide (polyamide 6), polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), and polyhexamethylene adipamide (polyamide 66).
- Polytetramethylene adipamide (polyamide 46), polypentamethylene adipamide (polyamide 56), polytetramethylene sebacamide (polyamide 410), polypentamethylene sebacamide (polyamide 510), polyhexamethylene sebaca Amide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polydecamethylene sebamide (nylon 1010), polydecamethylene dodecamide (nylon 1012), polymetaxylylene adipamide (MXD6) , Polymetaxylylene sebacamide (MXD10), polyparaxylylene sebacamide (PXD10), polynonamethylene terephthalamide (nylon 9T), polydecamethylene terephthalamide (polyamide 10T), polyundecamethylene terephthalamide (polyamide) 11T), polydodecamethylene terephthalamide (polyamide 12T), polypentamethylene terephthalamide / polyhexam
- polyamide homopolymers or copolymers Two or more of these polyamide homopolymers or copolymers can be used depending on the required properties such as heat resistance, toughness and surface properties.
- Particularly preferred polyamide homopolymers or copolymers are polyamide 6, polyamide 66, polyamide 56, polyamide 410, polyamide 510, polyamide 610, polyamide 6/66, polyamide 6/12, polyamide 9T, and polyamide 10T.
- the terminal-modified polyamide resin of the present invention has a terminal structure represented by the following general formula (I).
- Examples of the structural unit derived from the above-mentioned polyamide resin raw material include a terminal-modified polyamide resin having a terminal structure represented by the following general formula (I). Or what has the structure represented by the said general formula (I) at the terminal of the polyamide resin mentioned above can be mentioned.
- the resulting polymer Since the terminal structure represented by the following general formula (I) has an alkylene oxide structure, the resulting polymer has high molecular mobility and excellent affinity with an amide group.
- the terminal structure represented by the following general formula (I) at the terminal of the polyamide resin is interposed between the polyamide molecular chains, so that the free volume of the polymer increases and the entanglement decreases.
- the molecular mobility of the polymer can be significantly increased and the melt viscosity can be reduced, resulting in improved moldability.
- Such an effect is extremely high as compared with the case where the polyalkylene oxide structure is mainly included in the main chain of the polyamide resin.
- m represents a range of 2 to 100.
- m is preferably 5 or more, more preferably 8 or more, and further preferably 16 or more.
- m is preferably 70 or less, and more preferably 50 or less. From the viewpoint of maintaining the characteristics derived from the main structural unit of the polyamide resin, it is preferable to have the terminal structure represented by the general formula (I) only at the terminal.
- R 1 represents a divalent hydrocarbon group having 2 to 10 carbon atoms. From the viewpoint of affinity with the main structural unit of the polyamide resin, a hydrocarbon group having 2 to 6 carbon atoms is more preferable, and a hydrocarbon group having 2 to 4 carbon atoms is a more preferable embodiment. From the viewpoint of thermal stability of the terminal-modified polyamide resin and prevention of coloring, a saturated hydrocarbon group is preferable.
- R 1 examples include an ethylene group, a 1,3-trimethylene group, an isopropylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group, and a 1,6-hexamethylene group.
- m R 1 s are allowed even if they are a combination of hydrocarbon groups having different carbon numbers.
- R 1 is preferably composed of at least a divalent saturated hydrocarbon group having 2 carbon atoms and a divalent saturated hydrocarbon group having 3 carbon atoms. More preferably, the polyamide resin is composed of an ethylene group excellent in affinity with the main structural unit of the polyamide resin and an isopropylene group having a large free volume, and the effect of reducing the melt viscosity can be expressed more effectively.
- the terminal structure represented by the general formula (I) contains 10 or more ethylene groups and 6 or less isopropylene groups, and introduces a terminal structure having a desired amount into the polyamide resin. And the effect of reducing the melt viscosity can be further enhanced.
- R 2 represents H or a monovalent organic group.
- R 2 is preferably a monovalent hydrocarbon group having 1 to 30 carbon atoms from the viewpoint of affinity with the polyamide resin.
- R 2 is a monovalent hydrocarbon group, the smaller the carbon number of R 2 , the better the affinity with the main structural unit of the polyamide resin. Therefore, a hydrocarbon group having 1 to 20 carbon atoms is more preferable. More preferably, 10 to 10 hydrocarbon groups are used.
- R 2 is more preferably a monovalent saturated hydrocarbon group.
- R 2 includes, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl Group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, and eicosyl group.
- a methyl group and an ethyl group which are excellent in affinity with the main structural unit of the polyamide resin, are more preferable.
- —X— represents —NH—, —N (CH 3 ) —, — (C ⁇ O) — or —CH 2 —CH (OH) —CH 2 —O—.
- —NH— which is excellent in affinity with the main structural unit of the polyamide resin, is more preferable.
- the terminal-modified polyamide resin of the present invention has the terminal structure represented by the general formula (I) at least at a part of the polyamide resin terminal.
- the terminal-modified polyamide resin of the present invention contains 1 to 10% by mass of the terminal structure represented by the general formula (I) in 100% by mass of the terminal-modified polyamide resin.
- the content of the terminal structure represented by the general formula (I) is less than 1% by mass, the melt viscosity of the terminal-modified polyamide resin increases and the molding processability decreases.
- the content of the terminal structure represented by the general formula (I) is preferably 2% by mass or more, and more preferably 3% by mass or more.
- the content of the terminal structure represented by the general formula (I) exceeds 10% by mass, the average diameter of islands formed by the general formula (I) described later becomes larger than 50 nm, and the mechanical properties of the molded product Strength decreases.
- the content of the terminal structure represented by the general formula (I) is preferably 8% by mass or less, and more preferably 5% by mass or less.
- the content of the terminal structure represented by the general formula (I) in the terminal-modified polyamide resin is, for example, the terminal represented by the general formula (III) described later used when producing the terminal-modified polyamide resin. It can be adjusted to a desired range depending on the compounding amount of the modifying compound.
- the terminal-modified polyamide resin of the present invention has a melt viscosity of 8 Pa ⁇ s or less under a temperature condition of melting point + 60 ° C. and a shear rate of 9728 sec ⁇ 1 .
- the melt viscosity is preferably 7 Pa ⁇ s or less, more preferably 6 Pa ⁇ s or less, and still more preferably 5 Pa ⁇ s or less.
- the melt viscosity is 0.1 Pa ⁇ s or more. More preferably, it is 0.5 Pa ⁇ s or more, and further preferably 1 Pa ⁇ s or more.
- This melt viscosity can be measured with a capillary flow meter under the condition of a shear rate of 9728 sec ⁇ 1 after being retained for 5 minutes in order to melt the end-modified polyamide resin at a temperature of the melting point of the end-modified polyamide resin + 60 ° C. it can.
- the melting point + 60 ° C. is selected as a temperature condition in which the effect of good fluidization of the melt is likely to appear and the thermal decomposition is difficult to proceed in a short stay
- 9728 sec ⁇ 1 was selected as the shear rate, which is a high shear condition assuming the formation of small, complex, thin-walled and lightweight molded products.
- the melt viscosity of the terminal-modified polyamide resin is, for example, a compound for terminal modification represented by the general formula (III) described later or the general formulas (III) and (IV) used when the terminal-modified polyamide resin is produced. ) Can be adjusted to a desired range depending on the blending amount of the compound for terminal modification and reaction time.
- the terminal-modified polyamide resin of the present invention is a ratio of the weight average molecular weight Mw and the terminal structure content [mass%] represented by the general formula (I) (weight average molecular weight Mw / terminal structure represented by the general formula (I). Content ratio) is 6,000 or more.
- the amount of the terminal structure represented by the general formula (I) is larger than the weight average molecular weight Mw, and the ratio is less than 6000, the terminal structure represented by the general formula (I) is likely to aggregate, By making it easy to form, the average diameter of the island portion becomes larger than 50 nm, and the mechanical strength of the molded product is lowered.
- the ratio of the weight average molecular weight Mw and the terminal structure content represented by the general formula (I) is preferably 6100 or more, more preferably 6200 or more. On the other hand, from the viewpoint of moldability, the above ratio is 20000 or less. More preferably, it is 18000 or less, More preferably, it is 16000 or less.
- the melt viscosity can be lowered by lowering the weight average molecular weight Mw.
- lowering the weight average molecular weight Mw greatly reduces the mechanical strength, particularly the impact resistance. Therefore, introduction of a terminal structure represented by the terminal structure represented by the general formula (I) is effective as a method for lowering the melt viscosity while maintaining a high weight average molecular weight Mw, that is, maintaining high impact resistance. Yes, the melt viscosity decreases in proportion to the amount introduced.
- the introduction amount of the terminal structure represented by the terminal structure represented by the general formula (I) increases, a phenomenon in which an inflection point at which the mechanical strength, in particular, the bending elastic modulus and the bending strength are decreased, exists rapidly. Found experimentally.
- the content of the terminal structure represented by the terminal structure represented by the general formula (I) in the terminal-modified polyamide resin can be determined by 1 H-NMR measurement.
- the measurement method and calculation method are as follows.
- a deuterated sulfuric acid solution in which the concentration of the terminal-modified polyamide resin is 50 mg / mL is prepared, and 1 H-NMR measurement is performed with 256 integrations. From the spectral integral value of R 1, the spectral integral value of R 2 , and the spectral integral value of the repeating structural unit of the polyamide resin skeleton (repeating structural unit constituting the main chain of the polymer), the terminal represented by the general formula (I) The content (% by mass) of the structure can be calculated.
- the weight average molecular weight (Mw) is determined using hexafluoroisopropanol (added 0.005N-sodium trifluoroacetate) as a solvent and Shodex HFIP-806M (two) and HFIP-LG as columns. It is obtained by GPC measurement at 30 ° C.
- polymethyl methacrylate is used as the molecular weight reference material.
- the terminal-modified polyamide resin of the present invention preferably contains a terminal structure represented by the following general formula (II).
- a terminal structure represented by the following general formula (II) As described above, by introducing the terminal structure represented by the general formula (I) into the polyamide resin, the melt viscosity of the terminal-modified polyamide resin can be reduced and the molding processability can be improved.
- the terminal modifying compound represented by the general formula (III) when only the terminal structure represented by the general formula (I) is introduced into the polyamide resin by reacting the terminal modifying compound represented by the general formula (III) with the carboxyl terminal group of the polyamide resin, The amount of amino end groups of is increased.
- the polyamide resin having the terminal structure represented by the general formula (I) has one terminal modified with the structure represented by the general formula (I), but the other terminal is not modified.
- the amino terminal group serves as a base point, the cohesive force between polyamide resins increases, and the compatibility of the terminal structure represented by the polyamide resin skeleton (amide group) and the general formula (I) decreases. Therefore, originally, the terminal structure represented by the general formula (I) intervening between the polyamide molecular chains tends to aggregate due to a decrease in compatibility with the polyamide resin skeleton, resulting in the mechanical properties of the molded product. Strength decreases. The same applies to the case where the terminal structure compound represented by the general formula (III) is reacted with the amino group terminal of the polyamide resin.
- a terminal-modifying compound represented by the general formula (IV) described later is further added to the polyamide resin (that is, a polyamide resin in which only one terminal is modified with a structure represented by the general formula (I)).
- the terminal structure represented by the general formula (I) and the polyamide resin are obtained by modifying the other terminal by reacting, etc. to obtain a polyamide resin further having a terminal structure represented by the following general formula (II). It is possible to suppress a decrease in compatibility with the skeleton and to exhibit better mechanical strength of the molded product.
- the molecular weight at the time of melting residence is further increased. Change can be suppressed.
- the terminal structure represented by the general formula (I) by introducing the terminal structure represented by the general formula (I), it is possible to reduce the melt viscosity of the terminal-modified polyamide resin and at the same time to exhibit excellent mechanical strength. There is a tendency that the thermal decomposition of the terminal structure represented by the general formula (I) is likely to proceed during long-term melt residence. This is because the polyamide resin having only the terminal structure represented by the general formula (I) has one terminal modified with the terminal structure represented by the general formula (I), but the other terminal is modified. It remains as an amino terminal group or a carboxyl group.
- the amino terminal group and the carboxyl terminal group act as a thermal decomposition catalyst for the terminal structure represented by the general formula (I), and the thermal decomposition of the terminal structure represented by the general formula (I) easily proceeds. It is presumed that. Therefore, there is a demand for further reduction of the amino terminal group amount and the carboxyl terminal group amount. Therefore, for example, the polyamide resin (that is, only one terminal is modified with a structure represented by the general formula (I)). The other end is modified by, for example, further reacting a compound for terminal modification represented by the general formula (IV), which will be described later, with a terminal structure represented by the following general formula (II).
- R 3 represents a monovalent hydrocarbon group having 1 to 30 carbon atoms. As the number of carbon atoms in R 3 is small, is excellent in affinity with the main structural units of the polyamide resin, R 3 is preferably a hydrocarbon group having 1 to 30 carbon atoms.
- hydrocarbon group examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, Tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, eicosyl group, heneicosyl group, heneicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group Straight chain alkyl groups such as nonacosyl group and triacontyl group, branched chain alkyl groups such as isopropyl group, isobutyl group,
- Y— represents — (C ⁇ O) —.
- X in the general formula (I) is — (C ⁇ O) — or —CH 2 —CH (OH) —CH 2 —O—
- Y in the above general formula (II) is — NH— or —N (CH 3 ) — is represented.
- the terminal of the polyamide resin is composed of an amino terminal group and a carboxyl terminal group, and when the terminal modification compound represented by the general formula (III) has an amino terminal group, the terminal modification compound is a carboxyl terminal group of the polyamide resin.
- X in the general formula (I) becomes —NH— or —N (CH 3 ) —.
- the terminal-modified polyamide resin of the present invention contains the terminal structure represented by the general formula (II) in an amount of 0.1 to 5% by mass (0.1 to 5% by mass) in 100% by mass of the terminal-modified polyamide resin. Is a preferred embodiment.
- the content of the terminal structure represented by the general formula (II) is 0.1% by mass or more, thermal decomposition of the structure represented by the general formula (I) in the terminal-modified polyamide resin is suppressed during the residence time.
- the content of the terminal structure represented by the general formula (II) is more preferably 0.2% by mass or more, and further preferably 0.4% by mass or more. On the other hand, when the content of the terminal structure represented by the general formula (II) is 5% by mass or less, a decrease in mechanical strength can be suppressed.
- the content of the terminal structure represented by the general formula (II) is more preferably 3% by mass or less, and further preferably 1% by mass or less.
- the content of the terminal structure represented by the general formula (II) in the terminal-modified polyamide resin can be determined by 1 H-NMR measurement.
- the measurement and calculation method is as follows.
- a deuterated sulfuric acid solution in which the concentration of the terminal-modified polyamide resin is 50 mg / mL is prepared, and 1 H-NMR measurement is performed with 256 integrations.
- the content (% by mass) of the terminal structure (II) can be calculated from the spectral integral value of R 3 and the spectral integral value of the repeating structural unit of the polyamide resin skeleton (repeating structural unit constituting the main chain of the polymer). it can.
- the terminal-modified polyamide resin of the present invention has a main portion of the terminal-modified polyamide resin and a non-terminal-modified polyamide resin in the morphology of the cross section of the molded article made of the terminal-modified polyamide resin of the present invention, as observed by an electron microscope.
- the terminal structure represented by the general formula (I) forms an island, and the average diameter of the island formed by the terminal structure represented by the general formula (I) is preferably 10 nm or more and 50 nm or less. .
- the average diameter of the island part formed by the terminal structure represented by the general formula (I) is smaller than 50 nm, the stress is prevented from concentrating on the flexible island part, so that a decrease in mechanical strength can be suppressed. .
- the average diameter of the island part which the terminal structure represented by general formula (I) forms is larger than 10 nm, the outstanding mechanical strength can be expressed.
- the average diameter of the island portion formed by the terminal structure represented by the general formula (I) can be measured by the following method.
- the diameter of the island portion is confirmed by observing the cross section of the molded product.
- general formula (II) does not form an island part
- the island structure confirmed by observation shows the island part which general formula (I) formed.
- the island part which consists of a terminal structure represented by general formula (I) is a perfect circle, it points out the diameter, and it measures using the test piece for bending evaluation according to ISO178.
- the molding temperature was set to the melting point of the terminal-modified polyamide resin + about 30 ° C.
- the mold temperature was set to 80 ° C.
- the injection time and the holding time were combined for 10 seconds
- the cooling time was set to 10 seconds.
- the modified polyamide resin is injection-molded to produce the evaluation test piece.
- a 100 ⁇ m-thick section was cut out from the obtained test specimen for evaluation, the polyamide resin portion was stained by a phosphotungstic acid staining method, an ultrathin section was cut out, and a magnification of 2 using a transmission electron microscope (TEM).
- TEM transmission electron microscope
- the cutout location of the section from the test specimen for evaluation is not particularly limited.
- the diameter of the island part formed by at least 100 randomly selected terminal structures represented by the general formula (I) was measured, and the average diameter was determined.
- the major axis means the maximum distance between the parallel lines A when sandwiched between two parallel lines A so as to contact the island portion.
- the minor axis refers to the maximum distance between the parallel lines B when sandwiched between two parallel lines B perpendicular to the parallel lines A so as to contact the island part.
- the terminal-modified polyamide resin of the present invention preferably contains 10 to 80 mol / t (10 mol / t or more and 80 mol / t or less) of amino end group.
- the amino terminal group amount is 80 mol / t or less, thermal decomposition from the amino terminal group is less likely to occur during the melt retention during the molding process, and the decomposition product can be prevented from becoming a plasticizer. The decrease can be suppressed.
- the amino terminal group amount is more preferably 60 mol / t or less, and still more preferably 40 mol / t.
- the amino terminal group amount is 10 mol / t or more, a decrease in interaction between molecules can be suppressed, and a decrease in mechanical strength can be suppressed.
- the amino terminal group amount is more preferably 15 mol / t or more, and still more preferably 20 mol / t or more.
- the amount of amino terminal groups in the terminal-modified polyamide resin is obtained by dissolving the terminal-modified polyamide resin in a phenol / ethanol mixed solution (ratio: 83.5 / 16.5 mass ratio) and using thymol blue as an indicator. It can be measured by titrating with an aqueous hydrochloric acid solution.
- the content of the amino end group of the terminal-modified polyamide resin is, for example, a compound for terminal modification represented by the general formula (III) described later or the general formula used when producing a terminal-modified polyamide resin. It can be adjusted to a desired range depending on the blending amount of the compound for terminal modification represented by (III) and (IV) and the reaction time.
- the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the terminal-modified polyamide resin of the present invention is preferably 18,000 or more. By setting the weight average molecular weight to 18,000 or more, the mechanical properties can be further improved.
- the weight average molecular weight is more preferably 19,000 or more, and further preferably 20,000 or more.
- the weight average molecular weight is preferably 30,000 or less. By setting Mw to 30,000 or less, the melt viscosity can be further reduced and the molding processability can be further improved.
- the weight average molecular weight is more preferably 28,000 or less, and further preferably 26,000 or less.
- the method for measuring the weight average molecular weight (Mw) in the present invention is as described above.
- the weight average molecular weight of the terminal-modified polyamide resin is, for example, a compound for terminal modification represented by the following general formula (III) used when producing the terminal-modified polyamide resin, or the general formula (III) and It can be adjusted to a desired range depending on the blending amount of the compound for terminal modification represented by (IV) and the reaction time.
- the melting point (Tm) of the terminal-modified polyamide resin of the present invention is preferably 150 ° C. or higher, more preferably 200 ° C. or higher.
- the melting point of the terminal-modified polyamide resin can be determined by differential scanning calorimetry (DSC).
- DSC differential scanning calorimetry
- fusing point is as follows. Weigh 5-7 mg of terminal-modified polyamide resin. In a nitrogen atmosphere, the temperature is raised from a temperature of 20 ° C. to Tm + 30 ° C. at a heating rate of 20 ° C./min. Subsequently, the temperature is decreased to 20 ° C. at a temperature decrease rate of 20 ° C./min.
- Tm melting point
- terminal-modified polyamide resin having a melting point of 150 ° C. or higher examples include resins having a structure represented by the above general formula (I) at the terminal of the above-mentioned polyamide and copolymers thereof.
- the terminal-modified polyamide resin of the present invention preferably has a relative viscosity ( ⁇ r) in the range of 1.3 to 3.0 at a temperature of 25 ° C. in a 98% sulfuric acid solution having a resin concentration of 0.01 g / ml.
- ⁇ r relative viscosity
- the relative viscosity is more preferably 1.4 or more, and further preferably 1.5 or more.
- the moldability can be further improved.
- the relative viscosity is more preferably 2.1 or less, still more preferably 2.05 or less, and particularly preferably 2.0 or less.
- the relative viscosity of the terminal-modified polyamide resin is, for example, a compound for terminal modification represented by the general formula (III) described later or the general formula (III) used when the terminal-modified polyamide resin is produced. And it can adjust to the desired range with the compounding quantity of the compound for terminal modification represented by (IV), and reaction time.
- a polyamide resin, a compound for terminal modification represented by the following general formula (III), and, if necessary, a compound for terminal modification represented by the following general formula (IV) and other components above the melting point of the polyamide resin A method of melt-kneading and reacting in the above, a method of mixing these in a solution and reacting, and then removing the solvent, and (2) A raw material constituting the main structural unit of the polyamide resin, a compound for terminal modification represented by the following general formula (III), and a compound for terminal modification represented by the following general formula (IV) as necessary, and other Examples thereof include a method in which components are added and reacted (addition method during reaction).
- the raw material of the terminal-modified polyamide resin is charged into a reaction vessel, substituted with nitrogen, and reacted by heating. If the reaction time at this time is too short, not only the molecular weight does not increase, but also the oligomer component increases, so the mechanical strength may decrease. Therefore, the nitrogen flow time in the reaction time is preferably 15 minutes or more. On the other hand, if the reaction time is too long, thermal decomposition proceeds and coloration or the like occurs. Therefore, the nitrogen flow time in the reaction time is preferably 8 hours or less.
- m represents a range of 2 to 100. Similarly to m in the general formula (I), m is preferably 5 or more, more preferably 8 or more, and further preferably 16 or more. On the other hand, m is preferably 70 or less, and more preferably 50 or less.
- R 1 represents a divalent hydrocarbon group having 2 to 10 carbon atoms
- R 2 represents H or an organic group, and when the organic group is a hydrocarbon group, a monovalent hydrocarbon having 1 to 30 carbon atoms Groups are preferred.
- Z— represents H 2 N—, HN (CH 3 ) —, HO (C ⁇ O) —, or W—O—, and W represents a glycidyl group.
- Z- is more preferably H 2 N-, which is excellent in reactivity with the terminal of the polyamide.
- HY'-R 3 (IV) In the general formula (IV), R 3 represents a monovalent hydrocarbon group having 1 to 30 carbon atoms. Similarly to the general formula (II), R 3 is preferably a monovalent saturated hydrocarbon group from the viewpoint of thermal stability of the terminal-modified polyamide resin and prevention of coloring.
- the number average molecular weight of the compound for terminal modification represented by the general formula (III) is preferably 500 to 10,000. By setting the number average molecular weight to 500 or more, the melt viscosity can be further reduced.
- the number average molecular weight is more preferably 800 or more, and still more preferably 900 or more.
- the affinity with the main structural unit of the polyamide resin can be further improved.
- the number average molecular weight is more preferably 5000 or less, still more preferably 2500 or less, and further preferably 1500 or less.
- the number average molecular weight can be measured, for example, by gel permeation chromatography (GPC).
- the compounds for terminal modification when R 2 is a hydrocarbon group include methoxypoly (ethylene glycol) amine, methoxypoly (trimethylene glycol) amine, methoxypoly (propyleneglycol) amine, methoxypoly (tetramethyleneglycol) amine, methoxypoly (ethyleneglycol) ) Poly (propylene glycol) amine, methoxy poly (ethylene glycol) carboxylic acid, methoxy poly (trimethylene glycol) carboxylic acid, methoxy poly (propylene glycol) carboxylic acid, methoxy poly (tetramethylene glycol) carboxylic acid, methoxy poly (ethylene glycol) poly (propylene) Glycol) carboxylic acid, lauryl alcohol poly (ethylene glycol) amine, methoxypoly (trimethylene glycol) amine, methoxypoly (propyleneglycol) amine, methoxypoly (ethyleneglycol) ) Poly (propylene glycol)
- terminal modification compound represented by the general formula (IV) examples include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, undecanoic acid, lauric acid, tridecane.
- Aliphatic monocarboxylic acids such as acid, myristic acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, arachidic acid, and serotic acid, and cycloaliphatic monocarboxylic acids such as cyclohexanecarboxylic acid and methylcyclohexanecarboxylic acid , Aromatic monocarboxylic acids such as benzoic acid, toluic acid, ethylbenzoic acid, phenylacetic acid, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, nonylamine, Decylamine, Unde Aliphatic monoamines such as ruamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine
- a terminal-modified polyamide resin is produced by a method in which a polyamide resin raw material and a terminal-modifying compound are reacted at the time of polymerization, the reaction is performed at a temperature lower than the melting point of the polyamide resin and a melt polymerization method in which the reaction is performed at a temperature higher than the melting point of the polyamide resin. Any method of solid phase polymerization can be used.
- Examples of the raw material for the polyamide resin include the aforementioned amino acids, lactams, and mixtures of diamines and dicarboxylic acids.
- a terminal-modified polyamide resin is produced by melt-kneading a polyamide resin and a terminal-modifying compound
- the reaction is carried out at a temperature higher than the melting point (Tm) of the polyamide resin by 10 to 40 ° C. It is preferable to make it.
- Tm melting point
- the cylinder temperature of an extruder shall be the said range.
- a polymerization accelerator When producing a terminal-modified polyamide resin by a method in which a polyamide resin raw material and a compound for terminal modification are reacted at the time of polymerization, a polymerization accelerator can be added as necessary.
- the polymerization accelerator for example, phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid and inorganic phosphorus compounds such as alkali metal salts and alkaline earth metal salts thereof are preferable. Sodium phosphate and sodium hypophosphite are preferably used.
- the polymerization accelerator is preferably used in the range of 0.001 to 1 part by mass with respect to 100 parts by mass of the polyamide resin raw material (excluding the compound for terminal modification). By setting the addition amount of the polymerization accelerator to 0.001 to 1 part by mass, it is possible to obtain a terminal-modified polyamide resin having a better balance between mechanical properties and moldability.
- a polyamide resin composition containing a terminal-modified polyamide resin can be obtained by blending the terminal-modified polyamide resin of the present invention with fillers, other types of polymers, impact resistance improvers and various additives.
- any filler generally used as a filler for resins can be used, thereby further improving the strength, rigidity, heat resistance and dimensional stability of a molded product obtained from the polyamide resin composition.
- the filler include glass fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone koji fiber, and metal fiber.
- Fibrous inorganic filler wollastonite, zeolite, sericite, kaolin, mica, talc, clay, pyrophyllite, bentonite, montmorillonite, asbestos, aluminosilicate, alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, oxidation Iron, calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, glass beads, ceramic beads, boron nitride, silicon carbide, and silica How such non-fibrous inorganic fillers and the like.
- fillers Two or more kinds of these fillers can be contained. Moreover, a hollow-shaped filler can also be used as these fillers. Further, as the filler, a filler treated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, and an epoxy compound can also be used. Further, as the montmorillonite, an organic montmorillonite obtained by cation exchange of interlayer ions with an organic ammonium salt can also be used. Among the fillers, fibrous inorganic fillers are preferable, and glass fibers and carbon fibers are particularly preferably used.
- polymers include, for example, polyolefins such as polyethylene and polypropylene, elastomers such as polyamide elastomer and polyester elastomer, polyester, polycarbonate, polyphenylene ether, polyphenylene sulfide, liquid crystal polymer, polysulfone, polyethersulfone, ABS resin, SAN Examples thereof include resins and polystyrene. Two or more of these polymers can be contained.
- polyolefins such as polyethylene and polypropylene
- elastomers such as polyamide elastomer and polyester elastomer
- polyester polycarbonate
- polyphenylene ether polyphenylene sulfide
- liquid crystal polymer polysulfone
- polyethersulfone polyethersulfone
- ABS resin SAN Examples thereof include resins and polystyrene. Two or more of these polymers can be contained.
- polymers include modified polyolefins such as (co) polymers of olefinic compounds and / or conjugated diene compounds, polyamide-based elastomers, in order to improve the impact resistance of molded products obtained from polyamide resin compositions.
- impact resistance improvers such as polyester elastomers are preferably used.
- Examples of (co) polymers of olefin compounds and / or conjugated diene compounds include ethylene copolymers, conjugated diene polymers, and conjugated diene-aromatic vinyl hydrocarbon copolymers.
- Examples of the ethylene copolymer include copolymers of ethylene and ⁇ -olefins having 3 or more carbon atoms, non-conjugated dienes, vinyl acetate, vinyl alcohol, ⁇ , ⁇ -unsaturated carboxylic acids and derivatives thereof. Can be mentioned.
- Examples of the ⁇ -olefin having 3 or more carbon atoms include propylene and butene-1.
- Examples of the non-conjugated diene include 5-methylidene-2-norbornene, 5-ethylidene-2-norbornene, dicyclopentadiene, 1,4-hexadiene, and the like.
- Examples of the ⁇ , ⁇ -unsaturated carboxylic acid include acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and butenedicarboxylic acid.
- Examples of the ⁇ , ⁇ -unsaturated carboxylic acid derivatives include the above-mentioned ⁇ , ⁇ -unsaturated carboxylic acid alkyl esters, aryl esters, glycidyl esters, acid anhydrides, and imides.
- the conjugated diene polymer refers to at least one conjugated diene polymer.
- the conjugated diene include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene.
- a polymer obtained by reducing some or all of the unsaturated bonds of these polymers by hydrogenation is also used.
- the conjugated diene-aromatic vinyl hydrocarbon copolymer refers to a copolymer of conjugated diene and aromatic vinyl hydrocarbon, and includes a block copolymer and a random copolymer.
- Examples of the conjugated diene include 1,3-butadiene and isoprene.
- Examples of the aromatic vinyl hydrocarbon include styrene.
- a copolymer in which a part or all of unsaturated bonds other than double bonds other than the aromatic ring of the conjugated diene-aromatic vinyl hydrocarbon copolymer is reduced by hydrogenation is also used.
- impact modifiers include ethylene / methacrylic acid copolymers and some or all of the carboxylic acid moieties in these copolymers as salts with sodium, lithium, potassium, zinc, and calcium.
- additives include, for example, antioxidants, heat stabilizers (hindered phenols, hydroquinones, phosphites and their substitutes, copper halides, iodine compounds, etc.), weathering agents (resorcinols, salicylates).
- benzotriazole-based, benzophenone-based, hindered amine-based weathering agents), mold release agents and lubricants fatty alcohol, aliphatic amide, aliphatic bisamide, bisurea, polyethylene wax, etc.), pigments (cadmium sulfide, phthalocyanine) And carbon black), dyes (such as nigrosine and aniline black), plasticizers (such as octyl p-oxybenzoate and N-butylbenzenesulfonamide), antistatic agents (alkyl sulfate anionic antistatic agents, quaternary ammonium Salt-type cationic antistatic Agents, nonionic antistatic agents such as polyoxyethylene sorbitan monostearate, and betaine amphoteric antistatic agents), and flame retardants (hydramines such as melamine cyanurate, magnesium hydroxide, aluminum hydroxide, Ammonium polyphosphate, brominated polystyrene, brominated polypheny
- the terminal-modified polyamide resin of the present invention and the polyamide resin composition using the same are molded into a desired shape by any melt molding method such as injection molding, extrusion molding, blow molding, vacuum molding, melt spinning and film molding. can do. Molded articles obtained by molding a terminal-modified polyamide resin and a polyamide resin composition using the same are, for example, resin molded articles such as electric and electronic equipment parts, automobile parts and machine parts, and fibers such as clothing and industrial materials. It can be used as a packaging film and a film for magnetic recording.
- [Amino terminal group amount [NH 2 ]] 0.5 g of the end-modified polyamide resin or polyamide resin obtained in each Example and Comparative Example was precisely weighed, and 25 ml of a phenol / ethanol mixed solution (ratio: 83.5 / 16.5 mass ratio) was added and dissolved at room temperature. Then, titration with 0.02 N hydrochloric acid was performed using thymol blue as an indicator to determine the amino terminal group amount (mol / t).
- Thermal characteristics Using a differential scanning calorimeter (DSC Q20) manufactured by TA Instruments, 5 to 7 mg of the end-modified polyamide resin or polyamide resin obtained in each example and comparative example was weighed, and the temperature was 20 ° C. in a nitrogen atmosphere. The temperature was raised to a temperature of 250 ° C. at a heating rate of 20 ° C./min. Subsequently, the temperature was decreased to 20 ° C. at a temperature decrease rate of 20 ° C./min. Again, the peak of the endothermic peak that appears when the temperature was raised from 20 ° C. to Tm + 30 ° C. at a rate of temperature rise of 20 ° C./min was defined as Tm (melting point).
- DSC Q20 differential scanning calorimeter
- melt viscosity The terminal-modified polyamide resin or polyamide resin obtained in each Example and Comparative Example was dried in a vacuum dryer at a temperature of 80 ° C. for 12 hours or more.
- a capillary flow meter manufactured by Toyo Seiki Seisakusho Co., Ltd., Capillograph Type 1C
- the melt viscosity was measured under the condition of a shear rate of 9728 sec ⁇ 1 .
- the measurement was carried out after being retained for 5 minutes. It shows that it has high fluidity, so that the value of this melt viscosity is small.
- TEM transmission electron microscope
- the average diameter of the island portion was taken as the diameter
- the major axis was defined as the maximum distance between the parallel lines A when sandwiched between the two parallel lines A so as to contact the island portion.
- the minor axis was defined as the maximum distance between the parallel lines B when sandwiched between two parallel lines B perpendicular to the parallel lines A so as to contact the island part.
- the average diameter of the island portion is 10 to 50 nm is “ ⁇ ”
- the case where the average diameter of the island portion is less than 10 nm or larger than 50 nm is “ ⁇ ”.
- ⁇ ⁇ -Caprolactam Wako Special Grade, manufactured by Wako Pure Chemical Industries, Ltd.
- ⁇ Hexamethylenediamine Wako First Grade, manufactured by Wako Pure Chemical Industries, Ltd. Wako first grade manufactured by Yakuhin Kogyo Co., Ltd.
- Methoxypoly (ethylene glycol) poly (propylene glycol) amine represented by the following structural formula [Chemical Formula 2]: “JEFFAMINE” (registered trademark) M2070 (number average molecular weight Mn2000) manufactured by HUNTSMAN.
- Methoxyethylene glycol poly (propylene glycol) amine represented by the following structural formula [Chemical Formula 3]: “JEFFAMINE” (registered trademark) M600 (number average molecular weight Mn600) manufactured by HUNTSMAN.
- Lauryl alcohol poly (ethylene glycol) glycidyl ether represented by the following structural formula [Chemical Formula 4]: “Denacol” (registered trademark) EX171 (number average molecular weight Mn971) manufactured by Nagase ChemteX Corporation.
- Example 1 700 g of ⁇ -caprolactam, 175 g of ion-exchanged water, 53.9 g of “JEFFAMINE” M1000, and 1.4 g of acetic acid were charged in a reaction vessel, sealed, and purged with nitrogen.
- the set temperature of the heater on the outer periphery of the reaction vessel was set to 260 ° C., and heating was started.
- the internal pressure of the can reached 1.0 MPa
- the internal pressure of the can was maintained at 1.0 MPa while releasing moisture out of the system, and the temperature was increased until the internal temperature of the can reached 250 ° C.
- the set temperature of the heater was changed to 245 ° C., and the internal pressure of the can was adjusted to be normal pressure over 1 hour (internal temperature at the time of reaching normal pressure: 245 ° C. ).
- nitrogen was allowed to flow in the can (nitrogen flow) and held for 195 minutes to obtain a terminal-modified polyamide 6 resin (maximum temperature reached: 250 ° C.).
- the obtained terminal-modified polyamide 6 resin was subjected to Soxhlet extraction with ion-exchanged water to remove the unreacted terminal-modifying compound.
- the terminal-modified polyamide 6 resin thus obtained had a weight average molecular weight of 43,000, a melting point (Tm) of 220 ° C., and a melt viscosity of 7.8 Pa ⁇ s. Further, the obtained terminal-modified polyamide 6 resin includes a structure represented by the following [Chemical Formula 5] and a terminal-modified polyamide 6 resin having a structure represented by the following [Chemical Formula 6] at the terminal. It was. Other physical properties are shown in Table 1.
- Examples 2 to 20, Comparative Examples 1 to 11 After changing the raw materials to the compositions shown in Tables 1 to 3 and setting the pressure in the can to normal pressure, the time for keeping nitrogen flowing in the can (nitrogen flow time) is the time shown in Tables 1 to 3.
- a polyamide 6 resin was obtained in the same manner as in Example 1 except for the change.
- the polyamide resins obtained in Examples 2 to 13, 15, and 16 and Comparative Examples 1 to 9, and 11 are represented by the following [Chemical Formula 5] and the following [Chemical Formula 6].
- the terminal modified polyamide 6 resin which has the structure which is a terminal was included.
- the polyamide resin obtained in Example 14 and Comparative Example 10 contained a terminal-modified polyamide 6 resin having a structure represented by the following [Chemical Formula 5] at the terminal.
- polyamide resin obtained in Example 17 contains a terminal-modified polyamide 6 resin having a terminal structure having the structure represented by the following [chemical formula 7] and the structure represented by the following [chemical formula 6]. It was.
- the polyamide resin obtained in Example 18 includes a terminal-modified polyamide 6 resin having a structure represented by the following [Chemical Formula 8] and a structure represented by the following [Chemical Formula 6] at the terminal. It was.
- the polyamide resin obtained in Example 19 includes a terminal-modified polyamide 6 resin having a terminal structure having the structure represented by the following [chemical formula 9] and the structure represented by the following [chemical formula 6]. It was.
- the polyamide resin obtained in Example 20 includes a terminal-modified polyamide 6 resin having a terminal structure having the structure represented by the following [chemical formula 5] and the structure represented by the following [chemical formula 10]. It was.
- Example 21 A reaction vessel was charged with 331.2 g of hexamethylenediamine, 417.3 g of adipic acid, 175 g of ion-exchanged water, 30.1 g of “JEFFAMINE” M1000, and 5.6 g of acetic acid, and the atmosphere was replaced with nitrogen.
- the set temperature of the heater on the outer periphery of the reaction vessel was set to 290 ° C., and heating was started. After the internal pressure of the can reached 1.75 MPa, the internal pressure of the can was maintained at 1.75 MPa while releasing water out of the system, and the temperature was increased until the internal temperature of the can reached 260 ° C.
- the set temperature of the heater was changed to 265 ° C., and the internal pressure of the can was adjusted to be normal pressure over 1 hour (internal temperature when the normal pressure was reached: 270 ° C.). .
- the obtained polyamide resin contained a structure represented by the following [Chemical Formula 5] and a terminal-modified polyamide 66 resin having a structure represented by the following [Chemical Formula 6] at its terminal.
- Example 22 A reaction vessel was charged with 270.7 g of hexamethylenediamine, 471.2 g of sebacic acid, 175 g of ion-exchanged water, 30.1 g of “JEFFAMINE” M1000, and 5.6 g of acetic acid.
- the set temperature of the heater on the outer periphery of the reaction vessel was set to 260 ° C., and heating was started. After the internal pressure of the can reached 1.0 MPa, the internal pressure of the can was maintained at 1.0 MPa while releasing moisture out of the system, and the temperature was increased until the internal temperature of the can reached 240 ° C.
- the heater set temperature was changed to 245 ° C., and the can internal pressure was adjusted to be normal pressure over 1 hour (can internal temperature when reaching normal pressure: 243 ° C.). .
- the can internal pressure was adjusted to be normal pressure over 1 hour (can internal temperature when reaching normal pressure: 243 ° C.). .
- nitrogen flow while flowing nitrogen in the can (nitrogen flow), it was held for 195 minutes to obtain a terminal-modified polyamide 610 resin (maximum temperature reached: 250 ° C.).
- the obtained polyamide resin contained a structure represented by the following [Chemical Formula 5] and a terminal-modified polyamide 610 resin having a structure represented by the following [Chemical Formula 6] at the terminal.
- the terminal structure represented by formula (I) is contained in a specific range, has a specific range of melt viscosity, and has a specific range of weight average molecular weight Mw.
- a ratio of the terminal structure content [mass%] represented by the general formula (I) (weight average molecular weight Mw / ratio of the terminal structure content represented by the general formula (I))
- an excellent molding process It can be seen that both the properties and the mechanical strength of the molded product can be achieved.
- Example 4 By comparing Example 4 and Example 14 with the terminal structure represented by the general formula (II) in a specific range, the heat of the terminal structure represented by the general formula (I) at the time of retention during the molding process Since decomposition
- disassembly can be suppressed, the outstanding mechanical strength can be expressed.
- the average diameter of the island portion formed by the terminal structure represented by the general formula (I) is larger than 10 nm and smaller than 50 nm. It can be seen that the mechanical strength of the molded product can be improved.
- melt viscosity is 8 Pa ⁇ s or less, so that excellent moldability is obtained.
- Molded articles obtained by molding the terminal-modified polyamide resin of the present invention include, for example, resin molded articles such as electric parts, electronic equipment parts, automobile parts and machine parts, as fibers such as clothing and industrial materials, and packaging materials. And can be suitably used as a film for magnetic recording.
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Abstract
Description
[1]下記一般式(I)で表される末端構造を有する末端変性ポリアミド樹脂であって、前記末端変性ポリアミド樹脂100質量%中、下記一般式(I)で表される末端構造を1~10質量%含有し、重量平均分子量Mwと下記一般式(I)で表される末端構造含有量[質量%]の比(重量平均分子量/下記一般式(I)で表される末端構造含有量の比)が6,000以上20,000以下であり、融点+60℃の温度で、かつ、せん断速度9728sec-1の条件における溶融粘度が0.1Pa・s以上8Pa・s以下である、末端変性ポリアミド樹脂。
-X-(R1-O)m-R2 (I)
(上記一般式(I)中、mは2~100の範囲を表す。R1は炭素数2~10の2価の炭化水素基を表し、R2はHまたは1価の有機基を表す。-X-は-NH-、-N(CH3)-、-(C=O)-、または-CH2-CH(OH)-CH2-O-を表す。一般式(I)中に含まれるm個のR1は、同じでも異なっていてもよい。)
[2]前記末端変性ポリアミド樹脂が、さらに、下記一般式(II)で表される末端構造を0.1~5質量%含有する前記[1]に記載の末端変性ポリアミド樹脂。
-Y-R3 (II)
上記一般式(II)中、R3は炭素数1~30の1価の炭化水素基を表す。前記一般式(I)におけるXが-NH-または-N(CH3)-の場合、上記一般式(II)における-Y-は-(C=O)-を表し、前記一般式(I)におけるXが-(C=O)-の場合、上記一般式(II)におけるYは-NH-または-N(CH3)-を表す。
[3]前記一般式(I)中、R2が炭素数1~30の1価の炭化水素基であることを特徴とする前記[1]または[2]に記載の末端変性ポリアミド樹脂。
[4]電子顕微鏡により観察される、末端変性ポリアミド樹脂からなる成形品断面において、前記末端変性ポリアミド樹脂の主鎖および末端変性されていないポリアミド樹脂が海部を、一般式(I)で表される末端構造が島部を形成し、前記島部の平均径が10nm以上、50nm以下である、前記[1]~[3]のいずれかに記載の末端変性ポリアミド樹脂。
[5]末端変性ポリアミド樹脂中に、アミノ末端基が10~80[mol/t]含有されている、前記[1]~[4]のいずれかに記載の末端変性ポリアミド樹脂。
[6]重量平均分子量Mwが、18,000~30,000である、前記[1]~[5]のいずれかに記載の末端変性ポリアミド樹脂。
[7][1]~[6]のいずれかに記載の末端変性ポリアミド樹脂を含む成形品。
-X-(R1-O)m-R2 (I)
(上記一般式(I)中、mは2~100の範囲を表す。R1は炭素数2~10の2価の炭化水素基を表し、R2はHまたは1価の有機基を表す。そして、-X-は-NH-、-N(CH3)-、-(C=O)-、または-CH2-CH(OH)-CH2-O-を表す。一般式(I)中に含まれるm個のR1は、同じでも異なっていてもよい。)
本発明の末端変性ポリアミド樹脂は、アミノ酸、ラクタムおよび「ジアミンとジカルボン酸との混合物」から選ばれる1種以上を主たる原料として得ることができるポリアミド樹脂であって、前記の一般式(I)で表される末端構造を有するものである。言い換えると、本発明における末端変性ポリアミド樹脂は、ジアミンおよびジカルボン酸からなる組み合わせ、アミノ酸、ならびにラクタムからなる群より選ばれる少なくとも1種を主たる原料として得ることができるポリアミド樹脂であって、前記一般式(I)で表される末端構造を有するものである。
-X-(R1-O)m-R2 (I)
上記の一般式(I)中、mは2~100の範囲を表す。mが小さくなると、溶融粘度の低減効果が不十分となる。mは5以上であることが好ましく、8以上であることがより好ましく、16以上であることがさらに好ましい態様である。一方、mが大きくなりすぎると、耐熱性が不十分となる。mは70以下であることが好ましく、50以下であることがより好ましい態様である。ポリアミド樹脂の主たる構造単位に由来する特性を維持するという観点から、上記の一般式(I)で表される末端構造を末端のみに有することが好ましい。
そこで、例えば、前記ポリアミド樹脂(すなわち、一方の末端のみが一般式(I)で表される構造で変性されているポリアミド樹脂)に、後述する一般式(IV)で表される末端変性用化合物をさらに反応させることなどによって、当該他方の末端を変性せしめ、下記一般式(II)で表される末端構造をさらに導入することにより、一般式(I)で表される構造の熱分解を抑制し、発生したガス起因による機械的特性の低下を抑制することができる。
-Y-R3 (II)
上記の一般式(II)中、R3は炭素数1以上30以下の1価の炭化水素基を表す。R3の炭素数が少ないほど、ポリアミド樹脂の主たる構造単位との親和性に優れるため、R3は炭素数1~30の炭化水素基であることが好ましい。炭化水素基としては、具体的には、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、イコシル基、エイコシル基、ヘンイコシル基、ヘネイコシル基、ドコシル基、トリコシル基、テトラコシル基、ペンタコシル基、ヘキサコシル基、ヘプタコシル基、オクタコシル基、ノナコシル基、トリアコンチル基等の直鎖アルキル基、イソプロピル基、イソブチル基、tert-ブチル基、イソペンチル基、ネオペンチル基等の分岐鎖アルキル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基等のシクロアルキル基、フェニル基、トリル基等のアリール基、ベンジル基、および2-フェニルエチル基等のアラルキル基等が挙げられる。末端変性ポリアミド樹脂の熱安定性および着色防止の観点から、R3は、1価の炭素数1以上20以下の飽和炭化水素基またはアリール基であることがさらに好ましい態様である。
本発明の末端変性ポリアミド樹脂の融点(Tm)は、150℃以上であることが好ましく、200℃以上がより好ましい。ここで、末端変性ポリアミド樹脂の融点は、示差走査熱量測定(DSC)により求めることができる。融点の測定方法は、次のとおりである。末端変性ポリアミド樹脂5~7mgを秤量する。窒素雰囲気下中、20℃の温度から昇温速度20℃/分でTm+30℃まで昇温する。引き続き、降温速度20℃/分で20℃まで降温する。再度、20℃の温度から昇温速度20℃/分でTm+30℃まで昇温したときに現れる吸熱ピークの頂点の温度を融点(Tm)と定義する。
(1)ポリアミド樹脂、下記一般式(III)で表される末端変性用化合物ならびに必要に応じて下記一般式(IV)で表される末端変性用化合物およびその他の成分を、ポリアミド樹脂の融点以上において溶融混練し、反応せしめる方法や、これらを溶液中において混合し、反応せしめた後に溶媒を除く方法、および、
(2)ポリアミド樹脂の主たる構造単位を構成する原料、下記一般式(III)で表される末端変性用化合物ならびに必要に応じて下記一般式(IV)で表される末端変性用化合物およびその他の成分を、添加混合して反応させる方法(反応時添加方法)などが挙げられる。
Z-(R1-O)m-R2 (III)
上記の一般式(I)中、mは2~100の範囲を表す。前記の一般式(I)におけるmと同様に、mは5以上であることが好ましく、8以上であることがより好ましく、16以上であることがさらに好ましい態様である。一方、mは70以下であることが好ましく、50以下であることがより好ましい態様である。
H-Y’-R3 (IV)
上記の一般式(IV)中、R3は炭素数1~30の1価の炭化水素基を表す。前記の一般式(II)と同様に、末端変性ポリアミド樹脂の熱安定性および着色防止の観点から、R3は1価の飽和炭化水素基が好ましい。前記の一般式(III)におけるZが、H2N-、HN(CH3)-またはW-O-の場合、上記の一般式(IV)における-Y’-は、-O(C=O)-を表す。また、前記の一般式(III)におけるZがHO(C=O)-またはW-O-の場合、上記の一般式(IV)におけるY’は、-NH-または-N(CH3)-を表す。
R2が炭化水素基の場合の末端変性用化合物としては、メトキシポリ(エチレングリコール)アミン、メトキシポリ(トリメチレングリコール)アミン、メトキシポリ(プロピレングリコール)アミン、メトキシポリ(テトラメチレングリコール)アミン、メトキシポリ(エチレングリコール)ポリ(プロピレングリコール)アミン、メトキシポリ(エチレングリコール)カルボン酸、メトキシポリ(トリメチレングリコール)カルボン酸、メトキシポリ(プロピレングリコール)カルボン酸、メトキシポリ(テトラメチレングリコール)カルボン酸、メトキシポリ(エチレングリコール)ポリ(プロピレングリコール)カルボン酸、ラウリルアルコールポリ(エチレングリコール)グリシジルエーテル、およびフェノールポリ(エチレングリコール)グリシジルエーテルなどが挙げられる。2種類のポリアルキレングリコールが含まれる場合、ブロック重合構造をとっていてもよく、ランダム共重合構造をとることもできる。また、上記した末端変性用化合物を2種以上用いることもできる。
各実施例および比較例により得られた末端変性ポリアミド樹脂またはポリアミド樹脂の、樹脂濃度0.01g/mlの98%硫酸溶液について、25℃の温度でオストワルド式粘度計を用いて、相対粘度を測定した。
各実施例および比較例により得られた末端変性ポリアミド樹脂またはポリアミド樹脂2.5mgを、ヘキサフルオロイソプロパノール(0.005N-トリフルオロ酢酸ナトリウム添加)4mlに溶解し、得られた溶液を0.45μmのフィルターでろ過した。得られた溶液を用いて、GPC測定により、数平均分子量(Mn)および重量平均分子量(Mw)を測定した。測定条件を、次に示す。
・ポンプ:e-Alliance GPC system(Waters製)
・検出器:示差屈折率計 Waters 2414(Waters製)
・カラム:Shodex HFIP-806M(2本)+HFIP-LG
・溶媒:ヘキサフルオロイソプロパノール(0.005N-トリフルオロ酢酸ナトリウム添加)
・流速:1ml/分
・試料注入量:0.1ml
・温度:30℃
・分子量基準物質:ポリメチルメタクリレート。
各実施例および比較例により得られた末端変性ポリアミド樹脂またはポリアミド樹脂0.5gを精秤し、フェノール/エタノール混合溶液(比率:83.5/16.5質量比)25mlを加えて常温で溶解した後、チモールブルーを指示薬として、0.02規定の塩酸で滴定してアミノ末端基量(mol/t)を求めた。
実施例および比較例により得られた末端変性ポリアミド樹脂またはポリアミド樹脂について、日本電子(株)製FT-NMR JNM-AL400を用いて、1H-NMR測定を実施した。まず、測定溶媒として重水素化硫酸を用いて、試料濃度50mg/mLの溶液を調製した。積算回数256回で、ポリアミド樹脂の1H-NMR測定を実施した。一般式(I)で表される末端構造におけるR1およびR2由来部分のピーク、一般式(II)で表される末端構造におけるR3部分由来のピークおよびポリアミド樹脂骨格の繰り返し構造単位由来のピークを、それぞれ同定した。各ピークの積分強度を算出し、算出した積分強度と、それぞれの構造単位中の水素原子数とから、末端変性ポリアミド樹脂における一般式(I)で表される末端構造の含有量[I](質量%)および一般式(II)で表される末端構造の含有量[II](質量%)を、それぞれ算出した。
TAインスツルメント社製示差走査熱量計(DSC Q20)を用いて、各実施例および比較例により得られた末端変性ポリアミド樹脂またはポリアミド樹脂5~7mgを秤量し、窒素雰囲気下、20℃の温度から昇温速度20℃/分で250℃の温度まで昇温した。引き続き、降温速度20℃/分で20℃まで降温した。再度、20℃の温度から昇温速度20℃/分でTm+30℃まで昇温したときに現れる吸熱ピークの頂点を、Tm(融点)とした。
各実施例および比較例により得られた末端変性ポリアミド樹脂またはポリアミド樹脂を、80℃の温度の真空乾燥器中で12時間以上乾燥した。溶融粘度の測定装置として、キャピラリーフローメーター((株)東洋精機製作所製、キャピログラフ1C型)を用いて、径が0.5mmで、長さが5mmのオリフィスを用いて、融点+60℃の温度で、せん断速度9728sec-1の条件で溶融粘度を測定した。ただし、末端変性ポリアミド樹脂またはポリアミド樹脂を溶融させるため、5分間滞留させた後に測定を行った。この溶融粘度の値が小さいほど、高い流動性を有することを示す。
各実施例および比較例により得られた末端変性ポリアミド樹脂またはポリアミド樹脂を、80℃の温度の真空乾燥器中で12時間以上乾燥した。東芝機械(株)製IS55EPN射出成形機を用いて、シリンダー温度は、末端変性ポリアミド樹脂またはポリアミド樹脂の融点(Tm)+0℃、+5℃、および+10℃の3種類とし、金型温度は80℃とし、射出時間と保圧時間は合わせて10秒、冷却時間は10秒の成形サイクル条件で、試験片厚みが1/25インチ(約1.0mm)のASTM4号ダンベルを射出成形した。射出成形を5回実施し、成形片を5回全て採取できた場合を○とし、5回中1回でも金型への充填が不十分な場合、または成形品を採取できなかった場合を×とした。
各実施例および比較例により得られた末端変性ポリアミド樹脂またはポリアミド樹脂を、80℃の温度の真空乾燥器中で12時間以上乾燥した後、射出成形機(住友重機械社製SG75H-MIV)を使用し、シリンダー温度を融点+30℃、金型温度を80℃、射出速度100mm/sec、および射出圧を下限圧(最低充填圧力)+1MPaの条件で試験片を成形し、ISO178に従い23℃の温度で曲げ強度および曲げ弾性率を評価した。結果を、表1に示す。
ISO179に従い、23℃の温度でシャルピー衝撃強さ(ノッチ付き)を評価した。
前記曲げ強度/曲げ弾性率の項で得られた評価用射出成形片の表層から500μm深さの切削面を、透過型電子顕微鏡(TEM)を用いて、一般式(I)で表される末端構造が形成する島部の分散状態を観察した。射出成形片から厚み100μmの切片を切り出し、リンタングステン酸染色法によりポリアミド骨格成分を染色後、超薄切片を切り出したサンプルについて、透過型電子顕微鏡によって2万倍に拡大して観察を行った。少なくとも100個の一般式(I)で表される末端構造が形成する島部について観察を行い、平均径を求めた。島部が真円の場合は、円の直径を、島部が真円でない場合あるいは円形でない場合、島部の長径及び短径の平均値を径とした。ここで、長径を、島部に接するように2本の平行線Aで挟んだときの平行線A間の最大距離とした。短径を、当該島部に接するように上記平行線Aに垂直な2本の平行線Bで挟んだときの平行線B間の最大距離とした。なお、島部の平均径が10~50nmの場合を「〇」、島部の平均径が10nm未満または50nmより大きい場合を「×」とした。
実施例および比較例において、原料は次に示すものを用いた。
・ヘキサメチレンジアミン:和光純薬工業(株)製 和光一級
・アジピン酸:和光純薬工業(株)製 和光特級
・セバシン酸:和光純薬工業(株)製 和光一級。
・下記の構造式[化学式1]で表されるメトキシポリ(エチレングリコール)ポリ(プロピレングリコール)アミン:HUNTSMAN製“JEFFAMINE”(登録商標) M1000 (数平均分子量Mn1000)。
・酢酸:和光純薬工業(株)製 試薬特級
・安息香酸:和光純薬工業(株)製 試薬特級。
ε-カプロラクタム700g、イオン交換水175g、“JEFFAMINE”M1000 53.9g、および酢酸1.4gを反応容器に仕込み密閉し、窒素置換した。反応容器外周にあるヒーターの設定温度を260℃とし、加熱を開始した。缶内圧力が1.0MPaに到達した後、水分を系外へ放出させながら缶内圧力1.0MPaに保持し、缶内温度が250℃になるまで昇温した。缶内温度が240℃に到達した後、ヒーターの設定温度を245℃に変更し、1時間かけて常圧となるように缶内圧力を調節した(常圧到達時の缶内温度:245℃)。続けて、缶内に窒素を流しながら(窒素フロー)195分間保持して、末端変性ポリアミド6樹脂を得た(最高到達温度:250℃)。続いて得られた末端変性ポリアミド6樹脂を、イオン交換水でソックスレー抽出を行い、未反応の末端変性用化合物を除去した。このようにして得られた末端変性ポリアミド6樹脂の重量平均分子量は4.3万で、融点(Tm)は220℃であり、溶融粘度は7.8Pa・sであった。また、得られた末端変性ポリアミド6樹脂は、次の[化学式5]で表される構造と、次の[化学式6]で表される構造を末端に有する末端変性ポリアミド6樹脂を含むものであった。その他の物性を、表1に示す。
原料を、表1~3に示す組成に変更し、かつ缶内圧力を常圧とした後、缶内に窒素を流しながら保持する時間(窒素フロー時間)を、表1~3に示す時間に変更したこと以外は、実施例1と同様にしてポリアミド6樹脂を得た。ここで、実施例2~13、15、16および比較例1~9、11で得られたポリアミド樹脂は、次の[化学式5]で表される構造と、次の[化学式6]で表される構造を末端に有する末端変性ポリアミド6樹脂を含むものであった。
ヘキサメチレンジアミン331.2g、アジピン酸417.3g、イオン交換水175g、“JEFFAMINE”M1000 30.1g、酢酸5.6gを反応容器に仕込み密閉し、窒素置換した。反応容器外周にあるヒーターの設定温度を290℃とし、加熱を開始した。缶内圧力が1.75MPaに到達した後、水分を系外へ放出させながら缶内圧力1.75MPaに保持し、缶内温度が260℃になるまで昇温した。缶内温度が260℃に到達した後、ヒーターの設定温度を265℃に変更し、1時間かけて常圧となるよう缶内圧力を調節した(常圧到達時の缶内温度:270℃)。続けて、缶内に窒素を流しながら(窒素フロー)180分間保持して末端変性ポリアミド66樹脂を得た(最高到達温度:270℃)。ここで、得られたポリアミド樹脂は次の[化学式5]で表される構造と、次の[化学式6]表される構造を末端に有する末端変性ポリアミド66樹脂を含むものであった。
ヘキサメチレンジアミン270.7g、セバシン酸471.2g、イオン交換水175g、“JEFFAMINE”M1000 30.1g、酢酸5.6gを反応容器に仕込み密閉し、窒素置換した。反応容器外周にあるヒーターの設定温度を260℃とし、加熱を開始した。缶内圧力が1.0MPaに到達した後、水分を系外へ放出させながら缶内圧力1.0MPaに保持し、缶内温度が240℃になるまで昇温した。缶内温度が240℃に到達した後、ヒーターの設定温度を245℃に変更し、1時間かけて常圧となるよう缶内圧力を調節した(常圧到達時の缶内温度:243℃)。続けて、缶内に窒素を流しながら(窒素フロー)195分間保持して末端変性ポリアミド610樹脂を得た(最高到達温度:250℃)。ここで、得られたポリアミド樹脂は次の[化学式5]で表される構造と、次の[化学式6]表される構造を末端に有する末端変性ポリアミド610樹脂を含むものであった。
実施例1~19と比較例3~5、7~9、および11の比較により、一般式(I)で表される末端構造が形成する島部の平均径を10nmより大きく、かつ50nmより小さくすることにより、成形品の機械的強度を向上させることができることがわかる。
Claims (7)
- 下記一般式(I)で表される末端構造を有する末端変性ポリアミド樹脂であって、前記末端変性ポリアミド樹脂100質量%中、下記一般式(I)で表される末端構造を1~10質量%含有し、重量平均分子量Mwと下記一般式(I)で表される末端構造含有量[質量%]の比(重量平均分子量/下記一般式(I)で表される末端構造含有量の比)が6,000以上20,000以下であり、融点+60℃の温度で、かつ、せん断速度9728sec-1の条件における溶融粘度が0.1Pa・s以上8Pa・s以下である、末端変性ポリアミド樹脂。
-X-(R1-O)m-R2 (I)
(上記一般式(I)中、mは2~100の範囲を表す。R1は炭素数2~10の2価の炭化水素基を表し、R2はHまたは1価の有機基を表す。-X-は-NH-、-N(CH3)-、-(C=O)-、または-CH2-CH(OH)-CH2-O-を表す。一般式(I)中に含まれるm個のR1は、同じでも異なっていてもよい。) - 前記末端変性ポリアミド樹脂が、さらに、下記一般式(II)で表される末端構造を0.1~5質量%含有する請求項1に記載の末端変性ポリアミド樹脂。
-Y-R3 (II)
上記一般式(II)中、R3は炭素数1~30の1価の炭化水素基を表す。前記一般式(I)におけるXが-NH-または-N(CH3)-の場合、上記一般式(II)における-Y-は-(C=O)-を表し、前記一般式(I)におけるXが-(C=O)-の場合、上記一般式(II)におけるYは-NH-または-N(CH3)-を表す。 - 前記一般式(I)中、R2が炭素数1~30の1価の炭化水素基である、請求項1または2に記載の末端変性ポリアミド樹脂。
- 電子顕微鏡により観察される、末端変性ポリアミド樹脂からなる成形品断面において、前記末端変性ポリアミド樹脂の主鎖および末端変性されていないポリアミド樹脂が海部を、一般式(I)で表される末端構造が島部を形成し、前記島部の平均径が10nm以上、50nm以下である、請求項1~3のいずれかに記載の末端変性ポリアミド樹脂。
- 末端変性ポリアミド樹脂中に、アミノ末端基が10~80[mol/t]含有されている、請求項1~4のいずれかに記載の末端変性ポリアミド樹脂。
- 重量平均分子量Mwが、18,000~30,000である、請求項1~5のいずれかに記載の末端変性ポリアミド樹脂。
- 請求項1~6のいずれかに記載の末端変性ポリアミド樹脂を含む成形品。
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EP17876035.1A EP3549971A4 (en) | 2016-11-29 | 2017-11-16 | TERMINALLY MODIFIED POLYAMIDE RESIN |
KR1020197013913A KR20190086675A (ko) | 2016-11-29 | 2017-11-16 | 말단 변성 폴리아미드 수지 |
CN201780072445.2A CN109983056A (zh) | 2016-11-29 | 2017-11-16 | 末端改性聚酰胺树脂 |
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JP2004123927A (ja) * | 2002-10-03 | 2004-04-22 | Asahi Kasei Chemicals Corp | 共重合ポリアミド樹脂組成物 |
JP2015105331A (ja) * | 2013-11-29 | 2015-06-08 | チェイル インダストリーズ インコーポレイテッド | ポリアミド樹脂およびその製造方法 |
WO2015151410A1 (ja) * | 2014-04-02 | 2015-10-08 | 株式会社クラレ | ポリアミド |
WO2015182693A1 (ja) | 2014-05-30 | 2015-12-03 | 東レ株式会社 | 末端変性ポリアミド樹脂、その製造方法および成形品の製造方法 |
WO2017110918A1 (ja) * | 2015-12-25 | 2017-06-29 | 東レ株式会社 | 末端変性ポリアミド樹脂およびその製造方法 |
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US6956099B2 (en) * | 2003-03-20 | 2005-10-18 | Arizona Chemical Company | Polyamide-polyether block copolymer |
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