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WO2016031257A1 - Polyamide, procédé de production de polyamide, composition de polyamide, article moulé à base d'une composition de polyamide et son procédé de production - Google Patents

Polyamide, procédé de production de polyamide, composition de polyamide, article moulé à base d'une composition de polyamide et son procédé de production Download PDF

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Publication number
WO2016031257A1
WO2016031257A1 PCT/JP2015/004385 JP2015004385W WO2016031257A1 WO 2016031257 A1 WO2016031257 A1 WO 2016031257A1 JP 2015004385 W JP2015004385 W JP 2015004385W WO 2016031257 A1 WO2016031257 A1 WO 2016031257A1
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Prior art keywords
polyamide
diamine
acid
polyamide composition
dicarboxylic acid
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PCT/JP2015/004385
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English (en)
Japanese (ja)
Inventor
康一 永瀬
真次 家田
祐 日戸
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Asahi Kasei Chemicals Corp
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Asahi Kasei Chemicals Corp
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Priority claimed from JP2015164149A external-priority patent/JP2017078093A/ja
Priority claimed from JP2015164148A external-priority patent/JP2017078092A/ja
Application filed by Asahi Kasei Chemicals Corp filed Critical Asahi Kasei Chemicals Corp
Priority to JP2016544970A priority Critical patent/JPWO2016031257A1/ja
Publication of WO2016031257A1 publication Critical patent/WO2016031257A1/fr
Anticipated expiration legal-status Critical
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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
    • 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
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

  • the present invention relates to polyamide, a method for producing polyamide, a polyamide composition, a molded product of polyamide composition, and a method for producing the molded product.
  • Polyamides represented by polyamide 6 (hereinafter also referred to as “PA6”) and polyamide 66 (hereinafter also referred to as “PA66”) and the like are excellent in molding processability, mechanical properties, and chemical resistance. It is widely used as various parts materials for automobiles, electric and electronic, industrial materials, industrial materials, daily necessities, and household goods.
  • PA6T terephthalic acid and hexamethylenediamine
  • PA6T is composed of aliphatic polyamide such as polyamide 6 and polyamide 66 (hereinafter also referred to as PA6 and PA66, respectively), amorphous fragrance comprising isophthalic acid and hexamethylenediamine.
  • PA6T copolymers High melting point semi-aromatic polyamides (hereinafter also referred to as PA6T copolymers), etc., in which an aromatic polyamide (hereinafter also referred to as PA6I) is copolymerized and the melting point is lowered to about 220 to 340 ° C. have been proposed. .
  • Patent Document 1 discloses an aromatic polyamide (hereinafter referred to as “a mixture of hexamethylenediamine and 2-methylpentamethylenediamine”), which is composed of an aromatic dicarboxylic acid and an aliphatic diamine. , PA6T / 2MPDT). Although PA6T / 2MPDT can partially improve the problems of the conventional PA6T copolymer, the improvement level in terms of fluidity, moldability, toughness, molded product surface appearance and light resistance is insufficient. .
  • PA46 a high-melting point aliphatic polyamide
  • PA46 a high-melting point aliphatic polyamide
  • PA46 has a high water absorption rate, and also absorbs water.
  • the dimensional change and the deterioration of the mechanical properties due to the above are remarkably large, and the demand may not be satisfied in terms of the dimensional change required for automobile applications.
  • Patent Documents 2 and 3 include alicyclic polyamides composed of 1,4-cyclohexanedicarboxylic acid and hexamethylene diamine (hereinafter referred to as PA6C). And semi-alicyclic polyamides (hereinafter also referred to as PA6C copolymers) with other polyamides.
  • PA6C and PA6C copolymers disclosed in Patent Documents 2 and 3 also have problems such as high water absorption and insufficient fluidity.
  • Patent Document 4 discloses that a polyamide comprising a dicarboxylic acid unit containing 1,4-cyclohexanedicarboxylic acid and a diamine unit containing 2-methyl-1,8-octanediamine has light resistance, toughness, moldability, lightness,
  • the polyamide is disclosed to be excellent in heat resistance and the like, but this polyamide is also insufficiently improved in terms of toughness, strength and fluidity.
  • Patent Document 5 discloses a dicarboxylic acid component containing 10 to 80 mol% of 1,4-cyclohexanedicarboxylic acid having a trans isomer / cis isomer molar ratio of 50/50 to 97/3 among all carboxylic acid components.
  • a polyamide obtained by thermal polycondensation with an aliphatic diamine component is described, and a polyamide having a ratio of a trans isomer / cis isomer of a raw material monomer within a predetermined range is excellent in toughness and chemical resistance and moldability It is described that it is excellent.
  • Patent Document 6 describes a polyamide obtained by polymerizing a dicarboxylic acid containing an alicyclic dicarboxylic acid and a diamine containing a diamine having a substituent branched from the main chain.
  • Dicarboxylic acid is isomerized at a high temperature to have a certain ratio, and the cis isomer has a higher water solubility of the equivalent salt with diamine than the trans isomer, so the trans monomer / cis isomer molar ratio of the raw material monomer is It is described that it is preferable that there are many cis isomers, and that the trans isomer ratio of the whole alicyclic dicarboxylic acid in the polyamide is preferably 50 to 85 mol%.
  • Patent Document 7 describes a copolymerized polyamide using a dicarboxylic acid containing an alicyclic dicarboxylic acid and a diamine having 8 or more carbon atoms as raw materials. Similarly, a cis isomer is used as a raw material monomer. It is described that a large amount is preferable and that the trans isomer ratio in the portion derived from the alicyclic dicarboxylic acid of the copolyamide is preferably 65 to 80 mol%.
  • Patent Document 8 discloses a polyamide resin (hereinafter referred to as “dicarboxylic acid”) containing a terephthalic acid unit and a diamine containing a 1,9-nonanediamine unit and / or a 2-methyl-1,8-octanediamine unit. , "PA9T”), and a polyamide composition comprising titanium oxide, magnesium hydroxide, and a specific reinforcing agent is disclosed, and it is disclosed that this polyamide composition is excellent in heat resistance. Has been.
  • Patent Document 9 contains a semi-alicyclic polyamide blended with 70% or more of 1,4-cyclohexanedicarboxylic acid as a dicarboxylic acid unit, titanium oxide, and an inorganic filler, and their mass ratio.
  • a polyamide composition having a predetermined value is disclosed, and it is disclosed that this polyamide composition is excellent in reflow resistance, heat resistance and the like.
  • the conventional polyamide or polyamide composition disclosed in the above patent document requires further improvement in order to obtain higher level characteristics in heat discoloration resistance, extrusion processability and molding process stability.
  • JP-T 6-503590 Japanese National Patent Publication No. 11-512476 JP 2001-514695 A Japanese Patent Laid-Open No. 9-12868 International Publication No. 2002/048239 JP 2010-1111843 A International Publication No. 2012/093722 JP 2006-257314 A JP 2011-219697 A
  • the trans isomer ratio of the entire alicyclic dicarboxylic acid in the polyamide is within a predetermined range, In addition to the features of high melting point, toughness, and rigidity, it simultaneously achieves high-temperature rigidity due to high glass transition temperature, fluidity, which is usually opposite to heat resistance, and high crystallinity and low water absorption. It is described that it is possible.
  • the present invention has been made in view of the above circumstances, and provides a polyamide composition molded article excellent in hot strength and hot rigidity, a method for producing the molded article, and such a polyamide composition molded article. It is an object of the present invention to provide a possible polyamide, a method for producing the polyamide, and a polyamide composition containing the polyamide.
  • the polyamide composition molded article of the present invention is A dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid, a diamine unit containing at least an aliphatic diamine, and A polyamide composition molded article containing a polyamide comprising
  • the trans isomer ratio of 1,4-cyclohexanedicarboxylic acid monomer unit in the molded product is 71 to 100 mol%.
  • the trans isomer ratio mol% may be described as a trans / cis ratio (molar ratio) or a trans / cis isomer ratio. From the description of the cis isomer ratio, the trans isomer ratio mol% can be uniquely derived. When the total of the trans isomer ratio and the cis isomer ratio is 100, when expressed as a trans / cis ratio (molar ratio), one ratio indicates one isomer ratio (mol%). For example, when the trans / cis ratio (molar ratio) is 71/29, the trans isomer ratio is 71 mol%.
  • the content of 1,4-cyclohexanedicarboxylic acid is preferably at least 50 mol% in the dicarboxylic acid unit.
  • the molded article of the polyamide composition of the present invention is obtained when the heat of fusion ⁇ Hm obtained when the temperature is raised at 20 ° C./min and the temperature is lowered at 20 ° C./min in the differential scanning calorimetry according to JIS-K7121.
  • the ratio to the crystallization enthalpy ⁇ Hc obtained is ⁇ Hm / ⁇ Hc> 1.0 It is preferable that ⁇ Hm / ⁇ Hc ⁇ 1.5. It is preferable that
  • differential scanning calorimetry there are two measurement methods for differential scanning calorimetry according to JIS-K7121, input compensation DSC and thermal flow rate DSC.
  • differential scanning calorimetry is measured by input compensation DSC.
  • the “trans isomer ratio” in the polyamide of the present invention is the sum of the respective trans isomer ratios of a plurality of types when (a) the dicarboxylic acid monomer unit includes a plurality of types of geometric isomers. means.
  • the molded article of the polyamide composition of the present invention preferably has a melting peak temperature of 300 ° C. or higher in differential scanning calorimetry.
  • the polyamide composition molded article of the present invention preferably has a heat of fusion ⁇ Hm of 40 J / g or more.
  • the trans isomer ratio mol% is more preferably 80-100.
  • the aliphatic diamine unit is preferably a saturated aliphatic diamine having 4 to 12 carbon atoms, and more preferably a saturated aliphatic diamine having 6 to 10 carbon atoms.
  • the method for producing a polyamide composition molded article of the present invention comprises molding a polyamide composition containing a polyamide containing a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid and a diamine unit containing at least an aliphatic diamine.
  • the molded polyamide composition object is heat-treated at 200 ° C. or higher to produce a molded polyamide composition product.
  • the present inventors have further determined a polyamide having a specific trans isomer ratio and crystallinity ⁇ Hm1 / ⁇ Hc controlled, a polyamide composition thereof, and a polyamide composition molding. It was found that the product can solve the above problems.
  • the first polyamide of the present invention is (A) a dicarboxylic acid unit comprising at least 1,4-cyclohexanedicarboxylic acid; (B) a diamine unit containing at least an aliphatic diamine; A polyamide containing In the differential scanning calorimetry according to JIS-K7121, ⁇ Hm1 / which is the ratio between the heat of fusion ⁇ Hm1 obtained when the temperature is raised at 20 ° C./min and the crystallization enthalpy ⁇ Hc obtained when the temperature is lowered at 20 ° C./min. ⁇ Hc is 1.0 ⁇ Hm1 / ⁇ Hc ⁇ 2.2 And The trans isomer ratio mol% of the dicarboxylic acid monomer unit in the polyamide is 71 ⁇ trans isomer ratio ⁇ 75 It is.
  • the content of 1,4-cyclohexanedicarboxylic acid is preferably at least 50 mol% in the dicarboxylic acid unit.
  • all the dicarboxylic acid units are preferably 1,4-cyclohexanedicarboxylic acid.
  • the aliphatic diamine preferably has 6 to 12 carbon atoms.
  • the aliphatic diamine is hexamethylene diamine, 2-methyl-pentamethylene diamine, 2-methyl-1,8-octane diamine, nonamethylene diamine, decamethylene diamine, or dodecamethylene diamine. Preferably there is.
  • the aliphatic diamine is particularly preferably 2-methyl-pentamethylenediamine.
  • the first polyamide of the present invention is (A) a dicarboxylic acid unit comprising at least 1,4-cyclohexanedicarboxylic acid; (B) a diamine unit containing at least an aliphatic diamine; A polyamide containing The aliphatic diamine comprises a branched aliphatic diamine; The trans isomer ratio mol% of the dicarboxylic acid monomer unit in the polyamide is 71 ⁇ trans isomer ratio ⁇ 100 It may be.
  • the proportion of the branched aliphatic diamine in the (b) diamine unit is preferably 10 to 100 mol%.
  • ⁇ Hm1 / ⁇ Hc is 1.0 ⁇ Hm1 / ⁇ Hc ⁇ 1.4 It is preferable that
  • the first polyamide of the present invention has a ratio [NH 2 ] / ([NH 2 ] + [COOH] which is a ratio of the amino terminal amount [NH 2 ] to the active terminal total amount ([NH 2 ] + [COOH]). ]) [NH 2 ] / ([NH 2 ] + [COOH]) ⁇ 0.5 It is preferable that
  • the total amount of active ends ([NH 2 ] + [COOH]) ⁇ eq / g is 20 ⁇ [NH 2 ] + [COOH] ⁇ 60 It is preferable that
  • the sulfuric acid relative viscosity ⁇ r is preferably 1.8 ⁇ r.
  • the weight average molecular weight Mw / number average molecular weight Mn as the molecular weight distribution is: Mw / Mn ⁇ 3.5 It is preferable that
  • Tm1-Tc which is the difference between the melting peak temperature Tm1 of the polyamide and the crystallization peak temperature Tc of the polyamide, is preferably 40 ° C. ⁇ Tm1-Tc ⁇ 90 ° C.
  • the first polyamide composition of the present invention contains the first polyamide of the present invention and at least one selected from an inorganic filler, a nucleating agent, a heat stabilizer and a light stabilizer.
  • the first polyamide composition of the present invention may further contain titanium oxide.
  • the polyamide composition molded article of the present invention may be formed by molding the first polyamide composition of the present invention.
  • the method for producing the first polyamide of the present invention comprises: (A) a dicarboxylic acid unit comprising at least 1,4-cyclohexanedicarboxylic acid; (B) a diamine unit containing at least an aliphatic diamine, [NH 2 ] / ([NH 2 ] + [COOH]), which is the ratio of the amino terminal amount [NH 2 ] to the total active terminal amount ([NH 2 ] + [COOH]), [NH 2 ] / ([NH 2 ] + [COOH]) ⁇ 0.5 And Active terminal total amount ([NH 2 ] + [COOH]) ⁇ eq / g is 60 ⁇ [NH 2 ] + [COOH] ⁇ 110 Is heat-treated at 200 ° C. or higher and lower than the melting point for 10 hours or longer.
  • the “melting point” indicates a melting peak temperature Tm2 by differential scanning calorimetry (input compensation DSC) according to JIS-K7121.
  • the second polyamide of the present invention is (A) a dicarboxylic acid unit comprising at least 1,4-cyclohexanedicarboxylic acid; (B) a diamine unit containing at least an aliphatic diamine; A polyamide containing Sulfuric acid relative viscosity ⁇ r is 2.5 or more, In the differential scanning calorimetry according to JIS-K7121, ⁇ Hm1 / which is the ratio between the heat of fusion ⁇ Hm1 obtained when the temperature is raised at 20 ° C./min and the crystallization enthalpy ⁇ Hc obtained when the temperature is lowered at 20 ° C./min. ⁇ Hc is 1.0 ⁇ Hm1 / ⁇ Hc ⁇ 2.2 And The trans isomer ratio mol% of the dicarboxylic acid monomer unit in the polyamide is 75 ⁇ trans isomer ratio ⁇ 100 It is.
  • the content of 1,4-cyclohexanedicarboxylic acid is preferably at least 50 mol% in the dicarboxylic acid unit.
  • all the dicarboxylic acid units are preferably 1,4-cyclohexanedicarboxylic acid.
  • the aliphatic diamine preferably has 6 to 12 carbon atoms.
  • the aliphatic diamine is hexamethylenediamine, 2-methylpentamethylenediamine, 2-methyl-1,8-octanediamine, nonamethylenediamine, decamethylenediamine, or dodecamethylenediamine. It is preferable.
  • the aliphatic diamine is preferably 2-methylpentamethylenediamine or decamethylenediamine.
  • the second polyamide of the present invention is (A) a dicarboxylic acid unit comprising at least 1,4-cyclohexanedicarboxylic acid; (B) a diamine unit containing at least an aliphatic diamine; A polyamide containing The aliphatic diamine comprises a branched aliphatic diamine; Sulfuric acid relative viscosity ⁇ r is 2.5 or more, The trans isomer ratio mol% of the dicarboxylic acid monomer unit in the polyamide is 71 ⁇ trans isomer ratio ⁇ 100 It may be.
  • the proportion of the (b) branched aliphatic diamine in the diamine unit is preferably 10 to 100 mol%.
  • ⁇ Hm1 / ⁇ Hc is preferably 1.4 ⁇ Hm1 / ⁇ Hc ⁇ 2.2.
  • active end the total amount of amino-terminus weight [NH 2] is the ratio ([NH 2] + [COOH ]) [NH 2] / ([NH 2] + [COOH]) Is [NH 2 ] / ([NH 2 ] + [COOH]) ⁇ 0.5 It is preferable that
  • the weight average molecular weight Mw / number average molecular weight Mn indicating the molecular weight distribution is Mw / Mn ⁇ 3.5. It is preferable that
  • the second polyamide composition of the present invention preferably contains the second polyamide of the present invention and at least one selected from an inorganic filler, a heat stabilizer, and a light stabilizer.
  • the molded article of the polyamide composition of the present invention may be formed by molding the second polyamide composition of the present invention.
  • the second method for producing a polyamide of the present invention comprises (a) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid, and (b) a diamine unit containing at least an aliphatic diamine.
  • Active end the total amount of amino-terminus weight [NH 2] is the ratio ([NH 2] + [COOH ]) [NH 2] / ([NH 2] + [COOH]) is, [NH 2] / ([ NH 2 ] + [COOH]) ⁇ 0.5, and the active terminal total amount ([NH 2 ] + [COOH]) ⁇ eq / g is 110 ⁇ [NH 2 ] + [COOH] ⁇ 200 Is heat-treated at 200 ° C. or higher and lower than the melting point for 10 hours or longer.
  • the polyamide composition molded article of the present invention is a polyamide composition molded article containing a polyamide containing a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid and a diamine unit containing at least an aliphatic diamine, Since the trans isomer ratio of the dicarboxylic acid monomer unit in this molded product is 71 to 100 mol%, it can be excellent in hot strength and hot stiffness.
  • the method for producing a molded article of a polyamide composition according to the present invention comprises a polyamide composition containing a polyamide containing a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid and a diamine unit containing at least an aliphatic diamine. Since the molded polyamide composition body is heat-treated at 200 ° C. or higher, the trans isomer ratio of the dicarboxylic acid monomer unit in the molded product is 71 to 100 mol%, and is excellent in heat strength and heat rigidity. Polyamide composition molded articles can be produced.
  • the first polyamide of the present invention is a polyamide containing (a) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid, and (b) a diamine unit containing at least an aliphatic diamine, ⁇ Hm1 / ⁇ Hc, which is the ratio between the heat of fusion ⁇ Hm1 and the crystallization enthalpy ⁇ Hc obtained when the temperature is lowered at 20 ° C./min, is 1.0 ⁇ Hm1 / ⁇ Hc ⁇ 2.2, and the dicarboxylic acid monomer in the polyamide
  • the trans isomer ratio (mol%) of the unit is 71 ⁇ trans isomer ratio ⁇ 75.
  • the trans isomer ratio mol% can be made greater than 71 and 75 or less, and the heat resistance, reflow resistance, aging resistance, and release properties are excellent.
  • the polyamide composition molded article of the invention can be obtained.
  • the first polyamide production method of the present invention comprises (a) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid, and (b) a diamine unit containing at least an aliphatic diamine.
  • active end the total amount of end weight [NH 2] is the ratio ([NH 2] + [COOH ]) [NH 2] / ([NH 2] + [COOH]) is, [NH 2] / ([ NH 2 ] + [COOH]) ⁇ 0.5
  • the active terminal total amount ([NH 2 ] + [COOH]) ⁇ equivalent / g is 60 ⁇ [NH 2 ] + [COOH] ⁇ 110 , Heat treatment at 200 ° C.
  • ⁇ Hm1 / ⁇ Hc is 1.0 ⁇ Hm1 / ⁇ Hc ⁇ 2.2
  • the trans isomer ratio (mol%) of the dicarboxylic acid monomer unit in the polyamide is 71 ⁇ trans isomer ratio. It can be set to ⁇ 75, and a polyamide and a polyamide composition excellent in heat resistance, reflow resistance, aging resistance, and releasability can be provided.
  • the second polyamide of the present invention is a polyamide containing (a) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid, and (b) a diamine unit containing at least an aliphatic diamine, wherein the relative viscosity of sulfuric acid is ⁇ r is 2.5 or more, ⁇ Hm / ⁇ Hc is more than 1.0 and 2.2 or less, and the trans isomer ratio mol% of the dicarboxylic acid monomer unit is more than 75 and 100 or less.
  • the polyamide composition of the present invention can have a trans isomer ratio mol% of more than 75 and 100 or less, and is excellent in hot strength, hot rigidity, and low water absorption.
  • a composition molded article can be obtained.
  • the second polyamide production method of the present invention comprises (a) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid, and (b) a diamine unit containing at least an aliphatic diamine.
  • active end the total amount of end weight [NH 2] is the ratio ([NH 2] + [COOH ]) [NH 2] / ([NH 2] + [COOH]) is, [NH 2] / ([ NH 2 ] + [COOH]) ⁇ 0.5
  • the active terminal total amount ([NH 2 ] + [COOH]) ⁇ equivalent / g is 110 ⁇ [NH 2 ] + [COOH] ⁇ 200 , Heat treatment at 200 ° C.
  • the sulfuric acid relative viscosity ⁇ r is 2.5 or more, ⁇ Hm / ⁇ Hc is greater than 1.0 and 2.2 or less, and the trans isomer ratio mol% of the dicarboxylic acid monomer unit is 75%. Larger and less than 100 polyamides and polyamide compositions can be obtained.
  • the present embodiment a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
  • the following this embodiment is an illustration for demonstrating this invention, and is not the meaning which limits this invention to the following content.
  • the present invention can be implemented with various modifications within the scope of the gist.
  • the polyamide composition molded article of the present invention is a polyamide composition molded article containing a polyamide containing a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid and a diamine unit containing at least an aliphatic diamine,
  • the trans isomer ratio of the dicarboxylic acid monomer unit in the molded product is 71 to 100 mol%.
  • Such a polyamide composition molded article can be obtained by the following method.
  • One method is to mold a polyamide composition containing a polyamide obtained by polymerizing a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid and a diamine unit containing at least an aliphatic diamine.
  • a polyamide composition molded article is obtained by heat treatment at 200 ° C. or higher.
  • Another method is to mold the first polyamide composition or the second polyamide composition having a specific trans isomer ratio and ⁇ Hm1 / ⁇ Hc to obtain a polyamide composition molded article.
  • these methods will be described as a first embodiment to a third embodiment.
  • the polyamide composition molded article according to the first embodiment is a molded polyamide composition containing a polyamide containing a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid and a diamine unit containing at least an aliphatic diamine. Then, the molded polyamide composition object is heat-treated at 200 ° C. or higher to obtain a polyamide composition molded article.
  • the polyamide contained in the polyamide composition for obtaining the polyamide composition molded product according to the first embodiment, its structural unit, the polyamide composition containing the polyamide, and the method for producing the polyamide composition molded product will be described.
  • polyamide in the polyamide composition molded article and the method for producing the same of the present invention is a polyamide containing a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid and a diamine unit containing at least an aliphatic diamine.
  • polyamide means a polymer having an amide bond (—NHCO—) in the main chain.
  • the dicarboxylic acid unit is a dicarboxylic acid containing at least 1,4-cyclohexanedicarboxylic acid.
  • 1,4-cyclohexanedicarboxylic acid in the dicarboxylic acid unit, it is possible to obtain a polyamide that satisfies the strength, toughness, stability during heat, etc., has a high melting point, and is excellent in fluidity and low water absorption. it can.
  • the content of 1,4-cyclohexanedicarboxylic acid is preferably at least 50 mol%.
  • 1,4-cyclohexanedicarboxylic acid When the proportion of 1,4-cyclohexanedicarboxylic acid is at least 50 mol%, that is, 50 mol% or more, a polyamide having excellent strength and toughness and a high melting point can be obtained.
  • the proportion of 1,4-cyclohexanedicarboxylic acid is more preferably 60 to 100 mol%, still more preferably 70 to 100 mol%, and most preferably 100 mol%.
  • the proportion of dicarboxylic acid other than 1,4-cyclohexanedicarboxylic acid in the dicarboxylic acid unit is 0 to 50 mol%, preferably 0 to 40 mol%, more preferably 0 to 30 mol%.
  • 1,4-cyclohexanedicarboxylic acid there are trans isomers and cis geometric isomers.
  • 1,4-Cyclohexanedicarboxylic acid as a raw material monomer for polyamide has a trans isomer and a cis isomer, and even if either a trans isomer or a cis isomer is used, However, the raw material monomer is isomerized at a high temperature to have a certain ratio, and the cis isomer has higher water solubility in the equivalent salt with the diamine described later than the trans isomer.
  • the trans / cis ratio in terms of molar ratio is preferably 50/50 to 0/100, more preferably 40/60 to 10/90, and even more preferably 35/65 to 15/85. It is preferable.
  • the trans / cis ratio (molar ratio) of 1,4-cyclohexanedicarboxylic acid can be determined by nuclear magnetic resonance spectroscopy (NMR).
  • the dicarboxylic acid unit may contain a dicarboxylic acid other than 1,4-cyclohexanedicarboxylic acid, and examples thereof include aliphatic dicarboxylic acids and aromatic dicarboxylic acids.
  • examples of the aliphatic dicarboxylic acid include malonic acid, dimethylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylglutaric acid, 2,2-diethylsuccinic acid, and 2,3-diethylglutaric acid.
  • Glutaric acid 2,2-dimethylglutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecane
  • Examples thereof include linear or branched saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms such as diacid, eicosane diacid, and diglycolic acid.
  • aromatic dicarboxylic acid examples include unsubstituted or various terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, etc.
  • aromatic dicarboxylic acids having 8 to 20 carbon atoms substituted with a substituent.
  • Examples of the various substituents in the aromatic dicarboxylic acid include halogens such as alkyl groups having 1 to 4 carbon atoms, aryl groups having 6 to 10 carbon atoms, arylalkyl groups having 7 to 10 carbon atoms, chloro groups, and bromo groups. Groups, silyl groups having 1 to 6 carbon atoms, and sulfonic acid groups and sodium salts thereof.
  • aliphatic dicarboxylic acids are preferable from the viewpoint of heat resistance, fluidity, toughness, low water absorption, strength, etc., and the number of carbon atoms is 6 or more. Aliphatic dicarboxylic acids are more preferred. Of these, aliphatic dicarboxylic acids having 10 or more carbon atoms are preferred from the viewpoints of heat resistance and low water absorption.
  • Examples of the aliphatic dicarboxylic acid having 10 or more carbon atoms include sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and eicosanedioic acid.
  • sebacic acid or dodecanedioic acid is preferable from the viewpoint of heat resistance and the like.
  • Dicarboxylic acids other than 1,4-cyclohexanedicarboxylic acid may be used alone or in combination of two or more.
  • the dicarboxylic acid may further contain a trivalent or higher polyvalent carboxylic acid such as trimellitic acid, trimesic acid, pyromellitic acid and the like within a range not impairing the object of the present invention.
  • a trivalent or higher polyvalent carboxylic acid such as trimellitic acid, trimesic acid, pyromellitic acid and the like within a range not impairing the object of the present invention.
  • One type of polyvalent carboxylic acid may be used alone, or two or more types may be used in combination.
  • the dicarboxylic acid other than 1,4-cyclohexanedicarboxylic acid is not limited to the compounds described as the dicarboxylic acid, and may be a compound equivalent to the dicarboxylic acid.
  • the compound equivalent to the dicarboxylic acid is not particularly limited as long as it can be a dicarboxylic acid structure similar to the dicarboxylic acid structure derived from the dicarboxylic acid, and examples thereof include anhydrides and halides of dicarboxylic acids. .
  • the dicarboxylic acid other than 1,4-cyclohexanedicarboxylic acid includes an aliphatic dicarboxylic acid having 10 or more carbon atoms
  • 50 to 99.9 mol% of 1,4-cyclohexanedicarboxylic acid and preferably 10 or more carbon atoms are preferable.
  • the aliphatic dicarboxylic acid is 0.1 to 50 mol%, more preferably 1,4-cyclohexanedicarboxylic acid is 60 to 99 mol% and the aliphatic dicarboxylic acid having 10 or more carbon atoms is 1 to 40 mol%. More preferably, the amount of 1,4-cyclohexanedicarboxylic acid is 70 to 99 mol% and the aliphatic dicarboxylic acid having 10 or more carbon atoms is 1 to 30 mol%.
  • the diamine unit includes at least an aliphatic diamine.
  • an aliphatic diamine-containing component as the diamine unit, it is possible to obtain a polyamide that simultaneously satisfies the strength, toughness and the like and has excellent moldability.
  • the proportion of the aliphatic diamine in the diamine unit is preferably at least 50 mol%, more preferably 60 to 100 mol%, further 70 to 100 mol%, and particularly preferably 100 mol%.
  • a polyamide having higher strength and toughness and a high melting point can be obtained.
  • the aliphatic diamine is preferably a saturated aliphatic diamine having 2 to 20 carbon atoms, more preferably a saturated fat having 4 to 12 carbon atoms, from the viewpoint of heat resistance, fluidity, toughness, low water absorption and strength. It is preferably an aliphatic diamine, and more preferably a saturated aliphatic diamine having 6 to 10 carbon atoms.
  • One type of aliphatic diamine may be used alone, or two or more types may be used in combination.
  • saturated aliphatic diamine examples include ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, 2-methylpentamethylenediamine, hexamethylenediamine, 2-methylhexamethylenediamine, 2,4-dimethylhexamethylenediamine, hepta
  • saturated aliphatic diamines having 2 to 20 carbon atoms such as methylene diamine, octamethylene diamine, nonamethylene diamine, 2-methyloctamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, and tridecamethylene diamine. It is done. From the viewpoints of heat resistance, fluidity, toughness, low water absorption and strength, 2-methylpentamethylenediamine, hexamethylenediamine, decamethylenediamine, and dodecamethylenediamine are more preferable.
  • a trivalent or higher polyvalent aliphatic amine such as bishexamethylenetriamine may be further included within a range not impairing the object of the present invention.
  • a polyvalent aliphatic amine may be used individually by 1 type, and may be used in combination of 2 or more types.
  • a diamine other than an aliphatic diamine such as an aromatic diamine or an alicyclic diamine may be included as long as the object of the present invention is not impaired.
  • the aromatic diamine include metaxylylenediamine, paraxylylenediamine, paraphenylenediamine, metaphenylenediamine, and the like.
  • the alicyclic diamine include 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,3-cyclopentanediamine, and the like.
  • the polyamide may be a polyamide obtained by further copolymerizing lactam and / or aminocarboxylic acid from the viewpoint of toughness.
  • the lactam and / or aminocarboxylic acid means a lactam and / or aminocarboxylic acid that can be polymerized to polyamide.
  • a lactam and / or aminocarboxylic acid having 4 to 14 carbon atoms is preferable, and a lactam and / or aminocarboxylic acid having 6 to 12 carbon atoms is more preferable.
  • lactam examples include butyrolactam, pivalolactam, ⁇ -caprolactam, caprilactam, enantolactam, undecanolactam, laurolactam (dodecanolactam), and the like.
  • ⁇ -caprolactam and laurolactam are preferable, and ⁇ -caprolactam is more preferable.
  • aminocarboxylic acid examples include ⁇ -aminocarboxylic acid and ⁇ , ⁇ -amino acid that are compounds in which a lactam is ring-opened.
  • the aminocarboxylic acid is preferably a linear or branched saturated aliphatic carboxylic acid having 4 to 14 carbon atoms substituted with an amino group at the ⁇ position.
  • 6-aminocaproic acid, 11-aminoundecanoic acid Examples thereof include 12-aminododecanoic acid, and examples of the aminocarboxylic acid include paraaminomethylbenzoic acid.
  • a lactam and / or aminocarboxylic acid may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the addition amount of the lactam and / or aminocarboxylic acid is preferably 0 to 20 mol% with respect to the molar amount of the dicarboxylic acid unit, diamine unit, and lactam and / or aminocarboxylic acid.
  • End sealant Polyamide may use a known end-capping agent for molecular weight adjustment when polymerizing using the above-described dicarboxylic acid unit, diamine unit and, if necessary, lactam and / or aminocarboxylic acid. You may have the residue of terminal blocker at the terminal.
  • Examples of the end-capping agent include monocarboxylic acids, monoamines, acid anhydrides such as phthalic anhydride, monoisocyanates, monoacid halides, monoesters, monoalcohols, and the like, from the viewpoint of thermal stability. Monocarboxylic acids or monoamines are preferred. As a terminal blocker, one type may be used alone, or two or more types may be used in combination.
  • the monocarboxylic acid that can be used as the end-capping agent is not particularly limited as long as it has reactivity with an amino group.
  • the monocarboxylic acid one kind may be used alone, or two or more kinds may be used in combination.
  • the monoamine that can be used as the end-capping agent is not particularly limited as long as it has reactivity with a carboxyl group.
  • methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine Aliphatic monoamines such as decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine, and naphthylamine; and And cyclic amines such as pyrrolidine, piperidine, 3-methylpiperidine; and the like. Monoamines may be used alone or in combination of two or more.
  • the method for producing polyamide is not particularly limited, and examples thereof include the methods exemplified below. 1) A method in which an aqueous solution or a suspension of water of a dicarboxylic acid / diamine salt or a mixture thereof is heated and polymerized while maintaining a molten state (hereinafter referred to as hot melt polymerization method). 2) A method of increasing the degree of polymerization while maintaining the solid state of the polyamide obtained by the hot melt polymerization method at a temperature below the melting point (hereinafter referred to as a hot melt polymerization / solid phase polymerization method).
  • a method in which the dicarboxylic acid / diamine salt or a mixture thereof is polymerized in one step while maintaining the solid state (hereinafter referred to as a one-step solid phase polymerization method). 6) A method of polymerization using a dicarboxylic acid halide equivalent to a dicarboxylic acid and a diamine (hereinafter referred to as a solution method).
  • the polyamide production method is preferably 1) hot melt polymerization, 2) hot melt polymerization / solid phase polymerization, 4) prepolymer / solid phase polymerization, more preferably 1) hot melt polymerization, 2)
  • the hot melt polymerization / solid phase polymerization method is desirable, and the hot melt polymerization method is preferred from the viewpoint of shortening the polymerization cycle time of polyamide and improving the molecular weight.
  • the addition amount of the dicarboxylic acid unit and the addition amount of the diamine unit are preferably around the same molar amount.
  • the amount of diamine units escaped from the reaction system during the polymerization reaction is also considered in terms of the molar ratio, and the molar amount of the entire diamine unit is preferably 0.9 to 1 with respect to the molar amount 1 of the entire dicarboxylic acid unit. .2, more preferably 0.95 to 1.1, and further preferably 0.98 to 1.05.
  • a diamine is mentioned as an additive at the time of superposition
  • This diamine means a diamine to be added separately from the diamine unit used in the production of an equimolar amount of dicarboxylic acid / diamine salt.
  • the amount of the diamine added as an additive is preferably 0.1 to 10 mol%. More preferably, it is 0.5 to 5.0 mol%, more preferably 1.5 to 4.5 mol%, and still more preferably 2.6 to 4.0 mol%.
  • This diamine may be the same component as the diamine unit used in the production of the dicarboxylic acid / diamine salt or a different compound. By adding diamine or the like, the degree of polymerization can be increased or adjusted, which is effective as a method for controlling the molecular weight.
  • the polymerization form may be batch or continuous.
  • the reactor used by a method other than the solid phase polymerization method include an autoclave type reactor, a tumbler type reactor, and an extruder type reactor such as a kneader.
  • the reaction can be performed.
  • a tumbler reactor, a vibration dryer reactor, a Nauter mixer reactor, a stirring reactor, or the like can be used.
  • polyamide pellets, flakes, or powder is placed in the reactor to polymerize the polyamide.
  • it may be performed under a stream of inert gas such as nitrogen, argon or helium or under reduced pressure, or the inert gas may be supplied from the lower part of the reactor while pulling the internal gas to the reduced pressure at the upper part of the reactor.
  • the molecular weight of the polyamide can be improved by heating at a temperature below the melting point of the polyamide.
  • the reaction temperature of the solid phase polymerization is preferably 100 to 350 ° C, more preferably 120 to 300 ° C, and further preferably 150 to 270 ° C. After the polymerization, the heating is stopped, and the polyamide is taken out from the reactor after the reaction temperature is lowered preferably from 0 to 100 ° C., more preferably from room temperature to 60 ° C.
  • the hot melt polymerization method can be carried out in a known manner, but is preferably carried out under a temperature condition of 100 ° C. or higher, more preferably 120 ° C. or higher, and most preferably 170 ° C. or higher.
  • a mixture of 1,4-cyclohexanedicarboxylic acid and a dicarboxylic acid such as hexamethylene adipamide and a diamine, a solid salt or an aqueous solution is heated and concentrated at a temperature of 100 to 300 ° C., and the generated water vapor pressure is changed from normal pressure to The pressure is kept at about 5 MPa (gauge pressure), and finally the pressure is released, and polycondensation is performed at normal pressure or reduced pressure.
  • a solid phase polymerization method in which a mixture of dicarboxylic acid and diamine, a solid salt or a polycondensate is thermally polycondensed at a temperature below the melting point can be used. These methods may be combined as necessary.
  • the above-mentioned known end-capping agent is used for molecular weight adjustment when the polymerization is performed using the dicarboxylic acid unit and the diamine unit, and if necessary, lactam and / or aminocarboxylic acid. Further polymerization may be carried out by adding.
  • the molecular weight of the polyamide is based on the sulfuric acid relative viscosity ⁇ r at 25 ° C., and the sulfuric acid relative viscosity ⁇ r at 25 ° C. is preferably 2.3 or more. More preferably, it is 2.3 to 7.0, more preferably 2.5 to 6.5, and particularly preferably 3.0 to 6.5.
  • Effective methods for controlling the relative viscosity ⁇ r of sulfuric acid at 25 ° C. for polyamides include, for example, methods for controlling the addition amount of diamine and end-capping agent as additives during hot melt polymerization of polyamide, and polymerization conditions. Method.
  • the polyamide is excellent in mechanical properties such as toughness and strength. From the viewpoint of melt fluidity, a polyamide having excellent fluidity can be obtained when the sulfuric acid relative viscosity ⁇ r at 25 ° C. of 7.0 is 7.0 or less.
  • the relative viscosity of sulfuric acid at 25 ° C. can be measured at 25 ° C. in 98% sulfuric acid according to JIS-K6920.
  • a number average molecular weight Mn obtained by GPC (gel permeation chromatography), a weight average molecular weight Mw, and a molecular weight distribution Mw / Mn can be used.
  • the number average molecular weight Mn of the polyamide is preferably larger than 15000, more preferably 18000 or more, and further preferably 20000 or more.
  • Mw / Mn which shows the molecular weight distribution of (A) polyamide becomes like this.
  • Mn and Mw can produce
  • the melting point Tm2 of the polyamide is preferably 280 to 350 ° C. from the viewpoint of heat resistance. Melting
  • the melting point Tm2 is preferably 350 ° C. or lower, more preferably 340 ° C. or lower, further preferably 335 ° C. or lower, and still more preferably 330 ° C. or lower.
  • the melting point Tm2 of the polyamide is 280 ° C. or higher, a polyamide having excellent heat resistance can be obtained. Moreover, when the melting point Tm2 of the polyamide is 350 ° C. or less, the thermal decomposition of the polyamide in the melt processing such as extrusion and molding can be suppressed.
  • the heat of fusion ⁇ Hm2 of the polyamide is preferably 10 to 100 J / g, more preferably 14 to 100 J / g, and further preferably 20 to 100 J / g from the viewpoint of heat resistance.
  • the measurement of the melting point Tm2 and the heat of fusion ⁇ Hm2 of the polyamide can be performed according to JIS-K7121 as described in the following examples. Examples of the measuring device for melting point and heat of fusion include Diamond-DSC manufactured by PERKIN-ELMER.
  • the polyamide composition can contain an inorganic filler and other additives in addition to the polyamide.
  • an inorganic filler as the polyamide composition, the polyamide composition is excellent in heat resistance and thermal stability, and without damaging the properties of the polyamide having a high melting point, the polyamide composition also has heat resistance and thermal stability. While satisfying the above, etc., it is particularly excellent in strength and moldability.
  • inorganic filler It does not specifically limit as an inorganic filler which comprises the polyamide composition of this embodiment, A well-known material can be used.
  • a well-known material can be used.
  • One type of inorganic filler may be used
  • the glass fiber and the carbon fiber may have a round shape or a flat shape in cross section.
  • the flat cross section include a rectangle, an oval close to a rectangle, an ellipse, and a bowl shape with a narrowed central portion in the longitudinal direction.
  • the polyamide composition has a number average fiber diameter of 3 to 30 ⁇ m and a weight average fiber length of 100 to 750 ⁇ m.
  • a glass fiber or carbon fiber having an aspect ratio (L / D) of 10 to 100 between the weight average fiber length (L) and the number average fiber diameter (D) is preferably used.
  • the number average fiber diameter of the inorganic filler in the polyamide composition is, for example, putting the polyamide composition in an electric furnace, incinerating the organic matter contained in the polyamide composition, and, for example, 100 or more glass fibers from the residue.
  • the number average fiber diameter can be determined by arbitrarily selecting, observing with SEM, and measuring the fiber diameter.
  • the glass fiber is arbitrarily selected in the same manner, and the weight average fiber length is measured by measuring the fiber length using an SEM photograph at a magnification of 1000 times. be able to.
  • the inorganic filler reinforcing fibers having a weight average fiber length of 1 to 15 mm are more preferable.
  • the weight average fiber length of such reinforcing fibers is 1 to 15 mm, preferably 3 to 12 mm, from the viewpoint of improving mechanical strength, rigidity and moldability.
  • the weight average fiber length of the reinforcing fibers is the length of 400 reinforcing fibers arbitrarily selected using an image analyzer after observing with an optical microscope after burning or dissolving only the polyamide of the polyamide composition. It is calculated
  • the calculation formula for the weight average fiber length for each reinforcing fiber is expressed by the following formula.
  • “i” is an integer from 1 to 400.
  • Weight average fiber length ⁇ (Li 2 ) / ⁇ Li
  • a weight average fiber length is a value applied with respect to the reinforced fiber of the state contained in the polyamide composition of this embodiment. That is, the weight average fiber length of the reinforcing fiber before blending with the polyamide is not limited to the above.
  • the material of the reinforcing fiber is not particularly limited as long as it is a reinforcing fiber generally used for polyamide.
  • inorganic fiber such as glass fiber, carbon fiber, boron fiber, metal fiber (eg, stainless fiber, aluminum fiber, copper fiber), polyparaphenylene terephthalamide fiber, polymetaphenylene terephthalamide fiber, polyparaffin Organic materials such as phenylene isophthalamide fiber, polymetaphenylene isophthalamide fiber, wholly aromatic polyamide fiber such as fiber obtained from condensate of diaminodiphenyl ether and terephthalic acid or isophthalic acid, or wholly aromatic liquid crystal polyester fiber Is mentioned.
  • the said material may be used independently and 2 or more types may be used together. Especially, it is preferable that it is 1 or more types chosen from a glass fiber, a carbon fiber, a boron fiber, and a metal fiber from a viewpoint of an improvement of mechanical strength and rigidity, and a glass fiber and / or a carbon fiber are more preferable.
  • the reinforcing fiber is not particularly limited with respect to the average fiber diameter of the single fiber, but, for example, those having a diameter of 5 to 25 ⁇ m are generally used.
  • the average fiber diameter of single fibers is obtained by observing the reinforcing fibers to be used under an optical microscope and calculating the average value when measuring 400 fiber diameters arbitrarily selected using an image analyzer. It is done. Further, as the reinforcing fiber, it is preferable to use roving which is a continuous fiber in which single fibers are bundled.
  • the inorganic filler such as glass fiber or carbon fiber may be surface-treated with a silane coupling agent or the like.
  • the silane coupling agent is not particularly limited, and examples thereof include ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, and N- ⁇ - (aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane.
  • aminosilanes such as ⁇ -mercaptopropyltrimethoxysilane and ⁇ -mercaptopropyltriethoxysilane; epoxysilanes; vinylsilanes and the like. Of these, aminosilanes are preferable.
  • the silane coupling agent one kind may be used alone, or two or more kinds may be used in combination.
  • Fibrous inorganic fillers such as glass fibers and carbon fibers are further used as sizing agents, copolymers and epoxy containing carboxylic anhydride-containing unsaturated vinyl monomers and unsaturated vinyl monomers as constituent units.
  • Compounds, polyurethane resins, and homopolymers of acrylic acid, copolymers of acrylic acid and other copolymerizable monomers, and salts with primary, secondary, or tertiary amines thereof may be included.
  • a copolymer containing a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer as structural units containing carboxylic acid anhydride
  • a copolymer containing an unsaturated vinyl monomer and an unsaturated vinyl monomer excluding an unsaturated vinyl monomer containing a carboxylic acid anhydride as a structural unit), an epoxy compound, and a polyurethane resin are preferred, and a carboxylic acid anhydride More preferred are a copolymer containing a contained unsaturated vinyl monomer and an unsaturated vinyl monomer as structural units, and a polyurethane resin.
  • the sizing agent one type may be used alone, or two or more types may be used in combination.
  • the carboxylic acid anhydride-containing unsaturated vinyl monomer constituting the copolymer containing the carboxylic acid anhydride-containing unsaturated vinyl monomer and the unsaturated vinyl monomer as structural units is not particularly limited. Examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride, and maleic anhydride is preferred.
  • the unsaturated vinyl monomer constituting the copolymer containing carboxylic acid anhydride-containing unsaturated vinyl monomer and unsaturated vinyl monomer as structural units is not particularly limited, for example Styrene, ⁇ -methylstyrene, ethylene, propylene, butadiene, isoprene, chloroprene, 2,3-dichlorobutadiene, 1,3-pentadiene, cyclooctadiene, methyl methacrylate, methyl acrylate, ethyl acrylate, and ethyl methacrylate. Styrene and butadiene are preferred.
  • Examples of the copolymer containing a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer as structural units include, for example, a copolymer of maleic anhydride and butadiene, a maleic anhydride and ethylene. Copolymers and copolymers of maleic anhydride and styrene are preferred.
  • the copolymer containing a carboxylic anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer as constituent units has a weight average molecular weight of preferably 2,000 or more, and improves the fluidity of the polyamide composition. From this viewpoint, it is more preferably 2,000 to 1,000,000, and further preferably 2,000 to 900,000.
  • the weight average molecular weight can be measured by gel permeation chromatography (GPC).
  • the epoxy compound is not particularly limited, and examples thereof include ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, heptene oxide, octene oxide, nonene oxide, decene oxide, undecenoxide, and dodecene oxide.
  • Aliphatic epoxy compounds such as pentadecene oxide and eicosene oxide; glycidol, epoxypentanol, 1-chloro-3,4-epoxybutane, 1-chloro-2-methyl-3,4-epoxybutane, 1,4 -Dichloro-2,3-epoxybutane, cyclopentene oxide, cyclohexene oxide, cycloheptene oxide, cyclooctene oxide, methylcyclohexene oxide, vinylcyclohexe Alicyclic epoxy compounds such as oxide and epoxidized cyclohexene methyl alcohol; terpene epoxy compounds such as pinene oxide; aromatic epoxy compounds such as styrene oxide, p-chlorostyrene oxide and m-chlorostyrene oxide; epoxidized soybean oil; And epoxidized linseed oil.
  • Aliphatic epoxy compounds such as pentadecene oxide and eico
  • the polyurethane resin is not particularly limited, and those generally used as a sizing agent can be used.
  • isocyanates such as m-xylylene diisocyanate (XDI), 4,4′-methylenebis (cyclohexyl isocyanate) (HMDI), and isophorone diisocyanate (IPDI), polyester-based and polyether-based diols, Those synthesized from can be suitably used.
  • the weight average molecular weight is preferably 1,000 to 90,000, more preferably 1,000 to 25,000.
  • the polyacrylic acid may be in the form of a salt with a primary, secondary, or tertiary amine.
  • the amine is not particularly limited, and examples thereof include triethylamine, triethanolamine, and glycine.
  • the degree of neutralization of polyacrylic acid by having a salt form means the ratio of the acrylic acid component forming a salt out of the acrylic acid component of polyacrylic acid, and other concomitant drugs (silane coupling agents, etc.) From the standpoint of improving the stability of the mixed solution with) and reducing the amine odor, it is preferably 20 to 90%, more preferably 40 to 60%.
  • the weight-average molecular weight of the salt-form polyacrylic acid is preferably 3,000 to 50,000, and preferably 3,000 or more from the viewpoint of improving the converging property of glass fibers and carbon fibers. From the viewpoint of improving the mechanical properties of the product, it is preferably 50,000 or less.
  • the other copolymerizable monomer in the copolymer of acrylic acid and other copolymerizable monomer is not particularly limited, and examples thereof include acrylic acid, maleic acid, and methacrylic acid, which are monomers having a hydroxyl group and / or a carboxyl group. Vinyl acetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.
  • a monomer that is an ester of a monomer having a hydroxyl group and / or a carboxyl group can be suitably used.
  • the copolymer of acrylic acid and other copolymerizable monomer preferably has a weight average molecular weight of 1,000 to 90,000, more preferably 1,000 to 25,000.
  • the copolymer of acrylic acid and other copolymerizable monomers may be in the form of a salt with a primary, secondary, or tertiary amine.
  • the amine is not particularly limited, and examples thereof include triethylamine, triethanolamine, and glycine.
  • the degree of neutralization of the copolymer by having a salt form means the proportion of the acid component forming a salt in the acid component of the copolymer, and the mixed solution with other concomitant drugs (such as a silane coupling agent) From the viewpoint of improving the stability and reducing the amine odor, it is preferably 20 to 90%, more preferably 40 to 60%.
  • the weight average molecular weight of the salt-form copolymer is preferably 3,000 to 50,000, and preferably 3,000 or more from the viewpoint of improving the converging property of glass fiber or carbon fiber. From the viewpoint of improving the characteristics, it is preferably 50,000 or less.
  • the fibrous inorganic filler such as glass fiber and carbon fiber containing a sizing agent is obtained by using the above sizing agent in a known glass fiber or carbon fiber manufacturing process using a known method such as a roller type applicator. It is obtained by reacting continuously by drying fiber strands produced by applying to a fibrous inorganic filler such as carbon fiber.
  • the fiber strand may be used as it is as roving, or may be used as a chopped glass strand after further obtaining a cutting step.
  • the sizing agent is preferably imparted (added) in an amount corresponding to 0.2 to 3% by mass as a solid content with respect to 100% by mass of a fibrous inorganic filler such as glass fiber or carbon fiber. It is more preferable to apply (add) mass%.
  • the amount of sizing agent added is 100% by mass with respect to 100% by mass of fibrous inorganic fillers such as glass fibers and carbon fibers. Is preferably 0.2% by mass or more. From the viewpoint of improving the thermal stability of the polyamide composition, the addition amount of the sizing agent is preferably 3% by mass or less as the solid content. Moreover, drying of a strand may be performed after a cutting process, and you may cut
  • the polyamide composition When wollastonite is used as the inorganic filler constituting the polyamide composition, the polyamide composition has a number average fiber diameter of 3 to 30 ⁇ m, a weight average fiber length of 10 to 500 ⁇ m, and an aspect ratio (L / Those having D) of 3 to 100 are preferably used.
  • the inorganic filler when talc, mica, kaolin, silicon nitride or the like is used, the polyamide composition preferably has a number average fiber diameter of 0.1 to 3 ⁇ m.
  • additives that are conventionally used for polyamide, for example, colorants such as pigments and dyes (including colored master batches), flame retardants, fibrillating agents, and lubricants, as long as the object of the present invention is not impaired.
  • colorants such as pigments and dyes (including colored master batches), flame retardants, fibrillating agents, and lubricants, as long as the object of the present invention is not impaired.
  • Agent, fluorescent bleaching agent, plasticizer, antioxidant, light stabilizer, UV absorber, antistatic agent, fluidity improver, filler, reinforcing agent, spreading agent, nucleating agent, rubber, reinforcing agent and Other polymers can also be contained.
  • polyamide composition as a heat stabilizer, phenol stabilizer, phosphorus stabilizer, amine stabilizer, Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa of the periodic table
  • phenol stabilizer, phosphorus stabilizer, amine stabilizer, Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa of the periodic table One or more selected from the group consisting of metal salts of Group IVb and Group IVb elements and halides of alkali metals and alkaline earth metals can be blended.
  • the phenol-based stabilizer is not particularly limited, and examples thereof include hindered phenol compounds.
  • the phenol-based stabilizer has a property of imparting heat resistance and light resistance to resins and fibers such as polyamide.
  • the hindered phenol compound is not particularly limited, and examples thereof include N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropionamide).
  • Pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t-butyl-4 -Hydroxy-hydrocinnamamide), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 3,9-bis ⁇ 2- [3- (3- t-butyl-4-hydroxy-5-methylphenyl) propynyloxy] -1,1-dimethylethyl ⁇ -2,4,8,10-tetraoxapyro [5,5] undecane, 3 5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, And 1,3,5-tris (4
  • N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropionamide)] is preferable from the viewpoint of improving heat aging resistance.
  • the phenol-based stabilizer one type may be used alone, or two or more types may be used in combination.
  • the amount of the phenol stabilizer in the polyamide composition is preferably 0.01 to 1 part by mass, more preferably 0.1 to 100 parts by mass of the polyamide composition. ⁇ 1 part by mass.
  • the heat aging resistance can be further improved and the amount of generated gas can be further reduced.
  • the phosphorus stabilizer is not particularly limited, for example, pentaerythritol type phosphite compound, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl diphenyl phosphite, trisisodecyl phosphite, Phenyl diisodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl (tridecyl) phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4- Di-t-butylphenyl) phosphite, tris (2,4-di-t-but
  • pentaerythritol phosphite compounds and tris (2,4-di-t-butylphenyl) phosphite are preferable from the viewpoint of further improving the heat aging resistance and reducing the generated gas.
  • the pentaerythritol type phosphite compound is not particularly limited.
  • 2,6-di-t-butyl-4-methylphenyl phenyl pentaerythritol diphosphite 2,6-di-t- Butyl-4-methylphenyl methyl pentaerythritol diphosphite
  • bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite bis (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis ( 2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite and bis (2,6-di-t-octyl-4-methylphenyl) pentaerythritol diphosphite are preferred, and bis (2 , 6-Di-t-butyl-4-methylphenyl) pentaerythritol diphosphite is more preferred.
  • a phosphorus stabilizer may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the amount of the phosphorus stabilizer in the polyamide composition is 0.01 to 1 part by mass, more preferably 0.1 to 1 part per 100 parts by mass of the polyamide composition. Part by mass.
  • the heat aging resistance can be further improved and the amount of generated gas can be further reduced.
  • the amine stabilizer is not particularly limited, and examples thereof include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetra Methylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetra Methylpiperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpipe Gin, 4- (ethylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclohexylcarb
  • One type of amine stabilizer may be used alone, or two or more types may be used in combination.
  • the compounding amount of the amine stabilizer in the polyamide composition is preferably 0.01 to 1 part by mass, more preferably 0.1 to 100 parts by mass of the polyamide composition. ⁇ 1 part by mass.
  • the amount is within the above range, light resistance and heat aging resistance can be further improved, and the amount of generated gas can be further reduced.
  • the metal salt of the elements of Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa, and Group IVb of the periodic table is not particularly limited and is preferably a heat stabilizer. Copper salt.
  • the copper salt is not particularly limited.
  • copper halide copper iodide, cuprous bromide, cupric bromide, cuprous chloride, etc.
  • copper acetate copper propionate
  • benzoic acid examples thereof include copper oxide, copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate and copper stearate, and a copper complex salt in which copper is coordinated to a chelating agent such as ethylenediamine and ethylenediaminetetraacetic acid.
  • metal salt especially copper salt
  • a polyamide composition having excellent heat aging resistance and capable of suppressing metal corrosion (hereinafter also simply referred to as “metal corrosion”) of screws and cylinders during extrusion is obtained. be able to.
  • the said metal salt may be used individually by 1 type, and may be used in combination of 2 or more types.
  • the compounding amount of the copper salt in the polyamide composition is preferably 0.01 to 0.2 parts by mass, more preferably 0.02 to 0 parts per 100 parts by mass of the polyamide composition. 15 parts by mass.
  • the amount is within the above range, the heat aging resistance is further improved, and copper precipitation and metal corrosion can be suppressed.
  • the content of copper element is preferably 10 to 500 ppm, more preferably 30 to 500 ppm, still more preferably 50 to 300 ppm with respect to the total amount of the polyamide composition. .
  • Alkali metal and alkaline earth metal halides are not particularly limited, and examples thereof include potassium iodide, potassium bromide, potassium chloride, sodium iodide and sodium chloride, and mixtures thereof. Among these, potassium iodide and potassium bromide, and a mixture thereof are preferable, and potassium iodide is more preferable from the viewpoint of improving heat aging resistance and suppressing metal corrosion. As the halide, one kind may be used alone, or two or more kinds may be used in combination.
  • the blending amount of alkali and alkaline earth metal halides in the polyamide composition is preferably 0.05 to 5 with respect to 100 parts by mass of the polyamide composition. Part by mass, more preferably 0.2 to 2 parts by mass. When the amount is within the above range, the heat aging resistance is further improved, and copper precipitation and metal corrosion can be suppressed.
  • a mixture of a copper salt and a halide of an alkali or alkaline earth metal can be suitably used as a heat stabilizer.
  • the ratio of the copper salt to the alkali and alkaline earth metal halide may be contained in the polyamide composition so that the molar ratio of halogen to copper (halogen / copper) is 2/1 to 40/1. It is preferably 5/1 to 30/1.
  • the heat aging resistance of the polyamide composition can be further improved.
  • the molar ratio (halogen / copper) is 2/1 or more, it is preferable because copper precipitation and metal corrosion can be suppressed.
  • the molar ratio (halogen / copper) is 40/1 or less, corrosion of the screws of the molding machine can be prevented without substantially impairing mechanical properties such as toughness, which is preferable.
  • a method for producing the polyamide composition is not particularly limited as long as it is a method of mixing the above-described polyamide, an inorganic filler, and, if necessary, the above-described other additives.
  • a method of mixing the constituent materials of the polyamide composition for example, a method of mixing using a Henschel mixer and the like, supplying to a melt kneader and kneading, or a polyamide melted with a single screw or twin screw extruder, from a side feeder The method etc. which mix
  • all the components may be supplied to the same supply port at once, or the components may be supplied differently. You may supply from a mouth.
  • the melt kneading temperature is preferably about 250 to 375 ° C. as the resin temperature.
  • the melt kneading time is preferably about 0.5 to 5 minutes.
  • the apparatus for performing melt kneading is not particularly limited, and a known apparatus, for example, a melt kneader such as a single-screw or twin-screw extruder, a Banbury mixer, and a mixing roll can be used.
  • the method for producing a polyamide composition when the inorganic filler contained in the polyamide composition is a reinforcing fiber having a weight average fiber length of 1 to 15 mm is not particularly limited.
  • the polyamide composition preferably has a sulfuric acid relative viscosity ⁇ r at 25 ° C. of 2.3 or more. More preferably, it is 2.3 to 7.0, more preferably 2.5 to 6.5, and particularly preferably 3.0 to 6.5.
  • the sulfuric acid relative viscosity ⁇ r at 25 ° C. is 2.3 or more, the mechanical properties such as toughness and strength are excellent.
  • the polyamide relative viscosity ⁇ r at 25 ° C. is preferably 7.0 or less.
  • the relative viscosity of sulfuric acid at 25 ° C. can be measured at 25 ° C. in 98% sulfuric acid according to JIS-K6920.
  • the melting point of the polyamide composition is preferably 280 to 350 ° C. from the viewpoint of heat resistance. Melting
  • the melting point is preferably 350 ° C. or lower, more preferably 340 ° C. or lower, further preferably 335 ° C. or lower, and still more preferably 330 ° C. or lower.
  • the melting point of the polyamide composition is 280 ° C. or higher, the polyamide composition can have excellent heat resistance. Moreover, when the melting point is 350 ° C. or lower, thermal decomposition in melt processing such as extrusion and molding can be suppressed.
  • the melting point of the polyamide composition can be measured according to JIS-K7121, and basically has the same value as the melting point Tm2 of the polyamide.
  • the heat of fusion of the polyamide composition is preferably 10 to 100 J / g, more preferably 14 to 100 J / g, even more preferably 20 to 100 J / g from the viewpoint of heat resistance.
  • the heat of fusion of the polyamide composition can be measured according to JIS-K7121.
  • the value of the heat value is the ratio of the polyamide to the composition. Convert and calculate. Examples of the measuring device for melting point and heat of fusion include Diamond-DSC manufactured by PERKIN-ELMER.
  • the polyamide composition molded article of the present invention is a known molding method of the above-mentioned polyamide or polyamide composition, for example, press molding, injection molding, gas assist injection molding, welding molding, extrusion molding, blow molding, film molding, hollow molding. It can be obtained by heat treatment at 200 ° C. or higher after molding using multilayer molding, melt spinning, etc., and molding the molded polyamide composition.
  • the heat treatment method for the polyamide composition molded body is not particularly limited as long as heating at 200 ° C. or higher is possible.
  • an apparatus such as an electric furnace, a gear oven, a hot plate, or a molding die is used.
  • the heat treatment may be performed in the air, may be performed in an inert gas atmosphere, for example, a nitrogen gas atmosphere, or may be performed in a reduced pressure environment.
  • the heat treatment temperature is 200 ° C. or higher, preferably 220 ° C. to 300 ° C., more preferably 240 ° C. to 300 ° C. By setting the temperature to 200 ° C.
  • the trans isomer ratio of the 1,4-cyclohexanedicarboxylic acid monomer unit in the molded product can be set to 71 mol% or higher.
  • the temperature can be set to 300 ° C. or lower, it is possible to satisfactorily prevent the molded product from melting, so that the trans isomer ratio can be set to 71 mol% or higher.
  • the heat treatment time can be appropriately selected depending on the size and thickness of the molded product and the heat treatment temperature. For example, when the heat treatment time is 200 to 240 ° C., it is preferably 1 to 72 hours, more preferably about 1 to 48 hours.
  • the trans isomer ratio of the dicarboxylic acid monomer unit in the molded article is 71 to 100 mol%.
  • the dicarboxylic acid monomer unit means a unit derived from a dicarboxylic acid of a monomer as a raw material.
  • the trans isomer ratio mol% is more preferably more than 75 and 100 or less, more preferably 80 or more and 100 or less, and still more preferably 85 or more and 100 or less.
  • the trans isomer ratio (mol%) of the dicarboxylic acid monomer unit of the polyamide composition molded article can be determined by nuclear magnetic resonance spectroscopy (NMR).
  • the heat of fusion ⁇ Hm, crystallization enthalpy ⁇ Hc, melting peak temperature Tm of the polyamide composition molded product are each preferably 40 J / g or more, more preferably 45 J / g or more from the viewpoint of heat resistance, and 50 J / g. More preferably, it is the above.
  • the heat of fusion ⁇ Hm and the crystallization enthalpy ⁇ Hc of the polyamide composition molded product are preferably 80 J / g or less from the viewpoint of moldability.
  • the value of the heat value is relative to the composition. Calculated by converting the ratio of polyamide.
  • the ratio ( ⁇ Hm / ⁇ Hc) between the heat of fusion ⁇ Hm and the crystallization enthalpy ⁇ Hc of the polyamide composition molded article of the present invention is preferably greater than 1.0, more preferably 1.5 or more, further from the viewpoint of heat resistance. Is more preferably 1.8 or more.
  • the heat of fusion ⁇ Hm and the crystallization enthalpy ⁇ Hc of the polyamide composition molded product can be measured in accordance with JIS-K7121, and the heat of fusion ⁇ Hm is raised at a rate of temperature increase of 20 ° C./min.
  • This is the Tm peak area when the endothermic peak appearing on the highest temperature side of the endothermic peak (melting peak) appearing at the time of the first temperature rise (melting peak) is defined as the melting peak temperature Tm (° C.).
  • a peak having ⁇ H of 1 J / g or more is regarded as a peak, the highest temperature is defined as a melting peak temperature Tm, and ⁇ Hm is a sum of peak areas.
  • the crystallization enthalpy ⁇ Hc is the Tc value when the temperature of the exothermic peak (crystallization peak) that appears when the polyamide composition molded article is cooled at a temperature decrease rate of 20 ° C./min is the crystallization peak temperature Tc (° C.). It is the peak area.
  • Diamond-DSC manufactured by PERKIN-ELMER can be used as a measuring device.
  • the melting peak temperature Tm of the molded polyamide composition of the present invention is preferably 300 ° C. or higher, more preferably 310 ° C. or higher, from the viewpoint of heat resistance.
  • the polyamide composition molded article of the present invention is excellent in heat resistance, strength, heat strength, rigidity, heat stiffness, heat stability, and has LLC (Long Life Coolant) resistance as shown in the following examples. Since it is improved, it can be suitably used as various parts materials for automobiles, electric and electronic, industrial materials, extrusion applications, daily necessities and household goods.
  • Examples of automobile intake system parts include an air intake manifold, an intercooler inlet, an exhaust pipe cover, an inner bush, a bearing retainer, an engine mount, an engine head cover, a resonator, and a throttle body.
  • Examples of automobile cooling system parts include a chain cover, a thermostat housing, an outlet pipe, a radiator tank, an oil netter, and a delivery pipe.
  • Examples of automobile fuel system parts include fuel delivery pipes and gasoline tank cases.
  • interior parts include instrument panels, console boxes, glove boxes, steering wheels, and trims.
  • Examples of exterior parts include a mall, a lamp housing, a front grille, a mud guard, a side bumper, a door mirror stay, and a roof rail.
  • the trans isomer ratio mol% is more than 75 and 100 or less, it can be suitably used for automobile engine mounts, air ducts, cooling pipes, and vibration-proof components.
  • the electrical parts are not particularly limited, and examples thereof include connectors, wire harness connectors, motor parts, lamp sockets, sensor on-vehicle switches, and combination switches.
  • Examples of electrical and electronic products include connectors, switches, relays, printed wiring boards, electronic component housings, outlets, noise filters, coil bobbins, and motor end caps.
  • the trans isomer ratio mol% is greater than 71 and 75 or less, it can be suitably used as an LED reflector.
  • Examples of industrial materials include gears, cams, insulating blocks, valves, power tool parts, agricultural equipment parts, engine covers, and the like.
  • Examples of daily necessities and household items include buttons, food containers, and office furniture.
  • Extrusion applications include, for example, films, sheets, filaments, tubes, rods, and hollow molded products.
  • the polyamide composition molded article according to this embodiment is formed by molding a first polyamide composition containing a first polyamide having a specific trans isomer ratio and ⁇ Hm1 / ⁇ Hc. Details of the first polyamide, the first polyamide composition, and the molded polyamide composition will be described below.
  • the first polyamide of the present invention (hereinafter also simply referred to as “polyamide”) is (A) a dicarboxylic acid unit comprising at least 1,4-cyclohexanedicarboxylic acid; (B) a diamine unit containing at least an aliphatic diamine,
  • ⁇ Hm1 / which is the ratio between the heat of fusion ⁇ Hm1 obtained when the temperature is raised at 20 ° C./min and the crystallization enthalpy ⁇ Hc obtained when the temperature is lowered at 20 ° C./min.
  • ⁇ Hc is 1.0 ⁇ Hm1 / ⁇ Hc ⁇ 2.2
  • the trans isomer ratio mol% of the dicarboxylic acid monomer unit in the polyamide is 71 ⁇ trans isomer ratio ⁇ 75 It is.
  • the (A1) polyamide of the present invention contains as structural units (a) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid and (b) a diamine unit containing at least an aliphatic diamine.
  • the total amount of the above (a) dicarboxylic acid unit and (b) diamine unit is preferably 20 to 100 mol%, and preferably 50 to 100 mol%, relative to 100 mol% of all structural units of (A1) polyamide. More preferably, it is more preferably 90 to 100 mol%, and most preferably 100 mol%.
  • the ratio of the predetermined monomer unit constituting (A1) polyamide can be measured by nuclear magnetic resonance spectroscopy (NMR) or the like.
  • NMR nuclear magnetic resonance spectroscopy
  • the structural unit of (A1) polyamide other than the above (a) dicarboxylic acid unit and (b) diamine unit is not particularly limited.
  • (c) lactam and / or aminocarboxylic acid described later The unit which consists of is mentioned.
  • the polyamide of the present invention having ⁇ Hm1 / ⁇ Hc, which is the ratio between the heat of fusion ⁇ Hm1 and the crystallization enthalpy ⁇ Hc, and the trans isomer ratio as described above can be obtained by the polyamide structural unit and production method described below. .
  • the dicarboxylic acid unit contains at least a 1,4-cyclohexanedicarboxylic acid unit.
  • the dicarboxylic acid unit preferably contains 50 to 100 mol% of 1,4-cyclohexanedicarboxylic acid units (based on the total number of moles of dicarboxylic acid), more preferably 60 to 100 mol%, more preferably 70 to 100 mol. % Is more preferable, and 100 mol% is most preferable.
  • the unit (a) that may be contained in the dicarboxylic acid unit includes (a-1) an alicyclic dicarboxylic acid unit, (a-2) an aromatic dicarboxylic acid unit, and (A-3) Aliphatic dicarboxylic acid units.
  • alicyclic carboxylic acid unit is used to mean 1,4-cyclohexanedicarboxylic acid.
  • the alicyclic dicarboxylic acid constituting the alicyclic dicarboxylic acid unit is not limited to the following. However, examples thereof include alicyclic dicarboxylic acids having 3 to 12 carbon atoms in the alicyclic structure, and alicyclic dicarboxylic acids having 5 to 12 carbon atoms in the alicyclic structure are preferable. Examples of such (a-1) alicyclic dicarboxylic acid units include, but are not limited to, 1,3-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, and the like. .
  • the polyamide composition tends to be more excellent in heat resistance, low water absorption, rigidity, and the like.
  • the (a-1) alicyclic dicarboxylic acid constituting the alicyclic dicarboxylic acid unit may be used alone or in combination of two or more.
  • the alicyclic group of the alicyclic dicarboxylic acid unit may be unsubstituted or may have a substituent.
  • substituents include, but are not limited to, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group having 1 to 4 alkyl groups and the like.
  • Aromatic dicarboxylic acid unit (a-2)
  • the aromatic dicarboxylic acid constituting the aromatic dicarboxylic acid unit is not limited to the following, but examples thereof include dicarboxylic acids having a phenyl group or a naphthyl group. Examples include acids.
  • the aromatic group of the aromatic dicarboxylic acid unit may be unsubstituted or may have a substituent.
  • substituents include, but are not limited to, for example, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, a halogen group such as a chloro group and a bromo group, carbon Examples thereof include silyl groups of 1 to 6, sulfonic acid groups and salts thereof (sodium salts, etc.).
  • the aromatic dicarboxylic acid unit is not limited to the following, but specific examples include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, and 5-methylisophthalic acid. And an aromatic dicarboxylic acid having 8 to 20 carbon atoms which is unsubstituted or substituted with a predetermined substituent such as 5-sodium sulfoisophthalic acid. (A-2) As the aromatic dicarboxylic acid constituting the aromatic dicarboxylic acid unit, only one kind may be used alone, or two or more kinds may be used in combination.
  • Aliphatic dicarboxylic acid unit (a-3) Aliphatic dicarboxylic acid unit (a-3)
  • the aliphatic dicarboxylic acid constituting the aliphatic dicarboxylic acid unit is not limited to the following, but examples thereof include malonic acid, dimethylmalonic acid, and succinic acid.
  • the aliphatic dicarboxylic acid unit contains an aliphatic dicarboxylic acid having 6 or more carbon atoms, the heat resistance, fluidity, toughness, low water absorption, rigidity and the like of the polyamide composition are more excellent. This is preferable because of its tendency.
  • the aliphatic dicarboxylic acid unit is preferably an aliphatic dicarboxylic acid having 10 or more carbon atoms. By using such a dicarboxylic acid, the heat resistance and low water absorption of the polyamide composition tend to be more excellent.
  • the aliphatic dicarboxylic acid unit having 10 or more carbon atoms is not particularly limited, and examples thereof include sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and eicosanedioic acid. Among these, sebacic acid and dodecanedioic acid are preferable from the viewpoint of heat resistance of the polyamide composition. (A-3) As the aliphatic dicarboxylic acid constituting the aliphatic dicarboxylic acid unit, only one kind may be used alone, or two or more kinds may be used in combination.
  • the proportion (mol%) of dicarboxylic acids other than 1,4-cyclohexadicarboxylic acid units in the dicarboxylic acid units is preferably 0 to 50 mol%, and preferably 0 to 40 mol%. More preferred is 0 to 30 mol%.
  • the aliphatic dicarboxylic acid unit (a-3) having 10 or more carbon atoms 50 to 99.9 mol% of 1,4-cyclohexanedicarboxylic acid and (a-3) the aliphatic dicarboxylic acid unit is included. It is preferably 0.1 to 50 mol%, more preferably 60 to 95 mol% of 1,4-cyclohexanedicarboxylic acid and (a-3) 5 to 40 mol% of an aliphatic dicarboxylic acid unit, More preferably, the amount of 1,4-cyclohexanedicarboxylic acid is 80 to 95 mol% and (a-3) the aliphatic dicarboxylic acid unit is 5 to 20 mol%.
  • Polyamide that satisfies the excellent heat resistance, fluidity, toughness, low water absorption, rigidity, etc. at the same time when the ratio of the aliphatic dicarboxylic acid unit (a-3) having 10 or more carbon atoms is in the above range. There is a tendency to obtain a composition.
  • the dicarboxylic acid constituting the dicarboxylic acid unit is not limited to the compounds described as the dicarboxylic acid, and may be a compound equivalent to the dicarboxylic acid.
  • the “compound equivalent to dicarboxylic acid” refers to a compound that can have the same dicarboxylic acid structure as the dicarboxylic acid structure derived from the dicarboxylic acid. Examples of such compounds include dicarboxylic acid anhydrides and halides.
  • (A1) polyamide may further contain the unit derived from polyvalent carboxylic acid more than trivalence, such as trimellitic acid, trimesic acid, and pyromellitic acid, as needed. Only one trivalent or higher polyvalent carboxylic acid may be used alone, or two or more polycarboxylic acids may be used in combination.
  • the alicyclic dicarboxylic acid constituting the alicyclic dicarboxylic acid unit has a trans isomer and a cis geometric isomer.
  • a trans isomer or a cis isomer may be used, or a mixture containing a trans isomer and a cis isomer in a predetermined ratio may be used.
  • the diamine unit includes at least an aliphatic diamine unit.
  • the aliphatic diamine constituting the aliphatic diamine unit may be linear or branched.
  • Examples of (b) diamine units include, but are not limited to, (b-1) diamine units having a substituent branched from the main chain, and (b-2) linear aliphatic diamine units. Is mentioned.
  • Other diamine units may include (b-3) alicyclic diamine units and (b-4) aromatic diamine units.
  • the diamine unit preferably has 6 to 12 carbon atoms.
  • a carbon number of 6 or more is preferable because of excellent heat resistance, and a carbon number of 12 or less is preferable because of excellent crystallinity and releasability.
  • As for carbon number of a diamine unit 6-10 is more preferable.
  • (B-1) Aliphatic diamine unit having a substituent branched from the main chain (branched aliphatic diamine)
  • the (b) diamine unit preferably includes (b-1) an aliphatic diamine unit having a substituent branched from the main chain.
  • a polyamide having a high glass transition temperature Tg and high crystallinity ie, high ⁇ Hm1 / ⁇ Hc
  • Tg and high crystallinity ie, high ⁇ Hm1 / ⁇ Hc
  • the aliphatic diamine unit having a substituent branched from the main chain (b-1) may be simply referred to as (b-1).
  • the “substituent branched from the main chain” in (b-1) is not limited to the following, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group.
  • the diamine constituting such (b-1) is not limited to the following, but for example, 2-methylpentamethylenediamine (also referred to as 2-methyl-1,5-diaminopentane), 2 2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methyl-1,8-octanediamine (also called 2-methyloctamethylenediamine), and 2,4-dimethyloctane Examples thereof include branched saturated aliphatic diamines having 3 to 20 carbon atoms such as methylene diamine. Among these, 2-methylpentamethylenediamine and 2-methyl-1,8-octanediamine are preferable, and 2-methylpentamethylenediamine is more preferable. By including such (b-1), it tends to be a polyamide composition having superior heat resistance and rigidity. As the diamine constituting (b-1), only one kind may be used alone, or two or more kinds may be used in combination.
  • the (b) diamine unit preferably contains 10 mol% or more of (b-1).
  • the proportion (mol%) of (b-1) in the diamine unit is preferably 30 to 100 mol%, more preferably 50 to 100 mol%, still more preferably 60 to 100 mol%. More preferably 85 to 100 mol%, still more preferably 90 to 100 mol%, most preferably 100 mol%.
  • the ratio of (b-1) in the diamine unit is preferably in the above range from the viewpoint of obtaining a polyamide having a high glass transition temperature Tg and ⁇ Hm1 / ⁇ Hc within the range of the present application. For this reason, the polyamide composition using this polyamide tends to be a polyamide composition that is superior in fluidity, toughness, and rigidity.
  • (B-2) Linear aliphatic diamine unit may be simply referred to as (b-2).
  • the aliphatic diamine constituting (b-2) is not limited to the following, but examples include ethylene diamine, propylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine.
  • linear saturated aliphatic diamines having 2 to 20 carbon atoms such as nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, and tridecamethylenediamine.
  • (B-3) Alicyclic diamine unit may be simply referred to as (b-3).
  • the alicyclic diamine (hereinafter also referred to as “alicyclic diamine”) constituting (b-3) is not limited to the following, but for example, 1,4-cyclohexanediamine, 1,3 -Cyclohexanediamine, 1,3-cyclopentanediamine and the like.
  • (B-4) Aromatic diamine unit hereinafter, the (b-4) aromatic diamine unit may be simply referred to as (b-4).
  • Examples of the aromatic diamine constituting (b-4) include metaxylylenediamine, paraxylylenediamine, paraphenylenediamine, metaphenylenediamine, and the like.
  • diamine units (b-2) to (b-4), (b-2) and (b-3) are preferable, and a linear saturated aliphatic group having 4 to 13 carbon atoms is more preferable.
  • the polyamide composition tends to be excellent in heat resistance, fluidity, toughness, low water absorption, rigidity, and the like.
  • diamine may be used individually by 1 type and may be used in combination of 2 or more types.
  • the total proportion (mol%) of the diamine units (b-2) to (b-4) is preferably 0 to less than 50 mol%, and 0 to 40 mol% with respect to the entire diamine unit (b). More preferably, it is more preferably 0 to 30 mol%.
  • the polyamide composition tends to be excellent in fluidity, toughness, and rigidity.
  • the (A1) polyamide may further contain a trivalent or higher polyvalent aliphatic amine such as bishexamethylenetriamine, if necessary. Trivalent or higher polyvalent aliphatic amines may be used alone or in combination of two or more.
  • the (A1) polyamide of the present invention includes (a) and (b), (c) lactam units (c-1) and / or aminocarboxylic acid units (c-), as long as the object of the present invention is not impaired. 2) can be further contained. By including such a unit, a polyamide composition that is superior in toughness tends to be obtained.
  • the lactam and aminocarboxylic acid constituting the lactam unit (c-1) and aminocarboxylic acid (c-2) refer to a lactam and aminocarboxylic acid capable of polymerization or condensation polymerization.
  • lactam and aminocarboxylic acid constituting the lactam unit (c-1) and the aminocarboxylic acid unit (c-2) are not limited to the following, but for example, lactam and amino acid having 4 to 14 carbon atoms Carboxylic acids are preferred, and lactams having 6 to 12 carbon atoms and aminocarboxylic acids are more preferred.
  • the lactam constituting the lactam unit (c-1) is not limited to the following. Noractam) and the like. Among these, as the lactam, ⁇ -caprolactam, laurolactam and the like are preferable, and ⁇ -caprolactam is more preferable. By including such a lactam, it tends to be a polyamide composition having better toughness.
  • the aminocarboxylic acid constituting the aminocarboxylic acid unit (c-2) is not limited to the following, but examples thereof include ⁇ -aminocarboxylic acid and ⁇ , ⁇ -amino acid which are compounds in which a lactam is opened. Is mentioned.
  • the aminocarboxylic acid is preferably a linear or branched saturated aliphatic carboxylic acid having 4 to 14 carbon atoms substituted with an amino group at the ⁇ position.
  • Examples of such aminocarboxylic acids include, but are not limited to, 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid.
  • Examples of the aminocarboxylic acid include paraaminomethylbenzoic acid.
  • lactam and aminocarboxylic acid constituting the lactam unit (c-1) and aminocarboxylic acid unit (c-2) may each be used alone or in combination of two or more. .
  • the total ratio (mol%) of the lactam unit (c-1) and the aminocarboxylic acid unit (c-2) is preferably 0 to 20 mol%, more preferably 0 to It is 10 mol%, and more preferably 0 to 5 mol%.
  • the total ratio of the lactam unit (c-1) and the aminocarboxylic acid unit (c-2) is in the above range, effects such as improvement in fluidity tend to be obtained.
  • the terminal of (A1) polyamide used in the present invention may be end-capped with a known end-capping agent.
  • a known end-capping agent is also added as a molecular weight regulator in the production of (A1) polyamide from the above-described dicarboxylic acid and diamine and lactam and / or aminocarboxylic acid used as necessary. Can do.
  • end-capping agents include, but are not limited to, acid anhydrides such as monocarboxylic acids, monoamines, and phthalic anhydride, monoisocyanates, monoacid halides, monoesters, and monoalcohols. Etc. Among these, monocarboxylic acid and monoamine are preferable.
  • acid anhydrides such as monocarboxylic acids, monoamines, and phthalic anhydride
  • monoisocyanates monoacid halides
  • monoesters monoalcohols.
  • monocarboxylic acid and monoamine are preferable.
  • the monocarboxylic acid that can be used as the end-capping agent is not limited to the following as long as it has reactivity with the amino group that can be present at the terminal of the (A1) polyamide.
  • formic acid Aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid; cyclohexanecarboxylic acid, etc.
  • aromatic monocarboxylic acids such as benzoic acid, toluic acid, ⁇ -naphthalenecarboxylic acid, ⁇ -naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid.
  • acetic acid is particularly preferred.
  • a monocarboxylic acid may be used individually by 1 type, and may be used in combination of 2 or more type.
  • a monocarboxylic acid as a terminal blocking agent.
  • the addition amount of the monocarboxylic acid is preferably 0.1 to 2.0 mol%, more preferably 0.3 to 1.5 mol%, and still more preferably 0.5 to 0.1 mol%, based on the charged diamine. ⁇ 1.5 mol%.
  • the ratio [NH 2 ] / ([NH 2 ] + [COOH]) of the amino terminal amount to the total active terminal amount can be less than 0.5, and the trans isomer ratio Can be more than 71 mol% and 75 mol% or less.
  • the monoamine that can be used as the end-capping agent is not limited to the following as long as it has reactivity with the carboxyl group that can be present at the end of the (A1) polyamide, but for example, methylamine, Aliphatic monoamines such as ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; and aniline , Aromatic monoamines such as toluidine, diphenylamine, and naphthylamine. Only one monoamine may be used alone, or two or more monoamines may be used in combination.
  • the polyamide composition containing (A1) polyamide end-capped with an end-capping agent tends to be excellent in heat resistance, fluidity, toughness, low water absorption, and rigidity.
  • the method for producing a first polyamide of the present invention comprises (a) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid, and (b) a diamine unit containing at least an aliphatic diamine.
  • the first method for producing a polyamide of the present invention is a method for obtaining a polyamide having a specific terminal structure (hereinafter referred to as a precursor polyamide), and further heat-treating it below the melting point (A1) to obtain a polyamide.
  • a “hot melt polymerization / solid phase polymerization method” is preferable.
  • the method for obtaining the precursor polyamide (thermal melt polymerization method) and the heat treatment (solid phase polymerization method) will be described in detail.
  • the method for obtaining the precursor polyamide is not particularly limited, and examples thereof include the methods exemplified below. 1) A method in which an aqueous solution or a suspension of water of a dicarboxylic acid / diamine salt or a mixture thereof is heated and polymerized while maintaining a molten state (hereinafter referred to as hot melt polymerization method).
  • prepolymer ⁇ Called the extrusion polymerization method A method in which an aqueous solution or suspension of water of a dicarboxylic acid / diamine salt or a mixture thereof is heated, and the precipitated prepolymer is melted again with an extruder such as a kneader to increase the degree of polymerization (hereinafter referred to as prepolymer ⁇ Called the extrusion polymerization method).
  • prepolymer ⁇ Called the extrusion polymerization method A method of polymerizing using a dicarboxylic acid halide equivalent to a dicarboxylic acid and a diamine.
  • the hot melt polymerization method is preferable from the viewpoint of increasing the molecular weight by polymerization in a short time and suppressing gelation.
  • the addition amount of the dicarboxylic acid constituting the dicarboxylic acid unit and (b) the addition amount of the diamine constituting the diamine unit are about the same molar amount.
  • the dicarboxylic acid unit preferably contains 50 to 100 mol% of 1,4-cyclohexanedicarboxylic acid units (based on the total number of moles of dicarboxylic acid), more preferably 60 to 100 mol%, more preferably 70 to 100 mol. % Is more preferable, and 100 mol% is most preferable.
  • the trans isomer / cis isomer ratio (molar ratio) of the alicyclic dicarboxylic acid as the raw material monomer is preferably 50/50 to 0/100, more preferably 40/60 to 10/90. More preferably, it is 35/65 to 15/85.
  • the trans / cis ratio (molar ratio) of the alicyclic dicarboxylic acid can be determined by liquid chromatography (HPLC) or nuclear magnetic resonance spectroscopy (NMR).
  • the (b) diamine unit preferably includes (b-1) an aliphatic diamine unit having a substituent branched from the main chain, and the proportion thereof is preferably 10 to 100 mol%, more preferably 50 to 100 mol%. 60 to 100 mol% is more preferable, 85 to 100 mol% is still more preferable, 90 to 100 mol% is particularly preferable, and 100 mol% is most preferable.
  • (B-1) is most preferably 2-methyl-5-pentamethylenediamine.
  • a terminal blocking agent may be used for molecular weight and terminal adjustment.
  • the terminal blocking agent is not particularly limited, but acetic acid is preferable.
  • the amount of acetic acid added to the charged diamine is 0.1 to 2.0 mol%, more preferably 0.3 to 1.5 mol%, and still more preferably 0.5 to 1.5 mol% in terms of a molar ratio.
  • Such diamine is preferably 2-methyl-5-pentamethylenediamine.
  • the amount of added diamine with respect to the diamine unit is 1.0 to 5.0 mol%, more preferably 1.5 to 4.5 mol%, still more preferably 2.0 to 4.0 mol% in terms of molar ratio. It is.
  • a phosphorus compound as a heat stabilizer (catalyst) at the time of hot melt polymerization.
  • the heat stabilizer is not particularly limited, but sodium hypophosphite is preferable.
  • the method for producing polyamide preferably further includes a step of increasing the degree of polymerization of the polyamide. Moreover, the sealing process which seals the terminal of the obtained polymer with a terminal sealing agent may be included as needed.
  • the physical property of the precursor polyamide is the ratio of the amino terminal amount [NH 2 ] to the active terminal total amount ([NH 2 ] + [COOH]) [NH 2 ] / ([NH 2 ] + [COOH]) is 0. It is preferably less than 5, more preferably 0.2 or more and less than 0.5, and further preferably 0.2 to 0.4.
  • the total active terminal amount ([NH 2 ] + [COOH]) is preferably 60 or more and less than 110 ⁇ eq / g, more preferably 70 to 110 ⁇ eq / g, even more preferably 80 to 110 ⁇ eq / g, and 80 to 100 ⁇ m. Equivalent / g is particularly preferred.
  • the terminal structure of the polyamide is controlled by adjusting the amounts of the structural units (a) to (c) of the polyamide, the end-capping agent and the additional diamine. Can be obtained.
  • the heat treatment in the production method of the present invention is a method of heating the precursor polyamide at 200 ° C. or higher and lower than the melting point (Tm 2).
  • the heat treatment method is not particularly limited as long as heating at 200 ° C. or more and less than the melting point (Tm2) is possible.
  • apparatuses such as a dryer, an autoclave, an electric furnace, a gear oven, a hot plate, and a molding die This can be done by using
  • the heat treatment may be performed in the air, may be performed in an inert gas atmosphere, for example, a nitrogen gas atmosphere, or may be performed in a reduced pressure environment.
  • a solid phase polymerization method in which constituent units such as monomers and precursor polyamide are polymerized in a solid state at a temperature lower than the melting point is preferable.
  • the heat treatment temperature is 200 ° C to less than the melting point (Tm2), more preferably 220 ° C to less than the melting point (Tm2), and even more preferably 240 ° C to less than the melting point (Tm2).
  • Tm2 melting point
  • Tm2 melting point
  • Tm2 melting point
  • Tm2 melting point
  • Tm2 melting point
  • the trans isomer ratio of the dicarboxylic acid monomer unit in the polyamide is preferably more than 71 mol% and 75 mol% or less, more preferably 72 mol% or more and 75 mol% or less. Since the polyamide of the present invention is highly crystallized because the trans isomer ratio is in the above range, the polyamide and the polyamide composition of the present invention have a high melting point, toughness and rigidity, in addition to the characteristics of being high. It tends to have the property of simultaneously satisfying the thermal rigidity due to the glass transition temperature (Tg), the fluidity, which is usually a property contrary to heat resistance, and the high crystallinity.
  • Tg glass transition temperature
  • the trans isomer ratio of the dicarboxylic acid monomer unit in such a polyamide can be controlled by controlling the carboxyl terminal amount of the polyamide and the method for producing the polyamide of the present invention.
  • the trans isomer ratio (molar ratio) of the 1,4-cyclohexanedicarboxylic acid monomer unit of the polyamide composition molded article can be determined by nuclear magnetic resonance spectroscopy (NMR).
  • the sulfuric acid relative viscosity ⁇ r of the polyamide is preferably larger than 1.8. More than 1.8 and 3.0 or less are more preferable, and 2.0 or more and 2.5 or less are more preferable. When it is larger than 1.8, the mechanical properties of toughness and rigidity are excellent, and when it is 3.0 or less, the fluidity and moldability are excellent.
  • the sulfuric acid relative viscosity ⁇ r at 25 ° C. can be measured at 25 ° C. in 98% sulfuric acid according to JIS-K6920.
  • A1 As an index of the molecular weight of polyamide, the number average molecular weight Mn, the weight average molecular weight Mw, and the molecular weight distribution Mw / Mn obtained by GPC (gel permeation chromatography) can be used. The larger the Mn, the higher the molecular weight of the (A1) polyamide, and the smaller the Mn, the lower the molecular weight of the (A1) polyamide.
  • the Mn of the polyamide is preferably greater than 15000, more preferably 18000 or greater, and even more preferably 19000 or greater. Further, the Mw / Mn of the (A1) polyamide is preferably less than 3.5, more preferably 3.0 or less.
  • Mn and Mw can produce
  • the melting peak temperature Tm1 of the polyamide is preferably 300 ° C. or higher, more preferably 320 ° C. or higher, and further preferably 325 ° C. or higher.
  • the melting peak temperature Tm1 of (A1) polyamide is preferably 350 ° C. or lower, more preferably 345 ° C. or lower, and further preferably 340 ° C. or lower.
  • (A1) When the melting peak temperature Tm1 of the polyamide is 300 ° C. or higher, a polyamide composition excellent in heat resistance tends to be obtained. Moreover, when (A1) polyamide melting peak temperature Tm1 is 350 ° C. or less, (A1) thermal decomposition of polyamide in melt processing such as extrusion and molding tends to be further suppressed.
  • the melting peak temperature Tm2 of the polyamide is preferably 270 ° C. or higher, more preferably 275 ° C. or higher, and further preferably 280 ° C. or higher.
  • the melting peak temperature Tm2 of the (A1) polyamide is preferably 350 ° C. or lower, more preferably 340 ° C. or lower, further preferably 335 ° C. or lower, and still more preferably 330 ° C. or lower.
  • (A1) When the melting peak temperature Tm2 of the polyamide is 270 ° C. or higher, a polyamide composition excellent in heat resistance tends to be obtained. Moreover, when (A1) polyamide melting peak temperature Tm2 is 350 ° C.
  • thermo decomposition of polyamide in melt processing such as extrusion and molding tends to be further suppressed.
  • the melting peak temperatures Tm1 and Tm2 of the polyamide can be measured according to JIS-K7121 by the method described in Examples below.
  • the heat of fusion ⁇ Hm1 and crystallization enthalpy ⁇ Hc of the polyamide are each preferably 30 J / g or more, more preferably 35 J / g or more, and still more preferably 40 J / g or more.
  • the upper limit of the heat of fusion ⁇ Hm1 and the crystallization enthalpy ⁇ Hc is not particularly limited and is preferably as high as possible.
  • (A1) When the heat of fusion ⁇ Hm1 and the crystallization enthalpy ⁇ Hc of the polyamide are each 30 J / g or more, the heat resistance of the polyamide composition tends to be further improved.
  • the heat of fusion ⁇ Hm1 and the crystallization enthalpy ⁇ Hc of the polyamide can be measured according to JIS-K7121 by the methods described in the Examples below.
  • the heat of fusion ⁇ Hm1 and crystallization enthalpy ⁇ Hc of the (A1) polyamide described above can be measured according to JIS-K7121 by the method described later.
  • the heat of fusion ⁇ Hm2 of the polyamide is preferably 20 J / g or more, more preferably 25 J / g or more, and further preferably 30 J / g or more.
  • the upper limit of the heat of fusion ⁇ Hm2 is not particularly limited and is preferably as high as possible.
  • the heat resistance of the polyamide composition tends to be further improved.
  • the heat of fusion ⁇ Hm1 is a heat of fusion reflecting the heat history received by the polyamide during heat treatment or cooling, and is different from the heat of fusion inherent in the polyamide.
  • ⁇ Hc is a crystallization enthalpy obtained through a cooling process (slow cooling) after complete melting, and is equal to the heat of fusion inherent in polyamide. Therefore, ⁇ Hm1 / ⁇ Hc means the ratio between the heat of fusion inherent in polyamide and the heat of fusion of polyamide subjected to a thermal history.
  • Ratio ⁇ Hm1 / ⁇ Hc of polyamide heat of fusion ⁇ Hm1 and crystallization enthalpy ⁇ Hc is greater than 1.0 and less than or equal to 2.2, preferably greater than 1.0 and less than or equal to 1.4, more preferably 1 It is 1 or more and 1.4 or less, More preferably, it is 1.2 or more and 1.4 or less.
  • the ratio ⁇ Hm1 / ⁇ Hc between the heat of fusion ⁇ Hm1 of the polyamide and the crystallization enthalpy ⁇ Hc is greater than 1.0 and 2.2 or less, whereby the heat resistance of the polyamide composition tends to be improved.
  • Tm1-Tc ⁇ Difference between melting peak temperature Tm1 and crystallization peak temperature Tc (Tm1-Tc)> (A1)
  • Tm1-Tc is preferably higher than 40 ° C and lower than 90 ° C, and more preferably 50 ° C to 80 ° C.
  • the measurement of the heat of fusion ⁇ Hm1 and the crystallization enthalpy ⁇ Hc of the polyamide can be performed according to JIS-K7121, and the heat of fusion ⁇ Hm1 is measured when the temperature of the polyamide is raised at a rate of temperature increase of 20 ° C./min (the first temperature rise).
  • the endothermic peak appearing on the highest temperature side of the endothermic peak (melting peak) appearing at the time) is the peak area of Tm when the melting peak temperature is Tm (° C.).
  • a peak having ⁇ H of 1 J / g or more is regarded as a peak, the highest temperature is defined as a melting peak temperature Tm1, and ⁇ Hm1 is a sum of peak areas.
  • the crystallization enthalpy ⁇ Hc is the Tc value when the temperature of the exothermic peak (crystallization peak) that appears when the polyamide composition molded article is cooled at a temperature decrease rate of 20 ° C./min is the crystallization peak temperature Tc (° C.). It is the peak area.
  • Diamond-DSC manufactured by PERKIN-ELMER can be used as the measuring apparatus.
  • the glass transition temperature Tg of the polyamide is preferably 90 ° C. or higher, more preferably 110 ° C. or higher, still more preferably 120 ° C. or higher, even more preferably 130 ° C. or higher, and even more preferably. Is 135 ° C. or higher.
  • the glass transition temperature Tg of (A1) polyamide is preferably 170 ° C. or lower, more preferably 165 ° C. or lower, and further preferably 160 ° C. or lower. (A1) When the glass transition temperature Tg of polyamide is 90 ° C. or higher, a polyamide composition excellent in heat discoloration resistance and chemical resistance tends to be obtained.
  • the glass transition temperature Tg of (A1) polyamide can be measured according to JIS-K7121 as described in the following examples. Examples of the measuring device for the glass transition temperature Tg include Diamond-DSC manufactured by PERKIN-ELMER.
  • the amino terminal is a polymer terminal having an amino group (—NH 2 group) and is derived from the raw material (b) diamine unit.
  • the amino terminal amount ([NH 2 ]) is preferably 5 to 100 ⁇ equivalent / g, more preferably 5 to 70 ⁇ equivalent / g, and further preferably 5 to 50 ⁇ equivalent to 1 g of (A1) polyamide. / G, even more preferably 5 to 30 ⁇ eq / g, and particularly preferably 5 to 20 ⁇ eq / g.
  • the amino terminal amount is in the above range, the whiteness, reflow resistance, heat discoloration resistance, light discoloration resistance, hydrolysis resistance, and heat retention stability of the polyamide composition tend to be more excellent.
  • the amino terminal amount can be measured by neutralization titration. Specifically, 3.0 g of polyamide is dissolved in 100 mL of a 90 mass% phenol aqueous solution, and the obtained solution is titrated with 0.025N hydrochloric acid to obtain the amino terminal amount ( ⁇ equivalent / g). The end point is determined from the indicated value of the pH meter.
  • the carboxyl terminal is a polymer terminal having a carboxyl group (—COOH group) and is derived from the raw material (a) dicarboxylic acid.
  • the carboxyl terminal amount ([COOH]) is preferably 5 to 100 ⁇ equivalent / g, more preferably 5 to 70 ⁇ equivalent / g, and further preferably 5 to 50 ⁇ equivalent / g with respect to 1 g of (A1) polyamide. g, even more preferably 5 to 30 ⁇ eq / g, and particularly preferably 5 to 20 ⁇ eq / g.
  • the carboxyl end amount When the carboxyl end amount is in the above range, the whiteness, reflow resistance, heat discoloration resistance, and light discoloration resistance of the polyamide composition tend to be more excellent.
  • the carboxyl end amount can be measured by neutralization titration. Specifically, 4.0 g of polyamide is dissolved in 50 mL of benzyl alcohol, and the obtained solution is titrated with 0.1 N NaOH to obtain the carboxyl terminal amount ( ⁇ equivalent / g). The end point is determined from the discoloration of the phenolphthalein indicator.
  • the total amount of the amino terminal amount ([NH 2 ]) and the carboxyl terminal amount ([COOH]) is defined as the active terminal total amount ([NH 2 ] + [COOH]).
  • the total amount of active terminals is preferably 10 to 200 ⁇ eq / g, more preferably 10 to 150 ⁇ eq / g, still more preferably 10 to 100 ⁇ eq / g, based on 1 g of (A1) polyamide. Particularly preferred is 20 to 60 ⁇ equivalent / g. [NH 2 ] / ([NH 2 ] + [COOH]), which is a ratio of the amino terminal amount [NH 2 ] to the active terminal total amount ([NH 2 ] + [COOH]), is preferably 0.5.
  • ⁇ Hm1 / ⁇ Hc it is less than, More preferably, it is 0.2 or more and less than 0.5, More preferably, it is 0.2 or more and 0.4 or less, Most preferably, it is 0.2 or more and 0.3 or less. It is possible to control ⁇ Hm1 / ⁇ Hc to be larger than 1.0 and 2.2 or less because the ratio of the total amount of amino terminal and carboxyl terminal and the ratio of amino terminal to the total active terminal is within the above range. The whiteness, reflow resistance, heat discoloration resistance, and light discoloration resistance of the polyamide composition tend to be more excellent.
  • Examples of the method for controlling the ratio of the amino terminal amount to the total active terminal amount include a method of controlling the addition amount of diamine and terminal blocking agent as additives during hot melt polymerization of polyamide, and the polymerization conditions. .
  • the cyclic amino terminus is a polymer terminus having a cyclic amino group (a group represented by the following (formula 1)).
  • R represents a substituent bonded to the carbon constituting the piperidine ring.
  • Specific examples of R include a hydrogen atom, a methyl group, an ethyl group, and a t-butyl group.
  • the amount of the cyclic amino terminus is preferably 30 ⁇ eq / g or more and 100 ⁇ eq / g or less, more preferably 30 ⁇ eq / g or more and 80 ⁇ eq / g or less, relative to 1 g of (A1) polyamide. Preferably they are 35 microequivalent / g or more and 70 microequivalent / g or less.
  • the polyamide composition of the present invention tends to be more excellent in toughness, hydrolysis resistance, and processability.
  • the amount of the cyclic amino terminus can be measured using 1 H-NMR. For example, there is a method of calculation based on the integral ratio of hydrogen bonded to carbon adjacent to the nitrogen atom of the heterocyclic ring of nitrogen and hydrogen bonded to carbon adjacent to the nitrogen atom of the amide bond of the polyamide main chain.
  • Cyclic amino terminal can be generated by dehydration reaction of cyclic amine and carboxyl terminal, and can also be generated by deammonia reaction of amino terminal in the polymer molecule. Cyclic amine is added as end-capping agent. It can also be produced by the diamine having a pentamethylenediamine skeleton, which is a raw material for polyamide, and cyclizing by deammonia reaction.
  • the cyclic amino terminal is preferably derived from a raw material diamine. Without adding cyclic amine as an end-capping agent at the initial stage of polymerization, the cyclic amino terminal is generated from the raw material diamine, so that the low molecular weight carboxylic acid terminal is prevented from being blocked at the initial stage of polymerization. Thus, the polymerization reaction rate of the polyamide is maintained high, and as a result, a high molecular weight product tends to be obtained. As described above, when a cyclic amine is generated during the reaction, the carboxylic acid terminal is sealed with the cyclic amine at a later stage of the polymerization, so that a high molecular weight polyamide is easily obtained.
  • a cyclic amine that generates a cyclic amino terminus can be generated as a by-product during the polymerization reaction of polyamide.
  • the higher the reaction temperature the higher the reaction rate. Therefore, in order to make the cyclic amino terminal of the (A1) polyamide constant, it is preferable to promote the formation of a cyclic amine. Therefore, the reaction temperature for the polymerization of the precursor polyamide is preferably 300 ° C. or higher, and more preferably 320 ° C. or higher.
  • control is performed by appropriately adjusting the polymerization temperature, the holding time of the reaction temperature of 300 ° C. or more during the polymerization step, the addition amount of the amine forming the cyclic structure, and the like. The method of doing is mentioned.
  • the end by the sealant is an end formed when a sealant is added during polymerization.
  • the sealing agent include the above-described end sealing agents.
  • the other terminal is a polymer terminal not classified in the above 1) to 4), such as a terminal generated by deammonia reaction at the amino terminal or a terminal generated by decarboxylation from the carboxylic acid terminal. It is done.
  • the first polyamide composition contains the first polyamide and at least one of an inorganic filler, a nucleating agent, a heat stabilizer and a light stabilizer. Furthermore, titanium oxide may be included. By containing such a structural component, a polyamide composition excellent in heat resistance, whiteness, reflow resistance, aging resistance and releasability can be obtained.
  • an inorganic filler e.g., titanium oxide
  • titanium oxide e.g., titanium oxide
  • a polyamide composition excellent in heat resistance, whiteness, reflow resistance, aging resistance and releasability e.g., the components of the first polyamide composition will be described.
  • the first polyamide composition of the present invention may further contain (B) titanium oxide.
  • (B) titanium oxide include, but are not limited to, titanium monoxide (TiO), dititanium trioxide (Ti 2 O 3 ), and titanium dioxide (TiO 2 ). Of these, titanium dioxide is preferable.
  • the crystal structure of titanium oxide is not particularly limited, but is preferably a rutile type from the viewpoint of light resistance of the polyamide composition.
  • Titanium oxide is preferably in the form of particles, and the number average particle diameter of (B) titanium oxide is preferably 0.1 to 0.8 ⁇ m, more preferably 0.15 to 0.4 ⁇ m. More preferably 0.15 to 0.3 ⁇ m.
  • the number average particle diameter of titanium oxide is 0.1 ⁇ m or more, the extrusion processability of the polyamide composition tends to be further improved.
  • the number average particle diameter of titanium oxide is 0.8 ⁇ m or less, the toughness of the polyamide composition tends to be further improved.
  • the number average particle diameter of titanium oxide can be measured by an electron micrograph.
  • the polyamide composition is put in an electric furnace, the organic matter contained in the polyamide composition is incinerated, and, for example, 100 or more arbitrarily selected titanium oxides from the residue are observed with an electron microscope. By measuring the particle diameter, it is possible to determine the number average particle diameter of (B) titanium oxide.
  • the method for producing titanium oxide is not limited to the following, and examples thereof include a so-called sulfuric acid method in which a titanium sulfate solution is hydrolyzed, or a so-called chlorine method in which titanium halide is vapor-phase oxidized.
  • the titanium oxide has an inorganic coating layer and / or an organic coating layer on the surface.
  • titanium oxide having an inorganic coating layer on the surface of titanium oxide and an organic coating layer on the inorganic coating layer is preferable.
  • Titanium oxide may be coated using any known method.
  • the inorganic coating is not limited to the following, but preferably includes, for example, a metal oxide.
  • the organic coating is not limited to the following, but for example, it preferably contains one or more organic substances selected from the group consisting of carboxylic acids, polyols, alkanolamines, and organosilicon compounds.
  • the surface of (B) titanium oxide is more preferably coated using polyols and organosilicon compounds. From the viewpoint of reducing generated gas, it is more preferable that coating is performed using an organosilicon compound.
  • titanium oxide only 1 type may be used independently and it may be used in combination of 2 or more types.
  • the content of (B) titanium oxide in the first polyamide composition is preferably 5% by mass to 70% by mass, and preferably 20% by mass to 70% by mass with respect to 100% by mass of the first polyamide composition. More preferably, it is 25 to 60% by mass, still more preferably 30 to 50% by mass. (B) When the content of titanium oxide is in the above range, the whiteness of the polyamide composition tends to be more excellent.
  • the first polyamide composition may further contain (C) an inorganic filler other than (B) titanium oxide described above from the viewpoint of mechanical properties such as strength and rigidity.
  • the inorganic filler is not limited to the following, for example, glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, glass flake, hydrotalcite, carbonic acid Zinc, zinc oxide, calcium monohydrogen phosphate, wollastonite, silica, zeolite, alumina, boehmite, aluminum hydroxide, silicon oxide, magnesium oxide, calcium silicate, sodium aluminosilicate, magnesium silicate, ketjen black, acetylene Examples thereof include black, furnace black, carbon nanotube, graphite, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, montmorillonite, swellable fluorine mica, and apatite.
  • the inorganic filler (C) at least one selected from the group consisting of glass fiber, potassium titanate fiber, wollastonite, and clay is preferable, and wollastonite is more preferable.
  • the number average particle diameter of the inorganic filler is preferably from 0.1 to 20 ⁇ m, more preferably from 0.15 to 15 ⁇ m, from the viewpoint of whiteness, toughness and extrusion processability of the first polyamide composition.
  • the thickness is preferably 0.15 to 10 ⁇ m.
  • the content of the inorganic filler (C) in the first polyamide composition is preferably 1 to 30% by mass, more preferably 1 to 20% by mass with respect to 100% by mass of the polyamide composition. More preferably, it is 1 to 10% by mass.
  • (C) When content of an inorganic filler exists in said range, the intensity
  • the first polyamide composition preferably further contains a nucleating agent from the viewpoint of releasability.
  • Nucleating agent is a substance that can increase the crystallization peak temperature measured by differential scanning calorimetry by addition, or can improve the spherulite of the resulting molded product or make the size uniform. Means that.
  • nucleating agent examples include, but are not limited to, talc, boron nitride, mica, kaolin, calcium carbonate, barium sulfate, silicon nitride, carbon black, potassium titanate, and molybdenum disulfide. It is done.
  • a nucleating agent may be used individually by 1 type, and may combine 2 or more types. Of these, talc, boron nitride, and carbon black are preferable from the viewpoint of the nucleation effect, more preferably talc and boron nitride, and still more preferably talc.
  • the nucleating agent is preferably in the form of particles, and the number average particle diameter of the nucleating agent is preferably 0.01 to 10 ⁇ m, more preferably 0.5 to 5 ⁇ m. When the number average particle diameter of the nucleating agent is within the above range, the nucleating effect tends to be further improved.
  • the molded article of the polyamide composition is dissolved in a polyamide-soluble solvent such as formic acid, and, for example, 100 or more nucleating agents are obtained from the obtained insoluble components. It can be selected arbitrarily and observed and obtained with an optical microscope or a scanning electron microscope.
  • the blending amount of the nucleating agent is preferably 0.001 to 15% by mass, more preferably 0.001 to 5% by mass, and still more preferably 0.001 to 100% by mass of the polyamide composition. Is 3% by mass, and still more preferably 0.5-2.5% by mass.
  • the first polyamide composition may contain a heat stabilizer from the viewpoint of heat stability.
  • a heat stabilizer the following (E) metal hydroxide, (F) phosphorus compound, (G) phenol antioxidant and / or amine antioxidant can be mentioned.
  • the first polyamide composition may contain (E) a metal hydroxide as a heat stabilizer.
  • the metal hydroxide is represented by a general formula M (OH) x (M represents a metal element, and x represents a number corresponding to the multivalent value of M).
  • the metal element M is preferably a monovalent or higher metal. Examples of the monovalent or higher metal include, but are not limited to, sodium, potassium, lithium, calcium, magnesium, barium, zinc, aluminum, strontium, and the like.
  • the metal element M an alkaline earth metal is preferable.
  • the (E) metal hydroxide contained in the first polyamide composition is not limited to the following.
  • sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, hydroxide Aluminum, zinc hydroxide, manganese hydroxide, etc. are mentioned.
  • calcium hydroxide and magnesium hydroxide are preferable, and calcium hydroxide is more preferable.
  • a metal hydroxide may be used individually by 1 type, and may use 2 or more types together. Moreover, you may use these (E) metal hydroxide which performed the surface treatment in order to improve adhesiveness and a dispersibility.
  • the surface treatment agent examples include, but are not limited to, for example, silane coupling agents such as aminosilane and epoxysilane, organosilicon compounds such as silicone; organic titanium compounds such as titanium coupling agents; organic acids and polyols And organic substances such as
  • the (E) metal hydroxide in the first polyamide composition is preferably in the form of particles, and the average particle diameter is preferably 0.05 to 10 ⁇ m, more preferably 0.1 to 5 ⁇ m.
  • the average particle diameter is in the above range, the effects of reflow resistance and heat discoloration can be obtained in the polyamide composition.
  • grains of (E) metal hydroxide becomes like this. Preferably it is 1 mass% or less, More preferably, it is 0.1 mass% or less.
  • E By making the mass ratio of the particle
  • the purity of the (E) metal hydroxide in the first polyamide composition is preferably 99% or more, more preferably 99.5% or more, and further preferably 99.9% or more. Due to the high purity, the whiteness, reflow resistance, and light discoloration resistance of the first polyamide composition tend to be excellent.
  • the content of the metal hydroxide (E) described above is 0.1 to 20% by mass, preferably 0.1 to 10% by mass, more preferably 100% by mass with respect to the first polyamide composition. Is 0.3 to 5% by mass, more preferably 0.3 to 2% by mass, even more preferably 0.5 to 1.5% by mass, and still more preferably 0.5 to 1.% by mass. 0% by mass.
  • the polyamide composition tends to be more excellent in heat discoloration resistance, extrusion processing stability, and molding processing stability.
  • the first polyamide composition may further contain a metal compound other than the above-described (C) metal hydroxide from the viewpoint of whiteness and heat discoloration.
  • the metal compound other than the metal hydroxide is not limited to the following, and examples thereof include metal carbonates and metal halides.
  • a metal element contained in metal compounds other than a metal hydroxide For example, a monovalent or more metal element is preferable. Examples of such metal elements include, but are not limited to, sodium, potassium, lithium, calcium, magnesium barium, zinc, aluminum, strontium, and the like. As the metal element, an alkaline earth metal is preferable.
  • the metal hydroxide may be added during the polymerization of the (A1) polyamide, but is preferably added during the production of the polyamide composition to be mixed with the (A1) polyamide after the polymerization of the (A1) polyamide.
  • the thermal history can be reduced, (E) the decomposition of the metal hydroxide can be suppressed, whiteness, reflow resistance, heat discoloration resistance, extrusion processing And a polyamide composition excellent in molding process stability can be obtained.
  • the polyamide composition may contain (F) a phosphorus compound as a heat stabilizer.
  • (F) phosphorus compounds include, but are not limited to, 1) phosphoric acid, phosphorous acid, hypophosphorous acid, and intramolecular and / or intermolecular condensates thereof, 2) Examples thereof include phosphoric acid, phosphorous acid, hypophosphorous acid, and metal salts of intramolecular and / or intermolecular condensates thereof.
  • (F) phosphorus type compound may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the phosphoric acid, phosphorous acid, hypophosphorous acid, and intramolecular and / or intermolecular condensates thereof in 1) are not limited to the following, but examples include phosphoric acid, pyrophosphoric acid, and metalin. Examples thereof include acids, phosphorous acid, hypophosphorous acid, pyrophosphorous acid, and diphosphorous acid.
  • the metal salts of the above-mentioned 2) phosphoric acid, phosphorous acid, hypophosphorous acid, and intramolecular and / or intermolecular condensates thereof are not limited to the following. Mention may be made of salts of the compounds with Group 1 and 2 of the periodic table, manganese, zinc and aluminum.
  • More preferable (F) phosphorus compounds are selected from the group consisting of metal phosphates, metal phosphites, metal hypophosphites, intramolecular condensates of these metal salts, and intermolecular condensates of these metal salts. One or more selected.
  • the polyamide composition tends to be more excellent in whiteness, heat discoloration resistance, heat reflow resistance, and light discoloration resistance.
  • More preferable (F) phosphorus compound is a phosphorus compound selected from phosphoric acid, phosphorous acid and hypophosphorous acid, group 1 (alkali metal) and group 2 (alkaline earth metal) of the periodic table, manganese , Zinc, and a metal selected from aluminum, or an intramolecular condensate of these metal salts or an intermolecular condensate of these metal salts. More preferably (F) phosphorus compound is a metal salt containing a phosphorus compound selected from phosphoric acid, phosphorous acid and hypophosphorous acid, and a metal selected from Groups 1 and 2 of the periodic table. is there.
  • the metal salt as such a (F) phosphorus compound is not particularly limited.
  • sodium hypophosphite, calcium hypophosphite, and magnesium hypophosphite are preferable, and calcium hypophosphite and magnesium hypophosphite, which are alkaline earth metal salts, are more preferable.
  • a phosphorus compound (F) it tends to be more excellent in whiteness, heat discoloration resistance, light discoloration resistance and extrusion processability.
  • a phosphorus compound is a hypophosphite metal salt, the 1st polyamide composition excellent in extrusion processability and shaping
  • Metal of (F) phosphorus compound selected from the group consisting of metal phosphate, metal phosphite, metal hypophosphite, intramolecular condensate of these metal salts, and intermolecular condensate of these metal salts
  • the species is preferably the same as the metal species of (E) the metal hydroxide.
  • the metal species of the (F) phosphorus compound is preferably an alkaline earth metal.
  • the phosphorus compound is selected from the group consisting of metal salts, intramolecular condensates of metal salts, and intermolecular condensates of metal salts, and (F) the metal species of the phosphorus compound is (E) metal
  • the metal species of the hydroxide are the same, it is possible to obtain a polyamide composition having improved thermal stability and excellent extrusion processability and molding process stability. Furthermore, by using an alkaline earth metal as the metal species of the (F) phosphorus compound, a more excellent effect can be obtained in the above characteristics.
  • an anhydrous salt or a metal salt that does not contain a hydrate as the phosphorus compound By using an anhydrous salt or a metal salt that does not contain a hydrate as the phosphorus compound, the amount of water generated during processing can be suppressed, and a decrease in the molecular weight of polyamide and gas generation can be suppressed. .
  • phosphorus compound (F) selected from the group consisting of metal phosphates, metal phosphites, metal hypophosphites, intramolecular condensates of these metal salts, and intermolecular condensates of these metal salts. Those having low deliquescence are preferred, and those having no deliquescence are more preferred.
  • (F) By using a metal salt with low deliquescence as a phosphorus compound, processing is reduced due to a decrease in workability and an increase in the amount of water in the raw material component when mixing each raw material component during the production of the polyamide composition. It is possible to suppress the molecular weight reduction and gas generation of the polyamide at the time. By using a metal salt having low deliquescence, a polyamide composition excellent in whiteness, reflow resistance, heat discoloration resistance, extrusion processability, and molding process stability can be obtained.
  • the phosphorus compound may include an organic phosphorus compound.
  • organic phosphorus compounds include, but are not limited to, pentaerythritol phosphite compounds, trioctyl phosphites, trilauryl phosphites, tridecyl phosphites, octyl diphenyl phosphites, trisisodecyl phosphites.
  • phenyl diisodecyl phosphite phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl (tridecyl) phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, tris (2,4-di-tert-butyl-5-methylphenyl) phosphite, tris (butoxyethyl) phosphite, 4,4′-butylidene -Bis (3-methyl-6-t-butylphenyl-tetra-tridecyl) diphosphite, tetra (C12-C15 mixed alkyl) -4,
  • a pentaerythritol type phosphite compound tris (2,4-di-t-butylphenyl), from the viewpoint of further improving the heat aging resistance of the polyamide composition and reducing the generated gas.
  • Phosphites are preferred, and pentaerythritol phosphite compounds are more preferred.
  • pentaerythritol type phosphite compound examples include, but are not limited to, for example, 2,6-di-t-butyl-4-methylphenyl-phenyl-pentaerythritol diphosphite, 2,6-di- t-butyl-4-methylphenyl-methyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-2-ethylhexyl-pentaerythritol diphosphite, 2,6-di-t- Butyl-4-methylphenyl-isodecyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-lauryl-pentaerythritol diphosphite, 2,6-di-t-butyl-4- Methylphenyl-isotridecyl-pent
  • pentaerythritol type phosphite compounds listed above bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-) Ethylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-octyl-4-methylphenyl) penta Erythritol diphosphite and bis (2,4-dicumylphenyl) pentaerythritol diphosphite are preferred.
  • the content of the (F) phosphorus compound in the first polyamide composition is 0.1 to 20.0 mass% with respect to 100 mass% of the first polyamide composition. It is preferably 0.2 to 7.0% by mass, more preferably 0.5 to 3.0% by mass, still more preferably 0.5 to 2.5% by mass, and even more preferably 0.5%. It is -2.0 mass%, More preferably, it is 0.5-1.5 mass%.
  • the content of the (F) phosphorus compound in the first polyamide composition is preferably greater than (E) the metal hydroxide. (F) When the content of the phosphorus compound is within the above range, the first polyamide composition tends to be excellent in whiteness, reflow resistance, heat discoloration resistance, extrusion stability, and molding stability. is there.
  • the phosphorus compound (F) is preferably contained in an amount such that the phosphorus element concentration is 1,400 to 20,000 ppm relative to the first polyamide composition. More preferably, it is contained in an amount of 3,000 ppm, more preferably in an amount of 3,000 to 20,000 ppm, even more preferably in an amount of 3,000 to 10,000 ppm, More preferably, it is contained in an amount of 4,000 to 6,000 ppm.
  • the polyamide composition has whiteness, reflow resistance, heat discoloration resistance, extrusion stability, molding. Excellent processing stability.
  • (F) Phosphorus compound may be added during the polymerization of (A1) polyamide, but (A1) after the polyamide is polymerized, and added during the manufacture of the polyamide composition mixed with (E) the metal hydroxide described above. It is preferable to do. By adding it during the production of the polyamide composition, it is possible to reduce the heat history, (F) to suppress the decomposition of the phosphorus compound, etc., whiteness, reflow resistance, heat discoloration resistance, extrusion processability And a polyamide composition excellent in molding process stability can be obtained.
  • the metal element concentration can be measured by ICP emission spectroscopic analysis, and the metal element / phosphorus concentration derived from the (E) metal hydroxide and (F) phosphorus compound contained in the first polyamide composition.
  • (E) the metal hydroxide and (F) the phosphorus compound have a combined value of metal element concentrations derived from these components (excluding the phosphorus element) of 1,000 to 40, It is preferably contained in an amount of 000 ppm, more preferably in an amount of 2,000 to 30,000 ppm, further preferably in an amount of 3,000 to 25,000 ppm, Even more preferably, it is contained in an amount of ⁇ 20,000 ppm, and even more preferably in an amount of 5,000 ⁇ 10,000 ppm.
  • the metal element concentration is in the above range, the first polyamide composition tends to be more excellent in reflow resistance and light discoloration resistance.
  • the polyamide composition may contain a phenol-based antioxidant and / or an amine-based antioxidant as a heat stabilizer.
  • phenolic antioxidants include, but are not limited to, hindered phenolic compounds. Phenol-based antioxidants, particularly hindered phenol compounds, have the property of imparting heat resistance and light resistance to resins such as polyamide and fibers.
  • hindered phenol compound examples include, but are not limited to, for example, N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropylene Onamide), pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-tert-butyl- 4-hydroxy-hydrocinnamamide), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 3,9-bis ⁇ 2- [3- (3 -T-butyl-4-hydroxy-5-methylphenyl) propynyloxy] -1,1-dimethylethyl ⁇ -2,4,8,10-tetraoxaspiro [5,5] undecane 3,5-di-tert-butyl-4-
  • N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropionamide) )] is preferred.
  • the phenolic antioxidant mentioned above may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the content of the phenolic antioxidant in the first polyamide composition is preferably 0 to 1% by mass, more preferably 0.01 to 1% by mass with respect to 100% by mass of the first polyamide composition. %, More preferably 0.1 to 1% by mass.
  • the first polyamide composition tends to be superior in heat aging resistance and lower in the amount of generated gas.
  • amine-based antioxidants include, but are not limited to, poly (2,2,4-trimethyl-1,2-dihydroquinoline, 6-ethoxy-1,2-dihydro-2, 2,4-trimethylquinoline, phenyl- ⁇ -naphthylamine, 4,4-bis ( ⁇ , ⁇ -dimethyldendyl) diphenylamine, (p-toluenesulfonylamido) diphenylamine, N, N′-diphenyl-p-phenylenediamine, N, N′-di- ⁇ -naphthyl-p-phenylenediamine, N, N′-di (1,4-dimethylpentyl) -p-phenylenediamine, N-phenyl-N′-isopropyl-p-phenylenediamine, N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine, N- (1-methylheptyl
  • the content of the amine-based antioxidant in the first polyamide composition is preferably 0 to 1% by mass, more preferably 0.01 to 1% by mass with respect to 100% by mass of the first polyamide composition. %, More preferably 0.1 to 1% by mass.
  • the first polyamide composition tends to be superior in heat aging resistance and have a lower generated gas amount.
  • the first polyamide composition may further contain a light stabilizer from the viewpoint of light stability.
  • the light stabilizer has a property of imparting excellent heat resistance and light resistance to resins such as polyamide and fibers.
  • Examples of the light stabilizer include amine light stabilizers.
  • amine light stabilizers include, but are not limited to, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetra Methylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6, 6-tetramethylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6 6-tetramethylpiperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethyl Peridine, 4- (ethylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclo
  • amine light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) oxalate, bis (2, 2,6,6-tetramethyl-4-piperidyl) malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) ) Adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate, N, N′-bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedi Carboxamide and tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate are preferred.
  • bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N′-bis-2,2,6,6-tetramethyl-4 are used as amine light stabilizers.
  • -Piperidinyl-1,3-benzenedicarboxamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate are more preferred
  • N, N ′ -Bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedicarboxamide is more preferred.
  • the content of the amine light stabilizer in the first polyamide composition is preferably 0 to 2% by mass, more preferably 0.01 to 2% by mass with respect to 100% by mass of the first polyamide composition. %, More preferably 0.1 to 2% by mass.
  • the content of the amine light stabilizer is within the above range, the light stability and heat aging resistance of the polyamide composition can be further improved, and the amount of generated gas can be further reduced.
  • the first polyamide composition of the present invention may further contain other components as necessary.
  • other components include, but are not limited to, colorants such as pigments and dyes (including colored master batches), mold release agents, flame retardants, fibrillating agents, lubricants, and optical brighteners. , Plasticizers, copper compounds, alkali metal halide compounds, antistatic agents, fluidity improvers, reinforcing agents, spreader rubbers, reinforcing agents and other polymers.
  • suitable content ratios for the respective components are various. A person skilled in the art can easily set a suitable content for each of the other components described above.
  • the mixing method of (A1) polyamide and (B) titanium oxide is not limited to the following, but for example, (A1 ) Mixing polyamide, etc. and (B) titanium oxide using a tumbler, Henschel mixer, etc., supplying the resulting mixture to a melt kneader and kneading, or by using a single or twin screw extruder (A1) The method etc. which mix
  • the same method can also be used when blending a heat stabilizer.
  • A1 Polyamide or the like, (E) a metal hydroxide, and (F) a phosphorus compound are mixed, and the resulting mixture is obtained.
  • blend a phenol type / amine type antioxidant are mentioned.
  • the heat stabilizer (E) metal hydroxide, (F) phosphorus compound, and (G) phenol / amine antioxidant As a method of mixing the heat stabilizer (E) metal hydroxide, (F) phosphorus compound, and (G) phenol / amine antioxidant, a method of blending from a side feeder is preferred.
  • a method of blending from a side feeder By producing a polyamide composition by a method of blending from a side feeder, the polyamide composition tends to have excellent whiteness, reflow resistance, heat discoloration resistance, light discoloration resistance, and molding process stability.
  • the same method can also be used when blending (C) inorganic filler, (A1) polyamide etc. and (C) inorganic filler are mixed, and the resulting mixture is fed to a melt kneader.
  • examples thereof include a kneading method and a method of blending (C) an inorganic filler from a side feeder into (A1) polyamide or the like that has been melted with a single or twin screw extruder.
  • a method of supplying each component of the first polyamide composition to the melt kneader a method may be used in which all the components are supplied to the same supply port at a time, or each component is supplied from a different supply port. It is also possible to do it.
  • the melt kneading temperature is preferably 250 to 375 ° C. as the resin temperature.
  • the melt kneading time is preferably 0.25 to 5 minutes.
  • the apparatus for melt kneading is not particularly limited, and a known apparatus such as a single or twin screw extruder, a Banbury mixer, a mixing roll, or the like can be used.
  • the physical properties of the polyamide in the first polyamide composition of the present invention are equivalent to the physical properties of the first polyamide of the present invention. That is, the first polyamide of the present invention maintains its original physical properties even after it is melt-kneaded with other additives as necessary to form the first polyamide composition. For this reason, the polyamide contained in it can be specified by measuring said each physical property about the 1st polyamide in a 1st polyamide composition.
  • Trans isomer ratio, sulfuric acid relative viscosity ⁇ r, number average molecular weight Mn, molecular weight distribution Mw / Mn, melting peak temperature Tm1, Tm2, heat of fusion ⁇ Hm1, ⁇ Hm2, crystallization peak temperature Tc of the first polyamide composition of the present invention The ratio of crystallization enthalpy ⁇ Hc, glass transition temperature Tg, amino terminal, carboxyl terminal, and amino terminal amount to the total amount of active terminals can be measured by the method for measuring the physical properties of the polyamide described in the examples described later.
  • the value of the heat value is the ratio of polyamide to the composition. Calculate by converting. Since the measured values of the physical properties of the polyamide in the first polyamide composition of the present invention are in the same range as the measured values of the physical properties of the first polyamide of the present invention, the first polyamide composition of the present invention is Excellent heat resistance, whiteness, reflow resistance, aging resistance and releasability.
  • the polyamide composition molded article of the present invention (hereinafter sometimes simply referred to as a molded article) is formed by molding the above-mentioned first polyamide composition.
  • the polyamide composition molded article maintains a high trans isomer ratio of dicarboxylic acid monomer units, is excellent in reflow resistance, heat discoloration resistance, and light discoloration resistance, and can be suitably used for a reflector or the like.
  • the polyamide composition molded article can be obtained, for example, by molding the first polyamide composition described above by a known molding method.
  • Known molding methods include, but are not limited to, for example, press molding, injection molding, gas assist injection molding, welding molding, extrusion molding, blow molding, film molding, hollow molding, multilayer molding, and melting. Commonly known plastic molding methods such as spinning can be listed.
  • the polyamide composition molded article is excellent in heat resistance, whiteness, reflow resistance, aging resistance, and mold releasability.
  • the initial reflectance is preferably 96.5% or more.
  • the reflection retention after the reflow process is preferably 95% or more, and more preferably 96.2% or more.
  • the aging retention is preferably 86% or more, and more preferably 86.5% or more.
  • the polyamide composition molded product By including the first polyamide composition, the polyamide composition molded article is excellent in heat resistance, moldability, mechanical strength, and low water absorption. Therefore, the above-mentioned polyamide composition can be suitably used as various component materials such as reflectors, automobiles, electric and electronic, industrial materials, daily necessities and household goods, and for extrusion applications. It can be used suitably. About these specific uses, the thing similar to said 1st embodiment is mentioned.
  • the reflectance retention of the polyamide composition molded product can be measured by the method described in the examples described later.
  • the molded product containing the first polyamide composition of the present invention can be suitably used as a reflector.
  • the reflector by using a combination of (A1) polyamide, (E) metal hydroxide, and (F) phosphorus compound, it is possible to effectively suppress a decrease in reflectance due to heat.
  • A1 polyamide, (E) metal hydroxide, and (F) phosphorus compound it is possible to effectively suppress a decrease in reflectance due to heat.
  • About a reflectance it can measure by the method described in the Example mentioned later. It has been verified in Examples to be described later that the above-described combination can effectively suppress a decrease in reflectance in a reflector containing the polyamide composition of the present invention.
  • the polyamide composition molded article according to this embodiment is formed by molding a second polyamide composition containing a second polyamide having a specific trans isomer ratio and ⁇ Hm1 / ⁇ Hc. Details of the second polyamide, the second polyamide composition, and the molded polyamide composition will be described below.
  • the second polyamide of the present invention contains (a) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid, and (b) a diamine unit containing at least an aliphatic diamine.
  • Sulfuric acid relative viscosity ⁇ r is 2.5 or more, and obtained in the differential scanning calorimetry according to JIS-K7121, the heat of fusion ⁇ Hm1 obtained when the temperature is raised at 20 ° C./min and the temperature is lowered at 20 ° C./min.
  • ⁇ Hm / ⁇ Hc which is a ratio to the crystallization enthalpy ⁇ Hc obtained, 1.0 ⁇ Hm / ⁇ Hc ⁇ 2.2
  • the trans isomer ratio mol% of the dicarboxylic acid monomer unit in the polyamide is 75 ⁇ trans isomer ratio ⁇ 100.
  • the second polyamide of the present invention having the relative viscosity of sulfuric acid ⁇ r, ⁇ Hm1 / ⁇ Hc, which is the ratio of the heat of fusion ⁇ Hm1 and the crystallization enthalpy ⁇ Hc, and the trans isomer ratio as described above, is composed of the polyamide described below. It can be obtained by unit and manufacturing method. First, the structural unit of (A2) polyamide will be described in detail. ((A) dicarboxylic acid unit) As the dicarboxylic acid unit constituting the polyamide of the present embodiment, the same dicarboxylic acid as in the second embodiment can be used.
  • the diamine unit contains at least an aliphatic diamine. This aliphatic diamine may be linear or branched.
  • the diamine unit is not limited to the following, but for example, (b-1) an aliphatic diamine unit having a substituent branched from the main chain (branched aliphatic diamine), and (b-2) ) Linear aliphatic diamine unit and the like.
  • Other diamine units may include (b-3) alicyclic diamine units and (b-4) aromatic diamine units.
  • the aliphatic diamine unit preferably has 6 to 12 carbon atoms.
  • a carbon number of 6 or more is preferable because of excellent heat resistance and low water absorption, and a carbon number of 12 or less is preferable because of high temperature strength and crystallinity.
  • carbon number of a diamine unit 6-10 is more preferable.
  • (B-1) Aliphatic diamine unit having a substituent branched from the main chain (branched aliphatic diamine)
  • the (b) diamine unit preferably contains (b-1) an aliphatic diamine having a substituent branched from the main chain.
  • the diamine unit includes (b-1) a diamine unit having a substituent branched from the main chain, a polyamide having a high glass transition temperature Tg and high crystallinity (ie, high ⁇ Hm1 / ⁇ Hc) is obtained. Obtainable. For this reason, the polyamide composition of the present invention using this polyamide tends to satisfy more excellent fluidity, toughness, rigidity and the like at the same time.
  • the aliphatic diamine unit having a substituent branched from the main chain (b-1) may be simply referred to as (b-1).
  • the “substituent branched from the main chain” in (b-1) is not limited to the following, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group.
  • the diamine constituting such (b-1) is not limited to the following, but for example, 2-methylpentamethylenediamine (also referred to as 2-methyl-1,5-diaminopentane), 2 2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methyl-1,8-octanediamine (also called 2-methyloctamethylenediamine), and 2,4-dimethyloctane Examples thereof include branched saturated aliphatic diamines having 3 to 20 carbon atoms such as methylene diamine. Among these, 2-methylpentamethylenediamine and 2-methyl-1,8-octanediamine are preferable, and 2-methylpentamethylenediamine is more preferable. By including such (b-1), it tends to be a polyamide composition having superior heat resistance and rigidity. As the diamine constituting (b-1), only one kind may be used alone, or two or more kinds may be used in combination.
  • the (b) diamine unit preferably contains 10 mol% or more of (b-1).
  • the proportion (mol%) of (b-1) in the diamine unit is preferably 10 to 80 mol%, more preferably 20 to 60 mol%, still more preferably 30 to 50 mol%. is there.
  • the ratio of (b-1) in the diamine unit is preferably in the above range from the viewpoint of obtaining a polyamide having a high glass transition temperature Tg and ⁇ Hm1 / ⁇ Hc within the range of the present application. For this reason, the polyamide composition using this polyamide tends to be a polyamide composition that is superior in fluidity, toughness, and rigidity.
  • (B-2) Linear aliphatic diamine unit may be simply referred to as (b-2).
  • the aliphatic diamine constituting (b-2) is not limited to the following, but examples include ethylene diamine, propylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine.
  • linear saturated aliphatic diamines having 2 to 20 carbon atoms such as nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, and tridecamethylenediamine.
  • (B-3) Alicyclic diamine unit may be simply referred to as (b-3).
  • the alicyclic diamine (hereinafter also referred to as “alicyclic diamine”) constituting (b-3) is not limited to the following, but for example, 1,4-cyclohexanediamine, 1,3 -Cyclohexanediamine, 1,3-cyclopentanediamine and the like.
  • (B-4) Aromatic diamine unit hereinafter, the (b-4) aromatic diamine unit may be simply referred to as (b-4).
  • Examples of the aromatic diamine constituting (b-4) include metaxylylenediamine, paraxylylenediamine, paraphenylenediamine, metaphenylenediamine, and the like.
  • diamine units (b-2) to (b-4), (b-2) and (b-3) are preferable, and a linear saturated aliphatic group having 4 to 13 carbon atoms is more preferable.
  • the polyamide composition tends to be excellent in heat resistance, fluidity, toughness, low water absorption, rigidity, and the like.
  • diamine may be used individually by 1 type and may be used in combination of 2 or more types.
  • the total ratio (mol%) of the diamine units (b-2) to (b-4) is preferably 50 mol% or more, and preferably 60 mol% or more with respect to the entire diamine unit (b). More preferred.
  • the polyamide composition tends to be excellent in fluidity, toughness, and rigidity.
  • the (A2) polyamide may further contain a trivalent or higher polyvalent aliphatic amine such as bishexamethylene triamine, if necessary. Trivalent or higher polyvalent aliphatic amines may be used alone or in combination of two or more.
  • the (A2) polyamide of the present invention includes (c) a lactam unit (c-1) and / or an aminocarboxylic acid unit (c) in addition to the above (a) and (b), as long as the object of the present invention is not impaired. -2) can be further contained. By including such a unit, a polyamide composition that is superior in toughness tends to be obtained.
  • the lactam and aminocarboxylic acid constituting the lactam unit (c-1) and aminocarboxylic acid (c-2) refer to a lactam and aminocarboxylic acid capable of polymerization or condensation polymerization.
  • lactam and aminocarboxylic acid constituting the lactam unit (c-1) and aminocarboxylic acid unit (c-2) the same lactam and aminocarboxylic acid as in the second embodiment can be used.
  • the terminal of (A2) polyamide used in the present invention may be end-capped with a known end-capping agent.
  • a known end-capping agent is also added as a molecular weight regulator in the production of (A2) polyamide from the above-described dicarboxylic acid and diamine, and lactam and / or aminocarboxylic acid used as necessary. Can do.
  • end-capping agents include, but are not limited to, acid anhydrides such as monocarboxylic acids, monoamines, and phthalic anhydride, monoisocyanates, monoacid halides, monoesters, and monoalcohols. Etc. Among these, monocarboxylic acid and monoamine are preferable.
  • acid anhydrides such as monocarboxylic acids, monoamines, and phthalic anhydride
  • monoisocyanates monoacid halides
  • monoesters monoalcohols.
  • monocarboxylic acid and monoamine are preferable.
  • A2 When the terminal of the polyamide is sealed with a terminal sealing agent, it tends to be a polyamide composition having better thermal stability. Only one type of end capping agent may be used alone, or two or more types may be used in combination.
  • the monocarboxylic acid that can be used as the end-capping agent is not limited to the following as long as it has reactivity with an amino group that can be present at the terminal of the (A2) polyamide.
  • formic acid Aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid; cyclohexanecarboxylic acid, etc.
  • aromatic monocarboxylic acids such as benzoic acid, toluic acid, ⁇ -naphthalenecarboxylic acid, ⁇ -naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid.
  • acetic acid is particularly preferred.
  • a monocarboxylic acid may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the monoamine that can be used as the end-capping agent is not limited to the following as long as it has reactivity with the carboxyl group that can be present at the terminal of the (A2) polyamide, but for example, methylamine, Aliphatic monoamines such as ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; and aniline , Aromatic monoamines such as toluidine, diphenylamine, and naphthylamine. Monoamines may be used alone or in combination of two or more.
  • the polyamide composition containing (A2) polyamide end-capped with an end-capping agent tends to be excellent in heat resistance, fluidity, toughness, low water absorption, and rigidity.
  • the second method for producing a polyamide of the present invention comprises (a) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid, and (b) a diamine unit containing at least an aliphatic diamine.
  • the second method for producing a polyamide of the present invention is a method for obtaining a polyamide having a specific terminal structure (hereinafter referred to as a precursor polyamide) and further heat-treating it at a temperature lower than the melting point (A2) to obtain a polyamide.
  • a “hot melt polymerization / solid phase polymerization method” is preferable.
  • the method for obtaining the precursor polyamide (thermal melt polymerization method) and the heat treatment (solid phase polymerization method) will be described in detail.
  • the method for obtaining the precursor polyamide is not particularly limited, and examples thereof include the methods exemplified below. 1) A method in which an aqueous solution or a suspension of water of a dicarboxylic acid / diamine salt or a mixture thereof is heated and polymerized while maintaining a molten state (hereinafter referred to as hot melt polymerization method).
  • prepolymer ⁇ Called the extrusion polymerization method A method in which an aqueous solution or suspension of water of a dicarboxylic acid / diamine salt or a mixture thereof is heated, and the precipitated prepolymer is melted again with an extruder such as a kneader to increase the degree of polymerization (hereinafter referred to as prepolymer ⁇ Called the extrusion polymerization method).
  • prepolymer ⁇ Called the extrusion polymerization method A method of polymerizing using a dicarboxylic acid halide equivalent to a dicarboxylic acid and a diamine.
  • the hot melt polymerization method is preferable from the viewpoint of increasing the molecular weight by polymerization in a short time and suppressing gelation.
  • the addition amount of the dicarboxylic acid constituting the dicarboxylic acid unit and (b) the addition amount of the diamine constituting the diamine unit are about the same molar amount.
  • the dicarboxylic acid unit preferably contains 50 to 100 mol% of 1,4-cyclohexanedicarboxylic acid units (based on the total number of moles of dicarboxylic acid), more preferably 60 to 100 mol%, more preferably 70 to 100 mol. % Is more preferable, and 100 mol% is most preferable.
  • the trans isomer / cis isomer ratio (molar ratio) of the alicyclic dicarboxylic acid as the raw material monomer is preferably 50/50 to 0/100, more preferably 40/60 to 10/90. More preferably, it is 35/65 to 15/85.
  • the trans / cis ratio (molar ratio) of the alicyclic dicarboxylic acid can be determined by liquid chromatography (HPLC) or nuclear magnetic resonance spectroscopy (NMR).
  • the (b) diamine unit preferably includes (b-1) a diamine unit having a substituent branched from the main chain, and the proportion is preferably 10 to 80 mol%, more preferably 20 to 60 mol%, More preferred is ⁇ 50 mol%.
  • (B-1) is most preferably 2-methyl-5-pentamethylenediamine.
  • a diamine may be added in addition to (b) for adjusting the molecular weight and terminal.
  • the diamine to be added 2-methyl-5-pentamethylenediamine is preferable.
  • the amount of diamine added relative to the diamine is 0 to 5.0 mol%, more preferably 0 to 2.0 mol%, and still more preferably 0 to 1.0 mol% in terms of a molar ratio.
  • a phosphorus compound as a heat stabilizer (catalyst) at the time of hot melt polymerization.
  • the heat stabilizer is not particularly limited, but sodium hypophosphite is preferable.
  • the polyamide production method preferably further includes a step of increasing the degree of polymerization of the polyamide. Moreover, the sealing process which seals the terminal of the obtained polymer with a terminal sealing agent may be included as needed.
  • the physical property of the precursor polyamide is the ratio of the amino terminal amount [NH 2 ] to the active terminal total amount ([NH 2 ] + [COOH]) [NH 2 ] / ([NH 2 ] + [COOH]) is 0. It is preferably less than 5, more preferably from 0.01 to less than 0.5, and even more preferably from 0.05 to 0.4.
  • the total amount of active terminals ([NH 2 ] + [COOH]) is preferably 110 to 200 ⁇ eq / g, more preferably 110 to 180 ⁇ eq / g, and even more preferably 110 to 160 ⁇ eq / g.
  • the terminal structure of the polyamide is controlled by adjusting the amounts of the structural units (a) to (c) of the polyamide, the end-capping agent and the additional diamine. Can be obtained.
  • the heat treatment in the production method of the present invention can use the same method as the heat treatment in the second embodiment, and the preferred temperature range is also the same.
  • the trans isomer ratio of the dicarboxylic acid monomer unit in the second polyamide of the present invention is more than 75 mol% and not more than 100 mol%.
  • the trans isomer ratio is more preferably more than 75 mol% and 100 mol% or less, further preferably more than 75 mol% and 90 mol% or less, and more preferably 80 mol% or more and 90 mol% or less.
  • the polyamide of the present invention is highly crystallized because the trans isomer ratio is in the above range, the polyamide and the polyamide composition of the present invention have a high melting point, toughness and rigidity, in addition to the characteristics of being high. It tends to have the property of simultaneously satisfying the thermal rigidity due to the glass transition temperature (Tg), the fluidity, which is usually a property contrary to heat resistance, and the high crystallinity.
  • Tg glass transition temperature
  • the fluidity which is usually a property contrary to heat resistance
  • the trans isomer ratio of the dicarboxylic acid monomer unit in such a polyamide can be controlled by controlling the carboxyl terminal amount of the polyamide and the method for producing the polyamide of the present invention.
  • the trans isomer ratio (molar ratio) of the 1,4-cyclohexanedicarboxylic acid monomer unit of the polyamide composition molded article can be determined by nuclear magnetic resonance spectroscopy (NMR).
  • Sulfuric acid relative viscosity ⁇ r of polyamide uses sulfuric acid relative viscosity ⁇ r at 25 ° C. as an index.
  • the sulfuric acid relative viscosity ⁇ r at 25 ° C. is 2.5 or more. Preferably it is 2.6 to 5.0, more preferably 2.7 to 4.0.
  • Effective methods for controlling the relative viscosity ⁇ r of sulfuric acid at 25 ° C. for polyamides include, for example, methods for controlling the addition amount of diamine and end-capping agent as additives during hot melt polymerization of polyamide, and polymerization conditions. Method.
  • the polyamide When the sulfuric acid relative viscosity ⁇ r at 25 ° C. is 2.5 or more, the polyamide is excellent in mechanical properties such as toughness and strength. From the viewpoint of melt fluidity, a polyamide having excellent fluidity can be obtained when the sulfuric acid relative viscosity ⁇ r at 25 ° C. of the polyamide is 5.0 or less.
  • the relative viscosity of sulfuric acid at 25 ° C. can be measured at 25 ° C. in 98% sulfuric acid according to JIS-K6920.
  • a number average molecular weight Mn obtained by GPC (gel permeation chromatography), a weight average molecular weight Mw, and a molecular weight distribution Mw / Mn can be used.
  • the number average molecular weight Mn of the polyamide is preferably greater than 15000, more preferably 16000 or more, and even more preferably 17000 or more.
  • Mw / Mn which shows the molecular weight distribution of (A2) polyamide becomes like this.
  • Mn and Mw can produce
  • the melting peak temperature Tm1 of the polyamide is preferably 300 ° C. or higher, more preferably 310 ° C. or higher. Further, the melting peak temperature Tm1 of the polyamide is preferably 350 ° C. or lower, more preferably 345 ° C. or lower, and further preferably 340 ° C. or lower.
  • Tm1 of the polyamide is 300 ° C. or higher, a polyamide composition excellent in heat resistance tends to be obtained.
  • (A2) polyamide melting peak temperature Tm1 is 350 ° C. or lower, (A2) thermal decomposition of polyamide in melt processing such as extrusion and molding tends to be further suppressed.
  • the melting peak temperature Tm2 of the polyamide is preferably 270 ° C. or higher, more preferably 275 ° C. or higher, and further preferably 280 ° C. or higher. Further, the melting peak temperature Tm2 of (A2) polyamide is preferably 350 ° C. or lower, more preferably 340 ° C. or lower, further preferably 335 ° C. or lower, and still more preferably 330 ° C. or lower. (A2) When the melting peak temperature Tm2 of the polyamide is 270 ° C. or higher, a polyamide composition excellent in heat resistance tends to be obtained. Moreover, (A2) When the melting peak temperature Tm2 of the polyamide is 350 ° C.
  • the melting peak temperatures Tm1 and Tm2 of the polyamide can be measured according to JIS-K7121 by the method described in Examples below.
  • the heat of fusion ⁇ Hm1 and the crystallization enthalpy ⁇ Hc of the polyamide are each preferably 30 J / g or more, more preferably 35 J / g or more, and further preferably 40 J / g or more.
  • the upper limit of the heat of fusion ⁇ Hm1 and the crystallization enthalpy ⁇ Hc is not particularly limited and is preferably as high as possible.
  • the heat of fusion ⁇ Hm1 and the crystallization enthalpy ⁇ Hc of the polyamide are each 30 J / g or more, the heat resistance of the polyamide composition tends to be further improved.
  • the heat of fusion ⁇ Hm1 and the crystallization enthalpy ⁇ Hc of the polyamide can be measured according to JIS-K7121 by the method described later.
  • the heat of fusion ⁇ Hm2 of the polyamide is preferably 20 J / g or more, more preferably 25 J / g or more, and further preferably 30 J / g or more.
  • the upper limit of the heat of fusion ⁇ Hm2 is not particularly limited and is preferably as high as possible.
  • the heat resistance of the polyamide composition tends to be further improved.
  • the heat of fusion ⁇ Hm1 is a heat of fusion reflecting the heat history received by the polyamide during heat treatment or cooling, and is different from the heat of fusion inherent in the polyamide.
  • ⁇ Hc is a crystallization enthalpy obtained through a cooling process (slow cooling) after complete melting, and is equal to the heat of fusion inherent in polyamide. Therefore, ⁇ Hm1 / ⁇ Hc means the ratio between the heat of fusion inherent in polyamide and the heat of fusion of polyamide subjected to a thermal history.
  • the ratio ( ⁇ Hm1 / ⁇ Hc) between the heat of fusion ⁇ Hm1 and the crystallization enthalpy ⁇ Hc of the polyamide of the present invention is greater than 1.0 and less than or equal to 2.2, preferably greater than 1.4 and less than 2.2 from the viewpoint of heat resistance. Or less, more preferably 1.5 or more and 2 or less, still more preferably 1.6 or more and 2.2 or less, and particularly preferably 1.7 or more and 2.2 or less.
  • Tm1-Tc ⁇ Difference between Polyamide Melting Peak Temperature Tm1 and Crystallization Peak Temperature Tc (Tm1-Tc)> (A2)
  • Tm1-Tc is preferably higher than 40 ° C and lower than 90 ° C, and more preferably 50 ° C to 80 ° C.
  • the measurement of the heat of fusion ⁇ Hm1 and the crystallization enthalpy ⁇ Hc of the polyamide can be performed according to JIS-K7121, and the heat of fusion ⁇ Hm1 is measured when the temperature of the polyamide is raised at a rate of temperature increase of 20 ° C./min (the first temperature rise).
  • the endothermic peak appearing on the highest temperature side of the endothermic peak (melting peak) appearing at the time) is the peak area of Tm when the melting peak temperature is Tm (° C.).
  • a peak having ⁇ H of 1 J / g or more is regarded as a peak, the highest temperature is defined as a melting peak temperature Tm1, and ⁇ Hm1 is a sum of peak areas.
  • the crystallization enthalpy ⁇ Hc is the Tc value when the temperature of the exothermic peak (crystallization peak) that appears when the polyamide composition molded article is cooled at a temperature decrease rate of 20 ° C./min is the crystallization peak temperature Tc (° C.). It is the peak area.
  • Diamond-DSC manufactured by PERKIN-ELMER can be used as the measuring apparatus.
  • the melting peak temperature Tm2 and the heat of fusion ⁇ Hm2 of polyamide can be measured as follows. After the first temperature increase, the temperature is maintained for 2 minutes in the molten state at the maximum temperature increase, then the temperature is decreased to 30 ° C. at a temperature decrease rate of 20 ° C./min, maintained at 30 ° C. for 2 minutes, and then the temperature increase rate is 20.
  • the endothermic peak temperature that appears at the highest temperature side of the endothermic peak that appears when the temperature is similarly raised at the same temperature (° C./min) is the melting peak temperature Tm2 of the polyamide itself, and the peak area at this melting peak temperature. Is the heat of fusion ⁇ Hm2 of the polyamide.
  • the measurement of the melting peak temperature Tm2 and the heat of fusion ⁇ Hm2 of polyamide can be performed according to JIS-K7121 as described in the following examples.
  • Examples of the measuring device for the melting peak temperature and the heat of fusion include Diamond-DSC manufactured by PERKIN-ELMER.
  • the glass transition temperature Tg of the polyamide is preferably 90 ° C. or higher, more preferably 110 ° C. or higher, still more preferably 120 ° C. or higher, even more preferably 130 ° C. or higher, and even more preferably. Is 135 ° C. or higher. Further, the glass transition temperature Tg of the (A2) polyamide is preferably 170 ° C. or lower, more preferably 165 ° C. or lower, and further preferably 160 ° C. or lower. (A2) When the glass transition temperature Tg of the polyamide is 90 ° C. or higher, a polyamide composition excellent in heat discoloration resistance and chemical resistance tends to be obtained.
  • the glass transition temperature Tg of (A2) polyamide is 170 ° C. or less, a molded product having a good appearance tends to be obtained.
  • the glass transition temperature Tg of the polyamide can be measured according to JIS-K7121 as described in the following examples. Examples of the measuring device for the glass transition temperature Tg include Diamond-DSC manufactured by PERKIN-ELMER.
  • Polymer end> Although it does not specifically limit as a polymer terminal of the polyamide used for this invention, It can classify
  • the amino terminal is a polymer terminal having an amino group (—NH 2 group) and is derived from the raw material (b) diamine unit.
  • the amino terminal amount ([NH 2 ]) is preferably 5 to 100 ⁇ equivalent / g, more preferably 5 to 70 ⁇ equivalent / g, and further preferably 5 to 50 ⁇ equivalent / g with respect to 1 g of polyamide. More preferably 5 to 30 ⁇ eq / g, and even more preferably 5 to 20 ⁇ eq / g.
  • the amino terminal amount can be measured by neutralization titration. Specifically, 3.0 g of polyamide is dissolved in 100 mL of a 90 mass% phenol aqueous solution, and the obtained solution is titrated with 0.025N hydrochloric acid to obtain the amino terminal amount ( ⁇ equivalent / g). The end point is determined from the indicated value of the pH meter.
  • the carboxyl terminal is a polymer terminal having a carboxyl group (—COOH group) and is derived from the raw material (a) dicarboxylic acid.
  • the carboxyl terminal amount ([COOH]) is preferably 5 to 150 ⁇ equivalent / g, more preferably 5 to 140 ⁇ equivalent / g, and further preferably 5 to 130 ⁇ equivalent / g with respect to 1 g of polyamide. Even more preferably, it is 5 to 120 ⁇ eq / g, and even more preferably 5 to 110 ⁇ eq / g.
  • the carboxyl end amount When the carboxyl end amount is in the above range, the whiteness, reflow resistance, heat discoloration resistance, and light discoloration resistance of the polyamide composition tend to be more excellent.
  • the carboxyl end amount can be measured by neutralization titration. Specifically, 4.0 g of polyamide is dissolved in 50 mL of benzyl alcohol, and the obtained solution is titrated with 0.1 N NaOH to obtain the carboxyl terminal amount ( ⁇ equivalent / g). The end point is determined from the discoloration of the phenolphthalein indicator.
  • the total amount of the amino terminal amount ([NH 2 ]) and the carboxyl terminal amount ([COOH]) is defined as the active terminal total amount ([NH 2 ] + [COOH]).
  • the total amount of active terminals is preferably 10 to 200 ⁇ eq / g, more preferably 10 to 150 ⁇ eq / g, and still more preferably 10 to 120 ⁇ eq / g, based on 1 g of (A2) polyamide.
  • [NH 2 ] / ([NH 2 ] + [COOH]) which is the ratio of the amino terminal amount to the total active terminal amount, is preferably less than 0.5, more preferably less than 0.4, More preferably, it is less than 0.3, Most preferably, it is less than 0.1.
  • ⁇ Hm1 / ⁇ Hc can be controlled to be greater than 1.0 and less than or equal to 2.2 because the ratio of the amino terminal amount and the carboxyl terminal amount and the ratio of the amino terminal amount to the active terminal total amount are within the above ranges.
  • the heat discoloration resistance and light discoloration resistance of the polyamide composition tend to be more excellent.
  • Examples of the method for controlling the ratio of the amino terminal amount to the total active terminal amount include a method of controlling the addition amount of diamine and terminal blocking agent as additives during hot melt polymerization of polyamide, and the polymerization conditions. .
  • the cyclic amino terminus is a polymer terminus having a cyclic amino group (a group represented by the following (formula 1)).
  • R represents a substituent bonded to the carbon constituting the piperidine ring.
  • Specific examples of R include a hydrogen atom, a methyl group, an ethyl group, and a t-butyl group.
  • the amount of the cyclic amino terminal is preferably 0 ⁇ e equivalent / g or more and 65 ⁇ e equivalent / g or less, more preferably 10 ⁇ e equivalent / g or more and 60 ⁇ equivalent / g or less, with respect to 1 g of (A2) polyamide. Preferably they are 20 microequivalent / g or more and 55 microequivalent / g or less.
  • the polyamide composition of the present invention tends to be more excellent in toughness, hydrolysis resistance, and processability.
  • the amount of the cyclic amino terminus can be measured using 1 H-NMR. For example, there is a method of calculation based on the integral ratio of hydrogen bonded to carbon adjacent to the nitrogen atom of the heterocyclic ring of nitrogen and hydrogen bonded to carbon adjacent to the nitrogen atom of the amide bond of the polyamide main chain.
  • Cyclic amino terminal can be generated by dehydration reaction of cyclic amine and carboxyl terminal, and can also be generated by deammonia reaction of amino terminal in the polymer molecule. Cyclic amine is added as end-capping agent. It can also be produced by the diamine having a pentamethylenediamine skeleton, which is a raw material for polyamide, and cyclizing by deammonia reaction.
  • the cyclic amino terminal is preferably derived from a raw material diamine. Without adding cyclic amine as an end-capping agent at the initial stage of polymerization, the cyclic amino terminal is generated from the raw material diamine, so that the low molecular weight carboxylic acid terminal is prevented from being blocked at the initial stage of polymerization. Thus, the polymerization reaction rate of the polyamide is maintained high, and as a result, a high molecular weight product tends to be obtained. As described above, when a cyclic amine is generated during the reaction, the carboxylic acid terminal is sealed with the cyclic amine at a later stage of the polymerization, so that a high molecular weight polyamide is easily obtained.
  • a cyclic amine that generates a cyclic amino terminus can be generated as a by-product during the polymerization reaction of polyamide.
  • the higher the reaction temperature the higher the reaction rate. Therefore, in order to make the cyclic amino terminal of the polyamide (A2) constant, it is preferable to promote the generation of cyclic amine. Therefore, the reaction temperature for the polymerization of the precursor polyamide is preferably 300 ° C. or higher, and more preferably 320 ° C. or higher.
  • control is performed by appropriately adjusting the polymerization temperature, the holding time of the reaction temperature of 300 ° C. or more during the polymerization step, the addition amount of the amine forming the cyclic structure, and the like. The method of doing is mentioned.
  • the end by the sealant is an end formed when a sealant is added during polymerization.
  • the sealing agent include the above-described end sealing agents.
  • the other terminal is a polymer terminal not classified in the above 1) to 4), such as a terminal generated by deammonia reaction at the amino terminal or a terminal generated by decarboxylation from the carboxylic acid terminal. It is done.
  • the second polyamide composition of the present invention contains the first polyamide of the present invention and at least one selected from an inorganic filler, a heat stabilizer, and a light stabilizer.
  • an inorganic filler as the second polyamide composition, it has excellent heat resistance and stability under heat and has a high melting point.
  • the second polyamide composition does not impair the properties of the polyamide. It will be.
  • the components of the polyamide composition will be described.
  • inorganic filler It does not specifically limit as an inorganic filler which comprises the 2nd polyamide composition of this invention, A well-known material can be used.
  • a well-known material can be used.
  • An inorganic filler may be used
  • the glass fiber and the carbon fiber may have a round shape or a flat shape in cross section.
  • the flat cross section include a rectangle, an oval close to a rectangle, an ellipse, and a bowl shape with a narrowed central portion in the longitudinal direction.
  • the polyamide composition has a number average fiber diameter of 3 to 30 ⁇ m and a weight average fiber length of 100 to 750 ⁇ m.
  • a glass fiber or carbon fiber having an aspect ratio (L / D) of 10 to 100 between the weight average fiber length (L) and the number average fiber diameter (D) is preferably used.
  • the number average fiber diameter of the inorganic filler in the polyamide composition is, for example, putting the polyamide composition in an electric furnace, incinerating the organic matter contained in the polyamide composition, and, for example, 100 or more glass fibers from the residue.
  • the number average fiber diameter can be determined by arbitrarily selecting, observing with a SEM photograph, and measuring the fiber diameter.
  • the glass fiber is arbitrarily selected in the same manner, and the weight average fiber length is measured by measuring the fiber length using an SEM photograph at a magnification of 1000 times. be able to.
  • the inorganic filler reinforcing fibers having a weight average fiber length of 1 to 15 mm are more preferable.
  • the weight average fiber length of such reinforcing fibers is 1 to 15 mm, preferably 3 to 12 mm, from the viewpoint of improving mechanical strength, rigidity and moldability.
  • the weight average fiber length of the reinforcing fibers is the length of 400 reinforcing fibers arbitrarily selected using an image analyzer after observing with an optical microscope after burning or dissolving only the polyamide of the polyamide composition. It is calculated
  • the calculation formula for the weight average fiber length for each reinforcing fiber is expressed by the following formula.
  • “i” is an integer from 1 to 400.
  • Weight average fiber length ⁇ (Li 2 ) / ⁇ Li
  • a weight average fiber length is a value applied with respect to the reinforced fiber of the state contained in the polyamide composition of this invention. That is, the weight average fiber length of the reinforcing fiber before blending with the polyamide is not limited to the above.
  • the material of the reinforcing fiber is not particularly limited as long as it is a reinforcing fiber generally used for polyamide.
  • inorganic fiber such as glass fiber, carbon fiber, boron fiber, metal fiber (eg, stainless fiber, aluminum fiber, copper fiber), polyparaphenylene terephthalamide fiber, polymetaphenylene terephthalamide fiber, polyparaffin Organic materials such as phenylene isophthalamide fiber, polymetaphenylene isophthalamide fiber, wholly aromatic polyamide fiber such as fiber obtained from condensate of diaminodiphenyl ether and terephthalic acid or isophthalic acid, or wholly aromatic liquid crystal polyester fiber Is mentioned.
  • the said material may be used independently and 2 or more types may be used together. Especially, it is preferable that it is 1 or more types chosen from a glass fiber, a carbon fiber, a boron fiber, and a metal fiber from a viewpoint of an improvement of mechanical strength and rigidity, and a glass fiber and / or a carbon fiber are more preferable.
  • the reinforcing fiber is not particularly limited with respect to the average fiber diameter of the single fiber, but, for example, those having a diameter of 5 to 25 ⁇ m are generally used.
  • the average fiber diameter of single fibers is obtained by observing the reinforcing fibers to be used under an optical microscope and calculating the average value when measuring 400 fiber diameters arbitrarily selected using an image analyzer. It is done. Further, as the reinforcing fiber, it is preferable to use roving which is a continuous fiber in which single fibers are bundled.
  • An inorganic filler such as glass fiber or carbon fiber may be surface-treated with a surface treatment agent such as a silane coupling agent.
  • a surface treatment agent such as a silane coupling agent.
  • silane coupling agent the same one as in the first embodiment can be used.
  • the fibrous inorganic filler such as glass fiber or carbon fiber may further contain a sizing agent.
  • a sizing agent the same sizing agent as in the first embodiment can be used.
  • the polyamide composition may contain a heat stabilizer.
  • a heat stabilizer phosphorus stabilizer (phosphorus compound), phenolic antioxidant, amine antioxidant, Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa of the periodic table And one or more selected from the group consisting of metal salts of Group IVb elements and halides of alkali metals and alkaline earth metals. Specific examples of the heat stabilizer are shown below.
  • phosphorus compounds include organic phosphorus compounds.
  • organic phosphorus compounds include, but are not limited to, pentaerythritol phosphite compounds, trioctyl phosphites, trilauryl phosphites, tridecyl phosphites, octyl diphenyl phosphites, trisisodecyl phosphites.
  • phenyl diisodecyl phosphite phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl (tridecyl) phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, tris (2,4-di-tert-butyl-5-methylphenyl) phosphite, tris (butoxyethyl) phosphite, 4,4′-butylidene -Bis (3-methyl-6-t-butylphenyl-tetra-tridecyl) diphosphite, tetra (C12-C15 mixed alkyl) -4,
  • a pentaerythritol type phosphite compound tris (2,4-di-t-butylphenyl), from the viewpoint of further improving the heat aging resistance of the polyamide composition and reducing the generated gas.
  • Phosphites are preferred, and pentaerythritol phosphite compounds are more preferred.
  • pentaerythritol type phosphite compound examples include, but are not limited to, for example, 2,6-di-t-butyl-4-methylphenyl-phenyl-pentaerythritol diphosphite, 2,6-di- t-butyl-4-methylphenyl-methyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-2-ethylhexyl-pentaerythritol diphosphite, 2,6-di-t- Butyl-4-methylphenyl-isodecyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-lauryl-pentaerythritol diphosphite, 2,6-di-t-butyl-4- Methylphenyl-isotridecyl-pent
  • pentaerythritol type phosphite compounds listed above bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-) Ethylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-octyl-4-methylphenyl) penta Erythritol diphosphite and bis (2,4-dicumylphenyl) pentaerythritol diphosphite are preferred.
  • the content of the phosphorus compound in the polyamide composition is 0.1 to 20.0 mass% with respect to 100 mass% of the polyamide composition. It is preferably 0.2 to 7.0% by mass, more preferably 0.5 to 3.0% by mass, still more preferably 0.5 to 2.5% by mass, and even more preferably 0.5%. It is -2.0 mass%, More preferably, it is 0.5-1.5 mass%.
  • the polyamide composition tends to be excellent in whiteness, reflow resistance, heat discoloration resistance, extrusion process stability, and molding process stability.
  • the polyamide composition may contain a phenol-based antioxidant and / or an amine-based antioxidant as a heat stabilizer.
  • phenolic antioxidants include, but are not limited to, hindered phenolic compounds. Phenol-based antioxidants, particularly hindered phenol compounds, have the property of imparting heat resistance and light resistance to resins such as polyamide and fibers.
  • hindered phenol compound examples include, but are not limited to, for example, N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropylene Onamide), pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-tert-butyl- 4-hydroxy-hydrocinnamamide), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 3,9-bis ⁇ 2- [3- (3 -T-butyl-4-hydroxy-5-methylphenyl) propynyloxy] -1,1-dimethylethyl ⁇ -2,4,8,10-tetraoxaspiro [5,5] undecane 3,5-di-tert-butyl-4-
  • N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropionamide) )] is preferred.
  • the phenolic antioxidant mentioned above may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the content of the phenolic antioxidant in the polyamide composition is preferably 0 to 1% by mass, more preferably 0.01 to 1% by mass, even more preferably 100% by mass of the polyamide composition. Is 0.1 to 1% by mass. When the content of the phenolic antioxidant is within the above range, the polyamide composition tends to be superior in heat aging resistance and lower in the amount of generated gas.
  • amine-based antioxidants include, but are not limited to, poly (2,2,4-trimethyl-1,2-dihydroquinoline, 6-ethoxy-1,2-dihydro-2, 2,4-trimethylquinoline, phenyl- ⁇ -naphthylamine, 4,4-bis ( ⁇ , ⁇ -dimethyldendyl) diphenylamine, (p-toluenesulfonylamido) diphenylamine, N, N′-diphenyl-p-phenylenediamine, N, N′-di- ⁇ -naphthyl-p-phenylenediamine, N, N′-di (1,4-dimethylpentyl) -p-phenylenediamine, N-phenyl-N′-isopropyl-p-phenylenediamine, N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine, N- (1-methylheptyl
  • the content of the amine antioxidant in the polyamide composition is preferably 0 to 1% by mass, more preferably 0.01 to 1% by mass, and still more preferably 100% by mass of the polyamide composition. Is 0.1 to 1% by mass.
  • the polyamide composition tends to be more excellent in heat aging resistance and lower in the amount of generated gas.
  • the metal salt of the elements of Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa, and Group IVb of the periodic table is not particularly limited and is preferably a heat stabilizer. Copper salt.
  • the copper salt is not particularly limited.
  • copper halide copper iodide, cuprous bromide, cupric bromide, cuprous chloride, etc.
  • copper acetate copper propionate
  • benzoic acid examples thereof include copper oxide, copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate and copper stearate, and a copper complex salt in which copper is coordinated to a chelating agent such as ethylenediamine and ethylenediaminetetraacetic acid.
  • metal salt especially copper salt
  • a polyamide composition having excellent heat aging resistance and capable of suppressing metal corrosion (hereinafter also simply referred to as “metal corrosion”) of screws and cylinders during extrusion is obtained. be able to.
  • the said metal salt may be used individually by 1 type, and may be used in combination of 2 or more types.
  • the compounding amount of the copper salt in the polyamide composition is preferably 0.01 to 0.2 parts by mass, more preferably 0.02 to 0 parts per 100 parts by mass of the polyamide composition. 15 parts by mass.
  • the amount is within the above range, the heat aging resistance is further improved, and copper precipitation and metal corrosion can be suppressed.
  • the content of copper element is preferably 10 to 500 ppm, more preferably 30 to 500 ppm, still more preferably 50 to 300 ppm with respect to the total amount of the polyamide composition. .
  • Alkali metal and alkaline earth metal halides are not particularly limited, and examples thereof include potassium iodide, potassium bromide, potassium chloride, sodium iodide and sodium chloride, and mixtures thereof. Among these, potassium iodide and potassium bromide, and a mixture thereof are preferable, and potassium iodide is more preferable from the viewpoint of improving heat aging resistance and suppressing metal corrosion.
  • 1 type may be used independently and 2 or more types may be used in combination.
  • the blending amount of alkali and alkaline earth metal halides in the polyamide composition is preferably 0.05 to 5 with respect to 100 parts by mass of the polyamide composition. Part by mass, more preferably 0.2 to 2 parts by mass. When the amount is within the above range, the heat aging resistance is further improved, and copper precipitation and metal corrosion can be suppressed.
  • a mixture of a copper salt and a halide of alkali and alkaline earth metal can be suitably used as a heat stabilizer.
  • the ratio of the copper salt to the alkali and alkaline earth metal halide may be contained in the polyamide composition so that the molar ratio of halogen to copper (halogen / copper) is 2/1 to 40/1. It is preferably 5/1 to 30/1.
  • the heat aging resistance of the polyamide composition can be further improved.
  • the molar ratio (halogen / copper) is 2/1 or more, it is preferable because copper precipitation and metal corrosion can be suppressed.
  • the molar ratio (halogen / copper) is 40/1 or less, corrosion of the screws of the molding machine can be prevented without substantially impairing mechanical properties such as toughness, which is preferable.
  • the polyamide composition may contain a light stabilizer from the viewpoint of light stability.
  • the light stabilizer has a property of imparting excellent heat resistance and light resistance to resins such as polyamide and fibers.
  • Examples of the light stabilizer include amine light stabilizers.
  • amine light stabilizers include, but are not limited to, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetra Methylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6, 6-tetramethylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6 6-tetramethylpiperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethyl Peridine, 4- (ethylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy
  • amine light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) oxalate, bis (2, 2,6,6-tetramethyl-4-piperidyl) malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) ) Adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate, N, N′-bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedi Carboxamide and tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate are preferred.
  • bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N′-bis-2,2,6,6-tetramethyl-4 are used as amine light stabilizers.
  • -Piperidinyl-1,3-benzenedicarboxamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate are more preferred
  • N, N ′ -Bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedicarboxamide is more preferred.
  • the content of the amine light stabilizer in the polyamide composition is preferably 0 to 2% by mass, more preferably 0.01 to 2% by mass, and further preferably 100% by mass of the polyamide composition. Is 0.1 to 2% by mass.
  • the content of the amine light stabilizer is within the above range, the light stability and heat aging resistance of the polyamide composition can be further improved, and the amount of generated gas can be further reduced.
  • additives that are conventionally used for polyamide, for example, colorants such as pigments and dyes (including colored master batches), flame retardants, fibrillating agents, and lubricants, as long as the object of the present invention is not impaired.
  • colorants such as pigments and dyes (including colored master batches), flame retardants, fibrillating agents, and lubricants, as long as the object of the present invention is not impaired.
  • Containing agents, fluorescent bleaching agents, plasticizers, ultraviolet absorbers, antistatic agents, fluidity improvers, fillers, reinforcing agents, spreading agents, nucleating agents, rubbers, reinforcing agents and other polymers You can also.
  • the method for producing the polyamide composition is not particularly limited as long as it is a method of mixing the above-described second polyamide and, if necessary, the inorganic filler and other additives described above.
  • a method for mixing the constituent materials of the second polyamide composition for example, a method of mixing using a Henschel mixer or the like, supplying to a melt kneader and kneading, or a polyamide melted with a single screw or twin screw extruder, The method of mix
  • all the components may be supplied to the same supply port at the same time. You may supply from a different supply port.
  • the melt kneading temperature is preferably about 250 to 375 ° C. as the resin temperature.
  • the melt kneading time is preferably about 0.5 to 5 minutes.
  • the apparatus for performing melt kneading is not particularly limited, and a known apparatus, for example, a melt kneader such as a single-screw or twin-screw extruder, a Banbury mixer, and a mixing roll can be used.
  • the method for producing the polyamide composition when the inorganic filler contained in the second polyamide composition is a reinforcing fiber having a weight average fiber length of 1 to 15 mm is not particularly limited.
  • a pultrusion method in which polyamide is melt-kneaded with a twin-screw extruder, and the molten polyamide is impregnated into a roving of reinforcing fibers to obtain a polyamide-impregnated strand as described in JP-A-2008-221574
  • a method of sufficiently impregnating the polyamide by a process of twisting the impregnated strand in a spiral shape is mentioned.
  • the physical properties of the polyamide in the second polyamide composition of the present invention are equivalent to the physical properties of the second polyamide of the present invention.
  • the polyamide in the second polyamide composition maintains the physical properties of the second polyamide even after being melt-kneaded with other additives as necessary to obtain a composition. Has a measured value. Therefore, it is possible to specify the physical property of the polyamide contained in it by measuring each said physical property about a polyamide composition.
  • the ratio of crystallization enthalpy ⁇ Hc, glass transition temperature Tg, amino terminal, carboxyl terminal, and amino terminal amount to the total amount of active terminals can be measured by the method for measuring the physical properties of the polyamide described in the examples described later. Since the measured value in the second polyamide composition of the present invention is in the same range as the measured value of the second polyamide of the present invention, the polyamide composition of the present invention has low strength during heating, Excellent water absorption.
  • the value of the heat value is the value for the composition. Calculated by converting the ratio of the two polyamides.
  • the polyamide composition molded article of the present invention (hereinafter sometimes simply referred to as a molded article) is formed by molding the above-mentioned second polyamide composition.
  • the polyamide composition molded article maintains a high trans isomer ratio of the dicarboxylic acid monomer unit, and is excellent in hot strength, hot stiffness, and low water absorption, so it can be suitably used for automotive parts. it can.
  • the molded article of the polyamide composition of the present invention is a known molding method such as press molding, injection molding, gas assist injection molding, welding molding, extrusion molding, and blow molding of the second polyamide or the second polyamide composition described above. , Film molding, hollow molding, multilayer molding, melt spinning and the like.
  • the polyamide composition molded article is excellent in mechanical properties and low water absorption during heating.
  • the hot strength at 120 ° C. is preferably 120 MPa or more, and more preferably 125 MPa or more.
  • the thermal tensile elastic modulus at 120 ° C. is preferably 5.0 GPa or more, and more preferably 5.3 GPa or more.
  • the water absorption after 24 hours of 80 ° C. water is preferably less than 2.0%, more preferably 1.5% or less.
  • the retention is preferably 75% or more, and more preferably 80% or more.
  • the polyamide composition molded article of the present invention is excellent in heat resistance, strength, heat strength, rigidity, heat rigidity, heat stability, and has mold release and LLC resistance as shown in the following examples. Since it is improved, it can be suitably used as various parts materials for automobiles, electric and electronic, industrial materials, extrusion applications, daily necessities and household goods. About these specific uses, the thing similar to said 1st embodiment is mentioned.
  • the mol% of 1,4-cyclohexanedicarboxylic acid was determined by calculation as (number of moles of 1,4-cyclohexanedicarboxylic acid added as a raw material monomer / number of moles of all dicarboxylic acid units added as a raw material monomer) ⁇ 100. It was.
  • the mol% of the aliphatic diamine was determined by calculation as (number of moles of aliphatic diamine added as a raw material monomer / number of moles of all diamine units added as a raw material monomer) ⁇ 100.
  • the denominator and numerator do not include the number of moles of aliphatic diamine added as an additive during melt polymerization.
  • the melting peak temperature appearing on the highest temperature side of the endothermic peak (melting peak) appearing at the time of temperature rise was defined as Tm (° C.), and the peak area of Tm was defined as the heat of fusion ⁇ Hm (J / g).
  • the melting point Tm2 and the heat of fusion ⁇ Hm2 of the starting polyamide can be measured from the DSC of the molded product as follows. After the first temperature increase, the temperature is maintained for 2 minutes in the molten state at the maximum temperature increase, then the temperature is decreased to 30 ° C. at a temperature decrease rate of 20 ° C./min, maintained at 30 ° C.
  • the endothermic peak temperature that appears on the highest temperature side of the endothermic peak that appears when the temperature is similarly raised at the same temperature (° C./min) is the melting point of the polyamide itself, and the peak area at this melting point is the heat of fusion of the polyamide. ⁇ Hm2.
  • the temperature of the exothermic peak (crystallization peak) that appears when the temperature is lowered at a rate of temperature decrease of 20 ° C./min is defined as the crystallization peak temperature Tc (° C.), and the total peak area of Tc is the crystallization enthalpy ⁇ Hc (J / g). did.
  • the glass transition temperature Tg (° C.) was measured by using Diamond-DSC manufactured by PERKIN-ELMER according to JIS-K7121. The measurement conditions were that the polyamide composition molded products obtained in Examples and Comparative Examples were melted on a hot stage (EP80 manufactured by Mettler), and the molten sample obtained was rapidly cooled using liquid nitrogen and solidified. A measurement sample was obtained. Using 10 mg of the sample, the glass transition temperature was measured by raising the temperature in the range of 30 to 350 ° C. under a temperature raising speed of 20 ° C./min.
  • Trans isomer ratio 30-40 mg of the polyamide composition molded product obtained in Examples and Comparative Examples was dissolved in 1.2 g of hexafluoroisopropanol deuterated and measured by 1 H-NMR (ECA500 manufactured by JEOL).
  • Trans isomer ratio mol% of 1,4-cyclohexanedicarboxylic acid monomer unit of molded article, peak area of 2.00 ppm derived from trans isomer and peaks of 1.77 ppm and 1.87 ppm derived from cis isomer It calculated
  • Example 1-1 (Production of polyamide) The polymerization reaction of polyamide was carried out as follows by a hot melt polymerization method. CHDA 896 g (5.2 mol) as the dicarboxylic acid unit and 2PMD 604 g (5.2 mol) as the diamine unit were dissolved in 1500 g of distilled water to prepare an equimolar aqueous solution of about 50% by mass of the raw material monomer. The obtained aqueous solution was charged into an autoclave (made by Nitto Koatsu Co., Ltd.) having an internal volume of 5.4 L, kept warm until the liquid temperature (internal temperature) reached 50 ° C., and the inside of the autoclave was purged with nitrogen.
  • an autoclave made by Nitto Koatsu Co., Ltd.
  • the pressure in the autoclave tank (hereinafter also referred to simply as “inside the tank”) reaches about 2.5 kg / cm 2 as gauge pressure (hereinafter, all pressure in the tank is expressed as gauge pressure).
  • the liquid temperature was continuously heated from about 50 ° C. (the liquid temperature in this system was about 145 ° C.). In order to keep the pressure in the tank at about 2.5 kg / cm 2 , heating was continued while removing water out of the system, and the solution was concentrated until the concentration of the aqueous solution reached about 75% by mass (the liquid temperature in this system was about It was 160 ° C.).
  • the heater temperature was adjusted so that the final temperature of the resin temperature (liquid temperature) in the tank was about 340 ° C.
  • the resin temperature was kept at about 340 ° C., and the inside of the tank was maintained under a reduced pressure of about 79.9 kPa (about 600 torr) for 20 minutes by a vacuum apparatus to obtain a polymer.
  • the obtained polymer was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut, and discharged in a pellet form to obtain polyamide pellets.
  • the obtained polyamide composition was molded into a multi-purpose test piece (A type) by injection molding in accordance with ISO 3167, and then further heat treated at 240 ° C. in a reduced pressure environment at ⁇ 0.1 MPa (gauge pressure) for 2 hours. Thus, a molded article of the polyamide composition was obtained. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.
  • Example 1-2 A polyamide composition molded article was obtained in the same manner as in Example 1-1 except that the heat treatment time in (manufacturing the polyamide composition molded article) was 7 hours. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.
  • Example 1-3 (Production of polyamide) The polymerization reaction of polyamide was carried out as follows by a hot melt polymerization method. CHDA 795 g (4.62 mol) as a dicarboxylic acid unit, C10DA 517 g (3.00 mol) as a diamine unit, and 188 g (1.62 mol) of 2PMD are dissolved in 1500 g of distilled water, and an equimolar aqueous solution of about 50% by mass of the raw material monomer. Was made.
  • the obtained aqueous solution was charged into an autoclave (made by Nitto Koatsu Co., Ltd.) having an internal volume of 5.4 L, kept warm until the liquid temperature (internal temperature) reached 50 ° C., and the inside of the autoclave was purged with nitrogen.
  • the liquid temperature was continuously heated from about 50 ° C. until the pressure in the tank was about 2.5 kg / cm 2 as a gauge pressure (the liquid temperature in this system was about 145 ° C.).
  • water was removed from the system while heating was continued until the concentration of the aqueous solution reached about 75% by mass (the liquid temperature in this system was It was about 160 ° C.).
  • the heater temperature was adjusted so that the final temperature of the resin temperature (liquid temperature) in the tank was about 330 ° C.
  • the resin temperature was kept at about 340 ° C., and the inside of the tank was maintained under a reduced pressure of about 79.9 kPa (about 600 torr) for 20 minutes by a vacuum apparatus to obtain a polymer.
  • the obtained polymer was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut, and discharged in a pellet form to obtain polyamide pellets.
  • the obtained polyamide composition was molded into a multi-purpose test piece (A type) in accordance with ISO 3167, and then heat-treated at a temperature of 240 ° C. under a reduced pressure environment of ⁇ 0.1 MPa (gauge pressure) for 2 hours to obtain a polyamide composition.
  • a molded article was obtained.
  • Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.
  • Example 1-4 A polyamide composition molded article was obtained in the same manner as in Example 1-3, except that the heat treatment time in (manufacturing the polyamide composition molded article) was 7 hours. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.
  • Example 1-5 A polyamide composition molded article was obtained in the same manner as in Example 1-3, except that the heat treatment time in (manufacturing the polyamide composition molded article) was 24 hours. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.
  • Example 1-6 (Production of polyamide)
  • the polymerization reaction of polyamide was carried out as follows by a hot melt polymerization method. CHDA 802 g (4.66 mol) as a dicarboxylic acid unit, C10DA 481 g (2.79 mol) as a diamine unit, 216 g (1.86 mol) of 2PMD are dissolved in 1500 g of distilled water, and an equimolar aqueous solution of about 50% by mass of the raw material monomer. Was made.
  • the obtained aqueous solution was charged into an autoclave (made by Nitto Koatsu Co., Ltd.) having an internal volume of 5.4 L, kept warm until the liquid temperature (internal temperature) reached 50 ° C., and the inside of the autoclave was purged with nitrogen.
  • the liquid temperature was continuously heated from about 50 ° C. until the pressure in the tank was about 2.5 kg / cm 2 as a gauge pressure (the liquid temperature in this system was about 145 ° C.).
  • water was removed from the system while heating was continued until the concentration of the aqueous solution reached about 75% by mass (the liquid temperature in this system was It was about 160 ° C.).
  • the heater temperature was adjusted so that the final temperature of the resin temperature (liquid temperature) in the tank was about 320 ° C.
  • the resin temperature was kept at about 320 ° C., and the inside of the tank was maintained under a reduced pressure of about 79.9 kPa (about 600 torr) for 20 minutes with a vacuum apparatus to obtain a polymer.
  • the obtained polymer was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut, and discharged in a pellet form to obtain polyamide pellets.
  • the obtained polyamide composition was formed into a multi-purpose test piece (A type) in accordance with ISO 3167, and then heat-treated at a temperature of 240 ° C. under a reduced pressure environment of ⁇ 0.2 MPa (gauge pressure) for 2 hours.
  • Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.
  • Example 1-7 A polyamide composition molded article was obtained in the same manner as in Example 1-6 except that the heat treatment time in (manufacturing the polyamide composition molded article) was set to 7 hours. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.
  • Example 1-8 A polyamide composition molded article was obtained in the same manner as in Example 1-6, except that the heat treatment time in (manufacturing the polyamide composition molded article) was 24 hours. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.
  • Example 1-9 (Production of polyamide) The polymerization reaction of polyamide was carried out as follows by a hot melt polymerization method. CHDA 795 g (4.62 mol) as a dicarboxylic acid unit, C10DA 517 g (3.00 mol) and HMD 188 g (1.62 mol) as a diamine unit are dissolved in 1500 g of distilled water, and an equimolar aqueous solution of about 50% by mass of the raw material monomer is obtained. Was made.
  • the obtained aqueous solution was charged into an autoclave (made by Nitto Koatsu Co., Ltd.) having an internal volume of 5.4 L, kept warm until the liquid temperature (internal temperature) reached 50 ° C., and the inside of the autoclave was purged with nitrogen.
  • the liquid temperature was continuously heated from about 50 ° C. until the pressure in the tank was about 2.5 kg / cm 2 as a gauge pressure (the liquid temperature in this system was about 145 ° C.).
  • water was removed from the system while heating was continued until the concentration of the aqueous solution reached about 75% by mass (the liquid temperature in this system was It was about 160 ° C.).
  • the heater temperature was adjusted so that the final temperature of the resin temperature (liquid temperature) in the tank was about 330 ° C.
  • the resin temperature was kept at about 340 ° C., and the inside of the tank was maintained under a reduced pressure of about 79.9 kPa (about 600 torr) for 20 minutes by a vacuum apparatus to obtain a polymer.
  • the obtained polymer was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut, and discharged in a pellet form to obtain polyamide pellets.
  • the obtained polyamide composition was formed into a multi-purpose test piece (A type) in accordance with ISO 3167, and then heat-treated at a temperature of 240 ° C. under a reduced pressure environment of ⁇ 0.2 MPa (gauge pressure) for 2 hours.
  • Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.
  • Example 1-10 A polyamide composition molded product was obtained in the same manner as in Example 1-9, except that the heat treatment time in (Manufacturing the polyamide composition molded product) was set to 7 hours. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.
  • Example 1-11 A polyamide composition molded article was obtained in the same manner as in Example 1-9, except that the heat treatment time in (manufacturing the polyamide composition molded article) was 24 hours. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.
  • Example 1-2 A polyamide composition molded article was obtained in the same manner as in Example 1-3, except that the heat treatment in (Manufacturing the polyamide composition molded article) was not performed. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.
  • the resulting reaction liquid was stirred at a liquid temperature (internal temperature) of 100 ° C. for 30 minutes, and then heated to a liquid temperature of 210 ° C. over 2 hours. At this time, the pressure in the tank was increased to 22 kg / cm 2 . The reaction was continued for 1 hour at a liquid temperature of 210 ° C. and a pressure in the tank of 22 kg / cm 2 , then the temperature was raised to 230 ° C., and then the liquid temperature was maintained at 230 ° C. for 2 hours. The reaction was carried out while maintaining the internal pressure at 22 kg / cm 2 .
  • the pressure in the tank was lowered to 10 kg / cm 2 over 30 minutes, and the reaction was further continued for 1 hour to obtain a prepolymer having a sulfuric acid relative viscosity [ ⁇ r] of 1.25.
  • the obtained prepolymer was dried at 100 ° C. under reduced pressure for 12 hours, pulverized to a size of 2 mm or less, and then subjected to solid phase polymerization at 230 ° C. and 0.1 mmHg for 10 hours to obtain a polyamide (hereinafter referred to as "PA9T”) was obtained.
  • PA9T polyamide
  • the polyamide composition molded article of the present invention is a trans-rich polyamide composition molded article obtained only by heat treatment after molding, regardless of the ratio of cis-trans in the raw material or polyamide state, and is apparent from the results shown in Table 1A.
  • the polyamide composition molded products of Examples 1-1 to 1-11 had excellent characteristics in terms of hot strength and hot stiffness. In general, when the polymer absorbs water, degradation occurs due to hydrolysis and chemical penetration, and so-called LLC resistance decreases. However, the polyamide composition molded product of the present invention has improved LLC resistance as shown in the tensile strength retention after immersion. did.
  • the penetration rate (degradation rate) of LLC differs between the amorphous part and the crystalline part of the molded product, and the amorphous part deteriorates faster than the crystalline part.
  • the polyamide composition molded product of the present invention is not treated by heat treatment after molding. As a result of the decrease in the crystal portion and the increase in the crystal portion ( ⁇ Hm), it is considered that the LLC resistance was improved.
  • Comparative Example 1-1 the composition pellets before molding had a trans isomer ratio of 70 mol%, and even after melt molding, the ratio was 70 mol%. As a result, the hot strength, the hot stiffness, and the LLC resistance were insufficient. Also in Comparative Example 1-2, the composition pellets before molding had a trans isomer ratio of 70 mol%, and even after melt molding, the trans isomer ratio was 70 mol%. It was insufficient in terms of LLC resistance. On the other hand, Comparative Examples 1-3 and 1-4 were not sufficient in terms of hot strength, hot stiffness, and LLC resistance because no isomers were present.
  • Example 1-12 In the same manner as described above, the non-reinforced polyamide molded article not containing the inorganic filler was subjected to Examples and Comparative Examples as follows. [Example 1-12] In the same manner as in Example 1-1, except that the glass fiber in (manufacturing the polyamide composition) was not added and the heat treatment time in (manufacturing the polyamide composition) was set to 7 hours, the same was done. Got. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.
  • Example 1-13 In the same manner as in Example 1-3, except that the glass fiber in (Production of polyamide composition) was not added and the heat treatment time in (Production of polyamide composition product) was 24 hours, the same was done. Got. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.
  • Example 1-5 A polyamide composition molded product was obtained in the same manner as in Example 1-1 except that the glass fiber in (manufacturing the polyamide composition) was not added and heat treatment was not performed in (manufacturing the polyamide composition molded product). It was. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.
  • Example 1-6 A polyamide composition molded product was obtained in the same manner as in Example 1-3, except that the glass fiber in (manufacturing the polyamide composition) was not added and heat treatment was not performed in (manufacturing the polyamide composition molded product). It was. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods. Each physical property of the polyamide composition molded product obtained in Examples and Comparative Examples was measured based on the above method. The measurement results are shown in Table 1C.
  • the present example relates to a polyamide composition molded article obtained by molding the first polyamide composition using the first polyamide.
  • (A) Polyamide used in the examples and comparative examples was produced using the following (a) and (b) as appropriate.
  • (A) Dicarboxylic acid (1) 1,4-cyclohexanedicarboxylic acid (CHDA) (manufactured by Eastman Chemical Co., Ltd., trade name: 1,4-CHDA HP grade (trans isomer / cis isomer 25/75)
  • C6DA Hexamethylenediamine
  • C11DA Undecamethylenediamine
  • C12DA Dodecamethylenediamine
  • (B) Titanium oxide TiO 2 manufactured by Ishihara Sangyo Co., Ltd., trade name: Taipei (registered trademark) CR-63, number average particle size: 0.21 ⁇ m, coating: alumina, silica and siloxane compound
  • the number average particle diameter of (B) titanium oxide was measured as follows by an electron micrograph method.
  • the polyamide compositions of Examples and Comparative Examples to be described later are placed in an electric furnace, the organic matter contained in the polyamide composition is incinerated, and 100 or more titanium oxides arbitrarily selected from the residue are observed with an electron microscope. And the number average particle diameter of (B) titanium oxide was calculated
  • (C) The number average fiber diameter of an inorganic filler puts the polyamide composition of the Example and comparative example which are mentioned later into an electric furnace, and incinerates the organic substance contained in a polyamide composition. From the residue, 100 or more arbitrarily selected wollastonites were observed with an SEM, and the number average fiber diameter was determined by measuring the fiber diameters of these wollastonites.
  • the mol% of 1,4-cyclohexanedicarboxylic acid was determined by calculation as (number of moles of 1,4-cyclohexanedicarboxylic acid added as a raw material monomer / number of moles of all dicarboxylic acid units added as a raw material monomer) ⁇ 100. It was. Further, the mol% of the aliphatic diamine was obtained by calculation as (number of moles of aliphatic diamine added as raw material monomer / number of moles of all diamine units added as raw material monomer) ⁇ 100. In addition, when calculating by the above formula, the denominator and numerator do not include the number of moles of aliphatic diamine added as an additive during melt polymerization.
  • the melting peak temperature that appeared on the highest temperature side of the melting peak) was Tm1 (° C.), and the peak area of Tm1 was the heat of fusion ⁇ Hm1 (J / g).
  • the melting point Tm2 and the heat of fusion ⁇ Hm2 of the starting polyamide can be measured as follows. After the first temperature increase, the temperature is maintained for 2 minutes in the molten state at the maximum temperature increase, then the temperature is decreased to 30 ° C.
  • the endothermic peak temperature that appears at the highest temperature side of the endothermic peak that appears when the temperature is similarly raised at the same temperature (° C./min) is the melting peak temperature Tm2 of the polyamide itself, and the peak area at Tm2 is the polyamide area.
  • the temperature of the exothermic peak (crystallization peak) that appears when the temperature is lowered at a rate of temperature decrease of 20 ° C./min is defined as the crystallization peak temperature Tc (° C.), and the total peak area of Tc is the crystallization enthalpy ⁇ Hc (J / g). did.
  • Trans isomer ratio of polyamide The trans isomer ratio of the portion derived from 1,4-cyclohexadicarboxylic acid in the polyamide was measured as follows. 30-40 mg of polyamide was dissolved in 1.2 g of hexafluoroisopropanol deuteride, and the trans isomer ratio was measured by 1 H-NMR (ECA500 manufactured by JEOL) using the resulting solution. When the alicyclic dicarboxylic acid is 1,4-cyclohexanedicarboxylic acid, the ratio between the peak area of 1.98 ppm derived from the trans isomer and the peak areas of 1.77 ppm and 1.86 ppm derived from the cis isomer From which the trans isomer ratio was determined.
  • Polyamide molecular weight (Mn, Mw / Mn) Mw (weight average molecular weight) / Mn (number average molecular weight) of the polyamides obtained in Examples and Comparative Examples are GPC (gel permeation chromatography, manufactured by Tosoh Corporation, HLC-8020, hexafluoroisopropanol solvent, PMMA (poly It was calculated using Mw and Mn measured by methyl methacrylate) standard sample (manufactured by Polymer Laboratories).
  • the GPC column used was TSK-GEL GMHHR-M and G1000HHR.
  • Carboxyl end amount ([COOH]) In the polyamides obtained in the examples and comparative examples, the amount of carboxyl terminal bound to the polymer terminal was measured by neutralization titration as follows. 4.0 g of polyamide was dissolved in 50 mL of benzyl alcohol, and the resulting solution was titrated with 0.1N NaOH to obtain the carboxyl end amount ( ⁇ equivalent / g). The end point was determined from the discoloration of the phenolphthalein indicator.
  • the pressure inside the tank of the autoclave (hereinafter also simply referred to as “inside the tank”) is about 2.5 kg / cm 2 as gauge pressure (hereinafter, all the pressure inside the tank is expressed as gauge pressure (G)). Heating was continued until At this time, the liquid temperature was about 145 ° C. While maintaining the pressure in the tank at about 2.5 kg / cm 2 (G), heating was continued while removing water out of the system, and the aqueous solution in the tank was concentrated to a concentration of about 85% by mass.
  • the inside of the tank was maintained under a reduced pressure of 100 torr (1.33 ⁇ 10 4 Pa) for 10 minutes with a vacuum apparatus. Then, the inside of the tank was pressurized with nitrogen, and the product was discharged in a strand form from the lower nozzle (nozzle). Further, the strand-like product was cooled with water and cut to obtain a pellet-like precursor polyamide (precursor polyamide pellet).
  • the total active terminal amount ([NH 2 ] + [COOH]) of this precursor polyamide was 98 ⁇ eq / g, and the ratio of the amino terminal amount [NH 2 ] to the active terminal total amount ([NH 2 ] + [COOH]). [NH 2 ] / ([NH 2 ] + [COOH]) was 0.37.
  • the obtained polyamide was dried in a nitrogen stream to adjust the moisture content to less than about 0.2% by mass, and then each property of the polyamide was measured based on the above measurement method.
  • the total active terminal amount ([NH 2 ] + [COOH]) of the obtained precursor polyamide was 91 ⁇ equivalent / g, and the total active terminal amount of amino terminal amount [NH 2 ] ([NH 2 ] + [COOH]).
  • [NH 2 ] / ([NH 2 ] + [COOH]) which is the ratio to, was 0.49.
  • the obtained polyamide was dried in a nitrogen stream to adjust the moisture content to less than about 0.2% by mass, and then each property of the polyamide was measured based on the above measurement method.
  • the total active terminal amount ([NH 2 ] + [COOH]) of this precursor polyamide was 85 ⁇ eq / g, the ratio of the amino terminal amount [NH 2 ] to the active terminal total amount ([NH 2 ] + [COOH]).
  • [NH 2 ] / ([NH 2 ] + [COOH]) was 0.39.
  • the obtained polyamide was dried in a nitrogen stream to adjust the moisture content to less than about 0.2% by mass, and then each property of the polyamide was measured based on the above measurement method.
  • the total active terminal amount ([NH 2 ] + [COOH]) of this precursor polyamide was 102 ⁇ eq / g, the ratio of the amino terminal amount [NH 2 ] to the active terminal total amount ([NH 2 ] + [COOH]).
  • [NH 2 ] / ([NH 2 ] + [COOH]) was 0.55.
  • the obtained polyamide was dried in a nitrogen stream to adjust the moisture content to less than about 0.2% by mass, and then each property of the polyamide was measured based on the above measurement method.
  • the obtained polyamide was dried in a nitrogen stream to adjust the moisture content to less than about 0.2% by mass, and then each property of the polyamide was measured based on the above measurement method.
  • the obtained polyamide was dried in a nitrogen stream to adjust the moisture content to less than about 0.2% by mass, and then each property of the polyamide was measured based on the above measurement method.
  • the liquid temperature was continuously heated from about 50 ° C. to 210 ° C., and heating was continued while removing water out of the system in order to keep the pressure in the autoclave tank at 17.5 kg / cm 2 as a gauge pressure. Thereafter, the internal temperature was raised to 320 ° C., and the pressure was reduced while taking about 120 minutes until the pressure in the tank reached atmospheric pressure (gauge pressure was 0 kg / cm 2 ). Thereafter, nitrogen gas was allowed to flow through the tank for 30 minutes, and the heater temperature was adjusted so that the final temperature of the resin temperature (liquid temperature) was about 323 ° C. to obtain a polymer.
  • the obtained polymer was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut and discharged in a pellet form to obtain copolymer polyamide pellets.
  • Each physical property of the obtained polyamide was measured based on the above method.
  • the internal temperature was maintained at 160 ° C. for 30 minutes, and while continuing to heat while removing the steam from the system, the solution was concentrated until the concentration of the aqueous solution reached 70% by mass.
  • the removal of water was stopped and heating was continued until the internal pressure of the tank reached about 35 kg / cm 2 (the liquid temperature in this system was about 250 ° C.).
  • the prepolymer was obtained by reacting for 1 hour until the final temperature reached 300 ° C. while removing water out of the system.
  • the prepolymer was pulverized to a size of 3 mm or less, and then dried at 100 ° C. for 24 hours in an atmosphere in which nitrogen gas was flowed at a flow rate of 20 L / min. Thereafter, a prepolymer was subjected to solid phase polymerization at 280 ° C. for 10 hours in an atmosphere in which nitrogen gas was flowed at a flow rate of 200 mL / min, to obtain a polyamide.
  • the composition and polymerization conditions of this polyamide are shown in Table 2A.
  • the autoclave was heated up to 22 kg / cm 2 .
  • the reaction was continued as it was for 1 hour, then the temperature was raised to 230 ° C., and then the temperature was maintained at 230 ° C. for 2 hours, and the reaction was carried out while gradually removing water vapor and keeping the pressure at 22 kg / cm 2 .
  • the pressure was reduced to 10 kg / cm 2 over 30 minutes, and the reaction was further continued for 1 hour to obtain a prepolymer.
  • the prepolymer was dried at 100 ° C. under reduced pressure for 12 hours and pulverized to a size of 2 mm or less. This was solid-phase polymerized at 230 ° C. and 0.1 mmHg for 10 hours to obtain polyamide.
  • the polyamides (PA-1 to PA-9) obtained in the above Production Examples 1 to 9 were dried in a nitrogen stream and the moisture content was adjusted to about 0.2% by mass, and then the raw material for the polyamide composition Used as.
  • a twin screw extruder [ZSK-26MC: manufactured by Coperion (Germany)] was used as an apparatus for producing the polyamide composition.
  • the twin screw extruder has an upstream supply port in the first barrel from the upstream side of the extruder, a downstream first supply port in the sixth barrel, and a downstream second supply port in the ninth barrel.
  • L / D extruder cylinder length / extruder cylinder diameter
  • the number of barrels was 12.
  • the temperature from the upstream supply port to the die is set to the melting peak temperature Tm2 + 10 ° C. of each (A) polyamide produced in the above production example, the screw rotation speed is set to 250 rpm, and the discharge amount is set to 25 kg / h. did.
  • the inorganic filler (C) was supplied from the downstream second supply port of the twin-screw extruder in the types and proportions described in Table 2B below.
  • the raw materials supplied as described above were melt-kneaded with a twin-screw extruder to produce polyamide composition pellets.
  • the obtained polyamide composition pellets were dried in a nitrogen stream, and the water content in the polyamide composition was reduced to 500 ppm or less.
  • Various evaluations were performed as described above using the polyamide composition after adjusting the water content. The evaluation results are shown in Table 2B below.
  • the polyamide compositions of Examples 2-1 to 2-3 have high initial reflectivity, reflectivity retention after the reflow process, reflectivity retention after heat treatment, and excellent mold release properties. I understood that.
  • the comparative example in which the trans isomer ratio is out of the scope of the present invention was inferior to the examples, particularly in the reflectance retention and the aging retention after the reflow process.
  • Comparative Examples 2-1 and 2-2 in which the ratio of the trans isomer was low and the ratio of the amino terminal amount to the total active terminal amount was 0.5 or more were inferior to the Examples in terms of releasability. From the above results, it was shown that the polyamide composition of the present invention is excellent in reflectance retention, aging retention and releasability, and therefore can be suitably used for LED reflectors.
  • the present example relates to a polyamide composition molded article obtained by molding the second polyamide composition using the second polyamide.
  • Example 3 Measuring methods for raw materials and physical properties used in Examples and Comparative Examples are shown below.
  • C6DA Hexamethylenediamine
  • C10DA Decamethylenediamine
  • C11DA Undecamethylenediamine
  • C12DA Dodecamethylenediamine
  • the mol% of 1,4-cyclohexanedicarboxylic acid was determined by calculation as (number of moles of 1,4-cyclohexanedicarboxylic acid added as a raw material monomer / number of moles of all dicarboxylic acid units added as a raw material monomer) ⁇ 100. It was.
  • the mol% of the aliphatic diamine was determined by calculation as (number of moles of aliphatic diamine added as a raw material monomer / number of moles of all diamine units added as a raw material monomer) ⁇ 100.
  • the denominator and numerator do not include the number of moles of aliphatic diamine added as an additive during melt polymerization.
  • the melting point (Tm) of the sample at a heating rate of 20 ° C./min in the nitrogen atmosphere (first time) The melting peak temperature appearing on the highest temperature side of the endothermic peak (melting peak) appearing at the time of temperature rise was Tm1 (° C.), and the peak area of Tm1 was the heat of fusion ⁇ Hm1 (J / g). Further, the melting peak temperature Tm2 and the heat of fusion ⁇ Hm2 of the starting polyamide can be measured as follows. After the first temperature increase, the temperature is maintained for 2 minutes in the molten state at the maximum temperature increase, then the temperature is decreased to 30 ° C. at a temperature decrease rate of 20 ° C./min, maintained at 30 ° C.
  • the endothermic peak temperature that appears at the highest temperature side of the endothermic peak that appears when the temperature is similarly raised at the same temperature (° C./min) is the melting peak temperature Tm2 of the polyamide itself, and the peak area at Tm2 is the polyamide area.
  • the temperature of the exothermic peak (crystallization peak) that appears when the temperature is lowered at a rate of temperature decrease of 20 ° C./min is defined as the crystallization peak temperature Tc (° C.), and the total peak area of Tc is the crystallization enthalpy ⁇ Hc (J / g). did.
  • the glass transition temperature Tg (° C) was measured by using Diamond-DSC manufactured by PERKIN-ELMER according to JIS-K7121.
  • the measurement conditions were as follows: a sample obtained by melting the polyamide obtained in Examples and Comparative Examples on a hot stage (EP80 manufactured by Mettler) was rapidly cooled and solidified using liquid nitrogen, and the measurement sample and did. Using 10 mg of the sample, the glass transition temperature was measured by raising the temperature in the range of 30 to 350 ° C. under a temperature raising speed of 20 ° C./min.
  • Trans isomer ratio 30-40 mg of the polyamides obtained in Examples and Comparative Examples were dissolved in 1.2 g of hexafluoroisopropanol deuterated and measured by 1 H-NMR (ECA500 manufactured by JEOL).
  • the trans isomer ratio of the 1,4-cyclohexanedicarboxylic acid monomer unit of the polyamide is 2.00 ppm peak area derived from the trans isomer, and 1.77 ppm and 1.87 ppm peak area ratio derived from the cis isomer. I asked for it.
  • Molecular weight Number average molecular weight Mn, weight average molecular weight Mw, molecular weight distribution Mw / Mn are GPC (gel permeation chromatography, manufactured by Tosoh Corporation, HLC-8020, hexafluoroisopropanol solvent, PMMA (polymethyl methacrylate) standard sample. A calibration curve was prepared using the number average molecular weight Mn measured by Polymer Laboratories Co., Ltd., and the molecular weight of the polyamide obtained in this example and the comparative example was obtained.
  • the GPC column was TSK-GEL GMHHR. -M and G1000HHR were used.
  • Carboxyl end amount ([COOH]) In the polyamides obtained in the examples and comparative examples, the amount of carboxyl terminal bound to the polymer terminal was measured by neutralization titration as follows. 4.0 g of polyamide was dissolved in 50 mL of benzyl alcohol, and the resulting solution was titrated with 0.1N NaOH to obtain the carboxyl end amount ( ⁇ equivalent / g). The end point was determined from the discoloration of the phenolphthalein indicator.
  • Example 3-1 (Production of polyamide)
  • the polymerization reaction of polyamide was carried out as follows by a hot melt polymerization method. CHDA 802 g (4.66 mol) as a dicarboxylic acid unit, 2MC5DA 217 g (1.86 mol) and C10DA 482 g (2.79 mol) as a diamine unit are dissolved in 1500 g of distilled water, and an equimolar aqueous solution of about 50% by mass of the starting monomer is equimolar. Was made.
  • the obtained aqueous solution was charged into an autoclave having an internal volume of 5.4 L (manufactured by Nitto Koatsu), and 5.4 g of 2MC5DA was further added to the autoclave as an additional diamine.
  • the temperature was maintained until the liquid temperature (internal temperature) reached 50 ° C., and the inside of the autoclave was purged with nitrogen.
  • the pressure in the autoclave tank (hereinafter, also simply referred to as “inside the tank”) is about 2.5 kg / cm 2 (G) as gauge pressure (hereinafter, all pressure in the tank is expressed as gauge pressure).
  • the liquid temperature was continuously heated from about 50 ° C. until the temperature reached (the liquid temperature in this system was about 145 ° C.).
  • the heater temperature was adjusted so that the final temperature of the resin temperature (liquid temperature) in the tank was about 330 ° C. While the resin temperature was kept at about 330 ° C., the inside of the tank was maintained under a reduced pressure of about 50 kPa for 20 minutes with a vacuum apparatus to obtain a polymer. Thereafter, the obtained polymer was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut and discharged in a pellet form to obtain a precursor polyamide pellet (precursor polyamide pellet). .
  • the total active terminal amount ([NH 2 ] + [COOH]) of this precursor polyamide was 115 ⁇ eq / g, the ratio of the amino terminal amount [NH 2 ] to the active terminal total amount ([NH 2 ] + [COOH]).
  • [NH 2 ] / ([NH 2 ] + [COOH]) was 0.39.
  • Example 3-2 A polyamide composition molded article was obtained in the same manner as in Example 3-1, except that the amount of 2MC5DA additional diamine was 4.3 g. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.
  • the active terminal total amount ([NH 2 ] + [COOH]) of this precursor polyamide is 118 ⁇ equivalent / g, the active terminal total amount of amino terminal amount [NH 2 ] ([NH 2 ] + [COOH]).
  • the ratio to [NH 2 ] / ([NH 2 ] + [COOH]) was 0.29.
  • Example 3-3 A polyamide composition molded article was obtained in the same manner as in Example 3-1, except that the amount of 2MC5DA additional diamine was changed to 0 g. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.
  • the active terminal total amount ([NH 2 ] + [COOH]) of this precursor polyamide is 135 ⁇ equivalent / g, and the amino terminal amount [NH 2 ] active terminal total amount ([NH 2 ] + [COOH]).
  • [NH 2 ] / ([NH 2 ] + [COOH]) which is the ratio to, was 0.17.
  • Example 3-4 A polyamide composition molded article was obtained in the same manner as in Example 3-3, except that the precursor polyamide pellets obtained by melt polymerization were dried at 250 ° C. for 10 hours in a vacuum dryer. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.
  • Example 3-5 CHDA 795 g (4.62 mol) as dicarboxylic acid units, 2MC5DA 188 g (1.62 mol) and C10DA 517 g (3.00 mol) as diamine units were dissolved in 1500 g of distilled water, and an equimolar aqueous solution of about 50% by mass of raw material monomers was obtained.
  • a polyamide composition molded product was obtained in the same manner as in Example 3-3, except that was prepared. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.
  • the total active terminal amount of the precursor polyamide ([NH2] + [COOH]) is 132 ⁇ eq / g, based on the total active terminal amount of the amino terminal amount [NH 2 ] ([NH 2 ] + [COOH]).
  • the ratio [NH 2 ] / ([NH 2 ] + [COOH]) was 0.21.
  • Example 3-6 10 kg of the precursor polyamide pellet obtained by using melt polymerization was put in a vacuum dryer and sufficiently purged with nitrogen. After flowing nitrogen at 10 L / min, the precursor polyamide pellet was stirred at 235 ° C. for 10 hours while stirring. And heated. Thereafter, the temperature in the vacuum dryer was lowered to about 50 ° C. with nitrogen flowing, and the polyamide pellets were removed from the vacuum dryer in the form of pellets to obtain polyamide. Except for these, a polyamide composition molded article was obtained in the same manner as in Example 3-5. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.
  • Example 3-1 A polyamide composition molded product was obtained in the same manner as in Example 3-1, except that the amount of 2MC5DA additional diamine was 13 g, and the precursor polyamide pellets obtained by subsequent melt polymerization were dried at 150 ° C. for 10 hours in a vacuum dryer. Obtained. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods. The measurement results are shown in Table 3B.
  • the active terminal total amount ([NH 2 ] + [COOH]) of this precursor polyamide is 123 ⁇ equivalent / g, the active terminal total amount of amino terminal amount [NH 2 ] ([NH 2 ] + [COOH]). [NH 2 ] / ([NH 2 ] + [COOH]), which is the ratio to, was 0.55.
  • Comparative Example 3-2 A polyamide composition molded article was obtained in the same manner as in Comparative Example 3-1, except that the precursor polyamide pellets obtained by melt polymerization were dried at 200 ° C. for 10 hours in a vacuum dryer. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.
  • the liquid temperature is continuously heated from about 50 ° C. to 210 ° C., and the pressure in the autoclave tank is referred to as gauge pressure (hereinafter, all the pressure in the tank is expressed as gauge pressure (G)), 17.5 kg / Heating was continued while removing water out of the system to maintain cm 2 (G). Thereafter, the internal temperature was raised to 320 ° C., and the pressure was reduced while taking about 120 minutes until the pressure in the tank reached atmospheric pressure (gauge pressure was 0 kg / cm 2 ). Thereafter, nitrogen gas was allowed to flow through the tank for 30 minutes, and the heater temperature was adjusted so that the final temperature of the resin temperature (liquid temperature) was about 323 ° C. to obtain a polymer.
  • the obtained polymer was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut and discharged in a pellet form to obtain copolymer polyamide pellets.
  • a polyamide composition and a polyamide composition molded article were produced based on Example 3-1.
  • Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.
  • the solution in the autoclave was stirred and the internal temperature was raised to 160 ° C. over 50 minutes. Thereafter, the internal temperature was maintained at 160 ° C. for 30 minutes, and while continuing to heat while removing the steam from the system, the solution was concentrated until the concentration of the aqueous solution reached 70% by mass. The removal of water was stopped and heating was continued until the internal pressure of the tank reached about 35 kg / cm 2 (the liquid temperature in this system was about 250 ° C.). In order to keep the pressure in the tank at about 35 kg / cm 2 , the prepolymer was obtained by reacting for 1 hour until the final temperature reached 300 ° C. while removing water out of the system.
  • the prepolymer was pulverized to a size of 3 mm or less, and then dried at 100 ° C. for 24 hours in an atmosphere in which nitrogen gas was flowed at a flow rate of 20 L / min. Thereafter, a prepolymer was subjected to solid phase polymerization at 280 ° C. for 10 hours in an atmosphere in which nitrogen gas was flowed at a flow rate of 200 mL / min, to obtain a polyamide.
  • the production of the polyamide composition and the production of the molded article of the polyamide composition were based on Example 3-1, and a polyamide composition and its molded article were obtained.
  • Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.
  • the autoclave was heated up to 22 kg / cm 2 .
  • the reaction was continued as it was for 1 hour, then the temperature was raised to 230 ° C., and then the temperature was maintained at 230 ° C. for 2 hours, and the reaction was carried out while gradually removing water vapor and keeping the pressure at 22 kg / cm 2 .
  • the pressure was reduced to 10 kg / cm 2 over 30 minutes, and the reaction was further continued for 1 hour to obtain a prepolymer.
  • the prepolymer was dried at 100 ° C. under reduced pressure for 12 hours and pulverized to a size of 2 mm or less. This was solid-phase polymerized at 230 ° C. and 0.1 mmHg for 10 hours to obtain polyamide.
  • the polyamide composition and the polyamide composition molded article were produced based on Example 3-1.
  • Various physical properties of the obtained polyamide composition molded article were measured based on the above methods. The evaluation results are shown in Table 3A and Table 3B below.
  • the polyamides of the present invention have the polyamide compositions of Examples 3-1 to 3-6 by increasing the ratio of heat of fusion ⁇ Hm1 / crystallization enthalpy ⁇ Hc, which is an index of crystal growth.
  • the molded article had excellent properties in hot strength and hot stiffness. In general, when the polymer absorbs water, degradation occurs due to hydrolysis and chemical penetration, and so-called LLC resistance is lowered. However, the molded article containing the polyamide of the present invention is resistant to LLC as shown in the tensile strength retention after immersion. Improved.
  • the penetration rate (degradation rate) of LLC differs between the amorphous part and the crystalline part of the molded product, and the amorphous part deteriorates faster than the crystalline part.
  • the amorphous part after molding of the composition As a result of the decrease and increase in the crystal part ( ⁇ Hm), it is considered that the LLC resistance was improved.
  • the molded article of the polyamide composition of the present invention has industrial applicability as various parts such as LED reflectors, automobiles, electric and electronic, industrial materials, and daily and household products.

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Abstract

Le problème abordé par la présente invention est de pourvoir à un article moulé à base d'une composition de polyamide présentant une excellente résistance thermique et rigidité thermique. La solution selon l'invention porte sur un article moulé à base d'une composition de polyamide comprenant un polyamide dont les motifs acide dicarboxylique sont polymérisés, comprenant au moins des motifs acide 1,4-cyclohexanedicarboxylique et diamine, dont au moins une diamine aliphatique, caractérisée en ce que le taux d'isomères trans des motifs monomères acide 1,4-cyclohexanedicarboxylique dans l'article moulé est de 71 à 100 % en moles.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021235348A1 (fr) * 2020-05-18 2021-11-25 宇部興産株式会社 Résine de polyamide, composition contenant ladite résine de polyamide et corps moulé contenant ladite résine de polyamide et composition
JP2023092970A (ja) * 2021-12-22 2023-07-04 東洋インキＳｃホールディングス株式会社 表刷り用グラビア印刷インキ、それを用いた印刷物

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011027562A1 (fr) * 2009-09-07 2011-03-10 株式会社クラレ Réflecteur pour del et dispositif électroluminescent en étant équipé
WO2011030746A1 (fr) * 2009-09-11 2011-03-17 旭化成ケミカルズ株式会社 Réflecteur pour dispositif électroluminescent et dispositif électroluminescent
JP2011057976A (ja) * 2009-08-11 2011-03-24 Asahi Kasei Chemicals Corp 低吸水性ポリアミド組成物
JP2011057903A (ja) * 2009-09-11 2011-03-24 Asahi Kasei Chemicals Corp ポリアミド−ポリフェニレンエーテル樹脂組成物及び成形品
JP2011068869A (ja) * 2009-08-24 2011-04-07 Asahi Kasei Chemicals Corp ポリアミド組成物及びポリアミド組成物からなる成形品
JP2011074363A (ja) * 2009-09-04 2011-04-14 Asahi Kasei Chemicals Corp ポリアミド組成物を含む自動車部品
JP2011080056A (ja) * 2009-09-11 2011-04-21 Asahi Kasei Chemicals Corp ポリアミド及びポリアミド組成物
JP2014005407A (ja) * 2012-06-26 2014-01-16 Asahi Kasei Chemicals Corp 共重合ポリアミド
JP2014012773A (ja) * 2012-07-04 2014-01-23 Asahi Kasei Chemicals Corp ポリアミド組成物及び成形品

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011057976A (ja) * 2009-08-11 2011-03-24 Asahi Kasei Chemicals Corp 低吸水性ポリアミド組成物
JP2011068869A (ja) * 2009-08-24 2011-04-07 Asahi Kasei Chemicals Corp ポリアミド組成物及びポリアミド組成物からなる成形品
JP2011074363A (ja) * 2009-09-04 2011-04-14 Asahi Kasei Chemicals Corp ポリアミド組成物を含む自動車部品
WO2011027562A1 (fr) * 2009-09-07 2011-03-10 株式会社クラレ Réflecteur pour del et dispositif électroluminescent en étant équipé
WO2011030746A1 (fr) * 2009-09-11 2011-03-17 旭化成ケミカルズ株式会社 Réflecteur pour dispositif électroluminescent et dispositif électroluminescent
JP2011057903A (ja) * 2009-09-11 2011-03-24 Asahi Kasei Chemicals Corp ポリアミド−ポリフェニレンエーテル樹脂組成物及び成形品
JP2011080056A (ja) * 2009-09-11 2011-04-21 Asahi Kasei Chemicals Corp ポリアミド及びポリアミド組成物
JP2014005407A (ja) * 2012-06-26 2014-01-16 Asahi Kasei Chemicals Corp 共重合ポリアミド
JP2014012773A (ja) * 2012-07-04 2014-01-23 Asahi Kasei Chemicals Corp ポリアミド組成物及び成形品

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021235348A1 (fr) * 2020-05-18 2021-11-25 宇部興産株式会社 Résine de polyamide, composition contenant ladite résine de polyamide et corps moulé contenant ladite résine de polyamide et composition
JP2023092970A (ja) * 2021-12-22 2023-07-04 東洋インキＳｃホールディングス株式会社 表刷り用グラビア印刷インキ、それを用いた印刷物
JP7677135B2 (ja) 2021-12-22 2025-05-15 ａｒｔｉｅｎｃｅ株式会社 表刷り用グラビア印刷インキ、それを用いた印刷物

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