WO2021065205A1 - Composition de resine polyamide semi-aromatique renforcee inorganique - Google Patents

Composition de resine polyamide semi-aromatique renforcee inorganique Download PDF

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WO2021065205A1
WO2021065205A1 PCT/JP2020/030391 JP2020030391W WO2021065205A1 WO 2021065205 A1 WO2021065205 A1 WO 2021065205A1 JP 2020030391 W JP2020030391 W JP 2020030391W WO 2021065205 A1 WO2021065205 A1 WO 2021065205A1
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aromatic polyamide
semi
resin composition
acid
polyamide resin
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PCT/JP2020/030391
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English (en)
Japanese (ja)
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誠 玉津島
山田　潤
鮎澤　佳孝
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東洋紡株式会社
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Publication of WO2021065205A1 publication Critical patent/WO2021065205A1/fr

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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention has a semi-aromatic polyamide resin composition that is excellent in heat resistance, heat discoloration, and low outgassing properties, has a good balance of toughness and rigidity, and is suitable for molding automobile parts, bicycle parts, electric / electronic parts, and the like. Regarding things.
  • thermoplastic resins polyamide resins have been used for clothing, fibers for industrial materials, engineering plastics, etc., taking advantage of their excellent properties and ease of melt molding.
  • engineering plastics are not limited to automobile parts and industrial machine parts, but are widely used in various industrial parts, housing parts, electrical and electronic parts, and the like.
  • Patent Document 1 a small amount of polyolefin resin is blended with the polyamide resin. How to do it is shown.
  • the surface mounting method (flow method, reflow method) is rapidly becoming popular due to the miniaturization of parts, the high density of mounting, the simplification of processes and the cost reduction due to the miniaturization of product size. It has penetrated.
  • the resin used is inevitably required to have heat resistance at the above atmosphere temperature.
  • swelling and deformation of the mounting component due to the water absorption of the resin may become a problem, and the resin used is required to have low water absorption.
  • Resins satisfying these characteristics include 6T-based polyamides and 9T-based polyamides, and Patent Documents 2 and 3 and the like indicate that these aromatic polyamides can be used for surface mount type electrical and electronic components.
  • the color tone of the resin is likely to change in the manufacturing process or the usage environment, and there is room for improvement from the viewpoint of the color tone stability of the resin due to external factors.
  • the various semi-aromatic polyamide resins described above have a high melting point and inferior melt fluidity as compared with the aliphatic polyamide resin, and have the drawbacks of thickening during melt retention and easy gelation, resulting in processing stability and high fluidity. There is room for improvement in terms of sexuality (see, for example, Patent Document 4).
  • the invention has been improved in terms of color stability and gelation, it has a problem in that the mold is contaminated by the gas generated during melt molding and the productivity is deteriorated.
  • an object of the present invention is to have solder heat resistance, low water absorption, mechanical characteristics (particularly balance between rigidity and toughness) necessary for use in surface mount type electrical and electronic components, and to achieve heat resistance and heat discoloration. It is an object of the present invention to provide an inorganic reinforced semi-aromatic polyamide resin composition which is excellent, can suppress mold contamination due to outgas during melt molding, and is excellent in melt fluidity and gelation characteristics.
  • the present invention has the following configuration.
  • Inorganic reinforced semi-aromatic containing 30 to 73.5% by mass of semi-aromatic polyamide (A), 1.5 to 14% by mass of modified olefin polymer (B), and 25 to 65% by mass of inorganic reinforcing material (C).
  • Polyamide resin composition The mass ratio (A / B) of the semi-aromatic polyamide (A) to the modified olefin polymer (B) is 5.5 to 20.
  • the semi-aromatic polyamide (A) is at least one semi-aromatic polyamide containing a repeating unit composed of a condensation of at least one aliphatic diamine containing two or more carbon atoms and terephthalic acid.
  • the amino group terminal concentration (AEG), the carboxy group terminal concentration (CEG) of the semi-aromatic polyamide (A) in the inorganic reinforced semi-aromatic polyamide resin composition, and the terminal concentration in which the amino group terminal is blocked with a carboxylic acid An inorganic reinforced semi-aromatic polyamide resin composition in which the relationship of EC) satisfies the formulas (1) and (2). 0 eq / t ⁇ AEG + CEG ⁇ 140 eq / t ... (1) (AEG + CEG) / (AEG + CEG + EC) ⁇ 0.80 ... (2)
  • the semi-aromatic polyamide (A) is composed of an aliphatic aminocarboxylic acid (or lactam) having 11 to 18 carbon atoms in addition to a structural unit composed of a condensation of an aliphatic diamine having 2 to 12 carbon atoms and terephthalic acid. It is a copolymer containing at least one structural unit of a unit and a structural unit consisting of a condensation of an aliphatic diamine having 2 to 12 carbon atoms and an aliphatic dicarboxylic acid having 2 to 12 carbon atoms.
  • the inorganic reinforced semi-aromatic polyamide resin composition according to [1].
  • the copolymer of the semi-aromatic polyamide (A) contains 55 to 75 mol% of the constituent unit consisting of the condensation of hexamethylenediamine and terephthalic acid, and 45 to 25 mol% of the constituent unit consisting of 11-aminoundecanoic acid or undecantham.
  • R 1, R 2 is hydrogen, an alkyl group, an aryl group, a cycloalkyl group or an arylalkyl group
  • X 1 ⁇ X 3 is hydrogen, an alkyl group, an aryl group, a cycloalkyl group, an arylalkyl group, an alkali metal or an alkaline earth metal, may form a single linking to ring structure of the X 1 ⁇ X 3 in each formula R 1 ⁇ R 2)
  • the present invention has mechanical characteristics (particularly the balance between rigidity and toughness), is excellent in heat resistance and heat discoloration, can suppress mold contamination due to outgas during melt molding, and is excellent in melt fluidity and gelation characteristics.
  • an inorganic reinforced semi-aromatic polyamide resin composition can be provided.
  • the semi-aromatic polyamide (A) in the present invention means one containing a dicarboxylic acid or diamine having an aromatic skeleton in the repeating unit of the polyamide.
  • the semi-aromatic polyamide (A) in the present invention is at least one semi-aromatic polyamide containing a repeating unit consisting of a condensation of at least one aliphatic diamine containing two or more carbon atoms and terephthalic acid. It preferably contains 50 mol% or more of a structural unit composed of a condensation of an aliphatic diamine having two or more carbon atoms and terephthalic acid.
  • the structural unit is preferably 55 mol% or more, more preferably 55 to 75 mol%, still more preferably 60 to 70 mol%. If the structural unit composed of the condensation of diamine and terephthalic acid is less than 50 mol%, the crystallinity and mechanical characteristics are deteriorated.
  • the aliphatic diamine having two or more carbon atoms is preferably an aliphatic diamine having 2 to 12 carbon atoms.
  • the temperature may be lower than 290 ° C., so that the aliphatic diamine having 2 to 8 carbon atoms may have a melting point.
  • a semi-aromatic polyamide containing 50 mol% or more of a constituent unit composed of a condensation of diamine and terephthalic acid and having a melting point of 290 ° C. or higher is preferable.
  • the structural unit composed of the condensation of an aliphatic diamine having 2 to 8 carbon atoms and terephthalic acid is more preferably 55 mol% or more, further preferably 55 to 75 mol%, and particularly preferably 60 to 70 mol%.
  • Other than the aliphatic diamine having 2 to 12 carbon atoms there are 1,13-tridecamethylenediamine, 1,16-hexamethylenediamine, 1,18-octadecamethylenediamine and the like, which also impair the effect of the present invention. It can be used as a copolymerization component as long as it is in a small amount.
  • Examples of the copolymerizable dicarboxylic acid component include isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, and 2,2'-diphenyldicarboxylic acid.
  • Aromatic dicarboxylic acids such as 4,4'-diphenyl ether dicarboxylic acid, sodium isophthalic acid 5-sulfonate, 5-hydroxyisophthalic acid, fumaric acid, maleic acid, succinic acid, itaconic acid, adipic acid, azelaic acid, sebacic acid, 1,11-Undecanedioic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, 1,18-octadecandioic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1, Examples thereof include aliphatic and alicyclic dicarboxylic acids such as 2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid and dimer acid. Examples thereof include lactams such as ⁇ -caprolactam, 12-aminodo
  • the semi-aromatic polyamide (A) is composed of an aliphatic aminocarboxylic acid (or lactam) having 11 to 18 carbon atoms in addition to a structural unit composed of a condensation of an aliphatic diamine having 2 to 12 carbon atoms and terephthalic acid. It is preferable that the copolymer contains a unit and at least one structural unit of a structural unit consisting of a condensation of an aliphatic diamine having 2 to 12 carbon atoms and an aliphatic dicarboxylic acid having 2 to 12 carbon atoms.
  • the copolymerization component it is preferable that one or a plurality of aliphatic aminocarboxylic acids having 11 to 18 carbon atoms or aliphatic lactams having 11 to 18 carbon atoms are copolymerized.
  • the semi-aromatic polyamide (A) in the present invention preferably satisfies (i) 7.5 ⁇ [number of carbon atoms in polyamide / number of amide bonds in polyamide]. Further, the semi-aromatic polyamide in the present invention preferably satisfies 7.5 ⁇ [the number of carbon atoms in the polyamide / the number of amide bonds in the polyamide] ⁇ 8.2.
  • the semi-aromatic polyamide (A) in the present invention preferably satisfies (ii) [number of carbon atoms on aromatic ring in polyamide / total number of carbon atoms in polyamide] ⁇ 0.35. Further, the semi-aromatic polyamide in the present invention preferably satisfies 0.28 ⁇ [the number of carbon atoms on the aromatic ring in the polyamide / the total number of carbon atoms in the polyamide] ⁇ 0.35.
  • LED lighting parts and automobile interior / exterior parts receive ultraviolet rays when used outdoors, so the materials are required to have high UV resistance.
  • the number of carbon atoms on the aromatic ring in the polyamide / the total number of carbon atoms in the polyamide] exceeds 0.35, the absorption of light becomes large especially in the ultraviolet region, and the deterioration of the resin tends to be remarkable due to the light. ..
  • the presence of an aromatic ring makes it easier for the resin to form a conjugated structure that causes discoloration due to deterioration, and exhibits remarkable discoloration. Therefore, it is preferable that the aromatic ring concentration in the resin is low.
  • [the number of carbon atoms on the aromatic ring in the polyamide / the total number of carbon atoms in the polyamide] is preferably 0.28 or more.
  • Examples of the semi-aromatic polyamide in the present invention include hexamethylenediamine / terephthalic acid / aminoundecanoic acid (or undecalactam), hexamethylenediamine / terephthalic acid / aminododecanoic acid (or 12-lauryllactam), and decamethylenediamine / terephthal. Acids / aminoundecanoic acid (or undecalactam) and decamethylenediamine / terephthalic acid / aminododecanoic acid (or 12-lauryllactam) are particularly preferred, but from the viewpoint of high melting point, hexamethylenediamine and terephthalic acid are particularly preferable.
  • the copolymerized polyamide composed of 45 to 25 mol% of a constituent unit (also referred to as 11 units) composed of 11-aminoundecanoic acid or undecanlactam. It is more preferable that the copolymerized polyamide is composed of 60 to 70 mol% of 6T units and 40 to 30 mol% of 11 units.
  • the melting point (Tm) of the semi-aromatic polyamide in the present invention is preferably 290 to 350 ° C., more preferably 290 to 340 ° C., and even more preferably 300 to 330 ° C. If Tm exceeds the above upper limit, the processing temperature required for molding the semi-aromatic polyamide resin composition by injection molding or the like becomes extremely high, so that it may be decomposed during processing and the desired physical properties and appearance may not be obtained. is there. On the contrary, when Tm is less than the above lower limit, the crystallization rate becomes slow and molding becomes difficult in either case.
  • the total number of terminals which is the sum of the amino group terminal concentration (AEG), the carboxyl group terminal concentration (CEG), and the terminal concentration (EC) blocked with a carboxylic acid and / or amine, and the relative viscosity (RV) of the polyamide resin.
  • AEG amino group terminal concentration
  • CEG carboxyl group terminal concentration
  • EC terminal concentration
  • RV relative viscosity
  • EC refers to the terminal concentration in which the amino group terminal is blocked with a carboxylic acid.
  • the amino group terminal, the carboxyl group terminal, and the terminal sealed with a carboxylic acid or / and an amine may be referred to as AEG, CEG, and EC, respectively.
  • (AEG + CEG) of the semi-aromatic polyamide (A) which is a raw material used is used.
  • (AEG + CEG) is less than 10 eq / t, no reactive terminal group remains, and the viscosity cannot be increased to the relative viscosity (RV) at which the mechanical strength of the molded product can be ensured.
  • RV relative viscosity
  • (AEG + CEG) exceeds 140 eq / t the amount of terminal blockade is small and the amount of AEG and CEG remaining is large, so that the thickening and gelation occur during melt molding.
  • / (AEG + CEG + EC) is preferably 0.80 or less, more preferably 0.70 or less, further preferably 0.60 or less, particularly preferably 0.50 or less, and most preferably 0. It is .40 or less.
  • (AEG + CEG) / (AEG + CEG + EC) exceeds 0.80, the content of the terminal blocker is small and the residual amount of AEG and CEG is large, so that the thickening and gelation occur during melt molding.
  • the acid component of CEG causes a coloring reaction to occur, resulting in poor color stability and a resin that easily gels.
  • the semi-aromatic polyamide (A) satisfies the above-mentioned terminal group relationship.
  • the AEG, CEG, and EC of the semi-aromatic polyamide (A), which is the raw material, may satisfy the above-mentioned relationship, but the preferable ranges of each are as follows.
  • the AEG is preferably 5 to 70 eq / t, more preferably 10 to 40 eq / t, and even more preferably 15 to 40 eq / t.
  • the CEG is preferably 5 to 100 eq / t, more preferably 5 to 70 eq / t, and even more preferably 15 to 50 eq / t.
  • the EC is preferably 60 to 240 eq / t, more preferably 80 to 200 eq / t, and even more preferably 80 to 170 eq / t.
  • the relative viscosity (RV) of the semi-aromatic polyamide (A) in the present invention is preferably 1.3 to 3.5, more preferably 1.5 to 3.0, and even more preferably 1.8 to 1.8. It is 2.8, more preferably 1.9 to 2.5. If the RV is less than 1.3, the mechanical strength of the molded product cannot be obtained. When the RV is larger than 3.5, the fluidity at the time of melt molding becomes low, which is not preferable in terms of melt processability.
  • the semi-aromatic polyamide (A) in the present invention has a sum (P3) of phosphorus atom contents derived from phosphorus compounds detected in the structures of the structural formulas (P1) and (P2) in the semi-aromatic polyamide of 30 ppm or more. It is preferable that P3 is 10% or more with respect to the total amount of phosphorus atoms remaining in the semi-aromatic polyamide.
  • the phosphorus atom is derived from a phosphorus compound used as a catalyst. P3 is more preferably 40 ppm or more, still more preferably 50 ppm or more.
  • P3 When P3 is less than 30 ppm, the peroxide generated due to thermal oxidative deterioration cannot be suppressed, so that yellowing and coloring are likely to occur in a high temperature atmosphere. In addition, the peroxide generated by thermal oxidative deterioration results in a resin that easily gels.
  • P3 When P3 is less than 10% of the total residual phosphorus atomic weight, it means that the resin has been damaged by heat due to the thermal history during polymerization or that it has reacted with oxygen remaining in the polymerization system and oxidative deterioration has progressed. This means that the resin is easily colored and easily gelled.
  • the upper limit of the ratio of P3 to the total residual phosphorus atomic weight is not particularly determined, but is about 50% in the present invention.
  • the oxygen concentration in the storage tank was set to 10 ppm or less, and the polycondensation step was carried out at a low temperature to obtain a low-order condensate. After that, it can be achieved by adjusting the viscosity to a predetermined value by solid-phase polymerization having a small thermal history. Since P3 is 30 ppm or more with respect to the total residual phosphorus atomic weight, the total phosphorus atomic weight remaining in the semi-aromatic polyamide is preferably 200 to 400 ppm.
  • R 1, R 2 is hydrogen, an alkyl group, an aryl group, a cycloalkyl group or an arylalkyl group
  • X 1 ⁇ X 3 is hydrogen, an alkyl group, an aryl group, a cycloalkyl group, an arylalkyl group, an alkali metal or an alkaline earth metal, may form a single linking to ring structure of the X 1 ⁇ X 3 in each formula R 1 ⁇ R 2)
  • the phosphorus compound used as a catalyst will be described later, but when sodium hypophosphate is used as the catalyst, R 1 and R 2 are hydrogen, and X 1 to X 3 are hydrogen or sodium, respectively.
  • ⁇ Co-b before and after the semi-aromatic polyamide resin composition of the present invention is heat-treated in the air at 260 ° C. for 10 minutes. Can be 12 or less. Further, a semi-aromatic polyamide resin composition having a gelation time of 4 hours or more when heat-treated at 330 ° C. under a nitrogen stream can be obtained. ⁇ Cob and gelation time are set by the method described in the section of Examples described later.
  • the method for producing the semi-aromatic polyamide (A) in the present invention includes a step of preparing a raw material aqueous solution constituting the semi-aromatic polyamide and a raw material introduction step of continuously introducing the raw material aqueous solution into a tubular reactor.
  • An amidation step in which the raw material is passed through a tubular reactor and amidated to obtain a reaction mixture containing the amidate and condensed water, and the reaction mixture is introduced into a continuous reactor capable of separating and removing water to carry out melt polymerization.
  • This includes a step of performing solid phase polymerization under vacuum or a nitrogen stream.
  • Preparation step A predetermined amount of diamine and dicarboxylic acid are added to the pressure-resistant reaction can. At the same time, water is added so that the concentration of the raw material is 30 to 90% by weight, and a phosphorus compound as a polymerization catalyst and a carboxylic acid as a terminal blocker are charged. In addition, a foaming inhibitor is added to those that foam in the subsequent process.
  • Examples of the catalyst used in producing the semi-aromatic polyamide (A) in the present invention include compounds of dimethylphosphinic acid, phenylmethylphosphinic acid, hypophosphorous acid, ethyl hypophosphate, and phosphorous acid, and these. There are hydrolyzates and condensates. Alternatively, the metal salt, ammonium salt, and ester thereof can be mentioned. Specific examples of the metal species of the metal salt include potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, and antimony.
  • ester ethyl ester, isopropyl ester, butyl ester, hexyl ester, isodecyl ester, octadecyl ester, decyl ester, stearyl ester, phenyl ester and the like can be added.
  • sodium hypophosphate is preferable as the catalyst.
  • sodium hydroxide it is preferable to add sodium hydroxide.
  • the end-sealing agent is preferably added at the time of raw material preparation, but it may be at the start of polymerization, the late stage of polymerization, or the end of polymerization.
  • the terminal sequestering agent is not particularly limited as long as it is a monofunctional compound having reactivity with an amino group or a carboxyl group at the end of polyamide, but it is monocarboxylic acid or an acid anhydride such as monoamine or phthalic anhydride, or mono. Isocyanates, monoacid halides, monoesters, monoalcohols and the like can be used.
  • Aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, capric acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutylic acid are examples of the terminal blocker.
  • Aliphatic monocarboxylic acids such as acids and cyclohexanecarboxylic acids, benzoic acids, toluic acids, ⁇ -naphthalenecarboxylic acids, ⁇ -naphthalenecarboxylic acids, methylnaphthalenecarboxylic acids, aromatic monocarboxylic acids such as phenylacetic acid, maleic anhydride , Acid anhydrides such as phthalic acid anhydride and phthalic acid anhydride, and fats such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine and dibutylamine.
  • Aliphatic monoamines such as group monoamines, cyclohexylamines and dicyclohexylamines; aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine can be mentioned.
  • the terminal blocking agent is preferably a monocarboxylic acid, and among the above examples, acetic acid and benzoic acid are preferable.
  • the salt concentration of the raw material aqueous solution varies depending on the type of polyamide and is not particularly limited, but is generally preferably 30 to 90% by mass. If the salt concentration exceeds 90% by mass, slight fluctuations in temperature may cause salt to precipitate and clog the piping, and since it is necessary to increase the solubility of the salt, the equipment is equipped with high temperature and high pressure resistance specifications. Therefore, it is disadvantageous in terms of cost. On the other hand, when the salt concentration is less than 30% by mass, the amount of water evaporated after the initial polymerization step increases, which is disadvantageous in terms of energy and causes a cost increase due to a decrease in productivity.
  • the desired salt concentration is 35-85% by weight.
  • the salt aqueous solution is generally prepared in the temperature range of 60 to 180 ° C. and the pressure range of 0 to 1 MPa.
  • the equipment has a high temperature and high withstand voltage specification, which increases the equipment cost and is disadvantageous.
  • the temperature is less than 60 ° C or the pressure is less than 0 MPa, not only will it cause troubles such as clogging of the piping due to salt precipitation, but it will also be difficult to increase the salt concentration, resulting in productivity. It causes a decline.
  • Desirable conditions are a temperature of 70 to 170 ° C. and a pressure of 0.05 to 0.8 MPa, more preferably 75 to 165 ° C. and 0.1 to 0.6 MPa.
  • the salt aqueous solution prepared in this way is continuously supplied to the amidation step by the supply pump in the raw material introduction step.
  • the supply pump used here must be highly quantitative.
  • the fluctuation of the supply amount becomes the process fluctuation of the amidation step, and as a result, a polyamide having a large deviation in relative viscosity (RV) and unstable quality can be obtained. From this point of view, it is recommended to use a plunger pump with excellent quantification as the supply pump.
  • the atmospheric oxygen concentration at the time of raw material preparation greatly affects the color tone of the obtained polyamide. There is no problem if the atmospheric oxygen concentration at the time of raw material preparation is 10 ppm or less, but if the oxygen concentration exceeds 10 ppm, the yellowness of the obtained polyamide becomes strong and the quality of the product tends to deteriorate.
  • the lower limit of the oxygen concentration is not particularly defined, but is, for example, 0.05 ppm or more.
  • the oxygen concentration is less than 0.05 ppm, but in order to achieve less than 0.05 ppm, the oxygen removal process becomes more complicated than necessary, and the color tone and the like are started. There is almost no effect on other physical properties.
  • the range of desirable oxygen concentration is 0.05 ppm or more and 9 ppm or less, and more preferably 0.05 ppm or more and 8 ppm or less.
  • the raw material is supplied to a compounding tank (melting tank or raw material salt forming tank) in which oxygen is removed in advance and the oxygen concentration is 10 ppm or less, or the raw material is put into the compounding tank (melting tank or raw material salt forming tank). Later, oxygen may be removed to reduce the atmosphere in the compounding tank to an oxygen concentration of 10 ppm or less, or both may be used in combination. This may be selected from the aspect of equipment or operation. It is also preferable that the atmosphere in the storage tank has an oxygen concentration of 10 ppm or less.
  • Oxygen removal methods include vacuum substitution method, pressure substitution method, or a combination thereof.
  • the degree of vacuum or the degree of pressurization applied to the substitution and the number of substitutions may be selected from the conditions most efficient for achieving the desired oxygen concentration.
  • the salt aqueous solution prepared in the raw material preparation step is continuously introduced into the inlet of the tubular reactor in the amidation step by a supply pump through a pipeline.
  • amidation step In the amidation step, a salt aqueous solution continuously introduced into the inlet of the tubular reactor is passed through the tubular reactor to perform amidation, and the amidation product having a low degree of polymerization and condensed water are used. A reaction mixture containing and is obtained. Water is not separated and removed in the tubular reactor.
  • the tubular reactor preferably has an L / D of 50 or more, where the inner diameter of the tube is D (mm) and the length of the tube is L (mm).
  • the tubular reactor has merits such as no need for liquid level control due to its structure, high plug flow property, excellent pressure resistance, and low equipment cost.
  • L / D is less than 50, if L is small, the residence time of the reaction mixture flow is short and the degree of increase in relative viscosity (RV) is small, while if D is large, the plug flow property is small and retention is small. A time distribution is created, and the desired function is not performed.
  • the upper limit of L / D is not particularly defined, but is about 3000 in consideration of the residence time and the degree of increase in relative viscosity (RV).
  • the lower limit of L / D is more preferably 60 or more, the upper limit is more preferably 80 or more, the upper limit is more preferably 2000 or less, and further preferably 1000 or less.
  • the lower limit of L is preferably 3 m or more, more preferably 5 m or more, and the upper limit is preferably 50 m or less, more preferably 30 m or less.
  • the reaction conditions vary depending on the structure of the polyamide and the desired degree of polymerization.
  • the internal temperature is 110 to 310 ° C.
  • the internal pressure is 0 to 5 MPa
  • the average residence time of the reaction mixture in the tube is 10 to 120 minutes. is there.
  • the degree of polymerization of the amidation product can be controlled by the internal temperature, internal pressure and average residence time.
  • the average residence time is shorter than 10 minutes, the degree of polymerization of the amidation product having a low degree of polymerization becomes low, and as a result, the diamine component tends to scatter during the polycondensation step, making it difficult to adjust the terminal groups.
  • the average residence time is longer than 120 minutes, the amidation reaches equilibrium, the increase in RV reaches a plateau, and the thermal deterioration progresses, which is not preferable.
  • the desired average residence time is 12 to 110 minutes, more preferably 15 to 100 minutes.
  • the average residence time can be controlled by adjusting the inner diameter D of the tube of the tubular reactor, the length L of the tube, or changing the amount of raw material supplied.
  • the relative viscosity (RV) of the reaction mixture increases by 0.05 to 0.6 at the inlet and outlet of the tubular reactor by the polycondensation reaction in the amidation step.
  • RV relative viscosity
  • the increase in RV is smaller than 0.05, the diamine component tends to scatter during the polycondensation step, making it difficult to adjust the terminal groups.
  • the increase in RV is made larger than 0.6, thermal deterioration tends to proceed due to the influence of coexisting condensed water (in the case of the salt forming method, the water used for salt formation and the condensed water).
  • the reaction mixture having an excessively high viscosity may cause pipe blockage, which may adversely affect the operation.
  • the desired range of increase in RV in the amidation step is 0.15 to 0.5, more preferably 0.2 to 0.4.
  • the reaction conditions in the initial polymerization step are that the internal pressure is 0 to 5 MPa, the average residence time is 10 to 150 minutes, and the internal temperature is determined according to the melting point drop formula of Free by the residual water content in the can. Will be done. Desirable reaction conditions are an internal temperature of 230-285 ° C., an internal pressure of 0.5-4.5 MPa, an average residence time of 15-140 minutes, and a more desirable reaction condition is an internal temperature of 235-280. The temperature is ° C., the internal pressure is 1.0 to 4.0 MPa, and the average residence time is 20 to 130 minutes.
  • reaction conditions deviate from the lower limit of the above range, the degree of polymerization reached is too low, and the resin solidifies in the can, which is not preferable. If the reaction conditions deviate from the upper limit of the above range, decomposition of the P3 component and side reactions occur at the same time, and P3 becomes less than 30 ppm, which is disadvantageous for heat-resistant yellowing and gelation characteristics.
  • the solid-phase polymerization referred to in the present invention refers to a step of advancing the polymerization reaction under vacuum or a nitrogen stream at an arbitrary temperature within the range where the semi-aromatic polyamide does not melt.
  • the equipment for performing solid-phase polymerization is not particularly limited, and examples thereof include a blender and a vacuum dryer. Desirable reaction conditions are an internal temperature of 200 to 260 ° C. and an internal pressure of 0.7 KPa or less, and more desirable reaction conditions are an internal temperature of 210 to 250 ° C. and an internal pressure of 0.4 KPa or less.
  • the blending amount of the semi-aromatic polyamide (A) is 30 to 73.5% by mass, preferably 35 to 70% by mass, and more preferably 40, based on 100% by mass of the inorganic reinforced semi-aromatic polyamide resin composition. It is ⁇ 67% by mass, more preferably 45 to 65% by mass.
  • the blending amount is the content in the inorganic reinforced semi-aromatic polyamide resin composition as it is.
  • the modified olefin polymer (B) in the present invention is a polyolefin weight composed of a single or copolymer of an unsaturated compound having a double bond, including ethylene, propylene, ⁇ -olefin having 4 or more carbon atoms, and styrene. It is a polymer obtained by graft-reacting a compound having a functional group capable of reacting with an amino group in the coalescence. Examples of the functional group capable of reacting with the amino group include a carboxylic acid group and a carboxylic acid anhydride group.
  • Examples of the unmodified polyolefin polymer that can be used to obtain the above-mentioned modified olefin polymer (B) include homopolymers such as polyethylene, polypropylene, polybutene-1, polypentene-1, and polymethylpentene.
  • Examples thereof include polyolefins and styrene-based copolymers obtained by radical polymerization. Specific examples include an ethylene / propylene copolymer, an ethylene / butene-1 copolymer, an ethylene / hexene-1 copolymer, an ethylene / propylene / dicyclopentadiene copolymer, and an ethylene / propylene / 5-ethylidene-2.
  • the diene-based polymer is an AB-type or AB-A'type block copolymer elastic composed of a vinyl-based aromatic hydrocarbon and a conjugated diene, and the terminal blocks A and A'are
  • thermoplastic homopolymers or copolymers derived from vinyl-based aromatic hydrocarbons which may be the same or different and whose aromatic moiety may be monocyclic or polycyclic.
  • examples include styrene, ⁇ -methylstyrene, vinyltoluene, vinylxylene, ethylvinylxylene, vinylnaphthalene and mixtures thereof.
  • the intermediate polymer block B is composed of conjugated diene hydrocarbons, and examples thereof include polymers derived from 1,3-butadiene, 2,3-dimethylbutadiene, isoprene, 1,3-pentadiene and mixtures thereof. Further, the intermediate polymer block B of the block copolymer that has been hydrogenated can also be used.
  • the method for introducing a carboxylic acid group and / or a carboxylic acid anhydride group into the unmodified polyolefin and the styrene-based copolymer is not particularly limited, and graft-introducing the copolymer or the unmodified polyolefin into the unmodified polyolefin using a radical initiator, etc. Method can be used.
  • the amount of these functional group-containing components introduced is preferably in the range of 0.1 to 20 mol%, preferably 0.5 to 12 mol%, based on the total amount of the olefin monomer in the modified polyolefin.
  • a graft it is preferably in the range of 0.1 to 10% by mass, preferably 0.5 to 6% by mass with respect to the mass of the modified polyolefin. If the amount of the functional group-containing component introduced is too small, the impact resistance may not be sufficiently imparted, and if it is too large, the stability of the melt viscosity may be impaired. The amount of the functional group-containing component introduced is the same for the styrene-based copolymer.
  • olefin-based copolymer (B) having a carboxylic acid group and / and a carboxylic acid anhydride group include maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, ethylene / acrylic acid copolymer, and ethylene / methacryl. Acid copolymers, and some or all of the carboxylic acid portions in these copolymers as salts with sodium, lithium, potassium, zinc, and calcium, ethylene / methyl acrylate copolymers, ethylene / acrylic acids.
  • Ethyl copolymer ethylene / methyl methacrylate copolymer, ethylene / ethyl methacrylate copolymer, ethylene / ethyl acrylate-g-maleic anhydride copolymer (where "-g-" represents a graft (here, "-g-").
  • modified olefin polymer (B) examples include "Admer Q” (maleic anhydride-modified polypropylene, polyethylene) manufactured by Mitsui Chemicals, "Umex” (maleic anhydride-modified polyprepylene) manufactured by Sanyo Kasei, and "Mileic anhydride-modified polyprepylene” manufactured by Mitsui Chemicals.
  • Toughmer M maleic anhydride-modified ethylene-butene copolymer
  • Sumitomo Chemical's "Bond First” ethylene-glycidyl (meth) acrylicate copolymer
  • Asahi Kasei's "Toughtec M” maleic anhydride-modified SEBS
  • Modiper C1430G polypropylene-g-GMA / AS copolymer manufactured by Nichiyu Co., Ltd.
  • Epocross RPS-1005" oxazoline group-containing polystyrene manufactured by Nippon Catalyst Co., Ltd., and the like.
  • the blending amount of the modified olefin polymer (B) is 1.5 to 14% by mass, preferably 2 to 13% by mass, and 2 to 10% by mass with respect to 100% by mass of the inorganic reinforced semi-aromatic polyamide resin composition. More preferably by mass. If it is less than 1.5% by mass, the effect of imparting impact resistance is small, and if it exceeds 14% by mass, the viscosity of the resin composition increases and the fluidity during molding is inferior, and the mold is released from the mold. Sex gets worse.
  • the mass ratio (A / B) of the semi-aromatic polyamide (A) and the modified olefin polymer (B) in the present invention is 5.5 to 20. If this mass ratio exceeds 20, the effect of imparting impact resistance is small, and if it is less than 5.5, the viscosity of the resin composition increases and the fluidity during molding is inferior, and the mold is released from the mold. It is not preferable because it also reduces the sex.
  • the inorganic reinforcing material (C) in the present invention most effectively improves physical properties such as strength, rigidity and heat resistance, and specifically, glass fiber, carbon fiber, alumina fiber, silicon carbide fiber, etc.
  • glass fiber such as strength, rigidity and heat resistance
  • carbon fiber such as aluminum borate and potassium titanate
  • acicular warastonite such as acicular warastonite, and milled fibers.
  • glass fiber, carbon fiber and the like are particularly preferably used.
  • These inorganic reinforcing materials (C) may be only one type or a combination of two or more types.
  • fibrous reinforcing material is used as the inorganic reinforcing material (C), among the above, glass fiber, carbon fiber and the like are particularly preferably used.
  • These fibrous reinforcing materials are preferably those which have been pretreated with a coupling agent such as an organic silane compound, an organic titanium compound, an organic borane compound and an epoxy compound, and have a carboxylic acid group and / or a carboxylic acid. Those that easily react with the anhydride group are particularly preferable.
  • a polyamide-based resin composition containing glass fibers treated with a coupling agent is preferable because a molded product having excellent mechanical properties and appearance characteristics can be obtained.
  • other fibrous reinforcing materials can also be used after being added if the coupling agent has not been treated.
  • the inorganic reinforcing material (C) is glass fiber
  • a chopped strand-like material cut to a fiber length of about 1 to 20 mm can be preferably used.
  • a glass fiber having a circular cross section and a non-circular cross section can be used.
  • a glass fiber having a non-circular cross section is preferable from the physical characteristics.
  • Non-circular cross-section glass fibers include those having a substantially elliptical system, a substantially elliptical system, and a substantially cocoon-shaped cross section in a cross section perpendicular to the length direction of the fiber length, and have a flatness of 1.5 to 8. Is preferable.
  • the flatness is assumed to be a rectangle having the smallest area circumscribing a cross section perpendicular to the longitudinal direction of the glass fiber, the length of the long side of this rectangle is the major axis, and the length of the short side is the minor axis.
  • This is the ratio of major axis / minor axis when The thickness of the glass fiber is not particularly limited, but the minor axis is about 1 to 20 ⁇ m and the major axis is about 2 to 100 ⁇ m.
  • the blending amount of the inorganic reinforcing material (C) is 25 to 65% by mass, preferably 30 to 60% by mass, and more preferably 33 to 55% by mass with respect to 100% by mass of the inorganic reinforced semi-aromatic polyamide resin composition. %, More preferably 35 to 50% by mass. If the blending amount exceeds 65% by mass, the productivity deteriorates. Further, if it is less than 25% by mass, the effect of the reinforcing material may not be sufficiently exhibited, and the shearing force is insufficient at the time of kneading with the semi-aromatic polyamide (A) component, and the thickening reaction of the component (A) proceeds sufficiently. It may disappear.
  • the blending amount is the content in the inorganic reinforced semi-aromatic polyamide resin composition as it is.
  • a conductive filler other than the inorganic reinforcing material (C)
  • a conductive filler can be used for different purposes other than the reinforcing filler.
  • These fillers are not limited to one type alone, but may be used in combination of several types.
  • the shape is not particularly limited, but a needle shape, a spherical shape, a plate shape, an amorphous shape, or the like can be used.
  • the inorganic reinforced semi-aromatic polyamide resin composition of the present invention contains the amorphous polyamide (D) in addition to the semi-aromatic polyamide (A) to obtain a better molded product appearance and further dimensional stability. Can also be improved.
  • amorphous does not show a clear melting point peak when DSC is measured at a heating rate of 20 ° C./min according to JIS K7121.
  • amorphous polyamides particularly preferable ones are hexamethylenediamine and terephthalic acid / isophthalic acid copolymer (6T / 6I), 4,4'-diamino-3, 3'-dimethyl-dicyclohexylenemethane.
  • CA isophthalic acid
  • LL lauryllactam
  • TMD trimethyl-hexamethylenediamine
  • the mass ratio (A / D) of the semi-aromatic polyamide (A) and the amorphous polyamide (D) is preferably 5.5 to 20.
  • this mass ratio is larger than 20, the effect of improving the molding appearance and dimensional stability is reduced, and when it is less than 5.5, the mold releasability from the mold at the time of molding is deteriorated and the heat resistance is lowered.
  • AEG, CEG, and EC are preferably in the same range as the semi-aromatic polyamide (A).
  • additives for conventional polyamides can be used in the inorganic reinforced semi-aromatic polyamide resin composition of the present invention.
  • additives stabilizers, impact improvers, flame retardants, mold release agents, slidability improvers, colorants, plasticizers, crystal nucleating agents, semi-aromatic polyamides (A) and amorphous polyamides of the present invention.
  • examples thereof include a polyamide resin different from (D) and a thermoplastic resin other than the polyamide resin.
  • Stabilizers include organic antioxidants such as hindered phenolic antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants, thermal stabilizers, hindered amine-based, benzophenone-based, and imidazole-based light stabilizers. Examples include UV absorbers, metal deactivators, copper compounds and the like. Copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cupric chloride, cupric bromide, cupric iodide, cupric phosphate, cupric pyrophosphate, Copper salts of organic carboxylic acids such as copper sulfide, copper nitrate and copper acetate can be used.
  • the constituent components other than the copper compound preferably contain an alkali metal halide compound
  • the alkali metal halide compound includes lithium chloride, lithium bromide, lithium iodide, sodium fluoride, sodium chloride, and bromide.
  • Examples include sodium, sodium iodide, potassium fluoride, potassium chloride, potassium bromide, potassium iodide and the like. These additives may be used not only alone but also in combination of several.
  • the inorganic reinforced semi-aromatic polyamide resin composition of the present invention may be polymer-blended with a polyamide resin having a composition different from that of the semi-aromatic polyamide (A) and the amorphous polyamide (D).
  • thermoplastic resin other than the polyamide resin may be added to the inorganic reinforced semi-aromatic polyamide resin composition of the present invention.
  • thermoplastic resins can be blended in a molten state by melt-kneading, but the thermoplastic resin may be made into fibrous or particulate forms and dispersed in the composition of the present invention.
  • flame retardants examples include halogen-based flame retardants, non-halogen flame retardants, and flame retardants. These may be used alone or in combination.
  • brominated polystyrene brominated polystyrene, brominated polyphenylene ether, brominated bisphenol type epoxy polymer, brominated styrene anhydride maleic acid polymer, brominated epoxy resin, brominated phenoxy resin, decabromodiphenyl ether, decabromo
  • brominated polystyrene brominated polystyrene, brominated polyphenylene ether, brominated bisphenol type epoxy polymer, brominated styrene anhydride maleic acid polymer, brominated epoxy resin, brominated phenoxy resin, decabromodiphenyl ether, decabromo
  • examples thereof include biphenyl, brominated polycarbonate, perchlorocyclopentadecane and brominated crosslinked aromatic polymers.
  • non-halogen flame retardants include melamine cyanurate, red phosphorus, metal salts of phosphinic acid, and nitrogen-containing phosphoric acid compounds.
  • Flame retardant aids include antimony compounds such as antimony trioxide, antimony pentoxide, and sodium antimonate, zinc nitrate, zinc borate, zinc sulfide, molybdenum compounds, iron oxide, aluminum hydroxide, magnesium hydroxide, and silicone resins. , Fluororesin, montmorillonite, silica, metal carbonate and the like.
  • release agent examples include long-chain fatty acids or esters and metal salts thereof, amide compounds, polyethylene waxes, silicones, polyethylene oxides, and the like.
  • slidability improving material examples include high molecular weight polyethylene, acid-modified high molecular weight polyethylene, fluororesin powder, molybdenum disulfide, silicone resin, silicone oil, zinc, graphite, mineral oil and the like.
  • the inorganic reinforced semi-aromatic polyamide resin composition of the present invention has a total of 80 mass by mass of the semi-aromatic polyamide (A), the modified olefin polymer (B), the inorganic reinforcing material (C) and the amorphous polyamide (D). It occupies% or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more.
  • the method for producing the inorganic reinforced semi-aromatic polyamide resin composition of the present invention is not particularly limited, and for example, each component can be melt-kneaded by a conventionally known kneading method.
  • the specific kneading device is also not limited, and examples thereof include a single-screw or twin-screw extruder, a kneader, and a kneader, but a twin-screw extruder is particularly preferable in terms of productivity.
  • the screw arrangement is not particularly limited, but it is preferable to provide a kneading zone in order to disperse each component more evenly.
  • a semi-aromatic polyamide (A), a modified olefin polymer (B), an amorphous polyamide (D) and other additive components are preblended with a blender, and uniaxial or biaxial from the hopper.
  • the inorganic reinforcing material (C) is charged into the melt mixture by a feeder into a single-screw or twin-screw extruder. Examples thereof include a method in which the mixture is melt-kneaded and then discharged into a strand, cooled and cut.
  • the "terminal group of the semi-aromatic polyamide (A) in the inorganic reinforced semi-aromatic polyamide resin composition" is , Refers to the sum of the terminal groups of the semi-aromatic polyamide (A) and the amorphous polyamide (D) in the inorganic reinforced semi-aromatic polyamide resin composition.
  • the AEG and CEG of the semi-aromatic polyamide (A) and the amorphous polyamide (D) in the inorganic reinforced semi-aromatic polyamide resin composition of the present invention are usually the semi-aromatic polyamide (A) and the amorphous as raw materials used. It is smaller than the sex polyamide (D). This is because some of the terminal groups react with each other due to melt-kneading under high temperature conditions during production, resulting in slight thickening. In the composition containing 25% by mass or more of the inorganic reinforcing material (C), higher shear is applied to the polyamide, so that the thickening reaction further proceeds and AEG and CEG become smaller.
  • the amount of decrease in AEG and CEG cannot be unequivocally determined because it is affected by manufacturing conditions such as resin temperature, rotation speed, and kneading time. It decreases by the same amount.
  • the terminal group of the semi-aromatic polyamide (A) (and the amorphous polyamide (D)) in the inorganic reinforced semi-aromatic polyamide resin composition it is simply "inorganic reinforced semi-aromatic polyamide resin composition”. It may be abbreviated as "terminal group of”.
  • the inorganic reinforced semi-aromatic polyamide resin composition (AEG + CEG) is 0 to 140 eq / t, preferably 0 to 130 eq / t, and more preferably 0 to 120 eq / t.
  • (AEG + CEG) exceeds 140 eq / t, the amount of terminal blockade is small and the amount of AEG and CEG remaining is large, so that the mixture thickens and gels due to melting during molding.
  • the (AEG + CEG) / (AEG + CEG + EC) of the inorganic reinforced semi-aromatic polyamide resin composition of the present invention is 0.80 or less, preferably 0.70 or less, more preferably 0.60 or less, still more preferable. Is 0.50 or less, and particularly preferably 0.40 or less.
  • (AEG + CEG) / (AEG + CEG + EC) exceeds 0.80, the content of the terminal blocker is small and the residual amount of AEG and CEG is large, so that the thickening and gelation occur during melt molding.
  • the AEG, CEG, and EC of the inorganic reinforced semi-aromatic polyamide resin composition may satisfy the above-mentioned relationship, but the preferable ranges of each are as follows.
  • the AEG is preferably 0 to 70 eq / t, more preferably 0 to 40 eq / t, further preferably 0 to 30 eq / t, and particularly preferably 0 to 20 eq / t. ..
  • the CEG is preferably 0 to 130 eq / t, more preferably 0 to 100 eq / t, further preferably 0 to 70 eq / t, and particularly preferably 0 to 50 eq / t. ..
  • the EC is preferably 60 to 240 eq / t, more preferably 80 to 200 eq / t, and even more preferably 80 to 170 eq / t.
  • polyamide resins are thickened by the reaction between the amino group terminal and the carboxyl group terminal.
  • the reaction of CEG with EC may promote thickening. If AEG disappears (becomes 0) during the amidation reaction, the ends of the semi-aromatic polyamide become CEG and EC. Due to the acid catalytic effect of CEG due to the absence of AEG, CEG attacks the amide bond formed by the terminal blocker, causing an amide transesterification reaction. At this time, the thickening reaction proceeds while distilling the terminal blocker out of the reaction system. Therefore, the outgas component derived from the terminal blockant increases. In addition, the acid component of CEG causes a coloring reaction to occur, resulting in poor color stability and a resin that easily gels. In order to avoid such a phenomenon, it is important to satisfy the above equations (1) and (2).
  • the rate of decrease in bending strength calculated from the bending strength before and after 500 hours of treatment of the inorganic reinforced semi-aromatic polyamide resin composition of the present invention in a high temperature and high humidity environment of 80 ° C. and 95% RH is less than 15%. It is preferably less than 10%, even more preferably less than 8%. If it is 15% or more, the rigidity varies depending on the humidity, which adversely affects the characteristics of precise electronic components, which is not preferable.
  • the rate of decrease in bending strength can be measured by the method described in the section of Examples described later.
  • the amount of gas (outgas) generated when the inorganic reinforced semi-aromatic polyamide resin composition of the present invention is thermally decomposed at 350 ° C. for 10 minutes is preferably 300 ppm or less.
  • the semi-aromatic polyamide (A) is further kneaded with the inorganic reinforcing material (C) or the like, thermal decomposition proceeds, so that the amount of gas in the composition is larger than the amount of gas in the component (A) alone.
  • the amount of gas (outgas) can be measured by the method described in the section of Examples described later.
  • the inorganic reinforced semi-aromatic polyamide resin composition of the present invention preferably has a tensile fracture strain of 0.3 to 3.4%.
  • the inorganic reinforced semi-aromatic polyamide resin composition of the present invention can have a tensile fracture strain within this range by satisfying the above constitution. Having the tensile fracture strain within this range is advantageous in that cracking during assembly and use as a part can be suppressed, loosening of the fixed portion is suppressed, and a sufficient fixing force can be obtained.
  • the tensile fracture strain can be measured by the method described in the section of Examples described later.
  • the inorganic reinforced semi-aromatic polyamide resin composition of the present invention preferably has a tensile strength of 100 MPa or more. It is more preferably 150 MPa or more, still more preferably 180 MPa or more.
  • the inorganic reinforced semi-aromatic polyamide resin composition of the present invention can have a tensile strength within this range by satisfying the above constitution. Having the tensile strength in this range is advantageous in that cracking during assembly and use as a part can be suppressed. The tensile strength can be measured by the method described in the section of Examples described later.
  • the molded product obtained from the inorganic reinforced semi-aromatic polyamide resin composition of the present invention has excellent heat resistance and color stability in an actual usage environment. Therefore, connectors and switches that require heat resistance are required. , Relays, printed wiring boards and other electrical and electronic parts, LEDs, lighting fixture reflectors and other parts having a function of reflecting light, and the like.
  • the inorganic reinforced semi-aromatic polyamide resin composition of the present invention is excellent in heat resistance and melt processability, it is possible to highly fill a reinforcing material, a filler, etc., and high rigidity is required. It can be used for automobile parts such as engine peripheral parts, cooling parts, fuel parts, and industrial parts such as gears, screws, and other sliding parts.
  • RV t / t 0 (However, t 0 : the number of seconds for the solvent to fall, t: the number of seconds for the sample solution to fall)
  • 1 H-NMR analysis was performed using a 500 MHz Fourier transform nuclear magnetic resonance apparatus (AVANCE500 manufactured by BRUKER), and the AEG, CEG, EC, and composition of the semi-aromatic polyamide were determined from the integration ratio. ..
  • the inorganic reinforced semi-aromatic polyamide resin compositions AEG, CEG, and EC were dissolved in a mixed solvent, centrifuged, and the supernatant was taken out, and heavy formic acid was added dropwise to measure the results in the same manner.
  • the 31 P resonance frequency is 202.5 MHz
  • the flip angle of the detection pulse is 45 °
  • the data acquisition time is 1.5 seconds
  • the delay time is 1.0 second
  • the number of integrations is 1000 to 20000 times
  • the measurement temperature is room temperature.
  • the analysis was carried out under the condition of complete proton decoupling, and the molar ratio of the phosphorus compound represented by the structural formula (P1) to the phosphorus compound represented by the structural formula (P2) was determined from the integration ratio.
  • GEER OVEN GHPS-222 manufactured by TABAI heated to 260 ° C.
  • the test piece was heated in an air reflow furnace (AIS-20-82C manufactured by Atec) from room temperature to 150 ° C for 60 seconds, preheated, and then heated to 190 ° C at a heating rate of 0.5 ° C / min. A preheat was performed. Then, the temperature was raised to a predetermined set temperature at a rate of 100 ° C./min, held at a predetermined temperature for 10 seconds, and then cooled. The set temperature was increased from 240 ° C. to every 5 ° C., and the highest set temperature at which no surface swelling or deformation occurred was defined as the reflow heat resistance temperature and used as an index of solder heat resistance.
  • ⁇ Reflow heat resistant temperature is 260 ° C or higher
  • Reflow heat resistant temperature is 250 ° C or higher and lower than 260 ° C
  • Reflow heat resistant temperature is lower than 250 ° C
  • Synthesis example 1 9.13 kg (78.6 mol) of 1,6-hexamethylenediamine, 12.24 kg (73.7 mol) of terephthalic acid, 7.9 kg (39.7 mol) of 11-aminoundecanoic acid, hypophosphorous acid as a catalyst 30.4 g of sodium, 354 g (5.9 mol) of acetic acid as a terminal blocker, and 16.20 kg of ion-exchanged water adjusted to 0.5 ppm or less of dissolved oxygen by nitrogen bubbling were charged into a 50 liter autoclave, and the pressure was reduced to 0. pressurized with N 2 to 05MPa, was depressurized, it was returned to normal pressure.
  • This operation was performed 10 times, N 2 substitution was performed, and then the mixture was uniformly dissolved at 135 ° C. and 0.3 MPa with stirring. Then, the solution was continuously supplied by a liquid feed pump, the temperature was raised to 260 ° C. by a heating pipe, and heat was applied for 0.5 hours. Then, the reaction mixture was supplied to the pressurized reaction can, heated to 270 ° C., and a part of water was distilled off so as to maintain the internal pressure of the can at 3 MPa to obtain a low-order condensate. Then, this low-order condensate was taken out into a container at normal temperature and pressure in the air, and then dried in an environment of 70 ° C.
  • Synthesis example 2 The amount was changed to 8.84 kg (76.1 mol) of 1,6-hexamethylenediamine and 286 g (4.8 mol) of acetic acid as a terminal blocking agent, and vacuum drying was carried out in the same manner as in Synthesis Example 1 to obtain a low-order condensate. Then, using a blender (capacity 0.1 m 3 ), the reaction was carried out in an environment of 230 ° C. and a vacuum degree of 0.07 KPa for 8 hours to obtain a semi-aromatic polyamide A-2.
  • Synthesis example 3 The mixture was changed to 9.11 kg (78.4 mol) of 1,6-hexamethylenediamine and 612 g (5.0 mol) of benzoic acid as a terminal blocking agent, and vacuum dried in the same manner as in Synthesis Example 1 to obtain a low-order condensate. .. Then, using a blender (capacity 0.1 m 3 ), the reaction was carried out in an environment of 240 ° C. and a vacuum degree of 0.07 KPa for 8 hours to obtain a semi-aromatic polyamide A-3.
  • Synthesis example 4 1,6-Hexamethylenediamine 9.00 kg (77.4 mol), terephthalic acid 12.24 kg (73.7 mol), 11-aminoundecanoic acid 7.9 kg (39.7 mol), hypophosphorous acid as a catalyst 30.4 g of sodium, 226 g (3.8 mol) of acetic acid as a terminal blocker, and 16.20 kg of ion-exchanged water adjusted to 0.5 ppm or less of dissolved oxygen by nitrogen bubbling were charged into a 50 liter autoclave, and the pressure was reduced to 0. pressurized with N 2 to 05MPa, was depressurized, it was returned to normal pressure.
  • This operation was performed 10 times, N 2 substitution was performed, and then the mixture was uniformly dissolved at 135 ° C. and 0.3 MPa with stirring. Then, the solution was continuously supplied by a liquid feed pump, the temperature was raised to 260 ° C. by a heating pipe, and heat was applied for 0.5 hours. Then, the reaction mixture was supplied to the pressurized reaction can, heated to 290 ° C., and a part of water was distilled off so as to maintain the internal pressure of the can at 3 MPa to obtain a low-order condensate. Then, this low-order condensate was taken out into a container at normal temperature and pressure in the air, and then dried in an environment of 70 ° C.
  • Synthesis example 5 The weight was changed to 8.57 kg (73.8 mol) of 1,6-hexamethylenediamine and 150 g (2.5 mol) of acetic acid as a terminal blocking agent, and vacuum drying was carried out in the same manner as in Production Example 1 to obtain a low-order condensate. Then, using a blender (capacity 0.1 m 3 ), the reaction was carried out in an environment of 220 ° C. and a vacuum degree of 0.07 KPa for 4 hours to obtain a semi-aromatic polyamide A-5.
  • Synthesis example 6 The amount was changed to 8.72 kg (75.0 mol) of 1,6-hexamethylenediamine and 24 g (0.4 mol) of acetic acid as a terminal blocking agent, and vacuum drying was carried out in the same manner as in Production Example 1 to obtain a low-order condensate. Then, using a blender (capacity 0.1 m 3 ), the reaction was carried out in an environment of 180 ° C. and a vacuum degree of 0.07 KPa for 5 hours to obtain a semi-aromatic polyamide A-6.
  • Synthesis example 7 7.54 kg (65.0 mol) of 1,6-hexamethylenediamine, 10.79 kg (65.0 mol) of terephthalic acid, 7.04 kg (35.0 mol) of 11-aminoundecanoic acid, hypophosphorous acid as a catalyst charged sodium 9 g, the ion-exchanged water 17.52kg 50 liter autoclave, pressurized with N 2 from atmospheric pressure to 0.05 MPa, was relieved and returned to normal pressure. This operation was performed three times to perform N 2 substitution, and then the mixture was uniformly dissolved at 135 ° C. and 0.3 MPa with stirring. Then, the solution was continuously supplied by a liquid feed pump, heated to 240 ° C. by a heating pipe, and heated for 1 hour.
  • Modified olefin polymer (B): Maleic anhydride-modified SEBS (Asahi Kasei Corporation, Tough Tech M1943)
  • Inorganic reinforcing material (C): Glass fiber (manufactured by Nippon Electric Glass Co., Ltd., ECS03T-275H)
  • Comparative Example 1 shows that AEG + CEG> 140 eq / t, the residual amount of AEG and CEG is large, the resin composition is easily gelled, and the moldability and the appearance of the molded product are also poor. Further, it can be seen that (AEG + CEG) / (AEG + CEG + EC)> 0.80, and the amount of the terminal blocking agent is small, and the resin composition is easily gelled. In Comparative Example 2, since the P3 component did not remain because it was melt-polymerized by a twin-screw extruder and thickened to a predetermined RV, it can be seen that the outgas, ⁇ Cob, and gelation time were deteriorated.
  • Comparative Example 3 and Comparative Example 4 the mass ratio of the component (B) is out of the range, the former is inferior in continuous moldability and releasability, and the latter is inferior in toughness. Furthermore, Comparative Example 5 containing no component (B) had extremely low toughness. Further, in Examples 8 to 11 containing the amorphous polyamide (D), the dimensional stability was excellent.

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de résine polyamide semi-aromatique renforcée inorganique, laquelle composition possède des propriétés mécaniques (plus spécifiquement d'équilibre entre rigidité et dureté) et est excellente en termes de: résistance à la chaleur; résistance à la décoloration par la chaleur; suppression des taches sur le moule dues à la libération de gaz lors d'un moulage par fusion; fluidité en fusion; et caractéristiques de gélification. Plus spécifiquement, cette composition de résine polyamide semi-aromatique renforcée inorganique contient: 30 à 73,5 % en poids d'un polyamide semi-aromatique (A); 1,5 à 14 % en poids d'un polymère (B) de type oléfine modifiée; et 25 à 65 % en poids d'une substance renforcée inorganique (C), le rapport (A/B) en poids entre le polyamide semi-aromatique (A) et le polymère (B) de type oléfine modifiée étant compris entre 5,50 et 20. En outre, cette composition de résine polyamide semi-aromatique renforcée inorganique est telle que: le polyamide semi-aromatique (A) est au moins une sorte de polyamide semi-aromatique contenant des unités répétitives obtenues par condensation d'acide téréphtalique et d'au moins une sorte de diamine aliphatique contenant au moins deux atomes de carbone; dans la composition de résine, un groupe terminal du polyamide semi-aromatique (A) satisfait une relation spécifique.
PCT/JP2020/030391 2019-09-30 2020-08-07 Composition de resine polyamide semi-aromatique renforcee inorganique WO2021065205A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114163632A (zh) * 2022-01-04 2022-03-11 上海东睿化学有限公司 一种耐黄变共聚酰胺及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH083438A (ja) * 1994-06-24 1996-01-09 Japan Synthetic Rubber Co Ltd 成形材料
WO2006098434A1 (fr) * 2005-03-18 2006-09-21 Kuraray Co., Ltd. Resine polyamide semi-aromatique
JP2008179753A (ja) * 2006-12-26 2008-08-07 Kuraray Co Ltd ポリアミド樹脂組成物およびそれからなる成形品
WO2015019882A1 (fr) * 2013-08-05 2015-02-12 東洋紡株式会社 Composition de résine polyamide ignifuge
WO2017077901A1 (fr) * 2015-11-02 2017-05-11 東洋紡株式会社 Résine de polyamide semi-aromatique et son procédé de production
WO2017217447A1 (fr) * 2016-06-17 2017-12-21 東洋紡株式会社 Résine de polyamide semi-aromatique

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH083438A (ja) * 1994-06-24 1996-01-09 Japan Synthetic Rubber Co Ltd 成形材料
WO2006098434A1 (fr) * 2005-03-18 2006-09-21 Kuraray Co., Ltd. Resine polyamide semi-aromatique
JP2008179753A (ja) * 2006-12-26 2008-08-07 Kuraray Co Ltd ポリアミド樹脂組成物およびそれからなる成形品
WO2015019882A1 (fr) * 2013-08-05 2015-02-12 東洋紡株式会社 Composition de résine polyamide ignifuge
WO2017077901A1 (fr) * 2015-11-02 2017-05-11 東洋紡株式会社 Résine de polyamide semi-aromatique et son procédé de production
WO2017217447A1 (fr) * 2016-06-17 2017-12-21 東洋紡株式会社 Résine de polyamide semi-aromatique

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114163632A (zh) * 2022-01-04 2022-03-11 上海东睿化学有限公司 一种耐黄变共聚酰胺及其制备方法

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