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WO2021054050A1 - Composition de résine polyamide semi-aromatique pour article moulé plaqué et article moulé plaqué - Google Patents

Composition de résine polyamide semi-aromatique pour article moulé plaqué et article moulé plaqué Download PDF

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Publication number
WO2021054050A1
WO2021054050A1 PCT/JP2020/031722 JP2020031722W WO2021054050A1 WO 2021054050 A1 WO2021054050 A1 WO 2021054050A1 JP 2020031722 W JP2020031722 W JP 2020031722W WO 2021054050 A1 WO2021054050 A1 WO 2021054050A1
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WIPO (PCT)
Prior art keywords
semi
polyamide resin
aromatic polyamide
acid
resin composition
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Ceased
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PCT/JP2020/031722
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English (en)
Japanese (ja)
Inventor
万希 長谷部
誠 玉津島
山田　潤
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Toyobo Co Ltd
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Toyobo Co Ltd
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Priority to JP2021546557A priority Critical patent/JP7586086B2/ja
Publication of WO2021054050A1 publication Critical patent/WO2021054050A1/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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating

Definitions

  • the present invention relates to a semi-aromatic polyamide resin composition having excellent plating properties, low water absorption, and solder reflow resistance.
  • Polyamide resin has been used for clothing, fibers for industrial materials, engineering plastics, etc., taking advantage of its excellent properties and ease of melt molding.
  • the applications of polyamide resins have been further expanded, and they are used in various applications from automobile parts around engines to electrical and electronic parts represented by smartphones.
  • a method of imparting electromagnetic wave shielding property to the component parts of the device a method of applying metal vapor deposition or metal plating to the surface of the resin molded product is known. It is used in various fields because it is easier to reduce the weight than the parts themselves made of metal and can provide sufficient electromagnetic wave shielding properties.
  • Patent Document 1 discloses a polyamide resin composition having excellent adhesion characteristics between a polyamide, an inorganic filler, and a metal plating composed of a modified styrene / olefin copolymer.
  • the polyamide resin composition described in the document has a melting point lower than 280 ° C., it is difficult to withstand the solder reflow process used in the production of substrate parts.
  • Patent Document 2 discloses a resin composition for metal vapor deposition containing a polyamide resin, a styrene resin, and a filler.
  • the resin composition for metal vapor deposition described in the document describes the good adhesion to the metal film formed by the metal vapor deposition technique, and the metal plating technique of the present invention is based on the metal film forming process. Essentially different. Further, all of the resin compositions for metal vapor deposition described in the examples have a melting point lower than 280 ° C., and it is difficult to withstand the solder reflow process.
  • Patent Document 3 discloses a resin composition for forming a plating layer containing a semi-aromatic polyamide composed of terephthalic acid and a diamine component having an alkylene group having 4 to 25 carbon atoms, and an inorganic filler.
  • a resin composition for forming a plating layer containing a semi-aromatic polyamide composed of terephthalic acid and a diamine component having an alkylene group having 4 to 25 carbon atoms, and an inorganic filler.
  • Patent Document 4 discloses a molded product having a metal layer on the surface of the molded product obtained from a polyamide resin composition composed of terephthalic acid, 1,9-nonanediamine and a filler.
  • a polyamide resin composition composed of terephthalic acid, 1,9-nonanediamine and a filler.
  • the resin compositions described in the document are limited to polyamide resins.
  • Patent Document 5 describes an electroless plating layer using a resin composition in which a filler is mixed with a semi-aromatic polyamide resin selected from any of polyamide 10T, polyamide 9T, polyamide 6T, polyamide 4T, or polyphthalamide.
  • a semi-aromatic polyamide resin selected from any of polyamide 10T, polyamide 9T, polyamide 6T, polyamide 4T, or polyphthalamide.
  • the formation method of is disclosed.
  • the technique described in the document has a limitation in terms of equipment because it is necessary to set the mold temperature to 180 to 240 ° C. when molding a substrate to be plated using the resin composition. ..
  • the present invention has been devised in view of the current state of the prior art, and an object of the present invention is to provide a semi-aromatic polyamide resin composition having excellent plating properties, low water absorption, and solder reflow resistance. Furthermore, more advanced plating properties and appearance of plated molded products have been required in recent years, and for that purpose, moldability at the molded product stage before plating is also important, and the semi-aromatic polyamide resin of the present invention is required. The composition can also solve this problem.
  • the present inventor has diligently examined the type and blending amount of the filler in addition to the composition of the semi-aromatic polyamide resin, and as a result, it is excellent in good plating property, low water absorption and solder reflow resistance.
  • the present invention has the following configuration.
  • the semi-aromatic polyamide resin (A) is a semi-aromatic polyamide resin containing 50 to 100 mol% of a repeating unit composed of a diamine having 6 to 12 carbon atoms and terephthalic acid.
  • Semi-aromatic polyamide resin composition (3) The semi-aromatic according to (1) or (2), wherein the semi-aromatic polyamide resin (A) has a terminal carboxyl group concentration of 5 to 200 eq / ton and a terminal amino group concentration of 0 to 100 eq / ton. Polyamide resin composition.
  • the non-fibrous inorganic filler (B) is at least one selected from the group consisting of kaolin, wallastonite, glass beads, diatomaceous earth, and zeolite, according to any one of (1) to (3).
  • a plated molded product obtained by plating the semi-aromatic polyamide resin composition according to any one of (1) to (4).
  • the present invention it is possible to provide a semi-aromatic polyamide resin composition having good plating property, low water absorption, and solder reflow resistance, and a plated molded product using this semi-aromatic polyamide resin composition.
  • the semi-aromatic polyamide resin (A) used in the present invention is not particularly limited, and is a semi-aromatic polyamide having an acid amide bond (-CONH-) in the molecule and an aromatic ring (benzene ring). Is.
  • 6T-based polyamide for example, polyamide 6T / 6I composed of terephthalic acid / isophthalic acid / hexamethylenediamine, polyamide 6T / 66 composed of terephthalic acid / adipic acid / hexamethylenediamine, terephthalic acid / Polyamide 6T / 6I / 66 consisting of isophthalic acid / adipic acid / hexamethylenediamine, polyamide 6T / M-5T consisting of terephthalic acid / hexamethylenediamine / 2-methyl-1,5-pentamethylenediamine, terephthalic acid / hexamethylene Polyamide 6T / 6 consisting of diamine / ⁇ -caprolactam, polyamide 6T / 4T consisting of terephthalic acid / hexamethylenediamine / tetramethylenediamine), 9
  • the C / N ratio described in the present specification is the ratio of the number of carbon atoms (C) to the number of nitrogen atoms (N) in the repeating structural unit in the semi-aromatic polyamide (A) (hereinafter referred to as the C / N ratio). Described).
  • the C / N ratio represents the amide group concentration in the polyamide, and the larger the C / N ratio, the smaller the amide group concentration.
  • the amide group is easily coordinated with water molecules, so the C / N ratio is an index of water absorption of the polyamide resin.
  • the water absorption of the polyamide resin is high, that is, when the C / N ratio is small, the water content in the molded product is rapidly heated in a post-processing step such as solder reflow, and the volume expands to cause surface swelling (blister). ) Is often a problem.
  • the C / N ratio is important for producing industrially more stable products.
  • the semi-aromatic polyamide resin (A) used in the present invention needs to have a C / N ratio of 7.3 or more. Further, it is preferably 7.5 or more.
  • the upper limit of the C / N ratio is not particularly limited, but is preferably 10.0 or less, more preferably 9.0 or less, further preferably 8.5 or less, and particularly preferably 8.2 or less.
  • the semi-aromatic polyamide resin (A) used in the present invention is preferably the following semi-aromatic polyamide resin from the viewpoint of a C / N ratio of 7.3 or more.
  • the semi-aromatic polyamide resin (A) is preferably a semi-aromatic polyamide containing 50 to 100 mol% of a repeating unit composed of a diamine having 6 to 12 carbon atoms and terephthalic acid.
  • the semi-aromatic polyamide resin (A) has 50 to 100 mol% of repeating units composed of diamine having 6 to 12 carbon atoms and terephthalic acid, and 0 repeating units consisting of aminocarboxylic acid or lactam having 10 or more carbon atoms.
  • a semi-aromatic polyamide resin containing up to 50 mol% is more preferable, and the repeating unit composed of diamine having 6 to 12 carbon atoms and terephthalic acid is composed of 50 to 98 mol% and aminocarboxylic acid or lactam having 10 or more carbon atoms.
  • a semi-aromatic polyamide resin containing 2 to 50 mol% of repeating units is more preferable, and 55 to 98 mol% of repeating units consisting of diamine having 6 to 12 carbon atoms and terephthalic acid, and amino having 10 or more carbon atoms are used.
  • a semi-aromatic polyamide resin containing 2 to 45 mol% of a repeating unit composed of a carboxylic acid or lactam is particularly preferable.
  • the ratio of the repeating unit composed of diamine and terephthalic acid having 6 to 12 carbon atoms in the semi-aromatic polyamide resin (A) is less than 50 mol%, the water content in the molded product suddenly increases in the post-processing step such as solder reflow. Surface swelling (blister) often becomes a problem due to the expansion of the volume of the resin. In addition, changes in the dimensions of the product due to water absorption cause problems during assembly and a decrease in strength.
  • the diamine components having 6 to 12 carbon atoms constituting the semi-aromatic polyamide resin (A) include 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, and 1,9-. Examples thereof include nonamethylenediamine, 2-methyl-1,8-octamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, and 1,12-dodecamethylenediamine. These may be used alone or in plurality.
  • the aminocarboxylic acid having 10 or more carbon atoms or the lactam having 10 or more carbon atoms constituting the semi-aromatic polyamide resin (A) the aminocarboxylic acid or lactam having 11 to 18 carbon atoms is preferable. Of these, 11-aminoundecanoic acid, undecane lactam, 12-aminododecanoic acid, and 12-lauryl lactam are preferable. From the viewpoint of C / N ratio of 7.3 or more, as the copolymerization component, one or more kinds of aminocarboxylic acid having 11 to 18 carbon atoms or lactam having 11 to 18 carbon atoms are copolymerized. Is preferable.
  • the semi-aromatic polyamide resin (A) used in the present invention can be copolymerized with other components in an amount of 50 mol% or less of the constituent units.
  • copolymerizable diamine components include 1,13-tridecamethylenediamine, 1,16-hexadecamethylenediamine, 1,18-octadecamethylenediamine, 2,2,4 (or 2,4,4)-.
  • Aliper diamines such as trimethylhexamethylenediamine, piperazine, cyclohexanediamine, bis (3-methyl-4-aminohexyl) methane, bis- (4,4'-aminocyclohexyl) methane, alicyclic such as isophoronediamine.
  • aromatic diamines such as diamines, metaxylylene diamines, paraxylylene diamines, paraphenylenediamines and metaphenylenediamines, and hydrogenated products thereof.
  • copolymerizable acid components include isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, and 2,2'-diphenyldicarboxylic acid, 4 , 4'-Diphenyl ether dicarboxylic acid, sodium isophthalic acid 5-sulfonate, 5-hydroxyisophthalic acid and other aromatic dicarboxylic acids, 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
  • the aromatic polyamide resin (A) used in the present invention contains 50 to 100 mol% of a repeating unit composed of hexamethylenediamine and terephthalic acid, and 0 to 50 mol% of a repeating unit composed of aminoundecanoic acid or undecanlactam. It is preferably a semi-aromatic polyamide resin, and is semi-aromatic, containing 50 to 98 mol% of repeating units consisting of hexamethylenediamine and terephthalic acid, and 2 to 50 mol% of repeating units consisting of aminoundecanoic acid or undecanlactam.
  • a semi-aromatic polyamide resin more preferably a polyamide resin, containing 55-80 mol% of repeating units consisting of hexamethylenediamine and terephthalic acid and 20-45 mol% of repeating units consisting of aminoundecanoic acid or undecanthamictum. It is a semi-aromatic polyamide resin containing 60 to 70 mol% of the repeating unit consisting of hexamethylenediamine and terephthalic acid and 30 to 40 mol% of the repeating unit consisting of aminoundecanoic acid or undecanthamictum. Is particularly preferred.
  • the ratio of the repeating unit composed of hexamethylenediamine and terephthalic acid in the semi-aromatic polyamide resin (A) is less than 50 mol%, the water content in the molded product is rapidly heated in the post-processing step such as solder reflow. As the volume expands, surface swelling (blister) often becomes a problem. In addition, changes in the dimensions of the product due to water absorption cause problems during assembly and a decrease in strength.
  • Examples of the catalyst used in producing the semi-aromatic polyamide resin (A) include phosphoric acid, phosphorous acid, hypophosphorous acid or a metal salt thereof, an ammonium salt, and an ester.
  • 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.
  • Examples of the ester include ethyl ester, isopropyl ester, butyl ester, hexyl ester, isodecyl ester, octadecyl ester, decyl ester, stearyl ester, phenyl ester and the like. Further, from the viewpoint of improving melt retention stability, it is preferable to add an alkaline compound such as sodium hydroxide, potassium hydroxide, or magnesium hydroxide.
  • the relative viscosity (RV) of the semi-aromatic polyamide resin (A) measured at 20 ° C. in 96% concentrated sulfuric acid is preferably 0.4 to 4.0, more preferably 1.0 to 3.0, and further. It is preferably 1.5 to 2.5.
  • a means for adjusting the molecular weight can be mentioned.
  • the terminal carboxyl group concentration and the terminal amino group concentration of the semi-aromatic polyamide resin (A) are preferably 5 to 200 eq / ton and 0 to 100 eq / ton, respectively. If the terminal carboxyl group concentration is less than 5 eq / ton, the adhesion with the filler is insufficient, the compatibility with the polyamide resin is deteriorated, and the dispersibility of the filler is deteriorated. If the dispersibility of the filler is deteriorated, unevenness may not be sufficiently developed after the etching step, and the metal plating may float.
  • Terminal amino group concentration is suitable.
  • the terminal group weight and molecular weight of the polyamide are adjusted by a method of polycondensing by adjusting the molar ratio of the amino group amount and the carboxyl group or a method of adding a terminal sealant. Can be done.
  • the timing for adding the end-capping agent examples include the time when the raw material is charged, the time when the polymerization starts, the time when the polymerization is delayed, or the time when the polymerization ends.
  • the terminal encapsulant 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 monocarboxylic acid or an acid anhydride such as monoamine or phthalic anhydride, Monoisocyanates, monoacid halides, monoesters, monoalcohols and the like can be used.
  • Aliphatic products 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 as end-capping agents
  • Aliphatic monocarboxylic acids such as carboxylic acids and cyclohexylcarboxylic acids, benzoic acids, toluic acids, ⁇ -naphthalenecarboxylic acids, ⁇ -naphthalenecarboxylic acids, methylnaphthalenecarboxylic acids, aromatic monocarboxylic acids such as phenylacetic acid, maleine anhydride
  • Acid anhydrides such as acid, phthalic anhydride, hexahydrophthalic anhydride, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine
  • Examples thereof include alicyclic monoamines such as aliphatic monoamines, cyclohexylamines and dicyclohexylamines, and aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine.
  • the semi-aromatic polyamide resin (A) can be produced by a conventionally known method, and can be easily synthesized, for example, by subjecting a raw material monomer to a cocondensation reaction.
  • the order of the co-condensation polymerization reaction is not particularly limited, and all the raw material monomers may be reacted at once, or some raw material monomers may be reacted first, and then the remaining raw material monomers may be reacted.
  • the polymerization method is not particularly limited, but the process from the preparation of the raw material to the production of the polymer may be carried out in a continuous step, the oligomer is once prepared, and then the polymerization is carried out in another step by an extruder or the like, or the oligomer is solidified. A method such as increasing the molecular weight by phase polymerization may be used. By adjusting the charging ratio of the raw material monomer, the ratio of each structural unit in the synthesized copolymer polyamide can be controlled.
  • the non-fibrous inorganic filler (B) can be used without particular limitation as long as it is an inorganic filler that is not a fibrous inorganic filler, but the average aspect ratio of the non-fibrous inorganic filler (B) is preferably 100 or less, preferably 50 or less. Is more preferable.
  • the non-fibrous inorganic filler (B) preferably has an average particle size of 50 ⁇ m or less, more preferably 30 ⁇ m or less, and even more preferably 10 ⁇ m or less.
  • the blending amount of the non-fibrous inorganic filler (B) is 10 to 200 parts by mass, preferably 20 to 160 parts by mass, based on 100 parts by mass of the semi-aromatic polyamide resin (A).
  • the blending amount is 40 to 160 parts by mass. If the blending amount is less than 10 parts by mass, the adhesion strength of the metal plating is lowered and the reinforcing effect is reduced, which is not preferable. On the other hand, if the blending amount exceeds 200 parts by mass, the processability and the surface smoothness of the molded product are lowered, which is not preferable. In the semi-aromatic polyamide resin composition of the present invention, the blending amount becomes the content in the semi-aromatic polyamide resin composition as it is.
  • the non-fibrous inorganic filler (B) used in the present invention is formulated to improve the metal plating adhesion, strength, and dimensional stability of the semi-aromatic polyamide resin composition, and is a non-fibrous inorganic filler. Use at least one selected from.
  • the non-fibrous inorganic filler (B) include aluminum silicate (kaolin, zeolite), calcium silicate (warastonite), magnesium silicate (talc), mica, calcium carbonate, barium sulfate, and silicon dioxide. (Calcium silicate), glass beads, glass balloons and the like can be mentioned.
  • the semi-aromatic polyamide resin composition of the present invention has good metal plating adhesion, but from the viewpoint of particularly excellent plating adhesion, the non-fibrous inorganic filler (B) is kaolin, diatomaceous earth, or wax. At least one selected from lastnite, glass beads, and zeolite is preferred, at least one selected from kaolin, diatomaceous earth, and wallastnite is more preferred, and at least one selected from kaolin and diatomaceous earth is even more preferred.
  • Kaolin has an excellent appearance at the time of molding and does not dissolve in the etching solution used in the plating process, so that it easily develops irregularities and has excellent plating adhesion. The same applies to diatomaceous earth, and since the filler itself has many irregularities, it is easier to ensure plating adhesion. These are not limited to the single use of only one kind, but may be used in combination of several kinds.
  • the non-fibrous inorganic filler (B) is preferably treated with an organic treatment or a coupling agent in order to improve the affinity with the semi-aromatic polyamide resin (A).
  • an organic treatment or a coupling agent in order to improve the affinity with the semi-aromatic polyamide resin (A).
  • aminosilane coupling agents and epoxysilane coupling agents are preferable.
  • an etching solution is brought into contact with the surface of a molded product molded using the semi-aromatic polyamide resin composition for etching (surface roughening). ) Is performed to form an uneven structure on the surface of the molded product, and then metal plating is applied to the surface. It is presumed that excellent plating adhesiveness can be obtained by exhibiting the mechanical bonding effect of the unevenness formed by etching.
  • the semi-aromatic polyamide resin composition of the present invention is prepared by blending the semi-aromatic polyamide resin (A) with the non-fibrous inorganic filler (B) in a predetermined blending amount as described above on the surface of the molded product after etching. It is possible to form irregularities and improve the metal plating adhesion by the mechanical bonding effect.
  • additives used in the conventional polyamide resin composition can be used as long as the characteristics are not impaired.
  • Additives include tougheners, stabilizers, mold release agents, slidability improvers, colorants, plasticizers, crystal nucleating agents, polyamides different from the semi-aromatic polyamide resin (A), and thermoplastic resins other than polyamide. And so on.
  • the possible blending amounts of these components in the semi-aromatic polyamide resin composition are as described below, but the total of these components is preferably 30% by mass or less in the semi-aromatic polyamide resin composition, and is 20%. More preferably, it is 10% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.
  • the reinforcing agent examples include fibrous inorganic fillers, and specific examples thereof include glass fiber, potassium titanate fiber, needle-like wallastonite, and fibrous wallastonite. These fortifiers may be used alone or in combination of several.
  • the optimum amount of the toughening agent may be selected, but a maximum of 5 parts by mass can be added to 100 parts by mass of the semi-aromatic polyamide resin (A). If it exceeds 5 parts by mass, problems will occur in the appearance of metal plating and moldability, which is not preferable. More preferably, no fibrous inorganic filler is blended.
  • 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 optimum amount of the stabilizer may be selected, but a maximum of 5 parts by mass can be added to 100 parts by mass of the semi-aromatic polyamide resin (A).
  • Examples of the release agent include long-chain fatty acids or esters and metal salts thereof, amide compounds, polyethylene waxes, silicones, polyethylene oxides, and the like.
  • the long-chain fatty acid is particularly preferably having 12 or more carbon atoms, and examples thereof include stearic acid, 12-hydroxystearic acid, behenic acid, and montanic acid. Partial or total carboxylic acid is esterified with monoglycol or polyglycol. It may be formed or may form a metal salt.
  • Examples of the amide compound include ethylenebisterephthalamide and methylenebisstearylamide. These release agents may be used alone or as a mixture. The optimum amount of the release agent may be selected, but a maximum of 5 parts by mass can be added to 100 parts by mass of the semi-aromatic polyamide resin (A).
  • the semi-aromatic polyamide resin composition of the present invention may be polymer-blended with a polyamide having a composition different from that of the semi-aromatic polyamide resin (A).
  • the optimum amount of polyamide having a composition different from that of the semi-aromatic polyamide resin (A) may be selected, but a maximum of 50 parts by mass should be added to 100 parts by mass of the semi-aromatic polyamide resin (A). Is possible.
  • thermoplastic resin other than polyamide may be added to the semi-aromatic polyamide resin composition of the present invention.
  • Polymers other than polyamide include polyphenylene sulfide (PPS), liquid crystal polymer (LCP), aramid resin, polyetheretherketone (PEEK), polyetherketone (PEK), polyetherimide (PEI), thermoplastic polyimide, and polyamideimide.
  • PAI polyetherketoneketone
  • PPE polyphenylene ether
  • PES polyethersulfone
  • PSU polysalphon
  • PAR polyallylate
  • PC polyoxymethylene
  • POM polypropylene
  • PE polyethylene
  • TPX polymethylpentene
  • 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 polyamide resin composition of the present invention.
  • the optimum amount of the thermoplastic resin may be selected, but a maximum of 50 parts by mass can be added to 100 parts by mass of the semi-aromatic polyamide resin (A).
  • a reactive group capable of reacting with polyamide is copolymerized, and the reactivity
  • the group is a group capable of reacting with an amino group, a carboxyl group and a main chain amide group which are terminal groups of a polyamide resin.
  • Specific examples thereof include a carboxylic acid group, an acid anhydride group, an epoxy group, an oxazoline group, an amino group, and an isocyanate group.
  • the acid anhydride group has the most excellent reactivity.
  • the semi-aromatic polyamide resin composition of the present invention can be produced by blending each of the above-mentioned constituent components by a conventionally known method.
  • each component may be added during the polycondensation reaction of the semi-aromatic polyamide resin (A), the semi-aromatic polyamide resin (A) and other components may be dry-blended, or a twin-screw screw type extruder may be used. Examples thereof include a method of melt-kneading each component by using.
  • the semi-aromatic polyamide resin composition of the present invention can be made into a molded product by a known molding method such as injection molding.
  • the mold temperature in injection molding is preferably 180 ° C. or lower, more preferably 170 ° C. or lower, and 160 ° C. or lower. Is more preferable, and it is particularly preferable that the temperature is 150 ° C. or lower. If the mold temperature exceeds the above upper limit, molding defects such as the molded product remaining in the mold may occur.
  • the lower limit of the mold temperature is not particularly limited, but is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, from the viewpoint of resin fluidity, appearance of the molded product, and suppression of dimensional change in the actual use environment. , 100 ° C. or higher is more preferable, and 120 ° C. or higher is particularly preferable.
  • the semi-aromatic polyamide resin composition of the present invention can be used as a metal-plated molded product in which the surface of a molded product obtained by using the semi-aromatic polyamide resin composition is metal-plated.
  • the metal-plated molded product is superior to the conventional metal-plated molded product in metal plating adhesion, low water absorption, and solder reflow resistance.
  • the method for producing the metal-plated molded product using the semi-aromatic polyamide resin composition of the present invention is not particularly limited and can be produced by a known technique.
  • the roughened surface is used for neutralization, catalysis, activation, electroless plating, and acid activity.
  • Electroplating by the catalyst method which performs steps such as electroplating in order, the direct plating method, which omits the electroless plating step in this catalyst method, ultraviolet rays and laser light having a specific wavelength.
  • the catalyst application, activation, electroless plating, acid activity, electroplating, and other steps are performed in order using the modified surface, or this catalyst accelerator method.
  • a method of performing metal plating by a direct plating method or the like omitting the electroless plating step in the above can be mentioned. Etching and metal plating can be performed on the entire surface of the molded product for plating or a part thereof.
  • the optimum thickness of the metal plating of the metal plating molded product using the semi-aromatic polyamide resin composition of the present invention may be selected, but is preferably 0.5 to 200 ⁇ m, more preferably 1 to 150 ⁇ m. ..
  • the metal-plated molded product using the semi-aromatic polyamide resin composition of the present invention has excellent metal adhesion due to the non-fibrous inorganic filler blended in the semi-aromatic polyamide resin composition.
  • the metal plating peel strength of the metal plating molded product using the semi-aromatic polyamide resin composition of the present invention is measured by the method described in the item of the following Examples.
  • the metal plating peel strength is an item relating to the good plating property of the semi-aromatic polyamide resin composition of the present invention, and the metal plating peel strength needs to be 4.0 N / cm or more. Further, it is preferably 4.5 N / cm or more, more preferably 5.0 N / cm or more, further preferably 5.5 N / cm or more, and 5.7 N / cm or more. Especially preferable.
  • the metal plating peel strength is less than the above lower limit, the adhesion between the semi-aromatic polyamide resin composition and the metal plating is low, and the metal plating may float or peel off.
  • the metal-plated molded product using the semi-aromatic polyamide resin composition of the present invention is used for various applications such as automobile parts, electrical and electronic parts, OA equipment parts, electromagnetic wave shield parts, etc. by utilizing good metal plating adhesion. be able to.
  • Terminal amino group concentration (AEG), terminal carboxyl group concentration (CEG)
  • the terminal group concentration was measured.
  • Relative viscosity (RV) 0.25 g of a semi-aromatic polyamide resin was dissolved in 25 ml of 96% sulfuric acid, and the measurement was performed at 20 ° C. using an Ostwald viscometer.
  • Tm Melting point 5 mg of semi-aromatic polyamide resin was placed in an aluminum sample pan, sealed, and elevated to 350 ° C. using a differential scanning calorimetry (DSC) DSC-Q100 manufactured by TA Instruments Japan Co., Ltd. The temperature was measured at a temperature rate of 20 ° C./min, and the maximum peak temperature of the heat of fusion was determined as the crystal melting point.
  • DSC differential scanning calorimetry
  • the cylinder temperature is set to the melting point of the resin + 20 ° C
  • the mold temperature is set to 140 ° C
  • a flat plate with a length of 100 mm, a width of 100 mm, and a thickness of 2 mm is injected. It was molded to prepare a test piece for evaluation.
  • the obtained test piece was wiped with isopropyl alcohol, and then degreased at 60 ° C. for 3 minutes using a 50 g / l OPC-250 cleaner (manufactured by Okuno Pharmaceutical Industry Co., Ltd.). Then, the test piece was immersed in a chromic acid solution at 70 ° C.
  • A30 catalyst manufactured by Okuno Pharmaceutical Co., Ltd.
  • A30 catalyst manufactured by Okuno Pharmaceutical Co., Ltd.
  • Reflow heat resistant temperature is 260 ° C or higher
  • Reflow heat resistant temperature is less than 260 ° C
  • This example was carried out using a semi-aromatic polyamide resin (A) synthesized by the following method or a commercially available product.
  • Table 1 shows the physical characteristics of each semi-aromatic polyamide resin (A).
  • the solution was continuously supplied by a liquid feed pump, heated to 240 ° C. by a heating pipe, and heated for 1 hour.
  • 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.
  • the obtained semi-aromatic polyamide resin (A1) contained 65.1 mol% of a constituent unit composed of 1,6-hexamethylenediamine and terephthalic acid, and 34.9 mol% of a constituent unit composed of 11-aminoundecanoic acid. It was composed of a relative viscosity of 2.1, a melting point of 314 ° C., an AEG of 30 eq / ton, and a CEG of 140 eq / ton. The composition monomer ratio of the polyamide resin was confirmed by 1 H-NMR as in the AEG and CEG measurements.
  • the obtained semi-aromatic polyamide resin (A4) has a constituent unit of 55.1 mol% consisting of 1,6-hexamethylenediamine and terephthalic acid, and 44 constituent units of 1,6-hexamethylenediamine and adipic acid. It was composed of 9.9 mol%, had a relative viscosity of 2.3, a melting point of 305 ° C., AEG25 eq / ton, and CEG150 eq / ton.
  • the obtained semi-aromatic polyamide resin (A6) contained 66.6 mol% of a constituent unit composed of 1,6-hexamethylenediamine and terephthalic acid, and 33.4 mol% of a constituent unit composed of 11-aminoundecanoic acid. It was composed of a relative viscosity of 2.5, a melting point of 314 ° C., AEG40eq / ton, and CEG0eq / ton.
  • This example was carried out using a semi-aromatic polyamide resin composition prepared as illustrated below.
  • the components and mass ratios (parts by mass) shown in Tables 2 and 3 are melt-kneaded at the melting point of each polyamide raw material at + 20 ° C. using a twin-screw extruder STS-35 manufactured by Coperion Co., Ltd., and Examples 1 to 10 are used. , The semi-aromatic polyamide resin compositions of Comparative Examples 1 to 7 were obtained.
  • the raw materials used in the preparation of the semi-aromatic polyamide resin composition are as follows.
  • the release agent and stabilizer used as other additives were used in a mass ratio of 1: 5.
  • Semi-aromatic polyamide resin (A1) Semi-aromatic polyamide resin prepared based on the above Synthesis Example 1
  • Semi-aromatic polyamide resin (A2): PA10T (Vynyl (R) manufactured by KINGFA, Tm 310 ° C.)
  • Semi-aromatic polyamide resin (A5): PA6T / 6 (BASF Ultramide (R) KR4351, Tm 295 °C)
  • Magnesium stearate Stabilizer Pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (Irganox 1010 manufactured by Chiba Speciality Chemicals)
  • Examples 1 to 10 exhibit excellent metal plating peel strength, metal plating appearance, and moldability, and also have reflow solder resistance, indicating that they have excellent characteristics. .. Further, Examples 1 to 10 are also excellent in more advanced plating property and moldability which is an index of appearance, which have been required in recent years. On the other hand, in Comparative Example 1, since the non-fibrous inorganic filler (B) is not blended, the metal plating peel strength and the metal plating appearance are inferior and insufficient.
  • Comparative Example 5 semi-aromatic polyamides different from those of Examples 1 to 8 are used, and although they are excellent in metal plating peel strength and metal plating appearance, they are inferior in reflow solder resistance and moldability.
  • Comparative Examples 6 and 7 since the fibrous inorganic filler is used, the metal plating peel strength, the metal plating appearance, and the reflow solder resistance are good, but the moldability is inferior and insufficient.
  • the semi-aromatic polyamide resin composition of the present invention exhibits good metal plating adhesion and plating appearance by blending a specific inorganic filler in addition to the composition of the semi-aromatic polyamide resin, and also provides solder reflow resistance. Can also be satisfied, and a molded product requiring metal plating can be industrially advantageously produced.

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Abstract

Le problème à résoudre par la présente invention est de produire une composition de résine polyamide semi-aromatique ayant une bonne aptitude au placage, une faible absorption d'eau et une excellente résistance à la refusion. La solution, selon la présente invention, porte sur une composition de résine polyamide semi-aromatique pour un article moulé plaqué qui contient de 10 à 200 parties en masse d'une charge inorganique non fibreuse (B) par rapport à 100 parties en masse d'une résine polyamide semi-aromatique (A), et le rapport (rapport C/N) du nombre d'atomes de carbone (C) au nombre d'atomes d'azote (N) dans la résine polyamide semi-aromatique (A) est de 7,3 ou plus. Il est préférable que la résine polyamide semi-aromatique (A) contienne 50 à 100 % en moles d'un motif de répétition comprenant une diamine possédant de 6 à 12 atomes de carbone et un acide téréphtalique.
PCT/JP2020/031722 2019-09-17 2020-08-21 Composition de résine polyamide semi-aromatique pour article moulé plaqué et article moulé plaqué Ceased WO2021054050A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03197558A (ja) * 1989-07-07 1991-08-28 Mitsui Petrochem Ind Ltd メッキ層形成用樹脂組成物およびその用途
JPH0881627A (ja) * 1994-09-16 1996-03-26 Kuraray Co Ltd 成形体
JP2014521822A (ja) * 2011-08-19 2014-08-28 ソルベイ スペシャルティ ポリマーズ ユーエスエー， エルエルシー Ｌｅｄ用途のための改良されたポリアミド組成物
JP2014214247A (ja) * 2013-04-26 2014-11-17 宇部興産株式会社 ポリアミド樹脂および無機充填剤を含む組成物及びそれを用いて製造される成形品

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03197558A (ja) * 1989-07-07 1991-08-28 Mitsui Petrochem Ind Ltd メッキ層形成用樹脂組成物およびその用途
JPH0881627A (ja) * 1994-09-16 1996-03-26 Kuraray Co Ltd 成形体
JP2014521822A (ja) * 2011-08-19 2014-08-28 ソルベイ スペシャルティ ポリマーズ ユーエスエー， エルエルシー Ｌｅｄ用途のための改良されたポリアミド組成物
JP2014214247A (ja) * 2013-04-26 2014-11-17 宇部興産株式会社 ポリアミド樹脂および無機充填剤を含む組成物及びそれを用いて製造される成形品

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