WO2019059357A1 - Comprimé comprenant, en tant que constituant, un article moulé constitué d'une composition de résine polyamide semi-aromatique - Google Patents

Comprimé comprenant, en tant que constituant, un article moulé constitué d'une composition de résine polyamide semi-aromatique Download PDF

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Publication number
WO2019059357A1
WO2019059357A1 PCT/JP2018/035096 JP2018035096W WO2019059357A1 WO 2019059357 A1 WO2019059357 A1 WO 2019059357A1 JP 2018035096 W JP2018035096 W JP 2018035096W WO 2019059357 A1 WO2019059357 A1 WO 2019059357A1
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Prior art keywords
polyamide resin
acid
semi
mass
molded article
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PCT/JP2018/035096
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English (en)
Japanese (ja)
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誠 玉津島
順一 中尾
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東洋紡株式会社
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Priority to KR1020207008226A priority Critical patent/KR102615918B1/ko
Priority to JP2019506459A priority patent/JP7200927B2/ja
Priority to CN201880059313.0A priority patent/CN111133038B/zh
Publication of WO2019059357A1 publication Critical patent/WO2019059357A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/06—Copolymers with vinyl aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • C08L77/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino-carboxylic acids or of polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

  • the present invention has a structure in which a molded article made of a semiaromatic polyamide resin composition excellent in water absorption dimensional stability and heat resistance and a thermosetting resin containing glycidyl group have high adhesiveness and are directly intervened. It is related with the molded object which it has.
  • Polyamide resins have been used for clothing, industrial materials fibers, engineering plastics, etc., taking advantage of their excellent properties and ease of melt molding.
  • applications of polyamide resin are further expanded, and are used in various applications ranging from automobile parts around the engine to electric and electronic parts represented by smartphones.
  • thermosetting resin is becoming common in order to prevent malfunction of equipment due to a trace amount of moisture and foreign matter entering from the outside while the product is being refined. High adhesion to these thermosetting resins is strongly demanded for such polyamide resins.
  • polyamide resins In the case of polyamide resins, the influence of water absorption in the environment of use on product quality often becomes a problem.
  • the polyamide resin changes its dimensions when it absorbs water in the air, and therefore, the product dimensions change, leading to a defective assembly or operation of the product.
  • blisters of the product due to water absorption occur, leading to the occurrence of product defects.
  • PA6, PA66, modified PA6T, etc. widely used in the market, the saturated water absorption rate of the resin is as high as 6% or more, and the above problem is likely to occur. Therefore, a low water absorption polyamide resin that is less likely to absorb water is required.
  • Patent Document 1 discloses a carbon fiber reinforced polyamide resin composition which is excellent in metal adhesion and is composed of a semiaromatic polyamide, a carbon fiber, and an epoxy compound.
  • the technique described in the document contains an epoxy compound in the resin composition, and the low heat resistance of the epoxy compound increases outgassing at the time of processing at high temperature, and the appearance of the molded article There is a problem with processability such as a marked decrease.
  • Patent Document 2 discloses a semi-aromatic polyamide resin mainly made of PA9T, which is excellent in adhesion to other resins.
  • the amount of terminal amino groups of the semiaromatic polyamide is 60 to 120 ⁇ equivalent / g, and the ratio of (the amount of terminal amino groups) / (the amount of terminal carboxyl groups) is 6 or more
  • this document does not disclose a technique for expressing high adhesiveness with a polyamide resin having a high amount of terminal carboxyl groups.
  • Patent Document 3 discloses a molded article comprising a polyamide resin member and an adhesive layer in contact with the polyamide member, and a metal member.
  • the technique described in the document is essentially the thermoplastic polyolefin elastomer or thermoplastic polyether elastomer in which at least one of maleic acid and maleic anhydride is grafted to the adhesive layer, and the technique of the present invention and Is different.
  • the present invention has been made in view of the current state of the prior art, and its object is to improve the adhesion between a molded article made of a semi-aromatic polyamide resin composition and a thermosetting resin containing glycidyl group.
  • An object of the present invention is to provide a molded article excellent in water absorption dimensional stability and heat resistance, which has a structure directly interposed while having the resin.
  • the present inventor uses a resin composition containing a semiaromatic polyamide resin having specific physical properties such as the amount of end groups in addition to the composition, and a thermosetting resin having a glycidyl group It came to provide the molded object which has high water absorption dimensional stability, heat resistance, and adhesiveness by carrying out.
  • This molded body can also be understood as a composite molded body, since it is a molded body in which a molded article made of a semi-aromatic polyamide resin composition and a thermosetting resin having a glycidyl group are directly interposed. It has also been found that the adhesiveness is improved by further blending a styrene-maleimide copolymer in a specific ratio into the resin composition.
  • the present invention has the following constitution. (1) 100 parts by mass of a semiaromatic polyamide resin (A) satisfying the following requirements (a) to (c), containing 0 to 200 parts by mass of a reinforcing material (B), 80 ° C. 95% RH equilibrium A molded article having a structure in which a molded article (D) comprising a semi-aromatic polyamide resin composition (C) having a water absorption coefficient of 3.0% or less and a thermosetting resin (E) containing glycidyl group are directly interposed .
  • a semiaromatic polyamide resin A satisfying the following requirements (a) to (c), containing 0 to 200 parts by mass of a reinforcing material (B), 80 ° C. 95% RH equilibrium
  • a molded article having a structure in which a molded article (D) comprising a semi-aromatic polyamide resin composition (C) having a water absorption coefficient of 3.0% or less and a thermosetting resin (E) containing glycidyl
  • the semi-aromatic polyamide resin composition (C) is based on 100 parts by mass of the semi-aromatic polyamide resin (A), The molded article according to (1), further comprising 10 to 60 parts by mass of a styrene-maleimide copolymer (F).
  • the semi-aromatic polyamide resin (A) contains 50 to 100 mol% of a repeating unit consisting of a diamine having 6 to 12 carbon atoms and terephthalic acid, and no repeating unit consisting of an aminocarboxylic acid or lactam having 10 or more carbon atoms.
  • thermosetting resin (E) containing a glycidyl group is a one-component thermosetting epoxy resin.
  • a connector comprising the molded body according to any one of (1) to (5).
  • a switch part comprising the molded body according to any one of (1) to (5).
  • a camera part comprising the molded body according to any one of (1) to (5).
  • the semi-aromatic polyamide resin having high water absorption dimensional stability, heat resistance and adhesiveness comprising a molded article comprising a semi-aromatic polyamide resin composition and a thermosetting resin having a glycidyl group It is possible to provide a composite molded article in which molded articles made of the composition and a thermosetting resin having a glycidyl group are directly intervened.
  • directly intercalated means that they are directly adhered.
  • the molded article of the present invention contains 0 to 200 parts by mass of a reinforcing material (B) with respect to 100 parts by mass of a semiaromatic polyamide resin (A) satisfying the following requirements (a) to (c), Structure in which a molded article (D) comprising a semi-aromatic polyamide resin composition (C) having a 95% RH equilibrium water absorption of 3.0% or less and a thermosetting resin (E) containing glycidyl group are directly intervened It is characterized by having.
  • the semiaromatic polyamide resin composition (C) further contains styrene based on 100 parts by mass of the semiaromatic polyamide resin (A). It is a preferred embodiment that 10 to 60 parts by mass of the maleimide copolymer (F) is contained.
  • the semiaromatic polyamide resin (A) used in the present invention is not particularly limited, and is a semiaromatic polyamide having an acid amide bond (-CONH-) in the molecule and having an aromatic ring (benzene ring). It is.
  • semi-aromatic polyamides include 6T polyamides (for example, polyamide 6T6I consisting of terephthalic acid / isophthalic acid / hexamethylene diamine, polyamide 6T66 consisting of terephthalic acid / adipic acid / hexamethylene diamine, terephthalic acid / isophthalic acid / adipine Acid / hexamethylenediamine polyamide 6T6I66, terephthalic acid / hexamethylenediamine / 2-methyl-1, 5-pentamethylenediamine polyamide 6T / M-5T, terephthalic acid / hexamethylenediamine / ⁇ -caprolactam polyamide 6T6,
  • the semi-aromatic polyamide resin (A) used in the present invention needs to have a peak area ( ⁇ H Tc2 ) associated with temperature-drop crystallization measured by the method described in the section of the following examples at 40 mJ / mg or less. Also, it is preferably 35 mJ / mg or less, more preferably 30 mJ / mg or less.
  • ⁇ H Tc2 exceeds the above upper limit, the adhesion to the thermosetting resin (E) is lowered, and the strength necessary for the molded product may not be achieved, which is not preferable.
  • the lower limit of ⁇ H Tc2 is 5 mJ / mg, and 10 mJ / mg or more is more preferable. Below the above lower limit, the molding cycle time may be prolonged and the production efficiency may be reduced. Moreover, when the obtained molded object is subjected to secondary processing in a high temperature environment, dimensional change, deformation, etc. may occur, which is not preferable.
  • the semi-aromatic polyamide resin (A) used in the present invention needs to have a glass transition temperature (Tg) of 120 ° C. or less measured by the method described in the section of the following examples. Moreover, it is preferable that it is 110 degrees C or less, and it is more preferable that it is 100 degrees C or less.
  • Tg glass transition temperature
  • the lower limit of Tg is 50 ° C. or higher, preferably 60 ° C. or higher, and more preferably 70 ° C. or higher. Below the lower limit, depending on the use environment, the molded product may be softened, which may cause deformation or malfunction of the product, which is not preferable.
  • the semiaromatic polyamide resin (A) used in the present invention needs to have a sum (AEG + CEG) of terminal amino group concentration (AEG) and terminal carboxyl group concentration (CEG) of 70 eq / ton or more. Moreover, it is preferable that it is 80 eq / ton or more, and it is more preferable that it is 100 eq / ton or more.
  • (AEG + CEG) is less than the above-mentioned lower limit, adhesion with the thermosetting resin (E) may be lowered, and the strength necessary for the molded product may not be achieved, which is not preferable.
  • the upper limit of (AEG + CEG) is preferably 200 eq / ton or less, more preferably 180 eq / ton or less, and still more preferably 160 eq / ton. When it exceeds the above-mentioned upper limit, reaction of end groups with the heat at the time of processing arises, and a problem may arise in retention stability, and it is not preferable.
  • the terminal amino group concentration (AEG) of the semi-aromatic polyamide resin (A) used in the present invention is preferably 2 eq / ton or more, more preferably 10 eq / ton or more, and 15 eq / ton or more Is more preferably 20 eq / ton or more. Even when the terminal amino group concentration is below the above lower limit, the semi-aromatic polyamide resin (A) used in the present invention is excellent in adhesion to the thermosetting resin (E), and the molded article of the present invention has sufficient adhesion Although it has intensity
  • the semi-aromatic polyamide resin (A) used in the present invention preferably has a terminal carboxyl group concentration (CEG) of 20 eq / ton or more, more preferably 30 eq / ton or more, and 40 eq / ton or more Is more preferred. Since the adhesiveness with a thermosetting resin (E) can be improved by making terminal carboxyl group density
  • the semiaromatic polyamide resin (A) used in the present invention preferably has a larger CEG than AEG.
  • the CEG / AEG is preferably 2 or more, more preferably 5 or more.
  • the semi-aromatic polyamide resin (A) used in the present invention preferably has a DSC melting peak temperature (Tm) located at the lowest temperature side measured by the method described in the section of the following examples and is 280 ° C. or higher. Moreover, it is more preferable that it is 290 degreeC or more, and it is further more preferable that it is 300 degreeC or more.
  • Tm DSC melting peak temperature
  • Tm is less than the above lower limit
  • Tm 340 degrees C or less is preferable
  • 330 degrees C or less is more preferable
  • 320 degrees C or less is more preferable.
  • Tm exceeds the above-mentioned upper limit, processing temperature at the time of molding processing becomes extremely high, and decomposition of resin by heat may occur, which is not preferable.
  • the semiaromatic polyamide resin (A) used in the present invention is preferably the following semiaromatic polyamide resin from the viewpoint of ⁇ H Tc2 , Tg, and Tm.
  • the semi-aromatic polyamide resin (A) comprises 50 to 100 mol% of a repeating unit consisting of a diamine having 6 to 12 carbon atoms and terephthalic acid, and 0 to 50 mol of a repeating unit consisting of an aminocarboxylic acid or lactam having 10 or more carbon atoms.
  • the molding cycle time becomes longer due to the decrease of ⁇ H Tc2 and the Tm decreases. It is not preferable because there is a possibility that problems may occur due to the melting or deformation of the molded product in the solder reflow process due to the above, and the softening of the molded product in the use environment due to the decrease in Tg.
  • the semiaromatic polyamide resin (A) since ⁇ H Tc2 , Tg and Tm of the semiaromatic polyamide resin (A) can be appropriately improved, it is composed of a diamine having 6 to 12 carbon atoms and terephthalic acid in the semiaromatic polyamide resin (A) It is more preferable to set the proportion of repeating units to 55 mol% or more (45 mol% or less of repeating units consisting of an aminocarboxylic acid having 10 or more carbon atoms or lactams), and 60 mol% or more (aminocarboxylic acids having 10 or more carbon atoms) It is more preferable that the repeating unit consisting of lactam be 40 mol% or less).
  • Examples of the diamine component having 6 to 12 carbon atoms constituting the semiaromatic polyamide resin (A) include 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9- Nonamethylenediamine, 2-methyl-1,8-octamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine can be mentioned. These may be used alone or in combination.
  • the aminocarboxylic acid having 10 or more carbon atoms or the lactam having 10 or more carbon atoms constituting the semiaromatic polyamide resin (A) is preferably an aminocarboxylic acid or lactam having 11 to 18 carbon atoms.
  • 11-aminoundecanoic acid, undecanelactam, 12-aminododecanoic acid and 12-lauryl lactam are preferable.
  • other components can be copolymerized in 50% by mole or less of the constituent units.
  • Other copolymerizable diamine components include 1,13-tridecamethylenediamine, 1,16-hexadecamethylenediamine, 1,18-octadecamethylenediamine, 2,2,4 (or 2,4,4 (or 2,4,4) Aliphatic diamines such as) -trimethylhexamethylene diamine, fats such as piperazine, cyclohexane diamine, bis (3-methyl-4-aminohexyl) methane, bis- (4,4'-aminocyclohexyl) methane, isophorone diamine Aromatic diamines such as cyclic diamines, metaxylylene diamines, para-xylylene diamines, para-phenylene diamines, meta-phenylene diamines, and hydrogenated products thereof can be mentioned.
  • copolymerizable acid components include isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 2,2'-diphenyldicarboxylic acid
  • Aromatic dicarboxylic acids such as 4,4'-diphenyletherdicarboxylic acid, sodium 5-sulfonate isophthalic acid, 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-octadecanedioic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1 ,
  • one or more of an aminocarboxylic acid having 11 to 18 carbon atoms or a lactam having 11 to 18 carbons are copolymerized Is preferred.
  • the semiaromatic polyamide resin (A) used in the present invention contains 50 to 100 mol% of repeating units consisting of hexamethylene diamine and terephthalic acid, and 0 to 50 mol% of repeating units consisting of aminoundecanoic acid or undecanelactam.
  • a semi-aromatic polyamide resin preferably a semi-aromatic polyamide resin, containing 50 to 98 mol% of repeating units consisting of hexamethylene diamine and terephthalic acid, and 2 to 50 mol% of repeating units consisting of amino undecanoic acid or undecane lactam It is more preferable that the resin is a semi-aromatic polyamide resin containing 55 to 80 mol% of repeating units consisting of hexamethylene diamine and terephthalic acid and 20 to 45 mol% of repeating units consisting of aminoundecanoic acid or undecanelactam
  • a repeating unit composed of hexamethylenediamine and terephthalic acid 60-70 mol% contains a repeating unit composed of aminoundecanoic acid or undecanoic lactam 30-40 mol%, and particularly preferably is a semi-aromatic polyamide resin.
  • the molding cycle time becomes longer due to the decrease in ⁇ H Tc2 and the solder reflow process due to the decrease in Tm.
  • a failure may occur due to the melting or deformation of the molded product in the above, and the softening of the molded product in the use environment due to the decrease of Tg.
  • the Tm can be in the range of 300 ° C. to 320 ° C.
  • ⁇ H Tc2 can be made 10 to 35 mJ / mg
  • Tg can be made 70 to 100 ° C.
  • high adhesiveness with the thermosetting resin (E) can be obtained. And more preferred.
  • phosphoric acid, phosphorous acid, hypophosphorous acid or its metal salt, ammonium salt, ester are mentioned.
  • the metal species of the metal salt include potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, antimony and the like.
  • the ester include ethyl ester, isopropyl ester, butyl ester, hexyl ester, isodecyl ester, octadecyl ester, decyl ester, stearyl ester, phenyl ester and the like.
  • alkali compounds such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, from a viewpoint of melt
  • the relative viscosity (RV) measured at 20 ° C. in 96% concentrated sulfuric acid of the semiaromatic polyamide resin (A) is preferably 0.4 to 4.0, more preferably 1.0 to 3.0, and further Preferably, it is 1.5 to 2.5.
  • means for adjusting the molecular weight can be mentioned.
  • the semi-aromatic polyamide resin (A) is to adjust the amount of terminal groups and the molecular weight of polyamide by adjusting the molar ratio between the amount of amino groups and the carboxyl group and performing polycondensation or adding an end capping agent. Can.
  • the timing for adding the end-capping agent may be at the time of raw material charging, at the start of polymerization, at the end of polymerization, or at the end of polymerization.
  • the end capping agent is not particularly limited as long as it is a monofunctional compound having reactivity with an amino group or a carboxyl group at a polyamide end, and an acid anhydride such as monocarboxylic acid or monoamine, phthalic anhydride, Monoisocyanates, mono acid halides, monoesters, monoalcohols and the like can be used.
  • end capping agents include aliphatic monobasics such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyric acid and the like Alicyclic monocarboxylic acids such as carboxylic acids and cyclohexanecarboxylic acids, benzoic acids, toluic acids, ⁇ -naphthalenecarboxylic acids, ⁇ -naphthalenecarboxylic acids, aromatic monocarboxylic acids such as methylnaphthalenecarboxylic acids and phenylacetic acids, and maleic anhydride Acids, acid anhydrides such as phthalic anhydride and hexahydrophthalic anhydride, methylamine, ethylamine, propylamine, butylamine, butylamine, hexylamine, oc
  • the semi-aromatic polyamide resin (A) can be produced by a conventionally known method, and can be easily synthesized, for example, by co-condensation reaction of raw material monomers.
  • the order of the cocondensation 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 it may be carried out in a continuous process from raw material charging to polymer production, or once an oligomer is produced, then polymerization is advanced by an extruder or the like in another process, or the oligomer is solidified You may use methods, such as high molecular weight formation by phase polymerization. By adjusting the feed ratio of the raw material monomers, it is possible to control the proportion of each structural unit in the copolymerized polyamide to be synthesized.
  • the reinforcing material (B) used in the present invention is for improving the moldability of the semiaromatic polyamide resin composition (C) and the strength of the molded article (D) comprising the semiaromatic polyamide resin composition (C). It is preferable to use at least one selected from fibrous reinforcing materials and needle-like reinforcing materials.
  • fibrous reinforcing materials include glass fibers, carbon fibers, boron fibers, ceramic fibers, metal fibers and the like
  • needle-like reinforcing materials include potassium titanate whiskers, aluminum borate whiskers, zinc oxide whiskers, carbonates Calcium whiskers, magnesium sulfate whiskers, wollastonite and the like can be mentioned.
  • glass fibers it is possible to use chopped strands or continuous filament fibers having a length of 0.1 mm to 100 mm.
  • a cross-sectional shape of glass fiber glass fiber of circular cross section and non-circular cross section can be used.
  • the diameter of the round cross section glass fiber is 20 ⁇ m or less, preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less.
  • glass fibers having a non-circular cross section are preferable in terms of physical properties and fluidity.
  • the glass fibers having a non-circular cross section include those having a substantially oval shape, a substantially oval shape, or a substantially wedge shape in a cross section perpendicular to the length direction of the fiber length, and the flatness is 1.5 to 8 Is preferred.
  • the flatness is assumed to be a rectangle having a minimum area circumscribing the cross section perpendicular to the longitudinal direction of the glass fiber, and the length of the long side of this rectangle is the long diameter, and the length of the short side is the short diameter.
  • Ratio of major axis / minor axis when The thickness of the glass fiber is not particularly limited, but the minor diameter is about 1 to 20 ⁇ m and the major diameter is about 2 to 100 ⁇ m.
  • a fibrous reinforcing material that has been treated with an organic treatment or a coupling agent, or to use it together with the coupling agent at the time of melt compounding.
  • a coupling agent any of a coupling agent, a titanate coupling agent, and an aluminum type coupling agent may be used, an aminosilane coupling agent and an epoxy silane coupling agent are especially preferable among these.
  • the reinforcing material (B) used in the present invention needs to be 0 to 200 parts by mass with respect to 100 parts by mass of the semiaromatic polyamide resin (A). Also, 10 to 200 parts by mass is preferable, 10 to 180 parts by mass is more preferable, and 15 to 160 parts by mass is more preferable.
  • the proportion of the reinforcing material (B) exceeds the above-mentioned upper limit, the proportion of the semiaromatic polyamide resin (A) in direct contact with the thermosetting resin (E) decreases at the time of adhesion with the thermosetting resin (E) Adhesion, which is not preferable.
  • the lower limit of the ratio of the reinforcing material (B) is 0 parts by mass.
  • the amount is preferably 10 parts by mass or more, and more preferably 15 parts by mass or more.
  • the styrene-maleimide copolymer (F) used in the present invention is preferably 10 to 60 parts by mass with respect to 100 parts by mass of the semiaromatic polyamide resin (A). In addition, 12 to 50 parts by mass is preferable, and 15 to 40 parts by mass is more preferable. If the proportion of the styrene-maleimide copolymer (F) is below the above lower limit, the adhesion may be lowered upon adhesion with the thermosetting resin (E), which is not preferable. When the proportion of the styrene-maleimide copolymer (F) exceeds the above upper limit, the flowability at the time of injection molding may be reduced, and the appearance of the molded article may be deteriorated, which is not preferable.
  • the styrene-maleimide copolymer (F) used in the present invention is a copolymer containing a styrene monomer and a maleimide monomer as a component.
  • a maleic anhydride may be copolymerized with the styrene-maleimide copolymer (F) for the purpose of improving the compatibility with the semiaromatic polyamide resin (A).
  • the ratio of the components of the styrene-maleimide copolymer (F) is not particularly limited, examples of specific components include 25 to 40 mol% of a styrene monomer, N-phenylmaleimide 50 to 70 mol% and 5 to 15 mol% of maleic anhydride can be mentioned.
  • Commercially available products include Denka IP MS-NIP manufactured by Denka Co., Ltd.
  • the semi-aromatic polyamide resin composition (C) used in the present invention is a solder used not only for suppressing dimensional change of the molded product obtained according to the present invention under actual use environment but also for mounting of electric and electronic parts
  • the 80 ° C. 95% RH equilibrium water absorption as measured by the method described in the item of the following example needs to be 3.0% (3.0 mass%) or less .
  • 80 degreeC 95% RH equilibrium water absorption is 2.5% or less.
  • the 80 ° C 95% RH equilibrium water absorption rate exceeds the above upper limit, the water absorption dimensional change of the obtained molded article becomes large, and problems occur during product assembly or product operation or blisters occur in the solder reflow process, resulting in product failure It is not possible because it may lead.
  • the lower limit of 80 ° C. 95% RH equilibrium water absorption is 0%, about 1.0% is preferable in view of the characteristics of the semiaromatic polyamide resin (A) used in the present invention.
  • additives used in conventional polyamide resin compositions can be used in the semiaromatic polyamide resin composition (C) used in the present invention.
  • Additives include stabilizers, impact modifiers, mold release agents, slide improvers, colorants, plasticizers, crystal nucleating agents, polyamides different from semi-aromatic polyamide resins (A), thermoplastics other than polyamides Resin etc. are mentioned.
  • the possible blending amounts of these components in the semiaromatic polyamide resin composition (C) are as described below, but the total of these components is 30 mass% in the semiaromatic polyamide resin composition (C) % Or less is preferable, 20 mass% or less is more preferable, 10 mass% or less is more preferable, and 5 mass% or less is particularly preferable.
  • the semiaromatic polyamide resin composition (C) also includes the case where it is composed of only the semiaromatic polyamide resin (A), but also in that case, it is referred to as the semiaromatic polyamide resin composition (C) for convenience.
  • organic antioxidants and heat stabilizers such as hindered phenol type antioxidants, sulfur type antioxidants and phosphorus type antioxidants, light stabilizers such as hindered amine type, benzophenone type and imidazole type and the like UV absorbers, metal deactivators, copper compounds and the like can be mentioned.
  • a copper compound 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.
  • an alkali metal halide compound As a component other than the copper compound, it is preferable to contain an alkali metal halide compound, and as the alkali metal halide compound, lithium chloride, lithium bromide, lithium iodide, sodium iodide, sodium fluoride, sodium chloride, bromide Sodium, sodium iodide, potassium fluoride, potassium chloride, potassium bromide, potassium iodide and the like can be mentioned. These additives may be used not only singly but also in combination of several kinds. Although the addition amount of the stabilizer may be selected as an optimum amount, it is possible to add up to 5 parts by mass with respect to 100 parts by mass of the semiaromatic polyamide resin (A).
  • a polyamide having a composition different from that of the semiaromatic polyamide resin (A) may be polymer-blended.
  • the addition amount of the polyamide having a composition different from that of the semiaromatic polyamide resin (A) may be selected optimally, adding up to 50 parts by mass with respect to 100 parts by mass of the semiaromatic polyamide resin (A) Is possible.
  • thermoplastic resin other than polyamide may be added to the semiaromatic polyamide resin composition (C) used in the present invention.
  • polymers other than polyamide polyphenylene sulfide (PPS), liquid crystal polymer (LCP), aramid resin, polyetheretherketone (PEEK), polyetherketone (PEK), polyetherimide (PEI), thermoplastic polyimide, polyamideimide (PAI), polyether ketone ketone (PEKK), polyphenylene ether (PPE), polyether sulfone (PES), polysulfone (PSU), polyarylate (PAR), polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene na Phthalate, polycarbonate (PC), polyoxymethylene (POM), polypropylene (PP), polyethylene (PE), polymethylpentene (TPX), polystyrene ( S), polymethyl methacrylate, acrylonitrile - styrene cop
  • thermoplastic resins can be blended in a molten state by melt-kneading, they may be dispersed in the polyamide resin composition of the present invention into fibrous and particulate thermoplastic resins.
  • addition amount of the thermoplastic resin may be selected as an optimum amount, it is possible to add up to 50 parts by mass with respect to 100 parts by mass of the semi-aromatic polyamide resin (A).
  • Impact modifiers include ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid copolymer, ethylene- Methacrylic acid ester copolymer, polyolefin resin such as ethylene vinyl acetate copolymer, styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-isoprene -A vinyl polymer resin such as styrene copolymer (SIS) or acrylic ester copolymer, polybutylene terephthalate or polybutylene naphthalate as a hard segment, polytetramethylene glycol or polycaprolactone or poly Polyester block copolymer in which the turbo sulfonate di
  • the reactive group capable of reacting with the polyamide is co It is preferable to be polymerized, and the reactive group is a group capable of reacting with an amino group which is a terminal group of a polyamide resin, a carboxyl group and a main chain amide group. 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. Among these, the acid anhydride group is most excellent in reactivity.
  • a mold release agent a long chain fatty acid or ester or metal salt thereof, an amide based compound, polyethylene wax, silicone, polyethylene oxide and the like can be mentioned.
  • the long chain fatty acid preferably has 12 or more carbon atoms in particular, and examples thereof include stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, etc. Partial or whole carboxylic acid is esterified with monoglycol or polyglycol Or a metal salt may be formed.
  • ethylene bis terephthalamide, methylene bis stearyl amide, etc. are mentioned. These release agents may be used alone or as a mixture. The addition amount of the release agent may be selected as an optimum amount, but it is possible to add up to 5 parts by mass with respect to 100 parts by mass of the semiaromatic polyamide resin (A).
  • the semi-aromatic polyamide resin composition (C) used in the present invention can be produced by blending the above-mentioned respective components by a conventionally known method. For example, each component is added during the polycondensation reaction of the semiaromatic polyamide resin (A), the semiaromatic polyamide resin (A) and the other components are dry blended, or a twin screw extruder is used. The method of melt-kneading each component using can be mentioned.
  • the semiaromatic polyamide resin composition (C) used in the present invention can be made into a molded article (D) by a known molding method such as injection molding.
  • thermosetting resin (E) used in the present invention is a thermosetting resin characterized by containing a glycidyl group in the chemical structure, and one or more kinds of components having a glycidyl group may be contained.
  • the thermosetting resin containing a glycidyl group in the chemical structure means a resin in which the glycidyl group is bonded as a part of the chemical structure of the resin.
  • thermosetting resin containing a glycidyl group in the chemical structure bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, cyclic aliphatic epoxy resin, long chain aliphatic epoxy resin, glycidyl ester epoxy resin Epoxy resin, glycidyl amine type epoxy resin, flame retardant epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, etc. may be mentioned.
  • bisphenol A epoxy resin and bisphenol F epoxy resin are preferable from the viewpoints of adhesiveness with a semiaromatic polyamide resin (A), processability and versatility.
  • thermosetting resin (E) used in the present invention contains various curing agent components for the purpose of promoting the curing reaction.
  • curing agents aliphatic polyamines, aromatic amines, modified amines, polyamidoamines, secondary amines, tertiary amines, imidazole compounds, polymercaptan compounds, acid anhydrides, boron trifluoride-amine complexes, dicyandiamides, organic acids Hydrazide is mentioned.
  • aliphatic polyamines examples include diethylenetriamine, triethylenetriamine, tetraethylenepentamine, dipropenediamine, diethylaminopropylamine, N-aminoethylpiperazine, mensene diamine, isophorone diamine, 1,3-bisaminocyclohexane
  • aromatic amines examples include m-xylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone.
  • An example of a secondary amine includes piperidine.
  • tertiary amines examples include N, N-dimethylpiperazine, triethylenediamine, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol.
  • imidazole compound examples include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-aminoethyl-2-undecylimidazolium trimellitate, and an epoxy-imidazole adduct.
  • Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol bis trimellitate, glycerol tris trimellitate, maleic anhydride, tetrahydrophthalic anhydride, endo Methylenetetrahydrophthalic anhydride, Methyl endo methylenetetrahydrophthalic anhydride, Methylbutenyltetrahydrophthalic anhydride, Dodecenyl succinic anhydride, Hexahydrophthalic anhydride, Methylhexahydrophthalic anhydride, Succinic anhydride, Methylcyclohexene dicarboxylic anhydride, Alkylstyrene-maleic anhydride copolymer, chlorendic anhydride, polyazelaic anhydride can be mentioned.
  • the curing agent may be contained singly or in combination.
  • thermosetting resin (E) used in the present invention one-component and two-component thermosetting epoxy resins commercially available for bonding and sealing can be used. Among them, one-pack thermosetting epoxy resin is preferable.
  • thermosetting resin (E) used in the present invention may be heat-cured at a temperature suitable for each of the thermosetting resins, but preferably is heat-curable at 23 to 140 ° C., It is more preferable that the heat curing process can be performed at a temperature of 120 ° C., and further preferably, the heat curing process can be performed at 60 to 100 ° C. If the temperature at which the thermosetting treatment of the thermosetting resin (E) can be carried out is lower than the above lower limit, there is a possibility that a problem may occur that the thermosetting reaction does not proceed sufficiently.
  • thermosetting process of the thermosetting resin (E) When the temperature at which the thermosetting process of the thermosetting resin (E) can be carried out exceeds the above upper limit, crystallization and softening of the semiaromatic polyamide resin composition (C) occur by the heat applied during the curing reaction, and the obtained molded article is obtained There is a possibility that a defect may occur in the dimensions.
  • the adhesive strength between the thermosetting resin (E) and the molded article (D) comprising the semiaromatic polyamide resin composition (C) obtained in the present invention is measured by the method described in the section of the following examples.
  • the adhesive strength is an item related to the durability of the molded article obtained by the present invention.
  • the adhesive strength can achieve 1.5 MPa or more.
  • 2.0 MPa or more is preferable, 2.5 MPa or more is more preferable, and 3.0 MPa or more is more preferable.
  • the adhesive strength is less than the above lower limit, peeling of the adhesive surface between the molded article (D) comprising the semiaromatic polyamide resin (C) and the thermosetting resin (E) easily occurs, and the strength and sealing of the molded article There is a possibility that sex can not be satisfied. It is more preferable that the failure state at the time of the adhesive strength measurement is a state of base material failure in which the test piece itself is broken.
  • the semi-aromatic polyamide resin composition (C) contains a predetermined amount of the styrene-maleimide copolymer (F)
  • the molded product obtained in the present invention is a molded product obtained by assembling a molded product (D) comprising the semi-aromatic polyamide resin composition (C) and a thermosetting resin (E) containing a glycidyl group in the chemical structure.
  • a method of assembling a method of assembling by injecting or applying a thermosetting resin (E) to a molded article (D) comprising the semi-aromatic polyamide resin composition (C) is preferable.
  • the molded article (D) obtained in the present invention can be made into a composite molded article by bonding to the same material and different materials via the thermosetting resin (E).
  • the different material is not particularly limited, but examples thereof include resins other than the semi-aromatic polyamide resin (A) and metal materials.
  • the molded article of the present invention uses a semi-aromatic polyamide resin composition containing a semi-aromatic polyamide resin having specific physical properties such as the amount of end groups in addition to the composition, and a thermosetting resin having a glycidyl group
  • a semi-aromatic polyamide resin composition containing a semi-aromatic polyamide resin having specific physical properties such as the amount of end groups in addition to the composition, and a thermosetting resin having a glycidyl group
  • the molded article of the present invention can be widely used for automobile parts and electric and electronic parts, and is not particularly limited, but is particularly preferably used for various connectors, switches, and camera parts.
  • Connectors, switches, camera parts, etc. often have a small molded product size, and if dimensional change occurs due to water absorption, this may lead to contact failure with the terminals.
  • blisters may occur on the surface of the molded body due to the influence of water absorption.
  • displacement of the optical axis may occur due to dimensional change due to water absorption, which may cause a failure in the operation as a camera.
  • thermosetting resin is often used to seal a molded body for the purpose of preventing entry of moisture and foreign matter from the outside. If the adhesion to the thermosetting resin is low, the sealing property may be insufficient, and the product may be damaged due to the influence of moisture and foreign matter entering from the outside.
  • the present invention will be more specifically described by way of examples, but the present invention is not limited to these examples.
  • the measured value described in the Example is measured by the following method.
  • Peak area ( ⁇ H Tc2 ) associated with thermal crystallization Measure 10 mg of semi-aromatic polyamide resin dried under reduced pressure at 105 ° C for 15 hours in a pan made of aluminum (manufactured by SII Nano Technology Inc., part number 170421S), and use an aluminum lid (manufactured by SAI nano technology Inc, part number 170420) After preparing a measurement sample in a sealed state, the temperature was raised from room temperature at 20 ° C./min using a high sensitivity type differential scanning calorimeter DSC 7020 (manufactured by SII Nano Technology Inc.) and held at 350 ° C. for 3 minutes Later, the measurement sample pan was taken out, dipped in liquid nitrogen, and quenched.
  • the sample is taken out of liquid nitrogen and left at room temperature for 30 minutes, and then heated again from room temperature at a rate of 20 ° C./minute using a high sensitivity type differential scanning calorimeter DSC7020 (manufactured by SII Nano Technology Inc.) After holding at 350 ° C. for 3 minutes, the temperature was lowered to 30 ° C. at 10 ° C./min. The peak area of heat release derived from cold crystallization at the time of temperature lowering was taken as ( ⁇ H Tc2 ).
  • the sample is taken out of liquid nitrogen and left at room temperature for 30 minutes, and then heated again from room temperature at a rate of 20 ° C./minute using a high sensitivity type differential scanning calorimeter DSC7020 (manufactured by SII Nano Technology Inc.) And held at 350 ° C. for 3 minutes.
  • the peak temperature of endotherm due to melting at the time of temperature rise was taken as the melting point (Tm).
  • Tg Glass transition temperature Measure 10 mg of semi-aromatic polyamide resin dried under reduced pressure at 105 ° C for 15 hours in a pan made of aluminum (manufactured by SII Nano Technology Inc., part number 170421S), and use an aluminum lid (manufactured by SAI nano technology Inc, part number 170420) After preparing a measurement sample in a sealed state, the temperature was raised from room temperature at 20 ° C./min using a high sensitivity type differential scanning calorimeter DSC 7020 (manufactured by SII Nano Technology Inc.) and held at 350 ° C. for 3 minutes Later, the measurement sample pan was taken out, dipped in liquid nitrogen, and quenched.
  • the sample is taken out of liquid nitrogen and left at room temperature for 30 minutes, and then heated again from room temperature at a rate of 20 ° C./minute using a high sensitivity type differential scanning calorimeter DSC7020 (manufactured by SII Nano Technology Inc.) And held at 350 ° C. for 3 minutes.
  • the inflection point of the baseline at the time of temperature rise was taken as the glass transition temperature (Tg).
  • the cylinder temperature is set to the melting point + 20 ° C of the resin
  • the mold temperature is set to 140 ° C, 100mm long, 100mm wide, 1mm thick
  • the flat plate was injection-molded to prepare a test piece for evaluation. After annealing the test piece in an atmosphere at 150 ° C. for 2 hours, the mass was measured, and the mass at this time was taken as the mass at the time of drying. Further, the annealed test piece was allowed to stand in an atmosphere at 85 ° C.
  • the cylinder temperature is set to + 20 ° C of the melting point of the resin and the mold temperature is set to 140 ° C using an injection molding machine EC-100 made by Toshiba Machine, 100 mm long, 100 mm wide, A flat plate with a thickness of 1 mm was injection molded to prepare a test piece for evaluation. After annealing the test piece in an atmosphere at 150 ° C. for 2 hours, the dimensions in the parallel direction and the perpendicular direction to the film gate are measured with a caliper at a position of 50 mm from the end, respectively, I asked for. Moreover, the average dimension at this time was made into the average dimension at the time of drying.
  • Average dimension (mm) (dimension in parallel direction + dimension in perpendicular direction) / 2
  • FIG. 1 Bonding strength
  • the cylinder temperature is set to the melting point of the resin + 20 ° C
  • the mold temperature is set to 140 ° C
  • the evaluation test piece described in FIG. , Made The upper view of FIG. 1 is a top view seen from the top, and the lower view is a side view seen from the side.
  • 0.04 g of a thermosetting resin to the adhesive surface (area 310 mm 2 : total area of the arrow end in the upper view of FIG. 2) of the prepared test specimen for evaluation, the test specimen of the same shape is used. Heat treatment was performed for 60 minutes in an atmosphere of 100 ° C.
  • Bonding strength (MPa) test force at the time of specimen failure / bonding area (310 mm 2 )
  • Adhesion failure mode The state of failure when the adhesion strength was evaluated by the method described above was classified using the following index.
  • Base material No breakage occurs at the adhesive (thermosetting resin) portion or at the interface between the resin composition test piece and the adhesive, and the test piece itself is broken
  • Interface Adhesive (thermosetting resin) portion or resin composition Fracture at the interface of the specimen and adhesive
  • Reflowable temperature limit is 260 ° C or higher
  • Reflowable temperature limit is less than 260 ° C
  • This example was conducted using a semi-aromatic polyamide resin (A) synthesized as exemplified below.
  • Synthesis Example 1 7.54 kg of 1,6-hexamethylenediamine, 10.79 kg of terephthalic acid, 7.04 kg of 11-aminoundecanoic acid, 9 g of sodium hypophosphite as a catalyst, 40 g of acetic acid as a terminal regulator and 17.52 kg of ion exchanged water
  • the autoclave was charged with N 2 from atmospheric pressure to 0.05 MPa, released from pressure, and returned to atmospheric pressure. This operation was performed three times, and after performing N 2 substitution, it was uniformly dissolved at 135 ° C. and 0.3 MPa with stirring. Thereafter, the solution was continuously supplied by a liquid feed pump, and the temperature was raised to 240 ° C. by a heating pipe, and heat was applied for 1 hour.
  • reaction mixture was supplied to the pressure reaction vessel, heated to 290 ° C., and a portion of water was distilled off to maintain the internal pressure of the vessel at 3 MPa, to obtain a low-order condensate.
  • the polycondensation was advanced under melting to obtain a semi-aromatic polyamide resin (A-1).
  • Synthesis Example 2 8.57 kg of 1,6-hexamethylenediamine, 12.24 kg of terephthalic acid, 7.99 kg of 11-aminoundecanoic acid, 9 g of sodium hypophosphite as a catalyst, 150 g of acetic acid as an end blocking agent and 16.20 kg of ion exchanged water
  • the autoclave was charged with N 2 from atmospheric pressure to 0.05 MPa, released from pressure, and returned to atmospheric pressure. This operation was performed three times, and after performing N 2 substitution, it was uniformly dissolved at 135 ° C. and 0.3 MPa with stirring. Thereafter, the solution was continuously supplied by a liquid feed pump, and the temperature was raised to 240 ° C. by a heating pipe, and heat was applied for 1 hour.
  • the reaction mixture was supplied to the pressure reaction vessel, heated to 290 ° C., and a portion of water was distilled off to maintain the internal pressure of the vessel at 3 MPa, to obtain a low-order condensate.
  • the low-order condensate was taken out into a container under normal temperature and pressure in the air, and then dried under an environment of 70 ° C. and a vacuum degree of 50 Torr using a vacuum dryer. After drying, the lower condensate was reacted with a blender (volume 0.1 m 3 ) for 6 hours at 210 ° C. under a vacuum of 50 Torr for 6 hours to obtain a semi-aromatic polyamide resin (A-2).
  • the obtained semi-aromatic polyamide resin (A-2) has 65.3 mol% of a constituent unit consisting of 1,6-hexamethylenediamine and terephthalic acid and 34.7 mol of a constituent unit consisting of 11-aminoundecanoic acid % consists of a relative viscosity 2.03, melting point 313 ° C., was 1
  • Synthesis Example 3 13.22 kg of 1,6-hexamethylenediamine, 12.25 kg of terephthalic acid, 7.99 kg of 11-aminoundecanoic acid, 9 g of sodium diphosphite as a catalyst, 395 g of acetic acid as an end blocking agent and 12.68 kg of ion exchanged water
  • the autoclave was charged with N 2 from atmospheric pressure to 0.05 MPa, released from pressure, and returned to atmospheric pressure. This operation was performed three times, and after performing N 2 substitution, it was uniformly dissolved at 135 ° C. and 0.3 MPa with stirring. Thereafter, the solution was continuously supplied by a liquid feed pump, and the temperature was raised to 240 ° C. by a heating pipe, and heat was applied for 1 hour.
  • the reaction mixture was supplied to the pressure reaction vessel, heated to 290 ° C., and a portion of water was distilled off to maintain the internal pressure of the vessel at 3 MPa, to obtain a low-order condensate.
  • the low-order condensate was taken out into a container under normal temperature and pressure in the air, and then dried under an environment of 70 ° C. and a vacuum degree of 50 Torr using a vacuum dryer. After drying, the low-order condensate was reacted with a blender (volume 0.1 m 3 ) for 6 hours at 210 ° C. under a vacuum of 50 Torr for 6 hours to obtain a semiaromatic polyamide resin (A-3).
  • Synthesis Example 5 According to the method described in Comparative Example 3 of WO 2006/098434, terephthalic acid units, 1,9-nonanediamine units and 2-methyl-1,8-octanediamine units (1,9-nonanediamine units: 2-methyl)
  • end blocking agent is benzoic acid
  • This example was performed using the semi-aromatic polyamide resin composition (C) produced as illustrated below.
  • Semi-Aromatic Polyamide Resin (A-1): Semi-Aromatic Polyamide Resin Produced According to Synthesis Example 1
  • Semi-Aromatic Polyamide Resin (A-2): Semi-Production Produced According to Synthesis Example 2 Above Aromatic polyamide resin
  • Semi-aromatic polyamide resin (A-3): Semi-aromatic polyamide resin produced based on the above-mentioned Synthesis Example 3
  • Semi-aromatic polyamide resin produced Semi-aromatic polyamide resin (A-5): Semi-aromatic polyamide resin produced according to the above Synthesis Example 5
  • Semi-aromatic polyamide resin (A-6): PA10T (KINGFA SCI .
  • a molded article (D) comprising the semiaromatic polyamide resin composition (C) produced as described above and a thermosetting resin (E) were used. .
  • Examples 1 to 9 and Comparative Examples 1 to 5 were carried out according to the method described above using the semiaromatic polyamide resin composition (C) and the thermosetting resin (E) described in Tables 1 and 2.
  • Thermosetting resin (E-1) one-component thermosetting epoxy resin (manufactured by ThreeBond 2222P)
  • Thermosetting resin (E-2) One-component thermosetting epoxy resin (Taoka Chemical Co., Ltd. AH-3031T)
  • thermosetting resin (E) As apparent from Tables 1 and 2, in Examples 1 to 3 not only high adhesiveness with the thermosetting resin (E) can be expressed, but also the 80% 95% RH equilibrium water absorption dimensional change rate is small, and the solder reflow resistance It can be seen that it has excellent characteristics, such as satisfying the property. Further, in Example 4, although the AEG value is as low as 2 eq / ton and the adhesion to the thermosetting resin (E) is slightly reduced as compared with Examples 1 to 3, the adhesive strength is 2.9 MPa, Sufficient characteristics have been obtained for practical use. In Example 5, the thermosetting resin (E) is changed, but sufficient adhesive strength is obtained, and it can be seen that the resin has excellent properties.
  • Comparative Example 1 uses a semi-aromatic polyamide resin produced from the same monomers as in Examples 1 to 3, but the value of (AEG + CEG) is as low as 59 eq / ton, and a thermosetting resin (E) Adhesiveness with is insufficient.
  • Comparative Examples 2 and 3 use a semi-aromatic polyamide resin (PA9T / M8T) manufactured from monomers different from those of Examples 1 to 5, and in Comparative Example 2, the value of (AEG + CEG) is as low as 63 eq / ton.
  • ⁇ H Tc2 is large and Tg is high, adhesion to the thermosetting resin (E) is insufficient.
  • Comparative Example 3 Although the value of (AEG + CEG) is appropriate at 126 eq / ton, the adhesiveness with the thermosetting resin (E) is insufficient because ⁇ H Tc2 is large and Tg is high.
  • Comparative Example 4 uses a semi-aromatic polyamide resin (PA10T) produced from monomers different from those of Examples 1 to 5, and in addition to the low value of (AEG + CEG) of 44 eq / ton, ⁇ H Tc2 is large. Because of high Tg, adhesion to the thermosetting resin (E) is insufficient.
  • PA10T semi-aromatic polyamide resin
  • thermosetting resin (E) In Comparative Example 5, although the thermosetting resin (E) is changed, although the value of (AEG + CEG) is appropriate to 126 eq / ton as in Comparative Example 3, the ⁇ H Tc2 is large and the Tg is high. Adhesiveness with curable resin (E) is inadequate. Further, in Examples 6 to 9, since the adhesion strength is high and the adhesion failure mode is also the base material, it is understood that the adhesive property with the thermosetting resin (D) is excellent. Furthermore, the 80 ° C. 95% RH equilibrium water absorption rate, the 80 ° C. 95% RH equilibrium water absorption dimensional change rate is also low, and the dimensional stability at the time of water absorption is also excellent.
  • the molded article of the present invention uses a semi-aromatic polyamide resin composition containing a semi-aromatic polyamide resin having specific physical properties such as the amount of end groups in addition to the composition, and a thermosetting resin having a glycidyl group Therefore, it has high water absorption dimensional stability, heat resistance and adhesiveness, and a molded article (composite molded article) highly satisfying user needs can be industrially advantageously manufactured.

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Abstract

L'invention concerne un comprimé qui a une structure dans laquelle un article moulé (D) et une résine thermodurcissable (E) qui contient un groupe glycidyle sont directement mis en contact. L'article moulé (D) comprend une composition de résine polyamide semi-aromatique (C) qui a un taux d'absorption d'eau à l'équilibre inférieur ou égal à 3,0 % à 80°C et 95 % d'humidité relative (HR) et qui contient 0 à 200 parties en masse d'un matériau de renfort (B) pour 100 parties en masse d'une résine polyamide semi-aromatique (A) pour laquelle la surface de pic associée à la cristallisation par refroidissement mesurée par calorimétrie différentielle à balayage (DSC), la température de transition vitreuse et la somme de la concentration de groupes amino terminaux et de la concentration de groupes carboxyle terminaux satisfont à des conditions prescrites. Le comprimé a une stabilité dimensionnelle à l'absorption d'eau, une résistance à la chaleur et une adhésivité élevées.
PCT/JP2018/035096 2017-09-25 2018-09-21 Comprimé comprenant, en tant que constituant, un article moulé constitué d'une composition de résine polyamide semi-aromatique WO2019059357A1 (fr)

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