JP6354379B2 - Polyamide resin composition - Google Patents

Description

  The present invention relates to a polyamide resin composition.

  Thermoplastic resins, especially engineering plastics that are excellent in mechanical properties and thermal properties, are used in various applications by taking advantage of the excellent properties. Polyamide resin, which is a kind of engineering plastic, has an excellent balance between mechanical properties and toughness, and is used for various electrical / electronic parts, mechanical parts, automobile parts, etc., mainly for injection molding.

  Of these uses of engineering plastics, particularly in electrical and electronic parts, there is a strong demand for flame retardancy, and studies on imparting flame retardancy using various flame retardants have been conducted. To date, examples of the flame-retardant polyamide resin composition include a polyamide resin composition flame-retarded with magnesium hydroxide (see, for example, Patent Document 1), a thermoplastic resin, a brominated flame retardant, and radical generation. Containing flame retardant resin composition (for example, see Patent Document 2), an amide structural unit derived from aliphatic and alicyclic diamines having 6 to 12 carbon atoms and terephthalic acid, A flame retardant polyamide resin composition comprising a polyamide resin having a base concentration of 7 or more and a melting point of 280 ° C. or higher and lower than 325 ° C. and a non-halogen flame retardant (see, for example, Patent Document 3) Etc. have been proposed. Further, as a method for producing a flame retardant polymer, a method of adding a synergistic mixture of a sterically hindered alkoxyamine stabilizer and tris [3-bromo-2,2-bis (bromomethyl) propyl] phosphate to an olefin resin (for example, Patent Document 4) has been proposed. However, when a flame retardant is added in order to impart a high degree of flame retardancy, there is a problem that the mechanical properties of the molded product are deteriorated.

  In recent years, polyamide resins are often used in design parts among the applications of the engineering plastics, and high design properties, particularly weather resistance, are required. With respect to polyamide resins having excellent weather resistance, fishing lines made of a resin composition containing a polyamide resin, an ultraviolet absorber, a light stabilizer, and a coloring agent (see, for example, Patent Document 5) have been proposed. However, in order to use such a resin composition for the above applications, there is a problem that the flame retardancy is insufficient.

  In addition, in connector and casing applications, mobile parts such as mobile phones and notebook PCs are becoming thinner and smaller, so the polyamide resin composition used for these applications has fluidity. Improvement is required. As a polyamide resin composition excellent in fluidity, a polyamide resin composition obtained by blending a dendritic polyester resin has been proposed (see, for example, Patent Documents 6 to 7). In recent years, since a high degree of designability is required even in such applications, further improvement in weather resistance is required.

Japanese Patent Laid-Open No. 11-1000049 Japanese Patent Laid-Open No. 11-199784 JP-A-11-302534 JP 2011-168797 A JP 2000-300131 A JP 2009-114366 A JP 2011-195814 A

  An object of this invention is to provide the polyamide resin composition which can obtain the molded article excellent in a flame retardance, a mechanical characteristic, and a weather resistance.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention
(1) 1 to 100 parts by weight of a flame retardant (b), hindered amine stabilizer (c) having a molecular weight of 2600 or more and 0.1 to 5 parts by weight of a cyanoacrylate based on 100 parts by weight of a polyamide resin (a) It contains 0.1 to 5 parts by weight of an ultraviolet absorber (d),
All SANYO said hindered amine stabilizer (c) is sealed terminal amino group,
At least selected from the aromatic oxycarbonyl unit (S), the aromatic and / or aliphatic dioxy unit (T), and the aromatic dicarbonyl unit (U) with respect to 100 parts by weight of the polyamide resin (a). It contains one type of structural unit and trifunctional or higher functional organic residue (D), and the content of D is in the range of 7.5 to 50 mol% with respect to all monomers constituting the dendritic polyester. A polyamide resin composition comprising 0.5 to 10 parts by weight of a dendritic polyester resin (e) having a certain melt liquid crystallinity .
(2) The polyamide resin composition according to (1), wherein the flame retardant (b) is a nitrogen-based flame retardant.
(3) The polyamide resin composition according to (1) or (2), wherein 0.01 to 10 parts by weight of an acid anhydride (f) is further blended with 100 parts by weight of the polyamide resin (a).
(4) In the dendritic polyester resin (e), the aromatic oxycarbonyl unit (S), the aromatic and / or aliphatic dioxy unit (T), and the aromatic dicarbonyl unit (U) are each represented by the following formulae: When at least one structural unit selected from the structural units represented by (1) and the D content is 1 mol, the contents p, q and r of S, T and U are p + q + r. The polyamide resin composition according to any one of (1) to (3), which is in the range of = 1 to 10 mol.

(Here, R1, R2 and R3 are each at least one structural unit selected from structural units represented by the following formula.)

(Wherein, Y is at least one selected from a hydrogen atom, a halogen atom and an alkyl group. In the formula, n is an integer of 2 to 8.)
(5) The dendritic polyester resin (e) contains a basic skeleton represented by the formula (2) (1
The polyamide resin composition according to any one of (4) to (4) .

(Here, D is an organic residue of a trifunctional compound, and DD is bonded directly by an ester bond and / or an amide bond, or bonded via a structural unit selected from S, T and U. Yes.)
(6) The dendritic polyester resin (e) contains the basic skeleton represented by the formula (3) (1)
The polyamide resin composition according to any one of to (4) .

(Here, D is an organic residue of a tetrafunctional compound, and DD is bonded directly by an ester bond and / or an amide bond or via a structural unit selected from S, T and U. Yes.)
(7) The polyamide resin composition according to any one of (1) to (6), wherein the organic residue represented by D of the dendritic polyester resin (e) is an organic residue derived from an aromatic compound. .
(8) The organic residue represented by D of the dendritic polyester resin (e) is represented by the formula (5) or (6)
The polyamide resin composition according to (7), which is an organic residue represented by:

( 9 ) The polyamide resin composition according to any one of ( 3 ) to ( 8 ), wherein the acid anhydride (f) does not have an unsaturated hydrocarbon group.
( 10 ) A molded product obtained by molding the polyamide resin composition according to any one of (1) to ( 9 ).
( 11 ) The molded product according to ( 10 ), wherein the thinnest portion of the molded product is 0.5 mm or less.

  According to the polyamide resin composition of the present invention, a molded article excellent in flame retardancy, mechanical properties and weather resistance can be provided.

  The polyamide resin (a) used in the present invention is mainly composed of amino acids, lactams or diamines and dicarboxylic acids. Examples of these raw materials include aminocarboxylic acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and paraaminomethylbenzoic acid, lactams such as ε-caprolactam and ω-laurolactam, tetramethylenediamine, Pentamethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, Aliphatic diamines such as 5-methylnonamethylenediamine, aromatic diamines such as metaxylylenediamine and paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-amino) Cyclohexyl) propane, bis (aminopropyl) piperazine, alicyclic diamines such as aminoethylpiperazine, aliphatic dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2 -Aromatic dicarboxylic acids such as chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, 4-cyclohexanedicarboxylic acid, 1,3-si B hexane dicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-like alicyclic dicarboxylic acids such as cyclopentane dicarboxylic acid. In the present invention, two or more homopolymers or copolymers derived from these raw materials may be blended.

  Among the polyamide resins obtained from these raw materials, polycaprolactam (nylon 6) and polyhexamethylene adipamide (nylon 66) are preferable from the viewpoints of moldability and fluidity. From the viewpoint of further improving the weather resistance of the molded product, polyhexamethylene adipamide (nylon 66) is more preferable.

  The degree of polymerization of the polyamide resin (a) used in the present invention is not particularly limited, but the relative viscosity measured at 25 ° C. in a 98% concentrated sulfuric acid solution having a sample concentration of 0.01 g / ml is 1.5 to 4. Is preferably in the range of 0.0, more preferably in the range of 2.0 to 3.0.

  The flame retardant (b) used in the present invention is not particularly limited as long as it can impart flame retardancy to the polyamide resin composition of the present invention. Specific examples include phosphorous flame retardants, nitrogen flame retardants, non-halogen flame retardants that do not contain halogen atoms such as magnesium hydroxide, and halogen flame retardants such as bromine flame retardants. Two or more flame retardants may be blended. From the viewpoint of further improving the weather resistance of the molded article, a nitrogen-based flame retardant is preferred.

  In the polyamide resin composition of the present invention, the amount of the flame retardant (b) is 1 to 100 parts by weight with respect to 100 parts by weight of the polyamide resin. When the compounding quantity of a flame retardant (b) is less than 1 weight part, the flame retardance of a molded article falls. 3 parts by weight or more is preferable, and 5 parts by weight or more is more preferable. Moreover, when the compounding quantity of a flame retardant (b) exceeds 100 weight part, the fluidity | liquidity of a polyamide resin composition will fall remarkably and the mechanical characteristics of a molded article will also fall. From the viewpoint of further improving the mechanical properties of the molded product, it is preferably 70 parts by weight or less, more preferably 50 parts by weight or less, and still more preferably 40 parts by weight or less.

  Specific examples of the phosphorus flame retardant include polyphosphoric acid compounds such as red phosphorus, ammonium polyphosphate, and melamine polyphosphate, aromatic phosphate compounds, and aromatic bisphosphate compounds.

  Examples of the nitrogen-based flame retardant include cyanuric acid or a salt of isocyanuric acid and a triazine-based compound. The salt of cyanuric acid or isocyanuric acid and a triazine compound is an adduct of cyanuric acid or isocyanuric acid and a triazine compound, and is usually 1 to 1 (molar ratio), and sometimes 1 to 2 (mole). Ratio). Examples of the triazine compound include melamine, mono (hydroxymethyl) melamine, di (hydroxymethyl) melamine, tri (hydroxymethyl) melamine, benzoguanamine, acetoguanamine, 2-amide-4,6-diamino-1,3, 5-triazine etc. are mentioned, Melamine, benzoguanamine, and acetoguanamine are preferable.

Magnesium hydroxide is usually commercially available and is not particularly limited in terms of particle diameter, specific surface area, shape, etc., but the particle diameter is 0.1 to 20 μm, the specific surface area is 3 to 75 m ² / g, Spherical, needle-like or platelet-like ones are preferred. Magnesium hydroxide may or may not be surface treated. Examples of the surface treatment method include a method of coating with a thermosetting resin such as a silane coupling agent, an anionic surfactant, a polyfunctional organic acid, or an epoxy resin.

  The brominated flame retardant is not particularly limited as long as it is a compound containing bromine in the chemical structure, and generally known flame retardants can be used. For example, hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis (pentabromophenoxy) ethane, ethylenebis (tetrabromophthalimide) , Monomeric organic bromine compounds such as tetrabromobisphenol A, brominated polycarbonates (for example, polycarbonate oligomers produced from brominated bisphenol A or copolymers thereof with bisphenol A), brominated epoxy compounds (for example, bromine) Of diepoxy compounds and brominated phenols produced by the reaction of bisphenol A with epichlorohydrin and epichlorohydrin Monoepoxy compound), poly (brominated benzyl acrylate), brominated polyphenylene ether, brominated bisphenol A, cyanuric chloride and brominated phenol condensate, brominated polystyrene, poly (brominated styrene), cross-linked brominated Examples thereof include brominated polystyrene such as polystyrene, and halogenated polymer bromine compounds such as crosslinked or non-crosslinked brominated poly α-methylstyrene. Of these, ethylene bis (tetrabromophthalimide), brominated epoxy compounds, brominated polystyrene, crosslinked brominated polystyrene, brominated polyphenylene ether and brominated polycarbonate are preferred. Brominated polystyrene, crosslinked brominated polystyrene, brominated polyphenylene ether and bromine. Polycarbonate is more preferred.

  The polyamide resin composition of the present invention may contain a flame retardant aid that synergistically improves flame retardancy with the above flame retardant. Examples of flame retardant aids include antimony trioxide, antimony pentoxide, antimony tetraoxide, hexamonic trioxide, crystalline antimonic acid, sodium antimonate, lithium antimonate, barium antimonate, antimony phosphate, zinc borate Zinc stannate, basic zinc molybdate, calcium zinc molybdate, molybdenum oxide, zirconium oxide, zinc oxide, iron oxide, swellable graphite, carbon black and the like. Of these, antimony trioxide and antimony pentoxide are more preferable. The blending amount of the flame retardant aid is preferably 0.2 to 30 parts by weight with respect to 100 parts by weight of the polyamide resin (a) from the viewpoint of further improving the flame retardancy.

  The polyamide resin composition of the present invention includes a hindered amine stabilizer (c) having a molecular weight of 2000 or more as a light stabilizer (hereinafter sometimes referred to as “hindered amine stabilizer (c)”) and an ultraviolet absorber. A cyanoacrylate compound (d) is blended. By blending these, the weather resistance of the molded product can be improved.

  Examples of the hindered amine stabilizer (c) used in the present invention include dibutylamine, 2,4,6-trichloro-1,3,5-triazine, N, N′-bis (2,2,6,6). -Tetramethylpiperidin-4-yl) hexane-1,6-diyldiamine, N- (2,2,6,6-tetramethylpiperidin-4-yl) butylamine polycondensate, ethane-1,2-carboxylic acid Dimethyl ester, 4-hydroxy-2,2,6,6-tetramethyl-piperidineethanol polycondensate, propane-1,2-carboxylic acid, dimethyl ester, 4-hydroxy-2,2,6,6- Tetramethyl-piperidine ethanol polycondensate, poly [[6-[(1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4-diyl] [ 2,2,6,6-tetramethyl-4-piperidinyl) imino] -1,6-hexanediyl [(2,2,6,6-tetramethyl-4-piperidinyl) imino]], 1,6-hexane Diamine, N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl), 2,4,6-trichloro-1,3,5-triazine, N-butyl-1-butanamine, N -Butyl-2,2,6,6-tetramethyl-4-piperidiamine polycondensate and the like. Two or more of these may be blended. The molecular weight of the hindered amine stabilizer (c) is 2000 or more. When the molecular weight of the hindered amine stabilizer (c) is less than 2000, the weather resistance and mechanical properties of the molded product are deteriorated. Here, the molecular weight of the hindered amine stabilizer (c) can be measured by the GPC-LS method.

  It is preferable that the hindered amine stabilizer (c) has a terminal amino group sealed. By sealing the unreacted molecular terminal amino group of the hindered amine stabilizer that easily reacts with the polyamide resin (a), the fluidity of the polyamide resin composition can be improved. Further, it is possible to suppress the deterioration of the mechanical properties of the molded product due to the stay. Here, the unreacted molecular terminal amino group means a primary or secondary amino group at the molecular end, for example, 1,6-hexanediamine · N, N′-bis (2,2,6,6). -Tetramethyl-4-piperidinyl), 2,4,6-trichloro-1,3,5-triazine, 1-butanamine, 2,2,6,6-tetramethyl-4-piperidindiamine polycondensate, 2 , 2,6,6-tetramethyl-4-piperidyl group refers to a primary amine or secondary amine present in a molecule. Further, the term “sealing” means that an alkyl group substituent is added to these primary amino group or secondary amino group to suppress the reaction to form a tertiary amino group. Examples of the hindered amine stabilizer having a terminal amino group sealed include dibutylamine, 2,4,6-trichloro-1,3,5-triazine, N, N′-bis (2,2,6,6- And tetramethylpiperidin-4-yl) hexane-1,6-diyldiamine.N- (2,2,6,6-tetramethylpiperidin-4-yl) butylamine polycondensate.

  In the polyamide resin composition of the present invention, the amount of the hindered amine stabilizer (c) is 0.1 to 5 parts by weight with respect to 100 parts by weight of the polyamide resin (a). When the compounding quantity of the said hindered amine stabilizer (c) is less than 0.1 weight part, the weather resistance of a molded article will fall. Moreover, when the compounding quantity of the said hindered amine stabilizer (c) exceeds 5 weight part, the flame retardance of a molded article and a mechanical characteristic will fall, and the fall of the mechanical characteristic of the molded article by a residence will increase. 4 parts by weight or less is preferable.

  Examples of the cyanoacrylate ultraviolet absorber (d) used in the present invention include 2,2-bis {[2-cyano-3,3-diphenylacryloyloxy] methyl} propane-1,3-diyl = bis ( 2-cyano-3,3-diphenyl acrylate), ethyl-2-cyano-3,3-diphenyl acrylate, 2′-ethylhexyl-2-cyano-3,3-diphenyl acrylate, and the like. Two or more of these may be blended.

  In the polyamide resin composition of the present invention, the compounding amount of the cyanoacrylate ultraviolet absorber (d) is 0.1 to 5 parts by weight with respect to 100 parts by weight of the polyamide resin (a). When the compounding quantity of a cyanoacrylate type ultraviolet absorber (d) is less than 0.1 weight part, the weather resistance of a molded article will fall. Moreover, when the compounding quantity of a cyanoacrylate type ultraviolet absorber (d) exceeds 5 weight part, the flame retardance and mechanical characteristic of a molded article will fall. 4 parts by weight or less is preferable.

  The polyamide resin composition of the present invention preferably contains a dendritic polyester resin (e) exhibiting molten liquid crystallinity (hereinafter sometimes referred to as “dendritic polyester resin (e)”). By blending the dendritic polyester resin (e), the fluidity of the polyamide resin composition can be improved. Further, the hindered amine stabilizer (c) tends to be gelled at the time of residence, but the gelation of the hindered amine stabilizer (c) at the time of residence is suppressed by blending the dendritic polyester resin (e). In addition, it is possible to suppress the deterioration of the mechanical properties of the molded product due to retention. Conventionally, a molded product obtained by molding a polyamide resin composition containing a dendritic polyester resin has been apt to be colored and has a tendency to deteriorate in weather resistance. However, a hindered amine stabilizer (c) and a cyanoacrylate ultraviolet ray have been used. Since the polyamide resin composition of the present invention obtained by blending the absorbent (d) can suppress a decrease in the weather resistance of the molded article even when the dendritic polyester resin (e) is blended, it is dendritic. The polyamide resin composition obtained by blending the polyester resin (e) is particularly effective.

  In the polyamide resin composition of the present invention, the blending amount of the dendritic polyester resin (e) is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the polyamide resin (a). By making the blending amount of the dendritic polyester resin (e) 0.01% or more, the fluidity of the polyamide resin composition can be further improved. 0.1 parts by weight or more is more preferable, and 0.5 parts by weight or more is more preferable. Moreover, the coloring of a molded article can be suppressed and a weather resistance can be improved more because the compounding quantity of dendritic polyester resin (e) shall be 10 weight part or less. Further, the mechanical characteristics can be further improved.

  The dendritic polyester resin (e) used in the present invention is at least selected from an aromatic oxycarbonyl unit (S), an aromatic and / or aliphatic dioxy unit (T), and an aromatic dicarbonyl unit (U). One type of structural unit and a trifunctional or higher functional organic residue (D), and the D content is in the range of 7.5 to 50 mol% with respect to the total monomers constituting the dendritic polyester. A dendritic polyester resin.

  Here, in the dendritic polyester resin (e), the aromatic oxycarbonyl unit (S), the aromatic and / or aliphatic dioxy unit (T), and the aromatic dicarbonyl unit (U) are each represented by the following formulae: It is preferably at least one structural unit selected from the structural units represented by (1).

  Here, R1, R2, and R3 are each at least one structural unit selected from structural units represented by the following formulae.

  Here, Y in the formula is at least one selected from a hydrogen atom, a halogen atom and an alkyl group. As an alkyl group, a C1-C4 alkyl group is preferable. In the formula, n is an integer of 2 to 8.

  In the present invention, the dendritic polyester resin (e) is selected from S, T and U in which the trifunctional or higher functional organic residue (D) is directly by an ester bond and / or an amide bond, or is a branched structure part. The basic skeleton is a branched structure of 3 or more branches linked through structural units. The branched structure may be formed of a single basic skeleton such as three branches and four branches, or a plurality of basic skeletons such as three branches and four branches may coexist. It is not necessary for all of the polymers to be composed of the basic skeleton, and for example, other structures may be included at the ends for end capping. When D is a trifunctional organic residue, the dendritic polyester resin has a structure in which all three functional groups of D are reacted, a structure in which only two are reacted, and A structure in which only one reacts may be mixed. The structure in which all three functional groups of D are reacted is preferably 15 mol% or more, more preferably 20 mol% or more, and further preferably 30 mol% or more with respect to the entire D. When D is a tetrafunctional organic residue, the dendritic polyester resin has a structure in which all four functional groups of D have reacted, a structure in which only three have reacted, and 2 A structure in which only one reacts and a structure in which only one reacts may be mixed. The structure in which all four functional groups of D are reacted is preferably 10 mol% or more with respect to the whole D, and the structure in which three functional groups are reacted is preferably 20 mol% or more, more preferably four functional groups are reacted. And the structure in which three functional groups have reacted with respect to the entire D is 30 mol% or more, and more preferably the structure in which four functional groups have reacted with respect to the entire D. 25 mol% or more and the structure in which three functional groups have reacted is 35 mol% or more with respect to the entire D.

  D is preferably an organic residue of a trifunctional compound and / or a tetrafunctional compound, and more preferably an organic residue of a trifunctional compound.

  The above three-branch basic skeleton is schematically represented by the following formula (2). The above four-branch basic skeleton is schematically represented by the following formula (3).

  In the present invention, the dendritic polyester resin (e) preferably exhibits melt liquid crystallinity. The term “showing molten liquid crystallinity” means that the liquid crystal state is exhibited in a certain temperature range when the temperature is raised from room temperature. The liquid crystal state is a state showing optical anisotropy under shear.

  In order to exhibit molten liquid crystallinity, the basic skeleton in the case of three branches is composed of a structural unit in which the organic residue (D) is selected from S, T and U as shown in the following formula (5) It is preferable that they are bonded via the branch structure portion R.

  Similarly, the basic skeleton in the case of four branches is preferably a structure represented by the following formula (6).

  Although it does not specifically limit about the trifunctional organic residue represented by D, It is preferable that it is an organic residue of the compound containing the functional group chosen from a carboxyl group, a hydroxyl group, and an amino group. For example, residues of aliphatic compounds such as glycerol, methylolpropane, tricarballylic acid, diaminopropanol, diaminopropionic acid, trimesic acid, trimellitic acid, 4-hydroxy-1,2-benzenedicarboxylic acid, phloroglucinol, α Residual aromatic compounds such as resorcinic acid, β-resorcinic acid, γ-resorcinic acid, tricarboxynaphthalene, dihydroxynaphthoic acid, aminophthalic acid, 5-aminoisophthalic acid, aminoterephthalic acid, diaminobenzoic acid, melamine, cyanuric acid Examples include groups. Among these, a residue of an aromatic compound is preferable, and a residue represented by the following formula (4) is more preferable. Specifically, residues of trimesic acid and α-resorcinic acid are preferable, and residues of trimesic acid are more preferable.

  Further, the tetrafunctional or higher functional organic residue D is preferably an organic residue of a compound containing a functional group selected from a carboxyl group, a hydroxyl group and an amino group. For example, erythritol, pentaerythritol, threitol, xylitol, glucitol, mannitol, 1,2,3,4-butanetetracarboxylic acid, 1,2,4,5-cyclohexanetetraol, 1,2,3,4,5- Cyclohexanepentaneol, 1,2,3,4,5,6-cyclohexanehexaneol, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4,5-cyclohexanepentacarboxylic acid, 1, Residues of aliphatic compounds such as 2,3,4,5,6-cyclohexanehexacarboxylic acid, citric acid, tartaric acid, 1,2,4,5-benzenetetraol, 1,2,3,4-benzene Tetraol, 1,2,3,5-benzenetetraol, 1,2,3,4,5-benzenepentaneol, 1,2,3,4,5 6-benzenehexaneol, 2,2 ′, 3,3′-tetrahydroxybiphenyl, 2,2 ′, 4,4′-tetrahydroxybiphenyl, 3,3 ′, 4,4′-tetrahydroxybiphenyl, 3, 3 ', 5,5'-tetrahydroxybiphenyl, 2,3,6,7-naphthalenetetraol, 1,4,5,8-naphthalenetetraol, pyromellitic acid, merophanic acid, planitic acid, meritic acid, 2 , 2 ′, 3,3′-biphenyltetracarboxylic acid, 2,2 ′, 4,4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 3,3 ′, 5 , 5′-biphenyltetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalene Raol, 1,4,5,8-naphthalenetetraol, 1,2,4,5,6,8-naphthalenehexaol, 1,2,4,5,6,8-naphthalenehexacarboxylic acid, gallic acid, etc. And the residue of the aromatic compound. 1,2,4,5-benzenetetraol, 1,2,3,4-benzenetetraol, 1,2,3,5-benzenetetraol, pyromellitic acid, merophanic acid, planitic acid, gallic acid, etc. A residue is preferable, a residue of gallic acid is more preferable, and a residue represented by the following formula (7) is more preferable.

  In addition, the aromatic hydroxycarbonyl unit (S), aromatic and / or aliphatic dioxy unit (T), and aromatic dicarbonyl unit (U) of the dendritic polyester resin (e) are between the branches of the dendritic polyester resin. It is a unit constituting a branch structure part. p, q, and r are the average contents (molar ratio) of the structural units S, T, and U, respectively, and it is preferable that p + q + r is 1 to 10 when the content d of D is 1 mol. By setting p + q + r within the above range, it is possible to suppress reduction in effects such as shear responsiveness based on a rigid and detailed dendritic structure due to the branch chain length being too long. p + q + r is more preferably 2 or more. Further, p + q + r is more preferably 6 or less. The values of p, q, and r are obtained, for example, by dissolving dendritic polyester resin in a mixed solvent of 50% by weight of pentafluorophenol and 50% by weight of chloroform and performing nuclear magnetic resonance spectrum analysis of proton nuclei at 40 ° C. It can obtain | require from the peak intensity ratio derived from each structural unit. The average content is calculated from the peak area intensity ratio of each structural unit, and the three decimal places are rounded off. The average chain length of the branch portion R is calculated from the area intensity ratio with respect to the peak corresponding to the content d of the branched structure D, and is defined as p + q + r. In this case, the three decimal places are rounded off.

  The ratio of p to q and p to r (p / q, p / r) is preferably 5/95 to 95/5, more preferably 10/90 to 90/10, and even more preferably 20 / 80-80 / 20. By setting the ratio of p / q and p / r to 95/5 or less, the melting point of the dendritic polyester resin can be within an appropriate range, and p / q and p / r should be 5/95 or more. Thus, the melt liquid crystallinity of the dendritic polyester resin can be easily expressed.

  q and r are preferably substantially equimolar, but either component can be added in excess to control the end groups. The ratio of q / r is preferably in the range of 0.7 to 1.5, more preferably 0.9 to 1.1. Equimolar here means that the molar amount in the repeating unit is equal and does not include the terminal structure. Here, the term “end structure” means the end of the branch structure portion, and when the end is blocked, it means the end of the branch structure portion closest to the end.

  Furthermore, R1, R2, and R3 are the structural units.

  R1 is a structure derived from an aromatic oxycarbonyl unit, and examples thereof include structural units generated from p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid. Preferably, it is a structural unit derived from p-hydroxybenzoic acid, and a part derived from 6-hydroxy-2-naphthoic acid can be used in combination. In addition, a structural unit derived from an aliphatic hydroxycarboxylic acid such as glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid and the like may be contained as long as the effects of the present invention are not impaired.

  R2 is a structure derived from an aromatic and / or aliphatic dioxy unit, for example, 4,4′-dihydroxybiphenyl, hydroquinone, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl , T-butylhydroquinone, phenylhydroquinone, methylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane, 4,4′-dihydroxydiphenyl ether, ethylene glycol, Examples include structural units generated from 1,3-propylene glycol, 1,4-butanediol, and the like. Preferred are structural units formed from 4,4′-dihydroxybiphenyl, hydroquinone, and ethylene glycol, and include structural units formed from 4,4′-dihydroxybiphenyl and hydroquinone, or 4,4′-dihydroxybiphenyl and ethylene glycol. This is preferable from the viewpoint of controlling liquid crystallinity.

  R3 is a structural unit generated from an aromatic dicarbonyl unit. For example, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 1,2-bis (phenoxy) Examples thereof include structural units formed from ethane-4,4′-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4′-dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, and the like. A structural unit formed from terephthalic acid or isophthalic acid is preferred, and particularly when both are used in combination, the melting point can be easily adjusted. A part of a structural unit generated from an aliphatic dicarboxylic acid such as sebacic acid or adipic acid may be contained.

  The branch structure portion of the dendritic polyester resin (e) is preferably mainly composed of a polyester skeleton, but it is also possible to introduce a carbonate structure, an amide structure, a urethane structure, etc. to such an extent that the characteristics are not greatly affected. Among them, it is preferable to introduce an amide structure. By introducing such another bond, compatibility with a wide variety of polyamide resins can be adjusted, which is preferable. Examples of the method for introducing an amide bond include p-aminobenzoic acid, m-aminobenzoic acid, p-aminophenol, m-aminophenol, p-phenylenediamine, m-phenylenediamine, m-xylylenediamine, p -Aromatic amines such as xylylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2 , 4,4-trimethylhexamethylenediamine, aliphatic amines such as 5-methylnonamethylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3- Aminomethyl-3,5,5-trimethyl Chlorohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine, etc. A method of copolymerizing an alicyclic amine compound or the like is preferable, and a method of copolymerizing p-aminophenol or p-aminobenzoic acid is particularly preferable.

  Specific examples of the structure of R include a structural unit formed from p-hydroxybenzoic acid and a structural unit generated from 6-hydroxy-2-naphthoic acid, a structural unit generated from p-hydroxybenzoic acid, 6- A structural unit produced from hydroxy-2-naphthoic acid, a structural unit produced from 4,4′-dihydroxybiphenyl and a structural unit produced from terephthalic acid, a structural unit produced from p-hydroxybenzoic acid, 4,4 Structural units formed from '-dihydroxybiphenyl, structural units formed from terephthalic acid and structural units generated from isophthalic acid, structural units generated from p-hydroxybenzoic acid, generated from 4,4'-dihydroxybiphenyl Structural unit, structural unit generated from hydroquinone, terephthalic acid A structure composed of a structural unit generated from isophthalic acid, a structural unit generated from isophthalic acid, a structural unit generated from p-hydroxybenzoic acid, a structural unit generated from ethylene glycol, and a structural unit generated from terephthalic acid, p-hydroxy A structural unit generated from benzoic acid, a structural unit generated from ethylene glycol, a structural unit generated from 4,4′-dihydroxybiphenyl and a structural unit generated from terephthalic acid, a structural unit generated from p-hydroxybenzoic acid , A structural unit produced from hydroquinone, a structural unit produced from 4,4′-dihydroxybiphenyl, a structural unit produced from terephthalic acid and a structural unit produced from 2,6-naphthalenedicarboxylic acid, p-hydroxybenzoic acid Generated from Units, 6-hydroxy-2 structural unit derived from naphthoic acid, such structure comprising a structural unit derived from structural units and terephthalic acid was produced from hydroquinone.

  Particularly preferred is R composed of the following structural units (I), (II), (III), (IV) and (V) or the following structural units (I), (II), (VI) and (IV) R).

  In the case of R composed of the structural units (I), (II), (III), (IV) and (V), the content p of the structural unit (I) is based on the total p + q + r of the structural units. 30 to 70% is preferable, and more preferably 45 to 60%.

  Further, the content q (II) of the structural unit (II) is preferably 60 to 75%, more preferably 65 to 73% with respect to the total q of the structural units (II) and (III). Further, the content r (IV) of the structural unit (IV) is preferably 60 to 92%, more preferably 60 to 70%, still more preferably relative to the total r of the structural units (IV) and (V). 62-68%.

  Preferably, the sum q of structural units (II) and (III) and the sum r of (IV) and (V) are substantially equimolar, but the carboxylic acid component or hydroxyl to adjust the end groups of the polymer Ingredients may be added in excess. That is, “substantially equimolar” means that the unit constituting the polymer main chain excluding the terminal is equimolar, but the unit constituting the terminal is not necessarily equimolar. Here, when the terminal is a derivative or blocked, it means the terminal of the skeleton R.

  In the case of R composed of the structural units (I), (II), (VI) and (IV), the content p of the structural unit (I) is the structural units (I), (II) and ( 30-90 mol% is preferable with respect to the sum total of VI), and 40-80 mol% is more preferable. Moreover, 70-5 mol% is preferable with respect to the sum q of (II) and (VI), and, as for content q (VI) of structural unit (VI), 60-8 mol% is more preferable. Further, the structural unit (IV) is preferably substantially equimolar to the total of the structural units (II) and (VI), but either component may be added in excess.

  The terminal of the dendritic polyester resin (e) is preferably a carboxyl group, a hydroxyl group, an amino group or a derivative thereof. Examples of the hydroxyl group or carboxyl group derivative include alkyl esters such as methyl ester, aromatic esters such as phenyl ester and benzyl ester, monofunctional epoxy compounds, oxazoline compounds, orthoacetate compounds, isocyanate compounds, and the like. It is also possible to block the end using a compound, an acid anhydride compound or the like.

  The end-capping method includes adding a monofunctional organic compound in advance when synthesizing the dendritic polyester resin, or adding a monofunctional organic compound when the dendritic polyester resin skeleton is formed to some extent. The method of doing is mentioned.

  Specifically, when blocking the hydroxyl group terminal or the acetoxy terminal, benzoic acid, 4-t-butylbenzoic acid, 3-t-butylbenzoic acid, 4-chlorobenzoic acid, 3-chlorobenzoic acid, 4 Examples include a method of reacting with -methylbenzoic acid, 3-methylbenzoic acid, 3,5-dimethylbenzoic acid and the like.

  When the carboxylic acid terminal is blocked, acetoxybenzene, 1-acetoxy-4-t-butylbenzene, 1-acetoxy-3-t-butylbenzene, 1-acetoxy-4-chlorobenzene, 1-acetoxy-3 Examples include a method of reacting with -chlorobenzene, 1-acetoxy-4-cyanobenzene and the like.

  Of the terminal groups that are theoretically generated, the above-mentioned organic compounds used for end-capping can be end-capped by adding an equivalent amount of end-capping, but it is theoretically necessary from the viewpoint of sufficient end-capping. It is preferable to use 1.005 times or more, more preferably 1.008 times or more with respect to the amount of the terminal group. Moreover, from a viewpoint of suppressing the reaction rate fall and gas generation | occurrence | production by the excessive additive which remain | survives in a system, 1.01 times or less are preferable.

  Further, the content of the organic residue D is 7.5 mol% or more, more preferably 10 mol% or more, further preferably 20 mol, based on the content of all monomers constituting the dendritic polyester resin. % Or more. In such a case, the chain length of the branch structure portion is preferable because the dendritic polyester resin has a length suitable for taking a dendritic form. The upper limit of the content of the organic residue D is 50 mol% or less, preferably 45 mol% or less, and more preferably 40 mol% or less.

  Moreover, the dendritic polyester resin (e) may have a partially crosslinked structure as long as the properties are not affected.

  There is no restriction | limiting in particular in the manufacturing method of the said dendritic polyester resin (e) used for this invention, It can manufacture according to the well-known polycondensation method of polyester. After acylating the raw material monotonous constituting the structural unit represented by R1, R2 and R3, when the polyfunctional monomer is reacted, the addition amount (mole) of the polyfunctional monomer is charged all A method of producing such that it is 7.5 mol% or more based on the monomer (mol) is preferable. The addition amount of the polyfunctional monomer is more preferably 10 mol% or more, more preferably 15 mol% or more, and further preferably 20 mol% or more. Further, the addition amount of the polyfunctional monomer is preferably 50 mol% or less, more preferably 33 mol% or less.

For example, the production method of the dendritic polyester resin composed of R and trimesic acid composed of the structural units (I), (II), (III), (IV) and (V) is as follows. Is preferred.
(1) A liquid crystalline polyester oligomer is synthesized from p-acetoxybenzoic acid and 4,4'-diacetoxybiphenyl, diacetoxybenzene, terephthalic acid, and isophthalic acid by a deacetic acid polycondensation reaction, and trimesic acid is added to remove deacetic acid heavy A method for producing by condensation reaction.
(2) A method of producing from p-acetoxybenzoic acid and 4,4′-diacetoxybiphenyl, diacetoxybenzene and terephthalic acid, isophthalic acid and trimesic acid by a deacetic acid polycondensation reaction.
(3) p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl, hydroquinone and terephthalic acid, isophthalic acid is reacted with acetic anhydride to acylate the phenolic hydroxyl group, and then the liquid crystalline polyester is subjected to deacetic acid polycondensation reaction. A method in which oligomers are synthesized and trimesic acid is added and subjected to deacetic acid polycondensation reaction.
(4) Acetic anhydride is reacted with p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl, hydroquinone, terephthalic acid, isophthalic acid and trimesic acid to acylate the phenolic hydroxyl group, and then by deacetic acid polycondensation reaction. How to manufacture.
(5) A liquid crystalline polyester oligomer is synthesized from a phenyl ester of p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl, hydroquinone, terephthalic acid, and diphenyl ester of isophthalic acid by a dephenol polycondensation reaction, and trimesic acid is added. A method of producing by dephenol polycondensation reaction.
(6) A method of producing by dephenol polycondensation reaction from phenyl ester of p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl, hydroquinone and terephthalic acid, diphenyl ester of isophthalic acid and phenyl ester of trimesic acid.
(7) A predetermined amount of diphenyl carbonate is reacted with p-hydroxybenzoic acid and aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, trimesic acid, etc. to form phenyl esters, respectively, and then 4,4′-dihydroxybiphenyl, hydroquinone A method in which an aromatic dihydroxy compound such as is added and produced by a dephenol polycondensation reaction.

  Especially, the manufacturing method of (1)-(4) is preferable, and the manufacturing method of (3) or (4) is more preferable from the point of chain length control and a steric restriction.

  The amount of acetic anhydride used is preferably 0.95 equivalents or more and 1.10 equivalents or less, and more preferably 1.00 equivalents or more and 1.05 equivalents or less, in terms of chain length control.

  The dendritic polyester resin (e) preferably has a reactive carboxylic acid, a hydroxyl group or a derivative group at the terminal, and the amount of acetic anhydride can be adjusted according to the type of the polyamide resin (a) to be blended, It is possible to adjust the end groups by adding an excess of dihydroxy or dicarboxylic acid monomer. For example, in order to increase the molecular weight, it is preferable to add an excess of a dihydroxy monomer such as hydroquinone or 4,4'-dihydroxybiphenyl corresponding to the excess amount of carboxylic acid in trimesic acid to match the carboxylic acid with the hydroxyl equivalent. Moreover, when leaving a carboxylic acid preferentially to a terminal group, it is preferable not to perform excessive addition of a dihydroxy monomer. On the other hand, when the hydroxyl group is preferentially left at the terminal, it is preferable that the dihydroxy monomer is excessively added to the carboxylic acid equivalent of trimesic acid or more and the acetic anhydride molar ratio is less than 1.00.

  By these methods, the dendritic polyester resin (e) can be selectively provided with a terminal group structure rich in reactivity with the polyamide resin. On the other hand, in order to suppress the reactivity, it may be easier to adjust the dispersion state by selectively generating the terminal and then blocking the terminal with a monofunctional epoxy compound, monofunctional carboxylic acid or the like.

  When the dendritic polyester resin (e) is produced by a deacetic acid polycondensation reaction, the reaction is carried out at a temperature at which the dendritic polyester resin melts, sometimes under reduced pressure, to distill a predetermined amount of acetic acid, and to perform a polycondensation reaction. A melt polymerization method that completes is preferable.

  For example, in a reaction vessel having a predetermined amount of p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl, hydroquinone, terephthalic acid, isophthalic acid, acetic anhydride, a stirring blade, a distillation pipe, and a discharge port at the bottom. And heated with stirring under a nitrogen gas atmosphere to acetylate the hydroxyl group, and then heated to 200-350 ° C. to distill acetic acid and distill to 50% of the theoretical distillate. A method may be mentioned in which a predetermined amount of acid is added and acetic acid is distilled to 91% of the theoretical distillation amount to complete the reaction.

  The conditions for acetylation are usually in the range of 130 to 170 ° C., preferably in the range of 135 to 155 ° C., and are usually reacted for 0.5 to 6 hours, preferably 1 to 2 hours.

  The temperature for polycondensation is the melting temperature of the dendritic polyester resin, for example, in the range of 200 to 350 ° C., preferably the melting point of the dendritic polyester resin + 10 ° C. or higher, specifically 240 to 280 ° C. preferable. When polycondensation is performed, there is no problem even under atmospheric pressure nitrogen, but it is preferable to reduce the pressure because the reaction proceeds faster and the residual acetic acid in the system decreases. The degree of vacuum is usually 0.1 mmHg (13.3 Pa) to 200 mmHg (26600 Pa), preferably 10 mmHg (1330 Pa) to 100 mmHg (13300 Pa). In addition, acetylation and polycondensation may be performed continuously in the same reaction vessel, or acetylation and polycondensation may be performed in different reaction vessels.

The obtained dendritic polyester resin is pressurized to about 0.01 to 1.0 kg / cm ² (0.001 to 0.1 MPa) in the reaction vessel at a temperature at which it melts, It can be discharged in a strand form from the provided discharge port. A mechanism that opens and closes intermittently is provided at the discharge port, and it is also possible to discharge liquid droplets.

  The discharged dendritic polyester resin is cooled by passing through air or water, and then cut or pulverized as necessary.

  The obtained pellets, or granular or powdery dendritic polyester resin, can further remove water, acetic acid, etc. by heat drying or vacuum drying, if necessary. In order to do this, it is also possible to carry out solid phase polymerization.

  For example, under a nitrogen stream or under reduced pressure, the dendritic polyester resin is heated for 1 to 50 hours in the range of melting point −5 ° C. to melting point −50 ° C. (for example, 200 to 300 ° C.), polycondensed to a desired degree of polymerization, A method for completing the reaction may be mentioned.

  The polycondensation reaction of the dendritic polyester resin proceeds even without catalyst, but metal compounds such as stannous acetate, tetrabutyl titanate, potassium acetate, sodium acetate, antimony trioxide, and magnesium metal can also be used as a catalyst.

  The number average molecular weight of the dendritic polyester resin (e) in the present invention is preferably 1,000 to 40,000, more preferably 1,000 to 20,000, still more preferably 1,000 to 10,000, Most preferably, it is 1,000-5,000. The number average molecular weight is a value measured as an absolute molecular weight by a GPC-LS (gel permeation chromatography-light scattering) method using a solvent in which the dendritic polyester resin is soluble.

  Moreover, 0.01-30 Pa.s is preferable, as for the melt viscosity of the dendritic polyester resin (e) in this invention, 0.5-20 Pa.s is more preferable, and 1-10 Pa.s is further more preferable. In addition, this melt viscosity is a value measured by a Koka flow tester under the condition of the liquid crystal starting temperature of the dendritic polyester resin + 10 ° C. and the shear rate of 100 / s.

  It is preferable to mix | blend an acid anhydride (f) with the dendritic polyester resin (e) in the polyamide resin composition of this invention. Since the acid anhydride (f) reacts with the amino terminal group of the polyamide resin (a), the amino terminal group concentration of the polyamide resin (a) can be reduced. By blending the acid anhydride (f) with the dendritic polyester resin (e), the transesterification reaction between the polyamide resin (a) and the dendritic polyester resin (e) is suppressed, and the dendritic polyester resin (e) The effect of improving fluidity is more highly expressed. For this reason, even if there is little compounding quantity of dendritic polyester resin (e), sufficient fluidity improvement effect can be expressed, and coloring of a molded product is controlled more, ensuring sufficient fluidity of a polyamide resin composition. And weather resistance can be further improved.

  Specific examples of the acid anhydride (f) used in the present invention include benzoic anhydride, isobutyric anhydride, itaconic anhydride, octanoic anhydride, glutaric anhydride, succinic anhydride, acetic anhydride, dimethylmaleic anhydride , Decanoic anhydride, trimellitic anhydride, 1,8-naphthalic anhydride, phthalic anhydride, maleic anhydride and derivatives thereof. Two or more of these may be blended. Of these, phthalic anhydride and succinic anhydride are preferably used. Moreover, it is preferable not to have an unsaturated hydrocarbon group from a viewpoint of improving a weather resistance more, and a succinic anhydride is more preferable.

  As for the compounding quantity of the acid anhydride (f) in the polyamide resin composition of this invention, 0.01-10 weight part is preferable with respect to 100 weight part of polyamide resins (a). By setting the blending amount within the above range, the amino terminal group concentration of the polyamide resin (a) can be sufficiently reduced, and the flowability of the polyamide resin composition can be reduced with a small blending amount of the dendritic polyester resin (e). An improvement effect can be obtained. Furthermore, coloring of the molded product can be further suppressed, and weather resistance can be further improved. The compounding amount of the acid anhydride (f) is more preferably 0.1 parts by weight or more, and further preferably 0.3 parts by weight or more. Further, the blending amount of the acid anhydride (f) is preferably 5 parts by weight or less, particularly preferably 4 parts by weight or less.

  A filler can be blended with the polyamide resin composition of the present invention as long as the effects of the present invention are not impaired. The filler can be any of fiber, plate, powder, granule, etc. For example, glass fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, calcium carbonate whisker, wollastonite whisker, aluminum borate Fiscal fillers such as whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, masonry fiber, metal fiber, talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite Silicates such as bentonite, asbestos, alumina silicate, metal oxides such as silicon oxide, magnesium oxide, alumina, zirconium oxide, titanium oxide, iron oxide, carbonates such as calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, sulfuric acid Metal sulfate such as barium Non-fiber such as glass beads, ceramic beads, boron hydroxide, silicon carbide, calcium phosphate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide and other metal hydroxides, glass flakes, glass powder, carbon black, silica, graphite -Like fillers, montmorillonite, beidellite, nontronite, saponite, hectorite, soconite, etc. Swellable layered silicates such as swellable mica such as Na-type fluorine teniolite, Na-type tetrasilicon fluorine mica and Li-type tetrasilicon fluorine mica. In the swellable layered silicate, exchangeable cations existing between layers may be exchanged with organic onium ions, and examples of the organic onium ions include ammonium ions, phosphonium ions, and sulfonium ions. You may mix | blend 2 or more types of said filler. Among these fillers, a fibrous filler is preferable.

  Specific examples of fibrous fillers include glass fibers, PAN (polyacrylonitrile) and pitch-based carbon fibers, stainless steel fibers, metal fibers such as aluminum fibers and brass fibers, organic fibers such as aromatic polyamide fibers, and gypsum. Examples include fibers, whisker-like fillers such as fibers, ceramic fibers, asbestos fibers, zirconia fibers, alumina fibers, silica fibers, titanium oxide fibers, silicon carbide fibers, rock wool, potassium titanate whiskers, and silicon nitride whiskers. Among the fibrous fillers, PAN-based carbon fibers are preferably used when glass fibers and conductivity are required. The type of glass fiber is not particularly limited as long as it is generally used for reinforcing a resin, and for example, a long fiber type, a short fiber type chopped strand, a milled fiber, or the like can be used. Note that the surface of the fibrous filler used in the present invention may be treated with a known coupling agent (for example, a silane coupling agent, a titanate coupling agent, etc.) and the like. And antifreeze resistance can be further improved. The glass fiber may be coated or bundled with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin.

  The polyamide resin composition of the present invention may be blended with a copper compound as long as the effects of the present invention are not impaired, and long-term heat resistance can be improved. Specific examples of the copper compound include inorganic copper halides such as cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous iodide, cupric iodide, Cupric sulfate, cupric nitrate, copper phosphate, cuprous acetate, cupric acetate, cupric salicylate, cupric stearate, cupric benzoate and inorganic copper halides and xylylenediamine , 2-mercaptobenzimidazole, complex compounds with benzimidazole and the like. Of these, monovalent copper halide compounds are preferable, and cuprous iodide and the like are more preferable. 0.01-2 weight part is preferable with respect to 100 weight part of polyamide resins (a), and, as for the compounding quantity of a copper compound, 0.015-1 weight part is more preferable. By making the compounding quantity of a copper compound into said range, the release | extrication of metallic copper at the time of melt molding can be suppressed, and coloring can be suppressed more.

  The polyamide resin composition of the present invention can also contain an alkali halide together with a copper compound. Examples of the alkali halide compound include lithium chloride, lithium bromide, lithium iodide, potassium chloride, potassium bromide, potassium iodide, sodium bromide and sodium iodide. Sodium halide is preferred.

  The polyamide resin composition of the present invention can be blended with an impact resistance improving material as long as the effects of the present invention are not impaired. The impact resistance improving material is not limited as long as the impact resistance is improved by blending with the polyamide resin (a). For example, olefin resin, acrylic rubber, silicone rubber, fluorine rubber, urethane type Examples thereof include a so-called core-shell type multilayer structure comprising at least one layer composed of a rubbery component such as rubber, polyamide elastomer, and polyester elastomer, and one or more layers composed of different polymers. The number of layers constituting the multilayer structure may be two or more, and may be three layers or four or more. However, in the multilayer structure having one or more rubber layers (core layers) inside Preferably there is. The type of the rubber layer of the multilayer structure is not particularly limited as long as it is composed of a polymer component having rubber elasticity. For example, an acrylic component, a silicone component, a styrene component, a nitrile component, a conjugated diene component , A rubber constituted by polymerizing a urethane component, an ethylene component, a propylene component, an isobutene component, and the like. The type of layer other than the rubber layer of the multilayer structure is not particularly limited as long as it is composed of a polymer component having thermoplasticity, but it is a polymer component having a glass transition temperature higher than that of the rubber layer. Preferably there is. Polymers having thermoplastic properties include unsaturated carboxylic acid alkyl ester units, unsaturated carboxylic acid units, unsaturated glycidyl group-containing units, unsaturated dicarboxylic anhydride units, aliphatic vinyl units, aromatic vinyl units, cyanide. Examples thereof include polymers containing one or more units selected from vinyl units, maleimide units, unsaturated dicarboxylic acid units, and other vinyl units.

  Among these, an olefin resin is preferably used. As the olefin resin, a resin obtained by polymerizing or copolymerizing olefin monomers such as ethylene, propylene, butene, isoprene, and pentene is preferable. Specific examples include homopolymers and copolymers such as polyethylene, polypropylene, polystyrene, poly 1-butene, poly 1-pentene, polymethyl pentene, ethylene / α-olefin copolymers, ethylene / α, β-non-polymers. Hydrolyze at least part of saturated carboxylic acid ester copolymer, α-olefin / α, β-unsaturated carboxylic acid ester copolymer, [copolymer of (ethylene and / or propylene) and vinyl alcohol ester] Polyolefin obtained as above, [copolymer of (ethylene and / or propylene) and (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester)], [(ethylene and / or propylene) and (unsaturated carboxylic acid) And / or copolymer with unsaturated carboxylic acid ester)] Polyolefins also be obtained by partially with metal chlorides, block copolymers of a conjugated diene and a vinyl aromatic hydrocarbon, and, hydrides of the block copolymer. Among these, ethylene / α-olefin copolymers and ethylene / α, β-unsaturated carboxylic acid ester copolymers are preferable.

  As the ethylene / α-olefin copolymer, a copolymer of ethylene and at least one of α-olefin having 3 to 20 carbon atoms is preferable. Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 1-undecene. 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1 -Pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl -1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene and the like.Two or more of these may be used. Among these, C3-C12 alpha olefin is preferable and can improve a mechanical characteristic more. As described later, from the viewpoint that the compatibility with the polyamide resin (a) is further improved and the impact resistance is extremely excellent, ethylene modified with at least one compound selected from an unsaturated carboxylic acid or a derivative thereof and A copolymer with an α-olefin having 3 to 12 carbon atoms is more preferred. The α-olefin content of the ethylene / α-olefin copolymer is preferably 1 to 30 mol%, more preferably 2 to 25 mol%, still more preferably 3 to 20 mol%. Further, non-conjugated dienes such as 1,4-hexadiene, dicyclopentadiene, 2,5-norbornadiene, 5-ethylidenenorbornene, 5-ethyl-2,5-norbornadiene, 5- (1′-propenyl) -2-norbornene At least one of these may be copolymerized.

  An ethylene / α, β-unsaturated carboxylic acid ester copolymer is a polymer obtained by copolymerizing ethylene and an α, β-unsaturated carboxylic acid ester, and as an α, β-unsaturated carboxylic acid ester Examples include esters of α, β-unsaturated carboxylic acids such as methyl acrylate, ethyl acrylate, butyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, etc. Can do. Specific examples of the ethylene / α, β-unsaturated carboxylic acid ester copolymer include ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / butyl acrylate copolymer, ethylene / methacrylic acid. Methyl acid copolymer, ethylene / ethyl methacrylate copolymer, ethylene / butyl methacrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / glycidyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer , Ethylene / methyl acrylate / glycidyl methacrylate copolymer, ethylene / methyl methacrylate / glycidyl methacrylate copolymer, and the like. Of these, ethylene / glycidyl methacrylate copolymer, ethylene / methyl acrylate / glycidyl methacrylate copolymer, and ethylene / methyl methacrylate / glycidyl methacrylate copolymer are preferably used.

  The polyolefin resin may be modified with at least one compound selected from unsaturated carboxylic acids and / or derivatives thereof. By using such a modified polyolefin resin, the compatibility with the polyamide resin (a) is further improved, and the impact resistance is extremely excellent. Examples of the unsaturated carboxylic acid or derivative thereof include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, methylmaleic acid, methyl fumaric acid, mesaconic acid, citraconic acid, glutaconic acid and carboxylic acids thereof. Metal salts of, methyl hydrogen maleate, methyl itaconate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, 2-ethylhexyl methacrylate, meta Hydroxyethyl acrylate, aminoethyl methacrylate, dimethyl maleate, dimethyl itaconate, maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- (2,2,1) -5-heptene-2,3- Dicarboxylic acid, endobi Clo- (2,2,1) -5-heptene-2,3-dicarboxylic anhydride, maleimide, N-ethylmaleimide, N-butylmaleimide, N-phenylmaleimide, glycidyl acrylate, glycidyl methacrylate, ethacrylic acid Examples thereof include glycidyl, glycidyl itaconate, glycidyl citraconic acid, and 5-norbornene-2,3-dicarboxylic acid. Among these, unsaturated dicarboxylic acids and acid anhydrides that are derivatives thereof are preferable, and maleic acid and maleic anhydride are particularly preferable.

  There is no particular limitation on the method for introducing these unsaturated carboxylic acids and / or derivatives thereof into the polyolefin resin. For example, an olefin monomer as a main component and an unsaturated carboxylic acid and / or derivative thereof are copolymerized. And a method of graft-introducing an unsaturated carboxylic acid and / or a derivative thereof to a non-modified polyolefin resin using a radical initiator. The amount of unsaturated carboxylic acid and its derivative to be introduced is preferably 0.001 to 40 mol%, more preferably 0.01 to 35 mol%, based on 100 mol% of all olefin monomers of the polyolefin resin. .

  The blending amount of the impact resistance improving material in the polyamide resin composition of the present invention is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the polyamide resin (a). If the blending amount of the impact resistance improving material is 1 weight or more, a sufficient impact resistance improving effect is exhibited. 5 parts by weight or more is more preferable, and 10 parts by weight or more is more preferable. Moreover, if the compounding quantity of an impact-resistant improvement material is 100 weight part or less, a thickening can be suppressed and molding processability can be improved more. 80 parts by weight or less is more preferable, and 70 parts by weight or less is more preferable.

  The polyamide resin composition of the present invention may contain a heat-resistant agent such as a phenolic compound and can maintain thermal stability. The blending amount of the heat-resistant agent is preferably 0.01 parts by weight or more and more preferably 0.02 parts by weight or more with respect to 100 parts by weight of the polyamide resin (a) from the viewpoint of the heat resistance improving effect. Moreover, from a viewpoint of suppressing the gas component generated at the time of shaping | molding, 5 weight part or less is preferable and 1 weight part or less is more preferable.

  As the phenolic compound, a hindered phenolic compound is preferably used. Specific examples include triethylene glycol-bis [3-t-butyl- (5-methyl-4-hydroxyphenyl) propionate], N, N ′. Hexamethylene bis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane , Pentaerythrityltetrakis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-t-butyl-4- Hydroxybenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,1,3-tris (2-methyl-4-hydro) Loxy-5-tert-butylphenyl) butane, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxy-) Phenyl) propionate, 3,9-bis [2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl] -2,4,8,10 -Tetraoxaspiro [5,5] undecane, 1,3,5-trimethyl-2,4,6-tris- (3,5-di-t-butyl-4-hydroxybenzyl) benzene and the like.

  Among them, N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-). Hydroxyphenyl) propionate] methane and the like are preferably used. In order to reduce volatilization and decomposition of the heat-resistant agent in the polyamide resin composition, a heat-resistant agent having a high melting point is preferably used.

  For example, an arbitrary colorant such as an inorganic pigment, an organic pigment, a metallic pigment, or a dye may be blended in the polyamide resin composition of the present invention, and the design can be improved. Two or more of these colorants may be blended. For example, a deeper black color can be expressed by combining a dye such as red, green, and yellow to develop a black color.

  Examples of inorganic pigments include titanium oxide, carbon black, titanium yellow, iron oxide pigments, ultramarine blue, cobalt blue, chromium oxide, spinel green, lead chromate pigments, zinc oxide pigments, and cadmium pigments. .

  Organic pigments include, for example, azo lake pigments, benzimidazolone pigments, diarylide pigments, azo pigments such as condensed azo pigments, phthalocyanine pigments such as phthalocyanine blue, phthalocyanine green, isoindolinone pigments, quinophthalone pigments, quinacridone pigments, perylene Examples thereof include condensed polycyclic pigments such as pigments, anthraquinone pigments, perinone pigments, and dioxazine violet.

  Examples of metallic pigments include flake-like aluminum metallic pigments, spherical aluminum pigments used to improve weld appearance, mica powder for pearl-like metallic pigments, and other polyhedral particles of inorganic substances such as glass. The thing etc. which coat | covered the metal by plating and sputtering are mentioned.

  Examples of the dye include nitroso dyes, nitro dyes, azo dyes, stilbene azo dyes, ketoimine dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, quinoline dyes, methine / polymethine dyes, thiazole dyes, indamine / indophenol dyes, Examples thereof include azine dyes, oxazine dyes, thiazine dyes, sulfur dyes, amino ketone / oxyketone dyes, anthraquinone dyes, indigoid dyes, phthalocyanine dyes, perylene dyes, and perinone dyes.

  As a method for producing the polyamide resin composition of the present invention, a polyamide resin (a), a flame retardant (b), a hindered amine stabilizer (c), a cyanoacrylate ultraviolet absorber (d) and other components as necessary are melted. A method of kneading is preferred. Examples of the melt kneading method include a method of melt kneading at a temperature equal to or higher than the melting temperature of the polyamide resin (a) using a melt kneading apparatus such as a Banbury mixer, a rubber roll machine, a kneader, a single screw or a twin screw extruder. As the melt kneading apparatus, a twin screw extruder is preferable. More specifically, as a melt-kneading method, 1) a method of kneading a polyamide resin, a flame retardant, a hindered amine stabilizer, a cyanoacrylate-based UV absorber and other additives as needed, and 2) a polyamide resin first. A method of kneading the resin composition with a hindered amine stabilizer, a cyanoacrylate ultraviolet absorber and other additives after melt-kneading the flame retardant and other additives as required to obtain a resin composition; ) First, after a polyamide resin, a hindered amine stabilizer, a cyanoacrylate ultraviolet absorber and other additives as required are melt-kneaded to obtain a resin composition, the resin composition, the flame retardant and, if necessary, Other methods of kneading additives 4) Polyamide resin, hindered amine stabilizer, cyanoacrylate UV absorber A resin composition (master pellet) containing a high concentration of an additive and other additives as necessary is prepared, and then the resin composition, polyamide resin, flame retardant, and as necessary, so as to have a prescribed concentration Method of adding other additives and melt-kneading (master pellet method) 5) Producing a resin composition (master pellet) containing a flame retardant in polyamide resin and, if necessary, high concentration of other additives (master pellet) Examples of such a resin composition, polyamide resin, hindered amine stabilizer, cyanoacrylate ultraviolet absorber and other additives as required, and melt kneading (master pellet method) can do. These melt-kneading methods can also be carried out continuously using a twin screw extruder. For example, in the case of 2), after first adding a polyamide resin, a flame retardant and other additives as necessary from a supply port upstream of the extruder and melt-kneading, a hindered amine stabilizer from a supply port downstream of the extruder, A cyanoacrylate ultraviolet absorber and other additives can be added and kneaded. In the case of 3), first, polyamide resin, a hindered amine stabilizer, a cyanoacrylate ultraviolet absorber and other additives as necessary are fed from the supply port upstream of the extruder and melt-kneaded. A flame retardant and, if necessary, other additives can be added from the downstream supply port and kneaded. Among these methods, 1) and 3) are preferable.

  Various molded articles can be obtained by molding the polyamide resin composition of the present invention by any method such as injection molding, injection compression molding, compression molding, extrusion molding, blow molding, press molding, and spinning. Examples of the molded product include injection molded products, extrusion molded products, blow molded products, various films such as uniaxially stretched and biaxially stretched, sheets, various fibers such as unstretched yarn, stretched yarn, and superstretched yarn. In particular, in the present invention, it is possible to process various electric / electronic parts, automobile parts and the like by taking advantage of the excellent flame retardancy and weather resistance.

  The molded article of the present invention can be used for various applications such as automobile parts, electrical / electronic parts, building members, various containers, daily necessities, household goods and sanitary goods. Specific applications include air flow meters, air pumps, thermostat housings, engine mounts, ignition hobbins, ignition cases, clutch bobbins, sensor housings, idle speed control valves, vacuum switching valves, ECU housings, vacuum pump cases, inhibitor switches, rotations Sensor, acceleration sensor, distributor cap, coil base, actuator case for ABS, radiator tank top and bottom, cooling fan, fan shroud, engine cover, cylinder head cover, oil cap, oil pan, oil filter, fuel cap, fuel strainer , Distributor cap, vapor canister Housing, air cleaner housing, timing belt cover, brake booster parts, various cases, various tubes, various tanks, various hoses, various clips, various valves, various pipes, automotive underhood parts, torque control lever, safety belt parts, Car interior parts such as register blade, washer lever, window regulator handle, window regulator handle knob, passing light lever, sun visor bracket, various motor housings, roof rail, fender, garnish, bumper, door mirror stay, spoiler, food louver, Wheel covers, wheel caps, grill apron cover frames, lamp reflectors, lamp bezels, door handles, etc. Automotive exterior parts, wire harness connectors, SMJ connectors, PCB connectors, door grommet connectors and other automotive connectors, relay cases, coil bobbins, optical pickup chassis, motor cases, laptop housings and internal parts, CRT display housings and internal parts , Printer housings and internal parts, mobile terminal housings and internal parts such as mobile phones, mobile PCs, handheld mobiles, recording media (CD, DVD, PD, FDD, etc.) drive housings and internal parts, copier housings and internals Parts, facsimile housings and internal parts, parabolic antennas, electronic musical instruments, home game machines, portable game machines and other housing and internal parts, various gears, etc. Seed case, sensor, LEP lamp, connector, socket, resistor, relay case, switch, coil bobbin, capacitor, variable capacitor case, optical pickup, oscillator, various terminal boards, transformer, plug, printed wiring board, tuner, speaker, Microphone, headphone, small motor, magnetic head base, power module, semiconductor, liquid crystal, FDD carriage, FDD chassis, motor brush holder, transformer member, coil bobbin and other electrical / electronic parts, VTR parts, TV parts, iron, hair dryer, Rice cooker parts, microwave oven parts, acoustic parts, video equipment parts such as video cameras, projectors, laser discs (registered trademark), compact discs (CD), CD-ROM, CD-R, CD-RW, DVD- OM, DVD-R, DVD-RW, DVD-RAM, Blu-ray disc and other optical recording media substrates, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, home / office electrical product parts, sash dolly , Blind curtain parts, piping joints, curtain liners, blind parts, gas meter parts, water meter parts, water heater parts, roof panels, insulation walls, adjusters, plastic bundles, ceiling fishing gear, stairs, doors, floors and other building parts, fishing lines , Fishing nets, seaweed aquaculture nets, fishing bait bags, vegetation nets, vegetation mats, grass protection bags, grass protection nets, curing sheets, slope protection sheets, fly ash press sheets, drain sheets, water retention sheets, sludge -Civil engineering related materials such as sludge dewatering bags, concrete formwork, gears, screws Mechanical parts such as springs, bearings, levers, key stems, cams, ratchets, rollers, water supply parts, toy parts, cable ties, clips, fans, guts, pipes, cleaning jigs, motor parts, microscopes, binoculars, cameras, watches, etc. , Multi-film, tunnel film, bird-proof sheet, vegetation protection nonwoven, seedling pot, vegetation pile, seed string tape, germination sheet, house lining sheet, farm-bi stopper, slow-release fertilizer, root-proof sheet , Garden net, insect net, young tree net, print laminate, fertilizer bag, sample bag, sandbag, beast damage net, trigger string, windproof net, and other agricultural components, paper diapers, sanitary wrapping materials, cotton swabs, towels, toilet seats Hygiene products such as wipes, medical non-woven fabric (stitching reinforcement, adhesion prevention film, prosthetic repair material), wound dressing, scratch tape bandage, sticker base fabric, surgical suture, Fracture reinforcements, medical supplies such as medical films, stationery, clothing, food packaging films, trays, blisters, knives, forks, spoons, tubes, plastic cans, pouches, containers, tanks, baskets, etc. , Hot-fill containers, microwave cooking containers cosmetic containers, foam buffer, paper lami, shampoo bottle, beverage bottle, cup, candy packaging, shrink label, lid material, window envelope, fruit basket, hand cut Tapes, easy peel packaging, egg packs, HDD packaging, compost bags, recording media packaging, shopping bags, containers and packaging such as wrapping films for electrical and electronic parts, natural fiber composites, polo shirts, T-shirts, inners, uniforms, Various clothes such as sweaters, socks, ties, curtains, chairs, -Interior goods such as pets, tablecloths, futons, wallpaper, furoshiki, wraps, garbage bags, plastic bags, various nets, draining nets, tea packs, drainage filters, coating agents, adhesives, stationery, toothbrushes, body towels, Daily items such as hand towels, bags, tables, calendars, carrier tapes, print laminates, heat sensitive stencil printing films, release films, porous films, container bags, credit cards, cash cards, ID cards, IC cards, paper, leather Hot melt binders such as non-woven fabric, magnetic binder, powder binders such as zinc sulfide, electrode materials, optical elements, conductive embossed tape, IC trays, golf tees, cooler box chairs, clear files, kumade, hose reels, planters, Hose nozzle, table, desk table , Is a useful furniture panels, kitchen cabinet, pen cap, as household goods, such as gas lighters, is a useful excellent flame retardancy, various electrical and electronic components, such as connectors and taking advantage of the weather resistance, as a component of a motor vehicle.

  The molded article of the present invention is excellent in fluid flame retardancy, mechanical properties and weather resistance. Furthermore, since the polyamide resin composition formed by blending the dendritic polyester resin (e) is excellent in fluidity, a molded product formed by molding the polyamide resin composition has a thinnest portion of 0.5 mm or less. Suitable for goods. The thinnest part of the molded product refers to the thinnest part of the molded product. For example, the snap fit part of a molded product and the narrow pitch part of a connector molded product are mentioned.

  Hereinafter, although an example explains the present invention still in detail, the gist of the present invention is not limited only to the following example.

(Reference Example 1)
Manufacture of polyamide 6 resin (a-1) 1500 g of ε-caprolactam (manufactured by Toray Industries, Inc.) and 375 g of ion-exchanged water were weighed and charged into a polymerization can, and the final temperature reached 260 ° C. while stirring under normal pressure and nitrogen flow. As reacted. The polymer discharged into the water bath was pelletized with a strand cutter. The obtained pellets were treated in 95 ° C. hot water for 20 hours to extract and remove unreacted monomers and low polymer. The pellet after extraction was dried at 80 ° C. for 50 hours or more. It was 2.4 as a result of measuring the sulfuric acid relative viscosity of the obtained pellet. The sulfuric acid relative viscosity was measured at 25 ° C. in a 98% concentrated sulfuric acid solution having a sample concentration of 0.01 g / ml according to JIS-K6810.

(Reference Example 2)
Manufacture of polyamide 66 resin (a-2) 664 g (5.72 mol) of hexamethylenediamine, 836 g (5.72 mol) of adipic acid and 375 g of ion-exchanged water were weighed and charged in a polymerization vessel under normal pressure and nitrogen flow. The reaction was carried out at a final temperature of 290 ° C. with stirring. The polymer discharged into the water bath was pelletized with a strand cutter. The obtained pellets were treated in 95 ° C. hot water for 20 hours to extract and remove unreacted monomers and low polymer. The pellet after extraction was dried at 80 ° C. for 50 hours or more. The sulfuric acid relative viscosity of the obtained pellet was measured by the same method as in Reference Example 1 and was 2.48.

(Reference Example 3)
Production of Dendritic Polyester Resin (e-1) In a reaction vessel equipped with a stirring blade and a distilling tube, 48.0 g (0.35 mol) of p-hydroxybenzoic acid, 30.9 g of 4,4′-dihydroxybiphenyl (0 .17 mol), 5.41 g (0.033 mol) of terephthalic acid, 10.4 g (0.054 mol) of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g, 42.0 g (0.20 mol) of trimesic acid And 76.3 g of acetic anhydride (1.1 equivalent of the total of phenolic hydroxyl groups) were allowed to react at 145 ° C. for 1.5 hours with stirring under a nitrogen gas atmosphere. A condensation reaction was performed. The mixture was stirred for 4 hours, and when about 76% of the theoretical distillation amount of acetic acid was distilled, heating and stirring were stopped, and the contents were discharged into cold water to obtain a dendritic polyester resin (e-1).

  This dendritic polyester resin (e-1) was dissolved in a mixed solvent of 50% pentafluorophenol: 50% deuterated chloroform, and a nuclear magnetic resonance spectrum analysis of proton nuclei was performed at 40 ° C. As a result of the nuclear magnetic resonance spectrum analysis, the structure of the R portion has a p-oxybenzoate unit content p of 2.0, a 4,4′-dioxybiphenyl unit and ethylene oxide unit content q of 0.5, and a terephthalate unit content. The content r was 0.5, p + q + r = 3, and the branching point content was 25 mol%. The terminal structure had a carboxylic acid / acetyl group ratio of 75:25.

  The obtained dendritic polyester resin (e-1) had a melting point Tm of 180 ° C., a liquid crystal starting temperature of 159 ° C., and a number average molecular weight of 2100.

  The melting point (Tm) is determined by differential calorimetry. After observing the endothermic peak temperature (Tm1) observed when the polymer is measured at room temperature to 20 ° C./minute, the temperature is maintained at Tm1 + 20 ° C. for 5 minutes. Then, after once cooling to room temperature under a temperature drop condition of 20 ° C./min, the endothermic peak temperature (Tm) observed when measured again under a temperature rise condition of 20 ° C./min was used.

  The liquid crystal starting temperature starts to flow in the entire field of view with a shear stress heating device (CSS-450) at a shear rate of 1,000 (1 / second), a temperature increase rate of 5.0 ° C./min, and an objective lens 60 times. Temperature.

The number average molecular weight was measured by the following method using GPC.
Column: K-806M (2), K-802 (1) (Showa Denko)
Solvent: pentafluorophenol / chloroform = 35/65 (% by weight)
Flow rate: 0.8mL / min
Sample concentration: 0.08% (wt / vol)
Injection volume: 0.200 mL
Temperature: 23 ° C
Detector: differential refractive index (RI) detector (RI-8020 manufactured by Tosoh Corporation)
Calibration curve: A calibration curve using monodisperse polystyrene is used.

(Reference Example 4)
Production of Dendritic Polyester Resin (e-2) In a 500 mL reaction vessel equipped with a stirring blade and a distilling tube, 77.4 g (0.56 mol) of p-hydroxybenzoic acid and 9.78 g of 4,4′-dihydroxybiphenyl were used. (0.053 mol), 8.72 g (0.053 mol) of terephthalic acid, 32.0 g (0.19 mol) of gallic acid, 16.81 g of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g ( 0.088 mol) and 125.51 g of acetic anhydride (1.00 equivalent of the total of phenolic hydroxyl groups) were added and reacted at 145 ° C. for 2 hours with stirring under a nitrogen gas atmosphere. Thereafter, the temperature was raised to 280 ° C., and the mixture was stirred for 3 hours. When 70% of the theoretical distillation amount of acetic acid was distilled off, heating and stirring were stopped, and the contents were discharged into cold water.

  The obtained dendritic polyester resin (e-2) was subjected to nuclear magnetic resonance spectrum analysis in the same manner as in Reference Example 3. As a result, the content p of the p-oxybenzoate unit relative to the gallic acid residue was 2.66. The 4,4′-dioxybiphenyl unit and ethylene oxide unit content q was 0.67, the terephthalate unit content r was 0.67, and p + q + r = 4.00.

  With respect to the obtained dendritic polyester resin (e-2), the melting point Tm measured in the same manner as in Reference Example 3 was 175 ° C., the liquid crystal starting temperature was 135 ° C., and the number average molecular weight was 2000. The melt viscosity measured using a Koka flow tester at a temperature of 187 ° C. and a shear rate of 100 / s was 11 Pa · s.

The flame retardant and flame retardant aid used in each example and comparative example are as follows.
Flame retardant (b-1): melamine cyanurate (manufactured by Nissan Chemical Industries, Ltd .: trade name MC4000)
Flame retardant (b-2): Brominated polyphenylene oxide (PPO) resin (Daiichi Kogyo Seiyaku Co., Ltd .: trade name SR460B)
Flame retardant aid (b′-3): antimony trioxide (manufactured by Nippon Seiko Co., Ltd .: trade name PATOX-MK).

The stabilizers used in each example and comparative example are as follows. The molecular weight of the stabilizer was measured by GPC-LS method.
Stabilizer (c-1): hindered amine stabilizer (manufactured by BASF: trade name “CHIMASSORB” (registered trademark) 2020) molecular weight: 2600-3400, end-capping type stabilizer (c-2): hindered amine stabilizer ( Manufactured by BASF: trade name “CHIMASSORB” 944 ”molecular weight: 2600-3400, unblocked type stabilizer (c′-3): hindered amine stabilizer (manufactured by BASF: trade name“ TINUVIN ”(registered trademark) 770DF) Molecular weight: 481.

The ultraviolet absorbers used in the examples and comparative examples are as follows.
UV absorber (d-1): cyanoacrylate UV absorber (manufactured by BASF: trade name “UVINUL” (registered trademark) 3030)
Ultraviolet absorber (d′-2): Benzotriazole ultraviolet absorber (manufactured by BASF: trade name: “TINUVIN” 234).

The acid anhydrides used in each example and comparative example are as follows.
Acid anhydride (f-1): succinic anhydride (f-2): phthalic anhydride.

  Various physical properties in the following examples were evaluated by the following methods.

(1) Flame retardance The polyamide resin composition pellets obtained in each of the examples and comparative examples were injected under conditions of a cylinder temperature 20 ° C. higher than the melting point of the blended polyamide resin (a) and a mold temperature of 80 ° C. Molded to prepare 0.76 mm and 0.38 mm thick test pieces for UL94 test. About the obtained test piece, the flame retardance was evaluated by the method based on UL94 vertical combustion test.

(2) Mechanical properties The polyamide resin composition pellets obtained in each of the examples and comparative examples were injected at a cylinder temperature 20 ° C. higher than the melting point of the blended polyamide resin (a) at a mold temperature of 80 ° C. Molded to produce an ISO IA type test piece. Using the obtained test piece, tensile strength, bending strength and elastic modulus were measured according to the following standard method. In addition, the tensile strength calculated | required the average value measured about each five test pieces. The bending strength and the bending elastic modulus were obtained as average values measured for each of three test pieces.
Tensile strength: ISO 527-1, -2
Bending strength: ISO 178
Flexural modulus: ISO 178.

(3) Fluidity Using the polyamide resin composition pellets obtained in each Example and Comparative Example, MFR was measured according to the following standard method according to the type of the blended polyamide resin (a).
ISO 1133 (polyamide 6: temperature 250 ° C., load 325 g, polyamide 66: temperature 270 ° C., load 325 g).

(4) Weather resistance The polyamide resin composition pellets obtained in each Example and Comparative Example were injection molded at a cylinder temperature of about 20 ° C. higher than the melting point of the blended polyamide resin at a mold temperature of 120 ° C. A plate having a thickness of 3 mm, a width of 80 mm, and a length of 80 mm was produced.

  About the obtained board after shaping, using a SM color computer (manufactured by Suga Test Instruments Co., Ltd.), brightness (L value), redness (a value) and yellowness according to Hunter's color difference formula defined in JISZ8730 (B value) (initial value) was determined.

Next, the plate after molding was weatherometer Ci4000 (black panel temperature: 63 ° C., humidity: 55% RH, filter: borosilicate / borosilicate, light source output: 0.75 W / m ² , 420 nm, irradiation time. : After 100 hours), lightness (L value), redness (a value) and yellowness (b value) (measured values after light irradiation) were determined in the same manner. From the squares (ΔL ² , Δa ² , Δb ² ) of the differences between the initial values of the obtained L value, a value, and b value and the measured values after light irradiation, ΔE was calculated by the following equation.
ΔE = (ΔL ² + Δa ² + Δb ² ) ^0.5

(5) Retention characteristics After setting the pellets of the polyamide resin composition obtained in each example and comparative example to a temperature 20 ° C. higher than the melting point of the polyamide resin (a) blended with the cylinder temperature, after weighing in the cylinder No. 4 dumbbell test piece having a thickness of 1 mm as defined in JIS J6251 was produced using an injection molding machine in which the residence time was set to 0 minutes under the conditions of a mold temperature of 80 ° C. The tensile strength was measured according to ASTM D638 using the obtained test piece. The average value of the tensile strength for each of the five test pieces was taken as the tensile strength of the thin molded product before residence. Next, test pieces were prepared in the same manner as in the above method except that the residence time after weighing in the cylinder was set to 20 minutes for the polyamide resin composition pellets obtained in each of the examples and comparative examples. The tensile strength was measured according to ASTM D638. The average value of the tensile strength for each of the five test pieces was taken as the tensile strength of the thin molded article after residence.

From the tensile strength of the thin molded product before and after residence, the strength retention after residence was calculated by the following formula.
Strength retention after retention (%) = {(Tensile strength (MPa) of thin molded product after residence) / (Tensile strength (MPa) of thin molded product before residence)}} × 100.

[ Examples 4 to 14 , 16 and Comparative Examples 1 to 13 ]
Each raw material shown in Tables 1 to 4, 0.3 parts by weight of heat stabilizer ("IRGANOX" 1098 manufactured by BASF) and titanium dioxide ("Typaque" (registered trademark) CR-60 manufactured by Ishihara Sangyo Co., Ltd.) 0.2 μm)) 3.0 parts by weight of the mixture was dry blended, and the resulting mixture was fed from a hopper of a twin screw extruder (screw diameter: 30 mm, L / D: 28, cylinder temperature: 260 ° C., rotation speed: 150 rpm). After feeding, melt-kneading and extruding into a strand shape, it was cut by a pelletizer to obtain a pellet-shaped polyamide resin composition. Then, using the polyamide resin composition obtained by drying under reduced pressure at 80 ° C. for 12 hours, a test piece having a predetermined shape was prepared according to the method described above, and various physical properties were evaluated. The results are shown in Tables 1-4.

Molded articles using the polyamide resin compositions of Comparative Examples 10 and 12 were molded using the polyamide resin composition of Comparative Example 1 in which both the hindered amine stabilizer (c) and the ultraviolet absorber (d) were not blended. It had better weather resistance than the product. Moreover, the molded article using the polyamide resin composition of Example 4 was molded using the polyamide resin composition of Comparative Examples 3 and 4 in which no hindered amine stabilizer (c) or ultraviolet absorber (d) was blended. It had better weather resistance than the product. The molded article using the polyamide resin composition of Example 4 is a hindered amine stabilizer having a molecular weight of more than 2600 and a cyanoacrylate ultraviolet absorption of more than 5 parts by weight based on 100 parts by weight of the polyamide resin. The molded article using the polyamide resin composition of Comparative Example 5 containing the agent had good mechanical properties. Further, a molded article using the polyamide resin composition of Example 4 is a molded article using the polyamide resin composition of Comparative Example 6 in which a flame retardant exceeding 100 parts by weight is blended with 100 parts by weight of the polyamide resin. On the other hand, it had good mechanical properties. The molded article using the polyamide resin composition of Example 4 has weather resistance and mechanical properties compared to the molded article using the polyamide resin composition of Comparative Example 7 containing a hindered amine stabilizer having a molecular weight of less than 2600. Had. In addition, the molded article using the polyamide resin composition of Example 4 has better weather resistance than the molded article using the polyamide resin composition of Comparative Example 8 in which an ultraviolet absorber that is not cyanoacrylate is blended. It was.

  According to the polyamide resin composition of the present invention, a molded article excellent in flame retardancy, mechanical properties and weather resistance can be provided. The molded article of the present invention can be suitably used for electrical / electronic parts such as connectors, automobile parts and the like.

Claims (11)

1-100 parts by weight of a flame retardant (b), 0.1-5 parts by weight of a hindered amine stabilizer (c) having a molecular weight of 2600 or more, and a cyanoacrylate ultraviolet absorber with respect to 100 parts by weight of the polyamide resin (a) (D) 0.1-5 weight part is mix | blended,
All SANYO said hindered amine stabilizer (c) is sealed terminal amino group,
At least selected from the aromatic oxycarbonyl unit (S), the aromatic and / or aliphatic dioxy unit (T), and the aromatic dicarbonyl unit (U) with respect to 100 parts by weight of the polyamide resin (a). It contains one type of structural unit and trifunctional or higher functional organic residue (D), and the content of D is in the range of 7.5 to 50 mol% with respect to all monomers constituting the dendritic polyester. A polyamide resin composition comprising 0.5 to 10 parts by weight of a dendritic polyester resin (e) having a certain melt liquid crystallinity . The polyamide resin composition according to claim 1, wherein the flame retardant (b) is a nitrogen-based flame retardant. The polyamide resin composition according to claim 1 or 2, further comprising 0.01 to 10 parts by weight of an acid anhydride (f) per 100 parts by weight of the polyamide resin (a). In the dendritic polyester resin (e), the aromatic oxycarbonyl unit (S), the aromatic and / or aliphatic dioxy unit (T), and the aromatic dicarbonyl unit (U) are each represented by the following formula (1): And at least one structural unit selected from the structural units represented by the formula (1), and when the D content is 1 mol, the contents p, q, and r of S, T, and U are p + q + r = 1 to The polyamide resin composition according to any one of claims 1 to 3, which is in a range of 10 moles.

(Here, R1, R2 and R3 are each at least one structural unit selected from structural units represented by the following formula.)

(Wherein, Y is at least one selected from a hydrogen atom, a halogen atom and an alkyl group. In the formula, n is an integer of 2 to 8.) The polyamide resin composition according to any one of claims 1 to 4, wherein the dendritic polyester resin (e) contains a basic skeleton represented by the formula (2).

(Here, D is an organic residue of a trifunctional compound, and DD is bonded directly by an ester bond and / or an amide bond, or bonded via a structural unit selected from S, T and U. Yes.) The polyamide resin composition according to any one of claims 1 to 4, wherein the dendritic polyester resin (e) contains a basic skeleton represented by the formula (3).

(Here, D is an organic residue of a tetrafunctional compound, and DD is bonded directly by an ester bond and / or an amide bond or via a structural unit selected from S, T and U. Yes.) The polyamide resin composition according to any one of claims 1 to 6, wherein the organic residue represented by D of the dendritic polyester resin (e) is an organic residue derived from an aromatic compound. The polyamide resin composition according to claim 7, wherein the organic residue represented by D of the dendritic polyester resin (e) is an organic residue represented by the formula (5) or (6).

The polyamide resin composition according to any one of claims 3 to 8, wherein the acid anhydride (f) does not have an unsaturated hydrocarbon group. The molded article formed by shape | molding the polyamide resin composition of any one of the said Claims 1-9. The molded product according to claim 10, wherein the thinnest portion of the molded product is 0.5 mm or less.