JP2008038149A - Resin composition having excellent flame retardance - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition having excellent flame retardance, impact resistance, and moldability of thin-walled articles, generating remarkably decreased amount of gases in molding and effective for remarkably reducing the deposition in a mold in injection molding. <P>SOLUTION: The invention provides a resin composition comprising a polyamide having a specific viscosity number, polyphenylene ether, and a phosphinic acid salt represented by a specific formula. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The resin composition of the present invention has excellent flame retardancy, impact resistance, excellent moldability in thin parts such as connectors in the electrical and electronic fields, significant suppression of gas generation during processing, and gold during injection molding. It has excellent characteristics that can greatly suppress the formation of deposits (mold deposits) on the mold, and electrical and electronic parts such as connectors, breakers, and magnet switches, and electrical parts in the automotive field represented by relay blocks, The present invention relates to a resin composition that is suitably used for a component that is compatible with surface mounting technology (hereinafter sometimes referred to as SMT) that requires lead-free solder resistance.

Conventionally, polyamide has been used in many fields such as automobile parts, machine parts, and electric / electronic parts because of its excellent mechanical strength, heat resistance, and chemical resistance.
In particular, polyamides 6 and 6 have conventionally been used for relay blocks installed in the engine room of automobiles, but there has been a problem that dimensional changes during water absorption increase. For this reason, it has been gradually replaced by a polyamide / polyphenylene ether alloy. Auto parts, machine parts, and electrical / electronic parts tend to be complicated in shape, and are currently in the trend of becoming smaller and thinner.
In addition, as a recent trend, a new required characteristic of flame resistance is given to vehicle parts such as a relay block from the viewpoint of preventing a vehicle fire.

Conventionally, as a technique for making a polyamide flame-retardant, for example, a method of adding a chlorine-substituted polycyclic compound or a brominated flame retardant to a polyamide resin is known. Known brominated flame retardants include, for example, decabromodiphenyl ether, brominated polystyrene, brominated polyphenylene ether, brominated crosslinked aromatic polymer, brominated styrene-maleic anhydride polymer, and the like.
In recent years, halogen-free triazine-based flame retardants have attracted attention and many studies have been made on the background of increasing interest in environmental problems. For example, a technique using melamine as a flame retardant, a technique using cyanuric acid, and a technique using melamine cyanurate are well known. On the other hand, halogen-free flame retardant technology using melamine phosphate, melamine pyrophosphate or melamine polyphosphate, which is an intumescent flame retardant, as a glass fiber reinforced polyamide resin, a char-forming catalyst in addition to melamine polyphosphate in inorganic reinforced polyamide resin In addition, flame retardant technology using a char forming agent in combination, and flame retardant combination technology combining a phosphinate and a (reaction product of melamine and phosphoric acid) are being studied.

More recently, a technology for making a polyamide / polyphenylene ether resin composition flame retardant using phosphinates (Patent Document 1) and a styrene resin and / or a polyester resin include a polyamide resin and a polyphenylene ether resin. There has been proposed a technique for making a resin composition flame-retardant using phosphinates (Patent Document 2). However, in recent SMT-compatible parts represented by relay blocks, connectors, etc., the shape is complicated, downsized, and thinned, and deposits called mold deposits adhere to the mold during injection molding, There is a problem that the appearance of the molded piece is poor (hereinafter sometimes referred to as silver streak) due to the gas generated at the time of molding, and furthermore, thin parts cannot be molded well due to insufficient fluidity. In the technique proposed above, these problems cannot be solved, and the solution has been essential. Therefore, there has been a long-awaited development of a new technology that can solve the above-described problems and satisfy the requirements for recent relay blocks and SMT-compatible parts represented by connectors.
International Patent Publication No. 2005/118698 Pamphlet JP 2001-335699 A

  An object of the present invention is to provide a resin composition which is excellent in flame retardancy and impact resistance, and can obtain a molded product having excellent moldability in thin parts and surface appearance. Specifically, it has excellent fluidity and can greatly suppress the generation of gas during processing, and it generates deposits (hereinafter sometimes referred to as mold deposit) to the mold during injection molding. It is providing the resin composition which can suppress significantly.

  As a result of repeated studies to solve the above-mentioned problems, the present inventors have made the viscosity of the polyamide within a specific range when the phosphinic acid salts are used as a flame retardant and the polyamide / polyphenylene ether composition is made flame retardant. As a result, the inventors have found that the above-described problems can be solved, and have reached the present invention.

That is, the present invention relates to a composition comprising a specific viscosity polyamide, polyphenylene ether and phosphinates, and more specifically,
1. (A) Polyamide (however, a dicarboxylic acid unit (a) containing 60 to 100 mol% of terephthalic acid, a 1,9-nonanediamine unit (b-1) and a 2-methyl-1,8-octanediamine unit (b -2) except for a semi-aromatic polyamide comprising diamine units (b) containing 60 to 100 mol%), (B) polyphenylene ether, (C) phosphinic acid salt represented by the following formula (I), A resin composition comprising at least one phosphinic acid salt selected from diphosphinic acid salts represented by (II) and condensates thereof, wherein (A) a viscosity number of polyamide (ISO307: A resin composition characterized in that (measured in 96% sulfuric acid specified in 1997) is 50 ml / g to 250 ml / g.

[Wherein R ¹ and R ² are the same or different and are linear or branched C ₁ -C ₆ -alkyl and / or aryl or phenyl, and R ³ is linear or branched. C ₁ -C ₁₀ -alkylene, C ₆ -C ₁₀ -arylene, C ₆ -C ₁₀ -alkylarylene or C ₆ -C ₁₀ -arylalkylene, M is calcium (ion), magnesium (ion), aluminum ( Ion), zinc (ion), bismuth (ion), manganese (ion), sodium (ion), potassium (ion), and protonated nitrogen base, and m is 2 or 3 , N is 1 to 3, and x is 1 or 2. ]

2. (A) The resin composition according to 1 above, wherein the polyamide has a viscosity number (measured in 96% sulfuric acid defined by ISO 307: 1997) of 70 ml / g or more and 150 ml / g or less.
3. (A) The resin composition according to the above 1 or 2, wherein the polyamide has a viscosity number (measured in 96% sulfuric acid defined by ISO 307: 1997) of 100 ml / g or more and 150 ml / g or less.
4). (A) The resin composition according to any one of 1 to 3 above, wherein the polyamide has a terminal amino group concentration of 5 μmol / g or more and 60 μmol / g or less.
5. 2. The resin composition as described in 1 above, wherein the component (C) has an average particle size of 0.5 μm or more and 40 μm or less.

6). (A) The amount ratio of polyamide and (B) polyphenylene ether is 40 to 70 parts by mass of (A) polyamide and 60 to 30 parts by mass of (B) polyphenylene ether when the total of both is 100 parts by mass. 2. The resin composition as described in 1 above.
7). 2. The resin composition according to 1 above, wherein the amount of (C) phosphinate is 1 to 50 parts by mass with respect to 100 parts by mass in total of (A) polyamide and (B) polyphenylene ether.
8). 8. The resin composition according to 1 above, further comprising at least one appearance improver selected from mineral oil and wax as component (D). 9. The resin composition as described in 8 above, wherein the amount of the component (D) appearance improver is 0.1 to 10 parts by mass with respect to 100 parts by mass in total of (A) polyamide and (B) polyphenylene ether.
10. 2. The resin composition as described in 1 above, wherein the phosphinic acid salt of component (C) contains 90% by mass or more of the phosphinic acid salt represented by the following formula (I).

[Wherein, R ¹ and R ² are the same or different and are linear or branched C ₁ -C ₆ -alkyl and / or aryl or phenyl, and M is calcium (ion), magnesium (ion) , Aluminum (ion), zinc (ion), bismuth (ion), manganese (ion), sodium (ion), potassium (ion) and protonated nitrogen base, and m is 2 or 3. ]

11. As a component (E), a block copolymer containing at least one block mainly composed of an aromatic vinyl compound and at least one block mainly composed of a conjugated diene compound and / or a hydrogenated product of the block copolymer 2. The resin composition according to 1, further comprising an impact modifier comprising:
12 (F) Resin composition of said 1 which contains an inorganic filler as a component in the quantity of 1-70 mass% when the mass of all the resin compositions containing an inorganic filler is 100 mass%.
13. (A) Polyamide (however, a dicarboxylic acid unit (a) containing 60 to 100 mol% of terephthalic acid, a 1,9-nonanediamine unit (b-1) and a 2-methyl-1,8-octanediamine unit (b -2) except for semi-aromatic polyamides comprising diamine units (b) containing 60 to 100 mol%), (B) polyphenylene ether and (C) phosphinic acid salts represented by the following formula (I): A method for producing a resin composition comprising at least one phosphinic acid salt selected from diphosphinic acid salts represented by (II) and condensates thereof, wherein component (C) Is added to the molten mixture of the component (A) and the component (B).

[Wherein R ¹ and R ² are the same or different and are linear or branched C ₁ -C ₆ -alkyl and / or aryl or phenyl, and R ³ is linear or branched. C ₁ -C ₁₀ -alkylene, C ₆ -C ₁₀ -arylene, C ₆ -C ₁₀ -alkylarylene or C ₆ -C ₁₀ -arylalkylene, M is calcium (ion), magnesium (ion), aluminum ( Ion), zinc (ion), bismuth (ion), manganese (ion), sodium (ion), potassium (ion) and / or protonated nitrogen base, and m is 2 or 3, n is 1 to 3, and x is 1 or 2. ]

14 (A) Polyamide (however, a dicarboxylic acid unit (a) containing 60 to 100 mol% of terephthalic acid, a 1,9-nonanediamine unit (b-1) and a 2-methyl-1,8-octanediamine unit (b -2) except for a semi-aromatic polyamide comprising diamine units (b) containing 60 to 100 mol%), (B) polyphenylene ether, (C) phosphinic acid salt represented by the following formula (I), A method for producing a resin composition comprising at least one phosphinate selected from diphosphinates represented by (II) and condensates thereof, and (D) an appearance improver, and (E) an impact modifier. Because
(1) (D) Appearance improver is mixed with one or more selected from (A) polyamide, (B) polyphenylene ether and (E) impact modifier, and (2) the master A method for producing a resin composition, comprising at least two steps of at least two steps of melt-kneading a batch with the remaining components.

[Wherein R ¹ and R ² are the same or different and are linear or branched C ₁ -C ₆ -alkyl and / or aryl or phenyl, and R ³ is linear or branched. C ₁ -C ₁₀ -alkylene, C ₆ -C ₁₀ -arylene, C ₆ -C ₁₀ -alkylarylene or C ₆ -C ₁₀ -arylalkylene, M is calcium (ion), magnesium (ion), aluminum ( Ion), zinc (ion), bismuth (ion), manganese (ion), sodium (ion), potassium (ion), and protonated nitrogen base, and m is 2 or 3 , N is 1 to 3, and x is 1 or 2. ]

15. The pellet obtained from the manufacturing method in any one of said 13 or 14.
16. A molded product obtained from the resin composition according to any one of 1 to 12 above.
17. A molded part corresponding to the surface mounting technology obtained from the resin composition according to any one of 1 to 12 above.

  By using the resin composition of the present invention, it has excellent flame retardancy and impact resistance, has excellent moldability in thin-walled parts, and can greatly suppress the generation of gas during molding processing, Moreover, the resin composition which can suppress significantly the production | generation of the deposit | attachment (mold deposit) to the metal mold | die at the time of injection molding is obtained. As a result, a molded product having an excellent surface appearance can be provided.

The contents of the present invention will be described in detail below.
As the polyamide that can be used in the present invention, any polyamide having an amide bond {—NH—C (═O) —} in the repeating unit of the polymer main chain can be used.
Polyamides are generally obtained by ring-opening polymerization of lactams, polycondensation of diamine and dicarboxylic acid, polycondensation of ω-aminocarboxylic acid, etc., but are not limited to resins obtained by these methods.

  The diamine is roughly classified into aliphatic, alicyclic and aromatic diamines. Specific examples of the diamine include tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, tridecamethylene diamine, 2,2,4-trimethylhexamethylene diamine, 2,4,4-trimethylhexamethylene diamine. , 5-methylnonamethylenediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, ethylenediamine, propylenediamine, 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine 1,10-decanediamine, 1,12-dodecanediamine, 3-methyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1 , 6-hexanediamine, 5-methyl-1,9-nona Aliphatic diamine 1,3-bis-aminomethyl cyclohexane etc. diamine, 1,4-bis aminomethyl cyclohexane, m- phenylenediamine, p- phenylenediamine, m- xylylenediamine, etc. p- xylylenediamine.

Dicarboxylic acids are roughly classified into aliphatic, alicyclic and aromatic dicarboxylic acids. Specific examples of dicarboxylic acids include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,1,3-tridecanedioic acid, 1,3-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid Examples include acids and dimer acids.
Specific examples of lactams include ε-caprolactam, enantolactam, and ω laurolactam.
Specific examples of aminocarboxylic acids include ε-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminonanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and 13-aminotridecane. An acid etc. are mentioned.

In the present invention, these lactams, diamines, dicarboxylic acids, and ω-aminocarboxylic acids can be used alone or as a copolymerized polyamide obtained by polycondensation in a mixture of two or more.
Further, those obtained by polymerizing these lactams, diamines, dicarboxylic acids, and ω-aminocarboxylic acids up to a low molecular weight oligomer stage in a polymerization reactor and increasing the molecular weight in an extruder or the like can also be suitably used.

  Particularly, polyamides that can be suitably used in the present invention include polyamide 6, polyamide 6,6, polyamide 4,6, polyamide 11, polyamide 12, polyamide 6,10, polyamide 6,12, polyamide 6 / 6,6, Polyamide 6/6, polyamide MXD (m-xylylenediamine), 6, polyamide 6, T, polyamide 9, T, polyamide 6, I, polyamide 6/6, T, polyamide 6/6, I, polyamide 6 , 6/6, T, polyamide 6,6 / 6, I, polyamide 6/6, T / 6, I, polyamide 6,6 / 6, T / 6, I, polyamide 6/12/6, T, polyamide 6,6 / 12/6, T, polyamide 6/12/6, I, polyamide 6,6 / 12/6, I and the like. Of these, polyamides obtained by copolymerizing a plurality of polyamides with an extruder or the like can also be used. Among them, preferred polyamides are aliphatic polyamides polyamide 6, polyamide 6,6, polyamide 4,6, polyamide 11, polyamide 12; and semi-aromatic polyamides polyamide 9, T, polyamide 6/6, T, polyamide 6,6. / 6, T, polyamide 6,6 / 6, I, polyamide MXD, 6; and most preferably one or more selected from polyamide 6,6, polyamide 6, polyamide 9, T Polyamide.

The polyamide used in the present invention needs to have a viscosity number of 50 ml / g to 250 ml / g measured with 96% sulfuric acid according to ISO 307: 1994. By setting the viscosity number of the polyamide to 50 ml / g or more, processability such as extrusion is improved, flame retardancy is improved, and generation of gas during molding is greatly suppressed. Further, since the generation of mold deposits is small, the number of shots that can be normally molded at the time of injection molding can be dramatically increased, which leads to a significant improvement in moldability. Further, by setting the viscosity number to 250 ml / g or less, in addition to the above-described effects, a new effect such as improvement of moldability of a thin molded product can be expressed.
A preferred lower limit is 70 ml / g, and a more preferred lower limit is 100 ml / g. Moreover, a preferable upper limit is 200 ml / g and the most preferable upper limit is 150 ml / g.

Moreover, when the polyamide used in the present invention is a semi-aromatic polyamide such as polyamide 9, T, the preferred viscosity range is slightly different. A preferred lower limit of the viscosity number is 70 ml / g, and a more preferred lower limit is 100 ml / g. A more preferred upper limit is 150 ml / g, and a most preferred upper limit is 120 ml / g.
Various characteristics which are the effects of the present invention greatly vary depending on the viscosity number of the polyamide, and when the polyamide having a viscosity number within a specific range is used, the characteristics are improved specifically.

  The polyamide that can be used in the resin composition of the present invention may be a mixture of a plurality of polyamides having different viscosity numbers. When a plurality of polyamides are used, it is desirable that the viscosity number of the polyamide is 50% by mass or more (when all the polyamides are 100% by mass) within the above-mentioned range. More preferably, the viscosity number of the polyamide mixture itself is within the scope of the claims of the present invention. In order to confirm that the polyamide mixture is within the above-mentioned range of the viscosity number, it can be easily confirmed by actually measuring the viscosity number of the polyamide mixture mixed at a desired mixing ratio.

In the present invention, when a semi-aromatic polyamide is used as the polyamide, it is desirable to use a semi-aromatic polyamide described in detail below.
The semiaromatic polyamide which can be preferably used preferably contains 60 to 100 mol% of terephthalic acid units as the constituting dicarboxylic acid units (a). The content of the terephthalic acid unit in the dicarboxylic acid unit (a) is more preferably in the range of 75 to 100 mol%, further preferably in the range of 90 to 100 mol%, and substantially all The dicarboxylic acid unit is most preferably a terephthalic acid unit.

  As described above, the dicarboxylic acid unit (a) may contain a dicarboxylic acid unit other than the terephthalic acid unit as long as it is 40 mol% or less. Other dicarboxylic acid units include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethyl Aliphatic dicarboxylic acids such as succinic acid, azelaic acid, sebacic acid and suberic acid; alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; isophthalic acid and 2,6-naphthalene Dicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxydiacetic acid, diphenic acid, diphenylmethane-4,4′-dicarboxylic acid Acid, diphenylsulfone-4,4′-dicarboxylic acid, 4,4′-biphenyldicarboxylic acid, etc. Can be mentioned units derived from aromatic dicarboxylic acids, it can be used one or more of them. Of these, units derived from aromatic dicarboxylic acids are preferred. Furthermore, units derived from polyvalent carboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid may be included within a range in which melt molding is possible.

The content of the other dicarboxylic acid unit in the dicarboxylic acid unit (a) is more preferably 25 mol% or less, further preferably 10 mol% or less, and most preferably substantially free.
The diamine units (b) constituting the semi-aromatic polyamide usable in the present invention are 1,9-nonamethylenediamine units (b-1) and 2-methyl-1,8-octamethylenediamine units (b-2). ) In a total amount of 60 to 100 mol%.
The content of the 1,9-nonamethylenediamine unit (b-1) and the 2-methyl-1,8-octamethylenediamine unit (b-2) in the diamine unit (b) is 75 to 100 mol%. More preferably, it is more preferably 90-100 mol%, and substantially all diamine units are 1,9-nonamethylenediamine units (b-1) and 2-methyl-1,8-octa Most preferably, it is composed of a methylenediamine unit (b-2).

  In the present invention, in the diamine unit (b) in the semi-aromatic polyamide, if it is 40 mol% or less, other than 1,9-nonamethylenediamine unit and 2-methyl-1,8-octamethylenediamine unit Other diamine units may be included. Other diamine units in this case include ethylenediamine, propylenediamine, 1,4-butanediamine, 1,6-hexanediamine, 1,8-octamethylenediamine, 1,10-decanediamine, and 1,12-dodecanediamine. 3-methyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl-1,9- Aliphatic diamines such as nonamethylenediamine; cycloaliphatic diamines such as cyclohexanediamine, methylcyclohexanediamine, and isophoronediamine; p-phenylenediamine, m-phenylenediamine, xylylenediamine, 4,4′-diaminodiphenylmethane, 4,4 '-Diaminodiphenylsulfone, 4,4'-diaminodiphe Rue - can include units derived from aromatic diamines such as ether, it can comprise one or more of these. The content of these other diamine units in the diamine unit (b) is more preferably 25 mol% or less, still more preferably 10 mol% or less, and most preferably substantially free.

  In addition, when the total amount of 1,9-nonamethylenediamine unit (b-1) and 2-methyl-1,8-octamethylenediamine unit (b-2) in the diamine unit is 100 mol%. As a preferable ratio of the 1,9-nonamethylenediamine unit (b-1), the lower limit is preferably 60 mol%. A more preferred lower limit is 75 mol%, and still more preferably 80 mol%. By increasing the lower limit value, it is possible to enhance heat resistance and suppress water absorption. As an upper limit, 95 mol% is preferable. More preferably, it is 90 mol%, More preferably, it is 85 mol%. By lowering the upper limit, the mechanical properties such as impact resistance and tensile elongation can be improved, and the effect of improving the surface appearance of the molded product can be obtained.

The end groups of the polyamide are involved in the reaction with the polyphenylene ether.
Polyamide generally has an amino group or a carboxyl group as a terminal group. However, when the terminal carboxyl group concentration is generally increased, impact resistance is decreased, fluidity is improved, and conversely the terminal amino group concentration is decreased. When it is higher, impact resistance is improved and fluidity is lowered.
In the present invention, the terminal amino group / terminal carboxyl group concentration ratio of the polyamide is preferably 1.0 or less. More preferably, it exists in the range of 0.05-0.8. By setting it as this range, the balance between the fluidity and impact resistance of the composition can be maintained.
The terminal amino group concentration is preferably 1 to 80 μmol / g. More preferably, it is 5-60 micromol / g, More preferably, it is 10 micromol / g or more and less than 45 micromol / g, Most preferably, it is 20 micromol / g or more and 40 micromol / g or less. By setting the terminal amino group concentration within the above-mentioned range, the balance between fluidity and impact resistance of the composition can be maintained.

The terminal carboxyl group concentration is preferably 20 μmol / g to 150 μmol / g. More preferably, it is 30 μmol / g to 130 μmol / g. By setting the terminal carboxyl group concentration within the above-described range, the balance between fluidity and impact resistance of the composition can be maintained.
A known method can be used as a method for adjusting the end groups of these polyamide resins. For example, there may be mentioned a method of adding one or more selected from diamine compounds, monoamine compounds, dicarboxylic acid compounds, monocarboxylic acid compounds and the like so that a predetermined terminal concentration is obtained during polymerization of the polyamide resin.

The concentration of the terminal amino group and terminal carboxyl group in the present invention can be measured by various methods, but it is accurate and simple to obtain from the integrated value of the characteristic signal corresponding to each terminal group by ¹ H-NMR. This is preferable. For example, as a specific method for quantifying the end group concentration of semi-aromatic polyamide, it is recommended to follow the method described in Examples of JP-A-7-22889.

  When a semi-aromatic polyamide is used as the polyamide of the present invention, it is preferable that 10 to 95% of the end groups of the molecular chain are sealed with an end-capping agent. The lower limit of the ratio (terminal blocking ratio) in which the end groups of the molecular chain are sealed with the end-capping agent is more preferably 40%, and even more preferably 60%. By setting the terminal sealing rate to 10% or more, the viscosity change at the time of melt molding of the resin composition of the present invention can be reduced, and the physical properties such as the appearance of the obtained molded product and the heat resistance stability during processing can be reduced. This is desirable because it provides excellent effects. Further, the upper limit value of the end capping rate is preferably 95%, and more preferably 90%. By setting the upper limit to 95% or less, it is preferable because the effects of excellent impact resistance of the composition and surface appearance of the molded product can be obtained.

The end-capping rate of the semi-aromatic polyamide of the present invention was determined by measuring the number of terminal carboxyl groups, terminal amino groups, and terminal groups blocked by a terminal blocking agent present in the polyamide-based resin, respectively. It can be obtained according to 1).
Terminal sealing rate (%) = [(α−β) / α] × 100 (1)
[Wherein α represents the total number of terminal groups of the molecular chain (this is usually equal to twice the number of polyamide molecules), and β is the total number of carboxyl group terminals and amino group terminals remaining unsealed. Represents. ]

  The end capping agent is not particularly limited as long as it is a monofunctional compound having reactivity with the amino group or carboxyl group at the end of the polyamide resin, but from the viewpoint of reactivity and stability of the capping end, etc. Monocarboxylic acids or monoamines are preferred, and monocarboxylic acids are more preferred from the viewpoint of ease of handling. In addition, acid anhydrides, monoisocyanates, monoacid halides, monoesters, monoalcohols, and the like can be used as the end-capping agent.

  The monocarboxylic acid used as the end-capping agent is not particularly limited as long as it has reactivity with an amino group. For example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, laurin Aliphatic monocarboxylic acids such as acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; benzoic acid, toluic acid, α-naphthalenecarboxylic acid , Β-naphthalene carboxylic acid, methyl naphthalene carboxylic acid, aromatic monocarboxylic acid such as phenylacetic acid; any mixture thereof. Among these, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearin, etc. Acid and benzoic acid are preferable, and acetic acid and benzoic acid are particularly preferable.

  The monoamine used as the end-capping agent is not particularly limited as long as it has reactivity with a carboxyl group. For example, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearyl Aliphatic monoamines such as amine, dimethylamine, diethylamine, dipropylamine and dibutylamine; Cycloaliphatic monoamines such as cyclohexylamine and dicyclohexylamine; Aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine; any mixtures thereof Can be mentioned. Of these, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline are preferred from the viewpoint of reactivity, boiling point, sealing end stability, price, and the like, and butylamine, hexylamine, and octylamine are preferred. Particularly preferred.

In the present invention, a transition metal and / or halogen may be present in the resin composition for the purpose of further improving the heat resistance stability imparted to the resin composition by the polyamide resin.
Although there is no restriction | limiting in particular regarding the kind of transition metal, Copper, cerium, nickel, and cobalt are preferable, and copper is especially preferable. Of the halogens, bromine or iodine can be preferably used.
A preferable amount of the transition metal is 1 ppm or more and less than 200 ppm when the entire resin composition is 100% by mass. More preferably, it is 5 ppm or more and less than 100 ppm. Moreover, the preferable amount of halogen is similarly 500 ppm or more and less than 1500 ppm, More preferably, it is 700 ppm or more and less than 1200 ppm.

  Examples of methods for adding these transition metals and / or halogens to the resin composition include, for example, a method of adding a polyamide / polyphenylene ether composition as a powder when melt-kneading, a method of adding during polymerization of polyamide, Although the method etc. which add this master pellet to a resin composition after producing the master pellet added by the density | concentration are mentioned, any method may be taken. Among these methods, a preferable method is a method of adding at the time of polymerization of polyamide, or a method of adding after preparing master pellets added to polyamide at a high concentration.

  Moreover, in this invention, a well-known organic stabilizer other than the transition metal and / or halogen mentioned above can also be used without a problem. Examples of organic stabilizers include hindered phenol-based antioxidants typified by Irganox 1098 (manufactured by Ciba Specialty Chemicals Co., Ltd.), and Irgaphos 168 (manufactured by Ciba Specialty Chemicals Co., Ltd.). Phosphonic processing heat stabilizers, lactone processing heat stabilizers represented by HP-136 (manufactured by Ciba Specialty Chemicals Co., Ltd.), sulfur heat resistance stabilizers, hindered amine light stabilizers, and the like. Among these organic stabilizers, a hindered phenol antioxidant, a phosphorus processing heat stabilizer, or a combination thereof is more preferable. A preferable blending amount of these organic stabilizers is 0.001 to 1 part by mass with respect to 100 parts by mass of the polyamide resin.

  Specific examples of the polyphenylene ether of the present invention include, for example, poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like, and 2,6-dimethylphenol and other phenols (For example, a copolymer with 2,3,6-trimethylphenol or a copolymer with 2-methyl-6-butylphenol as described in JP-B-52-17880) Polyphenylene ether copolymers may also be mentioned.

Among these, particularly preferred polyphenylene ethers include poly (2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, or these It is a mixture.
The method for producing the polyphenylene ether used in the present invention is not particularly limited as long as it can be obtained by a known method. For example, U.S. Pat. Nos. 3,306,874, 3,306,875, and 3,257,357 are disclosed. And the production methods described in JP-A-3257358, JP-A-50-51197, JP-B52-17880, and 63-152628.

The preferred range of the reduced viscosity (measured with 0.5 g / dl chloroform solution, 30 ° C., Ubbelohde type viscosity tube) of the polyphenylene ether of the present invention is in the range of 0.30 dl / g to 0.80 dl / g. More preferably, it is in the range of 0.35 dl / g to 0.75 dl / g, and most preferably 0.38 dl / g to 0.55 dl / g. When the reduced viscosity of the polyphenylene ether is within this range, it is preferable because of excellent properties such as impact resistance and heat resistance.
In the present invention, a blend of two or more polyphenylene ethers having different reduced viscosities can be preferably used.

  In addition, the polyphenylene ether that can be used in the present invention may be a polyphenylene ether modified in whole or in part. The modified polyphenylene ether here means at least one carbon-carbon double bond or triple bond in the molecular structure, and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group or glycidyl group. And polyphenylene ether modified with at least one modifying compound. Use of the modified polyphenylene ether is preferable because it is possible to improve properties such as impact resistance and tensile strength.

  The modified polyphenylene ether can be produced by the following: (1) a modified compound without melting the polyphenylene ether in the temperature range of 100 ° C. or higher and lower than the glass transition temperature of the polyphenylene ether in the presence or absence of a radical initiator. (2) A method of reacting by melting and kneading with a modifying compound in a temperature range of not less than the glass transition temperature of polyphenylene ether and not more than 360 ° C., and (3) a polyphenylene ether at a temperature lower than the glass transition temperature of polyphenylene ether. And a method in which a modifying compound is reacted in a solution, and any of these methods may be used, but the method (1) or (2) is preferred.

Next, at least one modified compound having at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group or glycidyl group in the molecular structure. This will be specifically described.
Examples of the modified compound having a carbon-carbon double bond and a carboxylic acid group or an acid anhydride group in the molecule include maleic acid, fumaric acid, chloromaleic acid, cis-4-cyclohexene-1,2-dicarboxylic acid and These acid anhydrides are mentioned. Fumaric acid, maleic acid, and maleic anhydride are particularly preferable, and fumaric acid and maleic anhydride are particularly preferable. In addition, one in which one or two of the two carboxyl groups of the unsaturated dicarboxylic acid is an ester can be used.

Examples of the modified compound having a carbon-carbon double bond and a glycidyl group in the molecule include allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, epoxidized natural oil and fat, and the like. Among these, glycidyl acrylate and glycidyl methacrylate are particularly preferable.
Examples of the modified compound having a carbon-carbon double bond and a hydroxyl group in the molecule include general formulas C _n H _2n-3 OH such as allyl alcohol, 4-penten-1-ol, 1,4-pentadien-3-ol, and the like. (n is a positive integer) of unsaturated alcohols of the general formula _{C n H 2n-5 OH,} ( n is a positive integer) _{C n H 2n-7} OH include unsaturated alcohols such as.
The above-described modifying compounds may be used alone or in combination of two or more.

The amount of the modifying compound added when producing the modified polyphenylene ether is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass with respect to 100 parts by mass of the polyphenylene ether.
A preferable amount of the radical initiator when producing the modified polyphenylene ether using the radical initiator is 0.001 to 1 part by mass with respect to 100 parts by mass of the polyphenylene ether.
Further, the addition ratio of the modifying compound to the modified polyphenylene ether is preferably 0.01 to 5% by mass. More preferably, it is 0.1-3 mass%.
In the modified polyphenylene ether, the unreacted modified compound and / or polymer of the modified compound may remain if the amount is less than 1% by mass.
Moreover, in this invention, you may mix | blend a styrene-type thermoplastic resin if it is the quantity of less than 50 mass parts with respect to a total of 100 mass parts of polyamide and polyphenylene ether.

Examples of the styrenic thermoplastic resin in the present invention include homopolystyrene, rubber-modified polystyrene (HIPS), styrene-acrylonitrile copolymer (AS resin), styrene-rubber polymer-acrylonitrile copolymer (ABS resin). Etc.
Also, various stabilizers known for stabilizing polyphenylene ether can be suitably used. Examples of stabilizers are metal stabilizers such as zinc oxide and zinc sulfide, organic stabilizers such as hindered phenol stabilizers, phosphorus stabilizers, and hindered amine stabilizers. The amount is less than 5 parts by mass with respect to 100 parts by mass of polyphenylene ether.

Furthermore, you may add the well-known additive etc. which can be added to polyphenylene ether in the quantity of less than 10 mass parts with respect to 100 mass parts of polyphenylene ether.
In the present invention, the preferred amount ratio when using (A) polyamide and (B) polyphenylene ether is (A) 40 to 70 parts by mass of polyamide, and (B) polyphenylene ether 60 when the total of both is 100 parts by mass. It is in the range of -30 mass parts. More preferably, (A) 50-70 parts by mass of polyamide, (B) 50-30 parts by mass of polyphenylene ether, most preferably (A) 50-60 parts by mass of polyamide, (B) 50-40 parts by mass of polyphenylene ether. Within the range of the part. When the ratio of (A) and (B) is within this range, it is excellent in chemical resistance and heat resistance to aromatic hydrocarbons.

Further, in the present invention, as a preferable dispersion form of polyphenylene ether, it is preferable that polyamide forms a continuous phase and polyphenylene ether forms a dispersed phase. In particular, when observed with a transmission electron microscope, the polyphenylene ether particles are preferably present as a dispersed phase having an average particle size of 0.1 to 5 μm. More preferably, it exists in the range of 0.05-3 micrometers, Most preferably, it is 0.1-2 micrometers.
The phosphinic acid salt represented by the following formula (I) and / or the diphosphinic acid salt represented by the following formula (II) or a condensate thereof selected from the component (C) of the present invention: As phosphinates, as described in JP-A-2005-179362, European Patent Application Publication No. 699708 and JP-A-08-73720, phosphinic acid and metal carbonate, metal hydroxide or It is produced in an aqueous solution using a metal oxide. Although these are essentially monomeric compounds, depending on the reaction conditions, polymeric phosphinates that are condensates having a degree of condensation of 1 to 3 are also included depending on the environment.

[Wherein R ¹ and R ² are the same or different and are linear or branched C ₁ -C ₆ -alkyl and / or aryl or phenyl, and R ³ is linear or branched. C ₁ -C ₁₀ -alkylene, C ₆ -C ₁₀ -arylene, C ₆ -C ₁₀ -alkylarylene or C ₆ -C ₁₀ -arylalkylene, M is calcium (ion), magnesium (ion), aluminum ( Ion), zinc (ion), bismuth (ion), manganese (ion), sodium (ion), potassium (ion), and protonated nitrogen base, and m is 2 or 3 , N is 1 to 3, and x is 1 or 2. ]

The phosphinic acid salts of the present invention may be mixed in any composition as long as the effects of the present invention are not impaired. From the viewpoint of flame retardancy and suppression of mold deposit, the phosphinic acid salts of the present invention are represented by the above (I). The phosphinic acid salt is preferably contained in an amount of 90% by mass or more, more preferably 95% by mass or more, and most preferably 98% by mass or more.
Specific examples of phosphinic acid that can be preferably used in the present invention include dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid, methandi (methylphosphinic acid), benzene-1,4- (Dimethylphosphinic acid), methylphenylphosphinic acid, diphenylphosphinic acid, and mixtures thereof.

  The metal component that can be preferably used is at least one selected from calcium ions, magnesium ions, aluminum ions, zinc ions, bismuth ions, manganese ions, sodium ions, potassium ions) and / or protonated nitrogen bases. More preferably, it is at least one selected from calcium ions, magnesium ions, aluminum ions, and zinc ions.

  Specific examples of phosphinates that can be preferably used include calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, aluminum ethylmethylphosphinate , Zinc ethylmethylphosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, methyl-n-propyl Aluminum phosphinate, zinc methyl-n-propylphosphinate, calcium methanedi (methylphosphinate), meta Di (methylphosphinic acid) magnesium, methanedi (methylphosphinic acid) aluminum, methanedi (methylphosphinic acid) zinc, benzene-1,4- (dimethylphosphinic acid) calcium, benzene-1,4- (dimethylphosphinic acid) magnesium, Benzene-1,4- (dimethylphosphinic acid) aluminum, benzene-1,4- (dimethylphosphinic acid) zinc, calcium methylphenylphosphinate, magnesium methylphenylphosphinate, aluminum methylphenylphosphinate, zinc methylphenylphosphinate, Examples include calcium diphenylphosphinate, magnesium diphenylphosphinate, aluminum diphenylphosphinate, and zinc diphenylphosphinate.

Calcium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate especially from the viewpoint of flame retardancy and mold deposit control Aluminum diethylphosphinate and zinc diethylphosphinate are preferred. Of these, aluminum diethylphosphinate is particularly preferable.
In this invention, the quantity of a preferable phosphinic acid salt is 1-50 mass parts with respect to a total of 100 mass parts of (A) polyamide and (B) polyphenylene ether. More preferably, it is 2 to 25 parts by mass, particularly preferably 2 to 15 parts by mass, and most preferably 2 to 10 parts by mass. By setting the amount of phosphinates to 1 part by mass or more, sufficient flame retardancy can be exhibited. Further, it is preferable that the amount of the phosphinic acid salt is 50 parts by mass or less because a melt viscosity suitable for extrusion processing can be obtained.

In consideration of the mechanical strength and the appearance of the molded product obtained by molding the resin composition of the present invention, the preferred lower limit of the average particle diameter of phosphinates is 0.5 μm. A more preferred lower limit is 1.0 μm, and a most preferred lower limit is 2 μm. The upper limit of the average particle diameter of phosphinic acid salts is preferably 40 μm, more preferably 20 μm, still more preferably 15 μm, and most preferably 10 μm.
By setting the number average particle diameter of the phosphinates to 0.5 μm or more, handling properties and biting into an extruder are improved during processing such as melt kneading. Moreover, it is preferable that the average particle diameter is 40 μm or less because the mechanical strength of the resin composition is easily developed and the good surface appearance of the molded product is improved.

The average particle size of the phosphinates can be measured and analyzed by dispersing the phosphinates in water using a laser diffraction particle size distribution analyzer (for example, trade name: SALD-2000, manufactured by Shimadzu Corporation). The method for dispersing water in phosphinates can be achieved by adding water and phosphinates to an ultrasonic diffuser and / or a stirrer equipped with a stirrer. This dispersion is sent to a measurement cell of a laser diffraction particle size distribution meter via a pump, and the particle diameter is measured by laser diffraction. The number average particle size can be calculated from the frequency distribution of the particle size and the number of particles obtained by measurement.
In the phosphinic acid salts in the present invention, unreacted products or by-products may remain as long as the effects of the present invention are not impaired.

In the resin composition of the present invention, the phosphinic acid salts exhibit a dispersed state dispersed in polyamide and / or polyphenylene ether. Furthermore, it is preferable that the number of particles having a major axis of 30 μm or more of the phosphinate particles is 50 or less when the resin composition is observed on a continuous 3 mm ² surface of the resin composition using an optical microscope. . More preferably, it is 30 or less. There is no particular lower limit, but it is one because there is no problem even if about one exists.
When the number of phosphinates is 50 or less under the above-described conditions, the mechanical strength (particularly tensile elongation and surface impact strength) of the resin composition and the appearance of the molded piece are improved.

As a specific method for confirming the dispersion state of the phosphinates in the resin composition of the present invention, the following method is used. First, the resin composition is cut into a mirror surface using a microtome equipped with a glass knife. The cut surface is observed with reflected light at a magnification of 100 using an optical microscope (PME3: manufactured by Olympus), and a photograph is taken for an area of at least 3 mm ² . It is possible by visually counting the number of dispersed phosphinate particles having a major axis of 30 μm or more existing in an area of 3 mm ² . Regarding the observation direction, when the observation target is a cylindrical pellet shape, it is desirable to perform observation by cutting into a cross section substantially perpendicular to the long side of the pellet. In the case of a molded piece, it is desirable to observe an area of 3 mm ² at at least three different sites, and to express the average value.

There are various methods for controlling the number of particles having a major axis of 30 μm or more in the resin composition to 50 or less. For example, phosphinates are classified in advance using a sieve or the like, A method of removing lumps, a method of pulverizing by mechanical shearing using a step of melting and kneading together with the component (A) to form a master batch, etc. are mentioned, but a method of pulverizing in the master batch step is economical. More preferable from the viewpoint.
A preferable amount of the component (C) in the master batch containing the component (A) and the component (C) is in the range of 30 to 70% by mass when the master batch is 100% by mass. More preferably, it is 35-65 mass%, Most preferably, it exists in the range of 40-60 mass%.

  In the present invention, it is particularly preferable to use the phosphinic acid salt of component (C) alone in order to suppress mold deposit at the time of injection molding. Use as a flame retardant combination as described in the pamphlet of 2005/118698 is not limited. Examples of components that can constitute a flame retardant combination include adducts and zinc-containing compounds formed from melamine and phosphoric acid.

Specific examples of adducts formed from melamine and phosphoric acid include reaction products of melamine and polyphosphoric acid and / or reaction products of condensates of melamine and polyphosphoric acid, formula (NH ₄ ) _y H _{3 -y} PO ₄ or _(NH 4 _{PO 3) z} [wherein, y is 1 to 3, and z is 1 to 10000] the nitrogen-containing phosphates represented by the ammonium hydrogen phosphate, phosphoric acid 1 or more types chosen from ammonium dihydrogen and / or ammonium polyphosphate are mentioned. In particular, it is represented by the following chemical formula (C ₃ H ₆ N ₆ · HPO ₃ ) _n (where n represents the degree of condensation), and is substantially equal to melamine and phosphoric acid, pyrophosphoric acid, polyphosphoric acid, etc. Those obtained from molar reaction products can be used. More specifically, at least one selected from dimelamine pyrophosphate, melamine polyphosphate, melem polyphosphate, melam polyphosphate, melon polyphosphate, and mixed polysalts thereof, among these, melamine polyphosphate is the most It is used a lot.

Although there is no restriction | limiting in particular in these manufacturing methods, As an example regarding a melamine polyphosphate, the method etc. which heat-condensate melamine phosphate in nitrogen atmosphere etc. will be mentioned.
Specific examples of phosphoric acid constituting melamine phosphate include orthophosphoric acid, phosphorous acid, hypophosphorous acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid and the like, and in particular, orthophosphoric acid. In addition, melamine polyphosphate obtained by condensing an adduct with melamine using pyrophosphate is frequently used.
Examples of melamine polyphosphate include chain polyphosphoric acid called so-called condensed phosphoric acid, and equimolar addition salt of cyclic polymetaphosphoric acid and melamine. The condensation degree n of these polyphosphoric acids is not particularly limited and is usually from 3 to 50, but those having a condensation degree n of 5 or more are common.

  A method for producing a melamine polyphosphate addition salt is, for example, a slurry in which a mixture of melamine and polyphosphoric acid is dispersed in water. The slurry is mixed well to form both reaction products in the form of fine particles. Examples of the method include filtration, washing, drying, firing if necessary, and pulverizing the obtained solid to obtain a powder. These are preferably pre-blended when blended into the resin. For example, it is possible to use a material pre-blended using a high-speed mixer or the like.

  (C) It is preferable that the addition amount of the adduct formed from melamine and phosphoric acid with respect to 100 mass parts of component is 20 mass parts or less. More preferably, it is 10 mass parts or less, More preferably, it is 5 mass parts or less, Most preferably, it does not contain substantially. By adding an adduct formed from melamine and phosphoric acid within this range, the effect of slightly improving the fluidity can be expected, but it is formed from melamine and phosphoric acid to suppress mold deposits. It is desirable to be substantially free of adducts.

The average particle size of the adduct formed from melamine and phosphoric acid that can be used in the present invention is 0.5 μm or more and 40 μm or less. When used in the present invention, a fine powder having an average particle size of 0.5 μm or more and 20 μm or less can be selected.
The adduct formed from melamine and phosphoric acid may remain unreacted or by-product as long as the effects of the present invention are not impaired.
Furthermore, the zinc-containing compound that is the other component that can constitute the flame retardant combination specifically refers to an inorganic zinc-containing compound, and more specifically, zinc oxide, zinc sulfide, zinc borate, It refers to one or more selected from zinc stannate. _{xZnO · yB 2 O 3 · zH} 2 O (x> 0, y> 0, z> 0) zinc borate compound represented by are the most commonly _{used, 2ZnO · 3B 2 O 3 ·} 3.5H 2 Zinc borate represented by O, 4ZnO · B ₂ O ₃ · H ₂ O, 2ZnO · 3B ₂ O ₃ is common.

These zinc-containing compounds suppress the generation of gas that becomes fuel by decomposition of the resin by blocking the heat from the flame that is a heat source during combustion as a flame retardant aid (heat insulation ability), and flame retardant It is considered that it plays a role of forming a non-combustible layer (or a carbonized layer) necessary for the enhancement.
Further, these zinc-containing compounds may be those treated with a surface treatment agent such as a silane coupling agent or a titanate coupling agent.
The average particle size of the zinc-containing compound is generally 20 μm or less, and it is said that 7 μm or less is preferable from the mechanical characteristics.

  (C) As for the addition amount of the zinc-containing compound with respect to 100 mass parts of components, it is preferable that it is 10 mass parts or less. More preferably, it is 5 mass parts or less, More preferably, it is 3 mass parts or less, Most preferably, it does not contain substantially. By adding the zinc-containing compound within this range, the effect of improving the stability of the component (C) at a high temperature may be obtained. In order to improve mechanical properties while maintaining flame retardancy, it is desirable that the zinc-containing compound is not substantially contained. There is no particular limitation on the method of adding the above-mentioned (C) adduct formed from phosphinic acid salts, melamine and phosphoric acid, and zinc-containing compound to the present composition, and each is added alone to the composition. And a method in which two or three of these three types are premixed with a high-speed mixer (Henschel mixer) and then added to the composition.

Next, the appearance improving agent of the component (D) of the present invention will be described.
(D) The external appearance improving agent of a component is 1 or more types chosen from mineral oil and a wax.
In the present invention, mineral oil refers to one or more selected from aromatic compounds, naphthenic ring compounds and paraffinic compounds, and may be a mixture of three. When the mineral oil is a mixture, paraffinic mineral oil and / or naphthenic mineral oil with an aromatic compound of less than 30% can be preferably used from the viewpoint of (E) dispersibility and solubility in impact modifiers. It is.
The properties of these mineral oils are preferably those showing a kinematic viscosity at 37.8 ° C. of 20 to 500 cst, a pour point of −10 to −15 ° C. and a flash point of 170 to 300 ° C.

Examples of the wax that can be used in the present invention include paraffinic wax, polyethylene wax, polyolefin wax, fatty acid ester, aliphatic dibasic acid ester, phthalic acid ester, and aromatic carboxylic acid ester. Of these, paraffin wax and polyethylene wax can be preferably used.
These components (D) may be used alone or in combination of two or more.
The use amount of these components (D) is the lower limit of the use amount with respect to a total of 100 parts by mass of (A) polyamide and (B) polyphenylene ether from the viewpoint of improving the surface appearance and preventing bleeding out to the surface of the molded product. The value is preferably 0.1 parts by mass. A more preferred lower limit is 0.2 parts by mass. The upper limit of the amount used is preferably 10 parts by mass, and more preferably 5 parts by mass.

The component (D) of the present invention may be used as a master batch with at least one selected from (A) polyamide, (B) polyphenylene ether (E) impact modifier.
As an example of the method, a method by pre-blending, a method in which the pre-blend is melt-kneaded using a twin screw extruder or the like, a method in which the pre-blend product is heat equilibrated in an oven or the like can be mentioned. A more preferred method is a method in which the pre-blend product is subjected to a heat equilibration treatment using an oven or the like. At this time, the preferable content of the appearance improving agent in the master batch including the appearance improving agent is 1 to 50 parts by mass.
The (E) impact modifier of the present invention is a block copolymer comprising a polymer block mainly composed of at least one aromatic vinyl compound and a polymer block mainly composed of at least one conjugated diene compound, Or a hydrogenated product thereof.

Specific examples of the aromatic vinyl compound constituting the block copolymer include styrene, α-methylstyrene, vinyltoluene, and the like. Styrene is particularly preferable, but is not limited thereto. Two or more of these aromatic vinyl compounds may be used in combination.
Specific examples of the conjugated diene compound constituting the block copolymer include butadiene, isoprene, piperylene, 1,3-pentadiene and the like, but butadiene, isoprene or a combination thereof is preferable. It is not limited to these. Two or more of these conjugated diene compounds may be used in combination.

As used herein and in the appended claims, “mainly” means containing at least 50% or more, and more preferably containing 70% or more. To do.
When butadiene is used as the conjugated diene compound of the block copolymer, the microstructure of the polybutadiene block part contains 5-80% of the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds. Preferably, it is contained 10 to 50%, more preferably 15 to 40%. Usually, there are 1,2-vinyl bond, 3,4-vinyl bond, and 1,4-vinyl bond as the bond form of the conjugated diene compound. The vinyl bond amount referred to here is the conjugated diene compound at the time of polymerization. The ratio of the bonding form is shown. For example, the amount of 1,2-vinyl bond means the ratio of 1,2-vinyl bond in the above three bond forms and can be easily known by an infrared spectrophotometer, a nuclear magnetic resonance apparatus, or the like. I can do things.

  The block copolymer comprising a polymer block mainly composed of at least one aromatic vinyl compound and a polymer block mainly composed of at least one conjugated diene compound in the present invention is mainly composed of an aromatic vinyl compound. The polymer block [S] and the polymer block [B] mainly composed of a conjugated diene compound have a bonding form selected from the SB, SBS, and SSBSB types. It is preferable that it is a block copolymer. Among these, SBS type and SBS type are more preferable, and SBS type is most preferable. Of course, these may be a mixture.

  In the present invention, a hydrogenated block copolymer of an aromatic vinyl compound and a conjugated diene compound can also be used. The hydrogenated block copolymer means a product obtained by hydrogenating an aliphatic unsaturated double bond in the block copolymer of the above-described aromatic vinyl compound and conjugated diene compound. Before and after the hydrogenation reaction, the proportion of aliphatic unsaturated double bonds that are single-bonded is expressed as the hydrogenation rate. The hydrogenation rate can be known by a nuclear magnetic resonance apparatus or the like. A preferable hydrogenation rate of the hydrogenated block copolymer is 50% or more, more preferably 80% or more, and most preferably 95% or more.

In the present invention, the block copolymer of the aromatic vinyl compound and the conjugated diene compound (which is optionally hydrogenated) is preferably a block copolymer having a number average molecular weight of 100,000 or more. More preferably, it is a block copolymer of 150,000 or more.
The number average molecular weight as used in the field of this invention means the number average molecular weight measured with the ultraviolet spectroscopic detector using the gel permeation chromatography measuring apparatus, and converted with standard polystyrene. At this time, a low molecular weight component resulting from catalyst deactivation during polymerization may be detected. In this case, the low molecular weight component is not included in the calculation of the molecular weight. Usually, the molecular weight distribution thus calculated (weight average molecular weight / number average molecular weight) is in the range of 1.0 to 1.1.

  In the present invention, the number average molecular weight of one polymer block mainly composed of an aromatic vinyl compound is preferably 15,000 or more. More preferably, it is 30,000 or more. By setting the number average molecular weight of one polymer block mainly composed of an aromatic vinyl compound to 15,000 or more, variation in impact resistance (surface impact strength) of the resin composition can be suppressed.

The number average molecular weight of one polymer block mainly composed of an aromatic vinyl compound can be obtained by the following formula using the number average molecular weight of the block copolymer described above.
Mn (a) = {Mn × a / (a + b)} / N
[In the above formula, Mn (a) is the number average molecular weight of one polymer block mainly composed of an aromatic vinyl compound, and Mn is at least one polymer block composed mainly of at least one aromatic vinyl compound. The number average molecular weight of a block copolymer comprising a polymer block mainly composed of a conjugated diene compound, a is a mass% of a polymer block mainly composed of all aromatic vinyl compounds in the block copolymer, b is The mass% of the polymer block mainly composed of all conjugated diene compounds in the block copolymer, and N represents the number of polymer blocks mainly composed of the aromatic vinyl compound in the block copolymer. ]

  These block copolymers that can be used in the present invention are those having different bond types, different aromatic vinyl compound types, different conjugated diene compound types, and so on, unless contrary to the spirit of the present invention. , 2-bond vinyl content or 1,2-bond vinyl content and 3,4-bond vinyl content different, aromatic vinyl compound component content different, hydrogenation rate different, etc. You may mix and use 2 or more types.

In addition, these block copolymers used in the present invention may be block copolymers in which all or part of them are modified.
The modified block copolymer here means at least one carbon-carbon double bond or triple bond in the molecular structure, and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group or It refers to a block copolymer modified with at least one modifying compound having a glycidyl group.
The modified block copolymer can be produced by (1) melting and kneading with the modifying compound in the temperature range from the softening point temperature of the block copolymer to 250 ° C. in the presence or absence of a radical initiator. (2) a method of reacting the block copolymer and the modifying compound in a solution at a temperature below the softening point of the block copolymer, and (3) a temperature below the softening point of the block copolymer, Examples include a method of reacting the block copolymer and the modifying compound without melting them, and any of these methods may be used, but the method (1) is preferable, and among the methods (1), in the presence of a radical initiator. The method of performing is most preferred.

At least one modified compound having at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group or glycidyl group in the molecular structure referred to herein. Can be the same as the modified compound described for the modified polyphenylene ether.
The preferable amount of the (E) impact modifier in the present invention is 5 to 25 parts by mass when the total amount of polyamide and polyphenylene ether is 100 parts by mass. More preferably, it is 7-15 mass parts.

  The inorganic filler of the component (F) of the present invention is glass fiber, potassium titanate fiber, gypsum fiber, brass fiber, stainless steel fiber, steel fiber, ceramic fiber, boron whisker fiber, mica, talc, silica, calcium carbonate, Examples thereof include fiber-like, granular, plate-like, or needle-like inorganic reinforcing materials such as kaolin, calcined kaolin, wollastonite, zonotlite, apatite, glass beads, glass flakes, titanium oxide, and carbon black for coloring. Two or more of these inorganic fillers may be used in combination. Among these, more preferable inorganic fillers include talc, wollastonite, and glass fiber. In addition, the inorganic filler may be a surface treated by a known method using a surface treating agent such as a silane coupling agent.

A preferable amount of the inorganic filler in the present invention is 1 to 70% by mass when the mass of all the resin compositions including the inorganic filler is 100% by mass. A more preferred amount is 5 to 50% by mass, and most preferred is 10 to 45% by mass.
In the present invention, it is more preferable to add a compatibilizing agent in order to improve the compatibility between the polyamide and the polyphenylene ether. The main purpose of using the compatibilizer is to improve the physical properties of the polyamide-polyphenylene ether mixture.
The compatibilizing agent that can be used in the present invention refers to a polyfunctional compound that interacts with polyphenylene ether, polyamide, or both. This interaction may be chemical (eg, grafting) or physical (eg, changing the surface properties of the dispersed phase). In any case, the resulting polyamide-polyphenylene ether mixture exhibits improved compatibility.

Examples of compatibilizers that can be used in the present invention are described in detail in JP-A-8-48869 and JP-A-9-124926, and all of these known compatibilizers can be used. It can be used in combination.
Among these various compatibilizers, examples of particularly suitable compatibilizers include one or more selected from citric acid, maleic acid, itaconic acid, and anhydrides thereof. Of these, maleic anhydride and citric acid are most preferred.
The preferable amount of the compatibilizing agent in the present invention is 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.1 to 100 parts by mass of the mixture of polyamide and polyphenylene ether. -5 parts by mass.

Furthermore, various conductive fillers can be used in the resin composition of the present invention. Examples thereof include conductive carbon black, carbon nanotubes (carbon fibrils), graphite, and carbon fibers. These may be used in a mixture of two or more. Of these, carbon black for electrical conduction and carbon nanotubes (carbon fibrils) can be preferably used.
The amount of the conductive filler used is in the range of 0.5 to 40 parts by mass when the total of (A) polyamide and (B) polyphenylene ether is 100 parts by mass. Preferably it is 1-20 mass parts, More preferably, it is 1-10 mass parts. Most preferably, it is 1-6 mass parts.

  In the present invention, the method for adding the conductive filler is not particularly limited, but a preferable method includes a method in which the conductive filler is added in the form of a conductive masterbatch obtained by melt-kneading in polyamide in advance. At this time, the preferable amount of the conductive filler in the master batch is generally 5 to 30% by mass (when the conductive master batch is 100% by mass). When conductive carbon black is used as the conductive filler, 5 to 15% by mass is more preferable, and 8 to 12% by mass is most preferable. When a conductive filler other than conductive carbon black containing carbon nanotubes (carbon fibrils), graphite, and carbon fibers is used as the conductive filler, it is preferably 10 to 30% by mass, and most preferably 15 to 25% by mass.

As a manufacturing method of the conductive master batch, a method of manufacturing using a twin screw extruder is preferable. In particular, a method in which a conductive filler is added to molten polyamide and further melt-kneaded is preferable.
An example of a method for producing a conductive masterbatch is not particularly limited. (1) A method in which a polyamide and a conductive filler are mixed without melting and then melt-kneaded at a temperature at which the resin temperature is equal to or higher than the melting point of the polyamide. (2) A method in which a conductive filler is added to melted polyamide and melt-kneaded, (3) a mixture is prepared without melting the polyamide and conductive filler, and the mixture is supplied into the melted polyamide, Examples thereof include a melt kneading method, and (4) a method in which a conductive filler is supplied into melted polyamide and melt kneaded, and then polyamide is further supplied and melt kneaded.

  Among these, the most preferable embodiment is (3) a method in which a mixture is prepared in advance without melting the polyamide and the conductive filler, the mixture is supplied into the melted polyamide, and melt kneaded. By adopting this preferred production method, it is possible to greatly reduce the resin temperature during the production of the conductive masterbatch, which is very effective in suppressing mold deposits after the conductive resin composition is obtained.

The manufacturing method described above will be described with specific examples.
(1) Using a twin-screw extruder having one supply port in the upstream part, a mixture in which polyamide and conductive filler are mixed is supplied from the upstream part supply port, and melt kneaded at a temperature equal to or higher than the melting point of the polyamide. Method.
(2) Using a twin screw extruder having one supply port in the upstream portion and one supply port in the downstream portion, after supplying the polyamide from the upstream supply port and melt-kneading at a temperature equal to or higher than the melting point of the polyamide, Manufacturing method in which conductive filler is added from downstream supply port and further melt-kneaded (3) Upstream supply port using a twin screw extruder having one upstream port and one downstream supply port A part of the polyamide is supplied, melted and kneaded at a temperature equal to or higher than the melting point of the polyamide, and then mixed with the remaining polyamide and the conductive filler without melting from the downstream supply port, and further melt-kneaded. Method (4) Using a twin-screw extruder having one supply port in the upstream portion, one in the midstream portion, and one in the downstream portion, the polyamide is supplied from the upstream supply port, and the melting point of the polyamide is exceeded. After melt-kneading at temperature, Flow unit and further melt-kneaded with the addition of conductive filler than the supply port, a particularly preferred embodiment among these methods of further melt-kneading with addition of the polyamide downstream portion feed port is a process for the preparation of (3).

Moreover, there is no restriction | limiting in particular as a cylinder preset temperature of the processing machine at the time of manufacturing these master batches, but if it is the temperature more than melting | fusing point of a semi-aromatic polyamide as mentioned above, as a preferable range, it is 290-350. The temperature is preferably in the range of ° C. More preferably, it is the range of 300-330 degreeC.
Moreover, the resin composition of the present invention may further contain a flame retardant other than the component (C). As the flame retardant in this case, an inorganic or organic flame retardant containing substantially no halogen is more preferable.
In the present invention, “substantially free of halogen” means that the concentration of chlorine / iodine in the flame retardant is less than 2% by mass. More preferably, it is less than 1 mass%, More preferably, it is less than 0.5 mass%.

Examples of flame retardants that can be used include known inorganic flame retardants represented by magnesium hydroxide, aluminum hydroxide, and the like, triphenyl phosphate, triphenyl phosphate, bisphenol A bis (diphenyl phosphate), and the like. Phosphoric acid nitrogen compounds represented by organic phosphate esters, ammonium polyphosphate, etc., phosphazene compounds such as those described in JP-A No. 11-181429, silicone oils, red phosphorus and other publicly known compounds Flame retardants.
Moreover, in this invention, the fluorine-type polymer represented by the tetrafluoroethylene etc. which are known as a dripping prevention agent can also be used if it is the quantity below 2 mass% in a resin composition.

In the present invention, in addition to the above-described components, other additive components may be added at any stage as necessary within a range not impairing the effects of the present invention.
Examples of additive components include other thermoplastic resins such as polyesters and polyolefins, plasticizers (low molecular weight polyolefins, polyethylene glycols, fatty acid esters, etc.), antistatic agents, nucleating agents, fluidity improvers, fillers , Reinforcing agents, various peroxides, spreading agents, copper heat stabilizers, organic heat stabilizers typified by hindered phenolic antioxidants, antioxidants, UV absorbers, light stabilizers, etc. is there.
The specific preferable addition amount of these components is 10 mass% or less in a resin composition, respectively. A more preferred amount is less than 5% by weight, and most preferred is 3% by weight or less.

  Specific processing machines for obtaining the composition of the present invention include, for example, a single screw extruder, a twin screw extruder, a roll, a kneader, a Brabender plastograph, a Banbury mixer, etc. A twin-screw extruder provided with an upstream supply port and one or more downstream supply ports is most preferable.

An example of a production method using at least (A) polyamide, (B) polyphenylene ether, and (C) phosphinic acid salts is as follows.
(1) Using a twin-screw extruder having one supply port on the upstream side and one on the downstream side, supply polyphenylene ether and, if necessary, appearance improving material, impact improving material, and compatibilizing agent from the upstream supply port. A method of melt-kneading, adding a polyamide, phosphinates and, if necessary, an inorganic filler, a conductive filler, and other additives from a downstream supply port, and further melt-kneading.
(2) Using a twin-screw extruder with one supply port on the upstream side and one on the downstream side, polyphenylene ether and phosphinates from the upstream supply port and, if necessary, appearance improving material, impact improving material, compatibilization A method in which an agent is supplied, melted and kneaded, polyamide and, if necessary, an inorganic filler and conductive filler are supplied from a downstream supply port, and further melted and kneaded.

(3) Using a twin screw extruder having one supply port on the upstream side and two supply ports on the downstream side, polyphenylene ether and, if necessary, an appearance improver, impact modifier, and compatibilizer from the upstream supply port. Supply and melt knead, supply polyamide from the downstream first supply port (downstream supply port located upstream), melt knead, phosphinates from the downstream second supply port, if necessary inorganic filler, Examples thereof include a method of supplying a conductive filler and further melt-kneading.
(4) A masterbatch (polyamide, polyphenylene ether, impact modifier) containing at least polyphenylene ether and an appearance improver from the upstream supply port using a twin screw extruder having one supply port on each of the upstream side and the downstream side. Master batch consisting of one or more selected from the above and an appearance improver) If necessary, supply impact modifiers, compatibilizers, etc., melt and knead, and polyamide, phosphinates, and inorganic fillers as needed from the downstream supply port A method of supplying a material and a conductive filler and further melt-kneading.
(5) A master batch (polyamide, polyphenylene ether, impact containing at least polyphenylene ether and appearance modifier from the upstream supply port using a twin-screw extruder having one supply port on the upstream side and two supply ports on the downstream side. Master batch consisting of one or more types selected from improvement materials and appearance improvement agent), if necessary, supply impact improvement material, compatibilizer, melt knead, downstream first supply port (downstream side located upstream) A method of supplying polyamide from the supply port) and melt-kneading, supplying phosphinates and, if necessary, inorganic fillers and conductive fillers from the downstream second supply port, and further melt-kneading In the above, (3) The methods (4) and (5) are preferred.

The melt kneading temperature for obtaining the resin composition of the present invention is not particularly limited, but the conditions under which a suitable composition can be obtained are usually selected from 240 to 360 ° C. in consideration of the kneading state and the like. I can do things.
150-800 rpm is preferable and, as for the rotation speed of the extruder at the time of a process, 250-700 rpm is more preferable. In order to enhance the dispersibility of phosphinates, the rotational speed is preferably 150 rpm or higher, and in order to suppress the decomposition of the resin, it is desirable to set it to 800 rpm or lower.
The composition of the present invention thus obtained can be used as a molded body for various parts by various conventionally known methods such as injection molding.

As the resin composition of the present invention, a composition having an average combustion time of 25 seconds or less measured by vertical flame contact according to UL94 in a 1.6 mm thickness test piece can be suitably used for various applications. More preferably, according to the same measurement method, it has flame retardancy without causing cotton ignition by dripping, and most preferably the average burning time is 5 seconds or less.
The resin composition of the present invention can be suitably used particularly for electric and electronic parts and automobile electric and electronic parts. In particular, it can be suitably used for relay block materials, which are one of electric and electronic parts for automobiles, and SMT compatible parts in the electric / electronic field.

EXAMPLES Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to this Example.
The raw materials and measurement methods used in Examples and Comparative Examples are shown below.

[raw materials]
(A) Polyamide (A-1) Polyamide 9T (hereinafter abbreviated as PA9T-a)
Referring to the methods described in Examples of JP-A-2000-204239, 3256.2 g (19.6 mol) of terephthalic acid, 2690.9 g (17.0 mol) of 1,9-nonanediamine, 2-methyl-1 , 8-octanediamine 474.9 g (3.0 mol), benzoic acid 97.7 g (0.8 mol), sodium hypophosphite monohydrate 6.5 g (in total of the above four raw materials of polyamide) 0.1 mass%) and 6 liters of distilled water were placed in an autoclave having an internal volume of 20 liters, and the interior was replaced with nitrogen. After stirring at 100 ° C. for 30 minutes, the internal temperature was raised to 310 ° C. over 2 hours. At this time, the autoclave was pressurized to 22 kg / cm ² . After maintaining this state for 1 hour, the temperature was raised to 330 ° C., and then the temperature was maintained at 330 ° C. for 2 hours. Water vapor was gradually removed, and the reaction was carried out while maintaining the pressure at 22 kg / cm ² . Next, the pressure was reduced to 10 kg / cm ² over 30 minutes and the reaction was further continued for 1 hour to obtain a prepolymer having an intrinsic viscosity [η] of 0.30 dl / g. This prepolymer was dried under reduced pressure at a temperature of 100 ° C. for 12 hours and pulverized to a size of 2 mm or less. This was subjected to solid phase polymerization for 10 hours under the conditions of a temperature of 230 ° C. and a pressure of 0.1 mmHg to obtain a polyamide granular polymer. The obtained granular polymer was pelletized using a twin-screw extruder set at a cylinder temperature of 330 ° C., and this was designated as PA9T-a. When the obtained PA9T-a was analyzed, the melting point was 308 ° C., the viscosity number (measured in 96% sulfuric acid defined by ISO 307: 1997) was 100 ml / g, and the terminal amino group concentration was 40 μmol / g.
The melting point was measured with a differential scanning calorimeter (Piris-1: manufactured by Perkin Elmer), and the end capping rate and the end group concentration were the end capping described in the examples of JP-A-7-22889. It measured according to the measuring method of a stoppage rate.

(A-2) Polyamide 9T (hereinafter abbreviated as PA9T-b)
Polymerization was carried out in the same manner as in (1-1) except that terephthalic acid was changed to 3272.8 g (19.7 mol) as the dicarboxylic acid component and benzoic acid was changed to 73.26 g (0.6 mol) as the end-capping agent. To obtain a granular polymer of polyamide. The obtained granular polymer was processed into a pellet by using a twin screw extruder set at a cylinder temperature of 330 ° C., and this was designated as PA9T-b. The obtained PA9T-b was analyzed in the same manner as in (1-1). Melting point: 308 ° C., viscosity number (measured in 96% sulfuric acid specified by ISO307: 1997) 140 ml / g, terminal amino group concentration: It was 10 μmol / g.

(A-3) Polyamide 9T (hereinafter abbreviated as PA9T-c)
Polymerization was carried out in the same manner as in (1-1), except that 3222.9 g (19.4 mol) of terephthalic acid was used as the dicarboxylic acid component and 146.55 g (1.2 mol) of benzoic acid was used as the end-capping agent. To obtain a granular polymer of polyamide. The obtained granular polymer was processed into a pellet by using a twin screw extruder set at a cylinder temperature of 330 ° C., and this was designated as PA9T-c. The obtained PA9T-b was analyzed in the same manner as (1-1). Melting point: 308 ° C., viscosity number (measured in 96% sulfuric acid defined by ISO307: 1997) 60 ml / g, terminal amino group concentration: It was 50 μmol / g.

(A-4) Polyamide 9T (hereinafter abbreviated as PA9T-d)
Polymerization was carried out in the same manner as in (1-1) except that 109.9 g (0.9 mol) of benzoic acid was used as the terminal blocking agent, to obtain a granular polymer of polyamide. The obtained granular polymer part was processed into a pellet by using a twin screw extruder set at a cylinder temperature of 330 ° C., and this was designated as PA9T-c. The obtained PA9T-b was analyzed in the same manner as in (1-1). Melting point: 308 ° C., viscosity number (measured in 96% sulfuric acid defined by ISO307: 1997) 70 ml / g, terminal amino group concentration: It was 40 μmol / g.

(A-5) Polyamide 9T (hereinafter abbreviated as PA9T-e)
Polymerization was carried out in the same manner as in (1-1) except that the terminal blocking agent was changed to 42.7 g (0.35 mol) of benzoic acid to obtain a polyamide granular polymer. The obtained granular polymer was processed into a pellet by using a twin screw extruder set at a cylinder temperature of 330 ° C., and this was designated as PA9T-c. The obtained PA9T-b was analyzed in the same manner as in (1-1). Melting point: 309 ° C., viscosity number (measured in 96% sulfuric acid defined by ISO307: 1997) 160 ml / g, terminal amino group concentration: It was 25 μmol / g.

(A-6) Polyamide 66 (hereinafter abbreviated as PA66-a)
2400 g of equimolar salt of adipic acid and hexamethylenediamine, 100 g of adipic acid, and 2.5 liters of pure water were charged into a 5 liter autoclave and stirred well. After the atmosphere in the autoclave was sufficiently replaced with nitrogen, the temperature was raised from room temperature to 220 ° C. over about 1 hour with stirring. At this time, the gauge pressure in the autoclave was 1.76 MPa as a natural pressure by water vapor. Subsequently, the pressure was reduced by heating and valve opening / closing over about 30 minutes until the internal temperature reached 260 ° C. and the internal pressure reached 0.2 MPa. Then, it cooled rapidly to room temperature over about 1 hour. After cooling, the autoclave was opened, and about 2 kg of polymer was taken out and pulverized. The polyamide obtained had a viscosity number (measured in 96% sulfuric acid as defined in ISO 307: 1997) of 40 ml / g.

(A-7) Polyamide 66 (hereinafter abbreviated as PA66-b)
2400 g of equimolar salt of adipic acid and hexamethylenediamine, 100 g of adipic acid, and 2.5 liters of pure water were charged into a 5 liter autoclave and stirred well. After the atmosphere in the autoclave was sufficiently replaced with nitrogen, the temperature was raised from room temperature to 220 ° C. over about 1 hour with stirring. At this time, the gauge pressure in the autoclave was 1.76 MPa as a natural pressure by water vapor. Subsequently, heating was continued while removing water from the reaction system so that the pressure was not higher than 1.76 MPa. When the internal temperature reached 260 ° C. after 2 hours, the pressure was reduced until the internal pressure became 0.2 MPa over about 40 minutes by opening and closing the valve of the autoclave while continuing the heating. Then, it cooled to room temperature over about 8 hours. After cooling, the autoclave was opened, and about 2 kg of polymer was taken out and pulverized. The resulting polyamide had a viscosity number (measured in 96% sulfuric acid as defined in ISO 307: 1997) of 110 ml / g.

(A-8) Polyamide 66 (hereinafter abbreviated as PA66-c)
The ground polymer obtained by PA66-a was subjected to solid phase polymerization for 2 hours under the conditions of a temperature of 200 ° C. and a pressure of 0.1 mmHg, and the resulting viscosity number (measured in 96% sulfuric acid specified by ISO 307: 1997). ) 140 ml / g of polyamide 6,6 was produced.
(A-9) Polyamide 66 (hereinafter abbreviated as PA66-d)
The ground polymer obtained with PA66-a was subjected to solid state polymerization for 10 hours under the conditions of a temperature of 200 ° C. and a pressure of 0.1 mmHg, and the resulting viscosity number (measured in 96% sulfuric acid as defined by ISO 307: 1997). ) 260 ml / g of polyamide 6,6 was produced.

(B) Polyphenylene ether (hereinafter referred to as PPE)
Reduced viscosity: 0.52 dl / g (0.5 g / dl, chloroform solution, measured at 30 ° C.) poly (2,6-dimethyl-1,4-phenylene ether) was used.
(C) Phosphinates Aluminum diethylphosphinate (hereinafter abbreviated as DEP) was produced with reference to the production methods described in Examples of JP-A-2005-179362.
DEP masses were wet-ground in water and classified to obtain DEP having the following average particle size.
(DEP-a) Aluminum diethylphosphinate Average particle size = 3.1 μm
(DEP-b) Aluminum diethylphosphinate Average particle size = 38 μm
(DEP-c) Aluminum diethylphosphinate Average particle size = 45 μm
(D) Appearance improver (hereinafter referred to as PW)
Paraffinic oil [trade name: Diana Process Oil PW380, manufactured by Idemitsu Kosan Co., Ltd.] was used.

(E) Impact modifier (hereinafter referred to as SEBS)
A copolymer composed of each block of polystyrene-hydrogenated polybutadiene-polystyrene having the following physical properties was used.
Number average molecular weight = 246,000
Number average molecular weight per polystyrene block = 40,600
Styrene component total content = 33% by mass
1,2-vinyl bond amount = 33% by mass
Hydrogenation rate of polybutadiene part = 98% or more The number average molecular weight of the block copolymer is determined by using a gel permeation chromatography measuring device (hereinafter simply referred to as GPC) [GPC SYSTEM21: Showa Denko Co., Ltd.] It measured with the ultraviolet spectroscopic detector [UV-41: Showa Denko Co., Ltd.], and converted and calculated by standard polystyrene.
[Solvent: Chloroform, Temperature: 40 ° C., Column: Sample side (KG, K-800RL, K-800R), Reference side (K-805L × 2), Flow rate 10 ml / min, Measurement wavelength: 254 nm, Pressure 15-17 kg / cm < ² >]

(F) Inorganic filler (hereinafter referred to as GF)
Chopped strand glass fiber [trade name: CS03MA FT2A manufactured by Asahi Fiber Glass Co., Ltd.] was used.
[Compatibilizer] (hereinafter MAH)
Maleic anhydride (trade name: Crystal MAN, manufactured by NOF Corporation) was used.
[Nitrogen-containing flame retardant containing an adduct formed from melamine and phosphoric acid]
Melamine polyphosphate (hereinafter referred to as MPP) (trade name: Melapur 200/70, manufactured by Ciba Specialty Chemicals Co., Ltd.) was used.
[Zinc-containing compound] (hereinafter ZNB)
Zinc _{borate: 2ZnO · 3B 2 O 3 ·} 3.5H 2 O ( trade name: Firebrake ZB U.S. Borax Co., Ltd.) was used.

[Adjustment of phosphinates masterbatch]
Two shafts that have one supply port on the upstream side and one supply port on the downstream side (when the total length of the extruder cylinder is 1.0, one point at the 0.4 position: hereinafter referred to as the central supply port) The cylinder temperature of the extruder [ZSK-26MC: manufactured by Coperion (Germany)] was set to 280 ° C. PA66-c was supplied in an amount of 12 kg / h from the upstream supply port, DEP-a was supplied in an amount of 12 kg / h from the central supply port, and melt kneaded to obtain pellets. The screw rotation speed at this time was 400 rpm. Moreover, it was 298 degreeC when the molten resin temperature was measured. In order to adjust the moisture content of the obtained pellets, after extrusion, the pellets were dried in a dehumidifying dryer set at 80 ° C., and then put in an aluminum-coated moisture-proof bag. The moisture content of the pellets at this time was approximately 800 ppm. The master batch obtained at this time is abbreviated as DEP-MB.

[Preparation of appearance improver master batch]
The PW and SEBS were mixed at a ratio of 55 parts by mass and 100 parts by mass, and PBS was impregnated into SEBS. Subsequently, it was placed in an oven at 50 ° C. for 30 minutes to promote and equilibrate the impregnation of PW into SEBS to obtain an appearance improving agent master batch. Hereinafter, it is abbreviated as PW-SEBS.

[Measuring method]
(1) Flame retardancy (UL-94VB)
Using the method of UL94 (standard defined by Under Writers Laboratories Inc., USA), five samples were measured per sample. In addition, the test piece (length 127mm, width 12.7mm, thickness 1.6mm) was shape | molded using the injection molding machine (Toshiba machine Co., Ltd. product: IS-80EPN). The molding conditions were such that when polyamide 9T was used, the cylinder temperature was 320 ° C. and the mold temperature was 130 ° C., and when polyamide 66 was used, the cylinder temperature was 290 ° C. and the mold temperature was 80 ° C.

In the flame retardancy class, the flame retardance class classified by UL94 vertical flame test is shown. However, all the samples were judged by performing five tests.
The outline of the classification method is as follows. Other details conform to the UL94 standard.
V-0: Average combustion time 5 seconds or less Maximum combustion time 10 seconds or less No cotton ignition V-1: Average combustion time 25 seconds or less Maximum combustion time 30 seconds or less No cotton ignition V-2: Average combustion time 25 seconds or less Maximum combustion Time 30 seconds or less With cotton ignition Non-standard: Samples that do not correspond to the above three items and samples that have burned up to the clamp holding the test piece The average burning time (seconds) is 10 seconds for each sample twice, that is, a total of 10 It is the average burning time of the extinguishing time after the flame contact, and the maximum burning time (seconds) represents the burning time of the sample in which the combustion continued for the longest time among the flame extinguishing times after a total of 10 flames.
In the table, each burning time of 10 times flame contact and the presence or absence of dripping are also described.

(2) Amount of gas generated during processing After the resin was retained in the molding machine, the amount of silver streak generated by molding was evaluated. Specifically, when molding a test piece for UL94VB, the molding machine motor is stopped with the resin weighed (the cylinder heater remains on), the resin is retained in the cylinder for about 10 minutes, and then a flat plate test. A piece (length 150 mm, width 150 mm, thickness 2.5 mm) was molded. After resuming molding, the second shot test piece was collected, and the occurrence of silver streaks, which were traces of gas running on the molded piece, was used as the following index.
4 points: Some silver streaks occurred only in the runner part.
3 points: Silver streaks occurred in about 1/4 of the molded piece.
2 points: Silver streaks occurred in about half of the molded piece.
1 point: Silver streaks occurred over the entire surface of the molded piece.

(3) Surface appearance and mold deposit The resin composition pellets were molded with an injection molding machine (Toshiba Machine Co., Ltd .: IS-80EPN). When polyamide 9T is used, the molding conditions are set at a cylinder temperature of 320 ° C. and a mold temperature of 130 ° C., and when polyamide 66 is used, the cylinder temperature is set to 290 ° C. and the mold temperature is 80 ° C., and the injection time is 20 seconds. A flat plate test piece of 50 × 90 × 2.5 mm was formed at a cooling time of 30 seconds. The surface appearance of the test pieces from the 10th shot to the 20th shot was visually observed, and the surface appearance was evaluated according to the following criteria.
Further, the above-described molding was continued, and the number of shots until the mold deposit adhered to the mold was generated. The larger the number of mold deposit generation shots, the better the performance.
Surface appearance evaluation ○: No roughness or flow mark on the test piece table Δ: Roughness or flow mark occurred in an area of 30% or less of the test piece surface.
X: Roughness and flow marks occurred in an area of 30% or more on the surface of the test piece.

(4) Thin-wall moldability Resin composition pellets were molded using a test piece mold (length 127 mm, width 12.7 mm) in which the thickness of the test piece was 0.4 mm. The molding conditions are set at a cylinder temperature of 320 ° C. and a mold temperature of 130 ° C. when polyamide 9 and T are used, and a cylinder temperature of 290 ° C. and a mold temperature of 80 ° C. when polyamide 6 and 6 are used. The minimum injection pressure (hereinafter abbreviated as SSP) necessary for the inner filling was measured. (Unit: MPa (gauge pressure))
The smaller the required minimum injection pressure, the better the thin moldability.

(5) Deflection temperature under load and Izod impact strength Using the injection molding machine (Toshiba Machine Co., Ltd. product: IS-80EPN), the cylinder temperature is set to 320 ° C and the mold temperature is set to 140 ° C. The test piece for deflection temperature under load was formed into a strip-shaped piece (length 128 mm, width 12.8 mm) having a thickness of 6.4 mm and an Izod impact strength test piece having a thickness of 3.2 mm. The deflection temperature under load (low load HDT) under a load of 0.45 MPa was measured in accordance with ASTM D648. The notched Izod impact test was measured under a temperature condition of 23 ° C. in accordance with ASTM D256.

(6) Dispersion state confirmation method of phosphinates The resin composition pellets were cut into a mirror-like cross section substantially perpendicular to the long side of the pellets using a microtome equipped with a glass knife. The cut surface was observed with reflected light at a magnification of 100 using an optical microscope (PME3: manufactured by Olympus Corporation), and a photograph was taken for an area of 3 mm ² . The number of dispersed phosphinate particles having a major axis of 30 μm or more was visually counted.

[Examples 1 to 13, 16 to 18 and Comparative Examples 2 to 4]
Two on the upstream side and two supply ports on the downstream side (one at the 0.4 position and one at the 0.8 position when the total length of the extruder cylinder is 1.0) A shaft extruder [ZSK-26MC: manufactured by Coperion (Germany)] is prepared, and the cylinder temperature is set to a supply port (hereinafter referred to as a central supply) at a position of L = 0.4 from an upstream supply port (hereinafter referred to as an upstream supply port). Up to 320 ° C., when using polyamide 9T on the downstream side from the central supply port, it was set at 310 ° C. and when using polyamide 66, it was set at 280 ° C.

According to the composition described in Tables 1 to 4, each raw material was supplied and melt-kneaded to obtain pellets. In order to adjust the moisture content of the obtained pellets, after extrusion, the pellets were dried in a dehumidifying dryer set at 80 ° C., and then put in an aluminum-coated moisture-proof bag. The moisture content of the pellets at this time was approximately 300 to 400 ppm.
At this time, the screw speed of the extruder was 350 rpm, and the discharge rate was 12 kg / h. Further, openings were provided in the block immediately before the cylinder block having the central supply port and the cylinder block immediately before the die, and the remaining volatile components and oligomers were removed by vacuum suction. The degree of vacuum (absolute pressure) at this time was 60 Torr.

Each evaluation mentioned above was performed using the obtained pellet. The results are shown in Table 1.
Regarding Example 1 and Example 3, when the number of particles of phosphinic acid salts having a major axis of 30 μm or more existing in the observation range in 3 mm ² was confirmed using pellets of the resin composition, 5 in Example 1 were confirmed. In Example 3, there were two.

[Comparative Example 1]
Each raw material was supplied according to the composition described in Table 1 under the same conditions as in Example 1. Since the melt viscosity of the resin discharged from the die was too low, the strand could not be guided to the pellet cutter, and extrusion granulation could not be performed.

[Comparative Example 2]
Under the same conditions as in Example 1, according to the composition described in Table 1, melt-kneading was performed to obtain pellets. Although molding was performed with the obtained pellets, filling of the resin into the mold was not completed.

[Example 14]
Under the same conditions as in Example 1, according to the composition shown in Table 3, melt-kneading was performed to obtain pellets. Molding was performed with the obtained pellets, but filling of the resin into the mold could not be completed under the condition of a cylinder temperature of 320 ° C. Then, when the cylinder temperature was raised to 330 ° C. and the molding was performed again, it could be filled. The test piece was evaluated as described above.

[Example 15]
Under the same conditions as in Example 1, according to the composition shown in Table 3, melt-kneading was performed to obtain pellets. Molding was performed with the obtained pellets, but resin filling could not be completed under the condition of a cylinder temperature of 320 ° C. Then, when the cylinder temperature was raised to 330 ° C. and the molding was performed again, it could be filled. The test piece was evaluated as described above.

[Example 19]
Under the same conditions as in Example 1, according to the composition shown in Table 4, the mixture was melt-kneaded to obtain pellets. Molding was attempted with the obtained pellets, but resin filling could not be completed under the condition of a cylinder temperature of 320 ° C. Then, when the cylinder temperature was raised to 330 ° C. and the molding was performed again, it could be filled. The test piece was evaluated as described above.

When the viscosity number of the polyamide is outside the specified range as in Comparative Example 1 and Comparative Example 2, it is understood that extrusion granulation and molding processing, particularly thin-wall molding processing is difficult.
When Examples 1-7 are compared with Comparative Examples 2 and 3, the resin composition of the present invention is excellent in all of the properties of flame retardancy, gas generation amount, surface appearance, mold deposit, and thin-wall formability. I understand.
Moreover, when Example 1 and Example 4 are compared, it turns out that a flame retardance and a mold deposit are more excellent.
The resin compositions of the present invention using PA9, T of Examples 8 to 15 and Examples 16 to 19 are any of flame retardancy, gas generation amount, surface appearance, mold deposit, thin-wall formability and impact resistance. It can be seen that the characteristics are also excellent.

  Further, when the deflection temperature under load (low load HDT) was measured for Examples 16 to 19, all examples had heat resistance of 280 ° C. or higher, and applied to SMT compatible parts using lead-free solder. I understand that I can do it.

  The present invention is excellent in flame retardancy and impact resistance, excellent moldability for thin-walled parts, and further suppresses the generation of gas during processing, and deposits on the mold during injection molding (mold deposit) The resin composition which has the outstanding characteristics that production | generation of can be suppressed significantly can be provided. Therefore, it can be suitably used particularly for electric / electronic parts and automobile parts. In particular, it can be suitably used as a relay block material for SMT-compatible parts in the electric / electronic field and electric parts for automobiles.

Claims (17)

(A) Polyamide (however, a dicarboxylic acid unit (a) containing 60 to 100 mol% of terephthalic acid, a 1,9-nonanediamine unit (b-1) and a 2-methyl-1,8-octanediamine unit (b -2) except for a semi-aromatic polyamide comprising diamine units (b) containing 60 to 100 mol%) (B) polyphenylene ether, (C) phosphinic acid salt represented by the following formula (I), II) a resin composition comprising at least one phosphinate selected from diphosphinates and condensates thereof, wherein (A) the viscosity number of the polyamide (ISO307: 1997) (Measured in 96% sulfuric acid specified in the above) is 50 ml / g to 250 ml / g.
[Wherein R ¹ and R ² are the same or different and are linear or branched C ₁ -C ₆ -alkyl and / or aryl or phenyl, and R ³ is linear or branched. C ₁ -C ₁₀ -alkylene, C ₆ -C ₁₀ -arylene, C ₆ -C ₁₀ -alkylarylene or C ₆ -C ₁₀ -arylalkylene, M is calcium (ion), magnesium (ion), aluminum ( Ion), zinc (ion), bismuth (ion), manganese (ion), sodium (ion), potassium (ion), and protonated nitrogen base, and m is 2 or 3 , N is 1 to 3, and x is 1 or 2. ]   The resin composition according to claim 1, wherein (A) the polyamide has a viscosity number (measured in 96% sulfuric acid defined by ISO 307: 1997) of 70 ml / g or more and 150 ml / g or less.   The resin composition according to claim 1, wherein (A) the polyamide has a viscosity number (measured in 96% sulfuric acid defined by ISO 307: 1997) of 100 ml / g or more and 150 ml / g or less.   (A) The terminal amino group density | concentration of a polyamide is 5 to 60 micromol / g, The resin composition of Claims 1-3 characterized by the above-mentioned.   (C) The resin composition of Claim 1 whose average particle diameters of a component are 0.5 micrometer or more and 40 micrometers or less.   (A) The amount ratio of polyamide and (B) polyphenylene ether is 40 to 70 parts by mass of (A) polyamide and 60 to 30 parts by mass of (B) polyphenylene ether when the total of both is 100 parts by mass. The resin composition according to claim 1.   2. The resin composition according to claim 1, wherein the amount of (C) phosphinate is 1 to 50 parts by mass with respect to 100 parts by mass in total of (A) polyamide and (B) polyphenylene ether.   The resin composition according to claim 1, further comprising at least one appearance improver selected from mineral oil and wax as component (D).   The resin composition according to claim 8, wherein the amount of the appearance improving agent of component (D) is 0.1 to 10 parts by mass with respect to 100 parts by mass in total of (A) polyamide and (B) polyphenylene ether. The resin composition according to claim 1, wherein the phosphinic acid salt as the component (C) contains 90% by mass or more of the phosphinic acid salt represented by the following formula (I).
[Wherein, R ¹ and R ² are the same or different and are linear or branched C ₁ -C ₆ -alkyl and / or aryl or phenyl, and M is calcium (ion), magnesium (ion) , Aluminum (ion), zinc (ion), bismuth (ion), manganese (ion), sodium (ion), potassium (ion) and protonated nitrogen base, and m is 2 or 3. ]   As a component (E), a block copolymer containing at least one block mainly composed of an aromatic vinyl compound and at least one block mainly composed of a conjugated diene compound and / or a hydrogenated product of the block copolymer The resin composition according to claim 1, further comprising an impact modifier comprising:   (F) The resin composition of Claim 1 which contains an inorganic filler as a component in the quantity of 1-70 mass%, when the mass of all the resin compositions containing an inorganic filler is 100 mass%. (A) Polyamide (however, a dicarboxylic acid unit (a) containing 60 to 100 mol% of terephthalic acid, a 1,9-nonanediamine unit (b-1) and a 2-methyl-1,8-octanediamine unit (b -2) except for semi-aromatic polyamides comprising diamine units (b) containing 60 to 100 mol%), (B) polyphenylene ether and (C) phosphinic acid salts represented by the following formula (I): A method for producing a resin composition comprising at least one phosphinic acid salt selected from diphosphinic acid salts represented by (II) and condensates thereof, wherein component (C) Is added to the molten mixture of the component (A) and the component (B).
[Wherein R ¹ and R ² are the same or different and are linear or branched C ₁ -C ₆ -alkyl and / or aryl or phenyl, and R ³ is linear or branched. C ₁ -C ₁₀ -alkylene, C ₆ -C ₁₀ -arylene, C ₆ -C ₁₀ -alkylarylene or C ₆ -C ₁₀ -arylalkylene, M is calcium (ion), magnesium (ion), aluminum ( Ion), zinc (ion), bismuth (ion), manganese (ion), sodium (ion), potassium (ion) and / or protonated nitrogen base, and m is 2 or 3, n is 1 to 3, and x is 1 or 2. ] (A) Polyamide (however, a dicarboxylic acid unit (a) containing 60 to 100 mol% of terephthalic acid, a 1,9-nonanediamine unit (b-1) and a 2-methyl-1,8-octanediamine unit (b -2) except for a semi-aromatic polyamide comprising diamine units (b) containing 60 to 100 mol%), (B) polyphenylene ether, (C) phosphinic acid salt represented by the following formula (I), A method for producing a resin composition comprising at least one phosphinate selected from diphosphinates represented by (II) and condensates thereof, and (D) an appearance improver, and (E) an impact modifier. Because
(1) (D) a step of mixing an appearance modifier with one or more selected from (A) polyamide, (B) polyphenylene ether and (E) impact modifier, and (2) the master A method for producing a resin composition comprising at least two steps of melting and kneading a batch with the remaining components.
[Wherein R ¹ and R ² are the same or different and are linear or branched C ₁ -C ₆ -alkyl and / or aryl or phenyl, and R ³ is linear or branched. C ₁ -C ₁₀ -alkylene, C ₆ -C ₁₀ -arylene, C ₆ -C ₁₀ -alkylarylene or C ₆ -C ₁₀ -arylalkylene, M is calcium (ion), magnesium (ion), aluminum ( Ion), zinc (ion), bismuth (ion), manganese (ion), sodium (ion), potassium (ion), and protonated nitrogen base, and m is 2 or 3 , N is 1 to 3, and x is 1 or 2. ]   The pellet obtained from a manufacturing method in any one of Claim 13 or 14.   The molded product obtained from the resin composition in any one of Claims 1-12.   The molded component corresponding to the surface mounting technique obtained from the resin composition in any one of Claims 1-12.