JP2011012206A - Resin composition and pellet mixture and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pellet mixture suppressing the deterioration of impact resistance while keeping high flame retardancy level even when an inorganic fiber such as glass fiber is contained, and a molding and a cellular phone housing using the same.SOLUTION: The pellet mixture contains a first pellet containing (A) polyphenylene ether, (B) polyamide, (C) a flame retardant containing no halogen and (D) an inorganic filler and a second pellet containing (B) polyamide and (E) one or more of inorganic fiber selected from a group comprising glass fiber, carbon fiber, metal fiber and ceramic fiber.

Description

  The present invention relates to a mixture of pellets, a molded body, and a mobile phone casing.

Conventionally, crystalline polyamides are widely used as clothing, industrial material fibers, or general-purpose engineering plastics because they are excellent in mechanical strength and chemical resistance and are easily melt-molded. However, since the crystalline polyamide is a crystalline resin, problems such as warpage and burrs are likely to occur in the molded product and the appearance is inferior, and the dimensional stability is inferior due to water absorption.
On the other hand, polyphenylene ether, which is an amorphous resin, has low specific gravity and low water absorption, and is excellent in dimensional stability, flame retardancy, impact resistance and electrical properties, but inferior in molding processability and chemical resistance. .

  In order to improve each of these drawbacks, Patent Document 1 proposes an alloy (polyamide / polyphenylene ether alloy) technique in which polyamide is mixed with polyphenylene ether. Since then, various improvements have been made to the alloy, and it is now a material used in various applications such as electrical and electronic parts and automobile parts. As disclosed in Patent Document 2, Patent Document 3 and Patent Document 4, fiber reinforced resin materials which are further improved in rigidity and impact resistance by adding various fibrous fillers such as glass fibers to these parts. Is often used.

  Also, in recent years, there is a tendency to demand a halogen-free material for all parts used in the electrical and electronic industry, and a polyamide / polyphenylene ether alloy which does not contain a halogen and has excellent flame retardancy has been proposed (for example, a patent Reference 5).

Japanese Patent Publication No. 45-997 Japanese Patent Laid-Open No. 63-101442 JP-A-7-207153 JP-A-9-124923 JP 2008-38149 A

  By the way, as a recent trend, with the reduction in size and weight of mobile devices such as mobile phones and automobiles, the thinning is rapidly progressing. For this reason, a material superior in impact resistance and rigidity is required more than ever, and a high flame retardant level has become an essential condition. However, in the conventional polyamide / polyphenylene ether alloy containing inorganic fibers such as glass fiber, there is a reciprocal relationship between rigidity and impact resistance and flame retardancy, and all required physical properties of rigidity, impact resistance and flame retardancy are present. A polyamide / polyphenylene ether alloy satisfying the above conditions has not been obtained.

  The present invention has been made in view of the above circumstances, and even if it contains inorganic fibers such as glass fibers, it suppresses a decrease in impact resistance while maintaining a high flame retardant level, and further has excellent rigidity. It is an object to provide a pellet mixture that can form a body, a molded body, and a mobile phone casing.

  The inventor has intensively studied to achieve the above object. As a result, a resin pellet containing a polyphenylene ether, polyamide, a halogen-free flame retardant and an inorganic filler, and a resin pellet containing an inorganic fiber such as glass fiber and polyamide, respectively, were prepared. Thus, the inventors have found that the above object can be achieved and completed the present invention.

That is, the present invention is as follows.
[1] First pellets containing (A) polyphenylene ether, (B) polyamide, (C) halogen-free flame retardant and (D) inorganic filler, (B) polyamide, (E) glass fiber, carbon A pellet mixture containing a second pellet containing one or more inorganic fibers selected from the group consisting of fibers, metal fibers, and ceramic fibers.
[2] 40 to 90% by mass of the first pellet and 10 to 60% by mass of the second pellet with respect to the total amount of the first pellet and the second pellet, [1] Pellet mixture.
[3] One or more inorganic fibers selected from the group consisting of (E) glass fiber, carbon fiber, metal fiber, and ceramic fiber with respect to the total amount of the first pellet and the second pellet. The pellet mixture of [1] or [2] containing 5 to 60% by mass.
[4] The first pellet is 40 to 70% by mass of the (A) polyphenylene ether with respect to the total amount of the (A) polyphenylene ether and the (B) polyamide contained in the first pellet. The pellet mixture according to any one of [1] to [3], comprising (B) 30 to 60% by mass of the polyamide.
[5] The first pellet contains 20 to 90% by mass of the flame retardant containing no (C) halogen, based on 100 parts by mass of the (B) polyamide contained in the first pellet. ] The pellet mixture of any one of [4].
[6] The first pellet includes (D) 2 to 50 parts by mass of an inorganic filler with respect to a total of 100 parts by mass of the resin components contained in the first pellet. Any one pellet mixture.
[7] The second pellet includes 10 to 90% by mass of one or more inorganic fibers selected from the group consisting of (E) glass fiber, carbon fiber, metal fiber, and ceramic fiber. 6] Any one pellet mixture.
[8] The pellet mixture according to any one of [1] to [7], wherein the first pellet and / or the second pellet further includes (F) an impact modifier.
[9] The pellet mixture according to [8], wherein the impact improving material (F) includes more than 0 parts by weight and 150 parts by weight with respect to 100 parts by weight of the (A) polyphenylene ether.
[10] The impact modifier (F) is a block copolymer having 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 The pellet mixture of [8] or [9], which is a hydrogenated product of the block copolymer.
[11] The pellet mixture according to any one of [1] to [10], wherein the polyamide (B) is a polyamide having an aromatic ring in a repeating structural unit of the main chain.
[12] The pellet mixture according to any one of [1] to [11], wherein the flame retardant containing no halogen (C) has a number average particle size of 0.1 to 100 μm.
[13] The pellet mixture according to any one of [1] to [11], wherein the flame retardant containing no halogen (C) has a number average particle size of 5 to 60 μm.
[14] The pellet mixture according to any one of [1] to [13], wherein the flame retardant containing no (C) halogen is a phosphinate.
[15] The Mohs hardness of the (D) inorganic filler is equal to or less than the Mohs hardness of one or more inorganic fibers selected from the group consisting of (E) glass fiber, carbon fiber, metal fiber, and ceramic fiber. ] The pellet mixture of any one of [14].
[16] The pellet mixture according to any one of [1] to [15], wherein the (D) inorganic filler is zinc oxide and / or zinc sulfide.
[17] The pellet mixture according to any one of [1] to [16], wherein the (D) inorganic filler has a number average particle size of 0.1 to 0.8 μm.
[18] One or more inorganic fibers selected from the group consisting of (E) glass fiber, carbon fiber, metal fiber, and ceramic fiber are glass fibers according to any one of [1] to [17]. Pellet mixture as described.
[19] The pellet mixture according to any one of [1] to [18], wherein the cut length of the second pellet is 2 to 15 mm.
[20] The pellet mixture according to any one of [1] to [18], wherein the cut length of the second pellet is 5 to 15 mm.
[21] A molded body of the pellet mixture of any one of [1] to [20].
[22] The molded article according to [21], comprising (E) one or more inorganic fibers selected from the group consisting of glass fibers, carbon fibers, metal fibers, and ceramic fibers, having a weight average fiber length of 500 to 5000 μm.
[23] The molded product according to [21], comprising (E) one or more inorganic fibers selected from the group consisting of glass fibers, carbon fibers, metal fibers, and ceramic fibers, having a weight average fiber length of 2500 to 4000 μm.
[24] A molded product obtained by injection molding the pellet mixture of any one of [1] to [20].
[25] A mobile phone case obtained by injection molding the pellet mixture of any one of [1] to [20].

  According to the present invention, a pellet mixture and molding capable of forming a molded article that suppresses a decrease in impact resistance while maintaining a high flame retardant level even when containing inorganic fibers such as glass fibers, and further has excellent rigidity. A body and a mobile phone housing can be provided.

It is the figure which plotted the relationship between the Charpy impact strength and average flame retardance concerning an Example and a comparative example.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. However, the present invention is not limited to the following embodiment, and various modifications can be made without departing from the gist thereof.

  The pellet mixture of the present embodiment includes (A) a polyphenylene ether, (B) polyamide, (C) a halogen-free flame retardant, and (D) a first pellet which is a resin composition containing an inorganic filler; A pellet mixture containing polyamide and (E) a second pellet which is a resin composition containing at least one inorganic fiber selected from the group consisting of glass fiber, carbon fiber, metal fiber and ceramic fiber. It can be obtained by mixing the first pellet and the second pellet. Here, the mixing may be a generally known dry mixing method or melt mixing.

  The present embodiment has a feature that the object of the present invention is achieved by separately producing the first and second pellets by melt-kneading or the like and using them as a pellet mixture to obtain a molded body. Therefore, even if each material contained in the first and second pellets is melt-kneaded in one extruder, the object of the present invention cannot be achieved.

  The first pellet according to this embodiment is 40 to 70% by mass of (A) polyphenylene ether with respect to the total amount of (A) polyphenylene ether and (B) polyamide contained in the first pellet, (B ) 30 to 60% by mass of polyamide. More preferably, the first pellet contains (A) 40 to 60% by mass of polyphenylene ether, (B) 40 to 60% by mass of polyamide, and more preferably (A) polyphenylene ether, based on the total amount. Of 50 to 60% by mass and (B) 40 to 50% by mass of polyamide.

  The first pellet according to the present embodiment preferably includes 20 to 90 parts by mass of (C) a halogen-free flame retardant with respect to 100 parts by mass of the polyamide (B) contained in the first pellet, and more preferably. 30 to 85 parts by mass, more preferably 45 to 80 parts by mass, particularly preferably 55 to 70 parts by mass. The first pellet preferably contains (C) 20 parts by mass or more of a flame retardant that does not contain halogen in order to develop more sufficient flame retardancy in the molded body, and (C) in order to develop sufficient mechanical properties. It is preferable to contain 90 parts by mass or less of a flame retardant containing no halogen.

  The first pellet according to the present embodiment is preferably 2 to 50 parts by mass of (D) inorganic filler, more preferably 5 to 30 parts per 100 parts by mass of the total amount of resin components contained in the first pellet. Part by mass, more preferably 8-25 parts by mass. The first pellet preferably contains (D) 2 parts by mass or more of an inorganic filler in order to make the molded body exhibit sufficient flame retardancy and impact resistance, and suppresses an increase in melt viscosity during extrusion. (D) It is preferable that the inorganic filler is contained in an amount of 50 parts by mass or less.

  The content of one or more inorganic fibers selected from the group consisting of (E) glass fiber, carbon fiber, metal fiber and ceramic fiber contained in the second pellet according to this embodiment is the total amount of the second pellet. It is preferable that it is 10-90 mass% with respect to. In order to develop good mechanical strength, the more preferable lower limit of the content is 20% by mass, more preferably 35% by mass, and particularly preferably 45% by mass. Further, from the viewpoint of productivity, the upper limit is more preferably 80% by mass, still more preferably 70% by mass, and particularly preferably 65% by mass.

  Moreover, the 1st and / or 2nd pellet may contain the (F) impact improving material in order to further improve the impact resistance of a molded object. The preferred content of the (F) impact modifier contained in the first pellet and / or the second pellet is more than 0 parts by weight and not more than 150 parts by weight with respect to 100 parts by weight of (A) polyphenylene ether, and more. Preferably it exceeds 0 mass part and is 100 mass parts or less, More preferably, it exceeds 0 mass part and is 80 mass parts or less.

  The pellet mixture of the present embodiment preferably includes 40 to 90% by mass of the first pellet and 10 to 60% by mass of the second pellet with respect to the total amount of the first pellet and the second pellet. More preferably, the first pellet is contained in an amount of 60 to 80% by mass, and the second pellet is contained in an amount of 20 to 40% by mass. Thereby, the objective effect by this invention can be show | played more effectively and reliably.

  The content of one or more inorganic fibers selected from the group consisting of (E) glass fiber, carbon fiber, metal fiber, and ceramic fiber contained in the pellet mixture of the present embodiment is the total amount of the first and second pellets. It is preferable in it being 5-50 mass% with respect to this, More preferably, it is 5-30 mass%, More preferably, it is 10-20 mass%. (E) When the content in the mixed pellet of one or more inorganic fibers selected from the group consisting of glass fiber, carbon fiber, metal fiber and ceramic fiber is 5% by mass or more, the mechanical strength and resistance of the molded body The impact property can be maintained at a high level, and when it is 50% by mass or less, the moldability and the appearance of the molded product are improved.

ここで、式中、各Ｒは、それぞれ独立に、水素原子、ハロゲン原子、第１級若しくは第２級の炭素数１〜７のアルキル基、フェニル基、炭素数１〜７のハロアルキル基、炭素数１〜７のアミノアルキル基、炭素数１〜７のヒドロカルビロキシ基、又は炭素数１〜７のハロヒドロカルビロキシ基（ただし、少なくとも２個の炭素原子がハロゲン原子と酸素原子とを隔てている）を示す。 From this, the said (A)-(F) component contained in the 1st pellet and 2nd pellet which concern on this embodiment is demonstrated in detail.
The (A) polyphenylene ether contained in the first pellet according to this embodiment is preferably a homopolymer and / or a copolymer having a repeating structural unit represented by the following general formula (1).

Here, in the formula, each R is independently a hydrogen atom, a halogen atom, a primary or secondary alkyl group having 1 to 7 carbon atoms, a phenyl group, a haloalkyl group having 1 to 7 carbon atoms, carbon An aminoalkyl group having 1 to 7 carbon atoms, a hydrocarbyloxy group having 1 to 7 carbon atoms, or a halohydrocarbyloxy group having 1 to 7 carbon atoms (provided that at least two carbon atoms separate a halogen atom and an oxygen atom) Show).

  Specific examples of the polyphenylene ether according to this embodiment 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), and poly (2,6-dichloro-1,4-phenylene ether). Further, as the copolymer, for example, a copolymer of 2,6-dimethylphenol and another phenol compound (for example, 2,3,6-trimethylphenol described in JP-B-52-17880) Copolymer, copolymer with 2-methyl-6-butylphenol).

  Among these, particularly preferred polyphenylene ethers are poly (2,6-dimethyl-1,4-phenylene ether), 2,6-dimethyl-1,4-phenol and 2,3,6-trimethyl-1,4-phenol. Or a mixture thereof.

  When a copolymer of 2,6-dimethyl-1,4-phenol and 2,3,6-trimethyl-1,4-phenol is used as the polyphenylene ether, the total amount of the copolymer is 100 mass. %, It is preferable that 10 to 30% by mass of 2,3,6-trimethyl-1,4-phenol is contained as a monomer unit, more preferably 15 to 25% by mass, most preferably 20 -25% by mass.

  Further, a preferable molecular weight distribution (weight average molecular weight / number average molecular weight (Mw / Mn) in a copolymer of 2,6-dimethyl-1,4-phenol and 2,3,6-trimethyl-1,4-phenol, The degree of dispersion is also in the range of 2.5 to 4.0. The molecular weight distribution is more preferably in the range of 2.8 to 3.8, and still more preferably in the range of 3.0 to 3.5.

  The production method of polyphenylene ether used in the present embodiment is not particularly limited, and may be obtained by a known method. Examples of the polyphenylene ether include U.S. Pat. Nos. 3,306,874, 3,306,875, 3,257,357, and 3,257,358, JP-A-50-51197, and JP-B-52-17880. It can also be obtained by the production methods described in JP-A-63-152628 and the like.

  The reduced viscosity (ηsp / C: 0.5 g / dL chloroform solution, 30 ° C., measured with an Ubbelohde type viscosity tube) of the polyphenylene ether according to this embodiment is in the range of 0.15 to 0.70 dL / g. More preferably, it is the range of 0.25-0.60 dL / g, More preferably, it is the range of 0.27-0.55 dL / g.

  In the present embodiment, a blend of two or more polyphenylene ethers having different reduced viscosities can be used. As such a blend of polyphenylene ether, for example, a mixture of polyphenylene ether having a reduced viscosity of 0.45 dL / g or less and polyphenylene ether having a reduced viscosity of 0.50 dL / g or more, a reduced viscosity of 0.40 dL / g or less. A mixture of a low molecular weight polyphenylene ether and a polyphenylene ether having a reduced viscosity of 0.50 dL / g or more is included, but of course, the present invention is not limited thereto.

  The polyphenylene ether according to this embodiment is preferably functionalized with a compatibilizing agent so as to be compatible with the following polyamide when the first pellet is produced. As the compatibilizing agent, those described in detail in WO 01/81473 can be used. Among these compatibilizers, maleic acid, fumaric acid, citric acid and their anhydrides and mixtures thereof are preferred, and maleic acid and / or its anhydride are more preferred.

  Moreover, the usage-amount of the compatibilizing agent which concerns on this embodiment has the preferable range of 0.01-8 mass parts with respect to 100 mass parts of (A) polyphenylene ether. The amount used is more preferably 0.05 to 5 parts by mass, still more preferably 0.05 to 3 parts by mass. In order not to reduce the impact resistance of the resin composition (molded product), the amount of the compatibilizer used is preferably 0.01 parts by mass or more, and the occurrence of silver streaks during injection molding and mechanical properties In order to suppress the decrease, the amount used is preferably 8 parts by mass or less.

Various known stabilizers can also be suitably used for stabilizing the polyphenylene ether. Examples of the stabilizer include organic stabilizers such as hindered phenol stabilizers, phosphate ester stabilizers, and hindered amine stabilizers. The preferable compounding quantity of these stabilizers is less than 5 mass parts with respect to 100 mass parts of polyphenylene ether.
Furthermore, you may add the other well-known additive 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.

  The polyamide (B) contained in the first pellet and the second pellet according to the present embodiment has an amide bond (—NH—C (═O) —) in the repeating structure of the polymer main chain. For example, there is no particular limitation.

  (B) Specific examples of the polyamide include, for example, 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 6, I, Polyamide 6/6, T, Polyamide 6/6, I, Polyamide 6,6 / 6 T, polyamide 6,6 / 6, I, polyamide 6, T / 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, polyamide 9, T. Here, for example, polyamide 6, I means a polymerized polyamide resin of hexamethylenediamine and isophthalic acid, and polyamide 6/6, T means a co-polymer of ε-aminocaproic acid, hexamethylenediamine and terephthalic acid. It means a polymerized polyamide resin. Furthermore, polyamides obtained by further copolymerizing with two or more of these polyamide resins using an extruder or the like can also be used.

  Among these, a preferred polyamide is a polyamide having an aromatic ring in the repeating structural unit of the main chain. Specifically, polyamide MXD (m-xylylenediamine) · 6, polyamide 6T, polyamide 6I, polyamide 6 / 6T, polyamide 6 / 6I, polyamide 66 / 6T, polyamide 66 / 6I, polyamide 6T / 6I, polyamide 6 / 6T / 6I, polyamide 66 / 6T / 6I, polyamide 6/12 / 6T, polyamide 66/12 / 6T, polyamide 6/12 / 6I, polyamide 66/12 / 6I, polyamide 9T, etc. 66 / 6I, polyamide 6T / 6I, polyamide 66 / 6T / 6I, and polyamide 9T. Among these, polyamide 9T is particularly preferable. By using the aromatic polyamide, it is possible to suppress a decrease in flame retardancy of the molded product due to the blending of the glass fibers, and it is possible to greatly suppress a dimensional change due to water absorption.

  The method for producing the polyamide (B) according to this embodiment is not particularly limited, but methods such as ring-opening polymerization of lactams, polycondensation of diamine and dicarboxylic acid, polycondensation of aminocarboxylic acid, and the like. Can be mentioned. As another production method, there is also a method in which lactams, diamines, dicarboxylic acids, and / or aminocarboxylic acids are polymerized to a low molecular weight oligomer stage in a polymerization reactor and then further polymerized by an extruder or the like to obtain a polyamide. Can be mentioned.

  Examples of the lactams include ε-caprolactam, enantolactam, and ω-laurolactam.

  Examples of diamines include aliphatic diamines, alicyclic diamines, and aromatic diamines. Specific examples thereof include tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, tridecamethylenediamine, 1,9-nonamethylenediamine, 2-methyl-1,8-octamethylenediamine, 2 2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, m-phenylenediamine , P-phenylenediamine, m-xylylenediamine, and p-xylylenediamine.

  Dicarboxylic acids include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and aromatic dicarboxylic acids. Specific examples include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,1,3-tridecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid. , Isophthalic acid, naphthalenedicarboxylic acid, and dimer acid.

  Examples of the aminocarboxylic acid include ε-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and 13-aminotridecanoic acid. Can be mentioned.

  The viscosity of the polyamide (B) according to this embodiment is such that the intrinsic viscosity [η] measured under concentrated sulfuric acid at 30 ° C. is preferably 0.6 to 2.0 dL / g, 0.7 to It is more preferable that it is 1.4 dL / g, and it is still more preferable that it is 0.7-1.2 dL / g. In particular, by using a polyamide having an intrinsic viscosity in the range shown as the more preferable range as a polyamide, the fluidity in the mold at the time of injection molding is greatly improved, and a molded body when glass fiber or an inorganic filler is blended. It becomes possible to improve the appearance.

The “intrinsic viscosity” here is synonymous with a viscosity generally called an intrinsic viscosity. A specific method for determining the intrinsic viscosity is to measure ηsp / C of several measuring solvents having different concentrations in 96% concentrated sulfuric acid at a temperature of 30 ° C. Is obtained by extrapolating the concentration zero and obtaining nsp / C at that time. The value obtained by extrapolating this density zero is the intrinsic viscosity.
Details on how to determine these intrinsic viscosities are described in, for example, pages 291 to 294 of Polymer Process Engineering (Plentice-Hall, Inc 1994).
At this time, the number of points of several measuring solvents having different concentrations is preferably at least 4 from the viewpoint of accuracy. 0.05 g / dL, 0.1 g / dL, 0.2 g / dL, 0.4 g / dL It is preferable to make these 4 points.

  The lower limit value of the terminal amino group concentration of the polyamide (B) according to this embodiment is preferably 3 μmol / g, and more preferably 5 μmol / g. The upper limit of the concentration is preferably 80 μmol / g, more preferably 70 μmol / g, still more preferably 60 μmol / g, and particularly preferably 55 μmol / g.

  Although there is no restriction | limiting in particular in the terminal carboxyl group density | concentration of (B) polyamide which concerns on this embodiment, 20 micromol / g is preferable as a lower limit, More preferably, it is 30 micromol / g. The upper limit of the concentration is preferably 150 μmol / g, more preferably 100 μmol / g, still more preferably 80 μmol / g.

  In this embodiment, the molar ratio between the terminal amino group concentration and the terminal carboxyl group concentration of the polyamide (terminal amino group concentration / terminal carboxyl group concentration) has a great influence on the mechanical properties of the molded article, and therefore there is a preferable range. To do. The molar ratio between the terminal amino group concentration and the terminal carboxyl group concentration is preferably 1.0 or less, more preferably 0.9 or less, still more preferably 0.8 or less, and particularly preferably 0.7. It is as follows. The lower limit of the molar ratio is not particularly limited, but is preferably 0.1.

  As a method for adjusting the end group concentration of the polyamide, a known method can be used. For example, terminal amino groups such as diamine, monoamine, dicarboxylic acid, monocarboxylic acid, acid anhydride, monoisocyanate, monoacid halide, monoester, monoalcohol and the like so that a predetermined end group concentration is obtained during polymerization of polyamide. The method of adding the 1 type (s) or 2 or more types of the terminal regulator which reacts with the terminal regulator which reacts and / or a terminal carboxyl group is mentioned.

  Specifically, as a terminal regulator that reacts with the terminal amino group, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid , Aliphatic monocarboxylic acids such as isobutyric acid, alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid, benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, phenylacetic acid, etc. Aromatic monocarboxylic acids and a plurality of mixtures arbitrarily selected from these are mentioned. 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 preferred, and benzoic acid is most preferred.

  Examples of the terminal adjuster that reacts with the terminal carboxyl group include methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine. Examples thereof include alicyclic monoamines such as aliphatic monoamine, cyclohexylamine and dicyclohexylamine, aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine, and any mixture thereof. Among these, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline are preferable from the viewpoints of reactivity, boiling point, sealing end stability, price, and the like.

The concentration of the amino terminal group and the carboxyl terminal group is preferably determined from the integral value of the characteristic signal corresponding to each terminal group by ¹ H-NMR in terms of accuracy and simplicity. Specifically, the method described in Japanese Patent Application Laid-Open No. 7-228775 is recommended as a method for obtaining the concentration of these end groups. When this method is used, deuterated trifluoroacetic acid is useful as a measurement solvent. In addition, the number of ¹ H-NMR integrations is required to be at least 300 scans even when measured with an instrument having sufficient resolution. In addition, there is a measurement method by titration as described in JP-A-2003-055549, but in order to reduce the influence of mixed additives and lubricants as much as possible, quantification by ¹ H-NMR is required. More preferred.

  When the terminal group is adjusted with monoamine or monocarboxylic acid, the active terminal of the polyamide is sealed. For example, when benzoic acid is used as the monocarboxylic acid, a terminal group sealed with a terminal phenyl group is generated. There are preferable upper and lower limit values for the terminal group sealing rate, that is, the terminal blocking rate. The preferable lower limit is 20%, more preferably 40%, still more preferably 45%, and particularly preferably 50%. A preferred upper limit is 95%, more preferably 90%.

The above-mentioned end capping rate is obtained by measuring the number of terminal carboxyl groups, terminal amino groups and terminal groups blocked with a terminal capping agent present in the polyamide by ¹ H-NMR, respectively, and obtaining it according to the following formula. Possible end capping rate (%) = [(α−β) / α] × 100
Here, in the formula, α represents the total number of terminal groups of the molecular chain (usually equal to twice the number of polyamide molecules), and β is the total number of terminal carboxyl groups and terminal amino groups remaining unsealed. Indicates.

  The polyamide according to this embodiment preferably has a moisture content in the range of 500 ppm to 3000 ppm, more preferably 500 ppm to 2000 ppm. The water content is preferably 500 ppm or more from the viewpoint of suppressing the deterioration of the color tone of the first pellet, and the water content is preferably 3000 ppm or less from the viewpoint of suppressing a decrease in viscosity during processing.

The (C) halogen-free flame retardant contained in the first pellet according to the present embodiment is a compound having no halogen atom in its own molecule and / or having a halogen atom in the molecule as an impurity. It is a flame retardant that does not contain, and examples thereof include phosphate ester compounds, phosphazene compounds, and phosphinates. Of these, phosphinic acid salts are particularly preferable.
The phosphinic acid salt will be specifically described below.

  The phosphinic acid salt according to the present embodiment is preferably (I) phosphinic acid salt or (II) diphosphinic acid salt represented by the following general formula (I) and / or the following general formula (II). And mixtures. In the present specification, the term “phosphinic acid salt” may be used, including condensates and mixtures of phosphinic acid salts.

ここで、式中、Ｒ¹及びＲ²は、互いに同一であっても異なっていてもよく、直鎖状若しくは分岐状の炭素数１〜６のアルキル基又はアリール基（フェニル基を含む）を示し、Ｒ³は、直鎖状若しくは分岐状の炭素数１〜１０のアルキレン基、炭素数６〜１０のアリーレン基、炭素数６〜１０のアルキルアリーレン基又は炭素数６〜１０のアリールアルキレン基を示し、Ｍはカルシウムイオン、マグネシウムイオン、アルミニウムイオン、亜鉛イオン、ビスマスイオン、マンガンイオン、ナトリウムイオン、カリウムイオン、プロトン化された窒素塩基からなる群より選ばれる１種以上の化学種を示し、ｍは２又は３であり、ｎは１〜３の整数であり、ｘは１又は２である。

Here, in the formula, R ¹ and R ² may be the same as or different from each other, and are linear or branched alkyl groups having 1 to 6 carbon atoms or aryl groups (including phenyl groups). R ³ is a linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkylarylene group having 6 to 10 carbon atoms, or an arylalkylene group having 6 to 10 carbon atoms. M represents one or more chemical species selected from the group consisting of calcium ions, magnesium ions, aluminum ions, zinc ions, bismuth ions, manganese ions, sodium ions, potassium ions, and protonated nitrogen bases, m is 2 or 3, n is an integer of 1 to 3, and x is 1 or 2.

  These phosphinic acid salts include, for example, phosphinic acid and metal carbonate, metal hydroxide or metal oxide as described in European Patent Application Publication No. 699708 and JP-A-08-73720. And is produced in an aqueous solution.

  Specific examples of the phosphinic acid include dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid, methandi (methylphosphinic acid), benzene-1,4- (dimethylphosphinic acid), methyl Mention may be made of phenylphosphinic acid and diphenylphosphinic acid and mixtures thereof.

  In addition, preferable cations for forming the phosphinic acid salt of this embodiment include calcium ions, magnesium ions, aluminum ions, zinc ions, bismuth ions, manganese ions, sodium ions, potassium ions, and protonated nitrogen bases. 1 type or more chosen from the group which consists of. More preferably, it is at least one selected from calcium ions, magnesium ions, aluminum ions and zinc ions.

  Preferred examples of the phosphinic acid salt include calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, aluminum ethylmethylphosphinate, ethylmethyl Zinc phosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, aluminum methyln-propylphosphinate , Zinc methyl-n-propylphosphinate, methandi (methylphosphinic acid) calcium, methan (methyl) Sphinic 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, diphenylphosphinic acid Examples include calcium, magnesium diphenylphosphinate, aluminum diphenylphosphinate, and zinc diphenylphosphinate. These are used singly or in combination of two or more.

  Among the above-mentioned phosphinic acid salts, calcium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, aluminum ethylmethylphosphinate, ethylmethylphosphine are particularly preferable from the viewpoint of high flame retardancy. Zinc acid, calcium diethylphosphinate, aluminum diethylphosphinate, and zinc diethylphosphinate are preferred.

  (C) The lower limit of the number average particle diameter of the flame retardant containing no halogen, for example, phosphinate, is preferably 0.1 μm, more preferably 5 μm, and still more preferably 30 μm. The upper limit value of the number average particle diameter of the flame retardant containing no preferable (C) halogen is 100 μm, the more preferable upper limit value is 80 μm, and the still more preferable upper limit value is 60 μm. By making the number average particle diameter within these preferable ranges, the productivity of the first pellet can be improved, and thermal degradation of the polymer and (C) a flame retardant containing no halogen can be suppressed.

  (C) The number average particle diameter of the flame retardant containing no halogen is determined by using a laser diffraction particle size distribution analyzer (for example, trade name: SALD-2000, manufactured by Shimadzu Corporation), methanol / water = 50/50 mass%. It can be derived by dispersing and analyzing phosphinate in a solvent.

  As the inorganic filler (D) contained in the first pellet according to the present embodiment, wollastonite, talc, kaolin, zonotlite, titanium oxide, potassium titanate, silicon carbide whisker, silicon nitride whisker, graphite, fibrous oxidation At least one inorganic filler selected from the group consisting of aluminum, acicular titanium oxide, calcium carbonate, zinc sulfide, and zinc oxide can be used. Among them, talc, kaolin, calcium carbonate, zinc sulfide and zinc oxide are preferable, and zinc sulfide and zinc oxide are more preferable. An inorganic filler is used individually by 1 type or in combination of 2 or more types.

  The (D) Mohs hardness of the inorganic filler is equal to or less than the Mohs hardness of one or more inorganic fibers selected from the group consisting of (E) glass fiber, carbon fiber, metal fiber and ceramic fiber contained in the second pellet. It is preferable. For example, when glass fiber is used as the component (E), it is preferable to use an inorganic filler (D) having a Mohs hardness of 7 or less, which is the Mohs hardness of the glass fiber. Thereby, when mixing and shape | molding a 1st pellet and a 2nd pellet, it is 1 type chosen from the group which consists of (E) glass fiber, carbon fiber, metal fiber, and ceramic fiber contained in a 2nd pellet Bending and breaking the above inorganic fibers can be suppressed. Examples of the (D) inorganic filler having a Mohs hardness of 7 or less include wollastonite, talc, and kaolin.

  The inorganic filler is a derivative of higher fatty acid or its ester or salt (eg, stearic acid, oleic acid, palmitic acid, magnesium stearate, calcium stearate, aluminum stearate, stearic acid amide, stearic acid ethyl ester) or cup. Even if it is surface-treated with one or more known surface treating agents such as a ring agent (eg, silane, titanate, amine, polyether, aluminum, zirconium). Good.

  Examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (1, 1-epoxycyclohexyl) ethyltrimethoxysilane, and titanate coupling agents include, for example, isopropyltriisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropyltris (dioctylpyrophosphate) titanate, tetraisopropylbis (dioctyl) Phosphate) titanate, tetraoctyl bis (ditridecyl phosphite) titanate.

  As a usage-amount of a surface treating agent, it is preferable that it is 0.05-5 mass parts with respect to 100 mass parts of (D) inorganic fillers.

  The particle diameter of the inorganic filler (D) according to this embodiment is not particularly limited as long as it does not impair the object effects of the present invention, but when zinc sulfide is used as the inorganic filler, the number average particle diameter is 0. 0.1 to 0.8 μm is preferable, 0.15 to 0.5 μm is more preferable, and 0.2 to 0.4 μm is still more preferable. The number average particle size of the inorganic filler is measured by a laser diffraction particle size distribution meter.

  In this embodiment, adding the inorganic filler (D) to the first pellet is one of the conditions for expressing flame retardancy and impact resistance, and (D) in the first pellet. It is essential to include an inorganic filler.

  As the one or more inorganic fibers selected from the group consisting of (E) glass fiber, carbon fiber, metal fiber and ceramic fiber contained in the second pellet according to the present embodiment, there is no particular limitation, and the short fiber type Various inorganic fibers such as chopped strand and long fiber type roving can be used.

  Examples of the glass fiber include acid resistant and alkali resistant glass fibers. Examples of the carbon fiber include PAN-based carbon fiber and pitch-based carbon fiber. Examples of the metal fiber include stainless steel fiber, aluminum fiber, nickel fiber, and copper fiber. Examples of the ceramic fiber include a fiber synthesized with alumina and silica as main components.

  (E) The average fiber diameter of one or more inorganic fibers selected from the group consisting of glass fibers, carbon fibers, metal fibers, and ceramic fibers is not particularly limited, but from the viewpoint of convergence and resin impregnation properties. It is preferably 5 μm or more, preferably 20 μm or less from the viewpoint of improving mechanical strength, and more preferably 6 to 17 μm.

  In addition, the length of one or more inorganic fibers selected from the group consisting of (E) glass fiber, carbon fiber, metal fiber, and ceramic fiber is not particularly limited when a roving type is used. The inorganic fiber length in the case of the roving type is determined at the stage of cutting the second pellet, and the inorganic fiber length is longer than the cut length of the pellet. On the other hand, when the chopped strand type is used, the preferred inorganic fiber length is 0.5 mm or more, more preferably 2 mm or more, from the viewpoint of maintaining mechanical strength and impact resistance. In view of extrudability, the length of the inorganic fiber is preferably 10 mm or less, more preferably 5 mm or less, still more preferably 4 mm or less, particularly preferably 3.5 mm or less, and most preferably 3 mm or less.

  Here, the cut length of the second pellet is preferably 2 mm or more, more preferably 3 mm or more, and further preferably 5 mm from the viewpoint of maintaining ease of pellet cutting, mechanical strength, and impact resistance. That's it. Further, from the viewpoint of moldability, the cut length is preferably 15 mm or less.

  One or more inorganic fibers selected from the group consisting of (E) glass fiber, carbon fiber, metal fiber, and ceramic fiber according to this embodiment may be used in a state of being converged using a known sizing agent. .

  The (F) impact modifier that may be included in the first and / or second pellets includes at least one polymer block mainly composed of an aromatic vinyl compound and at least one polymer composed mainly of a conjugated diene compound. Examples thereof include one or more selected from the group consisting of a block copolymer having a polymer block and a hydrogenated product thereof, and an ethylene-α-olefin copolymer.

In addition, “mainly” in the polymer block mainly composed of the aromatic vinyl compound according to the present embodiment means that 50% by mass or more of the block is the aromatic vinyl compound. More preferably, 70% by mass or more of the block is an aromatic vinyl compound, more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
Further, “mainly” in a polymer block mainly composed of a conjugated diene compound indicates that 50% by mass or more of the block is a conjugated diene compound. More preferably, 70% by mass or more of the block is a conjugated diene compound, more preferably 80% by mass or more, and particularly preferably 90% by mass or more.

  In these cases, for example, even when a small amount of a conjugated diene compound or other compound is randomly bound in a polymer block mainly composed of an aromatic vinyl compound, 50% by mass or more of the block is aromatic. If it is formed from an aromatic vinyl compound, it is regarded as a block copolymer mainly composed of an aromatic vinyl compound. The same applies to the case of a conjugated diene compound.

  Specific examples of the aromatic vinyl compound include styrene, α-methylstyrene, and vinyltoluene. One or more compounds selected from the group consisting of these are preferable, and styrene is particularly preferable. Specific examples of the conjugated diene compound include butadiene, isoprene, piperylene and 1,3-pentadiene, and one or more compounds selected from the group consisting of these are preferable, and butadiene, isoprene and combinations thereof are particularly preferable. .

It is known that there are three types of conjugated diene compounds, 1,2-vinyl bond, 3,4-vinyl bond and 1,4-vinyl bond. The microstructure of the conjugated diene compound block portion of the block copolymer in the present embodiment has a 1,2-vinyl bond amount or a total amount of 1,2-vinyl bond amount and 3,4-vinyl bond amount of 5 It is preferably -80%, more preferably 10-50%, and still more preferably 15-40%. The vinyl bond amount here indicates the ratio of the bond form of the conjugated diene compound in the three bond forms. For example, the 1,2-vinyl bond amount is the sum of the three bond forms. It means the ratio of 1,2-vinyl bond to FT and can be easily known by FT-IR, ¹ H-NMR or the like.

  In the block copolymer in the present embodiment, the polymer block [A] mainly composed of an aromatic vinyl compound and the polymer block [B] mainly composed of a conjugated diene compound are AB type, AB It is preferably a block copolymer having a bonding form selected from the -A type and the ABAB type, and may be a mixture thereof. Among these, the ABA type, the ABAB type, or a mixture thereof is more preferable, and the ABA type is more preferable.

The block copolymer is more preferably a hydrogenated block copolymer. The hydrogenated block copolymer is an aliphatic double polymer block composed mainly of a conjugated diene compound by hydrogenating the block copolymer of the aromatic vinyl compound and the conjugated diene compound. The bond is controlled in the range of more than 0% to 100%. A preferable hydrogenation rate of the hydrogenated block copolymer is 80% or more, and more preferably 98% or more. The hydrogenation rate can be measured by ¹ H-NMR or the like.

These block copolymers may be a mixture of a non-hydrogenated block copolymer and a hydrogenated block copolymer.
In addition, these aromatic vinyl compound-conjugated diene compound block copolymers are different in bond type, different in aromatic vinyl compound type, different in conjugated diene compound type, unless contrary to the spirit of the present invention, A mixture of two or more of those having different total amounts of 1,2-bonded vinyl content and 3,4-bonded vinyl content and different aromatic vinyl compound component contents may be used. .

As the block copolymer according to this embodiment, a mixture of a low molecular weight block copolymer and a high molecular weight block copolymer can be preferably used. Specifically, it is a mixture of a low molecular weight block copolymer having a number average molecular weight of less than 120,000 and a high molecular weight block copolymer having a number average molecular weight of 120,000 or more. More preferably, it is a mixture of a low molecular weight block copolymer having a number average molecular weight of less than 120,000 and a high molecular weight block copolymer having a number average molecular weight of 170,000 or more.
The number average molecular weight of each block copolymer refers to the number average molecular weight measured with an ultraviolet spectroscopic detector using a gel permeation chromatography measuring device (GPC) and converted to standard polystyrene. At this time, a low molecular weight component due to catalyst deactivation during polymerization may be detected. In this case, the low molecular weight component is not included in the molecular weight calculation.
The molecular weight of the polymer block mainly composed of one aromatic vinyl compound in the block copolymer is more preferably in the range of 15,000 to 50,000.

The number average molecular weight of one polymer block mainly composed of an aromatic vinyl compound of one type of block copolymer can be obtained by the following formula (2) using the number average molecular weight of the block copolymer described above. it can.
Mn (a), n = {Mn × a / (a + b)} / N (a) (2)
Here, in the above formula (2), Mn (a), n is the number average molecular weight of one polymer block mainly composed of the aromatic vinyl compound of the block copolymer n, and Mn is the block copolymer n. Number average molecular weight, a is mass% of polymer block mainly composed of aromatic vinyl compound in block copolymer n, b is mass% of polymer block mainly composed of conjugated diene compound in block copolymer n , And N (a) represent the number of polymer blocks mainly composed of an aromatic vinyl compound in the block copolymer n.

  The mass ratio of the low molecular weight block copolymer to the high molecular weight block copolymer (low molecular weight block copolymer / high molecular weight block copolymer) is preferably 95/5 to 5/95, more preferably. 90/10 to 10/90.

  As the block copolymer, a block copolymer containing a polymer block mainly containing an aromatic vinyl compound in an amount of 55% by mass or more and less than 90% by mass, and a polymer block mainly containing an aromatic vinyl compound A mixture of two or more block copolymers composed of a block copolymer contained in an amount of 20% by mass or more and less than 55% by mass can be preferably used. Moreover, even if it is a block copolymer modified entirely, it may be a mixture of an unmodified block copolymer and a modified block copolymer.

  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, Alternatively, it refers to a block copolymer modified with at least one modifying compound having a glycidyl group.

  In addition to the components (A) to (F) contained in the first pellet and the second pellet according to the present embodiment, various additives may be added as necessary within the range not impairing the object and effects of the present invention. Can be blended into the first and second pellets by any method. The resin composition constituting the first and / or second pellets preferably contains a compound containing phosphorus element as a polyamide heat stabilizer. Examples of the compound containing phosphorus element include a metal phosphate, a metal phosphite, and a metal hypophosphite. The preferable content of such a compound is preferably 1 to 5000 ppm, more preferably 5 to 2500 ppm, and particularly preferably 50 in terms of phosphorus element with respect to the total amount of polyamide contained in the first and second pellet mixtures. -2000 ppm.

Further, the first pellet and the second pellet may contain a metal stabilizer as described in JP-A-1-163262 for the purpose of improving the heat stability of the polyamide. The metal based stabilizer, for example CuI, CuCl _2, copper acetate, and cerium stearate. In these, the copper compound represented by CuI, copper acetate, etc. is preferable, More preferably, it is CuI.

  The preferable compounding amount of these copper compounds is 1 to 400 ppm as copper element, more preferably 1 to 300 ppm, and further preferably 1 to 100 ppm with respect to the total amount of polyamide contained in the pellet mixture.

  Further, known anti-dripping agents, plasticizers, lubricants, colorants, antistatic agents, various peroxides, antioxidants, ultraviolet absorbers, and light stabilizers as additives are added to the first and / or second pellets. May be included. The preferable compounding amount of these additives is a range not exceeding 15% by mass with respect to the resin composition contained in the first pellet and the resin composition contained in the second pellet, respectively.

Here, the details of the manufacturing method of the first pellet will be described.
The production method for obtaining the first pellet according to the present embodiment includes, for example, a step of producing a functionalized polyphenylene ether as necessary, and melt-kneading (functionalized) polyphenylene ether and polyamide. Adding (C) halogen-free flame retardant and (D) inorganic filler, and (F) impact modifier as required in the process, polyphenylene ether, functionalized polyphenylene ether or polyphenylene ether / polyamide alloy And melt-kneading. More preferably, all of these steps are carried out in one extruder.

  As a specific method for producing the first pellet, for example, using a twin-screw extruder having one supply port on the upstream side and at least one supply port on the downstream side, from the upstream supply port, At least (A) a polyphenylene ether and / or a functionalized polyphenylene ether, a compatibilizer if necessary, and (F) an impact modifier if necessary, and a melt kneading step, and obtained through the step. The step of melt-kneading the molten mixture containing polyphenylene ether and at least (B) polyamide supplied from the downstream supply port, and (C) halogen-free from the upstream supply port and / or the downstream supply port The step of supplying a flame retardant and melt-kneading, the step (D) of supplying an inorganic filler from the upstream supply port and / or the downstream supply port, melt-kneading, and the obtained melt-kneaded product Method comprising the step of Tides (pelletizing) may be mentioned. (C) A flame retardant containing no halogen and (D) an inorganic filler may be added at any timing, but it is preferable to add them simultaneously with (B) the polyamide or after the (B) polyamide is melted. In the case of having a step of producing a functionalized polyphenylene ether, in that step, a small amount of polyamide, specifically, less than 25% by mass of polyamide may be mixed with respect to the polyamide contained in the first pellet. .

  In addition, you may use the flame retardant which does not contain the (C) halogen which concerns on this embodiment in the form of the flame retardant masterbatch previously mixed with (B) polyamide. The method for producing this flame retardant masterbatch is not particularly limited, and as a specific example, a method of melt-kneading a premixed mixture of polyamide and a flame retardant containing no halogen without melting, a flame retardant containing no halogen A method of adding it to a melted polyamide and further melt-kneading it can be mentioned. The flame retardant master batch may further contain (D) an inorganic filler.

  The inorganic filler (D) according to this embodiment may be added at the polymerization stage of (B) polyamide or (A) polyphenylene ether, and is an inorganic filler-containing masterbatch obtained by blending in advance in polyamide or polyphenylene ether. It is also possible to use it in the form. However, a method of adding an inorganic filler to molten polyamide or polyphenylene ether and kneading is preferred.

  The first pellet according to this embodiment preferably has a dispersion form in which (B) polyamide forms a continuous phase and (A) polyphenylene ether forms a dispersed phase in the form of particles. 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, the average particle diameter of the particles is in the range of 0.3 to 3 μm, and more preferably 0.5 to 2 μm. In order not to reduce the impact resistance of the resin composition (molded body), the average particle diameter of the particles is preferably 5 μm or less, and the deterioration of the fluidity (spiral flow distance) in the mold during injection molding is caused. In order to suppress it, the average particle diameter of the particles is preferably 0.1 μm or more.

  The average particle diameter of the PPE particles can be determined by electron micrograph and is derived as follows. That is, a transmission electron micrograph (5000 times) of an ultrathin section cut from a pellet or a molded body was taken, and the particle diameter di and particle number ni of each particle of PPE were determined, and the number average particle diameter (= (Σdini / Σni) is calculated to obtain the average particle size. In this case, when the particle shape cannot be regarded as a sphere, the minor axis and the major axis are measured, and ½ of the sum of the two is taken as the particle diameter. To calculate the average particle size, the particle size of at least 500 particles is measured.

Next, the details of the second pellet manufacturing method will be described.
The manufacturing method for obtaining the 2nd pellet which concerns on this embodiment is from the group which consists of (B) polyamide and (E) glass fiber, carbon fiber, metal fiber, and ceramic fiber, for example with a single screw or a twin screw extruder. Examples thereof include a method of melt-kneading one or more selected inorganic fibers, and a pultrusion method in which polyamide is impregnated while drawing a resin strand from a glass fiber roving as described in Japanese Patent Publication No. 52-3985. When using a single-screw or twin-screw extruder, kneading from the viewpoint of maintaining one or more inorganic fiber lengths selected from the group consisting of (E) glass fiber, carbon fiber, metal fiber and ceramic fiber when melt-kneading. A production method using an extruder having a screw pattern with reduced shearing force so as to be a transfer zone except for the zone is preferable. More preferred is a production method using a single screw extruder having a screw pattern with reduced shearing force, and further preferred is the pultrusion method using roving.

  When a single-screw or twin-screw extruder is used, a specific method for producing the second pellet is a twin-screw extruder having one supply port on the upstream side and at least one supply port on the downstream side. A step of supplying and melting and kneading at least (B) polyamide from the upstream supply port, and (E) glass fiber, carbon fiber, metal fiber and ceramic fiber from the upstream supply port and / or the downstream supply port And a step of supplying one or more inorganic fibers selected from the group consisting of: For example, when using a twin screw extruder having two downstream supply ports, (B) part of the polyamide is supplied from the upstream supply port, and the remaining polyamide and (E) glass fiber, carbon fiber, metal fiber are supplied. And one or more inorganic fibers selected from the group consisting of ceramic fibers can be optionally supplied from an upstream supply port and two downstream supply ports.

As a specific method for producing the second pellet by the pultrusion method using roving, at least (B) polyamide is melt-kneaded using a single-screw or twin-screw extruder to obtain a melt-kneaded product, and then The melt-kneaded product is impregnated with a roving of at least one inorganic fiber selected from the group consisting of (E) glass fiber, carbon fiber, metal fiber and ceramic fiber to obtain a strand. At this time, in order to impregnate (E) the roving of the inorganic fiber with the melt-kneaded product, it is preferable to provide an impregnation die on the most downstream side of the single-screw or twin-screw extruder, and to give a twist to the strand of the roving. .
Here, the length of the (E) inorganic fiber when twisted is longer than the cut length of the second pellet, and when the strand is taken up without twisting, the length of the (E) inorganic fiber is Substantially equal to the length of the pellet. That is, when adopting the pultrusion method using roving, the length of the (E) inorganic fiber is not less than the length of the second pellet.

  The second pellet is obtained by pelletizing the melt-kneaded product containing the inorganic fiber (E) obtained through the above steps.

  The molded body of the present embodiment is obtained by molding a pellet mixture obtained by mixing the manufactured first pellet and second pellet with a dry mixer such as a double cone type. In manufacturing a molded body using the pellet mixture, various generally used molding methods and molding apparatuses can be used according to the type, application, shape, etc. of the target molded body. The molding method and molding apparatus are not limited in any way, but the pellet mixture of the present embodiment can be formed by any molding method such as injection molding, extrusion molding, press molding, calendar molding, solution casting molding or the like. By molding, the molded body of the present embodiment can be manufactured, and can also be manufactured by combining these molding techniques. Among the above, injection molding is preferable from the viewpoint of excellent molding and manufacturing cycle of thin-walled microstructures, and particularly preferably, an injection molding machine for long fibers was used from the viewpoint of maintaining high mechanical properties and impact resistance. Injection molding is preferred.

  In the molded body of this embodiment, the weight average fiber length of the (E) inorganic fiber contained therein is preferably 500 to 5000 μm, more preferably 800 to 4000 μm, still more preferably 1000 to 4000 μm, and particularly preferably 2500 to 500 μm. 4000 μm. When the weight average fiber length is 500 μm or more, the mechanical strength and impact resistance of the molded product can be maintained at a high level, and when it is 5000 μm or less, the moldability becomes good. Here, the weight average fiber length of the (E) inorganic fiber contained in the molded body is measured according to the method described in the following examples.

  Since the pellet mixture of the present embodiment has many excellent properties, it undergoes the molding process as described above, and the cellular phone casing, mobile device casing, automobile parts, industrial materials, industrial materials, electrical and electronic parts, It is effectively used for the manufacture of machine parts, office equipment parts, household goods, and other molded articles of any other shape and application.

  Specific examples include, for example, cellular phone housings, IC tray materials, chassis such as various disk players, cabinets, OA parts and machine parts such as peripheral equipment, electrical and electronic parts such as SMT connectors, relay block materials, and the like. The electric parts of motorcycles and automobiles are listed.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to this Example.

(Raw materials used)
1. (A) Polyphenylene ether (PPE)
(A-1) Poly (2,6-dimethyl-1,4-phenylene ether), trade name “S201A”, manufactured by Asahi Kasei Chemicals Corporation, reduced viscosity: 0.52 dL / g (0.5 g / dL, chloroform solution, (Measured at 30 ° C)
(A-2) Poly (2,6-dimethyl-1,4-phenylene ether), trade name “S202A”, manufactured by Asahi Kasei Chemicals Corporation, reduced viscosity: 0.41 dL / g (0.5 g / dL, chloroform solution, (Measured at 30 ° C)
(A-3) Poly (2,6-dimethyl-1,4-phenylene ether), manufactured by Asahi Kasei Chemicals Corporation, reduced viscosity: 0.29 dL / g (0.5 g / dL, chloroform solution, measured at 30 ° C.)

2. (B) Polyamide (PA)
(B-1) Polyamide comprising terephthalic acid, 1,9-nonamethylenediamine and 2-methyl-1,8-octamethylenediamine, melting point: 308 ° C., intrinsic viscosity [η]: 0.80 dL / g, terminal Sealing rate: 90%, terminal amino group concentration: 19 μmol / g
(B-2) Polyamide comprising terephthalic acid, 1,9-nonamethylenediamine and 2-methyl-1,8-octamethylenediamine, melting point: 304 ° C., intrinsic viscosity [η]: 1.20 dL / g, terminal Sealing rate: 90%, terminal amino group concentration: 10 μmol / g
(B-3) Polyamide comprising adipic acid and hexamethylenediamine, terminal amino group concentration: 45 μmol / g, terminal carboxyl group concentration 75 μmol / g, formic acid solution viscosity VR: 46), manufactured by Asahi Kasei Chemicals

3. (C) Flame retardant containing no halogen (C-1) Aluminum diethylphosphinate, trade name “Exolit OP930”, manufactured by Clariant Japan, number average particle size: 5 μm
(C-2) Aluminum diethylphosphinate, trade name “Exolit OP1230”, manufactured by Clariant Japan, number average particle size: 40 μm

4). (D) Inorganic filler (D-1) Zinc sulfide, trade name “Sactris HD-S”, manufactured by Sacher Treben, average particle size: 0.3 μm
(D-2) Zinc oxide, trade name “Ginbae”, manufactured by Toho Zinc Co., Ltd., average particle size: 0.3 μm

5. (E) Inorganic fiber (E-1) Chopped strands bundled with a novolak epoxy compound, trade name “ECS03T-747”, manufactured by Nippon Electric Glass Co., Ltd., fiber diameter: 13 μm, chop length: 3.1 mm
(E-2) Glass fiber roving, trade name “ER2400T-448N”, manufactured by Nippon Electric Glass Co., Ltd., average glass fiber diameter: 17 μm, fineness (tex): 2400 g / 1000 m

6). (F) Impact modifier (F-1) Polystyrene-hydrogenated polybutadiene-polystyrene block copolymer (SEBS), trade name “H1387”, manufactured by Asahi Kasei Chemicals Corporation, number average molecular weight: 246000, styrene component total content: 33 %
(F-2) Polystyrene-hydrogenated polybutadiene-polystyrene block copolymer (SEBS), trade name “H1272”, manufactured by Asahi Kasei Chemicals Corporation, number average molecular weight: 197,000, styrene component total content: 35%

7). Compatibilizer Maleic anhydride (MAH), trade name “CRYSTALMAN-AB”, manufactured by NOF Corporation

(Evaluation methods)
<Bending strength and flexural modulus>
From the obtained pellet mixture, an injection molding machine “IS-80EPN (manufactured by Toshiba Machine Co., Ltd.)” (cylinder temperature set to 330 ° C., mold temperature set to 130 ° C.) or long fiber screw (compression ratio: 1.8) Was used to form a multi-purpose specimen A type (length 150 mm, narrow portion width 10.0 mm) having a thickness of 4 mm. The obtained test piece was processed into a shape of 80 × 10 × 4 mm, and its strength and bending elastic modulus were measured according to ISO178.

<Measurement of Charpy impact strength>
From the obtained pellet mixture, an injection molding machine “IS-80EPN (manufactured by Toshiba Machine Co., Ltd.)” (cylinder temperature set to 330 ° C., mold temperature set to 130 ° C.) or long fiber screw (compression ratio: 1.8) Was used to form a multi-purpose specimen A type (length 150 mm, narrow portion width 10.0 mm) having a thickness of 4 mm. The obtained test piece was processed into a shape of 80 × 10 × 4 mm, a notch was given to the obtained test piece, and Charpy impact strength was measured according to ISO179.

<Flame retardance>
Using the method of UL94 (standard defined by Under Writer's Laboratories Inc., USA), five samples were measured for each example or comparative example. The test piece (length 127 mm, width 12.7 mm, thickness 1.6 mm) is an injection molding machine (manufactured by Toshiba Machine Co., Ltd .: IS-80EPN) or a long fiber screw (compression ratio: 1.8). The pellet mixture was molded using an equipped molding machine “IS-80EPN (manufactured by Toshiba Machine Co., Ltd.)”. The molding conditions were a cylinder temperature of 330 ° C. and a mold temperature of 130 ° C.
As the flame retardant grade, a flame retardant class classified by UL94 vertical flame test was used. The outline is as follows, and other details conform to the UL94 standard.
V-0: average burning time 5 seconds or less, maximum burning time 10 seconds or less, no cotton ignition V-1: average burning time 25 seconds or less, maximum burning time 30 seconds or less, no cotton ignition V-2: average burning time 25 Less than 1 second, maximum burning 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 Each average burning time (seconds) is measured The flame extinguishing time after 10 seconds of indirect flame was measured twice, that is, the flame extinguishing time after 10 times in total flame contact was measured, and the arithmetic mean burning time was shown. Similarly, the maximum combustion time (seconds) indicates the combustion time in the measurement in which combustion continued for the longest time among the extinguishing times after 10 times of flame contact.

<Measurement of weight average fiber length of glass fiber>
After putting 2g of pellets into a porcelain crucible, using an electric muffle furnace (FP-31 type, manufactured by Yamato Kagaku, set temperature 600 ° C), polyamide is burned, and then the burned glass fiber is transferred onto a slide glass. Observed under a microscope, the length of 400 arbitrarily selected glass fibers was measured using an image analyzer, and the length was determined by the following formula.
Weight average fiber length = ΣLi ² / ΣLi
Here, Li represents the length of each glass fiber (L1, L2,..., L400), and Li ² is the square of the length of each corresponding glass fiber. (L1 ² , L2 ² ,..., L400 ² ).

[Examples 1-3, 7]
The 1st pellet was produced as follows using the twin-screw extruder (Toshiba machine "TEM-58SS"). One supply port was provided on the upstream side and one on the downstream side.
First, (A) polyphenylene ether powder and maleic anhydride were stirred with a tumbler for 20 minutes to obtain a premix. The preliminary mixture is supplied from the upstream supply port of the twin-screw extruder, melted and kneaded, and then (B) polyamide, (C) a halogen-free flame retardant, and (D) inorganic filler are supplied from the downstream supply port, respectively. Further, the mixture was melt-kneaded, extruded, and pelletized to obtain a first pellet. The cylinder temperature of the extruder at that time was set to 320 ° C. from the upstream supply port to the downstream supply port, 300 ° C. from the downstream supply port to the die, and 330 ° C. to the die head. At this time, the discharge amount of the kneaded material was 500 kg / hour, and the screw rotation speed was 500 rpm.

  Using the extruder in which the resin impregnation die was provided at the most downstream of the second pellet “ZSK-25 (manufactured by Coperion)”, the resin strand was drawn into the glass fiber roving (E-2). (B) A pultrusion method impregnated with polyamide and finally pelletized to produce. At this time, the cylinder temperature of the extruder was set to 340 ° C. for all stages, and the temperature of the impregnation die was set to 350 ° C. At this time, the nozzle of the die head was set to two, and the nozzle diameter was set to 2.9 mm each. The strand take-up speed at this time was 20 m / min, and the discharge rate was 23 kg / hr. The cut length of the produced second pellet was 10 mm.

  The 1st pellet produced as mentioned above and the 2nd pellet were mixed with the tumbler until it was confirmed that it mixed uniformly, and the pellet mixture was obtained. Table 1 shows the types and mixing ratios of the raw materials in the above steps. The obtained pellet mixture was molded into the predetermined shape by an injection molding machine “IS-80EPN (manufactured by Toshiba Machine Co., Ltd.)” to obtain a test piece, and each of the above evaluations was performed. The results are shown in Table 1.

[Examples 4 to 6]
A first pellet was obtained in the same manner as in Examples 1 to 3 and 7 except that the type and mixing ratio of each raw material were changed.
The 2nd pellet was produced as follows using the twin-screw extruder (Toshiba machine make, brand name "TEM-58SS"). One supply port was provided on the upstream side and one on the downstream side.
First, (B) polyamide was supplied to the upstream supply port and melt-kneaded. Thereafter, (E-1) chopped glass fiber was supplied from the downstream supply port, and further melt kneaded and extruded to obtain a second pellet. The cylinder temperature of the extruder at that time was set to 340 ° C. for all stages. At this time, the discharge amount of the kneaded material was 400 kg / hour, and the screw rotation speed was 200 rpm. The cut length of the produced second pellet was 10 mm.

  The 1st pellet produced as mentioned above and the 2nd pellet were mixed with the tumbler until it was confirmed that it mixed uniformly, and the pellet mixture was obtained. Table 1 shows the types and mixing ratios of the raw materials in the above steps. The obtained pellet mixture was molded into the predetermined shape by a molding machine “IS-80EPN (manufactured by Toshiba Machine Co., Ltd.)” equipped with a long fiber screw (compression ratio: 1.8) to obtain a test piece. Each evaluation of was performed. The results are shown in Table 1.

[Examples 8 to 11]
Except having changed the kind of each raw material and the mixture ratio as shown in Table 2, it carried out similarly to Examples 1-3 and 7, and obtained the 1st pellet and the 2nd pellet.

  The produced first pellets and second pellets were mixed with a tumbler until it was confirmed that they were uniformly mixed to obtain a pellet mixture. The obtained pellet mixture was molded into the predetermined shape by a molding machine “IS-80EPN (manufactured by Toshiba Machine Co., Ltd.)” equipped with a long fiber screw (compression ratio: 1.8) to obtain a test piece. Each evaluation of was performed. The results are shown in Table 2.

[Comparative Examples 1 to 11]
Using only a twin screw extruder (trade name “TEM-58SS” manufactured by Toshiba Machine Co., Ltd.), all raw materials were supplied into one extruder, and pellets were produced as follows. The supply port was provided at one location on the upstream side and two locations on the downstream side (one location on the upstream side and one location on the downstream side).

  First, (A) polyphenylene ether powder and maleic anhydride were stirred with a tumbler for 20 minutes to obtain a premix. The preliminary mixture is supplied from the upstream supply port of the twin-screw extruder, melted and kneaded, and, among the downstream supply ports, it is difficult to contain (B) polyamide and (C) halogen from the upstream supply port. A flame retardant and (D) inorganic filler were supplied, and among the downstream supply ports, (E-1) chopped glass fibers were supplied from a downstream supply port, and melt-kneaded and extruded to obtain pellets. The cylinder temperature of the extruder at that time is 320 ° C. from the upstream supply port to the upstream supply port of the downstream supply port, 300 ° C. from the downstream supply port to the die, and the die head to 330 ° C. Set. At this time, the discharge amount of the kneaded material was 500 kg / hour, and the screw rotation speed was 500 rpm.

Tables 2 and 3 show the types and mixing ratios of the raw materials in the above steps. The obtained pellets were molded into the predetermined shape by an injection molding machine “IS-80EPN (manufactured by Toshiba Machine Co., Ltd.)” to obtain a test piece, and each of the above evaluations was performed. The results are shown in Tables 2 and 3.

[Comparative Example 12]
A pellet mixture was obtained in the same manner as in Example 2 except that (D) the inorganic filler was not included in the first pellet. The obtained pellet mixture was molded into the predetermined shape by an injection molding machine “IS-80EPN (manufactured by Toshiba Machine Co., Ltd.)” to obtain a test piece, and each of the above evaluations was performed. The results are shown in Table 3.

  Moreover, about the said Example and comparative example, the plot figure which shows the correlation with the average combustion time of UL-94 and Charpy impact strength is shown in FIG.

  Since the pellet mixture of the present invention does not contain halogen and has achieved a high flame retardant level, it is particularly OA for mobile phone casings, IC tray materials, chassis such as various disk players, cabinets, peripheral devices, etc. It can be suitably used for electric parts such as parts and machine parts, electric and electronic parts such as SMT connectors, and motorcycles and automobiles represented by relay block materials.

Claims (25)

A first pellet comprising (A) polyphenylene ether, (B) polyamide, (C) a halogen-free flame retardant, and (D) an inorganic filler;
(B) a second pellet containing polyamide and (E) one or more inorganic fibers selected from the group consisting of glass fiber, carbon fiber, metal fiber and ceramic fiber;
Containing pellet mixture.   The first pellet is 40 to 90% by mass, and the second pellet is 10 to 60% by mass with respect to the total amount of the first pellet and the second pellet. Pellet mixture.   5-60 of 1 or more types of inorganic fiber chosen from the group which consists of said (E) glass fiber, carbon fiber, a metal fiber, and a ceramic fiber with respect to the total amount of a said 1st pellet and a said 2nd pellet. The pellet mixture according to claim 1 or 2, comprising mass%.   The first pellet comprises 40 to 70% by mass of the (A) polyphenylene ether with respect to the total amount of the (A) polyphenylene ether and the (B) polyamide contained in the first pellet. The pellet mixture according to any one of claims 1 to 3, comprising B) 30 to 60% by mass of polyamide.   The said 1st pellet contains 20-90 mass% of flame retardants which do not contain the said (C) halogen with respect to 100 mass parts of said (B) polyamide contained in a said 1st pellet. The pellet mixture according to any one of the above.   The said 1st pellet contains 2-50 mass parts of (D) inorganic filler with respect to a total of 100 mass parts of the resin component contained in a said 1st pellet, In any one of Claims 1-5. Pellet mixture as described.   The said 2nd pellet contains either 10-90 mass% of 1 or more types of inorganic fiber chosen from the group which consists of said (E) glass fiber, carbon fiber, a metal fiber, and a ceramic fiber. 2. The pellet mixture according to item 1.   The pellet mixture according to any one of claims 1 to 7, wherein the first pellet and / or the second pellet further includes (F) an impact modifier.   The pellet mixture according to claim 8, wherein the (F) impact modifier comprises more than 0 parts by weight and 150 parts by weight with respect to 100 parts by weight of the (A) polyphenylene ether.   (F) The impact modifier is a block copolymer having 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 the block. The pellet mixture according to claim 8 or 9, which is a hydrogenated product of a copolymer.   The pellet mixture according to any one of claims 1 to 10, wherein the (B) polyamide is a polyamide having an aromatic ring in a repeating structural unit of the main chain.   The number average particle diameter of the flame retardant which does not contain the said (C) halogen is 0.1-100 micrometers, The pellet mixture of any one of Claims 1-11.   The pellet mixture according to any one of claims 1 to 11, wherein the flame retardant containing no (C) halogen has a number average particle diameter of 5 to 60 µm.   The pellet mixture according to claim 1, wherein the flame retardant containing no (C) halogen is a phosphinate.   The Mohs hardness of the (D) inorganic filler is equal to or less than the Mohs hardness of one or more inorganic fibers selected from the group consisting of (E) glass fiber, carbon fiber, metal fiber, and ceramic fiber. The pellet mixture according to any one of the above.   The pellet mixture according to any one of claims 1 to 15, wherein the (D) inorganic filler is zinc oxide and / or zinc sulfide.   The number average particle diameter of the said (D) inorganic filler is a pellet mixture of any one of Claims 1-16 which is 0.1-0.8 micrometer.   The pellet mixture according to any one of claims 1 to 17, wherein the (E) one or more inorganic fibers selected from the group consisting of glass fibers, carbon fibers, metal fibers, and ceramic fibers are glass fibers.   The pellet mixture according to any one of claims 1 to 18, wherein a cut length of the second pellet is 2 to 15 mm.   The pellet mixture according to any one of claims 1 to 18, wherein a cut length of the second pellet is 5 to 15 mm.   The molded object of the pellet mixture of any one of Claims 1-20.   The molded article according to claim 21, comprising (E) one or more inorganic fibers selected from the group consisting of (E) glass fibers, carbon fibers, metal fibers and ceramic fibers having a weight average fiber length of 500 to 5000 µm.   The molded article according to claim 21, comprising (E) one or more inorganic fibers selected from the group consisting of (E) glass fibers, carbon fibers, metal fibers and ceramic fibers having a weight average fiber length of 2500 to 4000 µm.   The molded object obtained by injection-molding the pellet mixture of any one of Claims 1-20.   A mobile phone case obtained by injection molding the pellet mixture according to any one of claims 1 to 20.

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