JP2020172579A - Resin composition and molded article - Google Patents

Abstract

To provide a resin composition excellent in flame retardancy and mechanical strength, and a molded article.SOLUTION: The resin composition comprises only (A) 40-65 mass% of a polyamide resin, (B) 35-60 mass% of reinforcing fibers having a circular cross section, (C) 1-15 mass% of a phosphorus-based flame retardant containing at least one of a phosphinate and a diphosphinate, (D) 0.01-2 mass% of a wax, and (E) 0-20 mass% of an additive. The additive does not contain zinc borate and polyphenylene ether. The total amount of the components (A)-(E) is 100 mass%.SELECTED DRAWING: None

Description

The present invention relates to resin compositions and molded articles.

Polyamide resins are applied to various fields because they are excellent in various performances.
In particular, when it is used in a field where mechanical strength is required, reinforcing fibers are blended. Further, when used in a field where flame retardancy is required, a flame retardant is blended.

For example, Patent Document 1 contains (A) a polyamide resin, (B) a phosphorus-based flame retardant, and (C) a glass fiber having a non-circular cross section in consideration of improving flame retardancy and mechanical strength. The flame-retardant resin composition is composed of 15 to 78% by weight of (A) polyamide resin and 2 to 20% by weight of (B) phosphorus-based flame retardant, respectively. C) A flame-retardant resin composition in which the glass fiber having a non-circular cross section is 20 to 65% by weight is disclosed.

Further, Patent Document 2 includes at least two opposing walls, and a passage for receiving the insertion of a contact pin is defined between them, and the wall is formed of a polyamide polymer, a flame retardant system, and a fibrous material. A fine pitch electrical connector socket formed from a fiber reinforced flame retardant thermoplastic polymer composition comprising a reinforcing agent, wherein the polyamide polymer has at least one half of a melting temperature Tm-A of at least 280 ° C. Includes a crystalline polyamide (A) and optionally a second polyamide (B); the polyamide polymer has a crystallization enthalpy ΔHc of at least 50 J / g, said melting temperature Tm-A and crystallization enthalpy. ΔHc was measured by DSC at a heating and cooling rate of 20 ° C. in a manner compliant with ISO11357-1 / 3; the flame retardant system was composed of (C-1) dialkylphosphinic acid and / or a metal salt of diphosphinic acid. (C-2) Including the combination with the metal phosphate; (C-1) and (C-2) are the total amount of 5 to 35% by weight based on the total weight of the composition, and 95/5 to 95. Presented at a weight ratio of C-1 / C-2 in the range of 55/45; the socket has a thermal strain temperature of at least 265 ° C. as measured according to ISO75-1 / 2, socket disclosed. Has been done.

Japanese Unexamined Patent Publication No. 2008-163317 Special Table 2017-500705

The resin composition is excellent in flame retardancy and mechanical strength, but further new materials are required depending on the application. In particular, there is a demand for a resin composition which is a formulation using a phosphorus-based flame retardant as a flame retardant and has excellent flame retardancy and mechanical strength.
An object of the present invention is to solve such a problem, and an object of the present invention is to provide a resin composition having excellent flame retardancy and mechanical strength and a molded product thereof.

As a result of studies by the present inventor based on the above problems, it has been found that the above problems can be solved by using wax as a release agent and adjusting the contents of the polyamide resin, the reinforcing fiber and the flame retardant. I found it. Specifically, the above problems have been solved by the following means.

（式（Ｉ）中、Ｒ¹およびＲ²は、それぞれ独立に、直鎖もしくは分枝鎖の炭素数１〜６のアルキル基、または炭素数６〜１０のアリール基を表す。Ｍはカルシウムイオン、アルミニウムイオン、マグネシウムイオン、または亜鉛イオンを表す。ｍはＭの価数を表す自然数である。）

（式（ＩＩ）中、Ｒ⁴およびＲ⁵は、それぞれ独立に、直鎖もしくは分枝鎖の炭素数１〜６のアルキル基、または炭素数６〜１０のアリール基を表す。Ｒ³は直鎖もしくは分枝鎖の炭素数１〜１０のアルキレン基、炭素数６〜１０のアリーレン基、炭素数７〜１０のアルキルアリーレン基、または炭素数７〜１０のアリールアルキレン基を表す。Ｍはカルシウムイオン、アルミニウムイオン、マグネシウムイオン、または亜鉛イオンを表す。ｎはＭの価数を表す自然数である。ｎ、ａ、ｂは、２×ｂ＝ｎ×ａの関係式を満たす自然数である。）
＜５＞＜１＞〜＜４＞のいずれか１つに記載の樹脂組成物から形成された成形品。 <1> (A) 40 to 65% by mass polyamide resin,
(B) Reinforcing fiber having a circular cross section of 35 to 60% by mass,
(C) A phosphorus-based flame retardant containing at least 1 to 15% by mass of phosphinate and diphosphinate.
(D) 0.01 to 2% by mass of wax, and
(E) Consists of only 0 to 20% by mass of additives
The additive is free of zinc borate and polyphenylene ethers.
A resin composition in which the total amount of the components (A) to (E) is 100% by mass.
<2> (B) The resin composition according to <1>, wherein the reinforcing fiber contains glass fiber.
<3> The resin composition according to <1> or <2>, wherein the (A) polyamide resin is a semi-aromatic polyamide resin.
<4> Described in any one of <1> to <3>, wherein the flame retardant contains at least one of a compound represented by the following formula (I) and a compound represented by the following formula (II). Resin composition.

In formula (I), R ¹ and R ² independently represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms in a straight chain or a branched chain, respectively. M is a calcium ion. , Aluminum ion, magnesium ion, or zinc ion. M is a natural number representing the valence of M.)

(In formula (II), R ⁴ and R ⁵ independently represent an alkyl group having 1 to 6 carbon atoms in a straight chain or a branched chain, or an aryl group having 6 to 10 carbon atoms, respectively. R ³ is a direct chain. The chain or branched chain represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkyl arylene group having 7 to 10 carbon atoms, or an arylalkylene group having 7 to 10 carbon atoms. It represents an ion, an aluminum ion, a magnesium ion, or a zinc ion. N is a natural number representing a valence of M. n, a, b are natural numbers satisfying the relational expression of 2 × b = n × a).
<5> A molded product formed from the resin composition according to any one of <1> to <4>.

INDUSTRIAL APPLICABILITY According to the present invention, it has become possible to provide a resin composition and a molded product having excellent flame retardancy and mechanical strength.

The contents of the present invention will be described in detail below. In addition, in this specification, "~" is used in the meaning that the numerical values described before and after it are included as the lower limit value and the upper limit value.

The resin composition of the present invention comprises (A) 40 to 65% by mass of a polyamide resin, (B) a reinforcing fiber having a circular cross section of 35 to 60% by mass, and (C) 1 to 15% by mass of phosphinate and diphosphine. It consists only of a phosphorus-based flame retardant containing at least one of the acid salts, (D) 0.01 to 2% by mass of wax, and (E) 0 to 20% by mass of an additive, which is a boric acid. It is characterized in that it does not contain zinc and polyphenylene ether, and the total amount of the components (A) to (E) is 100% by mass.
With such a configuration, when a molded product is formed, it is possible to improve mechanical properties while maintaining excellent flame retardancy.
This mechanism is presumed to be as follows. When the content of the phosphorus-based flame retardant is large in the resin composition containing the polyamide resin, the reinforcing fiber and the flame retardant, the gas derived from the phosphorus-based flame retardant is likely to be released. Therefore, it is conceivable to reduce the content of the flame retardant. However, if the content of the flame retardant is reduced, the flame retardancy is naturally inferior. Therefore, it is conceivable to improve the mechanical strength by relatively increasing the content of the reinforcing fibers, and at the same time, relatively reduce the content of the polyamide resin and reduce the content of the flammable resin component. .. However, in a resin composition having a high content of reinforcing fibers and a relatively small proportion of polyamide resin, the shear stress between the reinforcing fibers and the polyamide resin becomes high, and there is a concern that heat may be generated during compounding or molding. If a fatty acid metal salt is contained as a release agent, it causes a metathesis reaction with the flame retardant phosphinate and releases a phosphorus-derived acid. Such acids attack the polyamide resin and reduce its mechanical strength. On the other hand, in the resin composition of the present invention, since wax is used instead of the fatty acid metal salt as the release agent, the shearing between the glass fiber and the polyamide resin is reduced, and the reaction of releasing acid is further performed. I was able to suppress it. As a result, it is considered that both flame retardancy and mechanical strength have been achieved.
Further, by making the resin composition of the present invention free of zinc borate and polyphenylene ether, it is possible to more effectively suppress the decrease in flame retardancy. Further, by adopting a structure that does not contain zinc borate, a decrease in mechanical strength can be suppressed more effectively.
Hereinafter, the present invention will be described.

<(A) Polyamide resin>
The type of the polyamide resin used in the present invention is not particularly specified, and a known polyamide resin can be used. The polyamide resin may be an aliphatic polyamide resin, a semi-aromatic polyamide resin, or may contain both. In the present invention, it is preferable to include a semi-aromatic polyamide resin.

Aliphatic polyamide resins include, for example, polyamides 6, 11, 12, 46, 66, 610, 612, 6/66, polybis (4-aminocyclohexyl) methanedodecamide, and polybis (3-methyl-4-aminocyclohexyl) methane. Examples thereof include dodecamide and polyisophorone adipamide.

The semi-aromatic polyamide resin is composed of a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, and is 20 to 80 mol% (preferably 30) of the total structural unit of the diamine-derived structural unit and the dicarboxylic acid-derived structural unit. ~ 70 mol%) is a structural unit containing an aromatic ring. By using such a semi-aromatic polyamide resin, the mechanical strength of the obtained molded product can be increased. The semi-aromatic polyamide resin is, for example, polyamide 4T, 6I, 6T, 6T / 6I, 6 / 6T, 66 / 6T, 66 / 6T / 6I, 9T, 10T, xylylenediamine-based polyamide resin, polytrimethylhexamethylene terephthal. Examples thereof include amides and polyundecamethylene hexahydroterephthalamides. The above-mentioned "I" indicates an isophthalic acid component, and "T" indicates a terephthalic acid component.

The polyamide resin used in the present invention is composed of a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, and it is preferable that 70 mol% or more of the diamine-derived structural unit is derived from xylylenediamine. In the present specification, such a polyamide resin may be referred to as a xylylenediamine-based polyamide resin. Further, in the present invention, a polyamide resin in which 50 mol% or more of the constituent unit derived from the dicarboxylic acid of the xylylenediamine-based polyamide resin is derived from the α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms is preferable.

As the xylylenediamine, metaxylylenediamine and paraxylylenediamine can be used. In the present invention, the xylylenediamine is preferably only metaxylylenediamine or a mixture (copolymer) of metaxylylenediamine and paraxylylenediamine.
The ratio of m-xylylenediamine to paraxylylenediamine in xylylenediamine is preferably 100: 0 to 10:90, and may be 95: 5 to 15:85, 90: 10 to 50. : 50 may be used, or 80:20 to 60:40 may be used.
The diamine-derived structural unit of the xylylenediamine-based polyamide resin is preferably 50 mol% or more, more preferably 60 mol% or more, still more preferably 70 mol% or more, still more preferably 80 mol% or more, still more preferably. More than 90 mol%, even more preferably 95 mol% or more, is derived from xylylenediamine. The dicarboxylic acid-derived constituent unit of the xylylene diamine-based polyamide resin is more preferably 70 mol% or more, further preferably 80 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and carbon. It is derived from α, ω-linear aliphatic dicarboxylic acid having a number of 4 to 20.

Examples of diamines other than xylylenediamine that can be used as the raw material diamine component of the xylylenediamine-based polyamide resin include tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, heptamethylenediamine, and octamethylenediamine. Aliphatic diamines such as nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,3-bis (aminomethyl) cyclohexane , 1,4-bis (aminomethyl) cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis ( Examples thereof include alicyclic diamines such as aminomethyl) decalin and bis (aminomethyl) tricyclodecane, diamines having an aromatic ring such as bis (4-aminophenyl) ether, paraphenylenediamine, and bis (aminomethyl) naphthalene. It is possible to use one kind or a mixture of two or more kinds.

Examples of the α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms preferable to be used as the raw material dicarboxylic acid component of the xylylene diamine-based polyamide resin include succinic acid, glutaric acid, pimeric acid, suberic acid, and adipic acid. , Adipic acid, suberic acid, undecanedioic acid, dodecanedioic acid and other aliphatic dicarboxylic acids can be exemplified, and one kind or a mixture of two or more kinds can be used. Of these, adipic acid or sebacic acid is more preferred, and adipic acid is even more preferred.

Examples of the dicarboxylic acid component other than the α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms include phthalic acid compounds such as isophthalic acid, terephthalic acid and orthophthalic acid, 1,2-naphthalenedicarboxylic acid and 1,3. −Naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalene Examples of naphthalenedicarboxylic acids such as dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid can be exemplified, and one kind or a mixture of two or more kinds can be used.

As an example of the embodiment of the polyamide resin used in the present invention, the following blend of the polyamide resin (a1) and the polyamide resin (a2) is exemplified. The blend ratio (mass ratio) of the polyamide resin (a1) and the polyamide resin (a2) is preferably 10: 1 to 5: 1, more preferably 9: 1 to 6: 1, and 8.5. : 1 to 6.5: 1 is more preferable.
<< Polyamide resin (a1) >>
It is composed of a diamine-derived structural unit and a dicarboxylic acid-derived structural unit. 70 mol% or more of the diamine-derived structural unit is derived from xylylenediamine, and 50 mol% or more of the dicarboxylic acid-derived structural unit is carbon. Polyamide resin << polyamide resin (a2), which is derived from α, ω-linear aliphatic dicarboxylic acid (preferably adipic acid) of several 4 to 20, and 90 mol% or more of the xylylenediamine is m-xylylenediamine. ＞＞
It is composed of a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, and 70 mol% or more of the diamine-derived structural unit is derived from xylylenediamine, and 50 mol% or more of the dicarboxylic acid-derived structural unit is carbon. It is derived from α, ω-linear aliphatic dicarboxylic acid (preferably adipic acid) of the number 4 to 20, and the molar ratio of the metaxylylenediamine to the paraxylylenediamine is 95: 5 to 15:85. Polyamide resin As for the more preferable range of the above-mentioned polyamide resin (a1) and the polyamide resin (a2), those described in the case of the xylylenediamine-based polyamide resin are used as long as there is no above-mentioned discrepancy.

The polyamide resin used in the present invention is composed mainly of a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, but does not completely exclude other structural units, such as ε-caprolactam and laurolactam. It goes without saying that the constituent units derived from lactams such as lactams such as, aminocaproic acid, and aliphatic aminocarboxylic acids such as aminoundecanoic acid may be contained. Here, the main component means that, among the structural units constituting the polyamide resin, the total number of the structural units derived from diamine and the structural unit derived from dicarboxylic acid is the largest among all the structural units. In the present invention, the total of the diamine-derived structural unit and the dicarboxylic acid-derived structural unit in the polyamide resin preferably occupies 90% by mass or more, and more preferably 95% by mass or more of all the structural units.

The lower limit of the number average molecular weight (Mn) of the polyamide resin is preferably 6,000 or more, more preferably 8,000 or more, further preferably 10,000 or more, and 15,000 or more. Is even more preferable, 20,000 or more is even more preferable, and 22,000 or more is even more preferable. The upper limit of Mn is preferably 35,000 or less, more preferably 30,000 or less, further preferably 28,000 or less, and even more preferably 26,000 or less. Within such a range, heat resistance, elastic modulus, dimensional stability, and molding processability become better.

The proportion of the polyamide resin in the resin composition of the present invention is 40% by mass to 65% by mass, preferably 41% by mass or more, more preferably 42% by mass or more, and 43% by mass or more. It is more preferable to have. The upper limit of the content is usually 64% by mass or less, preferably 55% by mass or less, more preferably 53% by mass or less, further preferably 50% by mass or less, 48. It may be 5% by mass or less, or 45% by mass or less.
The polyamide resin may contain only one type, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

The resin composition of the present invention may contain a thermoplastic resin other than the polyamide resin. Examples of the thermoplastic resin other than the polyamide resin include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate, polystyrene resins, and acrylic resins. In the molded product of the present invention, the content of the thermoplastic resin other than the polyamide resin is preferably 5% by mass or less, more preferably 3% by mass or less, and 1% by mass or less of the molded product of the present invention. It is more preferable to have.
In the resin composition of the present invention, the xylylenediamine-based polyamide resin preferably occupies 85% by mass or more, more preferably 95% by mass or more, and further occupies 99% by mass or more of the resin component. preferable.

<(B) Reinforcing fiber>
The resin composition of the present invention contains reinforcing fibers having a circular cross section. The term "circle" here is intended to include, in addition to a perfect circle in the geometrical sense, what is usually referred to as a circle in the technical field of the present invention. Reinforcing fibers having a circular cross section tend to have lower flame retardancy than reinforcing fibers having a flat cross section. In the present invention, high flame retardancy has been successfully maintained while using reinforcing fibers having such a circular cross section.

The reinforcing fiber may be an organic reinforcing fiber or an inorganic reinforcing fiber, and the inorganic reinforcing fiber is preferable. Examples of the reinforcing fiber include plant fiber, carbon fiber, glass fiber, alumina fiber, boron fiber, ceramic fiber, aramid fiber and the like, more preferably selected from carbon fiber and glass fiber, and further preferably glass fiber. preferable.

As the glass fiber, a fiber obtained by melt-spinning glass such as E glass, C glass, A glass, S glass, and alkali resistant glass, which are generally supplied, is used, but any glass fiber can be used. It can be used, and is not particularly limited. In the present invention, it is preferable to include E glass.

The glass fiber shall be surface-treated with a surface treatment agent such as a silane coupling agent such as γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, or γ-aminopropyltriethoxysilane. Is preferable. The amount of the surface treatment agent adhered is preferably 0.01 to 1% by mass of the glass fiber. Further, if necessary, a fatty acid amide compound, a lubricant such as silicone oil, an antistatic agent such as a quaternary ammonium salt, a resin having a film-forming ability such as an epoxy resin and a urethane resin, a resin having a film-forming ability, and heat. It is also possible to use a surface-treated mixture of a stabilizer, a flame retardant and the like.

The glass fiber used in the resin composition of the present invention is available as a commercially available product. Examples of commercially available products include T286H, T756H, T289, T289DE, T289H, T296GH manufactured by Nippon Electric Glass (NEG); Owens Corning, DEFT2A, PPG, HP3540; Nitto Boseki, CSG3PA-810S. , CSG3PA-820; manufactured by Central Glass Fiber Co., Ltd., EFH50-31 (both are trade names) and the like.

The reinforcing fibers used in the resin composition of the present invention preferably have a number average fiber length of 1 mm or more, more preferably 2 mm or more, and even more preferably 3 mm or more. The upper limit is preferably 10 mm or less, more preferably 8 mm or less, and even more preferably 5 mm or less.

The reinforcing fibers used in the resin composition of the present invention preferably have a number average fiber diameter of 1 μm or more, more preferably 2 μm or more, and further preferably 5 μm or more. The upper limit is preferably 50 μm or less, more preferably 30 μm or less, and even more preferably 20 μm or less.

The lower limit of the ratio of the reinforcing fibers (preferably glass fibers) in the resin composition of the present invention is 35% by mass or more, preferably 38% by mass or more, and more preferably 40% by mass or more. , 42% by mass or more, more preferably 45% by mass or more. The upper limit of the content is 60% by mass or less, usually 59% by mass or less, preferably 55% by mass or less, and more preferably 52% by mass or less. By setting it to the above lower limit value or more, the mechanical strength can be improved and the flame retardancy can be improved. On the other hand, by setting the amount of the reinforcing fibers to the above upper limit value or less, the moldability tends to be further improved.
The molded product of the present invention may contain only one type of reinforcing fiber or may contain two or more types of reinforcing fibers. When two or more types are included, the total amount is preferably in the above range.

<(C) Phosphorus flame retardant>
The resin composition of the present invention contains a phosphorus-based flame retardant containing at least one of phosphinate and diphosphanate.
The phosphinate or diphosphinate preferably contains at least one of a compound represented by the following formula (I) and a compound represented by the following formula (II).

（式（Ｉ）中、Ｒ¹およびＲ²は、それぞれ独立に、直鎖もしくは分枝鎖の炭素数１〜６のアルキル基、または炭素数６〜１０のアリール基を表す。Ｍはカルシウムイオン、アルミニウムイオン、マグネシウムイオン、または亜鉛イオンを表す。ｍはＭの価数を表す自然数である。）

In formula (I), R ¹ and R ² independently represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms in a straight chain or a branched chain, respectively. M is a calcium ion. , Aluminum ion, magnesium ion, or zinc ion. M is a natural number representing the valence of M.)

In the formula (I), R ¹ and R ² independently represent an alkyl group having 1 to 6 carbon atoms in a straight chain or a branched chain, or an aryl group having 6 to 10 carbon atoms, and are a methyl group and an ethyl group, respectively. , Apropyl group, or phenyl group is preferable. M represents calcium ion, aluminum ion, magnesium ion, or zinc ion. m is a natural number representing the valence of M, preferably 2 or 3.

（式（ＩＩ）中、Ｒ⁴およびＲ⁵は、それぞれ独立に、直鎖もしくは分枝鎖の炭素数１〜６のアルキル基、または炭素数６〜１０のアリール基を表す。Ｒ³は直鎖もしくは分枝鎖の炭素数１〜１０のアルキレン基、炭素数６〜１０のアリーレン基、炭素数７〜１０のアルキルアリーレン基、または炭素数７〜１０のアリールアルキレン基を表す。Ｍはカルシウムイオン、アルミニウムイオン、マグネシウムイオン、または亜鉛イオンを表す。ｎはＭの価数を表す自然数である。ｎ、ａ、ｂは、２×ｂ＝ｎ×ａの関係式を満たす自然数である。）
式（ＩＩ）において、Ｒ⁴およびＲ⁵は、それぞれ独立に、直鎖もしくは分枝鎖の炭素数１〜６のアルキル基、または炭素数６〜１０のアリール基を表し、メチル基、エチル基、プロピル基、またはフェニル基であることが好ましい。Ｒ³は直鎖もしくは分枝鎖の炭素数１〜１０のアルキレン基、炭素数６〜１０のアリーレン基、炭素数７〜１０のアルキルアリーレン基、または炭素数７〜１０のアリールアルキレン基を表し、メチレン基、エチレン基、プロピレン基、フェニレン基であることが好ましい。Ｍはカルシウムイオン、アルミニウムイオン、マグネシウムイオン、または亜鉛イオンを表す。ｎはＭの価数を表す自然数である。ｎ、ａ、ｂは、２×ｂ＝ｎ×ａの関係式を満たす自然数である。ｎは２または３であることが好ましい。ｂは１、２または３であることが好ましく、１または３であることがより好ましい。ａは１または２であることが好ましい。

(In formula (II), R ⁴ and R ⁵ independently represent an alkyl group having 1 to 6 carbon atoms in a straight chain or a branched chain, or an aryl group having 6 to 10 carbon atoms, respectively. R ³ is a direct chain. The chain or branched chain represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkyl arylene group having 7 to 10 carbon atoms, or an arylalkylene group having 7 to 10 carbon atoms. It represents an ion, an aluminum ion, a magnesium ion, or a zinc ion. N is a natural number representing a valence of M. n, a, b are natural numbers satisfying the relational expression of 2 × b = n × a).
In formula (II), R ⁴ and R ⁵ independently represent an alkyl group having 1 to 6 carbon atoms in a straight chain or a branched chain, or an aryl group having 6 to 10 carbon atoms, and are a methyl group and an ethyl group, respectively. , Apropyl group, or phenyl group is preferable. R ³ represents a linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkyl arylene group having 7 to 10 carbon atoms, or an arylalkylene group having 7 to 10 carbon atoms. , Methylene group, ethylene group, propylene group, phenylene group are preferable. M represents calcium ion, aluminum ion, magnesium ion, or zinc ion. n is a natural number representing the valence of M. n, a, and b are natural numbers that satisfy the relational expression of 2 × b = n × a. n is preferably 2 or 3. b is preferably 1, 2 or 3, and more preferably 1 or 3. a is preferably 1 or 2.

Specific examples of the phosphinate or diphosphinate include those produced in an aqueous medium using phosphinic acid and a metal carbonate, a metal hydroxide or a metal oxide. The phosphinate or diphosphinate is basically a monomeric compound, but depending on the reaction conditions, it may be a polymer phosphinate having a degree of condensation of 1 to 3 depending on the environment.

Examples of phosphinic acid or diphosphinic acid include dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid, methanedi (methylphosphinic acid), and benzene-1,4-di (methylphosphinic acid). , Methylphenylphosphinic acid, diphenylphosphinic acid and the like.

Examples of the phosphinate include calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphite, Calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, aluminum methyl-n-propylphosphite, methyl-n -Zinc propylphosphinate, calcium methylphenylphosphinate, magnesium methylphenylphosphinate, aluminum methylphenylphosphinate, zinc methylphenylphosphinate, calcium diphenylphosphinate, magnesium diphenylphosphinate, aluminum diphenylphosphinate, zinc diphenylphosphine, etc. Can be mentioned.

Diphosphinates include methanedi (methylphosphinic acid) calcium, methanedi (methylphosphinic acid) magnesium, methanedi (methylphosphinic acid) aluminum, methanedi (methylphosphinic acid) zinc, and benzene-1,4-di (methylphosphinic acid). Examples thereof include calcium, benzene-1,4-di (methylphosphinic acid) magnesium, benzene-1,4-di (methylphosphinic acid) aluminum, and benzene-1,4-di (methylphosphinic acid) zinc.

Among these phosphinates or diphosphinates, aluminum ethylmethylphosphite, aluminum diethylphosphinate, and zinc diethylphosphinate are particularly preferable from the viewpoint of flame retardancy and electrical properties. Specific products include those manufactured by Clariant, Exolit OP 1230 (aluminum phosphine), and OP 1400, all of which have trade names.

The content of the phosphorus-based flame retardant in the resin composition of the present invention is 1% by mass or more, preferably 2% by mass or more, and more preferably 2.5% by mass or more in the resin composition. It is preferably 3% by mass or more, and more preferably 3% by mass or more. The upper limit is 15% by mass or less, preferably 12% by mass or less, more preferably 10% by mass or less, 8% by mass or less, or 7% by mass or less. It may be 6% by mass or less. Too much flame retardant can cause gas to be released from the nozzle.

The resin composition of the present invention may or may not contain a phosphorus-based flame retardant other than the phosphorus-based flame retardant selected from the phosphinate and the diphosphanate. Examples of phosphorus-based flame retardant agents other than phosphinate and diphosphinate include phosphorus, phosphate, phosphoric acid ester, phosphazene, and reaction products of melamine and phosphoric acid. The reaction product of melamine and phosphoric acid can be referred to in paragraph 0028 of JP-A-2018-065974, the contents of which are incorporated herein by reference.
The content of the other flame retardant is said to be 30% by mass or less, preferably 20% by mass or less, of the total amount of at least one phosphorus-based flame retardant of phosphinate and diphosphinate. It may be 5% by mass or less, 1% by mass or less, or 0.1% by mass or less.

<(D) Wax>
The resin composition of the present invention contains wax. Wax refers to a fat-like substance having a temperature of room temperature or higher, and usually has a melting point of 50 ° C. or higher. As the wax, polyolefin wax, ketone wax, amide wax, ester wax and paraffin wax are preferable.

<< (D-1) Polyolefin Wax >>
Examples of polyolefin waxes include low molecular weight polyethylene, low molecular weight polyethylene copolymers, or modified polyethylene waxes in which polar groups have been introduced by oxidative modification or acid modification thereof. Further, when the modified polyethylene wax having a polar group introduced by oxidative modification or acid modification is blended in an amount of 1 to 10% by mass of the polyolefin wax, the dispersibility in the polyamide resin can be improved, and more. preferable.
The number average molecular weight (Mn) of the polyolefin wax may be appropriately selected and determined, but is preferably less than 20,000, more preferably 500 to 15,000, and more preferably 1,000 to 10,000. Is more preferable, and 1,000 to 9,000 is particularly preferable. The Mn of the polyolefin wax can be measured by gel permeation chromatography (GPC). For other detailed analysis conditions, paragraph 0020 of JP-A-2017-171880 can be referred to, and the contents thereof are incorporated in the present specification.
The polyolefin wax used in the present invention preferably has a melting point of 60 to 145 ° C.
Examples of the polyolefin wax include High Wax 800P (trade name) HDPE-WAX manufactured by Mitsui Chemicals, Inc., Mn8000.

<< (D-2) Ketone Wax >>
Examples of the ketone wax include compounds represented by the following formula (G1).
Equation (G1): R ^11- CO-R ¹²
In formula (G1), R ¹¹ and R ¹² are each independently a linear or branched hydrocarbon group having 9 or more and 25 or less carbon atoms.
Specific examples of the ketone wax include dilignoceryl ketone, dibehenyl ketone, distearyl ketone, dieicosyl ketone, dipalmityl ketone, dimyristyl ketone, dilauryl ketone, lauryl myristyl ketone, lauryl palmityl ketone, and myristyl. Examples thereof include palmityl behenyl ketone, myristyl stearyl ketone, myristyl behenyl ketone, palmityl stearyl ketone, palmityl behenyl ketone and stearyl behenyl ketone.
Specific products include Khao Wax T1 (Kao Corporation, Ketone Wax (Distaryl Ketone)).

<< (D-3) Amide Wax >>
Amide waxes are fatty acid monoamides and / or bisamides. Examples of the fatty acid monoamide include oleic acid amide, erucic acid amide, stearic acid amide, palmitic acid amide, and lauric acid amide, and examples of the fatty acid bisamide include methylene bisstearic acid amide, ethylene bisoleic acid amide, and ethylene bislauric acid amide. Can be mentioned.
Specific products include light amide WH255 (fatty acid bisamide (polycondensation product of stearic acid, sebacic acid and ethylenediamine) manufactured by Kyoeisha Chemical Co., Ltd.).

<< (D-4) Ester Wax >>
Ester wax is an ester of an aliphatic carboxylic acid and an alcohol. As the aliphatic carboxylic acid, for example, the same one as the above-mentioned aliphatic carboxylic acid can be used. On the other hand, examples of alcohols include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, a monohydric or polyhydric saturated alcohol having 30 or less carbon atoms is preferable, and an aliphatic saturated monohydric alcohol or an aliphatic saturated polyhydric alcohol having 30 or less carbon atoms is more preferable. Here, the aliphatic term also contains an alicyclic compound. Specific examples include montanic acid ester wax, beeswax (mixture containing myricyl palmitate as the main component), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate, and glycerin distea. Examples thereof include rate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

<< (D-5) Paraffin Wax >>
Examples of paraffin wax include saturated aliphatic hydrocarbons such as n-paraffin and / or i-paraffin, or low molecular weight polyethylene having a hydroxyl group at the end and having a waxy appearance. The molecular weight of the saturated aliphatic hydrocarbon measured by the GPC method is usually 300 to 1500, preferably 300 to 1000.

The resin composition of the present invention contains wax in an amount of 0.01 to 2% by mass. The lower limit value is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.2% by mass or more. The upper limit value is preferably 1.8% by mass or less, more preferably 1.5% by mass or less, and further preferably 1.0% by mass or less. One type of wax may be used, or two or more types of wax may be used. When two or more types are used, the total amount is within the above range.
The resin composition of the present invention may or may not contain a mold release agent other than wax. In the resin composition of the present invention, it is preferable that the release agent is substantially composed of wax only. Substantially here means, for example, that the content of the other mold release agent is 10% by mass or less of the wax, preferably 5% by mass or less, and 3% by mass or less. It may be 1% by mass or less, 0.1% by mass or less, or 0.01% by mass or less. Needless to say, the resin composition of the present invention may contain a fatty acid metal salt as long as it does not affect the effects of the present invention.

<(E) Other additives>
The resin composition of the present invention may contain an additive (E) 0 to 20% by mass other than the above components (A) to (D). That is, in the resin composition of the present invention, the total amount of the components (A) to (E) is 100% by mass.
Additives include nuclear agents, flame retardant aids, heat stabilizers, light stabilizers, antioxidants, optical brighteners, anti-dripping agents, antistatic agents, anti-fog agents, anti-blocking agents, and fluidity improvers. , Plasticizers, dispersants, antibacterial agents, colorants and other additives. These details can be taken into consideration in paragraphs 0130 to 0155 of Japanese Patent No. 4894982, and these contents are incorporated in the present specification.
The total of these is 0 to 20% by mass, preferably 0.1% by mass or more of the resin composition. Further, the upper limit value is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, and further preferably 1% by mass or less. .. Only one of these additives may be used, or two or more of these additives may be used in combination. When two or more types are used, the total amount is preferably in the above range.

The resin composition of the present invention does not contain zinc borate. Zinc borate is a compound known as a flame retardant aid for phosphorus-based flame retardants, but as a result of examination by the present inventor, the resin composition of the present invention may rather reduce the flame retardancy. Do you get it. In addition, it was found to reduce mechanical strength.
In the present invention, zinc borate is not contained, in addition to the case where the content of zinc borate is completely 0, a small amount of zinc borate is contained within a range that does not affect the effect of the present invention. The purpose is to include the case where it is. For example, the case where it is mixed as an impurity or the case where it is below the detection limit by a normal measurement method is exemplified.

Moreover, the composition of the present invention does not contain polyphenylene ether. Polyphenylene ether is one of the resins that can be blended with the polyamide resin, but as a result of the study by the present inventor, it has been found that the resin composition of the present invention is reduced in flame retardancy when polyphenylene ether is blended.
In the present invention, the term "not containing polyphenylene ether" means that the content of polyphenylene ether is completely 0 and that a small amount of polyphenylene ether is contained within a range that does not affect the effect of the present invention. Is also included. For example, the case where it is mixed as an impurity or the case where it is below the detection limit by a normal measurement method is exemplified.

<< Nuclear agent >>
The nucleating agent is preferably talc and calcium carbonate, more preferably talc.
The lower limit of the average particle size of the nucleating agent is preferably 0.1 μm or more, more preferably 1 μm or more, and further preferably 3 μm or more. The upper limit of the average particle size of the nucleating agent is preferably 40 μm or less, more preferably 30 μm or less, further preferably 28 μm or less, further preferably 15 μm or less, and even more preferably 10 μm or less. Is even more preferable.
The content of the nucleating agent is preferably 0.1 to 2% by mass in the resin composition.

<< Colorant >>
Colorants include inorganic pigments (black pigments such as carbon black, red pigments such as iron red oxide, orange pigments such as molybdate orange, and white pigments such as titanium oxide) and organic pigments (yellow pigments, orange pigments, and red pigments). , Blue pigments, green pigments, etc.).
The content of the colorant is preferably 0.01 to 10% by mass of the composition. The colorant may contain only one kind or two or more kinds. When two or more types are included, the total amount is preferably in the above range.

<Characteristics of resin composition>
When the resin composition of the present invention is molded into an ISO tensile test piece (4 mm thick) in accordance with ISO178, the bending strength in an environment of a temperature of 23 ° C. and a humidity of 50% is 330 MPa or more. It is more preferably 350 MPa or more, further preferably 360 MPa or more, and even more preferably 368 MPa or more. The upper limit of the bending strength is not particularly defined, but the required performance is satisfied even at 400 MPa or less.

When the resin composition of the present invention is molded into an ISO tensile test piece (4 mm thick) in accordance with ISO178, the flexural modulus in an environment of a temperature of 23 ° C. and a humidity of 50% is 13 GPa or more. Is more preferable, 15 GPa or more is more preferable, and 17 GPa or more is further preferable. The upper limit is not particularly determined, but 25 GPa or less is practical, and even if it is less than 25 GPa, the required performance is satisfied.
The mechanical properties are measured by the methods described in Examples described below.

When the resin composition of the present invention is molded into an ISO tensile test piece (4 mm thick) in accordance with ISO179-1 and ISO, the notched Charpy impact strength in an environment of a temperature of 23 ° C. and a humidity of 50% is , is preferably 10 kJ / m ² or more, more preferably 11 kJ / m ² or more. The upper limit is not specified, but 20 kJ / m ² or less is practical, and even if it is less than that, the required performance is satisfied.

When the resin composition of the present invention is molded into a test piece having a thickness of 1.5 mm, it is preferably evaluated as V-0 in the UL94 test. Details of the UL94 test are measured according to the methods described in Examples below.

<Manufacturing method of resin composition>
In the present invention, the method for producing the resin composition is not particularly specified, and a known method for producing the thermoplastic resin composition can be widely adopted. Specifically, each component is premixed using various mixers such as a tumbler and a Henschel mixer, and then melt-kneaded with a Banbury mixer, a roll, a brabender, a single-screw extruder, a twin-screw extruder, a kneader, or the like. The resin composition can be produced by the above.

Further, for example, the resin composition can be produced without mixing each component in advance, or by mixing only a part of the components in advance and supplying the components to an extruder using a feeder to melt and knead them.
Further, for example, a composition obtained by premixing some components and supplying them to an extruder to melt and knead is used as a masterbatch, and this masterbatch is mixed with the remaining components again and melt-kneaded. Pellets can also be produced.

<Manufacturing method of molded products>
The molded article of the present invention is formed from the resin composition of the present invention.
The method for producing the molded product of the present invention is not particularly defined.
For example, in the molded product of the present invention, each component may be melt-kneaded and then directly molded by various molding methods, or each component may be melt-kneaded and pelletized, and then melted again to form various moldings. It may be molded by the method.

The method for molding the molded product is not particularly limited, and a conventionally known molding method can be adopted. For example, an injection molding method, an injection compression molding method, an extrusion molding method, a deformed extrusion method, a transfer molding method, a hollow molding method, etc. Gas assist hollow molding method, blow molding method, extrusion blow molding, IMC (in-mold coating molding) molding method, rotary molding method, multi-layer molding method, two-color molding method, insert molding method, sandwich molding method, foam molding method, addition A pressure molding method and the like can be mentioned.

The shape of the molded product of the present invention is not particularly limited and may be appropriately selected depending on the intended use and purpose of the molded product. For example, a plate shape, a plate shape, a rod shape, a sheet shape, a film shape, or a cylindrical shape. , Circular shape, circular shape, elliptical shape, gear shape, polygonal shape, deformed product, hollow product, frame shape, box shape, panel shape and the like.
The field of use of the molded product of the present invention is not particularly defined, and transport machine parts such as automobiles, general machine parts, precision machine parts, electronic / electrical equipment parts, OA equipment parts, building materials / housing related parts, medical equipment, etc. Widely used in leisure sports equipment, play equipment, medical products, daily necessities such as food packaging films, defense and aerospace products, etc.

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<Raw materials>
(A) Polyamide resin MXD6 (6000): Polymethaxylylene adipamide, manufactured by Mitsubishi Gas Chemical Company, MX nylon 6000
Modified MXD6 (MP6): Synthesized according to the following synthesis example.
<Synthesis of MP6>
7220 g (49.4 mol) of adipic acid (Roadia) and sodium acetate / hypophosphorous acid in a reaction vessel equipped with a stirrer, a splitter, a total crimp, a thermometer, a dropping funnel and a nitrogen introduction tube, and a strand die. 11.66 g of sodium monohydrate (molar ratio = 1 / 1.5) was charged, sufficiently replaced with nitrogen, and then heated and melted to 170 ° C. while stirring the inside of the system under a small amount of nitrogen stream. ..
6647 g of mixed xylylenediamine (34.16 mol of metaxylylenediamine, 14.64 mol of paraxylylenediamine, manufactured by Mitsubishi Gas Chemical Company, Inc.) having a molar ratio of metaxylylenediamine and paraxylylenediamine of 70/30 was placed in a reaction vessel. The inside temperature was continuously raised to 260 ° C. over 2.5 hours while being dropped onto the melt inside under stirring and the generated condensed water was discharged to the outside of the system. After completion of the dropping, the internal temperature was raised, and when the temperature reached 270 ° C., the pressure inside the reaction vessel was reduced, and the internal temperature was further raised to continue the melt polycondensation reaction at 280 ° C. for 20 minutes. Then, the inside of the system was pressurized with nitrogen, and the obtained polymer was taken out from the strand die and pelletized to obtain a polyamide resin. Hereinafter, it may be referred to as "MP6".

(B) Reinforcing fiber T275H: Glass fiber having a circular cross section (manufactured by Nippon Electric Glass Co., Ltd., E glass, chopped strand cut into 3 mm, number average fiber diameter 10 μm)

(C) Phosphorus-based flame retardant EXOLIT OP1400: Metallic phosphinic acid salt manufactured by Clariant Chemicals, Inc.

(D) Wax Ketone Wax: Kao Wax T1
PE Wax: Mitsui Chemicals, High Wax 800P
Amide wax: Light Amide WH255 manufactured by Kyoeisha Chemical Co., Ltd.
(D') Release agent other than wax CS-8CP: Calcium montanate, manufactured by Nitto Kasei Kogyo Co., Ltd. St-Ca: Calcium stearate, manufactured by Nitto Kasei Kogyo Co., Ltd.

(E) Nuclear agent Nuclear agent MW5000S: Talc, manufactured by Hayashi Kasei Co., Ltd., number average particle diameter 5 μm
(F) Colorant Carbon black: Mitsubishi Chemical, carbon black # 45 (furness black, DBP absorption amount 53 g / 100 cm ³ )

Other PPE: Modified polyphenylene ether resin (modified PPE) obtained by the following production method, SEBS content 13% by mass
<Manufacturing method>
Polyphenylene ether resin (Polyxylenol Singapore "trade name: PX100L", poly (2,6-dimethyl-1,4-phenylene) ether having an intrinsic viscosity of 0.47 dL / g measured in chloroform at a temperature of 30 ° C. ) 100 parts by mass and 0.8 parts by mass of maleic anhydride (first-class reagent) and hydrogen additive of styrene resin (styrene compound / conjugated diene compound block copolymer) (Shell's "trade name: Clayton G1652", A number average molecular weight of 49,000) 15 parts by mass was sufficiently mixed with a super mixer, and the obtained mixture was melt-kneaded using a twin-screw extruder (“TEX30XCT” manufactured by Japan Steel Works, Ltd.) to be pelletized.
Zinc borate: zinc borate, borax Japan Co., Ltd. "product name: Fire break _{ZB", 2ZnO · 3B 2 O 3 ·} 3.5H 2 O, the number average particle diameter 7~9μm

Examples 1 to 3 and Comparative Examples 1 to 9
<Compound>
Of the components listed in Table 1 or Table 2, the components excluding glass fibers are weighed (Tables 1 and 2 are indicated by parts by mass), blended with a tumbler, and twin-screw extruder (Toshiba Machine Co., Ltd.). It was poured from the root of TEM26SS manufactured by the company and melted. Then, the glass fiber was side-fed to prepare a pellet of a polyamide resin. The temperature of the twin-screw extruder was set to 280 ° C.

<Flexural strength and flexural modulus>
After the polyamide resin pellets obtained by the above manufacturing method are dried at 120 ° C. for 3 hours, the cylinder temperature is 280 ° C. and the mold temperature is 130 ° C. in an injection molding machine (“NEX140III” manufactured by Nissei Resin Industry Co., Ltd.). An ISO tensile test piece (4 mm thick) was injection-molded under the condition of a molding cycle of 50 seconds.
In accordance with ISO178, the flexural strength (unit: MPa) and flexural modulus (unit: GPa) were measured in an environment of a temperature of 23 ° C. and a humidity of 50% using the above ISO tensile test piece (4 mm thickness). .. The results are shown in Table 1 or Table 2 below.

<Charpy impact strength with notch>
In accordance with ISO179-1 and ISO, the notched Charpy impact strength was measured using the above ISO tensile test piece (4 mm thick) in an environment of a temperature of 23 ° C. and a humidity of 50% using a 1J hammer. The results are shown in Table 1 or Table 2 below.

<Flame retardant (UL94 test)>
The polyamide resin pellets obtained by the above-mentioned production method were dried at 120 ° C. for 4 hours, and then injection-molded using a J50-EP type injection molding machine manufactured by Japan Steel Works, and had a length of 125 mm and a width of 13 mm. A combustion piece for UL test having a thickness of 1.5 mm was molded. The cylinder temperature and the mold temperature were set between 280 ° C and 130 ° C, respectively.
The UL test combustion piece obtained by the above method was humidity-controlled for 48 hours in a thermostatic chamber at a temperature of 23 ° C. and a humidity of 50%, and was carried out in accordance with the UL94 test. The results are shown in Table 1 or Table 2 below.

<Gas ejected from the nozzle>
The amount of gas ejected from the nozzle during resin replacement when molding the above-mentioned UL test combustion piece was visually evaluated.
The results are shown in Table 1 or Table 2 below.
A: A thin gas gently rises upward from the resin discharged from the nozzle B: The gas is thicker than A and / or the gas is vigorously injected together with the resin discharged from the nozzle than A <Releasability>
After the polyamide resin pellets obtained by the above manufacturing method are dried at 120 ° C. for 3 hours, the cylinder temperature is 280 ° C. and the mold temperature is 130 ° C. A 100 mm × 100 mm × 2 mm flat plate was injection-molded under the condition of a molding cycle of 30 seconds, and the presence or absence of warpage when the molded product was taken out from the mold was confirmed. If the releasability of the material is extremely low, the releasability of the flat plate molded product increases, and the flat plate molded product is strongly pressed by the protruding pin to be deformed and confirmed as warpage.
The results are shown in Table 1 or Table 2 below.
A: No warpage was confirmed B: A visually recognizable level of warpage was confirmed (other than A above).

As is clear from the above results, the resin composition of the present invention was able to achieve both good mechanical strength and high flame retardancy. Furthermore, there was no gas ejected from the nozzle of the flame retardant, and the releasability was also good.
On the other hand, in Comparative Examples 1, 2 and 5 in which the fatty acid metal salt was used instead of the wax, the mechanical strength was not improved. Further, even if wax was used, when the amount of the flame retardant was large (Comparative Example 3), the mechanical strength was not improved. In addition, gas was ejected from the nozzle. When the content of glass fiber was low (Comparative Examples 4 and 5), the flame retardancy was inferior.
Moreover, when wax was not contained (Comparative Example 6), the releasability was inferior.
Further, when the amount of the flame retardant was small (Comparative Example 7), the flame retardancy was inferior.
In addition, when it contained polyphenylene ether or zinc borate (Comparative Examples 8 and 9), the flame retardancy was inferior. In particular, Comparative Example 9 containing zinc borate was also inferior in mechanical strength.
In particular, when the content of glass fiber is low (Comparative Examples 4 and 5), glass has the same mechanical strength and flame retardancy regardless of the type of mold release agent (wax, fatty acid metal salt). It was found that the effect of the present invention was surprising in that as the fiber content increased (Example 1, Comparative Example 1), there was a significant difference in mechanical strength.

Claims (5)

(A) 40-65% by mass polyamide resin,
(B) Reinforcing fiber having a circular cross section of 35 to 60% by mass,
(C) A phosphorus-based flame retardant containing at least 1 to 15% by mass of phosphinate and diphosphinate.
(D) 0.01 to 2% by mass of wax, and
(E) Consists of only 0 to 20% by mass of additives
The additive is free of zinc borate and polyphenylene ethers.
A resin composition in which the total amount of the components (A) to (E) is 100% by mass. (B) The resin composition according to claim 1, wherein the reinforcing fiber contains glass fiber. The resin composition according to claim 1 or 2, wherein the polyamide resin (A) is a semi-aromatic polyamide resin. The resin composition according to any one of claims 1 to 3, wherein the flame retardant contains at least one compound represented by the following formula (I) and a compound represented by the following formula (II).

In formula (I), R ¹ and R ² independently represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms in a straight chain or a branched chain, respectively. M is a calcium ion. , Aluminum ion, magnesium ion, or zinc ion. M is a natural number representing the valence of M.)

(In formula (II), R ⁴ and R ⁵ independently represent an alkyl group having 1 to 6 carbon atoms in a straight chain or a branched chain, or an aryl group having 6 to 10 carbon atoms, respectively. R ³ is a direct chain. The chain or branched chain represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkyl arylene group having 7 to 10 carbon atoms, or an arylalkylene group having 7 to 10 carbon atoms. It represents an ion, an aluminum ion, a magnesium ion, or a zinc ion. N is a natural number representing a valence of M. n, a, b are natural numbers satisfying the relational expression of 2 × b = n × a). A molded product formed from the resin composition according to any one of claims 1 to 4.