JP6618604B1 - Flame retardant resin composition, cable, molded body, flame retardant master batch and flame retardant using the same - Google Patents

Abstract

An object of the present invention is to provide a flame-retardant resin composition having excellent flame retardancy and capable of suppressing separation of a flame retardant. A base resin (A) containing a polyolefin resin, an organic phosphorus compound (B), and a hindered amine compound (C), wherein the organic phosphorus compound (B) is represented by the following general formula (1): A flame-retardant resin composition wherein the hindered amine compound (C) has a piperidine ring. (In the general formula (1), X1 and X2 represent a hydrocarbon group which may have a substituent and may be the same or different.)

Description

  The present invention relates to a flame retardant resin composition, a cable using the same, a molded article, a flame retardant master batch, and a flame retardant.

  Polyolefin resins have excellent mechanical properties and are widely used in building materials, packaging materials, OA equipment, automobile members, cables, and the like. Since polyolefin resin is a flammable substance, it is used in a state in which various flame retardants such as halogen flame retardant, phosphorus flame retardant, metal hydrate flame retardant and the like are added. However, although halogen-based flame retardants can impart excellent flame retardancy, they are likely to generate toxic gases and smoke during combustion and are subject to regulation in some countries. Therefore, in recent years, a flame retardant resin composition using a non-halogen flame retardant has been demanded. As such a flame retardant resin composition, a flame retardant resin composition using a phosphate ester and a NOR-type hindered amine compound in combination is known (see Patent Document 1 below).

JP 2017-66299 A

  The flame retardant resin composition described in Patent Document 1 exhibits excellent flame retardancy. However, the flame retardant resin composition described in Patent Document 1 has room for improvement in terms of suppressing separation of the flame retardant. Here, the separation of the flame retardant means that when the flame retardant is kneaded with the resin, the flame retardant is separated (not mixed), or once dispersed in the resin composition, the flame retardant is left as it is or decomposed. Thus, it is discharged in the solid or liquid state on the surface of the resin composition, and the flame retardancy is also lowered.

  The present invention has been made in view of the above circumstances, and has a flame retardant resin composition that has excellent flame retardancy and can suppress the separation of the flame retardant, a cable, a molded body, and a flame retardant master using the same. The object is to provide batches and flame retardants.

  The present inventors have repeatedly studied in order to solve the above problems. As a result, it has been found that the above problem can be solved by a flame retardant resin composition in which a specific organic phosphorus compound and a specific hindered amine compound are blended with a base resin containing a polyolefin resin.

（上記一般式（１）中、Ｘ^１及びＸ^２は、置換基を有してもよい炭化水素基を表し、同一でも異なってもよい）

（上記一般式（２）中、Ｒ^１〜Ｒ^４は各々独立に、炭素数１〜８のアルキル基を表し、Ｒ^５は、炭素数１〜５０のアルキル基、炭素数５〜１２のシクロアルキル基、炭素数７〜２５のアラルキル基又は炭素数６〜１２のアリール基を表す。） That is, the present invention includes a base resin (A) containing a polyolefin resin, an organic phosphorus compound (B), and a hindered amine compound (C), and the organic phosphorus compound (B) is represented by the following general formula (1). The hindered amine compound (C) is a flame retardant resin composition having a group represented by the following general formula (2).

(In the general formula (1), X ¹ and X ² represent a hydrocarbon group which may have a substituent, and may be the same or different.)

(In the general formula (2), R ^{1 to} R ⁴ each independently represents an alkyl group having 1 to 8 carbon atoms, and R ⁵ represents an alkyl group having 1 to 50 carbon atoms and a cyclohexane having 5 to 12 carbon atoms. Represents an alkyl group, an aralkyl group having 7 to 25 carbon atoms, or an aryl group having 6 to 12 carbon atoms.)

  The flame retardant resin composition of the present invention has excellent flame retardancy and can suppress separation of the flame retardant.

  In addition, the present inventors guess as follows about the reason why the flame retardant resin composition of the present invention has excellent flame retardancy.

  That is, since the organophosphorus compound (B) represented by the general formula (1) contains a large amount of phosphorus in the molecular structure and is difficult to separate from the base resin (A), it has excellent flame retardancy. On the other hand, the hindered amine compound (C) also has a group represented by the general formula (2), and can impart excellent flame retardancy. As a result, it is considered that the flame retardant resin composition has excellent flame retardancy.

  In addition, although the reason why the flame retardant resin composition of the present invention suppresses the separation of the flame retardant is not clear, the present inventors presume as follows.

  That is, since the organophosphorus compound has a spiro ring structure, it has a high melting point, does not melt during molding of the flame retardant resin composition, and is difficult to separate from the polyolefin resin. On the other hand, when the flame retardant resin composition does not contain the organophosphorus compound (B), the hindered amine compound (C) is melted when the flame retardant resin composition is molded, as compared with the organophosphorus compound (B). Tends to be easily separated from the polyolefin resin. On the other hand, since the flame retardant resin composition contains the organophosphorus compound (B), the general formula (2) of the organophosphorus compound (B) and the hindered amine compound (C) in the flame retardant resin composition of the present invention. ), The hindered amine compound (C) is difficult to separate from the organophosphorus compound (B) even when the flame retardant resin composition is molded. For this reason, it becomes difficult to separate the hindered amine compound (C) from the polyolefin resin even when the flame retardant resin composition is molded. As a result, it is considered that separation of the flame retardant is suppressed in the flame retardant resin composition.

In the flame retardant resin composition, in the general formula (1), the hydrocarbon group represented by X ¹ and X ² is, for example, an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

In the flame retardant resin composition, in the general formula (1), the hydrocarbon group represented by X ¹ and X ² is preferably an aromatic hydrocarbon group.

  In this case, the hydrolysis resistance of the flame retardant resin composition can be further improved. The reason why the hydrolysis resistance is thus improved is not clear, but the aromatic hydrocarbon group becomes a steric hindrance to the water molecule, or due to electronic action, the hydrolysis of the organophosphorus compound (B). It is thought that it is because it is preventing.

  In the flame retardant resin composition, the aromatic hydrocarbon group is preferably a phenylmethyl group (benzyl group).

  In this case, the hydrolysis resistance and flame retardancy of the flame retardant resin composition can be improved more effectively.

In the flame retardant resin composition, the number of groups represented by the general formula (2) per 1 g (hereinafter referred to as “amine number”) in the hindered amine compound (C) is 1 × 10 ²¹ or more. It is preferable that

In this case, the flame retardancy of the flame retardant resin composition can be further improved as compared with a case where the number of amines per 1 g in the hindered amine compound (C) is less than 1 × 10 ²¹ .

  In the said flame-retardant resin composition, it is preferable that the said hindered amine compound (C) has two or more groups represented by the said General formula (2) in 1 molecule.

  In this case, the hindered amine compound (C) can further improve the flame retardancy of the flame retardant resin composition as compared with the case where only one group represented by the general formula (2) is included in one molecule. it can.

In the flame-retardant resin composition, wherein in the general formula (2), R ⁵ is an alkyl group having 1 to 30 carbon atoms, or preferably represents a cycloalkyl group having 5 to 12 carbon atoms.

In this case, in the general formula (2), compared to the case where R ⁵ is neither an alkyl group having 1 to 30 carbon atoms nor a cycloalkyl group having 5 to 12 carbon atoms, the flame retardancy of the flame retardant resin composition Can be further improved.

  In the said flame-retardant resin composition, it is preferable that the said hindered amine compound (C) is a solid at 25 degreeC.

  In this case, the processability of the flame retardant resin composition is further improved as compared with the case where the hindered amine compound (C) is liquid at 25 ° C.

  In the said flame-retardant resin composition, it is preferable that the said hindered amine compound (C) has a decomposition temperature of 240 degreeC or more.

  In this case, compared with the case where the decomposition temperature of a hindered amine compound (C) is less than 240 degreeC, the flame retardance and workability of a flame-retardant resin composition improve more.

  In the said flame-retardant resin composition, it is preferable that the said hindered amine compound (C) contains a triazine ring.

  In this case, compared with the case where a hindered amine compound (C) does not contain a triazine ring, the flame retardance and workability of a flame retardant resin composition can be improved more.

In the flame-retardant resin composition, in the general formula (2), R ⁵ represents an example cycloalkyl group having 5 to 12 carbon atoms.

  In the said flame-retardant resin composition, it is preferable that the said hindered amine compound (C) has a decomposition temperature of 250 degreeC or more.

  In this case, compared with the case where the decomposition temperature of a hindered amine compound (C) is less than 250 degreeC, the flame retardance and workability of a flame retardant resin composition can be improved more.

In the flame-retardant resin composition, wherein in the general formula (2), R ⁵ is preferably an alkyl group having 1 to 30 carbon atoms.

In this case, in the general formula (2), the flame retardancy and workability of the flame retardant resin composition can be further improved as compared to the case where R ⁵ is not an alkyl group having 1 to 30 carbon atoms.

  In the said flame-retardant resin composition, it is preferable that the said hindered amine compound (C) does not contain a triazine ring.

  In this case, compared with the case where the hindered amine compound (C) contains a triazine ring, coloring (yellowing) during deterioration due to heat or light can be further suppressed.

  The flame retardant resin composition preferably further contains an anti-drip agent (D).

  In this case, it becomes possible to suppress dripping at the time of combustion of the flame retardant resin composition.

  Moreover, this invention is equipped with the transmission medium comprised with a conductor or an optical fiber, and the insulator which coat | covers the said transmission medium, and the said insulator contains the insulation part comprised with the flame-retardant resin composition mentioned above. The cable.

  According to the cable of the present invention, the insulating portion is composed of a flame retardant resin composition that has excellent flame retardancy and can suppress the separation of the flame retardant. For this reason, the cable of this invention has the outstanding flame retardance, and it becomes possible to maintain the flame retardance over a long period of time. Therefore, the cable of the present invention does not need to be replaced for a long period.

  Moreover, this invention is a molded object containing the said flame retardant resin composition.

  This molded object has the flame retardance which was excellent and can suppress isolation | separation of a flame retardant. For this reason, the molded object of this invention has the outstanding flame retardance, and it becomes possible to maintain the flame retardance over a long period of time. For this reason, the molded article of the present invention does not require replacement over a long period of time.

  The molded body may include at least one sheet layer containing the flame retardant resin composition.

  Moreover, this invention is a flame retardant masterbatch which consists of the said flame retardant resin composition.

  The flame retardant masterbatch of the present invention comprises the flame retardant resin composition, and the flame retardant resin composition has excellent flame retardancy and can suppress the separation of the flame retardant. For this reason, even if the flame retardant masterbatch of this invention knead | mixes with other resin and manufactures a molded object, the molded object has the outstanding flame retardance and can suppress isolation | separation of a flame retardant.

（上記一般式（１）中、Ｘ^１及びＸ^２は置換基を有してもよい炭化水素基を表し、同一でも異なってもよい。）

（上記一般式（２）中、Ｒ^１〜Ｒ^４は各々独立に、炭素数１〜８のアルキル基を表し、Ｒ^５は、炭素数１〜５０のアルキル基、炭素数５〜１２のシクロアルキル基、炭素数７〜２５のアラルキル基又は炭素数６〜１２のアリール基を表す。） Furthermore, the present invention includes an organic phosphorus compound (B) and a hindered amine compound (C), wherein the organic phosphorus compound (B) is represented by the following general formula (1), and the hindered amine compound (C) is A flame retardant having a group represented by formula (2).

(In the general formula (1), X ¹ and X ² represent a hydrocarbon group which may have a substituent, and may be the same or different.)

(In the general formula (2), R ^{1 to} R ⁴ each independently represents an alkyl group having 1 to 8 carbon atoms, and R ⁵ represents an alkyl group having 1 to 50 carbon atoms and a cyclohexane having 5 to 12 carbon atoms. Represents an alkyl group, an aralkyl group having 7 to 25 carbon atoms, or an aryl group having 6 to 12 carbon atoms.)

  This flame retardant can impart excellent flame retardancy to a flame retardant resin composition when it is kneaded with a base resin (A) containing a polyolefin resin to produce a flame retardant resin composition. Moreover, since the flame retardant of the present invention is hardly separated from the base resin (A) even when kneaded with the base resin (A) containing the polyolefin resin, it is possible to suppress the separation of the flame retardant in the flame retardant resin composition.

In the flame retardant, in the general formula (1), the hydrocarbon group represented by X ¹ and X ² is, for example, an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

In the flame retardant, in the general formula (1), the hydrocarbon group represented by X ¹ and X ² is preferably an aromatic hydrocarbon group.

  This flame retardant can further improve the hydrolysis resistance of the flame retardant resin composition when it is kneaded with a base resin (A) containing a polyolefin resin to produce a flame retardant resin composition.

  In the flame retardant, the aromatic hydrocarbon group is preferably a phenylmethyl group.

  This flame retardant, when kneaded with a base resin (A) containing a polyolefin resin to produce a flame retardant resin composition, makes the hydrolysis resistance and flame resistance of the flame retardant resin composition more effective. Can be improved.

In the present invention, the “decomposition temperature” of a hindered amine compound refers to a decomposition temperature measured by thermogravimetric / differential analysis (TG / DTA). Specifically, for a sample comprising a hindered amine compound, the following measurement is performed. The decomposition temperature measured using the apparatus under the following measurement conditions. Here, the decomposition temperature is a temperature when the weight of the hindered amine compound is reduced by 1%.
(measuring device)
Product name “TG / DTA6300” (manufactured by Hitachi High-Tech Science Co., Ltd.)
(Measurement condition)
Sample amount: about 5mg
Measurement temperature: From 25 ° C. to 600 ° C. Measurement atmosphere: Air flow (200 mL / min)
Temperature rising rate: 10 ° C / min Sample container material: Aluminum (Al)

  ADVANTAGE OF THE INVENTION According to this invention, it has the flame retardance which was excellent, and the flame retardant resin composition which can suppress isolation | separation of a flame retardant, the cable using this, a molded object, a flame retardant masterbatch, and a flame retardant are provided.

It is a partial side view which shows 1st Embodiment of the cable of this invention. It is sectional drawing along the II-II line of FIG. It is sectional drawing which shows 2nd Embodiment of the cable of this invention.

  Hereinafter, embodiments of the present invention will be described in detail.

（上記一般式（１）中、Ｘ^１及びＸ^２は、置換基を有してもよい炭化水素基を表し、同一でも異なってもよい。）

（上記一般式（２）中、Ｒ^１〜Ｒ^４は各々独立に、炭素数１〜８のアルキル基を表し、Ｒ^５は、炭素数１〜５０のアルキル基、炭素数５〜１２のシクロアルキル基、炭素数７〜２５のアラルキル基又は炭素数６〜１２のアリール基を表す。） <Flame-retardant resin composition>
The flame retardant resin composition of the present invention contains a base resin (A) containing a polyolefin resin and a flame retardant, and the flame retardant contains an organic phosphorus compound (B) and a hindered amine compound (C). Here, the organic phosphorus compound (B) is represented by the following general formula (1), and the hindered amine compound (C) has a group represented by the following general formula (2).

(In the general formula (1), X ¹ and X ² represent a hydrocarbon group which may have a substituent, and may be the same or different.)

(In the general formula (2), R ^{1 to} R ⁴ each independently represents an alkyl group having 1 to 8 carbon atoms, and R ⁵ represents an alkyl group having 1 to 50 carbon atoms and a cyclohexane having 5 to 12 carbon atoms. Represents an alkyl group, an aralkyl group having 7 to 25 carbon atoms, or an aryl group having 6 to 12 carbon atoms.)

  The flame retardant resin composition of the present invention has excellent flame retardancy and can suppress separation of the flame retardant. Moreover, in the flame retardant resin composition of the present invention, the flame retardant is difficult to separate from the base resin (A). For this reason, the flame retardant resin composition of the present invention is useful as a flame retardant masterbatch containing a flame retardant at a high concentration.

  Hereinafter, the base resin (A), the organic phosphorus compound (B), and the hindered amine compound (C) will be described in detail.

(A) Base resin Base resin (A) contains polyolefin resin. The polyolefin resin has a structural unit derived from an olefin (unsaturated aliphatic hydrocarbon) in the molecule, and is composed of a non-modified polyolefin resin or a modified polyolefin resin. These may be used alone or in admixture of two or more.

(A1) Non-modified polyolefin resin Examples of the non-modified polyolefin resin include ethylene-based polymers, propylene-based polymers, and olefin-based thermoplastic elastomers. These can be used alone or in admixture of two or more.

  An ethylene polymer is a polymer containing a structural unit derived from ethylene. Examples of the ethylene polymer include polyethylene, ethylene-α olefin copolymer, and ethylene propylene diene copolymer.

  Examples of polyethylene include high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear polyethylene (LLDPE), very low density polyethylene (VLDPE), and metallocene very low density polyethylene. It is done. These may be used alone or in admixture of two or more.

  A propylene-type polymer means the polymer containing the structural unit mainly derived from propylene. Examples of the propylene polymer include homopolypropylene, propylene-ethylene copolymer, and propylene-α olefin copolymer. Examples of the α-olefin include 1-butene, 2-butene, 1-hexene and 2-hexene.

  When the propylene-based polymer is a copolymer such as a propylene-ethylene copolymer or a propylene-α-olefin copolymer, the copolymer may be a block copolymer or a random copolymer, It is preferably a coalescence. When this copolymer is a block copolymer, the abrasion resistance of the flame-retardant resin composition can be further improved as compared with the case of a random copolymer.

  Examples of the olefin elastomer include polypropylene elastomer and olefin-ethylene-butylene-olefin copolymer such as olefin crystal-ethylene-butylene-olefin crystal block copolymer (CEBC copolymer). These can be used alone or in combination of two or more.

  The non-modified polyolefin resin preferably contains an olefin elastomer from the viewpoint of improving impact resistance.

(A2) Modified polyolefin resin The modified polyolefin resin refers to a resin obtained by modifying the above-described polyolefin resin or a precursor thereof by grafting or copolymerization. Examples of the functional group introduced by modification include a carboxyl group, an acid anhydride group, a methacryloxy group, an acryloxy group, an acrylic group, an acetyl group, and an alkoxy group (for example, a methoxy group or an ethoxy group). Among these, a carboxyl group and an acid anhydride group are preferable. In this case, the abrasion resistance of the flame retardant resin composition can be improved more effectively than when the functional group introduced by modification is a functional group other than a carboxyl group and an acid anhydride group. Substances used for grafting or copolymerization include acids, acid anhydrides and derivatives thereof. Examples of the acid include carboxylic acids such as acetic acid, acrylic acid, maleic acid, and methacrylic acid. Examples of the acid anhydride include carboxylic anhydrides such as maleic anhydride.

  Examples of the modified resin include ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid ester copolymer, maleic acid modified polyolefin, maleic anhydride modified polyolefin, maleic acid modified styrene elastomer, and Examples thereof include maleic anhydride-modified styrene elastomer.

(A3) Non-polyolefin resin The base resin (A) may further contain a non-polyolefin resin in addition to the polyolefin resin. The non-polyolefin resin preferably contains a non-olefin elastomer from the viewpoint of improving impact resistance. Examples of the non-olefin elastomer include styrene-butadiene rubber (SBR), styrene-ethylene-butadiene-styrene copolymer (SEBS copolymer), styrene-propylene-butadiene-styrene copolymer (SPBS copolymer), Block copolymers of olefin and styrene, such as styrene-butadiene-styrene copolymer (SBS copolymer) and styrene-isoprene-styrene copolymer (SIS copolymer), and hydrogenation to reform them Hydrogenated products (hydrogenated SBR, hydrogenated SEBS copolymer, hydrogenated SPBS copolymer, hydrogenated SBS copolymer, hydrogenated SIS copolymer). These can be used alone or in combination of two or more.

(B) Organophosphorus Compound The organophosphorus compound (B) is a flame retardant and is represented by the following general formula (1) as described above.

In the general formula (1), X ¹ and X ² represents a hydrocarbon group which may have a substituent. X ¹ and X ² may be the same as or different from each other.

  Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group.

  The aliphatic hydrocarbon group may have any of cyclic, linear, and branched structures. Examples of the aliphatic hydrocarbon group include an alkyl group and a cycloalkyl group.

  Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, and the like. Group, hexadecyl group, heptadecyl group, octadecyl group and the like.

  Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cycloundecyl group, and a cyclododecyl group.

  The number of carbon atoms of the aliphatic hydrocarbon group is not particularly limited, but is usually 1 to 10, preferably 1 to 4.

  Examples of the aromatic hydrocarbon group include an aryl group and an aralkyl group.

  Examples of the aryl group include a phenyl group, a naphthyl group, and an anthryl group.

  Examples of the aralkyl group include phenylmethyl group (benzyl group), phenylethyl group, phenylpropyl group, naphthylmethyl group, naphthylethyl group, anthrylmethyl group, anthrylethyl group and the like.

In the general formula (1), X ¹ and X ² are preferably aromatic hydrocarbon groups. In this case, the hydrolysis resistance of the flame retardant resin composition can be further improved.

Among these, the aromatic hydrocarbon group is preferably a phenylmethyl group (benzyl group). In this case, compared with the case where X ¹ and X ² in the general formula (1) are not phenylmethyl groups, the hydrolysis resistance and flame retardancy of the flame retardant resin composition can be improved more effectively. .

  The blending ratio of the organophosphorus compound (B) with respect to 100 parts by mass of the base resin (A) is not particularly limited, but is preferably 0.1 parts by mass or more. In this case, the flame retardancy of the flame retardant resin composition is further improved as compared with the case where the blending ratio of the organophosphorus compound (B) to 100 parts by mass of the base resin (A) is less than 0.1 parts by mass. Can do.

  The blending ratio of the organophosphorus compound (B) to 100 parts by mass of the base resin (A) is more preferably 1 part by mass or more. In this case, the flame retardancy of the flame retardant resin composition can be further improved compared to the case where the blending ratio of the organophosphorus compound (B) to 100 parts by mass of the base resin (A) is less than 1 part by mass. . From the viewpoint of further improving the flame retardancy of the flame retardant resin composition, the blending ratio of the organophosphorus compound (B) to 100 parts by mass of the base resin (A) is more preferably 3 parts by mass or more. It is still more preferable that it is more than a mass part.

  The blending ratio of the organophosphorus compound (B) to 100 parts by mass of the base resin (A) is preferably 50 parts by mass or less. In this case, the workability of the flame retardant resin composition can be further improved as compared with the case where the blending ratio of the organic phosphorus compound (B) with respect to 100 parts by mass of the base resin (A) exceeds 50 parts by mass.

(C) Hindered amine compound The hindered amine compound (C) is a flame retardant and may be any one having a group represented by the following general formula (2).

In the general formula (2), R ^{1 to} R ⁴ each independently represents an alkyl group having 1 to 8 carbon atoms, and R ⁵ represents an alkyl group having 1 to 50 carbon atoms or a cycloalkyl having 5 to 12 carbon atoms. Group, an aralkyl group having 7 to 25 carbon atoms or an aryl group having 6 to 12 carbon atoms.

In the general formula (2), examples of the alkyl group represented by R ^{1 to} R ⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.

  Here, the “alkyl group” includes not only an unsubstituted alkyl group but also a substituted alkyl group. As the substituted alkyl group, an unsubstituted alkyl group in which a hydrogen atom is substituted can be used.

In the general formula (2), examples of the alkyl group represented by R ⁵ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, Examples include an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group.

Examples of the cycloalkyl group represented by R ⁵ include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cycloundecyl group, and a cyclododecyl group.

Examples of the aralkyl group represented by R ⁵ include a phenylmethyl group (benzyl group), a phenylethyl group, a phenylpropyl group, a naphthylmethyl group, a naphthylethyl group, an anthrylmethyl group, and an anthrylethyl group.

Examples of the aryl group represented by R ⁵ include a phenyl group and a naphthyl group.

（上記式（３）中、Ｒ^６〜Ｒ^９はアルキルアミノ基を表し、Ｒ^１０〜Ｒ^１４は上記一般式（２）で表される基を表し、Ｒ^１５及びＲ^１６はアルキレン基を表し、Ｒ^１７はアルキルイミノ基を表す。ｎは１〜１５の整数を表す。）

（上記式（４）中、Ｒ^１８〜Ｒ^２０は下記一般式（５）で表される基を表す。）

（上記式（５）中、Ｒ^２１〜Ｒ^２４は上記一般式（２）で表される基又はアルキル基を表し、Ｒ^２１〜Ｒ^２４のうち少なくとも２つは上記一般式（２）で表される基を表す。） Specific examples of the hindered amine compound (C) include a compound represented by the following formula (3) and a compound represented by the following formula (4).

(In the formula (3), R ^{6 to} R ⁹ represent an alkylamino group, R ^{10 to} R ¹⁴ represent a group represented by the general formula (2), and R ¹⁵ and R ¹⁶ represent an alkylene group. And R ¹⁷ represents an alkylimino group, and n represents an integer of 1 to 15.)

(In the formula ^{(4), R} 18 ~R ²⁰ represents a group represented by the following general formula (5).)

(In the above formula (5), R ^{21 to} R ²⁴ represent a group or an alkyl group represented by the above general formula (2), and at least two of R ^{21 to} R ²⁴ are represented by the above general formula (2). Represents a group to be

The number of amines per gram in the hindered amine compound (C) is not particularly limited, but is preferably 1 × 10 ²¹ or more.

In this case, the flame retardancy of the flame retardant resin composition can be further improved as compared with a case where the number of amines per 1 g in the hindered amine compound (C) is less than 1 × 10 ²¹ .

However, the number of amines per gram in the hindered amine compound (C) is preferably 3 × 10 ²¹ or less.

  The hindered amine compound (C) preferably has a plurality of groups represented by the general formula (2) in one molecule.

  In this case, compared with the hindered amine compound (C) which has only one group represented by General formula (2) in 1 molecule, the flame retardance of a flame-retardant resin composition can be improved more.

In the general formula (2), ^{R 5} is an alkyl group having 1 to 30 carbon atoms, or preferably represents a cycloalkyl group having 5 to 12 carbon atoms.

In this case, in the general formula (2), compared to the case where R ⁵ is neither an alkyl group having 1 to 30 carbon atoms nor a cycloalkyl group having 5 to 12 carbon atoms, the flame retardancy of the flame retardant resin composition Can be further improved.

  The hindered amine compound (C) may be solid or liquid at 25 ° C., but is preferably solid. In this case, the processability of the flame retardant resin composition is further improved as compared with the case where the hindered amine compound (C) is liquid at 25 ° C.

  The decomposition temperature of the hindered amine compound (C) is not particularly limited, but is preferably 240 ° C. or higher.

  In this case, compared with the case where the decomposition temperature of a hindered amine compound (C) is less than 240 degreeC, the flame retardance of a flame-retardant resin composition improves more. Moreover, the moldability of a flame-retardant resin composition improves more compared with the case where the decomposition temperature of a hindered amine compound (C) is less than 240 degreeC. That is, the hindered amine compound (C) is hardly decomposed during molding of the flame retardant resin composition, and fluctuations in the discharge amount from the molding apparatus, generation of bubbles, and the like are sufficiently suppressed.

  The hindered amine compound (C) may or may not contain a triazine ring, but preferably contains it.

  In this case, compared with the case where a hindered amine compound (C) does not contain a triazine ring, the flame retardance and workability of a flame retardant resin composition can be improved more.

  The hindered amine compound (C) preferably has a decomposition temperature of 250 ° C. or higher. In this case, compared with the case where the decomposition temperature of a hindered amine compound (C) is less than 250 degreeC, the flame retardance of a flame-retardant resin composition can be improved more. Moreover, the moldability of the flame retardant resin composition is more sufficiently improved than when the hindered amine compound (C) has a decomposition temperature of less than 250 ° C. That is, the hindered amine compound (C) is more difficult to decompose during molding of the flame retardant resin composition, and fluctuations in the discharge amount from the molding device, generation of bubbles, and the like are more sufficiently suppressed.

In the flame-retardant resin composition, wherein in the general formula (2), R ⁵ is preferably an alkyl group having 1 to 30 carbon atoms.

In this case, in the general formula (2), the flame retardancy and workability of the flame retardant resin composition can be further improved as compared to the case where R ⁵ is not an alkyl group having 1 to 30 carbon atoms.

  The blending ratio of the hindered amine compound (C) with respect to 100 parts by mass of the base resin (A) is not particularly limited, but is preferably 0.01 parts by mass or more. In this case, the flame retardancy of the flame retardant resin composition can be further improved as compared with the case where the blending ratio of the hindered amine compound (C) to 100 parts by mass of the base resin (A) is less than 0.01 parts by mass. it can.

  The blending ratio of the hindered amine compound (C) to 100 parts by mass of the base resin (A) is preferably 0.05 parts by mass or more. In this case, the flame retardancy of the flame retardant resin composition can be further improved as compared with the case where the blending ratio of the hindered amine compound (C) to 100 parts by mass of the base resin (A) is less than 0.05 parts by mass. it can. The blending ratio of the hindered amine compound (C) to 100 parts by mass of the base resin (A) is more preferably 0.1 parts by mass or more from the viewpoint of further improving the flame retardancy of the flame retardant resin composition. It is still more preferable that it is 0.15 mass part or more.

  The blending ratio of the hindered amine compound (C) to 100 parts by mass of the base resin (A) is preferably 15 parts by mass or less. In this case, the workability of the flame retardant resin composition can be further improved as compared with the case where the blending ratio of the hindered amine compound (C) to 100 parts by mass of the base resin (A) exceeds 15 parts by mass. The blending ratio of the hindered amine compound (C) to 100 parts by mass of the base resin (A) is more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less.

(D) Anti-drip agent The flame retardant resin composition preferably further contains an anti-drip agent (D) in addition to the base resin (A), the organic phosphorus compound (B) and the hindered amine compound (C). In this case, it becomes possible to suppress dripping at the time of combustion of the flame retardant resin composition.

  As the anti-drip agent, a fluorine-based anti-drip agent is preferable.

  The fluorine-based anti-drip agent may contain any fluorine-containing compound containing fluorine and can prevent dripping of the resin during combustion. Examples of such fluorine-containing compounds include fluorine resins such as polytetrafluoroethylene (hereinafter referred to as “PTFE”), polyvinylidene fluoride, and polyhexafluoropropylene. The fluorine-containing compound may be an unmodified fluorine-containing compound or a modified fluorine-containing compound, but is preferably modified. In this case, compared with the case where the fluorine-containing compound is not modified, the fluorine-containing compound is efficiently fibrillated, and the dispersibility in the flame-retardant resin composition is further improved. As a result, the anti-drip function of the anti-drip agent (D) can be further improved. Moreover, since the melt tension of the flame retardant resin composition becomes larger, the processability and moldability of the flame retardant resin composition can be further improved. Examples of the fluorine-containing compound that has been modified include acid-modified polytetrafluoroethylene.

  In the said flame-retardant resin composition, it is preferable that a drip inhibitor (D) is further mix | blended in the ratio of more than 0 mass part and 5 mass parts or less with respect to 100 mass parts of base resin (A).

  In this case, unlike the case where the blending ratio of the anti-drip agent (D) with respect to 100 parts by mass of the base resin (A) is 0 parts by mass, the anti-drip performance is exhibited and the anti-drip agent with respect to 100 parts by mass of the base resin (A) Compared with the case where the blending ratio of (D) exceeds 5 parts by mass, the melt viscosity of the flame retardant resin composition is sufficiently suppressed from becoming too high, and the processability of the flame retardant resin composition is further improved. To do.

  The blending ratio of the anti-drip agent (D) with respect to 100 parts by mass of the base resin (A) is more preferably 0.2 parts by mass or more. In this case, more excellent flame retardancy is obtained in the flame retardant resin composition than when the blending ratio of the anti-drip agent (D) to 100 parts by mass of the base resin (A) is less than 0.2 parts by mass. It is done. Furthermore, the blending ratio of the anti-drip agent (D) with respect to 100 parts by mass of the base resin (A) is more preferably 2 parts by mass or more.

  The flame retardant resin composition is an antioxidant, thermal degradation inhibitor, ultraviolet absorber, ultraviolet degradation inhibitor, antifogging agent, crosslinking agent, and foaming agent as long as flame retardancy and processability are not affected. Further, a conductive filler, a heat dissipation agent, a color pigment, a processing aid and the like may be further included as necessary.

  The flame retardant resin composition can be obtained by kneading the base resin (A), the organic phosphorus compound (B), and the hindered amine compound (C). Kneading is a kneader that can be processed by applying heat necessary for melting the base resin (A) and shear necessary for dispersing the organophosphorus compound (B) and the hindered amine compound (C). Can be used. As a kneading machine, for example, an open roll, a twin screw extruder, a Banbury mixer, a pressure kneader, or the like can be used.

<Cable>
(Cable first embodiment)
Next, a first embodiment of the cable of the present invention will be described with reference to FIGS. FIG. 1 is a partial side view showing a first embodiment of a cable according to the present invention, and FIG. 2 is a sectional view taken along line II-II in FIG.

  As shown in FIGS. 1 and 2, the cable 10 includes a conductor 1 as a transmission medium and an insulator 2 that covers the conductor 1. The insulator 2 includes a first insulating layer 3 as an insulating portion that covers the conductor 1 and a second insulating layer 4 as an insulating portion that covers the first insulating layer 3.

  Here, the 1st insulating layer 3 and the 2nd insulating layer 4 are comprised with the flame-retardant resin composition mentioned above, the flame-retardant resin composition mentioned above has the outstanding flame retardance, and is a flame retardant. Separation can be suppressed. For this reason, the 1st insulating layer 3 and the 2nd insulating layer 4 which are comprised with the said flame-retardant resin composition have the outstanding flame retardance, and can maintain the flame retardance over a long period of time It becomes. Therefore, the cable 10 does not need to be replaced for a long period.

(conductor)
The conductor 1 may be configured by only one strand, or may be configured by bundling a plurality of strands. Moreover, the conductor 1 is not specifically limited about a conductor diameter, the material of a conductor, etc., It can determine suitably according to a use. As a material of the conductor 1, for example, copper, aluminum, or an alloy containing them is preferable, but a conductive substance such as a carbon material can also be used as appropriate.

(Second embodiment of cable)
Next, a second embodiment of the cable of the present invention will be described with reference to FIG. FIG. 3 is a cross-sectional view showing an optical fiber cable as a second embodiment of the cable of the present invention.

  As shown in FIG. 3, the cable 20 includes two tension members 22 and 23, an optical fiber 24 as a transmission medium, and an insulator 25 that covers them. Here, the optical fiber 24 is provided so as to penetrate the insulator 25. Here, the insulator 25 is composed of an insulating portion that covers the optical fiber 24, and the insulating portion is a flame-retardant resin that constitutes the first insulating layer 3 and the second insulating layer 4 in the first embodiment of the cable. Consists of a composition.

  Here, the flame-retardant resin composition described above has excellent flame retardancy and can suppress separation of the flame retardant. For this reason, the insulator 25 comprised with the said flame-retardant resin composition has the outstanding flame retardance, and it becomes possible to maintain the flame retardance over a long period of time. For this reason, the optical fiber cable 20 does not need to be replaced for a long period of time.

<Molded body>
Next, the molded product of the present invention will be described.

  The molded body of the present invention includes the above-described flame retardant resin composition, and the flame retardant resin composition has excellent flame retardancy and can suppress separation of the flame retardant. For this reason, a molded object has the outstanding flame retardance and it becomes possible to maintain the flame retardance over a long period of time. Therefore, the molded article of the present invention does not need to be replaced over a long period. The molded body of the present invention can be used to replace, for example, a television back panel, a capacitor case, an insulating film inside a keyboard, a panel inside a heater, a flame retardant sheet for a building, an automobile dashboard, packaging materials, a housing for home appliances, etc. It is suitable for applications that require a lot of work.

  The shape of the molded product of the present invention is not particularly limited. Examples of the shape of the molded body include a sheet shape, a spherical shape, a rectangular parallelepiped shape, a cubic shape, and a foam shape. The shape of the molded body is preferably a sheet shape.

  When the shape of a molded object is a sheet form, a molded object has a sheet layer comprised with the flame-retardant resin composition mentioned above. In this case, the molded body may be composed of only one sheet layer, or may be composed of a laminate of a plurality of sheet layers.

  The molded body can be obtained by molding the flame retardant resin composition described above using, for example, an extrusion molding method, an injection molding method, a vacuum molding method, a press molding method, a blow molding method, an inflation molding method, or the like. . The molded body may be composed of a flame retardant resin composition alone, or may be composed of a combination of a flame retardant resin composition and a reinforcing material such as glass cloth or paper depending on the application.

<Flame Retardant>
Next, the flame retardant of the present invention will be described.
The flame retardant of the present invention contains an organophosphorus compound (B) and a hindered amine compound (C). However, the flame retardant of the present invention does not contain a resin. The organophosphorus compound (B) is represented by the general formula (1), and the hindered amine compound (C) has a group represented by the general formula (2).

  The organophosphorus compound (B) and the hindered amine compound (C) are as described above.

  The flame retardant of the present invention can impart excellent flame retardancy to a flame retardant resin composition when it is kneaded with a base resin (A) containing a polyolefin resin to produce a flame retardant resin composition. Moreover, even if the flame retardant of this invention knead | mixes with the base resin (A) containing polyolefin resin, it is hard to isolate | separate from a base resin (A), and can suppress isolation | separation of the flame retardant in a flame retardant resin composition.

In the flame retardant, the hydrocarbon group represented by X ¹ and X ² in the general formula (1) is, for example, an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

In the general formula (1), the hydrocarbon group represented by X ¹ and X ² is preferably an aromatic hydrocarbon group. This flame retardant can further improve the hydrolysis resistance of the flame retardant resin composition when it is kneaded with a base resin (A) containing a polyolefin resin to produce a flame retardant resin composition.

  In the flame retardant, the aromatic hydrocarbon group is preferably a phenylmethyl group.

  In this case, when a flame retardant is kneaded with a base resin (A) containing a polyolefin resin to produce a flame retardant resin composition, the hydrolysis resistance and flame resistance of the flame retardant resin composition are more effective. Can be improved.

  In the flame retardant, the mixing ratio of the organophosphorus compound (B) and the hindered amine compound (C) is not particularly limited, but it is assumed that the base resin (A) is contained in the flame retardant, and the above What is necessary is just to make it the same with the mixture ratio of the organophosphorus compound (B) and the hindered amine compound (C) with respect to 100 mass parts of base resin (A) in a flame-retardant resin composition.

<Flame retardant master batch>
Next, the flame retardant master batch of the present invention will be described.
The flame retardant masterbatch of the present invention comprises the above flame retardant resin composition.

  The flame retardant masterbatch of the present invention comprises the flame retardant resin composition, and the flame retardant resin composition has excellent flame retardancy and can suppress the separation of the flame retardant. For this reason, even if the flame retardant masterbatch of this invention knead | mixes with other resin and manufactures a molded object, the molded object has the outstanding flame retardance and can suppress isolation | separation of a flame retardant.

  In the flame retardant masterbatch of the present invention, the blending ratio of the organic phosphorus compound (B) to 100 parts by mass of the base resin (A) is preferably 5 parts by mass or more, and more preferably 20 parts by mass or more. However, the blending ratio of the organophosphorus compound (B) to 100 parts by mass of the base resin (A) is preferably 200 parts by mass or less. In this case, the dispersibility of the flame retardant is superior to the case where the blending ratio of the organophosphorus compound (B) with respect to 100 parts by mass of the base resin (A) exceeds 200 parts by mass. The blending ratio of the organophosphorus compound (B) to 100 parts by mass of the base resin (A) is more preferably 100 parts by mass or less.

  In the flame retardant masterbatch of the present invention, the blending ratio of the hindered amine compound (C) to 100 parts by mass of the base resin (A) is preferably 0.5 parts by mass or more, and preferably 2 parts by mass or more. More preferred. However, the blending ratio of the hindered amine compound (C) to 100 parts by mass of the base resin (A) is preferably 50 parts by mass or less. In this case, the dispersibility of the flame retardant is superior to the case where the blending ratio of the hindered amine compound (C) to 100 parts by mass of the base resin (A) exceeds 50 parts by mass.

  The present invention is not limited to the above embodiment. For example, in the above embodiment, the cable 10 has only one conductor 1, but the cable of the present invention is not limited to a cable having only one conductor 1, and a plurality of conductors 1 that are separated from each other are included. The cable may have.

  Moreover, in the said embodiment, although the 1st insulating layer 3 and the 2nd insulating layer 4 are comprised with said flame retardant resin composition, the 1st insulating layer 3 is comprised with said flame retardant resin composition. Instead, only the second insulating layer 4 may be composed of the flame retardant resin composition. Or the 2nd insulating layer 4 may not be comprised with said flame-retardant resin composition, and only the 1st insulating layer 3 may be comprised with said flame-retardant resin composition.

  In the cable 20, the insulator 25 is formed of an insulating portion, but the insulator 25 may further include a covering portion that covers the insulating portion. Here, the covering portion may or may not be composed of the flame retardant resin composition constituting the first insulating layer 3 and the second insulating layer 4 in the above embodiment, It is preferable to be comprised with the flame retardant resin composition which comprises the 1st insulating layer 3 and the 2nd insulating layer 4 in a form.

  Moreover, in the said embodiment, although the cable 20 has the tension members 22 and 23, in the cable of this invention, a tension member is not necessarily required and can be abbreviate | omitted.

  Hereinafter, the content of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

(Examples 1-58 and Comparative Examples 1-10)
A base resin (A), an organophosphorus compound (B) and a hindered amine compound (C) are blended in the blending amounts shown in Tables 1 to 9, and kneaded at 190 ° C. using a Banbury mixer. I got a thing. In Tables 1 to 9, the unit of the blending amount of each blending component is part by mass.

Specific examples of the base resin (A), the organic phosphorus compound (B), and the hindered amine compound (C) are as follows.
(A) Base resin (A1) Polypropylene (PP)
(A1-1) Block copolymer of propylene and ethylene (block PP)
Product name “NOVATEC BC4BSW”, manufactured by Nippon Polypro Co., Ltd., crystallinity, melting point: 165 ° C.
(A1-2) Homopolypropylene (HomoPP)
Product name “NOVATEC MA3”, manufactured by Nippon Polypro Co., Ltd., crystallinity, melting point: 165 ° C.
(A1-3) Random copolymer of propylene and ethylene (random PP)
Product name “Wintech WFW4M”, manufactured by Nippon Polypro Co., Ltd., crystallinity, melting point: 135 ° C.
(A2) Polyethylene (PE)
Product name “Excellen GMH GH030”, manufactured by Sumitomo Chemical Co., Ltd., crystallinity, melting point: 101 ° C.
(A3) Ethylene-ethyl acrylate copolymer (EEA)
Product name “Lex Pearl A1150”, manufactured by Nippon Polyethylene Co., Ltd.
(A4) Propylene-α-olefin copolymer trade name “Toughmer PN2060”, manufactured by Mitsui Chemicals, Inc., crystallinity, melting point: 160 ° C.
(A5) Ethylene-α-olefin copolymer trade name “Toughmer DF810”, manufactured by Mitsui Chemicals, Inc., crystallinity, melting point: 66 ° C.
(A6) Hydrogenated styrene butadiene rubber (HSBR)
Product name “Dynalon 1320P”, manufactured by JSR Corporation, amorphous, glass transition point: lower than 100 ° C. (<100 ° C.)
(A7) Olefin-based elastomer olefin crystal-ethylene-butylene-olefin crystal block copolymer (CEBC), trade name “Dynalon 6200P”, manufactured by JSR Corporation, crystallinity, melting point: 90 ° C.
(A8) Maleic anhydride modified polyolefin (maleic anhydride PO)
Product name “Tuffmer MA8510”, manufactured by Mitsui Chemicals, Inc., crystallinity, melting point: 70 ° C.

（Ｂ２）有機リン化合物２
下記構造式で表される有機リン化合物（一般式（１）において、Ｘ^１及びＸ^２がメチル基である）、融点：２４０℃より高い、リン含有量：２４％

（Ｂ３）有機リン化合物３
下記構造式で表される有機リン化合物、融点：９６℃、リン含有量：１０質量％

（Ｂ４）有機リン化合物４
下記構造式で表されるレゾルシノールビス−ジキシレニルフォスフェート、融点：９２℃、リン含有量：９．０質量％

（Ｂ５）有機リン化合物５
下記構造式で表される有機リン化合物（一般式（１）において、Ｘ^１及びＸ^２がエチル基である）、融点：２４０℃より高い、リン含有量：２２質量％

（Ｂ６）有機リン化合物６
下記構造式で表される有機リン化合物（一般式（１）において、Ｘ^１及びＸ^２がプロピル基である）、融点：２４０℃より高い、リン含有量：２０質量％

（Ｂ７）有機リン化合物７
下記構造式で表される有機リン化合物（一般式（１）において、Ｘ^１及びＸ^２がフェニルエチル基である）、融点：２４０℃より高い、リン含有量：１４質量％

（Ｂ８）有機リン化合物８
下記構造式で表される有機リン化合物（一般式（１）において、Ｘ^１及びＸ^２がフェニルプロピル基である）、融点：２４０℃より高い、リン含有量：１３質量％

（Ｂ９）有機リン化合物９
下記構造式で表される有機リン化合物（一般式（１）において、Ｘ^１及びＸ^２がナフチルメチル基である）、融点：２４０℃より高い、リン含有量：１２質量％

(B) Organophosphorus compound (B1) Organophosphorus compound 1
Organophosphorus compound represented by the following structural formula (in the general formula (1), X ¹ and X ² are phenylmethyl groups (benzyl groups)), melting point: higher than 240 ° C. (> 240 ° C.), phosphorus content : 15% by mass

(B2) Organophosphorus compound 2
Organophosphorus compound represented by the following structural formula (in general formula (1), X ¹ and X ² are methyl groups), melting point: higher than 240 ° C., phosphorus content: 24%

(B3) Organophosphorus compound 3
Organophosphorus compound represented by the following structural formula, melting point: 96 ° C., phosphorus content: 10% by mass

(B4) Organophosphorus compound 4
Resorcinol bis-dixylenyl phosphate represented by the following structural formula, melting point: 92 ° C., phosphorus content: 9.0% by mass

(B5) Organophosphorus compound 5
Organophosphorus compound represented by the following structural formula (in general formula (1), X ¹ and X ² are ethyl groups), melting point: higher than 240 ° C., phosphorus content: 22% by mass

(B6) Organophosphorus compound 6
Organophosphorus compound represented by the following structural formula (in formula (1), X ¹ and X ² are propyl groups), melting point: higher than 240 ° C., phosphorus content: 20% by mass

(B7) Organophosphorus compound 7
Organophosphorus compound represented by the following structural formula (in general formula (1), X ¹ and X ² are phenylethyl groups), melting point: higher than 240 ° C., phosphorus content: 14% by mass

(B8) Organophosphorus compound 8
Organophosphorus compound represented by the following structural formula (in general formula (1), X ¹ and X ² are phenylpropyl groups), melting point: higher than 240 ° C., phosphorus content: 13% by mass

(B9) Organophosphorus compound 9
Organophosphorus compound represented by the following structural formula (in formula (1), X ¹ and X ² are naphthylmethyl groups), melting point: higher than 240 ° C., phosphorus content: 12% by mass

（Ｃ２）ヒンダードアミン化合物２
下記構造式で表されるヒンダードアミン化合物、商品名「Ｆｌａｍｅｓｔａｂ ＮＯＲ１１７ ＦＦ」、ＢＡＳＦ社製、融点：１２１℃、分解温度：２４７℃、１ｇ当たりのアミン数：１．６×１０^２１個、トリアジン環の有無：あり

（Ｃ３）ヒンダードアミン化合物３
下記構造式で表されるヒンダードアミン化合物、商品名「アデカスタブＬＡ−８１」、ＡＤＥＫＡ社製、融点：２５℃で液体、分解温度：２３９℃、１ｇ当たりのアミン数：１．７７×１０^２１個、トリアジン環の有無：なし

（Ｃ４）ヒンダードアミン化合物４
下記構造式で表されるヒンダードアミン化合物、商品名「Ｈｏｓｔａｖｉｎ ＮＯＷ」、クラリアント社製、融点：９５℃、分解温度：２３６℃、１ｇ当たりのアミン数：２．８８×１０^２０個、トリアジン環の有無：なし

(C) Hindered amine compound (C1) Hindered amine compound 1
A hindered amine compound represented by the following structural formula, trade name “TINUVIN NOR371 FF”, manufactured by BASF, melting point: 104 ° C., decomposition temperature: 264 ° C., number of amines per gram: 1.48 × 10 ^{21 to} 1.67 × 10 ²¹ with or without triazine ring: yes

(C2) Hindered amine compound 2
A hindered amine compound represented by the following structural formula, trade name “Flamestab NOR117 FF”, manufactured by BASF, melting point: 121 ° C., decomposition temperature: 247 ° C., number of amines per gram: 1.6 × 10 ²¹ , triazine ring Existence: Yes

(C3) Hindered amine compound 3
A hindered amine compound represented by the following structural formula, trade name “ADK STAB LA-81”, manufactured by ADEKA, melting point: liquid at 25 ° C., decomposition temperature: 239 ° C., number of amines per gram: 1.77 × 10 ²¹ , Presence or absence of triazine ring: None

(C4) Hindered amine compound 4
A hindered amine compound represented by the following structural formula, trade name “Hostavin NOW”, manufactured by Clariant, melting point: 95 ° C., decomposition temperature: 236 ° C., number of amines per gram: 2.88 × 10 ²⁰ , presence or absence of triazine ring : None

[Characteristic evaluation]
About the flame-retardant resin compositions of Examples 1 to 58 and Comparative Examples 1 to 10 obtained as described above, the effect of suppressing the separation of the flame retardant, flame retardancy and hydrolysis resistance as follows. Evaluation was performed. Moreover, about the flame-retardant resin composition of Examples 46-49, processability evaluation was also performed, and about the flame-retardant resin composition of Examples 55-58, the coloring property at the time of deterioration was also evaluated.

<Test sheet>
In order to evaluate the flame retardant separation suppressing effect, flame retardancy, and hydrolysis resistance, a test sheet 1 having a thickness of 0.1 mm was prepared as follows. That is, after the flame retardant resin compositions of Examples 1 to 58 and Comparative Examples 1 to 10 were kneaded at 190 ° C. with a Banbury mixer, the dimensions of 350 mm × 100 mm × 0.1 mm (thickness) were measured by press molding. A test sheet 1 was prepared. Moreover, about the flame-retardant resin composition of Examples 18-54, in order to evaluate a flame retardance, the test similar to said test sheet 1 except having made thickness into 0.3 mm and 0.5 mm. Sheets 2 and 3 were further produced.

<Inhibition effect of flame retardant separation>
The test sheet 1 is subjected to surface observation or tentacle confirmation, and the test sheet 1 is placed in a constant temperature bath at 85 ° C. and left for 48 hours, and then the surface observation or tentacle confirmation is performed, and foreign matter is confirmed on the surface of the test sheet 1. This foreign matter was used as an indicator of whether or not the flame retardant was separated. Then, “◯” or “×” was determined for the test sheets 1 to 3 based on the following determination criteria. The results are shown in Tables 1-9. In addition, when the test sheet 1 was determined as “◯”, the test sheet 1 was accepted, and when the test sheet 1 was determined as “x”, the test sheet 1 was rejected.
(Criteria)
◯: Test sheets 1 to 3 do not correspond to any of the following (i) and (ii) ×: Test sheets 1 to 3 correspond to at least one of the following (i) and (ii) (i) Test Foreign matter was confirmed on the surface of the sheet 1 (ii) Foreign matter was confirmed on the surface of the test sheet 1 after being left in a constant temperature bath at 85 ° C. for 48 hours.

<Flame retardance>
For the test sheets 1 to 3, FMVSS (Federal Motor-Vehicle Safety Standard) No. The flame retardancy was evaluated by performing a combustion test of automotive interior materials based on 302. Specifically, the test sheets 1 to 3 are held horizontally with a pair of U-shaped metal jigs, and a 38 mm size flame is indirectly flamed on the back of one end of the test sheets 1 to 3 for 15 seconds, The presence / absence of self-extinguishing and the burning time (burning rate) for the distance 254 mm between the A and B marked lines displayed on the jig were calculated. Each U-shaped metal jig is composed of two parallel extending portions that are separated from each other and a connecting portion that connects these extending portions, and the test sheet 1 is formed by the two extending portions. Both edges of the test sheet were fixed along the longitudinal direction of -3. Further, one of the two extending portions has an A marked line and a B marked line separated by 254 mm and crossing the extending portion (along the direction orthogonal to the extending direction). Displayed).

Then, “◯” or “×” was determined for the test sheets 1 to 3 based on the following determination criteria. The results are shown in Tables 1-9. The test sheets 1 to 3 determined as “◯” were accepted and the test sheets 1 to 3 determined as “x” were rejected.
(Criteria)
◯: Self-extinguishing was observed, or self-extinguishing was not performed, and the burning rate was 102 mm / min or less. X: Self-extinguishing was not performed, and the burning rate exceeded 102 mm / min.

<Hydrolysis resistance>
The test sheet 1 is placed in a constant temperature bath at 85 ° C. and 85% RH and left for 48 hours, and then surface observation or tentacle confirmation is performed to check whether foreign matter is confirmed on the surface of the test sheet 1. Foreign matter was used as an index of hydrolysis resistance. Then, “◯” or “×” was determined for the test sheets 1 to 3 based on the following determination criteria. The results are shown in Tables 1-9.
(Criteria)
◯: No foreign matter was confirmed on the surface of the test sheet 1 ×: Foreign matter was confirmed on the surface of the test sheet 1

<Processability>
A T-die was connected to a single screw extruder (product name “Laboplast Mill”, manufactured by Toyo Seiki Seisakusho Co., Ltd.), and the flame retardant resin compositions of Examples 46 to 49 were charged into the single screw extruder, and the thickness was 0. A 1 mm workability evaluation sheet was prepared. At this time, the discharge amount of the sheet and the take-up speed were constant. Moreover, the workability evaluation sheet was prepared for each of the processing temperatures in the single-screw extruder set to 230 ° C, 240 ° C, and 250 ° C. And the presence or absence of the formation of the hole in the workability evaluation sheet was examined during the extrusion for 30 minutes, and the presence or absence of the formation of this hole was used as an index of workability. Here, the formation of holes suggests a decrease in workability due to variations in the discharge amount and the generation of bubbles. And based on the following criteria, the determination of “◯” or “×” was performed on the workability evaluation sheet. The results are shown in Tables 1-9.
(Criteria)
◯: No hole formation was confirmed in the workability evaluation sheet ×: Hole formation was confirmed in the workability evaluation sheet

<Colorability at the time of deterioration>
In order to evaluate the colorability, a test sheet 4 was further prepared in the same manner as the test sheet 1 except that the flame retardant resin compositions of Examples 55 to 58 were used and the thickness was 1 mm. The test sheet 4 was placed in a constant temperature bath at 85 ° C. and allowed to stand for 5 days, and then the surface was observed to examine whether the sheet was discolored. Then, “◯” or “x” was determined for the test sheet 4 based on the following determination criteria. The results are shown in Table 8.
(Criteria)
○: No discoloration was observed on the sheet ×: Discoloration was observed on the sheet

  From the results shown in Tables 1 to 9, in Examples 1 to 58, the evaluation results of flame retardancy when the thickness of the test sheet is 0.1 mm are all “◯”, and Examples 1 to 58 are It proved to be acceptable in terms of flame retardancy. On the other hand, in Comparative Examples 1-10, the evaluation results of flame retardancy when the thickness of the test sheet is 0.1 mm are all “x”, and Comparative Examples 1-10 are in terms of flame retardancy. It turned out to be a failure.

  In addition, from the results shown in Tables 1 to 9, in Examples 1 to 58, the evaluation results of the flame retardant separation inhibiting effect are all “◯”, and Examples 1 to 58 are the flame retardant separation inhibiting effect. It turned out to be a pass. On the other hand, in Comparative Examples 1 to 10, the evaluation results of the flame retardant separation inhibiting effect are all “x”, and Comparative Examples 1 to 10 are found to be rejected in terms of the flame retardant separation inhibiting effect. It was.

  From the above, it was confirmed that the flame retardant resin composition of the present invention has excellent flame retardancy and can suppress the separation of the flame retardant.

1 ... Conductor (Transmission medium)
2, 25 ... insulator 3 ... first insulating layer (insulating portion)
4 ... 2nd insulating layer (insulating part)
10, 20 ... cable 24 ... optical fiber (transmission medium)

Claims (19)

A base resin (A) containing a polyolefin resin;
An organophosphorus compound (B);
A hindered amine compound (C),
The organophosphorus compound (B) is represented by the following general formula (1):
The flame-retardant resin composition in which the hindered amine compound (C) has a group represented by the following general formula (2).

(In the above general formula (1), X ¹ and X ² are hydrocarbon groups which may have a substituent and represent a hydrocarbon group containing an aromatic hydrocarbon group , which may be the same or different.)

(In the general formula (2), R ^{1 to} R ⁴ each independently represents an alkyl group having 1 to 8 carbon atoms, and R ⁵ represents an alkyl group having 1 to 50 carbon atoms and a cyclohexane having 5 to 12 carbon atoms. Represents an alkyl group, an aralkyl group having 7 to 25 carbon atoms, or an aryl group having 6 to 12 carbon atoms.) The flame-retardant resin composition according to claim 1 , wherein the aromatic hydrocarbon group is a phenylmethyl group. The flame-retardant resin composition according to claim 1 or 2 , wherein the number of groups represented by the general formula (2) per 1 g in the hindered amine compound (C) is 1 × 10 ²¹ or more. The flame-retardant resin composition according to any one of claims 1 to 3 , wherein the hindered amine compound (C) has a plurality of groups represented by the general formula (2) in one molecule. In the general formula (2), ^{R 5} represents an alkyl group having 1 to 30 carbon atoms, or represents a cycloalkyl group having 5 to 12 carbon atoms, a flame retardant according to any one of claims 1-4 Resin composition. The flame-retardant resin composition according to any one of claims 3 to 5 , wherein the hindered amine compound (C) is solid at 25 ° C. The flame-retardant resin composition according to any one of claims 3 to 6 , wherein the hindered amine compound (C) has a decomposition temperature of 240 ° C or higher. The flame-retardant resin composition according to any one of claims 1 to 7 , wherein the hindered amine compound (C) contains a triazine ring. The flame retardant resin composition according to claim 8 , wherein in the general formula (2), R ⁵ represents a cycloalkyl group having 5 to 12 carbon atoms. The flame-retardant resin composition according to any one of claims 7 to 9 , wherein the hindered amine compound (C) has a decomposition temperature of 250 ° C or higher. In the general formula (2), ^{R 5} represents an alkyl group having 1 to 30 carbon atoms, a flame retardant resin composition according to claim 10. The flame retardant resin composition according to any one of claims 1 to 6 , wherein the hindered amine compound (C) does not contain a triazine ring. The flame-retardant resin composition according to any one of claims 1 to 12 , further comprising an anti-drip agent (D). A transmission medium composed of a conductor or an optical fiber;
An insulator covering the transmission medium,
It said insulator comprises an insulating portion composed of a flame-retardant resin composition according to any one of claims 1 to 13 cable. Shaped body comprising a flame-retardant resin composition according to any one of claims 1 to 13. The molded object of Claim 15 provided with at least one sheet layer containing the said flame-retardant resin composition. Flame retardant master batch consisting flame retardant resin composition according to any one of claims 1 to 13. An organophosphorus compound (B);
A hindered amine compound (C),
The organophosphorus compound (B) is represented by the following general formula (1),
The flame retardant which the said hindered amine compound (C) has group represented by following General formula (2).

(In the above general formula (1), X ¹ and X ² are hydrocarbon groups which may have a substituent and represent a hydrocarbon group containing an aromatic hydrocarbon group , which may be the same or different.)

(In the general formula (2), R ^{1 to} R ⁴ each independently represents an alkyl group having 1 to 8 carbon atoms, and R ⁵ represents an alkyl group having 1 to 50 carbon atoms and a cyclohexane having 5 to 12 carbon atoms. Represents an alkyl group, an aralkyl group having 7 to 25 carbon atoms, or an aryl group having 6 to 12 carbon atoms.) The flame retardant according to claim 18 , wherein the aromatic hydrocarbon group is a phenylmethyl group.

Images