阅读说明：本技术 阻燃性树脂组合物、线缆用阻燃性树脂组合物、使用其的线缆、成型体和阻燃剂母料以及阻燃剂 (Flame-retardant resin composition, flame-retardant resin composition for cables, cable using same, molded article, flame-retardant master batch, and flame retardant ) 是由 岩田诚之 中村详一郎 于 2019-12-14 设计创作，主要内容包括：阻燃性树脂组合物包含基体树脂(A)和阻燃剂阻燃剂,所述基体树脂(A)包含聚烯烃树脂。阻燃剂包含有机磷化合物(B)和受阻胺化合物(C),有机磷化合物(B)由下述通式(1)表示,受阻胺化合物(C)具有下述通式(2)所示的基团。(所述通式(1)中,X～1和X～2表示可具有取代基的烃基,可以相同也可以不同)(所述通式(2)中,R～1～R～4各自独立地表示碳原子数1～8的烷基、R～5表示碳原子数1～50的烷基、碳原子数5～12的环烷基、碳原子数7～25的芳烷基或碳原子数6～12的芳基)(The flame-retardant resin composition comprises a base resin (A) and a flame retardant, wherein the base resin (A) comprises a polyolefin resin. The flame retardant comprises 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) has a group represented by the following general formula (2). (in the general formula (1), X 1 And X 2 May be the same or different and represent a hydrocarbon group which may have a substituent (in the general formula (2), R 1 ～R 4 Each independently represents an alkyl group having 1 to 8 carbon atoms, R 5 Represents an alkyl group having 1 to 50 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an aralkyl group having 7 to 25 carbon atoms or an aryl group having 6 to 12 carbon atoms))

1. A flame-retardant resin composition comprising a base resin (A) and a flame retardant, the base resin (A) comprising a polyolefin resin,

the flame retardant comprises an organic phosphorus compound (B) and a hindered amine compound (C),

the organic phosphorus compound (B) is represented by the following general formula (1),

the hindered amine compound (C) has a group represented by the following general formula (2),

in the general formula (1), X¹And X²The alkyl groups which may have a substituent(s) may be the same or different,

in the general formula (2), R¹～R⁴Each independently represents an alkyl group having 1 to 8 carbon atoms, R⁵Represents an alkyl group having 1 to 50 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an aralkyl group having 7 to 25 carbon atoms or an aryl group having 6 to 12 carbon atoms.

2. The flame-retardant resin composition according to claim 1, wherein in the general formula (1),from X¹And X²Said hydrocarbon group represented by (A) is an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

3. The flame-retardant resin composition according to claim 2, wherein in the general formula (1), X represents¹And X²Said hydrocarbon group represented by (A) is an aromatic hydrocarbon group.

4. The flame-retardant resin composition according to claim 3, wherein the aromatic hydrocarbon group is a phenylmethyl group.

5. The flame-retardant resin composition according to claim 3 or 4, wherein foreign matter is not observed on the surface when the flame-retardant resin composition is placed in a thermostatic bath at 85 ℃ and 85% RH and left for 48 hours and then the surface of the flame-retardant resin composition is observed or confirmed by hand touch.

6. The flame-retardant resin composition according to any one of claims 1 to 5, wherein the hindered amine compound (C) is blended in a proportion of less than 0.4 part by mass with respect to 100 parts by mass of the base resin (A).

7. The flame-retardant resin composition according to any one of claims 1 to 6, wherein the mass ratio of the organophosphorus compound (B) to the hindered amine compound (C) is 5.6 or more.

8. The flame-retardant resin composition according to claim 7, wherein the mass ratio of the organophosphorus compound (B) to the hindered amine compound (C) is 11.1 or less.

9. The flame-retardant resin composition according to any one of claims 1 to 8, wherein the number of the groups represented by the general formula (2) per 1g of the hindered amine compound (C) is 1 x 10²¹More than one.

10. The flame-retardant resin composition according to any one of claims 1 to 9, wherein the hindered amine compound (C) has a plurality of groups represented by the general formula (2) in 1 molecule.

11. The flame-retardant resin composition according to any one of claims 1 to 10, wherein R in the general formula (2)⁵Represents an alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 5 to 12 carbon atoms.

12. The flame-retardant resin composition according to any one of claims 9 to 11, wherein the hindered amine compound (C) is a solid at 25 ℃.

13. The flame-retardant resin composition according to any one of claims 9 to 12, wherein the hindered amine compound (C) has a decomposition temperature of 240 ℃ or higher.

14. The flame-retardant resin composition according to any one of claims 1 to 13, wherein the hindered amine compound (C) contains a triazine ring.

15. The flame-retardant resin composition according to claim 14, wherein, in the general formula (2), R⁵Represents a cycloalkyl group having 5 to 12 carbon atoms.

16. The flame-retardant resin composition according to any one of claims 13 to 15, wherein the hindered amine compound (C) has a decomposition temperature of 250 ℃ or higher.

17. The flame-retardant resin composition according to claim 16, wherein, in the general formula (2), R⁵Represents an alkyl group having 1 to 30 carbon atoms.

18. The flame-retardant resin composition according to any one of claims 1 to 12, wherein the hindered amine compound (C) does not contain a triazine ring.

19. The flame-retardant resin composition according to any one of claims 1 to 18, further comprising an anti-dripping agent (D).

20. The flame-retardant resin composition according to any one of claims 1 to 19, wherein the organic phosphorus compound (B) has a melting point higher than a melting temperature of the base resin (A),

the melting point of the hindered amine compound (C) is lower than the melting temperature of the base resin (a).

21. The flame-retardant resin composition according to claim 20, wherein the melting point of the organic phosphorus compound (B) is higher than the melting temperature of the base resin (A) by 40 ℃ or more.

22. The flame-retardant resin composition according to claim 20 or 21, wherein the melting point of the hindered amine compound (C) is lower than the melting temperature of the base resin (a) by 3 ℃ or more.

23. The flame-retardant resin composition according to any one of claims 1 to 5 and 7 to 22, wherein the blending ratio of the hindered amine compound (C) is 0.5 parts by mass or more with respect to 100 parts by mass of the base resin (A).

24. The flame-retardant resin composition according to any one of claims 1 to 23, wherein the blending ratio of the organic phosphorus compound (B) to 100 parts by mass of the base resin (A) is 5 parts by mass or more.

25. The flame-retardant resin composition according to any one of claims 1 to 24, wherein the flame retardant consists only of the organic phosphorus compound (B) and the hindered amine compound (C).

26. The flame-retardant resin composition according to any one of claims 1 to 25, wherein any one of (i) and (ii) which does not conform to the following,

(i) foreign matter was observed on the surface of the flame-retardant resin composition when the surface of the flame-retardant resin composition was observed or confirmed by touching with a hand,

(ii) after the flame-retardant resin composition was left in a thermostatic bath at 85 ℃ for 48 hours, foreign matters were observed on the surface of the flame-retardant resin composition when the surface of the flame-retardant resin composition was observed or confirmed by touching with a hand.

27. The flame-retardant resin composition according to any one of claims 1 to 26, wherein the flame-retardant resin composition satisfies either of the following requirements (a) or (b) when subjected to a combustion test of an automotive interior material based on FMVSS No.302,

(a) self-extinguishing of the fire was observed,

(b) no self-extinguishing was observed, but the burning rate was 102 mm/min or less.

28. A flame-retardant resin composition for cables, which comprises the flame-retardant resin composition according to any one of claims 1 to 27.

29. A cable comprising a transmission medium made of a conductor or an optical fiber, and an insulator covering the transmission medium,

the insulator comprises an insulating part composed of the flame-retardant resin composition according to any one of claims 1 to 27.

30. A molded article comprising the flame-retardant resin composition according to any one of claims 1 to 27.

31. The molded article according to claim 30, wherein at least one sheet layer comprising the flame-retardant resin composition is provided.

32. A flame retardant masterbatch comprising the flame-retardant resin composition according to any one of claims 1 to 27.

33. A flame retardant comprising an organic phosphorus compound (B) and a hindered amine compound (C),

the organic phosphorus compound (B) is represented by the following general formula (1),

the hindered amine compound (C) has a group represented by the following general formula (2),

in the general formula (1), X¹And X²The alkyl groups which may have a substituent(s) may be the same or different,

in the general formula (2), R¹～R⁴Each independently represents an alkyl group having 1 to 8 carbon atoms, R⁵Represents an alkyl group having 1 to 50 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an aralkyl group having 7 to 25 carbon atoms or an aryl group having 6 to 12 carbon atoms.

34. The flame retardant according to claim 33, wherein in the general formula (1), X represents¹And X²Said hydrocarbon group represented by (A) is an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

35. The flame retardant according to claim 34, wherein in the general formula (1), X represents¹And X²Said hydrocarbon group represented by (A) is an aromatic hydrocarbon group.

36. The flame retardant according to claim 34 or 35, wherein the aromatic hydrocarbon group is a phenylmethyl group.

37. A flame retardant according to any one of claims 33 to 36, wherein the organophosphorus compound (B) has a melting point higher than that of the hindered amine compound (C).

38. A flame retardant according to any one of claims 33 to 37, consisting only of the organophosphorus compound (B) and the hindered amine compound (C).

39. The flame retardant according to any one of claims 33 to 38, wherein the mass ratio of the organophosphorus compound (B) to the hindered amine compound (C) is 5.6 or more.

40. The flame retardant according to claim 39, wherein the mass ratio of the organophosphorus compound (B) to the hindered amine compound (C) is 11.1 or less.

Technical Field

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

Background

Polyolefin resins are excellent in mechanical properties and are widely used for building materials, packaging materials, OA equipment, automobile parts, cables, and the like. Since polyolefin resins are flammable, they are used in the state of being added with various flame retardants such as halogen flame retardants, phosphorus flame retardants, and metal hydrate flame retardants. However, although the halogen-based flame retardant can provide excellent flame retardancy, it is liable to generate toxic gas and smoke during combustion, and is subject to regulation depending on the country. Therefore, in recent years, there has been a demand for a flame-retardant resin composition using a non-halogen flame retardant. As such a flame-retardant resin composition, a flame-retardant resin composition using a phosphate and a NOR-type hindered amine compound in combination is known (see patent document 1 below).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2017-66299.

Disclosure of Invention

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 suppression of separation of the flame retardant. Here, the separation of the flame retardant means that the flame retardant is separated (not mixed) or dispersed in the resin composition once when the flame retardant is kneaded with the resin, and then the flame retardant is discharged to the surface of the resin composition in a solid or liquid state while being kept as it is or decomposed, thereby lowering the flame retardancy.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a flame-retardant resin composition having excellent flame retardancy and capable of suppressing separation of a flame retardant, a cable using the same, a flame-retardant resin composition for a cable, a molded article, a flame retardant masterbatch, and a flame retardant.

The present inventors have made extensive studies to solve the above problems. As a result, they have found that the above problems can be solved by a flame-retardant resin composition comprising a base resin comprising a polyolefin resin and a specific organic phosphorus compound and a specific hindered amine compound blended therein.

That is, the present invention is a flame-retardant resin composition comprising a base resin (a) comprising a polyolefin resin and a flame retardant comprising an organic phosphorus compound (B) represented by the following general formula (1) and a hindered amine compound (C) having a group represented by the following general formula (2).

(in the above general formula (1), X¹And X²Represents an optionally substituted hydrocarbon group which may be the same or different)

(in the above general formula (2), R¹～R⁴Each independently represents an alkyl group having 1 to 8 carbon atoms, R⁵Represents an alkyl group having 1 to 50 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, 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.

The present inventors presume that the reason why the flame-retardant resin composition of the present invention has excellent flame retardancy is as follows.

That is, the organic phosphorus compound (B) represented by the above general formula (1) contains a large amount of phosphorus in the molecular structure and is not easily separated from the base resin (a), and thus 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 does not have excellent flame retardancy.

The reason why the separation of the flame retardant is suppressed in the flame-retardant resin composition of the present invention is not yet determined, and the present inventors presume as follows.

That is, the organic phosphorus compound has a spiro structure, and therefore has a high melting point, and is not melted at the time of molding the flame-retardant resin composition, and is not easily separated from the polyolefin resin. On the other hand, when the flame-retardant resin composition does not contain the organic phosphorus compound (B), the hindered amine compound (C) tends to be melted at the time of molding of the flame-retardant resin composition and to be easily separated from the polyolefin resin, as compared with the organic phosphorus compound (B). On the other hand, since the flame-retardant resin composition contains the organic phosphorus compound (B), the hindered amine compound (C) is less likely to be separated from the organic phosphorus compound (B) even during molding of the flame-retardant resin composition due to the interaction between the organic phosphorus compound (B) and the group represented by the general formula (2) of the hindered amine compound (C) in the flame-retardant resin composition of the present invention. Therefore, the hindered amine compound (C) is not easily separated from the polyolefin resin even at the time of molding of the flame-retardant resin composition. As a result, it is considered that separation of the flame retardant in the flame-retardant resin composition is suppressed.

In the flame-retardant resin composition, X is represented by the general formula (1)¹And X²The hydrocarbon group represented is, for example, an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

In the flame-retardant resin composition, X is represented by the general formula (1)¹And X²The hydrocarbon group represented 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 improved in this manner is not known, but it is considered that the aromatic hydrocarbon group acts as a steric hindrance against water molecules or inhibits the hydrolysis of the organic phosphorus compound (B) by the action of electrons.

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

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

With respect to the above flame-retardant resin composition, in the general formula (1), X is¹And X²When the hydrocarbon group represented by (a) is an aromatic hydrocarbon group or a phenylmethyl (benzyl group), it is preferable that the surface of the substrate is observed or confirmed by touching with a hand after the substrate is placed in a thermostatic bath at 85 ℃ and 85% RH for 48 hours.

The flame-retardant resin composition has more excellent hydrolysis resistance.

In the flame-retardant resin composition, the hindered amine compound (C) is preferably blended in a proportion of less than 0.4 part by mass with respect to 100 parts by mass of the base resin (a).

In this case, the flame-retardant resin composition can further suppress odor as compared with the case where the hindered amine compound (C) is added in a proportion of 0.4 parts by mass or more.

The reason why the odor is suppressed by the flame-retardant resin composition is not known, but the present inventors presume as follows.

That is, the odor is considered to be caused by the amine-based substance generated by the decomposition of the hindered amine compound, and as described above, the hindered amine compound (C) is not easily separated from the organic phosphorus compound (B) and is in a small amount, and therefore the generated amine-based substance is also considered to be not easily separated from the organic phosphorus compound (B). As a result, it is considered that odor due to the amine-based substance is not easily released into the flame-retardant resin composition, and odor is suppressed.

In the flame-retardant resin composition, the mass ratio of the organic phosphorus compound (B) to the hindered amine compound (C) is preferably 5.6 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 mass ratio of the organic phosphorus compound (B) to the hindered amine compound (C) is less than 5.6.

In the flame-retardant resin composition, the mass ratio of the organic phosphorus compound (B) to the hindered amine compound (C) is preferably 11.1 or less.

In this case, the flame retardancy of the flame retardant resin composition can be further improved as compared with the case where the mass ratio of the organic phosphorus compound (B) to the hindered amine compound (C) exceeds 11.1.

In the above flame-retardant resin composition, the number of groups represented by the general formula (2) (hereinafter, referred to as "amine number") per 1g of the hindered amine compound (C) is preferably 1 × 10²¹The above.

In this case, the number of amines per 1g in the hindered amine compound (C) is less than 1X 10²¹Can further improve the flame retardancyFlame retardancy of the resin composition.

In the flame-retardant resin composition, it is preferable that the hindered amine compound (C) has a plurality of groups represented by the general formula (2) in 1 molecule.

In this case, the flame retardancy of the flame retardant resin composition can be further improved as compared with the case where the hindered amine compound (C) has only 1 group represented by the general formula (2) in 1 molecule.

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

In this case, in the general formula (2), with R⁵The flame retardancy of the flame-retardant resin composition can be further improved as compared with the case where the alkyl group having 1 to 30 carbon atoms or the cycloalkyl group having 5 to 12 carbon atoms is not used.

In the above flame-retardant resin composition, the hindered amine compound (C) is preferably a solid at 25 ℃.

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 ℃.

In the above flame-retardant resin composition, the hindered amine compound (C) preferably has a decomposition temperature of 240 ℃ or higher.

In this case, the flame retardancy and the processability of the flame retardant resin composition are further improved as compared with the case where the decomposition temperature of the hindered amine compound (C) is less than 240 ℃.

In the flame-retardant resin composition, the hindered amine compound (C) preferably contains a triazine ring.

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

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

In the above flame-retardant resin composition, the hindered amine compound (C) preferably has a decomposition temperature of 250 ℃ or higher.

In this case, the flame retardancy and the processability of the flame retardant resin composition can be further improved as compared with the case where the decomposition temperature of the hindered amine compound (C) is less than 250 ℃.

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

In this case, in the general formula (2), with R⁵The flame retardancy and the processability of the flame-retardant resin composition can be further improved compared with the case where the alkyl group having 1 to 30 carbon atoms is not included.

In the flame-retardant resin composition, the hindered amine compound (C) preferably 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-dripping agent (D).

In this case, the flame-retardant resin composition can be prevented from dripping (dripping) during combustion.

In the above flame-retardant resin composition, it is preferable that the organic phosphorus compound (B) has a melting point higher than the melting temperature of the base resin (a), and the hindered amine compound (C) has a melting point lower than the melting temperature of the base resin (a).

In this case, the flame-retardant resin composition can more sufficiently suppress separation of the flame retardant.

The reason why the separation of the flame retardant is more sufficiently suppressed by the flame-retardant resin composition of the present invention is not yet determined, but the present inventors presume as follows.

That is, the organic phosphorus compound has a spiro structure, and therefore has a high melting point, and is not melted during molding of the flame-retardant resin composition, and is not easily separated from the polyolefin resin. On the other hand, since the hindered amine compound (C) has a melting point lower than the melting temperature of the base resin (a) and the organic phosphorus compound (B) has a melting point higher than the melting temperature of the base resin (a), when the flame-retardant resin composition does not contain the organic phosphorus compound (B), the flame-retardant resin composition tends to be easily separated from the polyolefin resin when the flame-retardant resin composition is molded at the melting temperature of the base resin (a). In contrast, in the flame-retardant resin composition of the present invention, the flame-retardant resin composition contains the organic phosphorus compound (B), and when the flame-retardant resin composition is molded at the melting temperature of the base resin (a), the hindered amine compound (C) penetrates into the solid organic phosphorus compound (B) dispersed in the base resin (a), and is captured by the organic phosphorus compound (B). Therefore, in the flame-retardant resin composition of the present invention, the hindered amine compound (C) is less likely to be separated from the polyolefin resin even when the flame-retardant resin composition is molded at the melting temperature of the base resin (a). As a result, it is considered that the separation of the flame retardant in the flame-retardant resin composition is more sufficiently suppressed.

In the flame-retardant resin composition, the melting point of the organic phosphorus compound (B) is higher than, for example, the melting temperature of the base resin (A) by 40 ℃ or more.

In the flame-retardant resin composition, the melting point of the hindered amine compound (C) is lower than, for example, the melting temperature of the base resin (a) by 3 ℃.

In the flame-retardant resin composition, 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.

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 0.5 part by mass.

In the flame-retardant resin composition, 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.

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 organic phosphorus compound (B) to 100 parts by mass of the base resin (a) is less than 5 parts by mass.

In the above flame-retardant resin composition, the flame retardant is preferably composed of only the organic phosphorus compound (B) and the hindered amine compound (C).

The flame-retardant resin composition described above does not meet either of the following (i) and (ii).

(i) Foreign matter was observed on the surface of the flame-retardant resin composition

(ii) After the flame-retardant resin composition was left in a thermostatic bath at 85 ℃ for 48 hours, foreign matters were observed on the surface of the flame-retardant resin composition

The flame-retardant resin composition satisfies the following requirements (a) or (b) when subjected to a combustion test of an automotive interior material based on FMVSS No. 302.

(a) Self-extinguishment was observed

(b) No self-extinguishing was observed, but the burning rate was 102 mm/min or less

The present invention is also a flame-retardant resin composition for cables, which comprises the above flame-retardant resin composition.

The flame-retardant resin composition for a cable of the present invention can impart excellent flame retardancy to a cable when used as at least a part of an insulator of the cable, and can maintain the flame retardancy in the cable for a long time. Therefore, the flame retardant resin composition for cables of the present invention can eliminate the need to replace cables for a long period of time.

The present invention is a cable comprising a transmission medium made of a conductor or an optical fiber, and an insulator covering the transmission medium, wherein the insulator comprises an insulating portion made of the flame-retardant resin composition.

According to the cable of the present invention, the insulating portion has excellent flame retardancy, and is made of a flame-retardant resin composition capable of suppressing separation of the flame retardant. Therefore, the cable of the present invention has excellent flame retardancy and can maintain the flame retardancy for a long time. Thus, the cable of the present invention can be replaced for a long time without the need for replacement.

The present invention is also a molded article comprising the flame-retardant resin composition.

The molded article contains a flame-retardant resin composition having excellent flame retardancy, and capable of suppressing separation of a flame retardant. Therefore, the molded article of the present invention has excellent flame retardancy and can maintain the flame retardancy for a long period of time. Therefore, the molded article of the present invention can be replaced for a long period of time without any need.

The molded article may have at least one sheet layer containing the flame-retardant resin composition.

The present invention is also a flame retardant masterbatch comprising the above flame retardant resin composition.

The flame retardant master batch of the present invention is composed of the flame retardant resin composition, and the flame retardant resin composition has excellent flame retardancy and can inhibit separation of the flame retardant. Therefore, even when the flame retardant master batch of the present invention is kneaded with another resin to produce a molded article, the molded article has excellent flame retardancy, and separation of the flame retardant can be suppressed.

Further, the present invention is a flame retardant comprising an organic phosphorus compound (B) represented by the following general formula (1) and a hindered amine compound (C) having a group represented by the following general formula (2).

(in the above general formula (1), X¹And X²Represents an optionally substituted hydrocarbon group which may be the same or different)

(in the above general formula (2), R¹～R⁴Each independently represents an alkyl group having 1 to 8 carbon atoms, R⁵Represents an alkyl group having 1 to 50 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an aralkyl group having 7 to 25 carbon atoms or an aryl group having 6 to 12 carbon atoms)

When the flame retardant is kneaded with a base resin (a) containing a polyolefin resin to produce a flame-retardant resin composition, excellent flame retardancy can be imparted to the flame-retardant resin composition. In addition, the flame retardant of the present invention is not easily separated from the matrix resin (a) even when kneaded with the matrix resin (a) containing a polyolefin resin, and therefore, separation of the flame retardant in the flame-retardant resin composition can be suppressed.

In the above flame retardant, in the general formula (1), X is¹And X²The hydrocarbon group represented is, for example, an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

In the above flame retardant, in the general formula (1), X is¹And X²The hydrocarbon group represented is preferably an aromatic hydrocarbon group.

When the flame retardant is kneaded with a base resin (a) containing a polyolefin resin to produce a flame-retardant resin composition, the hydrolysis resistance of the flame-retardant resin composition can be further improved.

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

When the 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 retardancy of the flame-retardant resin composition can be more effectively improved.

In the above flame retardant, it is preferable that the melting point of the organic phosphorus compound (B) is higher than that of the hindered amine compound (C).

When the flame retardant is kneaded with a base resin (a) comprising a polyolefin resin at the melting temperature of the base resin (a) to produce a flame-retardant resin composition, excellent flame retardancy can be imparted to the flame-retardant resin composition. In addition, the flame retardant of the present invention is not easily separated from the base resin (a) even when kneaded with the base resin (a) containing a polyolefin resin at the melting temperature of the base resin (a), and therefore, separation of the flame retardant in the flame-retardant resin composition can be more sufficiently suppressed.

Among the above flame retardants, it is preferable to be constituted only by the organic phosphorus compound (B) and the hindered amine compound (C).

In the above flame retardant, the mass ratio of the organic phosphorus compound (B) to the hindered amine compound (C) is preferably 5.6 or more.

When the flame retardant is kneaded with a base resin (a) containing a polyolefin resin to produce a flame-retardant resin composition, the flame retardancy of the flame-retardant resin composition can be further improved.

In the above flame retardant, the mass ratio of the organic phosphorus compound (B) to the hindered amine compound (C) is preferably 11.1 or less.

When the flame retardant is blended in a flame-retardant resin composition, the flame retardancy of the flame-retardant resin composition can be further improved as compared with the case where the mass ratio of the organic phosphorus compound (B) to the hindered amine compound (C) exceeds 11.1.

In the present invention, the "decomposition temperature" of the hindered amine compound means a decomposition temperature measured by thermogravimetric/differential analysis (TG/DTA), and specifically means a decomposition temperature measured on a sample composed of the hindered amine compound under the following measurement conditions using the following measurement apparatus. Here, the decomposition temperature means a temperature at which the weight of the hindered amine compound is reduced by 1%.

(measurement device)

The product name "TG/DTA 6300" (manufactured by High tech science, K.K.)

(measurement conditions)

Sample amount: about 5mg

Measuring temperature: from 25 ℃ to 600 DEG C

And (3) measuring atmosphere: air flow (200 mL/min)

Temperature rise rate: 10 ℃/min

Material of the sample container: aluminum (Al)

In the present invention, the "melting temperature" of the matrix resin (a) is a temperature below.

(1) When the matrix resin (A) is composed of only a crystalline polymer, the melting point (. degree. C.) +30 ℃ of the matrix resin (A) is set

(2) When the matrix resin (A) is composed of only an amorphous polymer, the glass transition point (. degree. C.) +30 ℃ of the matrix resin (A) is set

(3) When the matrix resin (A) is a mixture (physical blend, copolymer, or the like) of a crystalline polymer and an amorphous polymer, the melting point or glass transition temperature of the most abundant component of the crystalline polymer and the amorphous polymer is +30 DEG C

The "+ 30 ℃ C" is a value that is considered to be set to a temperature higher by 30 ℃ than the melting point or glass transition point of the resin in general when the resin is melt-processed.

In the present invention, the melting point of the matrix resin (a) is determined by the method defined in JIS K7121. Specifically, the melt was heated once to a molten state by a Differential Scanning Calorimeter (DSC), and then crystallized at a cooling rate of 5 ℃/min to eliminate the thermal history, and the DSC curve was measured again at a temperature increase rate of 10 ℃/min, and the top of the melting peak at this time was defined as the melting point.

In the present invention, the glass transition point of the matrix resin (a) is determined by the method specified in JIS K7121. Specifically, the glass transition temperature was determined as the midpoint of the change in the baseline by removing the thermal history by heating the material to a molten state with a Differential Scanning Calorimeter (DSC) and then crystallizing the material at a cooling rate of 5 ℃/min, measuring the DSC curve again at a temperature increase rate of 20 ℃/min, and taking the midpoint of the change in the baseline at that time as the glass transition temperature.

According to the present invention, a flame-retardant resin composition having excellent flame retardancy and capable of suppressing separation of a flame retardant, a flame-retardant resin composition for a cable, a cable using the same, a molded article, a flame retardant master batch, and a flame retardant can be provided.

Drawings

Fig. 1 is a partial side view showing embodiment 1 of a cable according to the present invention.

Fig. 2 is a sectional view taken along line II-II of fig. 1.

Fig. 3 is a cross-sectional view showing embodiment 2 of the cable of the present invention.

Detailed Description

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

< flame retardant resin composition >

The flame-retardant resin composition of the present invention comprises a base resin (a) comprising a polyolefin resin and a flame retardant comprising an organic phosphorus compound (B) and a hindered amine compound (C). The organophosphorus 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 above general formula (1), X¹And X²Represents an optionally substituted hydrocarbon group which may be the same or different)

(in the above general formula (2), R¹～R⁴Each independently represents an alkyl group having 1 to 8 carbon atoms, R⁵Represents an alkyl group having 1 to 50 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, 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 the flame-retardant resin composition of the present invention, the flame retardant is not easily separated from the base resin (a). Therefore, the flame-retardant resin composition of the present invention is useful as a flame retardant master batch containing a flame retardant at a high concentration.

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

(A) Matrix resin

The base resin (a) contains a 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. They may be used alone or in combination of 2 or more.

(A1) Non-modified polyolefin resin

Examples of the non-modified polyolefin resin include ethylene polymers, propylene polymers, and olefin thermoplastic elastomers. They may be used alone or in combination of 2 or more.

The ethylene polymer is a polymer containing a constituent unit derived from ethylene, and examples of the ethylene polymer include polyethylene, ethylene- α -olefin copolymer, ethylene-propylene-diene copolymer, and the like.

Examples of the 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. They may be used alone or in combination of 2 or more.

The propylene polymer refers to a polymer containing a constituent unit mainly derived from propylene. Examples of the propylene polymer include homopolypropylene, a propylene-ethylene copolymer, and a propylene- α -olefin copolymer. Examples of the α -olefin include 1-butene, 2-butene, 1-hexene, and 2-hexene.

When the propylene 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, and is preferably a block copolymer. If the 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-based elastomer include a polypropylene elastomer and an olefin-ethylene-butene-olefin copolymer such as an olefin crystal-ethylene-butene-olefin crystal block copolymer (CEBC copolymer). They may be used alone or in combination of 2 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 is a resin obtained by modifying the above polyolefin resin or its precursor 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, an alkoxy group (for example, a methoxy group or an ethoxy group), and the like. Among them, carboxyl group and acid anhydride group are preferable. In this case, the abrasion resistance of the flame-retardant resin composition can be more effectively improved than in the case where the functional group introduced by the modification is a functional group other than a carboxyl group and an acid anhydride group. Examples of the material 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 acid anhydrides such as maleic anhydride.

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

(A3) Non-polyolefin resin

The base resin (a) may 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 block copolymers of olefins and styrene such as styrene-butadiene rubber (SBR), styrene-ethylene-butadiene-styrene copolymer (SEBS copolymer), styrene-propylene-butadiene-styrene copolymer (SPBS copolymer), styrene-butadiene-styrene copolymer (SBS copolymer), and styrene-isoprene-styrene copolymer (SIS copolymer), and hydrogenated products (hydrogenated SBR, hydrogenated SEBS copolymer, hydrogenated SPBS copolymer, hydrogenated SBS copolymer, and hydrogenated SIS copolymer) modified by hydrogenation of these. They may be used alone or in combination of 2 or more.

(B) Organic phosphorus compounds

The organic phosphorus compound (B) is a flame retardant, and is represented by the following general formula (1) as described above.

In the above general formula (1), X¹And X²Represents a hydrocarbon group which may have a substituent. X¹And X²May 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 a cyclic, a linear, and a branched structure. Examples of the aliphatic hydrocarbon group include an alkyl group and a cycloalkyl group.

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

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 a phenylmethyl group (benzyl group), a phenylethyl group, a phenylpropyl group, a naphthylmethyl group, a naphthylethyl group, an anthrylmethyl group, and an anthrylethyl group.

In the above general formula (1), X¹And X²Aromatic hydrocarbon groups are preferred. In this case, the hydrolysis resistance of the flame-retardant resin composition can be further improved.

Among them, the aromatic hydrocarbon group is preferably a phenylmethyl (benzyl) group. At this time, with X in the general formula (1)¹And X²The hydrolysis resistance and flame retardancy of the flame-retardant resin composition can be more effectively improved than in the case where the phenyl methyl group is not used.

The blending ratio of the organic phosphorus compound (B) to 100 parts by mass of the matrix resin (a) is not particularly limited, and is preferably 0.1 part 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 organic phosphorus compound (B) to 100 parts by mass of the base resin (a) is less than 0.1 part by mass.

The blending ratio of the organic phosphorus compound (B) to 100 parts by mass of the matrix 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 as compared with the case where the blending ratio of the organic phosphorus 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 organic phosphorus compound (B) to 100 parts by mass of the base resin (a) is more preferably 3 parts by mass or more, and still more preferably 5 parts by mass or more.

The blending ratio of the organic phosphorus compound (B) to 100 parts by mass of the base resin (a) is preferably 50 parts by mass or less. In this case, the processability 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) to 100 parts by mass of the base resin (a) exceeds 50 parts by mass.

(C) Hindered amine compound

The hindered amine compound (C) may be a flame retardant as long as it has a group represented by the following general formula (2).

In the above general formula (2), R¹～R⁴Each independently represents an alkyl group having 1 to 8 carbon atoms, R⁵Represents an alkyl group having 1 to 50 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an aralkyl group having 7 to 25 carbon atoms or an aryl group having 6 to 12 carbon atoms.

In the above general formula (2), R is¹～R⁴Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl.

Here, "alkyl" includes not only unsubstituted alkyl but also substituted alkyl. As the substituted alkyl group, an alkyl group obtained by substituting a hydrogen atom of an unsubstituted alkyl group, or the like can be used.

In the above general formula (2), R is⁵Examples of the alkyl group 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, and a decyl groupUndecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, and the like.

As R⁵Examples of the cycloalkyl group include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, and the like.

As R⁵Examples of the aralkyl group include a phenylmethyl (benzyl), phenylethyl, phenylpropyl, naphthylmethyl, naphthylethyl, anthrylmethyl, and anthrylethyl group.

As R⁵Examples of the aryl group include phenyl and naphthyl.

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 above formula (3), R⁶～R⁹Represents alkylamino, R¹⁰～R¹⁴Represents a group represented by the above general formula (2), R¹⁵And R¹⁶Represents an alkylene group, R¹⁷Represents an alkylimino group. n represents an integer of 1 to 15)

(in the above formula (4), R¹⁸～R²⁰Represents a group represented by the following general formula (5)

(in the above formula (5), R²¹～R²⁴Represents a group represented by the general formula (2) or an alkyl group, R²¹～R²⁴At least 2 of the above-mentioned groups represented by the general formula (2)

Each of the hindered amine compound (C)The number of amines of 1g is not particularly limited, but is preferably 1X 10²¹More than one.

In this case, the number of amines per 1g in the hindered amine compound (C) is less than 1X 10²¹In this case, the flame retardancy of the flame retardant resin composition can be further improved.

However, the total number of amines per 1g of the hindered amine compound (C) is preferably 3X 10²¹The following.

The hindered amine compound (C) preferably has a plurality of groups represented by the general formula (2) in 1 molecule.

In this case, the flame retardancy of the flame-retardant resin composition can be further improved as compared with the hindered amine compound (C) having only 1 group represented by the general formula (2) in 1 molecule.

In the general formula (2), R⁵Preferably represents an alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 5 to 12 carbon atoms.

At this time, with R in the general formula (2)⁵The flame retardancy of the flame-retardant resin composition can be further improved as compared with the case where the alkyl group having 1 to 30 carbon atoms or the cycloalkyl group having 5 to 12 carbon atoms is not used.

The hindered amine compound (C) may be solid or liquid at 25 ℃, and 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 ℃.

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

In this case, the flame retardancy of the flame-retardant resin composition is further improved as compared with the case where the decomposition temperature of the hindered amine compound (C) is less than 240 ℃. Further, the moldability of the flame-retardant resin composition is further improved as compared with the case where the decomposition temperature of the hindered amine compound (C) is less than 240 ℃. That is, the hindered amine compound (C) is not easily decomposed during molding of the flame-retardant resin composition, and fluctuation 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, and is preferably contained.

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

The hindered amine compound (C) preferably has a decomposition temperature of 250 ℃ or higher. In this case, the flame retardancy of the flame-retardant resin composition can be further improved as compared with the case where the decomposition temperature of the hindered amine compound (C) is less than 250 ℃. Further, the moldability of the flame-retardant resin composition is more sufficiently improved than that in the case where the decomposition temperature of the hindered amine compound (C) is less than 250 ℃. That is, the hindered amine compound (C) is less likely to decompose during molding of the flame-retardant resin composition, and variations in the amount of discharge from the molding apparatus, the generation of bubbles, and the like are more sufficiently suppressed.

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

At this time, with R in the general formula (2)⁵The flame retardancy and the processability of the flame-retardant resin composition can be further improved compared with the case where the alkyl group having 1 to 30 carbon atoms is not included.

The blending ratio of the hindered amine compound (C) to 100 parts by mass of the base resin (a) is not particularly limited, and is preferably 0.01 part 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 part by mass.

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. From the viewpoint of further improving the flame retardancy of the flame-retardant resin composition, the blending ratio of the hindered amine compound (C) to 100 parts by mass of the base resin (a) is more preferably 0.1 part by mass or more, still more preferably 0.15 part by mass or more, and particularly preferably 0.5 part by mass 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 processability 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) is more than 15 parts by mass with respect to 100 parts by mass of the base resin (a). 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.

The blending ratio of the hindered amine compound (C) to 100 parts by mass of the base resin (a) may be less than 0.4 part by mass. In this case, the odor of the flame-retardant resin composition can be further suppressed 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 0.4 parts by mass or more. Therefore, the flame-retardant resin composition is particularly useful for materials requiring odor suppression, such as interior materials for automobiles and ducts for air conditioners. From the viewpoint of further suppressing the odor of the flame-retardant resin composition, the blending ratio of the hindered amine compound (C) to 100 parts by mass of the base resin (a) is more preferably 0.3 parts by mass or less, and still more preferably 0.2 parts by mass or less.

The mass ratio of the organic phosphorus compound (B) to the hindered amine compound (C), i.e., the mass ratio R represented by the following formula, is not particularly limited, but is preferably 5.6 or more.

R＝m_B/m_C

(in the above formula, m_BRepresents the mass of the organic phosphorus compound (B), m_CRepresents the mass of the hindered amine compound (C)

In this case, the flame retardancy of the flame retardant resin composition can be further improved as compared with the case where the mass ratio R is less than 5.6.

The mass ratio R is preferably 6.3 or more.

However, the mass ratio R is preferably 11.1 or less. In this case, the flame retardancy of the flame retardant resin composition can be further improved as compared with the case where the mass ratio R exceeds 11.1. The mass ratio R is more preferably 10.5 or less.

In the flame-retardant resin composition, the melting point T of the organic phosphorus compound (B) is preferably_BHigher in melting temperature T (. degree. C.) than the matrix resin (A), is subjected toMelting Point T of hindered amine Compound (C)_CLower in (. degree. C.) than the melting temperature T (. degree. C.) of the matrix resin (A). In this case, the flame-retardant resin composition can more sufficiently suppress separation of the flame retardant.

At this time, the melting point T of the organic phosphorus compound (B)_BThe temperature (DEG C) may be higher than the melting temperature T (DEG C) of the matrix resin (A), and T may be_BT is, for example, 40 ℃ or higher. However, when the stability of the temperature at the time of processing the flame-retardant resin composition is taken into consideration, T_B-T is preferably above 20 ℃.

Melting Point T of hindered amine Compound (C)_CThe temperature (DEG C) may be lower than the melting temperature T (DEG C) of the matrix resin (A), and T may be_CT is, for example, -3 ℃ or lower. However, T_C-T is preferably below-20 ℃. T considering the stability of temperature at the time of processing of the flame-retardant resin composition_CMore preferably, -T is-30 ℃ or lower.

In the above flame-retardant resin composition, the flame retardant comprises the organic phosphorus compound (B) and the hindered amine compound (C), and the flame retardant is preferably composed of only the organic phosphorus compound (B) and the hindered amine compound (C).

(D) Anti-dripping agent

The flame-retardant resin composition preferably further contains an anti-dripping agent (D) in addition to the base resin (a), the organic phosphorus compound (B), and the hindered amine compound (C). In this case, the flame-retardant resin composition can be prevented from dripping (dripping) during combustion.

The anti-dripping agent is preferably a fluorine-based anti-dripping agent.

The fluorine-based anti-dripping agent may contain a fluorine-containing compound and can prevent dripping (dripping) of the resin during combustion. Examples of such a fluorine-containing compound include fluorine-containing 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, and is preferably modified. In this case, the fluorine-containing compound is fibrillated more efficiently than in the case where the fluorine-containing compound is not modified, and the dispersibility in the flame-retardant resin composition is further improved. As a result, the anti-dripping function of the anti-dripping agent (D) can be further improved. Further, since the melt tension of the flame-retardant resin composition is further increased, the processability and moldability of the flame-retardant resin composition can be further improved. Examples of the modified fluorine-containing compound include acid-modified polytetrafluoroethylene.

In the flame-retardant resin composition, the anti-dripping agent (D) is preferably further blended in a proportion of more than 0 part by mass and 5 parts by mass or less with respect to 100 parts by mass of the base resin (a).

In this case, unlike the case where the compounding ratio of the anti-dripping agent (D) to 100 parts by mass of the base resin (a) is 0 part by mass, the anti-dripping performance is exhibited, and the melt viscosity of the flame-retardant resin composition is more sufficiently suppressed and the processability of the flame-retardant resin composition is further improved than the case where the compounding ratio of the anti-dripping agent (D) to 100 parts by mass of the base resin (a) exceeds 5 parts by mass.

The blending ratio of the anti-dripping agent (D) to 100 parts by mass of the base resin (a) is more preferably 0.2 parts by mass or more. In this case, the flame-retardant resin composition can obtain more excellent flame retardancy than a case where the blending ratio of the anti-dripping agent (D) to 100 parts by mass of the base resin (a) is less than 0.2 part by mass. Further, the blending ratio of the anti-dripping agent (D) to 100 parts by mass of the base resin (a) is more preferably 2 parts by mass or more.

The flame-retardant resin composition described above does not meet either of the following (i) and (ii).

(i) When the flame-retardant resin composition was observed on the surface or confirmed by touching with hand, foreign matter was observed on the surface of the flame-retardant resin composition

(ii) After the flame-retardant resin composition was left at 85 ℃ for 48 hours in a thermostatic bath, foreign matters were observed on the surface of the flame-retardant resin composition when the surface of the flame-retardant resin composition was observed or confirmed by touching with a hand

Here, the "foreign matter" refers to the flame retardant or its decomposition product contained in the flame-retardant resin composition. Further, the surface observation or the confirmation by touch of (i) was performed without leaving the flame-retardant resin composition in a thermostatic bath at 85 ℃ for 48 hours.

The flame-retardant resin composition satisfies the following requirements (a) or (b) when subjected to a combustion test of an automotive interior material based on FMVSS No. 302.

(a) Self-extinguishment was observed

(b) No self-extinguishing was observed, but the burning rate was 102 mm/min or less

Further, the flame-retardant resin composition represented by the general formula (1) is represented by X¹And X²When the hydrocarbon group represented by (a) is an aromatic hydrocarbon group or a phenylmethyl (benzyl group), it is preferable that foreign matter is not observed on the surface when the flame-retardant resin composition is placed in a thermostatic bath at 85 ℃ and 85% rh (relative humidity) and left for 48 hours and then the flame-retardant resin composition is observed on the surface or confirmed by hand touch.

The flame-retardant resin composition has more excellent hydrolysis resistance. The "foreign matter" refers to the flame retardant or its decomposition product contained in the flame-retardant resin composition.

The flame-retardant resin composition may further contain, if necessary, an antioxidant, a thermal deterioration inhibitor, an ultraviolet absorber, an ultraviolet deterioration inhibitor, an antifogging agent, a crosslinking agent, a foaming agent, a conductive filler, a heat dissipation agent, a coloring pigment, a processing aid, and the like, within a range that does not affect flame retardancy or processability.

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). The kneading may be carried out using a kneader capable of processing by applying heat necessary for melting the matrix resin (a) and shear necessary for dispersing the organic phosphorus compound (B) and the hindered amine compound (C). Examples of the kneading machine include an open roll, a twin-screw extruder, a Banbury mixer, and a pressure kneader.

< Cable >

(embodiment 1 of the Cable)

Next, embodiment 1 of the cable of the present invention will be described with reference to fig. 1 and 2. Fig. 1 is a partial side view showing a1 st embodiment of a cable according to the present invention, and fig. 2 is a sectional view taken along line II-II of fig. 1.

As shown in fig. 1 and 2, the cable 10 includes a conductor 1 as a transmission medium and an insulator 2 covering the conductor 1. The insulator 2 includes a1 st insulating layer 3 as an insulating portion for covering the conductor 1 and a2 nd insulating layer 4 as an insulating portion for covering the 1 st insulating layer 3.

Here, the 1 st insulating layer 3 and the 2 nd insulating layer 4 are formed of the flame-retardant resin composition, and the flame-retardant resin composition has excellent flame retardancy and can suppress separation of the flame retardant. Therefore, the 1 st insulating layer 3 and the 2 nd insulating layer 4 formed of the flame-retardant resin composition have excellent flame retardancy, and can maintain the flame retardancy for a long time. Therefore, the cable 10 can be replaced for a long time without need.

(conductor)

The conductor 1 may be constituted by only 1 bare wire, or may be constituted by bundling a plurality of bare wires. The conductor 1 is not particularly limited in terms of conductor diameter, conductor material, and the like, and may be appropriately determined according to the application. As the material of the conductor 1, for example, copper, aluminum, or an alloy containing them is preferable, and a conductive substance such as a carbon material can be used as appropriate.

(embodiment 2 of the Cable)

Next, embodiment 2 of the cable of the present invention will be described with reference to fig. 3. Fig. 3 is a cross-sectional view showing an optical fiber cable as embodiment 2 of the cable of the present invention.

As shown in fig. 3, the cable 20 includes 2 tension members 22 and 23, an optical fiber 24 as a transmission medium, and an insulator 25 covering these members. Here, the optical fiber 24 is disposed to penetrate the insulator 25. Here, the insulator 25 is constituted by an insulating portion of the coated optical fiber 24, and the insulating portion is constituted by the flame-retardant resin composition constituting the 1 st insulating layer 3 and the 2 nd insulating layer 4 in the above-described embodiment 1 of the cable.

Here, the flame-retardant resin composition has excellent flame retardancy, and separation of the flame retardant can be suppressed. Therefore, the insulator 25 made of the flame-retardant resin composition can have excellent flame retardancy and can maintain the flame retardancy for a long time. Therefore, the optical fiber cable 20 does not need to be replaced for a long time.

< shaped body >

Next, the molded article of the present invention will be explained.

The molded article of the present invention comprises the above flame-retardant resin composition, and the flame-retardant resin composition has excellent flame retardancy and can suppress separation of the flame retardant. Therefore, the molded article has excellent flame retardancy and can maintain the flame retardancy for a long time. Therefore, the molded article of the present invention does not need to be replaced for a long time. The molded article of the present invention is suitable for applications requiring a large amount of work for replacement, such as a back panel of a television, a case of a capacitor, an insulating film in a keyboard, a panel in a heater, a flame retardant sheet for a building, an instrument panel for an automobile, a packaging material, and a housing for a home appliance.

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

When the molded article is in the form of a sheet, the molded article has a sheet layer made of the flame-retardant resin composition. In this case, the molded article may be composed of only 1 sheet, or may be composed of a laminate of a plurality of sheets.

The molded article can be obtained by molding the flame-retardant resin composition by, for example, extrusion molding, injection molding, vacuum molding, press molding, blow molding, inflation molding, or the like. The molded article may be composed of the flame-retardant resin composition alone, or may be composed of the flame-retardant resin composition in combination with 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 explained.

The flame retardant of the present invention comprises an organic phosphorus compound (B) and a hindered amine compound (C). However, the flame retardant of the present invention does not contain a resin. The organic phosphorus compound (B) is represented by the above general formula (1), and the hindered amine compound (C) has a group represented by the above general formula (2).

The organic phosphorus compound (B) and the hindered amine compound (C) are as already described.

When the flame retardant of the present invention is kneaded with a base resin (a) containing a polyolefin resin to produce a flame-retardant resin composition, excellent flame retardancy can be imparted to the flame-retardant resin composition. In addition, the flame retardant of the present invention is not easily separated from the matrix resin (a) even when kneaded with the matrix resin (a) containing a polyolefin resin, and separation of the flame retardant in the flame-retardant resin composition can be suppressed.

In the above flame retardant, in the general formula (1), X is¹And X²The hydrocarbon group represented is, for example, an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

In the above general formula (1), X¹And X²The hydrocarbon group represented is preferably an aromatic hydrocarbon group. When the flame retardant is kneaded with a base resin (a) containing a polyolefin resin to produce a flame-retardant resin composition, the hydrolysis resistance of the flame-retardant resin composition can be further improved.

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

In this case, when the flame retardant is kneaded with the base resin (a) containing the polyolefin resin to produce the flame-retardant resin composition, hydrolysis resistance and flame retardancy of the flame-retardant resin composition can be more effectively improved.

The blending ratio of the organic phosphorus compound (B) and the hindered amine compound (C) in the flame retardant is not particularly limited, and it is sufficient if the flame retardant contains the base resin (a) in the same manner as the blending ratio of the organic phosphorus compound (B) and the hindered amine compound (C) to 100 parts by mass of the base resin (a) in the flame retardant resin composition.

In the flame retardant, the mass ratio R of the organic phosphorus compound (B) to the hindered amine compound (C) is preferably 5.6 or more. In this case, the flame retardant can further improve the flame retardancy of the flame-retardant resin composition, as compared with the case where the mass ratio R is less than 5.6.

The mass ratio R is preferably 6.3 or more.

Among them, the mass ratio R is preferably 11.1 or less. In this case, the flame retardant can further improve the flame retardancy of the flame-retardant resin composition, as compared with the case where the mass ratio R exceeds 11.1. The mass ratio R is more preferably 10.5 or less.

The organic phosphorus compound (B) and the hindered amine compound (C) are as described in the description of the flame-retardant resin composition.

< flame retardant masterbatch >

Next, the flame retardant master batch of the present invention will be explained.

The flame retardant masterbatch of the present invention is composed of the flame retardant resin composition.

The flame retardant master batch of the present invention is composed of the flame retardant resin composition, and the flame retardant resin composition has excellent flame retardancy and can inhibit separation of the flame retardant. Therefore, even when the flame retardant master batch of the present invention is kneaded with another resin to produce a molded article, the molded article has excellent flame retardancy, and separation of the flame retardant can be suppressed.

In the flame retardant master batch 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 organic phosphorus 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 that in the case where the blending ratio of the organic phosphorus compound (B) to 100 parts by mass of the matrix resin (a) exceeds 200 parts by mass. The blending ratio of the organic phosphorus 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 master batch 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 more preferably 2 parts by mass or more. 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 that in 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.

In the flame retardant master batch of the present invention, the blending ratio of the hindered amine compound (C) to 100 parts by mass of the base resin (a) may be less than 0.4 part by mass from the viewpoint of suppressing the odor of the flame retardant master batch. In this case, the blending ratio of the hindered amine compound (C) to 100 parts by mass of the base resin (a) is more preferably 0.3 part by mass or less. However, the blending ratio of the hindered amine compound (C) to 100 parts by mass of the base resin (a) is preferably 0.01 part by mass or more. In this case, the flame retardancy is more excellent than 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 part by mass.

In the flame retardant master batch, the mass ratio R of the organic phosphorus compound (B) to the hindered amine compound (C) is preferably 5.6 or more. In this case, the flame retardant master batch can further improve the flame retardancy of the flame retardant resin composition, as compared with the case where the mass ratio R is less than 5.6.

The mass ratio R is preferably 6.3 or more.

However, the mass ratio R is preferably 11.1 or less. In this case, the flame retardant master batch can further improve the flame retardancy of the flame retardant resin composition, as compared with the case where the mass ratio R exceeds 11.1. The mass ratio R is more preferably 10.5 or less.

The organic phosphorus compound (B) and the hindered amine compound (C) are as described in the description of the flame-retardant resin composition.

The present invention is not limited to the above embodiments. For example, although the cable 10 has only 1 conductor 1 in the above embodiment, the cable of the present invention is not limited to a cable having only 1 conductor 1, and may be a cable having a plurality of conductors 1 separated from each other.

In the above embodiment, the 1 st insulating layer 3 and the 2 nd insulating layer 4 are made of the flame retardant resin composition, but the 1 st insulating layer 3 may be made of the flame retardant resin composition, and only the 2 nd insulating layer 4 may be made of the flame retardant resin composition. Alternatively, the 2 nd insulating layer 4 may not be composed of the flame retardant resin composition described above, and only the 1 st insulating layer 3 may be composed of the flame retardant resin composition described above.

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 be composed of the flame retardant resin composition constituting the 1 st insulating layer 3 and the 2 nd insulating layer 4 in the above embodiment, or may not be composed of it, and is preferably composed of the flame retardant resin composition constituting the 1 st insulating layer 3 and the 2 nd insulating layer 4 in the above embodiment.

In the above embodiment, the cable 20 has the tensile members 22 and 23, but the tensile members are not necessarily required in the cable of the present invention and may be omitted.

Examples

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples.

Examples 1 to 121 and comparative examples 1 to 14

The base resin (A), the organic phosphorus compound (B) and the hindered amine compound (C) were compounded in the compounding amounts shown in tables 1 to 22, and kneaded at 190 ℃ using a Banbury mixer to obtain a flame-retardant resin composition. In tables 1 to 22, the unit of the amount of each component is part by mass.

As the matrix resin (a), the organic phosphorus compound (B) and the hindered amine compound (C), specifically, the following compounds are used.

(A) Matrix resin

(A1) Polypropylene (PP)

(A1-1) Block copolymer of propylene with ethylene (Block PP)

Trade name "NOVATEC BC4 BSW", manufactured by Polypro corporation, japan, crystallinity, melting point: 165 deg.C

(A1-2) homopolypropylene (sym PP)

Trade name "NOVATEC MA 3", manufactured by Polypro corporation, japan, crystallinity, melting point: 165 deg.C

(A1-3) random copolymer of propylene with ethylene (random PP)

Trade name "WINTEC WFW 4M", manufactured by Polypro corporation, japan, crystallinity, melting point: 135 deg.C

(A2) Polyethylene (PE)

Trade name "EXCELLEN GMH GH 030", manufactured by Sumitomo chemical Co., Ltd., crystallinity, melting point: 101 deg.C

(A3) Ethylene-ethyl acrylate copolymer (EEA)

Trade name "REXPERL A1150", manufactured by Japan polyethylene Co., Ltd., crystallinity, melting point: 100 deg.C

(A4) Propylene-alpha olefin copolymer

Trade name "TAFMER PN 2060", manufactured by Mitsui chemical Co., Ltd., crystallinity, melting point: 160 deg.C

(A5) Ethylene-alpha olefin copolymer

Trade name "TAFMER DF 810", manufactured by Mitsui chemical Co., Ltd., crystallinity, melting point: 66 deg.C

(A6) Hydrogenated Styrene Butadiene Rubber (HSBR)

Trade name "DYNARON 1320P", manufactured by JSR corporation, amorphous, glass transition point: below 100 ℃ (< 100 ℃)

(A7) Olefin elastomer

Olefin crystal-ethylene-butene-olefin crystal block copolymer (CEBC) with trade name "dynanaron 6200P", manufactured by JSR corporation, crystallinity, melting point: 90 deg.C

(A8) Maleic anhydride modified polyolefin (maleic anhydride PO)

Trade name "TAFMER MA 8510", manufactured by Mitsui chemical Co., Ltd., crystallinity, melting point: 70 deg.C

(B) Organic phosphorus compounds

B1) Organic phosphorus Compound 1

An organophosphorus compound represented by the following structural formula (in the general formula (1), X¹And X²Phenylmethyl (benzyl)), melting point: above 240 ℃ (> 240 ℃), phosphorus content: 15 mass%

(B2) Organic phosphorus Compound 2

An organophosphorus compound represented by the following structural formula (in the general formula (1), X¹And X²Methyl), melting point: above 240 ℃, phosphorus content: 24 percent of

(B3) Organic phosphorus Compound 3

An organophosphorus compound represented by the following structural formula, melting point: 96 ℃, phosphorus content: 10% by mass

(B4) Organic phosphorus Compound 4

Resorcinol dixylyl phosphate of the following formula, melting point: 92 ℃, phosphorus content: 9.0% by mass

(B5) Organic phosphorus compound 5

An organophosphorus compound represented by the following structural formula (in the general formula (1), X¹And X²Ethyl), melting point: above 240 ℃, phosphorus content: 22% by mass

(B6) Organic phosphorus Compound 6

An organophosphorus compound represented by the following structural formula (in the general formula (1), X¹And X²Propyl), melting point: above 240 ℃, phosphorus content: 20% by mass

(B7) Organic phosphorus Compound 7

An organophosphorus compound represented by the following structural formula (in the general formula (1), X¹And X²Is phenylethyl), melting point: above 240 ℃, phosphorus content: 14% by mass

(B8) Organic phosphorus Compound 8

An organophosphorus compound represented by the following structural formula (in the general formula (1), X¹And X²Is phenylpropyl), melting point: above 240 ℃, phosphorus content: 13% by mass

(B9) Organic phosphorus Compound 9

An organophosphorus compound represented by the following structural formula (in the general formula (1), X¹And X²Naphthylmethyl), melting point: above 240 ℃, phosphorus content: 12% by mass

(C) Hindered amine compound

(C1) Hindered amine compound 1

Hindered amine compound represented by the following structural formula, having a melting point of "TINUVIN NOR371 FF", manufactured by BASF corporation: 104 ℃, decomposition temperature: 264 ℃, number of amines per 1 g: 1.48X 10²¹～1.67×10²¹Presence or absence of triazine ring: is provided with

(C2) Hindered amine compound 2

Hindered amine compound represented by the following structural formula, trade name "Flamestab NOR117 FF", manufactured by BASF corporation, melting point: 121 ℃, decomposition temperature: 247 ℃, number of amines per 1 g: 1.6X 10²¹Presence or absence of triazine ring: is provided with

(C3) Hindered amine compound 3

A hindered amine compound represented by the following structural formula, having a melting point of "Adekastab LA-81", manufactured by ADEKA: liquid at 25 ℃, decomposition temperature: 239 ℃, number of amines per 1 g: 1.77X 10²¹Presence or absence of triazine ring: is free of

(C4) Hindered amine compound 4

A hindered amine compound represented by the following structural formula, having a melting point of: 95 ℃, decomposition temperature: 236 ℃, number of amines per 1 g: 2.88X 10²⁰Presence or absence of triazine ring: is free of

[ Table 1]

[ Table 2]

[ Table 3]

[ Table 4]

[ Table 5]

[ Table 6]

[ Table 7]

[ Table 8]

[ Table 9]

[ Table 10]

[ Table 11]

[ Table 12]

[ Table 13]

[ Table 14]

[ Table 15]

[ Table 16]

[ Table 17]

[ Table 18]

[ Table 19]

[ Table 20]

[ Table 21]

[ Table 22]

[ Property evaluation ]

The flame-retardant resin compositions of examples 1 to 121 and comparative examples 1 to 14 thus obtained were evaluated for separation-suppressing effect and flame retardancy of the flame retardant as follows. The flame-retardant resin compositions of examples 1 to 121 and comparative examples 1 to 6 were evaluated for hydrolysis resistance as follows. Further, the flame retardant resin compositions of examples 26 to 29, 31 to 32, 43, 46 to 49, 83 to 121 and comparative examples 11 to 14 were evaluated for odor as follows. The flame-retardant resin compositions of examples 46 to 49 and 107 to 110 were also evaluated for processability, and the flame-retardant resin compositions of examples 55 to 58 and 118 to 121 were also evaluated for coloring properties upon deterioration.

< test piece >

In order to evaluate the separation inhibiting effect of the flame retardant, flame retardancy, hydrolysis resistance and odor, test piece 1 having a thickness of 0.1mm was produced as follows. That is, the flame-retardant resin compositions of examples 1 to 121 and comparative examples 1 to 14 were kneaded at 190 ℃ by a Banbury mixer, and then pressure-molded to prepare a test piece 1 having dimensions of 350mm × 100mm × 0.1mm (thickness). Further, test pieces 2 and 3 were produced in the same manner as the above test piece 1 except that the flame retardant resin compositions of examples 1 to 5, 18 to 57, 59 to 70, and 88 to 117 were made to have thicknesses of 0.3mm and 0.5mm for the purpose of evaluating flame retardancy.

< separation-inhibiting effect of flame retardant >

The test piece 1 was subjected to surface observation or hand touch confirmation, and the test piece 1 was placed in a thermostatic bath at 85 ℃ for 48 hours and then subjected to surface observation or hand touch confirmation to investigate whether or not foreign matter was confirmed on the surface of the test piece 1, and the foreign matter was used as an index for whether or not the flame retardant was separated. Then, the test piece 1 was judged to be "good" or "poor" based on the following judgment criteria. The results are shown in tables 1 to 22. When the test piece 1 is determined to be "good", the test piece 1 is acceptable, and when the test piece 1 is determined to be "x", the test piece 1 is not acceptable.

(criteria for determination)

Good: the test piece 1 does not conform to either of (i) and (ii) below

X: the test piece 1 satisfies at least one of the following (i) and (ii)

(i) When the surface of the test piece 1 was observed or confirmed by touching with hand, foreign matter was confirmed on the surface of the test piece 1

(ii) After the test piece 1 was left in a thermostatic bath at 85 ℃ for 48 hours, foreign matter was observed on the surface of the test piece 1 when the surface of the test piece 1 was observed or confirmed by touching with a hand

< flame retardancy >

(1) Evaluation of flame retardancy based on Combustion test of automotive interior Material according to FMVSS (Federal Motor-Vehicle Safety Standard) No.302

The flame retardancy of the test pieces 1 to 3 was evaluated by conducting a combustion test of the automobile interior material based on FMVSS No. 302. Specifically, the test pieces 1 to 3 were held horizontally by a pair of U-shaped metal jigs, and a flame having a size of 38mm was brought into contact with the rear surface of one end of the test pieces 1 to 3 for 15 seconds, to calculate the presence or absence of self-extinguishing and the combustion time (combustion speed) of 254mm from the distance between the a mark and the B mark displayed on the jigs. Each U-shaped metal jig is composed of 2 parallel extending portions separated from each other and a connecting portion connecting these extending portions, and both edge portions of the test piece are fixed in the longitudinal direction of the test pieces 1 to 3 by the 2 extending portions. In addition, 1 of the 2 extended portions was displayed so that the a-line and the B-line were separated by 254mm and passed across the extended portion (in a direction orthogonal to the extending direction).

Then, the test pieces 1 to 3 were evaluated for "good" or "poor" based on the following evaluation criteria. The results are shown in tables 1 to 22. The test pieces 1 to 3 judged to be "good" were acceptable in terms of flame retardancy, and the test pieces 1 to 3 judged to be "poor" were not acceptable in terms of flame retardancy.

(criteria for determination)

Good: self-extinguishment, or no self-extinguishment, was observed and the combustion rate was 102 mm/min or less

X: does not self-extinguish and has a burning rate of over 102 mm/min

(2) Evaluation of flame retardancy in VTM test based on UL94 Standard

For examples 1 to 82 and comparative examples 1 to 10, 5 pieces of the above test piece 1 were prepared, and the flame retardancy was evaluated by performing VTM test of UL94 standard on these 5 pieces of the test piece 1. Specifically, the test piece 1 was wound around a mandrel having a diameter of 13mm to prepare a sample composed of a cylindrical body having a length of 350 mm. Then, one end of the sample was fixed by a clip, and the sample was disposed so that the center axis thereof was parallel to the vertical direction. At this time, the sample was disposed so that a position 125mm from the lower end of the sample marked a reticle. On the other hand, absorbent cotton was developed and arranged below the sample. Then, the tip of the burner was placed 10mm away from the lower end of the sample for 3 seconds, and the lower end of the sample was brought into contact with the flame. After contacting the flame, the burner was moved away from the sample and the after flame time t1 was measured. Immediately after the afterflame was stopped, the burner was moved to a position below the sample, and the burner was again brought into contact with the flame, and after the contact with the flame, the burner was moved away from the sample, and the afterflame time t2 and the afterflame time t3 were measured. Further, it was observed whether the test piece burned to the marked line, and whether the test piece ignited the cotton wool by dropping the fuming substance or the dropping substance.

Then, the test piece 1 was evaluated based on the following evaluation scale. The results are shown in tables 1 to 14. The flame retardance is increased in the order of NOT, VTM-2, VTM-1 and VTM-0.

(evaluation grade)

VTM－0

In all test pieces 1, t1 or t2 is 10 seconds or less

T1+ t2 (total of afterflame times of 10 contacts with flame) of 5 samples of 50 seconds or less

For all test pieces 1, t2+ t3 was 30 seconds or less

The sample did not burn to the mark and the absorbent cotton did not catch fire due to smoke or drips

VTM－1

In all test pieces 1, t1 or t2 is 30 seconds or less

T1+ t2 (total of afterflame times of 10 contacts with flame) of 5 samples of 250 seconds or less

For all test pieces 1, t2+ t3 was 60 seconds or less

The sample did not burn to the mark, the absorbent cotton did not catch fire due to the dropping of the fuming substance,

VTM－2

in all test pieces 1, t1 or t2 is 30 seconds or less

T1+ t2 (total of afterflame times of 10 contacts with flame) of 5 samples of 250 seconds or less

For all test pieces 1, t2+ t3 was 60 seconds or less

The sample did not burn to the mark and the absorbent cotton did not catch fire due to smoke or drips

NOT

Is not applicable to any one of VTM-0, VTM-1 and VTM-2

< hydrolysis resistance >

In examples 1 to 121 and comparative examples 1 to 6, the test piece 1 was placed in a thermostatic bath at 85 ℃ and 85% RH for 48 hours, and then surface observation or hand touch confirmation was performed to examine whether or not foreign matter was confirmed on the surface of the test piece 1, and the foreign matter was used as an index of hydrolysis resistance. Then, the test piece 1 was judged to be "good" or "poor" based on the following judgment criteria. The results are shown in tables 1 to 12 and tables 14 to 21.

(criteria for determination)

Good: no foreign matter was observed on the surface of the test piece 1

X: foreign matter was observed on the surface of the test piece 1

< odor >

The odor was evaluated on the test pieces 1 of examples 26 to 29, 31 to 32, 43, 46 to 49, 83 to 121 and comparative examples 11 to 14 based on the following evaluation criteria. The results are shown in tables 14 to 22.

(criteria for determination)

1: no odor was substantially felt

2: a slight odor was felt

3: strongly feel the odor

< processability >

A T-die was connected to a uniaxial extruder (trade name "LABPLAST MILL", manufactured by Toyo Seiki Seisaku-Sho Ltd.), and the flame-retardant resin compositions of examples 46 to 49 and 107 to 110 were charged into the uniaxial extruder to prepare a sheet having a thickness of 0.1mm for processability evaluation. At this time, the discharge amount and the drawing speed of the sheet were made constant. The sheets for workability evaluation were prepared by setting the processing temperature of a single-screw extruder to 230 ℃, 240 ℃ and 250 ℃. Then, the presence or absence of the formation of the holes in the sheet for workability evaluation in the extrusion for 30 minutes was examined, and the presence or absence of the formation of the holes was used as an index of workability. Here, the formation of the hole suggests a reduction in workability due to a variation in the discharge amount and the generation of bubbles. Then, the workability evaluation sheet was evaluated for "good" or "poor" based on the following evaluation criteria. The results are shown in tables 6 and 19.

(criteria for determination)

Good: no formation of holes was observed in the workability evaluation sheet

X: formation of holes was confirmed in the workability evaluation sheet

< colorability upon deterioration >

A test piece 4 was further produced in the same manner as the test piece 1 described above, except that the flame-retardant resin compositions of examples 55 to 58 and 118 to 121 were used to make a thickness of 1mm for evaluation of colorability. The test piece 4 was placed in a thermostatic bath at 85 ℃ and after standing for 5 days, surface observation was carried out to investigate whether the piece was discolored. Then, the test piece 4 is judged to be "good" or "poor" based on the following judgment criteria. The results are shown in tables 8 and 21.

(criteria for determination)

Good: no discoloration was observed in the sheet

X: discoloration was observed on the sheet

From the results shown in tables 1 to 22, it is understood that the evaluation results of the flame retardancy of the test piece (test piece 1) having a thickness of 0.1mm in examples 1 to 121 are all good, and examples 1 to 121 are acceptable in terms of flame retardancy. On the other hand, it is understood that the test pieces (test piece 1) having a thickness of 0.1mm were all evaluated as "x" in comparative examples 1 to 14, and comparative examples 1 to 14 failed in flame retardancy.

From the results shown in tables 1 to 22, it is understood that the evaluation results of the separation inhibiting effect of the flame retardant in examples 1 to 121 are good, and examples 1 to 121 are satisfactory in terms of the separation inhibiting effect of the flame retardant. On the other hand, it is understood that the evaluation results of the separation suppression effect of the flame retardant in comparative examples 1 to 14 are "x", and comparative examples 1 to 14 are not satisfactory in the separation suppression effect of the flame retardant.

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

From the results shown in tables 14 to 22, the results of odor determination in examples 43 and 83 to 121 were both "1" or "2". On the other hand, the results of odor determination in examples 26 to 29, 31 to 32, and 46 to 49 and comparative examples 11 to 14 were all "3". Therefore, it is found that the flame-retardant resin composition in which the blending ratio of the hindered amine compound (C) to 100 parts by mass of the base resin (a) is less than 0.4 part by mass can suppress the odor more than the flame-retardant resin composition in which the blending ratio of the hindered amine compound (C) to 100 parts by mass of the base resin (a) is 0.4 part by mass or more.

Further, from the results shown in Table 11, for example, in examples 64 and 71 to 75 in which the mass ratio R was 5.6 or more, the evaluation results of the flame retardancy of the test piece (test piece 1) having a thickness of 0.1mm (the evaluation results of the VTM test based on the UL94 standard) were all "VTM-0". In contrast, in example 76 in which the mass ratio R was less than 5.6, the test piece (test piece 1) having a thickness of 0.1mm was evaluated for flame retardancy to find "VTM-2". From the results shown in Table 12, in examples 56 and 77 to 81 in which the mass ratio R was 5.6 or more, the evaluation results of the flame retardancy of the test piece (test piece 1) having a thickness of 0.1mm (the evaluation results of the VTM test based on the UL94 standard) were all "VTM-0". In contrast, in example 82 in which the mass ratio R was less than 5.6, the test piece (test piece 1) having a thickness of 0.1mm was evaluated for flame retardancy as "VTM-2". From this, it is found that the flame retardancy of the test piece having the mass ratio R of 5.6 or more can be further improved as compared with the test piece having the mass ratio R of less than 5.6.

Description of the symbols

1 … conductor (transmission medium)

2. 25 … insulator

3 … insulating layer 1 (insulating part)

4 … insulating layer 2 (insulating part)

10. 20 … Cable

24 … optical fiber (Transmission Medium)