Patent Application
20220025156
One or more embodiments of the present invention relate to a flame-retardant resin composition, a flame-retardant resin composition for a cable, a cable, a molded body, a flame-retardant master batch using the same, and a flame retardant.
Polyolefin resins have excellent mechanical properties, and is widely used for building materials, packaging materials, OA equipment, automotive members, cables, and the like. Since polyolefin resins are combustible substances, they are used with various flame retardants such as a halogen flame retardant, a phosphorus flame retardant, a metal hydrate flame retardant added. However, the halogen flame retardant is likely to generate poisonous gases or smoke at the time of combustion and is subject to regulations depending on countries although the halogen flame retardant can impart excellent flame retardancy. Therefore, in recent years, a flame-retardant resin composition using a non-halogen flame retardant is required. As such a flame-retardant resin composition, a flame-retardant resin composition simultaneously using a phosphoric acid ester and an NOR-type hindered amine compound is known (see the following Patent Document 1).
Patent Document 1: JP 2017-66299 A
The flame-retardant resin composition described in the Patent Document 1 exhibits excellent flame retardancy. However, the flame-retardant resin composition described in the Patent Document 1 has room for improvement in terms of inhibiting separation of a flame retardant. Here, separation of a flame retardant means that when the flame retardant is kneaded with a resin, the flame retardant is separated (not mixed), or the flame retardant itself or the decomposed flame retardant is discharged to a surface of a resin composition in a solid state or a liquid state after the flame retardant is once dispersed into the resin composition, and also means that the flame retardancy is lowered.
One or more embodiments of the present invention provide a flame-retardant resin composition having excellent flame retardancy and capable of suppressing separation of the flame retardant, a cable, a flame-retardant resin composition for a cable, a molded body, a flame-retardant master batch using the same, and a flame retardant.
One or more embodiments of the present invention provide a flame-retardant resin composition obtained by blending a specific organic phosphorus compound and a specific hindered amine compound to a base resin containing a polyolefin resin.
Namely, one or more embodiments of the present invention provide a flame-retardant resin composition which contains a base resin (A) containing a polyolefin resin and a flame retardant, in which the flame retardant includes an organic phosphorus compound (B) and a hindered amine compound (C), and in which the organic phosphorus compound (B) is represented by the following general formula (1) and the hindered amine compound (C) contains a group represented by the following general formula (2).
(In the general formula (1), X1 and X2 each represent a hydrocarbon group which may have a substituent, and may be the same or different.)
(In the general formula (2), R1 to R4 each independently represent an alkyl group having 1 to 8 carbon atoms, R5 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.)
The flame-retardant resin composition of one or more embodiments of the present invention has excellent flame retardancy and can suppress separation of the flame retardant.
The reason why the flame-retardant resin composition of one or more embodiments of the present invention has excellent flame retardancy is as follows:
That is, the organic phosphorus compound (B) represented by the general formula (1) has excellent flame retardancy since the organic phosphorus compound contains a large amount of phosphorus in the molecular structure and is difficult to be separated from the base resin (A). On the other hand, the hindered amine compound (C) also can impart excellent flame retardancy since has a group represented by the general formula (2). As a result, it is considered that the flame-retardant resin composition has excellent flame retardancy.
The reason why the separation of the flame retardant is suppressed, is not clearly understood, but one or more embodiments of the present invention presume the reason as follows:
That is, the organic phosphorus compound has a high melting point, does not melt during molding of the flame-retardant resin composition, and is difficult to be separated from the polyolefin resin since the organic phosphorus compound has a spiro ring structure. On the other hand, in a case where the flame-retardant resin composition does not contain an organic phosphorus compound (B), the hindered amine compound (C) tends to be easily separated from the polyolefin resin by melting at the time of molding the flame-retardant resin composition, compared to the organic phosphorus compound (B). In contrast, since the flame-retardant resin composition contains the organic phosphorus compound (B), the hindered amine compound (C) is difficult to be separated from the organic phosphorus compound (B) even at the time of molding the flame-retardant resin composition by the interaction between the organic phosphorus compound (B) in the flame-retardant resin composition and the group represented by the general formula (2) of the hindered amine compound (C). Therefore, even when the flame-retardant resin composition is molded, the hindered amine compound (C) is difficult to be separated from the polyolefin resin. As a result, it is considered that separation of the flame retardant is suppressed in the flame-retardant resin composition.
In the flame-retardant resin composition, the hydrocarbon group represented by X1 and X2 in the general formula (1) is, for example, an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
In the flame-retardant resin composition, the hydrocarbon group represented by X1 and X2 may be an aromatic hydrocarbon group in the general formula (1).
In this case, hydrolysis resistance of the flame-retardant resin composition can be further improved. The reason why the hydrolysis resistance is thus improved is not clearly understood, but it is considered that the aromatic hydrocarbon group prevents hydrolysis of the organic phosphorus compound (B) due to a steric hindrance to the water molecule or by an electronic action.
In the flame-retardant resin composition, the aromatic hydrocarbon group may be a phenylmethyl group (benzyl group).
In this case, hydrolysis resistance and flame retardancy of the flame-retardant resin composition can be more effectively improved.
In the flame-retardant resin composition, it is preferable that when the hydrocarbon group represented by X1 and X2 in the general formula (1) is an aromatic hydrocarbon group or a phenylmethyl group (benzyl group), a foreign matter be not confirmed on the surface in a case where surface observation or touch confirmation is performed after the flame-retardant resin composition is left in a constant temperature bath of 85° C. and 85% RH for 48 hours.
This flame-retardant resin composition has excellent hydrolysis resistance.
In the flame-retardant resin composition, it is preferable that the hindered amine compound (C) be blended at a ratio of less than 0.4 parts by mass to 100 parts by mass of the base resin (A).
In this case, compared with a case where the hindered amine compound (C) is blended at a ratio of 0.4 parts by mass or more, the flame-retardant resin composition can further suppress an odor.
The reason why the flame-retardant resin composition can suppress an odor is not clear, but the reason presumes as follows.
That is, the odor is considered to be caused by an amine-based substance generated by the decomposition of the hindered amine compound. However, since the hindered amine compound (C) is difficult to be separated from the organic phosphorus compound (B) and its amount is small, as described above, the generated amine-based substance is considered to be difficult to be separated from the organic phosphorus compound (B). As a result, it is considered that the odor due to the amine-based substance is difficult to be released into the flame-retardant resin composition and the 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, compared with a case where the mass ratio of the organic phosphorus compound (B) to the hindered amine compound (C) is less than 5.6, the flame retardancy of the flame-retardant resin composition can be further improved.
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, compared with a case where the mass ratio of the organic phosphorus compound (B) to the hindered amine compound (C) exceeds 11.1, the flame retardancy of the flame-retardant resin composition can be further improved.
In the flame-retardant resin composition, it is preferable that the number of groups represented by the general formula (2) (hereinafter referred to as “amine number”) per gram in the hindered amine compound (C) is 1×1021 or more.
In this case, the flame retardancy of the flame-retardant resin composition can be further improved as compared with a case where the amine number per gram in the hindered amine compound (C) is less than 1×1021.
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 one molecule.
In this case, compared with a case where the hindered amine compound (C) has only one group represented by the general formula (2) in one molecule, the flame retardancy of the flame-retardant resin composition can be further improved.
In the flame-retardant resin composition, R5 in the general formula (2) is preferably an alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 5 to 12 carbon atoms.
In this case, the flame retardancy of the flame-retardant resin composition can be further improved as compared with a case where R5 in the general formula (2) is neither an alkyl group having 1 to 30 carbon atoms nor a cycloalkyl group having 5 to 12 carbon atoms.
In the flame-retardant resin composition, the hindered amine compound (C) is preferably a solid at 25° C.
In this case, compared with a case where the hindered amine compound (C) is a liquid at 25° C., the processability of the flame-retardant resin composition is further improved.
In the flame-retardant resin composition, it is preferable that the hindered amine compound (C) has a decomposition temperature of 240° C. or higher.
In this case, compared with a case where the decomposition temperature of the hindered amine compound (C) is less than 240° C., the flame retardancy and processability of the flame-retardant resin composition are further improved.
In the flame-retardant resin composition, the hindered amine compound (C) preferably contains a triazine ring.
In this case, compared with a case where the hindered amine compound (C) does not contain a triazine ring, the flame retardancy and processability of the flame-retardant resin composition can be further improved.
In the flame-retardant resin composition, R5 in the general formula (2) represents, for example, a cycloalkyl group having 5 to 12 carbon atoms.
In the flame-retardant resin composition, the hindered amine compound (C) preferably has a decomposition temperature of 250° C. or higher.
In this case, compared with a case where the decomposition temperature of the hindered amine compound (C) is less than 250° C., the flame retardancy and processability of the flame-retardant resin composition can be further improved.
In the flame-retardant resin composition, R5 in the general formula (2) is preferably an alkyl group having 1 to 30 carbon atoms.
In this case, the flame retardancy and processability of the flame-retardant resin composition can be further improved as compared with a case where R5 in the general formula (2) is not an alkyl group having 1 to 30 carbon atoms.
In the flame-retardant resin composition, the hindered amine compound (C) preferably does not contain a triazine ring.
In this case, compared with a case where the hindered amine compound (C) contains a triazine ring, coloration (yellowing) at the time of deterioration due to heat or light can be further suppressed.
The flame-retardant resin composition preferably further contains a drip preventing agent (D).
In this case, resin sagging (dripping) during combustion of the flame-retardant resin composition can be suppressed.
In the flame-retardant resin composition, it is preferable that the melting point of the organic phosphorus compound (B) be higher than the melting temperature of the base resin (A), and the melting point of the hindered amine compound (C) be lower than the melting temperature of the base resin (A).
In this case, the flame-retardant resin composition can sufficiently suppress the separation of the flame retardant.
The reason why the separation of the flame retardant is sufficiently suppressed by the flame-retardant resin composition of one or more embodiments of the present invention is not clear, but the reason may be as follows.
That is, the organic phosphorus compound has a high melting point, does not melt during molding of the flame-retardant resin composition, and is difficult to be separated from the polyolefin resin since the organic phosphorus compound has a spiro ring structure. On the other hand, the melting point of the hindered amine compound (C) is lower than the melting temperature of the base resin (A) and the melting point of the organic phosphorus compound (B) is higher than the melting temperature of the base resin (A). For this reason, the molten hindered amine compound (A) tends to be easily separated from the polyolefin resin at the time of molding the flame-retardant resin composition at the melting temperature of the base resin (A) in a case where the flame-retardant resin composition does not contain the organic phosphorus compound (B). In contrast, in the flame-retardant resin composition of one or more embodiments of the present invention, the flame-retardant resin composition contains an organic phosphorus compound (B), and the hindered amine compound (C) infiltrates into a solid organic phosphorus compound (B) dispersed in the base resin (A) and thereby captured by the organic phosphorus compound (B) when the flame-retardant resin composition is molded at the melting temperature of the base resin (A). Therefore, in the flame-retardant resin composition of one or more embodiments of the present invention, even when the flame-retardant resin composition is molded at the melting temperature of the base resin (A), the hindered amine compound (C) is difficult to be separated from the polyolefin resin. As a result, it is considered that separation of the flame retardant is more sufficiently suppressed in the flame-retardant resin composition.
In the flame-retardant resin composition, the melting point of the organic phosphorus compound (B) is at least 40° C. higher than the melting temperature of the base resin (A), for example.
In the flame-retardant resin composition, the melting point of the hindered amine compound (C) is at least 3° C. lower than the melting temperature of the base resin (A), for example.
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, compared with a 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 parts by mass, the flame retardancy of the flame-retardant resin composition can be further improved.
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 a 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 flame-retardant resin composition, it is preferable that the flame retardant consist of the organic phosphorus compound (B) and the hindered amine compound (C).
The flame-retardant resin composition does not fall under any of the following (i) and (ii).
(i) A foreign matter is confirmed on the surface of the flame-retardant resin composition.
(ii) A foreign matter is confirmed on the surface of the flame-retardant resin composition after the flame-retardant resin composition is left in a constant temperature bath at 85° C. for 48 hours.
The flame-retardant resin composition satisfies either of the following requirement (a) or (b) when a combustion test of an automotive interior material based on FMVSS No. 302 is performed.
(a) Self-extinguishing is observed
(b) Self-extinguishing is not observed but the combustion rate is 102 mm/min or less.
One or more embodiments of the present invention provide a flame-retardant resin composition for a cable including the above-mentioned flame-retardant resin composition.
The flame-retardant resin composition for a cable of one or more embodiments of the present invention can impart excellent flame retardancy to a cable when used as at least a part of the insulator of the cable, and can maintain the flame retardancy of the cable for a long period of time. Therefore, the flame-retardant resin composition for a cable of one or more embodiments of the present invention can eliminate the need for a cable to be replaced for a long period of time.
One or more embodiments of the present invention provide a cable including a transmission medium composed of a conductor or an optical fiber, and an insulator covering the transmission medium, wherein the insulator includes an insulating part composed of the flame-retardant resin composition.
According to the cable of one or more embodiments of the present invention, the insulating part is composed of the flame-retardant resin composition having excellent flame retardancy and capable of suppressing separation of the flame retardant. Therefore, the cable of one or more embodiments of the present invention has excellent flame retardancy and can maintain its flame retardancy for a long period of time. Therefore, the cable of one or more embodiments of the present invention does not need to be replaced for a long period of time.
One or more embodiments of present invention is a molded body containing the flame-retardant resin composition.
The molded body includes the flame-retardant resin composition having excellent flame retardancy and capable of suppressing separation of the flame retardant. Therefore, the molded body of one or more embodiments of the present invention has excellent flame retardancy and can maintain its flame retardancy for a long period of time. Therefore, the molded body of one or more embodiments of the present invention does not need to be replaced for a long period of time.
The molded body may further comprise at least a sheet layer containing the flame-retardant resin composition.
One or more embodiments of present invention provide a flame retardant master batch composed of the flame-retardant resin composition.
The flame-retardant master batch is composed of the flame-retardant resin composition, and the flame-retardant resin composition has excellent flame retardancy and can suppress the separation of the flame retardant. Therefore, even if the flame-retardant master batch is produced by kneading with another resin, the molded body has excellent flame retardancy and can suppress the separation of the flame retardant.
Further, one or more embodiments of the present invention provide a flame retardant including an organic phosphorus compound (B) and a hindered amine compound (C), in which 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), X1 and X2 each represent a hydrocarbon group which may have a substituent, and may be the same or different.)
(In the general formula (2), R1 to R4 each independently represent an alkyl group having 1 to 8 carbon atoms, R5 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.)
The flame retardant can impart excellent flame retardancy to the flame-retardant resin composition when the flame-retardant resin composition is produced by kneading the flame retardant with a base resin (A) containing a polyolefin resin. In addition, the flame retardant of one or more embodiments of the present invention is difficult to be separated from the base resin (A) even when kneaded with the base resin (A) containing the polyolefin resin. Therefore, separation of the flame retardant in the flame-retardant resin composition can be suppressed.
In the flame retardant, the hydrocarbon group represented by X1 and X2 in the general formula (1) is, for example, an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
In the flame retardant, the hydrocarbon group represented by X1 and X2 in the general formula (1) is preferably an aromatic hydrocarbon group.
The flame retardant can further improve the hydrolysis resistance of the flame-retardant resin composition when the flame-retardant resin composition is produced by kneading the flame retardant with a base resin (A) containing a polyolefin resin.
In the flame retardant, it is preferable that the aromatic hydrocarbon group is a phenylmethyl group.
The flame retardant can more effectively improve the hydrolysis resistance and flame retardancy of the flame-retardant resin composition when the flame-retardant resin composition is produced by kneading the flame retardant with a base resin (A) containing a polyolefin resin.
In the flame retardant, the melting point of the organic phosphorus compound (B) is preferably higher than the melting point of the hindered amine compound (C).
The flame retardant can impart excellent flame retardancy to the flame-retardant resin composition when the flame-retardant resin composition is produced by kneading the flame retardant with a base resin (A) containing a polyolefin resin at a melting temperature of the base resin (A). In addition, the flame retardant of one or more embodiments of the present invention is difficult to be separated from the base resin (A) even when kneaded with the base resin (A) containing the polyolefin resin at the melting temperature of the base resin (A). Therefore, separation of the flame retardant in the flame-retardant resin composition can be sufficiently suppressed.
The flame retardant preferably consists of the organic phosphorus compound (B) and the hindered amine compound (C).
In the flame retardant, the mass ratio of the organic phosphorus compound (B) to the hindered amine compound (C) is preferably 5.6 or more.
The flame retardant can further improve the flame retardancy of the flame-retardant resin composition when the flame-retardant resin composition is produced by kneading the flame retardant with a base resin (A) containing a polyolefin resin.
In the flame retardant, the mass ratio of the organic phosphorus compound (B) to the hindered amine compound (C) is preferably 11.1 or less.
The flame retardant can further improve the flame retardancy of the flame-retardant resin composition compared with a case where the mass ratio of the organic phosphorus compound (B) to the hindered amine compound (C) exceeds 11.1 when the flame retardant is blended into the flame-retardant resin composition.
In one or more embodiments of the present invention, the “decomposition temperature” of the hindered amine compound means a decomposition temperature measured by the Thermogravimetry/Differential thermal analysis (TG/DTA), and specifically means a decomposition temperature measured under the following measurement conditions using the following measuring device for a sample comprising a hindered amine compound. Here, the decomposition temperature is a temperature at which the weight of the hindered amine compound is reduced by 1%.
Product name “TG/DTA6300” (manufactured by Hitachi High-Tech Science Corporation)
Sample amount: about 5 mg
Measurement temperature: from 25° C. to 600° C.
Measurement atmosphere: air flow (200 mL/min)
Temperature rising rate is 10° C./min
Material of a sample container: aluminum (Al)
In one or more embodiments of the present invention, the “melting temperature” of the base resin (A) refers to the temperature below.
(1) the melting point (° C.) of the base resin (A)+30° C. when the base resin (A) is composed of only a crystalline polymer.
(2) the glass transition point (° C.) of the base resin (A)+30° C. when the base resin (A) is composed of only an amorphous polymer.
(3) The melting point or the glass transition temperature of the component having the highest content among a crystalline polymer and an amorphous polymer+30° C. when the base resin (A) is composed of a mixture of the crystalline polymer and the amorphous polymer (a physical blend or a copolymer).
“+30° C.” is a value determined considering that a temperature at the time of melt-processing a resin is generally set at 30° C. higher than the melting point or the glass transition point of the resin.
In one or more embodiments of the present invention, the melting point of the base resin (A) is determined by the method specified in JIS K 7121. Specifically, when heating is once performed to a molten state by a differential scanning calorimeter (DSC), the heat history is erased by crystallization at a cooling rate of 5° C./min and a DSC curve is measured under the condition of a temperature rise rate of 10° C./min again, the molten peak is determined as a melting point.
In one or more embodiments of the present invention, the glass transition point of the base resin (A) is determined by the method specified in JIS K 7121. Specifically, when heating is once performed to a molten state by a differential scanning calorimeter (DSC), the heat history is erased by crystallization at a cooling rate of 5° C./min and a DSC curve is measured under the condition of a temperature rise rate of 20° C./min, the intermediate point of the change in the base line is determined as a glass transition temperature.
According to one or more embodiments of 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, a molded body, and a flame-retardant master batch using the same and a flame retardant are provided.
Embodiments of the present invention are described in detail below.
<Flame-Retardant Resin Composition>
This flame-retardant resin composition of one or more embodiments of the present invention contains a base resin (A) containing a polyolefin resin and a flame retardant, and the flame retardant contains an organic phosphorus compound (B) and a hindered amine compound (C). Here, the organic phosphorus compound (B) is represented by the following general formula (1), and the hindered amine compound (C) has a group represented by the following general formula (2).
(In the general formula (1), X1 and X2 each represent a hydrocarbon group which may have a substituent, and may be the same or different.)
(In the general formula (2), R1 to R4 each independently represent an alkyl group having 1 to 8 carbon atoms, R5 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.
The flame-retardant resin composition of one or more embodiments of the present invention has excellent flame retardancy and can suppress the separation of the flame retardant. In the flame-retardant resin composition of the present invention, the flame retardant is difficult to be separated from the base resin (A). Therefore, the flame-retardant resin composition of one or more embodiments of the present invention is useful as a flame retardant master batch in which a flame retardant is blended at a high concentration.
The base resin (A), the organophosphorus compound (B) and the hindered amine compound (C) are described in detail below.
(A) Base 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. These may be used alone or in combination of two or more.
(A1) Non-Modified Polyolefin Resin
Examples of the non-modified polyolefin resin include an ethylene polymer, a propylene polymer and an olefinic thermoplastic elastomer. These can be used alone or in combination of two or more.
The ethylene polymer is a polymer containing a structural unit derived from ethylene, and examples of the ethylene polymer include polyethylene, an ethylene-α-olefin copolymer, an 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), ultra-low density polyethylene (VLDPE), metallocene ultra-low density polyethylene, and the like. These may be used alone or in combination of two or more.
The propylene-based polymer refers to a polymer mainly containing a constituent unit derived from propylene. Examples of the propylene polymer include homopolypropylene, propylene-ethylene copolymer, and propylene-α-olefin copolymer. Examples of the α-olefin include 1-butene, 2-butene, 1-hexene and 2-hexene.
When the propylene 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. However, the copolymer is preferably a block copolymer. When the copolymer is a block copolymer, the abrasion resistance of the flame-retardant resin composition can be further improved as compared with a case where the copolymer is a random copolymer.
Examples of the olefinic elastomer include a polypropylene elastomer and an olefin-ethylene-butylene-olefin copolymer such as an olefin crystal-ethylene-butylene-olefin crystal block copolymer (CEBC copolymer). These can be used alone or in combination of two or more.
The non-modified polyolefin resin preferably contains an olefin elastomer from the viewpoint of improving impact resistance.
(A2) Modified Polyolefin Resin
The modified polyolefin resin is a resin obtained by modifying the polyolefin resin or a precursor thereof by grafting or copolymerization. Examples of the functional group introduced by modification include a carboxyl group, an acid anhydride group, a methacryloxy group, an acryloxy group, an acrylic group, an acetyl group, an alkoxy group (for example, a methoxy group or an ethoxy group). Among them, a carboxyl group and an acid anhydride group are preferable. In this case, the abrasion resistance of the flame-retardant resin composition can be more effectively improved compared with a case where the functional group introduced by modification is a functional group other than the carboxyl group and the acid anhydride group. Examples of the substance used for grafting or copolymerization include an acid, an acid anhydride and a derivative 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 an anhydrous carboxylic acid such as maleic anhydride.
Examples of the modified resin include an ethylene-vinyl acetate copolymer, an ethylene-acrylic ester copolymer, an ethylene-methacrylic acid ester copolymer, a maleic acid-modified polyolefin, a maleic anhydride-modified polyolefin, a maleic acid-modified styrene elastomer, and a maleic anhydride-modified styrene elastomer.
(A3) Non-Polyolefin Resin
The base resin (A) may further contain a non-polyolefin resin in addition to the polyolefin resin. From the viewpoint of improving impact resistance, the non-polyolefin resin preferably contains a non-olefinic elastomer. Examples of the non-olefin elastomer include a block copolymer of olefin and stylene 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), styrene-isoprene-styrene copolymer (SIS copolymer); and a hydrogenated product obtained by hydrogenating and modifying these (a hydrogenated SBR, a hydrogenated SEBS copolymer, a hydrogenated SPBS copolymer, a hydrogenated SBS copolymer and a hydrogenated SIS copolymer). These can be used alone or in combination of two or more.
(B) Organic Phosphorus Compound
The organic phosphorus compound (B) is a flame retardant, and as described above, the organic phosphorus compound is represented by the following general formula (1).
In the general formula (1), X1 and X2 each represent a hydrocarbon group which may have a substituent. X1 and X2 may be the same or different from each other.
Examples of the hydrocarbon group include, for example, an aliphatic hydrocarbon group and an aromatic hydrocarbon group.
The aliphatic hydrocarbon group may have any structure of a cyclic, linear or branched structure. Examples of the aliphatic hydrocarbon group include an alkyl group, a cycloalkyl group and the like.
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, a 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 a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cycloundecyl group, and a cyclododecyl group.
The carbon number 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 anthryl methyl group and an anthryl ethyl group.
In the general formula (1), X1 and X2 are preferably an aromatic hydrocarbon group. In this case, hydrolysis resistance of the flame-retardant resin composition can be further improved.
In particular, the aromatic hydrocarbon group is preferably a phenylmethyl group (benzyl group). In this case, compared with a case where X1 and X2 in the general formula (1) are not a phenylmethyl group, 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) to 100 parts by mass of the base resin (A) is not particularly limited, but is preferably 0.1 parts by mass or more. In this case, the flame retardancy of the flame-retardant resin composition can be further improved as compared with a 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 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 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 a 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. 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 more preferably 5 parts by mass or more, from the viewpoint of 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 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 a 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) is a flame retardant and has only to have a group represented by the following general formula (2).
In the general formula (2), R1 to R4 each independently represent an alkyl group having 1 to 8 carbon atoms, R5 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.
Examples of the alkyl group represented by R1 to R4 in the above general formula (2) include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group.
Here, “alkyl group” includes not only a non-substituted alkyl group but also a substituted alkyl group. As the substituted alkyl group, a substituted alkyl group obtained by substituting a hydrogen atom of a non-substituted alkyl group can be used.
Examples of the alkyl group represented by R5 in the general formula (2) include, for example, 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, a undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group.
Examples of the cycloalkyl group represented by R5 include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cycloundecyl group, and a cyclododecyl group.
Examples of the aralkyl group represented by R5 include a phenylmethyl group (benzyl group), a phenylethyl group, a phenylpropyl group, a naphthylmethyl group, a naphthylethyl group, an anthryl methyl group, and an anthryl ethyl group.
Examples of the aryl group represented by R5 include a phenyl group and a naphthyl group.
Specific examples of the hindered amine compound (C) include a compound represented by the following formula (3), a compound represented by the following formula (4), and the like.
(In the formula (3), R6 to R9 each represent an alkylamino group, R10 to R14 represent a group represented by the general formula (2), R15 and R16 represent an alkylene group, and R17 represents an alkyl imino group. n is an integer of 1 to 15.)
(In the formula (4), R18 to R20 represent a group represented by the following general formula (5).)
(In the formula (5), R21 to R24 represent a group represented by the general formula (2) or an alkyl group, and at least two of R21 to R24 represent a group represented by the general formula (2).)
The amine number per gram in the hindered amine compound (C) is not particularly limited but is preferably 1×1021 or more.
In this case, the flame retardancy of the flame-retardant resin composition can be further improved as compared with a case where the amine number per gram in the hindered amine compound (C) is less than 1×1021.
However, the amine number per gram in the hindered amine compound (C) is preferably 3×1021 or less.
The hindered amine compound (C) preferably has a plurality of groups represented by the general formula (2) in one molecule.
In this case, the flame retardancy of the flame-retardant resin composition can be further improved as compared with a hindered amine compound (C) having only one group represented by the general formula (2) in one molecule.
It is also preferable that R5 in the general formula (2) represent an alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 5 to 12 carbon atoms.
In this case, the flame retardancy of the flame-retardant resin composition can be further improved as compared with a case where R5 in the general formula (2) is neither an alkyl group having 1 to 30 carbon atoms nor a cycloalkyl group having 5 to 12 carbon atoms.
The hindered amine compound (C) may be a solid or a liquid at 25° C., but is preferably a solid. In this case, compared with a case where the hindered amine compound (C) is a liquid at 25° C., the processability of the flame-retardant resin composition is further improved.
The decomposition temperature of the hindered amine compound (C) is not particularly limited but is preferably 240° C. or higher.
In this case, compared with a case where the decomposition temperature of the hindered amine compound (C) is less than 240° C., the flame retardancy of the flame-retardant resin composition is further improved. The moldability of the flame-retardant resin composition is further improved as compared with a case where the decomposition temperature of the hindered amine compound (C) is less than 240° C. That is, the hindered amine compound (C) is difficult to be decomposed at the time of molding the flame-retardant resin composition, and the variation in the discharge amount from a molding device and the generation of air bubbles are sufficiently suppressed.
The hindered amine compound (C) may or may not contain a triazine ring. However, the hindered amine compound (C) preferably contain a triazine ring.
In this case, compared with a case where the hindered amine compound (C) does not contain a triazine ring, the flame retardancy and processability of the flame-retardant resin composition can be further improved.
The hindered amine compound (C) preferably has a decomposition temperature of 250° C. or higher. In this case, the flame retardancy of the flame-retardant resin composition can be further improved as compared with a case where the decomposition temperature of the hindered amine compound (C) is less than 250° C. In addition, compared with a case where the decomposition temperature of the hindered amine compound (C) is less than 250° C., the moldability of the flame-retardant resin composition is more sufficiently improved. That is, the hindered amine compound (C) is more difficult to be decomposed at the time of molding the flame-retardant resin composition, and the variation in the discharge amount from a molding device and the generation of air bubbles are more sufficiently suppressed.
In the flame-retardant resin composition, R5 in the general formula (2) preferably represents an alkyl group having 1 to 30 carbon atoms.
In this case, the flame retardancy and processability of the flame-retardant resin composition can be further improved as compared with a case where R5 in the general formula (2) is not an alkyl group having 1 to 30 carbon atoms.
The blending ratio of the hindered amine compound (C) to 100 parts by mass of the base resin (A) is not particularly limited, but is preferably 0.01 parts by mass or more. In this case, the flame retardancy of the flame-retardant resin composition can be further improved as compared with a case where the blending ratio of the hindered amine compound (C) to 100 parts by mass of the base resin (A) is less than 0.01 parts by mass.
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, compared with a 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, the flame retardancy of the flame-retardant resin composition can be further improved. The blending ratio of the hindered amine compound (C) to 100 parts by mass of the base resin (A) is more preferably 0.1 parts by mass or more, even more preferably 0.15 parts by mass or more, particularly preferably 0.5 parts by mass or more, from the viewpoint of 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 preferably 15 parts by mass or less. In this case, compared with a case where the blending ratio of the hindered amine compound (C) to 100 parts by mass of the base resin (A) exceeds 15 parts by mass, the processability of the flame-retardant resin composition can be further improved. 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, even more preferably 5 parts by mass or less.
In addition, 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 parts by mass. In this case, compared with a 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, the odor of the flame-retardant resin composition can be further suppressed. Therefore, the flame-retardant resin composition is particularly useful for materials to which the suppression of odor is particularly required such as interior materials of automobiles and ducts of air conditioners. 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, even more preferably 0.2 parts by mass or less, from the viewpoint of suppressing the odor of the flame-retardant resin composition.
The mass ratio of the organic phosphorus compound (B) to the hindered amine compound (C), that is, 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 formula, mB represents the mass of the organic phosphorus compound (B), and mC represents the mass of the hindered amine compound (C).)
In this case, compared with a case where the mass ratio R is less than 5.6, the flame retardancy of the flame-retardant resin composition can be further improved.
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 a 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, it is preferable that the melting point TB (° C.) of the organic phosphorus compound (B) be higher than the melting temperature T (° C.) of the base resin (A), and that the melting point Tc (° C.) of the hindered amine compound (C) be lower than the melting temperature T (° C.) of the base resin (A). In this case, the flame-retardant resin composition can sufficiently suppress the separation of the flame retardant.
At this time, the melting point TB (° C.) of the organic phosphorus compound (B) has only to be higher than the melting temperature T (° C.) of the base resin (A), and the TB−T is, for example, 40° C. or higher. However, TB−T is preferably 20° C. or higher in consideration of the temperature stability of the flame-retardant resin composition at the time of processing.
The melting point Tc (° C.) of the hindered amine compound (C) is lower than the melting temperature T (° C.) of the base resin (A), and Tc−T is, for example, −3° C. or less. However, Tc−T is preferably −20° C. or less. Tc−T is more preferably −30° C. or less in consideration of the temperature stability of the flame-retardant resin composition at the time of processing.
In the flame-retardant resin composition, the flame retardant contains an organic phosphorus compound (B) and a hindered amine compound (C). However, the flame retardant is preferably composed of only an organic phosphorus compound (B) and a hindered amine compound (C).
(D) Drip Preventing Agent
The flame-retardant resin composition preferably further contains a drip preventing agent (D) in addition to the base resin (A), the organophosphorus compound (B), and the hindered amine compound (C). In this case, resin sagging (dripping) during combustion of the flame-retardant resin composition can be suppressed.
Fluorine drip preventing agent is preferable as the drip preventing agent.
The fluorine drip preventing agent contain a fluorine-containing compound containing fluorine and has only to be an fluorine drip preventing agent which can prevent resin sagging (dripping) during combustion. Examples of such fluorine-containing compounds include fluorine resins such as polytetrafluoroethylene (hereinafter referred to as “PTFE”), polyvinylidene fluoride, and polyhexafluoropropylene. The fluorine-containing compound may be a non-modified fluorine-containing compound or a modified fluorine-containing compound, but it is preferable that the fluorine-containing compound be modified. In this case, compared with a case where the fluorine-containing compound is not modified, the fluorine-containing compound is efficiently fibrillated and the dispersibility in the flame-retardant resin composition is further improved. As a result, the drip prevention function of the drip preventing agent (D) can be further improved. Further, since the melt tension of the flame-retardant resin composition becomes greater, 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, it is preferable that the drip preventing agent (D) be further blended at a ratio of more than 0 part by mass and 5 parts by mass or less to 100 parts by mass of the base resin (A).
In this case, unlike a case where the blending ratio of the drip preventing agent (D) to 100 parts by mass of the base resin (A) is 0 mass part, the drip prevention performance is exhibited. Compared with a case where the blending ratio of the drip preventing agent (D) to 100 parts by mass of the base resin (A) exceeds 5 parts by mass, it is more sufficiently suppressed that the melt viscosity of the flame-retardant resin composition becomes too high, and the processability of the flame-retardant resin composition is further improved.
The blending ratio of the drip preventing 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, compared with a case where the blending ratio of the drip preventing agent (D) to 100 parts by mass of the base resin (A) is less than 0.2 parts by mass, more excellent flame retardancy can be obtained in the flame-retardant resin composition. The blending ratio of the drip preventing 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 does not fall under any of the following (i) and (ii).
(i) A foreign matter is confirmed on the surface of the flame-retardant resin composition when surface observation or touch confirmation is performed on the flame-retardant resin composition.
(ii) A foreign matter is confirmed on the surface of the flame-retardant resin composition when surface observation or touching confirmation is performed on the flame-retardant resin composition after the flame-retardant resin composition is left in a constant temperature bath at 85° C. for 48 hours.
Here, the “foreign matter” is a flame retardant contained in the flame-retardant resin composition or a decomposition product thereof. The surface observation or touching confirmation of (i) is carried out without allowing the flame-retardant resin composition to be left for 48 hours in a constant temperature bath of 85° C.
The flame-retardant resin composition satisfies either of the following requirement (a) or (b) when performing a combustion test for automotive interior materials based on FMVSS No. 302.
(a) Self-extinguishing is observed
(b) Self-extinguishing is not observed but the combustion rate is 102 mm/min or less.
In a case where the hydrocarbon group represented by X1 and X2 in the general formula (1) is an aromatic hydrocarbon group or a phenylmethyl group (benzyl group), it is preferable that no foreign matter be confirmed on the surface when surface observation or touch confirmation is carried out on the flame-retardant resin composition after the flame-retardant resin composition is left in a constant temperature bath at 85° C. and 85% RH (Relative Humidity) for 48 hours.
The flame-retardant resin composition has more excellent hydrolysis resistance. The “foreign matter” is a flame retardant contained in the flame-retardant resin composition or a decomposition product thereof.
The flame-retardant resin composition may further contain an antioxidant, a thermal deterioration inhibitor, an ultraviolet absorber, an ultraviolet deterioration inhibitor, an anti-fogging agent, a crosslinking agent, a foaming agent, a conductive filler, a heat dissipating agent, a coloring pigment, or a processing aid in a range not affecting flame retardancy and processability, as needed.
The flame-retardant resin composition can be obtained by kneading the base resin (A), the organophosphorus compound (B), and the hindered amine compound (C). Kneading can be carried out by using a kneader capable of performing processing by applying necessary heat for melting the base resin (A), and necessary shearing for dispersing the organic phosphorus compound (B) and the hindered amine compound (C). As the kneader, for example, an open roll, a twin-screw extruder, a Banbury mixer, a pressure kneader or the like can be used.
<Cable>
(First Embodiment of Cable)
Next, a first embodiment of the cable of the present invention is described with reference to
As shown in
Here, the first insulating layer 3 and the second insulating layer 4 are composed of the flame-retardant resin composition described above, and the flame-retardant resin composition has excellent flame retardancy and can suppress the separation of the flame retardant. Therefore, the first insulating layer 3 and the second insulating layer 4 composed of the flame-retardant resin composition have excellent flame retardancy and can maintain the flame retardancy for a long period of time. Therefore, the cable 10 does not need to be replaced for a long period of time.
(Conductor)
The conductor 1 may be composed of only one element wire and may be constituted by bundling a plurality of element wires. The conductor 1 is not particularly limited on the conductor diameter, the material of the conductor, or the like, and can 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, but a conductive substance such as a carbon material can be suitably used.
(Second Embodiment of Cable)
Next, a second embodiment of the cable of the present invention is described with reference to
As shown in
Here, the flame-retardant resin composition has excellent flame retardancy and can suppress the separation of the flame retardant. Therefore, the insulator 25 composed of the flame-retardant resin composition has excellent flame retardancy and can maintain the flame retardancy for a long period of time. Therefore, the optical fiber cable 20 does not need to be replaced for a long period of time.
<Molded Body>
Next, the molded body of one or more embodiments of the present invention is described.
The molded body of one or more embodiments of the present invention contains the flame-retardant resin composition described above, and the flame-retardant resin composition has excellent flame retardancy and can suppress the separation of the flame retardant. Therefore, the molded body has excellent flame retardancy and can maintain its flame retardancy for a long period of time. Therefore, the molded body of one or more embodiments of the present invention does not need to be replaced for a long period of time. The molded body of one or more embodiments of the present invention is suitable for applications requiring a great deal of work for replacement such as, for example, a television back panel, a capacitor case, an insulating film inside a keyboard, a panel inside a heater, a flame-retardant sheet of a building, a dashboard of an automobile, a packaging material, and a housing of a household electric appliance.
The shape of the molded body of one or more embodiments of the present invention is not particularly limited. Examples of the shape of the molded body includes, for example, a sheet-like shape, a spherical shape, a rectangular parallelepiped shape, a cubic shape, a foam shape. However, the shape of the molded body is preferably a sheet-like shape.
When the shape of the molded body is a sheet-like shape, the molded body has a sheet layer composed of the flame-retardant resin composition described above. In this case, the molded body may be composed of only one sheet layer and may be composed of a laminate of a plurality of sheet layers.
The molded body can be obtained by molding the above flame-retardant resin composition using, for example, an extrusion molding method, an injection molding method, a vacuum molding method, a press molding method, a blow molding method, an inflation molding method, and the like. The molded body may be composed of a flame-retardant resin composition alone, or, in some applications, the molded body may be composed of a combination of the flame-retardant resin composition and a reinforcing material such as glass cloth or paper.
<Flame Retardant>
Next, the flame retardant of one or more embodiments of the present invention is described.
The flame retardant of one or more embodiments of the present invention includes an organic phosphorus compound (B) and a hindered amine compound (C). However, the flame retardant of one or more embodiments of the present invention does not contain a resin. The organic phosphorus compound (B) is represented by the general formula (1), and the hindered amine compound (C) has a group represented by the general formula (2).
The organic phosphorus compound (B) and the hindered amine compound (C) are as already described.
The flame retardant of one or more embodiments of the present invention can impart excellent flame retardancy to the flame-retardant resin composition when the flame-retardant resin composition is produced by kneading the flame retardant with a base resin (A) containing a polyolefin resin. The flame retardant is difficult to be separated from the base resin (A) even when kneaded with a base resin (A) containing a polyolefin resin, and separation of the flame retardant in the flame-retardant resin composition can be suppressed.
In the flame retardant, the hydrocarbon group represented by X1 and X2 in the general formula (1) is, for example, an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
In the general formula (1), the hydrocarbon group represented by X1 and X2 is preferably an aromatic hydrocarbon group. The flame retardant can further improve the hydrolysis resistance of the flame-retardant resin composition when the flame-retardant resin composition is produced by kneading the flame retardant with a base resin (A) containing a polyolefin resin.
In the flame retardant, the aromatic hydrocarbon group is preferably a phenylmethyl group.
In this case, when the flame-retardant resin composition is produced by kneading the flame retardant with a base resin (A) containing a polyolefin resin, hydrolysis resistance and flame retardancy of the flame-retardant resin composition can be more effectively improved.
In the flame retardant, the blending ratio of the organic phosphorus compound (B) and the hindered amine compound (C) is not particularly limited, but may be the same 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 when it is assumed that the base resin (A) is contained in the flame retardant.
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, compared with a case where the mass ratio R is less than 5.6, the flame retardant can further improve the flame retardancy of the flame-retardant resin composition.
The mass ratio R is preferably 6.3 or more.
However, the mass ratio R is preferably 11.1 or less. In this case, compared with a case where the mass ratio R exceeds 11.1, the flame retardant can further improve the flame retardancy of the flame-retardant resin composition. The mass ratio R is more preferably 10.5 or less.
The organic phosphorus compound (B) and the hindered amine compound (C) are as already described in the description of the flame-retardant resin composition.
<Flame Retardant Master Batch>
Next, the flame retardant master batch of one or more embodiments of the present invention is described.
The flame retardant master batch of one or more embodiments of the present invention is composed of the flame-retardant resin composition.
The flame-retardant master batch of one or more embodiments of the present invention is composed of the flame-retardant resin composition, and the flame-retardant resin composition has excellent flame retardancy and can suppress the separation of the flame retardant. Therefore, even if a molded body is produced by kneading the flame retardant master batch of one or more embodiments of the present invention with other resins, the molded body has excellent flame retardancy and can suppress the separation of the flame retardant.
In the flame retardant master batch of one or more embodiments 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, compared with a case where the blending ratio of the organic phosphorus compound (B) to 100 parts by mass of the base resin (A) exceeds 200 parts by mass, the dispersibility of the flame retardant is excellent. It is more preferable that the blending ratio of the organic phosphorus compound (B) to 100 parts by mass of the base resin (A) be 100 parts by mass or less.
In the flame retardant master batch of one or more embodiments 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, compared with a case where the blending ratio of the hindered amine compound (C) to 100 parts by mass of the base resin (A) exceeds 50 parts by mass, the dispersibility of the flame retardant is excellent.
In the flame retardant master batch of one or more embodiments of the present invention, from the viewpoint of suppressing the odor of the flame retardant master batch, 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 parts by mass. 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 parts 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 parts by mass or more. In this case, compared with a case where the blending ratio of the hindered amine compound (C) to 100 parts by mass of the base resin (A) is less than 0.01 parts by mass, the flame retardancy is more excellent.
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, compared with a case where the mass ratio R is less than 5.6, the flame retardant master batch can further improve the flame retardancy of the flame-retardant resin composition.
The mass ratio R is preferably 6.3 or more.
However, the mass ratio R is preferably 11.1 or less. In this case, compared with a case where the mass ratio R exceeds 11.1, the flame-retardant master batch can further improve the flame retardancy of the flame-retardant resin composition. The mass ratio R is more preferably 10.5 or less.
The organic phosphorus compound (B) and the hindered amine compound (C) are as already described in the description of the flame-retardant resin composition.
The present invention is not limited to the above embodiments. For example, in the above one or more embodiments, the cable 10 has only one conductor 1, but the cable of the present invention is not limited to the cable having only one conductor 1. The cable may be a cable having a plurality of conductors 1 separated from each other.
In the above one or more embodiments, the first insulating layer 3 and the second insulating layer 4 are composed of the flame-retardant resin composition, but the first insulating layer 3 is not composed of the flame-retardant resin composition, and only the second insulating layer 4 may be composed of the above flame-retardant resin composition. Alternatively, the second insulating layer 4 is not composed of the flame-retardant resin composition, and only the first insulating layer 3 may be composed of the above flame-retardant resin composition.
In the cable 20, the insulator 25 is composed of an insulating part. However, the insulator 25 may further include a coating part covering the insulating part. Here, the coating part may or may not be composed of the flame-retardant resin composition constituting the first insulating layer 3 and the second insulating layer 4 in the one or more embodiments, but it is preferable that the coating part be composed of the flame-retardant resin composition constituting the first insulating layer 3 and the second insulating layer 4 in the one or more embodiments.
In the above embodiments, the cable 20 has tension members 22 and 23, but in the cable of one or more embodiments of the present invention, the tension member is not necessarily required and can be omitted.
Hereinafter, the content of the present invention is more specifically described with reference to the following Examples, but the present invention is not limited to the following Examples.
A base resin (A), an organic phosphorus compound (B) and a hindered amine compound (C) were blended with the blending amount shown in Tables 1 to 22, and kneaded at 190° C. using a Banbury mixer to obtain a flame-retardant resin composition. In Tables 1 to 22, the units of the blending amounts of the respective blending components are parts by mass.
As the base resin (A), the organophosphorus compound (B) and the hindered amine compound (C), the followings were specifically used.
Product name “Novaltec BC4BSW”, manufactured by Japan Polypropylene Corporation, crystalline, melting point: 165° C.
(A1-2) Homopolypropylene (homo PP)
Product name “Novaltec MA3”, manufactured by Japan Polypropylene Corporation, crystalline, melting point: 165° C.
Product name “WINTEC WFW4M”, manufactured by Japan Polypropylene Corporation, crystalline, melting point: 135° C.
Product name “EXCELLEN GMH GH030”, manufactured by SUMITOMO CHEMICAL COMPANY, LIMITED, crystalline, melting point: 101° C.
Product name “REXPEARL A1150”, manufactured by Japan Polyethylene Corporation, crystalline, melting point: 100° C.
(A4) Propylene-α Olefin Copolymer Product name “TAFMER PN2060”, manufactured by Mitsui Chemicals, Inc., crystalline, melting point: 160° C.
(A5) Ethylene-α Olefin Copolymer Product name “TAFMER DF810”, manufactured by Mitsui Chemicals, Inc., crystalline, melting point: 66° C.
Product name “DYNARON 1320P”, manufactured by JSR Corporation, amorphous, glass transition point: lower than 100° C. (<100° C.)
Olefin crystal-ethylene-butylene-olefin crystal block copolymer (CEBC), product name “DYNARON 6200P”, manufactured by JSR Corporation, crystalline, melting point: 90° C.
Product name “TAFMER MA8510”, manufactured by Mitsui Chemicals, Inc., crystalline, melting point: 70° C.
Organic phosphorus compound represented by the following structural formula (In the general formula (1), X1 and X2 are phenylmethyl groups (benzyl groups), melting point: higher than 240° C. (>240° C.) and phosphorus content: 15 mass %
Organic phosphorus compound represented by the following structural formula (In the general formula (1), X1 and X2 are methyl groups), melting point: higher than 240° C., phosphorus content: 24%
Organic phosphorus compound represented by the following structural formula, melting point: 96° C., phosphorus content: 10 mass %
Resorcinol bis-dixylenylphosphate represented by the following structural formula, melting point: 92° C., phosphorus content: 9.0 mass %
Organic phosphorus compound represented by the following structural formula (In the general formula (1), X1 and X2 are ethyl groups), melting point: higher than 240° C., phosphorus content: 22 mass %
Organic phosphorus compound represented by the following structural formula (In the general formula (1), X1 and X2 are propyl groups), melting point: higher than 240° C., phosphorus content: 20 mass %
Organic phosphorus compound represented by the following structural formula (In the general formula (1), X1 and X2 are phenylethyl groups), melting point: higher than 240° C., phosphorus content: 14 mass %
Organic phosphorus compound represented by the following structural formula (In the general formula (1), X1 and X2 are phenylpropyl groups), melting point: higher than 240° C., phosphorus content: 13 mass %
Organic phosphorus compound represented by the following structural formula (In the general formula (1), X1 and X2 are naphthylmethyl groups), melting point: higher than 240° C., phosphorus content: 12 mass %
Hindered amine compound represented by the following structural formula, product name “TINUVIN NOR371 FF”, manufactured by BASF, melting point: 104° C., decomposition temperature: 264° C. amine number per 1 g: 1.48×1021 to 1.67×1021, presence or absence of triazine ring: present
Hindered amine compound represented by the following structural formula, product name “Flamestab NOR117 FF”, manufactured by BASF, melting point: 121° C., decomposition temperature: 247° C., amine number per 1 g: 1.6×1021, presence or absence of triazine ring: present
Hindered amine compound represented by the following structural formula, product name “ADK STAB LA-81”, manufactured by ADEKA Corporation, melting point: liquid at 25° C., decomposition temperature: 239° C., amine number per 1 g: 1.77×1021, and presence or absence of a triazine ring: absence
Hindered amine compound represented by the following structural formula, product name “Hostavin NOW”, manufactured by Clariant, melting point: 95° C., decomposition temperature: 236° C., amine number per 1 g: 2.88×1020, presence or absence of a triazine ring: absence
[Characteristic Evaluation]
For the flame-retardant resin compositions of Examples to 121 and Comparative Examples 1 to 14 obtained as described above, an effect of suppressing the separation of the flame retardant and flame retardancy were evaluated as follows. For the flame-retardant resin compositions of Examples 1 to 121 and Comparative Examples 1 to 6, hydrolysis resistance was evaluated as follows. Further, for 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, an odor was evaluated as follows. For the flame-retardant resin compositions of Examples 46 to 49 and 107 to 110, processability was also evaluated, and for the flame-retardant resin compositions of Examples 55 to 58 and 118 to 121, coloring at the time of deterioration was also evaluated.
<Test Sheet>
A test sheet 1 having a thickness of 0.1 mm was produced in the following manner in order to evaluate the effect of suppressing separation of the flame retardant, flame retardancy, hydrolysis resistance and odor. That is, after the flame-retardant resin compositions of Examples 1 to 121 and Comparative Examples 1 to 14 were kneaded at 190° C. with a Banbury mixer, a test sheet 1 having a dimension of 350 mm×100 mm×0.1 mm (thickness) was produced by press forming. For the flame-retardant resin compositions of Examples 1 to 5, 18 to 57, 59 to 70 and 88 to 117, test sheets 2 and 3 similar to the test sheet 1 except that the thickness was 0.3 mm or 0.5 mm were produced in order to evaluate flame retardancy.
<Effect of Suppressing Separation of Flame Retardant>
For the test sheet 1, surface observation or touch confirmation was carried out, and surface observation or touch confirmation was carried out after the test sheet 1 was left in a constant temperature bath at 85° C. for 48 hours. And then, it was checked whether or not the foreign matter is confirmed on the surface of the test sheet 1. The foreign matter was used as an indicator of whether the flame retardant is separated. For the test sheet 1, determination of “0” or “X” was made. The results are shown in Tables 1 to 22. When determination of “0” was made for the test sheet 1, the test sheet 1 was judged to be acceptable, and when determination of “X” was made for the test sheet 1, the test sheet 1 was judged to be unacceptable.
(Determination Criteria)
O: the test sheet 1 does not fall under any of the following (i) and (ii).
X: the test sheet 1 falls under at least one of the following (i) and (ii).
(i) A foreign matter is confirmed on the surface of the test sheet 1 when surface observation or touch confirmation is performed on the test sheet 1.
(ii) A foreign matter is confirmed on the surface of the test sheet 1 when surface observation or touch confirmation is performed on the test sheet 1 after the test sheet 1 is left in a constant temperature bath at 85° C. for 48 hours.
<Flame-Retardancy>
For the test sheets 1 to 3, flame retardancy was evaluated by performing a combustion test for automobile interior materials based on FMVSS No. 302. Specifically, the test sheets 1 to 3 were held horizontally with a pair of U-shaped metal jigs, and the flame having a size of 38 mm was contacted to the rear surface of one end of the test sheets 1 to 3 for 15 seconds. Confirmation for the presence or absence of self-extinguishing and calculation for the combustion time (combustion speed) to the distance 254 mm between the A target line and the B target line displayed on the jig was performed. Each U-shaped metal jig was composed of two parallel extension parts separated from each other and a connection part connecting the extension parts, and both edge parts of the test sheet were fixed along the longitudinal direction of the test sheets 1 to 3 by the two extension parts. In one extension part of the two extension parts, the A target line and the B target line are displayed such that they are separated by 254 mm and cross the extension part (along the direction orthogonal to the extending direction).
On the basis of the following determination criteria, determination of “0” or “X” was made for the test sheets 1 to 3. The results are shown in Tables 1 to 22. The test sheets 1 to 3 determined to be “0” were judged to be acceptable in terms of flame-retardancy, and the test sheets 1 to 3 determined to be “X” were judged to be unacceptable in terms of flame-retardancy.
O: Self-extinguishing is observed, or no self-extinguishing is observed and a combustion speed is 102 mm/minute or less.
X: No self-extinguishing is observed and a combustion speed exceeds 102 mm/minute.
For each of Examples 1 to 82 and Comparative Examples 1 to 10, five test sheets 1 were prepared, and the flame retardancy was evaluated by performing a VTM test of the UL 94 standard for these five test sheets 1. Specifically, the test sheet 1 was wound around a mandrel having a diameter of 13 mm and a sample composed of a cylindrical body having a length of 350 mm was prepared. One end of the sample was fixed with a clamp, and the sample was arranged so that its central axis is parallel to the vertical direction. At this time, the sample was arranged so that the target line is marked at a position of 125 mm from the lower end of the sample. On the other hand, an absorbent cotton was spread and arranged below the sample. A tip of a burner was arranged at a position of 10 mm from the lower end of the sample for three seconds, and was brought into contact with the lower end of the sample. After the flame contact, the burner was separated from the sample and the afterflame time t1 was measured. After the remaining flame stopped, the burner was immediately moved under the sample, the flame was again brought into contact with the sample. The burner was separated from the sample after the flame contact. The afterflame time t2 and the afterglow time t3 were measured. Further, it was observed whether the sample was burnt up to the target line or whether the sample made the absorbent cotton ignite by dropping a smoking substance or a dropping product.
Then, the test sheet 1 was evaluated on the basis of the following evaluation rank. The results are shown in Tables 1 to 14. The flame retardancy becomes higher in the order of NOT, VTM-2, VTM-1 and VTM-0.
Test sheet 1 does not fall under any of VTM-0, VTM-1 and VTM-2
<Hydrolysis Resistance>
For each of Examples 1 to 121 and Comparative Examples to 6, surface observation or touch confirmation was performed on the test sheet 1 after the test sheet 1 was left in a constant temperature bath at 85° C. and 85% RH for 48 hours, and it was checked whether a foreign matter is confirmed on the surface of the test sheet 1. The foreign matter was used as an index of hydrolysis resistance. On the basis of the following determination criteria, determination of “0” or “X” was made for the test sheet 1. The results are shown in Tables 1 to 12 and Tables 14 to 21.
O: No foreign matter is confirmed on the surface of the test sheet 1.
X: A foreign matter is confirmed on the surface of the test sheet 1.
<Odor>
odor was determined for the test sheet 1 of Examples 26 to 29, 31 to 32, 43, 46 to 49, 83 to 121 and Comparative Examples 11 to 14 on the basis of the following determination criteria. The results are shown in Tables 14 to 22.
1: Odor is not almost felt.
2: Slight odor is felt.
3: Strong odor is felt.
<Processability>
A T-die was connected to a single-screw extruder (product name “LABO PLASTOMILLS”, manufactured by Toyo Seiki Seisaku-sho, Ltd.), and each of flame-retardant resin compositions of Examples 46 to 49 and 107 to 110 was charged into a single-screw extruder to prepare a sheet for evaluation of processability having a thickness of 0.1 mm. At this time, the discharge amount and the take-up speed of the sheet were made constant. The sheet for evaluation of processability was prepared for each of the processing temperatures of 230° C., 240° C. and 250° C. in the single-screw extruder. The presence or absence of the formation of holes in the sheet for evaluation of processability was checked during 30 minutes extrusion, and the presence or absence of the formation of holes was used as an index of processability. Here, the formation of holes suggests a decrease in processability due to the variation of the discharge amount or the generation of air bubbles. On the basis of the following determination criteria, determination of “0” or “X” for the sheet for evaluation of processability was performed. The results are shown in Tables 6 and 19.
O: No hole formation is confirmed in the sheet for evaluation of processability.
X: Hole formation is confirmed in the sheet for evaluation of processability.
<Coloring Property at the Time of Deterioration>
In order to evaluate the coloring property, the test sheets 4 were further prepared in the same manner as the test sheet 1 except that the flame-retardant resin compositions of Examples 55 to 58 and 118 to 121 were used and the thickness was set to 1 mm. Surface observation was performed on the test sheet 4 after the test sheet 4 is left in a constant temperature bath at 85° C. for 5 days, and it was checked whether the sheet is discolored. On the basis of the following determination criteria, determination of “0” or “X” was performed for the test sheets 4. The results are shown in Tables 8 and 21.
O: No discoloration is observed in the sheet.
X: Discoloration is observed in the sheet.
From the results shown in Tables 1 to 22, it was found that the evaluation results of flame retardancy for any of the test sheets (test sheets 1) having a thickness of 0.1 mm were “0” in Examples 1 to 121, and Examples 1 to 121 were acceptable in terms of flame retardancy. In contrast, it was found that the evaluation results of flame retardancy for any of the test sheets (test sheets 1) having a thickness of 0.1 mm were “X” in Comparative Examples 1 to 14, and Comparative Examples 1 to 14 were not acceptable in terms of flame retardancy.
From the results shown in Tables 1 to 22, it was found that any evaluation results of the separation suppressing effect of the flame retardant were “O” in
Examples 1 to 121, and Examples 1 to 121 were acceptable in terms of the separation suppressing effect of the flame retardant. In contrast, it was found that any evaluation results of the separation suppressing effect of the flame retardant were “X” in Comparative Examples 1 to 14, and Comparative Examples 1 to 14 were not acceptable in terms of the separation suppressing effect of the flame retardant.
From the above, it was confirmed that the flame-retardant resin composition in accordance with one or more embodiments of the present invention has excellent flame retardancy and can suppress the separation of the flame retardant.
From the results shown in Tables 14 to 22, the determination results of odor were “1” or “2” in any of Examples 43 and 83 to 121. In contrast, in any of Examples 26 to 29, 31 to 32, 46 to 49, and Comparative Examples 11 to 14, the determination results of odor were “3”. Therefore, it was 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 parts by mass can suppress 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 parts by mass or more.
From the results shown in Table 11, for example, in any of Examples 64 and 71 to 75, the evaluation result of the flame retardancy of the test sheets (test sheets 1) having a thickness of 0.1 mm (evaluation result based on the VTM test of the UL 94 standard) were “VTM-0”. In contrast, in Example 76 where the mass ratio R is less than 5.6, the evaluation result of the flame retardancy of the test sheet (test sheet 1) having a thickness of 0.1 mm was “VTM-2”. From the results shown in Table 12, the evaluation results of the test sheets (test sheets 1) having a thickness of 0.1 mm (evaluation result based on the VTM test of the UL 94 standard) were “VTM-0” in any of Examples 56 and 77 to 81 in which the mass ratio R is 5.6 or more. In contrast, in Example 82 where the mass ratio R is less than 5.6, the evaluation result of the flame retardancy of the test sheet (test sheet 1) having a thickness of 0.1 mm was “VTM-2”. From this, it was found that a test sheet having a mass ratio R of 5.6 or more can further improve flame retardancy compared with a test sheet having a mass ratio R of less than 5.6.
Although the disclosure has been described with respect to only a limited number of embodiments, those skilled in the art, having benefit of this disclosure, will appreciate that various other embodiments may be devised without departing from the scope of the present invention. Accordingly, the scope of the invention should be limited only by the attached claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2018-236828 | Dec 2018 | JP | national |
| 2018-236829 | Dec 2018 | JP | national |
| 2019-141849 | Jul 2019 | JP | national |
| 2019-141850 | Jul 2019 | JP | national |
| 2019-141851 | Jul 2019 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2019/049073 | 12/14/2019 | WO | 00 |
