Patent Application
20230095019
The present invention is related to a flame retardant composition for a thermoplastic resin and a flame retardant thermoplastic resin composition using it. The flame retardant composition and flame retardant thermoplastic resin composition of the present invention can be used for molded products such as an automobile upholstery, a packaging material, a material for electrical devices, a sheet or film for building materials, a material covering electric wire and the like.
A thermoplastic resin has been used in a wide variety of fields, such as automotive parts, housings for electric equipments, electric insulating materials, packaging films, building materials, floor materials, and the like. This is from the viewpoints that it is easy to mold a thermoplastic resin, the number of steps for molding a thermoplastic resin is small, and molded products of a thermoplastic resin can be recycled. In addition, although most thermoplastic resins are flammable, there are actually many cases where it is desired to use a thermoplastic resin to produce a molded product for a use in which a flame retardance is required. Therefore, in order to provide a flame retardance to a thermoplastic resin, flame retardants such as a halogen-based flame retardant, a metal hydroxide such as aluminum hydroxide or magnesium hydroxide, red phosphorus which has been subjected to a coating treatment or the like, a polyphosphate salt such as ammonium polyphosphate, and an aromatic organic phosphate ester have been used.
However, a halogen-based flame retardant has a problem in that when a molded product containing it is discarded and incinerated, smoke and harmful gasses are generated. In addition, when a metal hydroxide is used as a flame retardant, it is necessary to add a very large amount. Therefore, it is likely to cause deterioration in the physical properties of the thermoplastic resin.
In view of the above, as a non-halogen-based flame retardant, Patent document 1 discloses that a phosphate ester amide and a hindered amine compound are used in combination. However, such a composition has a disadvantage in that the performance of the thermoplastic resin is deteriorated. For example, there is a disadvantage in that when the thermoplastic resin composition is molded, bleed-out is likely to be generated. In addition, Patent document 2 discloses a hindered amine compound having an unsaturated bond, Patent document 3 discloses a hindered amine compound having a carbonate skeleton. However, the flame retardants which are disclosed in these documents have a disadvantage in that the flame retardance of the thermoplastic resin is insufficient or the performance of the thermoplastic resin is deteriorated.
In view of the above, a non-halogen-based flame retardant for a thermoplastic resin which has a high flame retardant effect and causes a low level of bleed-out regardless of the amount of an added flame retardant has been required.
In view of the above-described current status, the present inventors intensively studied. As a result, it was reached that a phosphoramidate compound having a certain structure and a hindered amine compound are used in combination, and optionally a triazine-based compound is further used in combination such that it is possible to provide a non-halogen-based flame retardant composition and a flame retardant thermoplastic resin composition using it which has a high flame retardant effect and causes a low level of bleed-out regardless of the amount of an added flame retardant.
Specifically, in accordance with the present invention, for example, the following compositions are provided.
A flame retardant composition for a thermoplastic resin, wherein the composition comprises component (A) and component (B), wherein
the component (A) is a phosphoramidate compound represented by the following general formula (I):
wherein R1 and R2 are each independently a hydrogen atom or an alkyl group in which the number of carbon atoms is 1 to 3, R11 and R12 are each independently an alkylene group in which the number of carbon atoms is 1 to 3, R13 is an alkylene group in which the number of carbon atoms is 1 to 6, B1 is a hydrogen atom or an alkyl group in which the number of carbon atoms is 1 to 6, and A is a hydrogen atom or an organic group represented by general formula (II):
wherein R3 and R4 are each independently a hydrogen atom or an alkyl group in which the number of carbon atoms is 1 to 3, R14 and R15 are each independently an alkylene group in which the number of carbon atoms is 1 to 3, and B2 is a hydrogen atom or an alkyl group in which the number of carbon atoms is 1 to 6, and
wherein when A is a hydrogen atom and B1 is an alkyl group in which the number of carbon atoms is 1 to 6, then B1 and R13-A may be bound to form a nitrogen-containing heterocycle with the nitrogen atom to which they are bound, and
when A is an organic group represented by the general formula (II), B2 is an alkyl group in which the number of carbon atoms is 1 to 6, and B1 is an alkyl group in which the number of carbon atoms is 1 to 6, then B1 and B2 may be bound to form a nitrogen-containing heterocycle with the nitrogen atom to which they are bound and R13, and
wherein the component (B) is a hindered amine compound.
The flame retardant composition according to item 1, wherein in the general formula (I), A is an organic group represented by the general formula (II).
The flame retardant composition according to any one of items 1 to 2, wherein in the general formula (I), R1 and R2 are methyl groups, and R11 and R12 are methylene groups.
The flame retardant composition according to any one of items 1 to 3, wherein in the general formula (I), A is an organic group represented by the general formula (II), R3 and R4 are methyl groups, and R14 and R15 are methylene groups.
The flame retardant composition according to item 4, wherein in the general formula (I), R13 is an alkylene group in which the number of carbon atoms is 1 to 4.
The flame retardant composition according to item 5, wherein in the general formula (I), R13 is an alkylene group in which the number of carbon atoms is 1 to 2.
The flame retardant composition according to any one of items 4 to 6, wherein in the general formula (I), B1 and B2 are hydrogen atoms.
The flame retardant composition according to any one of items 1 to 7, wherein the component (B) is a compound which has a piperidine structure.
The flame retardant composition according to any one of items 1 to 7, wherein the component (B) is an NOR-type hindered amine compound.
The flame retardant composition according to item 9, wherein the component (B) is an NOR-type hindered amine compound, and wherein a chain alkyl is bound to an oxygen atom in the NOR-type hindered amine structure.
The flame retardant composition according to any one of items 1 to 7, wherein the component (B) comprises an NOR-type hindered amine structure which has the piperidine structure represented by the following general formula (B3):
wherein RB5 is a straight chain or branched chain alkyl group in which the number of carbon atoms is 1 to 30, a straight chain or branched chain alkenyl group in which the number of carbon atoms is 2 to 30, a cycloalkyl group in which the number of carbon atoms is 5 to 18, a cycloalkenyl group in which the number of carbon atoms is 5 to 18, or a straight chain or branched chain alkyl group substituted with a phenyl group in which the number of carbon atoms in the alkyl group is 1 to 4, wherein, RB5 may be substituted with at least one hydroxyl group;
RB6, RB7, RB8 and RB9 are each independently a straight chain or branched chain alkyl group in which the number of carbon atoms is 1 to 4; and
RB10 is any organic group.
The flame retardant composition according to item 11, wherein the component (B) is selected from the group consisting of the following general formulas (B4-a), (B4-b) and (B4-c):
wherein na1, na2 and na3 are each independently an integer of 1 to 4, Ra1 to Ra4 are each independently a hydrogen atom or an organic group of the following formula (B4-a-i), with the proviso that at least one of Ra1 to Ra4 is an organic group of the following formula (B4-a-i):
wherein, Ra5 and Ra6 each independently have the same meaning as the meaning of RB5,
Ra7, Ra8, Ra9 and Ra10 each independently have the same meaning as the meaning of RB6, RB7, RB8 and RB9,
Ra11, Ra12, Ra13 and Ra14 each independently have the same meaning as the meaning of RB6, RB7, RB8 and RB9, and
Ra15 and Ra16 are each independently a hydrogen atom, a straight chain or branched chain alkyl group in which the number of carbon atoms is 1 to 12 or a straight chain or branched chain alkenyl group in which the number of carbon atoms is 2 to 12;
wherein nb1 is an integer of 2 to 8,
nb2 is an integer of 1 to 10,
Rb1 and Rb2 each independently have the same meaning as the meaning of RB5,
Rb3, Rb4, Rb5 and Rb6 each independently have the same meaning as the meaning of RB6, RB7, RB8 and RB9,
Rb7, Rb8, Rb9 and Rb10 each independently have the same meaning as the meaning of RB6, RB7, RB8 and RB9,
Rb11 is a nitrogen-containing substituent T1 of the following formula (B4-b-i), and
Rb12 and Rb13 are each independently any organic group,
wherein Rb16 and Rb15 are each independently a hydrogen atom, a straight chain or branched chain alkyl group in which the number of carbon atoms is 1 to 8 or a substituent T2 of the following formula (B4-b-ii),
wherein Rb16 has the same meaning as the meaning of RB5,
Rb17, Rb18, Rb19 and Rb20 each independently have the same meaning as the meaning of RB6, RB7, RB8 and RB9,
wherein, Rb14 and Rb15 may be bound to form a morpholino group, a piperidino group or a 1-piperazinyl group with the nitrogen atom to which they are bound; and
wherein Rc1 represents an alkyl group or a hydroxyalkyl group in which the number of carbon atoms is 1 to 30, or an alkenyl group in which the number of carbon atoms is 2 to 30, and nc1 represents an integer of 1 to 6,
wherein when nc1=1, then Rc2 represents an alkyl group in which the number of carbon atoms is 1 to 22, an alkenyl group in which the number of carbon atoms is 2 to 22 or a group of the following general formula (B4-c-i):
wherein Rc3 represents an alkyl group or a hydroxyalkyl group in which the number of carbon atoms is 1 to 30, or an alkenyl group in which the number of carbon atoms is 2 to 30, and
wherein when nc1=2 to 6, then Rc2 represents an nc1-valent organic group in which the number of carbon atoms is 2 to 20.
The flame retardant composition according to item 12, wherein the component (B) is selected from the group consisting of the following formulas (i), (ii) and (iii):
wherein in the formula (i), Rj are each independently a hydrogen atom or the following organic group, with the proviso that at least one Rj is the following organic group:
wherein, in the formula (ii), nb is an integer of 1 to 10.
The flame retardant composition according to item 11, wherein, in the formula (B3), RB5 is substituted with at least one hydroxyl group.
The flame retardant composition according to any one of items 1 to 14, further comprising a triazine-based compound (component (C)) having a 1,3,5-triazine structure or a 1,3,5-triazine fused ring structure.
The flame retardant composition according to item 15, wherein the component (C) is a cyanurate salt of an amine compound having a 1,3,5-triazine structure or a 1,3,5-triazine fused ring structure.
A flame retardant thermoplastic resin composition, which comprises the flame retardant composition according to any one of items 1 to 16 and a thermoplastic resin (component (D)).
The flame retardant thermoplastic resin composition according to item 17, wherein the thermoplastic resin (component (D)) is a polyolefin resin.
The flame retardant thermoplastic resin composition according to item 18, wherein the polyolefin resin is polypropylene, polyethylene, or a copolymer comprising propylene or ethylene.
The flame retardant thermoplastic resin composition according to any one of items 17 to 19, which comprises the flame retardant composition according to item 15 and a thermoplastic resin (component (D)).
In accordance with the present invention, a flame retardant thermoplastic resin composition which has a high flame retardant effect and causes a low level of bleed-out and a flame retardant composition which can provide the above-described functions are provided.
The present invention provides a flame retardant composition and a flame retardant thermoplastic resin composition.
The flame retardant composition of the present invention comprises a phosphoramidate compound (component (A)) and a hindered amine compound (component (B)). Optionally, the flame retardant composition of the present invention further comprises a compound having a 1,3,5-triazine structure or 1,3,5-triazine fused ring structure (component (C)).
The flame retardant thermoplastic resin composition of the present invention comprises a phosphoramidate compound (component (A)), a hindered amine compound (component (B)) and thermoplastic resin (component (D)). Optionally, the flame retardant composition of the present invention further comprises a compound having a 1,3,5-triazine structure or 1,3,5-triazine fused ring structure (component (C)).
As component (A), the composition of the present invention uses a phosphoramidate compound. The phosphoramidate compound of component (A) consists of the phosphoramidate compound represented by the general formula (I):
wherein R1 and R2 are each independently a hydrogen atom or an alkyl group in which the number of carbon atoms is 1 to 3, R11 and R12 are each independently an alkylene group in which the number of carbon atoms is 1 to 3, R13 is an alkylene group in which the number of carbon atoms is 1 to 6, B1 is a hydrogen atom or an alkyl group in which the number of carbon atoms is 1 to 6, and A is a hydrogen atom or an organic group represented by general formula (II):
wherein R3 and R4 are each independently a hydrogen atom or an alkyl group in which the number of carbon atoms is 1 to 3, R14 and R15 are each independently an alkylene group in which the number of carbon atoms is 1 to 3, and B2 is a hydrogen atom or an alkyl group in which the number of carbon atoms is 1 to 6, and
wherein when A is a hydrogen atom and B1 is an alkyl group in which the number of carbon atoms is 1 to 6, then B1 and R13-A may be bound to form a nitrogen-containing heterocycle with the nitrogen atom to which they are bound, and
when A is an organic group represented by the general formula (II), B2 is an alkyl group in which the number of carbon atoms is 1 to 6, and B1 is an alkyl group in which the number of carbon atoms is 1 to 6, then B1 and B2 may be bound to form a nitrogen-containing heterocycle with the nitrogen atom to which they are bound and R13.
It should be noted that an “alkyl group” in the present specification refers to a monovalent group resulting from loss of one hydrogen atom from a chain or cyclic aliphatic hydrocarbon (alkane). In the cases of chain alkyl, the alkyl group is generally represented by CkH2k+1— (wherein k is a positive integer). A chain alkyl group may be a straight chain or a branched chain. A cyclic alkyl group may consist of a cyclic structure, or may have a structure in which a chain alkyl group is further linked to the cyclic structure. An “alkylene group” in the present specification refers to a divalent group resulting from loss of one more hydrogen atom from an alkyl group. For example, an “ethylene group” refers to a divalent group resulting from loss of one more hydrogen atom from an ethyl group.
Examples of the alkyl group in which the number of carbon atoms is 1 to 3 in the general formulas (I) and (II), include a methyl group, an ethyl group, an n-propyl group and an isopropyl group. Among these groups, a methyl group and an ethyl group are preferable. From the viewpoint of flame retardance, a methyl group is particularly preferable. Examples of the alkylene group in which the number of carbon atoms is 1 to 3 include a methylene group, an ethylene group, an n-propylene group and a 1,2-propylene group. Among these, a methylene group and an ethylene group are preferable, and from the viewpoint of flame retardance, a methylene group is particularly preferable.
Examples of the alkyl group in which the number of carbon atoms is 1 to 6 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group and the like. Among these, a methyl group and an ethyl group are preferable. From the viewpoint of the flame retardance, a methyl group is particularly preferable. Examples of the alkylene group in which the number of carbon atoms is 1 to 6 include a methylene group, an ethylene group, an n-propylene group and a 1,2-propylene group, an n-butylene group, a 1,1-dimethylethylene group, an n-pentylene group, an n-hexylene group and the like. Among these, a methylene group, an ethylene group, an n-propylene group, a 1,2-propylene group, an n-butylene group and a 1,1-dimethylethylene group are preferable. From the viewpoint of the flame retardance, a methylene group and an ethylene group are preferable, and an ethylene group is particularly preferable.
When A is a hydrogen atom, an aliphatic nitrogen-containing heterocycle formed by binding of B1 and R13 is a 3- to 13-membered, preferably 4- to 8-membered, more preferably 6-membered heterocycle containing one nitrogen atom.
A nitrogen-containing heterocycle that may be formed when A is an organic group represented by the general formula (II) is a 5-membered to 20-membered, preferably 5-membered to 8-membered, more preferably 6-membered or 7-membered, further preferably 6-membered heterocycle containing two nitrogen atoms.
Examples of phosphoramidate compounds represented by the general formula (I) include:
a compound represented by general formula (III) where B1 is an alkyl group in which the number of carbon atoms is 1 to 6, A is a hydrogen atom, B1 and R13-A are bound to form a nitrogen-containing heterocycle with the nitrogen atom to which they are bound,
wherein R1, R2, R11, and R12 are the same as the definitions in the general formula (I), and R16 is an alkylene group in which the number of carbon atoms is 2 to 12;
a compound represented by general formula (IV) where A is an organic group represented by the general formula (II), B1 and B2 are each independently a hydrogen atom or an alkyl group in which the number of carbon atoms is 1 to 6:
wherein R1, R2, R11, R12, and R13 are the same as the definitions in the general formula (I), R3, R4, R14, and R15 are the same as the definitions in the general formula (II), and B1 and B2 are each independently a hydrogen atom or an alkyl group in which the number of carbon atoms is 1 to 6; and a compound represented by general formula (V) where B1 is an alkyl group in which the number of carbon atoms is 1 to 6, A is an organic group represented by the general formula (II), B2 is an alkyl group in which the number of carbon atoms is 1 to 6, B1 and B2 are bound to form a nitrogen-containing heterocycle with the nitrogen atom to which they are bound and R13:
wherein the definitions of R1, R2, R11, R12, and R13 are the same as the definitions in relation to the general formula (I), the definitions of R3, R4, R14, and R15 are the same as the definitions in relation to the general formula (II), and R17 is an alkylene group in which the number of carbon atoms is 2 to 12; and the like.
Examples of compounds represented by the general formula (III) include compounds of the following formulas (1) to (3) and the like.
Examples of compounds represented by the general formula (IV) include compounds of the following formulas (4) to (9) and the like.
Examples of compounds represented by the general formula (V) include compounds of the following formulas (10) to (14) and the like.
Among the phosphoramidate compounds represented by the general formula (I), a compound in which R1 and R2 are methyl groups and R11 and R12 are methylene groups is preferable from the viewpoint of flame retardance.
A in the general formula (I) is preferably an organic group represented by the general formula (II). From the viewpoint of flame retardance, it is preferable that R3 and R4 are methyl groups and R14 and R15 are methylene groups.
Regarding R13 of the general formula (I), the number of carbon atoms is 1 to 6. From the viewpoint of flame retardance, the number of carbon atoms is preferably 1 to 5, more preferably 1 to 4, and further preferably 1 to 2.
When A of the general formula (I) is an organic group represented by the general formula (II), if B1 of the general formula (I) and B2 of the general formula (II) are not bound, B1 and B2 are preferably both hydrogen atom from the viewpoint of flame retardance. If B1 and B2 are bound, it is preferable that B1 and B2 are taken together to form an ethylene group or a propylene group. It is more preferable that B1 and B2 are taken together to form an ethylene group. In addition, it is preferable that they are taken together to form a 5-membered to 8-membered nitrogen-containing heterocycle with the nitrogen atom to which they are bound and R13, more preferably to form a 6-membered to 7-membered nitrogen-containing heterocycle, and further preferably to form a 6-membered nitrogen-containing heterocycle.
When A in the general formula (I) is an organic group represented by the general formula (II), it is preferable that R1 and R2 as well as R11 and R12 of the general formula (I) are the same as R3 and R4 as well as R14 and R15 of the general formula (II), respectively. That is, it is preferable that the two phosphorus-containing ring structures are the same. If the two phosphorus-containing ring structures are the same, it has the advantage in that it is easy to synthesize such a compound.
Among the compounds of the above-described formulas (1) to (14), examples of preferable compounds include compounds of formulas (1), (4) to (7), (10) and (12). Compounds of the formulas (1), (4) to (6) and (10) are more preferable and compounds of the formulas (4) to (6) and (10) are further preferable.
A method of synthesizing the phosphoramidate compound represented by the general formula (I) is not particularly limited. A known synthesis method of a phosphoramidate compound represented by the general formula (I) may be used without a change. For example, it may be synthesized according to the method described in U.S. Patent Application Laid-open Publication No. 2016/0244582. In addition, the known synthetic method may also be appropriately modified. Therefore, a phosphoramidate compound represented by the general formula (I) can be synthesized by applying various reactions known for the synthesis of a phosphoramidate compound.
When the flame retardant composition or the flame retardant thermoplastic resin composition of the present invention is prepared, it is preferable to make particles of the phosphoramidate compound of component (A) having a small particle diameter and use the small particles in the preparation. If the particle diameter is small, then it is made easy to uniformly disperse the phosphoramidate compound into a thermoplastic resin. Specifically, an average particle diameter of particles of the phosphoramidate compound is preferably 50 μm or lower, and further preferably the average particle diameter is 20 μm or lower. The lower limit of the average particle diameter is not particularly limited. However, for example, those wherein the average particle diameter is 0.1 μm or more, or 1 μm or more can be used. When particles having a very small average particle diameter are produced, a cost for producing the particles may be expensive. A method for measuring a particle diameter is not particularly limited. For example, a laser diffraction particle diameter distribution measurement device (SALD(registered trade mark)-2300 made by Shimadzu Corporation) and the like can be used.
In the composition of the present invention, as component (B), a hindered amine compound is used.
In the present specification, a hindered amine compound refers to an organic compound which has a nitrogen atom bound to a carbon atom wherein there is a substituent near the nitrogen atom which provides steric hindrance.
A hindered amine compound has a property wherein it is possible to capture a radical. Therefore, a hindered amine compound is generally used as an antioxidant or light stabilizer. Such a hindered amine compound which is used as an antioxidant or a light stabilizer can be used in the present invention.
The hindered amine compound may be a primary amine, a secondary amine, a tertiary amine, or a quaternary amine. The hindered amine compound is preferably a secondary amine or a tertiary amine. That is, it is preferable that two or three of the three valences of the nitrogen atom in the hindered amine compound are used for bonds to carbon atoms.
Regarding a specific chemical structure, it is preferable that the hindered amine compound has a structure in which one nitrogen atom is sandwiched between two carbon atoms. In addition, it is preferable that in the hindered amine compound, the nitrogen atom is bonded to an oxygen atom. In one embodiment, the nitrogen atom in the hindered amine compound is bonded to two carbon atoms and one oxygen atom. It is preferable that the oxygen atom is further bound to a carbon atom.
In one preferable embodiment, the nitrogen atom in the hindered amine compound has three single bonds between the nitrogen atom and three adjacent atoms. In this case, the hindered amine compound is represented by the following formula (B1).
In this formula, Ra, Rb and Rc are each independently any organic groups. If necessary, Ra and Rb may be bound to form a ring structure which consists of Ra, Rb and the nitrogen atom.
Specific examples of the hindered amine compound of formula (B1) include, for example, Tinuvin144, PA144, 249, 292, 494AR, 622SF, 765, 770DF, 783FDL, XT833, 5050, 5060, 5100, 5151 (made by BASF), Chimassorb119, 944FDL, 944LD, 2020FDL (made by BASF), Adekastab LA-52, LA-57, LA-63, LA-68, LA-77Y, LA-82, LA-87, LA-94 (made by ADEKA) and the like.
In one embodiment, two of the three single bonds are bonds to the carbon atoms of the hydrocarbon and one is a bond to an oxygen atom. It is preferable that this oxygen atom is further bound to a carbon atom. In this regard, the structure in which the nitrogen atom is bound to an oxygen atom and the oxygen atom is bound to a carbon atom is referred to as an NOR-type structure. In this case, the hindered amine compound is represented by the following formula (B2).
In the formula, Rd is any organic group. It should be noted that again, if necessary, Ra and Rb may be bound to form a ring structure which consists of Ra, Rb and the nitrogen atom.
In the above formulas (B1) or (B2), when Ra and Rb are bound to form a ring structure, it is preferable that the ring structure has such a size that the ring structure is stable. For example, a 5- to 7-membered ring is preferable, and a 6-membered ring is most preferable. When Ra and Rb are bound to form a ring structure, then the atoms which constitute the ring formed by binding Ra and Rb are preferably a nitrogen atom, carbon atom or oxygen atom, and are more preferably a nitrogen atom or carbon atom. In one preferable embodiment, one nitrogen atom and four to six carbon atoms form a 5- to 7-member ring.
In one preferable embodiment, the hindered amine compound is an NOR-type hindered amine compound, which has a structure in which a nitrogen atom is bound to an oxygen atom, and the oxygen atom is further bound to an organic group (for example, an aliphatic or aromatic hydrocarbon group). Examples of an aliphatic hydrocarbon group include, for example, alkyl and alkenyl. The alkyl may be chain alkyl or cycloalkyl. The chain alkyl may be straight chain alkyl or branched chain alkyl. A number of the carbon atoms of the chain alkyl is preferably 1 to 30, more preferably 2 to 15, and further preferably 3 to 14. The chain alkyl may be substituted with at least one hydroxyl group. A number of carbon atoms of the cycloalkyl is preferably 5 to 18, more preferably 5 to 7, and further preferably 6. The cycloalkyl may be substituted with at least one hydroxyl group. The alkenyl may be chain alkenyl or cycloalkenyl. The chain alkenyl may be straight chain alkenyl or branched chain alkenyl. A number of carbon atoms of the chain alkenyl is preferably 2 to 30. The chain alkenyl may be substituted with at least one hydroxyl group. A number of carbon atoms of the cycloalkenyl is preferably 5 to 18, more preferably 5 to 7, and further preferably 6. The cycloalkenyl may be substituted with at least one hydroxyl group. Examples of an aromatic hydrocarbon group include, for example, aryl or arylalkyl. The aryl is preferably phenyl. The aryl may be substituted with at least one hydroxyl group. The arylalkyl is preferably phenylalkyl, and a number of carbon atoms thereof is preferably 7 to 15. The arylalkyl may be substituted with at least one hydroxyl group.
In one preferable embodiment, the hindered amine compound has a piperidine structure. In the present specification, a piperidine structure refers to a saturated 6-membered ring structure which consists of five carbon atoms and one nitrogen atom. The nitrogen atom in the piperidine structure is preferably bound to an oxygen atom. Further the oxygen atom is preferably bound to an aliphatic or aromatic hydrocarbon group. The hindered amine compound may have one piperidine structure, two piperidine structures or three or more piperidine structures in one molecule. A hindered amine compound which has a plurality of piperidine structures is referred to as an oligomeric or polymeric hindered amine compound.
In one preferable embodiment, the hindered amine compound has the structure of the following formula (B3):
RB5 is a straight chain or branched chain alkyl group in which the number of carbon atoms is 1 to 30, a straight chain or branched chain alkenyl group in which the number of carbon atoms is 2 to 30, a cycloalkyl group in which the number of carbon atoms is 5 to 18, a cycloalkenyl group in which the number of carbon atoms is 5 to 18, or a straight chain or branched chain alkyl group substituted with a phenyl group in which the number of carbon atoms in the alkyl group is 1 to 4. In this regard, RB5 may be substituted with at least one hydroxyl group.
RB6, RB7, RB8, and RB9 are each independently a straight chain or branched chain alkyl group in which the number of carbon atoms is 1 to 4.
RB10 is any organic group, and in one embodiment, it is a monovalent organic group. In one embodiment, it is a divalent or higher-valent organic group.
In one embodiment, a hindered amine compound in which RB5 in the above-described formula (B3) is substituted with at least one hydroxyl group can be used in the present invention. This compound is described in the publication of Japanese Laid-open Publication No. 2000-302758.
Specific examples of the hindered amine compound of formula (B3) include, for example, Tinuvin 123, 152 (made by BASF), XT55FB, XT100, XT200, XT847, XT850, XT855 (made by BASF), and the like.
In one embodiment, the hindered amine compound has a plurality of piperidine structures. For example, a compound which has 2 to 32 piperidine structures in one molecule can be used in the present invention.
The compound having a plurality of piperidine structures has a relatively large molecular weight, and has an advantage in that the hindered amine compound is not easily separated from a polyolefin resin. However, when the molecular weight is too large, then there may be a case where it is difficult to homogeneously mix it with a resin.
In one embodiment, the hindered amine compound of the following formula (B4-a) can be used in the present invention.
na1, na2, and na3 in the formula (B4-a) are each independently any integer, and in one preferable embodiment, they are each independently an integer of 1 to 4. Ra1 to Ra4 are each independently a hydrogen atom or an organic group of the following formula (B4-a-i), with the proviso that at least one of Ra1 to Ra4 is an organic group of the following formula (B4-a-i). It is preferable that Ra1, Ra2, and Ra3 are an organic group of the following formula (B4-a-i), or Ra1, Ra2, and Ra4 are an organic group of the following formula (B4-a-i). In one embodiment, all of Ra1 to Ra4 are organic groups of the following formula (B4-a-i).
Ra5 and Ra6 in the formula (B4-a-i) are each independently any organic group, and in one preferable embodiment, each independently has the same meaning as the above-described meaning of RBS.
Ra7, Ra8, Ra9 and Ra10 are each independently any organic group, and in one preferable embodiment, each independently has the same meaning as the above-described meaning of RB6, RB7, RB8, and RB9.
Ra11, Ra12, Ra13 and Ra14 are each independently any organic group, and in one preferable embodiment, each independently has the same meaning as the above-described meaning of RB6, RB7, RB8, and RB9.
Ra15 and Ra16 are a hydrogen atom, a straight chain or branched chain alkyl group in which the number of carbon atoms is 1 to 12 or a straight chain or branched chain alkenyl group in which the number of carbon atoms is 2 to 12.
Specific examples of compounds of the above-described formula (B4-a) include, for example, N,N′,N″-tris{2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) n-butylamino]-sym-triazine-6-yl}-3,3′-ethylenediiminodipropylamine, N,N′,N″-tris{2,4-bis[(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)n-butylamino]-sym-triazin-6-yl}-3,3′-ethylenediiminodipropylamine, N,N′,N″-tris{2,4-bis[(1-methoxy-2,2,6,6-tetramethylpiperidin-4-yl)n-butylamino]-sym-triazin-6-yl}-3,3′-ethylenediiminodipropylamine.
Specific examples of the hindered amine compound of formula (B4-a) include, for example, Flamestab NOR116 (made by BASF), and the like.
In one embodiment, regarding the hindered amine compound, a compound represented by the following formula (B4-b) can be used in the present invention.
In the formula (B4-b), nb1 is any integer, and in one preferable embodiment, it is an integer of 2 to 8.
nb2 is any integer, and in one preferable embodiment, it is an integer of 1 to 10.
Rb1 and Rb2 are each independently any organic group, and in one preferable embodiment, each independently has the same meaning as the above-described meaning of RB5.
Rb3, Rb4, Rb5 and Rb6 are each independently any organic group, and in one preferable embodiment, each independently has the same meaning as the above-described meaning of RB6, RB7, RB8, and RB9.
Rb7, Rb8, Rb9 and Rb10 are each independently any organic group, and in one preferable embodiment, each independently has the same meaning as the above-described meaning of RB6, RB7, RB8, and RB9.
Rb11 is any organic group, and in one preferable embodiment, it is a nitrogen-containing substituent T1 of the following formula (B4-b-i):
In the formula (B4-b-i), Rb14 and Rb15 are each independently any organic group, and in one preferable embodiment, they are each independently a hydrogen atom, a straight chain or branched chain alkyl group in which the number of carbon atoms is 1 to 8 or a substituent T2 of the following formula (B4-b-ii):
In the formula (B4-b-ii), Rb16 is any organic group, and in one preferable embodiment, it has the same meaning as the above-described meaning of RB5.
Rb17, Rb18, Rb19 and Rb20 are each independently any organic group, and in one preferable embodiment, each independently has the same meaning as the above-described meaning of RB6, RB7, RB8, and RB9.
In this regard, Rb14 and Rb15 may be bound to form a morpholino group, piperidino group or 1-piperazinyl group with the nitrogen atom to which they are bound.
Rb12 is any organic group, and in one preferable embodiment, it is a hydrogen atom, a straight chain or branched chain acyl group in which the number of carbon atoms is 2 to 4, a carbamoyl group substituted with a straight chain or branched chain alkyl group in which the number of carbon atoms is 2 to 4, or a substituent T3 of the following formula (B4-b-iii):
Rb21 and Rb22 in the formula (B4-b-ii) are each independently any organic group, and in one preferable embodiment, each independently has the same meaning as the above-described meaning of substituent Rb14.
Rb13 is any organic group, and in one preferable embodiment, it is a nitrogen-containing substituent T4 of the following formula (B4-b-iv) or a substituent T5 of the following formula (B4-b-v):
Rb23 and Rb24 in the formula (B4-b-iv) are each independently any organic group, and in one preferable embodiment, they are each independently a hydrogen atom, a straight chain or branched chain alkyl group in which the number of carbon atoms is 1 to 8, or the above-described substituent T2.
In the formula (B4-b-v), nb3 is any integer, and in one preferable embodiment, it is an integer of 2 to 8.
Rb25 and Rb26 are each independently any organic group, and in one preferable embodiment, they each independently have the same meaning as the above-described meaning of RB5.
Rb27, Rb28, Rb29 and Rb30 are each independently any organic group, and in one preferable embodiment, they each independently have the same meaning as the above-described meaning of RB6, RB7, RB8, and RB9.
Rb31, Rb32, Rb33 and Rb34 are each independently any organic group, and in one preferable embodiment, they each independently have the same meaning as the above-described meaning of RB6, RB7, RB8, and RB9.
Rb35 is any organic group, and in one preferable embodiment, it is a hydrogen atom, a straight chain or branched chain acyl group in which the number of carbon atoms is 2 to 4, a carbamoyl group substituted with a straight chain or branched chain alkyl group in which the number of carbon atoms in the alkyl group is 2 to 4, or substituent T6 of the following formula (B4-b-vi).
Rb36 and Rb37 in the formula (B4-b-vi) are each independently any organic group, and in one preferable embodiment, they are each independently a hydrogen atom or a straight chain or branched chain alkyl group in which the number of carbon atoms is 1 to 18.
Specific examples of the hindered amine compound of the formula (B4-b) include, for example, Tinuvin371 (made by BASF), and the like.
In one embodiment, the hindered amine compound may be a compound which has a carbonate bond (—O—C(═O)—O—).
Specifically, for example, the hindered amine compound may be a compound represented by the following general formula (B4-c):
wherein Rc1 represents an alkyl group or a hydroxyalkyl group in which the number of carbon atoms is 1 to 30, or an alkenyl group in which the number of carbon atoms is 2 to 30, and nc1 represents an integer of 1 to 6, wherein when nc1=1, then Rc2 represents an alkyl group in which the number of carbon atoms is 1 to 22, an alkenyl group in which the number of carbon atoms is 2 to 22 or a group of the following general formula (B4-c-i):
wherein Rc3 represents an alkyl group or hydroxyalkyl group in which the number of carbon atoms is 1 to 30, or an alkenyl group in which the number of carbon atoms is 2 to 30, and
wherein when nc1=2 to 6, then Rc2 represents an nc1-valent organic group in which the number of carbon atoms is 2 to 20.
Specific examples of the hindered amine compound of formula (B4-c) include, for example, Adekastab LA-81 (made by ADEKA), and the like.
The hindered amine compound which is used in the present invention may have, in the molecule, a 1,3,5-triazine structure or 1,3,5-triazine fused ring structure, which is described later in relation to the compound of component (C). In one preferable embodiment, the hindered amine compound does not have a 1,3,5-triazine structure or 1,3,5-triazine fused ring structure in the molecule.
It should be noted that in the present specification, a compound which has both a structure of the hindered amine and a 1,3,5-triazine structure or 1,3,5-triazine fused ring structure in one molecule is included in the hindered amine compound of component (B).
In the composition of the present invention, optionally, as component (C), a triazine-based compound which has a 1,3,5-triazine structure or 1,3,5-triazine fused ring structure can be used.
It should be noted that in the present specification, a compound which has both a structure of the hindered amine and a 1,3,5-triazine structure or 1,3,5-triazine fused ring structure in one molecule is encompassed in component (B) and is not encompassed in component (C). That is, in the present specification, a triazine-based compound refers to a compound which does not have a structure of the above-described hindered amine.
The 1,3,5-triazine structure is a 6-membered ring structure consisting of three carbon atoms and three nitrogen atoms.
In the present specification, the 1,3,5-triazine fused ring means a fused ring formed by fusing a plurality of 1,3,5-triazine rings. In the present specification, a 1,3,5-triazine fused ring structure means a structure of a fused ring formed by fusing a plurality of 1,3,5-triazine rings.
The compound of component (C) may be a compound having one 1,3,5-triazine structure, or may be a compound having a plurality of 1,3,5-triazine structures. Specifically, the compound having one 1,3,5-triazine structure is a compound represented by the following general formula (C1).
In the above-described formula (C1), R21, R22 and R23 are each independently a hydrogen atom or any monovalent substituent. Preferably, at least one of R21, R22 and R23 is other than a hydrogen atom. More preferably, at least one of R21, R22 and R23 is an amino group or a substituted amino group. Further preferably, R21, R22 and R23 are each independently an amino group or a substituted amino group. Particularly preferably, R21, R22 and R23 are each an amino group.
The above-described any monovalent substituent is preferably an alkyl group in which the number of carbon atoms is 1 to 12, an aryl group in which the number of carbon atoms is 6 to 10, an alkyl group having a carbon-carbon unsaturated bond in which the number of carbon atoms is 1 to 12, an alkylcarbonyl group in which the number of carbon atoms is 1 to 12, a hydroxyl group, an alkoxy group in which the number of carbon atoms is 1 to 12, or a mercapto group.
The above-described substituted amino group represents an amino group in which at least one of the hydrogen atoms bonded to the nitrogen atom in the amino group is substituted with any monovalent substituent. Preferably, it is a substituted amino group which is substituted with an alkyl group in which the number of carbon atoms is 1 to 12, an aryl group in which the number of carbon atoms is 6 to 10, an alkyl group having an unsaturated carbon-carbon bond in which the number of carbon atoms is 1 to 12, or an alkylcarbonyl group in which the number of carbon atoms is 1 to 12.
In the compound of component (C), an amine compound having a 1,3,5-triazine structure refers to a compound having a 1,3,5-triazine ring structure and an amino group. Examples of the amine compound having a 1,3,5-triazine structure are, for example, compounds in which at least one of R21, R22 and R23 in the above-described formula (C1) is an amino group or a substituted amino group. Alternatively, it may be a compound in which at least one of R21, R22 and R23 comprises an amino group or a substituted amino group. For example, it may be a compound in which at least one of R21, R22 and R23 is an aminoalkyl group. Preferably, each of R21, R22 and R23 is independently an amino group or a substituted amino group. More preferably, each of R21, R22 and R23 is an amino group.
The compound having the structure of the above-described formula (C1) may be a salt. For example, a salt of melamine can be used. As a type of the salt, for example, an acid addition salt in which an acidic compound is added to a basic nitrogen in the compound (for example, a melamine cyanurate, melamine phosphate, melamine pyrophosphate (a salt in which the molar ratio of “pyrophosphoric acid:melamine” is 1:1)), and the like are included. As the acid addition salt, it is preferably a cyanurate salt.
Among the salts of the compounds having the structure of the above-described formula (C1), preferable salts are a cyanurate salt, phosphate salt or pyrophosphate salt of the compounds of the above-described formula (C1). More preferably, the salt is a cyanurate salt of melamine.
In one preferable embodiment, one, two or three of R21, R22 and R23 of the amine compound having a 1,3,5-triazine ring structure of the above-described formula (C1) are amino groups, and at least one of the amino groups forms a salt with an acidic compound (e.g., a compound having a phosphoric acid group). Also from this viewpoint that an amino group forms a salt with an acidic compound, a cyanurate salt, a phosphate salt and a pyrophosphate salt of melamine are preferable.
It should be noted that in the present specification, a cyanurate salt refers to a salt of cyanuric acid and a triazine-based compound of component (C), and the molar ratio of “cyanuric acid a triazine-based compound” is not particularly limited. That is, it may be a salt in which only one molecule of a triazine-based compound is bound to one cyanuric acid molecule, or it may be a salt in which a plurality of triazine-based compound molecules are bound to cyanuric acid. In addition, it may be a salt in which only one molecule of triazine-based compound is bound to plural cyanuric acid molecules. Preferably, the molar ratio of “cyanuric acid:a triazine-based compound” is 1:1.
In the present specification, a melamine cyanurate refers to a salt of cyanuric acid and melamine, and the molar ratio of “cyanuric acid melamine” is not particularly limited. That is, it may be a salt in which only one molecule of melamine is bound to one molecule of cyanuric acid, or it may be a salt in which plural melamine molecules are bound to one molecule of cyanuric acid. In addition, it may be a salt in which only one melamine molecule is bound to plural molecules of cyanuric acid. Preferably, the molar ratio of “cyanuric acid:melamine” is 1:1.
The compound having a plurality of 1,3,5-triazine structures may be a compound in which at least one of R21 to R23 in the above-described formula (C1) has a 1,3,5-triazine structure. That is, it may be a compound having a structure in which a plurality of 1,3,5-triazine structures are connected (for example, melam).
The 1,3,5-triazine fused ring is formed, for example, by deammonia condensation of melamine. Examples of the compound having a 1,3,5-triazine fused ring structure include, for example, a compound represented by the following general formula (C2).
In the above-described formula (C2), R24, R25 and R26 may be independently a hydrogen atom or any monovalent substituent. Preferably, at least one of R24, R25 and R26 is other than a hydrogen atom. More preferably, at least one of R24, R25 and R26 is an amino group or a substituted amino group. More preferably, R24, R25 and R26 are each independently an amino group or a substituted amino group. Particularly preferably, each of R24, R25 and R26 is an amino group.
The above-described any monovalent substituent is preferably an alkyl group in which the number of carbon atoms is 1 to 12, an aryl group in which the number of carbon atoms is 6 to 10, an alkyl group having an unsaturated carbon-carbon bond in which the number of carbon atoms is 1 to 12, an alkylcarbonyl group in which the number of carbon atoms is 1 to 12, a hydroxyl group, an alkoxy group in which the number of carbon atoms is 1 to 12, or a mercapto group.
The above-described substituted amino group represents an amino group in which at least one of the hydrogen atoms bonded to the nitrogen atom in the amino group is substituted with any monovalent substituent. Preferably, it is a substituted amino group which is substituted with an alkyl group in which the number of carbon atoms is 1 to 12, an aryl group in which the number of carbon atoms is 6 to 10, an alkyl group having an unsaturated carbon-carbon bond in which the number of carbon atoms is 1 to 12, or an alkylcarbonyl group in which the number of carbon atoms is 1 to 12.
In relation to the compound of component (C), an amine compound having a 1,3,5-triazine fused ring structure refers to a compound which has a 1,3,5-triazine fused ring structure and an amino group. Examples of amine compounds having a 1,3,5-triazine fused ring structure include, for example, the compounds of the above-described formula (C2) wherein at least one of R24, R25 and R26 are an amino group or substituted amino group. Alternatively, they may be compounds wherein at least one of R24, R25 and R26 comprise an amino group or substituted amino group. For example, they may be compounds wherein at least one of R24, R25 and R26 are an amino alkyl group. Preferably, R24, R25 and R26 are each independently an amino group or substituted amino group. More preferably, each of R24, R25 and R26 is an amino group.
The compound having the structure of the above-described formula (C2) may be a salt. For example, salts of compounds having a structure in which a plurality of melamine molecules are fused can be used. Types of the salts include, for example, acid addition salts in which an acidic compound is added to basic nitrogen in the compound (for example, melem cyanurate, melem phosphate, or melem pyrophosphate). As the acid addition salt, a cyanurate salt is preferable.
Among the salts of the compounds having the structure of the above-described formula (C2), preferable salts are a cyanurate salt, phosphate salt or pyrophosphate salt of the compounds of the above-described formula (C2). More preferable salts are a cyanurate salt of the compound having the structure in which a plurality of melamine molecules are fused.
In one preferable embodiment, one, two or three of R24, R25 and R26 of the amine compound having a 1,3,5-triazine fused ring structure of the above-described formula (C2) are amino groups, and at least one of the amino groups forms a salt with an acidic compound (for example, a compound having a cyanuric acid group or a phosphoric acid group). Also from this viewpoint that an amino group forms a salt with an acidic compound, a cyanurate salt, a phosphate salt and a pyrophosphate salt of a compound having a structure in which a plurality of melamine molecules are fused are preferable.
The compound having plurality of 1,3,5 triazine fused ring structures may be a compound of the above-described formula (C2) wherein at least one of R24 to R26 has a 1,3,5-triazine fused ring structure. That is, it may be a compound having a structure in which a plurality of 1,3,5-triazine fused ring structures are connected (for example, melone).
In addition, the compound having plurality of 1,3,5-triazine fused ring structures may be a compound having a structure in which a plurality of 1,3,5-triazine fused ring structures are bound to at least one skeleton structure. That is, it may be a compound having a structure in which a plurality of 1,3,5-triazine fused ring structures are bound to the main chain (for example, melem pyrophosphate or melem polyphosphate).
In addition, the compound having a 1,3,5-triazine fused ring structure may be a compound of the above-described formula (C2) wherein at least one of R24 to R26 has a 1,3,5-triazine structure. That is, it may be a compound having a structure in which a plurality of 1,3,5-triazine structures and a plurality of 1,3,5-triazine fused ring structures are connected.
In addition, a compound which has a plurality of 1,3,5-triazine structures and a plurality of 1,3,5-triazine fused ring structures may be a compound having a structure in which a plurality of 1,3,5-triazine ring structures and a plurality of 1,3,5-triazine fused ring structures are bound to at least one skeleton structure. That is, the compound may have a structure in which a plurality of 1,3,5-triazine structures and a plurality of 1,3,5-triazine fused ring structures are bound to the main chain.
Specific examples of the triazine-based compound having a 1,3,5-triazine structure and the amine compound having a 1,3,5-triazine structure include, for example, melamine, ureidomelamine, N2,N4-diethylmelamine, N,N′-diallylmelamine, hexamethylmelamine, melam, ammeline, ammelide, melamine phosphate, melam phosphate, melamine phosphonate, melamine phosphinate, melamine sulfate, melamine nitrate, melamine borate, melamine pyrophosphate, melam pyrophosphate, melamine polyphosphate, melam polyphosphate, melamine metaphosphate, melam metaphosphate, melamine cyanurate, melam cyanurate, melem cyanurate, melone cyanurate, and a homopolymer of 2-piperazinylene-4-morpholino-1,3,5-triazine, acetoguanamine, benzoguanamine, acryloguanamine, methacryloguanamine, 2,4-diamino-6-nonyl-1,3,5-triazine, 2,4-diamino-6-hydroxy-1,3,5-triazine, 2-amino-4,6-dihydroxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-ethoxy-1,3,5-triazine, 2,4-diamino-6-propoxy-1,3,5-triazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-mercapto-1,3,5-triazine and 2-amino-4,6-dimercapto-1,3,5-triazine, and their cyanurate salt, phosphate salt, pyrophosphate salt or polyphosphate salt and the like.
Also, the triazine-based compound having a 1,3,5-triazine structure may be a compound represented by the following formula (C3), or a cyanurate salt, phosphate salt, pyrophosphate salt or polyphosphate salt of a compound of the following formula (C3).
In the formula, k represents an integer of 1 or more, and preferably k is an integer of 1 to 4. R31 and R32 are the same or different and are a hydrogen atom or an alkyl group. R33 and R34 are the same or different and are a hydrogen atom, an alkyl group, a cyanoalkyl group, a carboxyalkyl group, an alkoxycarbonylalkyl group, an aryloxycarbonylalkyl group, a haloformylalkyl group, or a guanamylalkyl group. The number of the carbon atoms of each of the alkyl group and the alkoxy group is preferably 1 to 6. The number of the carbon atoms of the aryl is preferably 6 to 12.
Specific examples of the triazine-based compound having a 1,3,5-triazine fused ring structure and the amine compound having a 1,3,5-triazine fused ring structure include, for example, melem, melone, melem cyanurate, melem pyrophosphate, melem polyphosphate, melone cyanurate, melone pyrophosphate, melone polyphosphate and the like. It should be noted that in the present specification, “melone” refers to a compound having a structure in which melem is fused. Melone cyanurate refers to a compound having a structure in which melone is bonded to cyanuric acid.
Specific examples of the triazine-based compounds of component (C) preferably include a melamine cyanurate, melam cyanurate, melem cyanurate, melone cyanurate, melamine phosphate, melam phosphate, melem phosphate, melone phosphate, melamine metaphosphate, melam metaphosphate, melem metaphosphate, melone metaphosphate, melamine pyrophosphate, melam pyrophosphate, melem pyrophosphate, melone pyrophosphate, melamine polyphosphate, melam polyphosphate, melem polyphosphate, and melone polyphosphate. A melamine cyanurate, melam cyanurate, melem cyanurate, and melone cyanurate are more preferable, and a melamine cyanurate is further preferable.
The flame retardant composition of the present invention comprises the above-described component (A) and the above-described component (B).
The phosphoramidate compound represented by the general formula (I) is used in combination with a hindered amine compound to exert an excellent flame retardant effect. When it is added to a resin, bleed-out does not occur. In a preferable embodiment, a value of a blending ratio (mass ratio) (A)/(B) can be higher than 1, and thereby a significantly high flame retardant performance can be achieved.
A lower limit value of the mass ratio of a blending ratio (A)/(B) of the phosphoramidate compound represented by the general formula (I) and the hindered-amine compound is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, still more preferably 7 or more, and particularly preferably 10 or more. In addition, an upper limit value of the mass ratio of (A)/(B) is preferably 1,000 or lower, more preferably 100 or lower, and further preferably 50 or lower. When the value of the ratio (A)/(B) is too low or too high, the flame retardant performance or a property of the thermoplastic resin is likely to be lowered.
The flame retardant composition of the present invention optionally comprises component (C) in addition to the above-described component (A) and the above-described component (B). By combining the above-described component (C) with the above-described component (A) and the above-described component (B), it is possible to suppress bleed-out when it is added to a resin, and a further higher flame retardant performance can be provided than a case when only the above-described component (A) and the above-described component (B) are used.
The phosphoramidate compound represented by the general formula (I) exerts a further excellent flame retardant effect by a use in combination with a hindered amine compound and component (C), and when it is added to a resin, bleed-out does not occur. In a preferable embodiment, values of blending ratios (mass ratios) (A)/(B) and (C)/(B) can be higher than 1, and thereby a significantly high flame retardant performance can be achieved.
When component (C) is used in the composition of the present invention, a lower limit value of the mass ratio of a blending ratio (A)/(B) of component (A) and component (B) and a lower limit value of the mass ratio of a blending ratio (C)/(B) of component (C) and component (B) are each independently preferably 1 or more, more preferably 1.3 or more, further preferably 1.5 or more, still more preferably 1.7 or more, and particularly preferably 2 or more. In addition, an upper limit value of the mass ratio of (A)/(B) and an upper limit value of the mass ratio of (C)/(B) are each independently preferably 50 or lower, more preferably 30 or lower, further preferably 25 or lower, still more preferably 20 or lower, and particularly preferably 15 or lower. When the value of the ratio of (A)/(B) or (C)/(B) is too low or too high, the flame retardant performance would be lower in comparison with the case where the value of (A)/(B) or (C)/(B) is within a preferable range.
The flame retardant composition of the present invention can be suitably used as a flame retardant composition for a thermoplastic resin in a preferable embodiment, and as a flame retardant composition for a polyolefin resin in a more preferable embodiment.
The flame retardant composition of the present invention can be effectively used for a thermoplastic resin. In addition, for the thermoplastic resin composition of the present invention, as component (D), a thermoplastic resin is used.
The types of the thermoplastic resin are not particularly limited. The resin may be a polymer wherein vinyl groups are radically polymerized, or a polymer which is polymerized by condensation polymerization. A polymer formed by radical polymerization is preferable. More preferably, the resin is a polyolefin resin.
In addition, the polymer may be a homopolymer or a copolymer.
The thermoplastic resin of component (D) is preferably a polyolefin resin, and more preferably polyethylene, polypropylene and a copolymer containing propylene or ethylene.
It should be noted that, in the present specification, in relation to a composition of a copolymer, the term “ethylene” means a moiety derived from ethylene in a polymer which is obtained when a monomer mixture comprising ethylene or propylene as a raw material is polymerized. In addition, in relation to a composition of a copolymer, the term “propylene” means a moiety derived from propylene in a polymer which is obtained when a monomer mixture comprising propylene as a raw material is polymerized.
The types of polyethylene are not particularly limited. The polyethylene can be a high density polyethylene (HDPE), can be a linear low density polyethylene (LLDPE), can be a branched low density polyethylene (LDPE), and can be ultra high molecular weight polyethylene (UHMWPE).
The types of polypropylene are not particularly limited. The polypropylene can be isotactic polypropylene, can be syndiotactic polypropylene, and can be atactic polypropylene.
The copolymer containing propylene or ethylene can be a copolymer of propylene and another monomer, can be a copolymer of ethylene and another monomer, and can be a copolymer of propylene, ethylene and another monomer.
Regarding the copolymer, when a property of polyethylene is desired, a ratio of ethylene in the copolymer is preferably 10 mol % or more, more preferably 30 mol % or more, further preferably 50 mol % or more, and particularly preferably 70 mol % or more.
Regarding the copolymer, when a property of polypropylene is desired, a ratio of propylene in the copolymer is preferably 10 mol % or more, more preferably 30 mol % or more, further preferably 50 mol % or more, and particularly preferably 70 mol % or more.
Regarding the copolymer, when properties of both of polyethylene and polypropylene are desired, a ratio of a total amount of ethylene and propylene in the copolymer is preferably 10 mol % or more, more preferably 30 mol % or more, further preferably 50 mol % or more, and particularly preferably 70 mol % or more.
Regarding the copolymer, if necessary, it is possible to copolymerize a halogen-containing monomer (for example, vinyl chloride monomer). However, a halogen-containing monomer is not preferable from the viewpoint of environmental problems. Therefore, in a preferable embodiment, a copolymer does not comprise a halogen-containing monomer.
As the thermoplastic resin of component (D), a halogen-containing thermoplastic resin (for example, a polyvinyl chloride resin) can be also used. However, a halogen-containing thermoplastic resin is not preferable from the viewpoint of environmental problems. Therefore, in a preferable embodiment, the thermoplastic resin of component (D) does not comprise a halogen-containing thermoplastic resin.
In one embodiment, it is also possible to use, as the thermoplastic resin of component (D), a halogen-containing thermoplastic resin by mixing it with a thermoplastic resin containing no halogen. However, from the viewpoint of environmental problems, it is preferable that the amount of a halogen-containing thermoplastic resin is small. A content of a halogen-containing thermoplastic resin is preferably 30% by mass or lower, more preferably 10% by mass or lower, further preferably 5% by mass or lower, and particularly preferably 1% by mass or lower with respect to a total amount of the halogen-containing thermoplastic resin and a thermoplastic resin containing no halogen.
The flame retardant thermoplastic resin composition of the present invention can be obtained by mixing each of the components of the flame retardant composition and a thermoplastic resin. Regarding preparation of the flame retardant thermoplastic resin composition, it is possible to use a method wherein a step of mixing each of the components of the flame retardant composition is performed to prepare a flame retardant composition, and thereafter, the prepared flame retardant composition and a thermoplastic resin are mixed. It is also possible to use a method wherein a step of preparing a flame retardant composition is not performed and each of the components of the flame retardant composition and a thermoplastic resin are mixed.
An amount of component (A) which is blended in the thermoplastic resin composition is not particularly limited. However, the amount is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and particularly preferably 1 parts by mass or more with respect to 100 parts by mass of a total amount of component (A) to component (D). In addition, the amount is preferably 45 parts by mass or lower, more preferably 40 parts by mass or lower, further preferably 35 parts by mass or lower, still further preferably 30 parts by mass or lower, and particularly preferably 25 parts by mass or lower with respect to 100 parts by mass of a total amount of component (A) to component (D). When the amount is too small, it is unlikely to achieve an effect by adding it. When the amount is too large, a physical property of the thermoplastic resin composition may be deteriorated.
An amount of component (B) which is blended in the thermoplastic resin composition is not particularly limited. However, the amount is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, further preferably 0.3 parts by mass or more, and particularly preferably 0.5 parts by mass or more with respect to 100 parts by mass of a total amount of component (A) to component (D). In addition, the amount is preferably 15 parts by mass or lower, more preferably 10 parts by mass or lower, further preferably 7 parts by mass or lower, and particularly preferably 5 parts by mass or lower with respect to 100 parts by mass of a total amount of component (A) to component (D). When the amount is too small, it is unlikely to achieve an effect by adding it. When the amount is too large, a physical property of the thermoplastic resin composition may be deteriorated.
An amount of component (C) which is blended in the thermoplastic resin composition is not particularly limited. However, the amount is preferably 1 part by mass or more, more preferably 2 parts by mass or more, further preferably 3 parts by mass or more, and particularly preferably 5 parts by mass or more with respect to 100 parts by mass of a total amount of component (A) to component (D). In addition, the amount is preferably 30 parts by mass or lower, more preferably 25 parts by mass or lower, further preferably 20 parts by mass or lower, and particularly preferably 17 parts by mass or lower with respect to 100 parts by mass of a total amount of component (A) to component (D). When the amount is too small, it is unlikely to achieve an effect by adding it. When the amount is too large, a physical property of the thermoplastic resin composition may be deteriorated.
A total amount of the component (A) and the component (B) to be blended in the thermoplastic resin composition is not particularly limited. However, the total amount of the component (A) and the component (B) is preferably 1 part by mass or more, more preferably 2 parts by mass or more, further preferably 3 parts by mass or more, still further preferably 5 parts by mass or more, and particularly preferably 7 parts by mass or more with respect to 100 parts by mass of a total amount of component (A) to component (D). When a total amount of the component (A) and the component (B) to be blended is too small, there may be cases where a high flame retardance is not achieved. In addition, a total amount of the component (A) and the component (B) to be blended is preferably 50 parts by mass or lower, more preferably 45 parts by mass or lower, further preferably 40 parts by mass or lower, still further preferably 35 parts by mass or lower, particularly preferably 30 parts by mass or lower, and most preferably 25 parts by mass or lower with respect to 100 parts by mass of a total amount of component (A) to component (D). Furthermore, in one embodiment, a total amount of the component (A) and the component (B) to be blended can be 20 parts by mass or lower, can be 15 parts by mass or lower, and can be 10 parts by mass or lower. When a total amount of the component (A) and the component (B) to be blended is too large, a physical property of the resin may be deteriorated.
A total amount of the component (A), the component (B) and the component (C) to be blended in the thermoplastic resin composition is not particularly limited. However, the total amount of the component (A), the component (B) and the component (C) to be blended is preferably 1 part by mass or more, more preferably 2 parts by mass or more, further preferably 3 parts by mass or more, still further preferably 5 parts by mass or more, and particularly preferably 7 parts by mass or more with respect to 100 parts by mass of a total amount of component (A) to component (D). When a total amount of the component (A), the component (B) and the component (C) to be blended is too small, there may be cases where a high flame retardance is not achieved. When a total amount of the component (A), the component (B) and the component (C) to be blended is too large, a physical property of the resin may be deteriorated. In addition, a total amount of the component (A), the component (B) and the component (C) to be blended is preferably 50 parts by mass or lower, more preferably 45 parts by mass or lower, further preferably 40 parts by mass or lower, still further preferably 35 parts by mass or lower, particularly preferably 30 parts by mass or lower, and most preferably 25 parts by mass or lower. Furthermore, in one embodiment, a total amount of the component (A), the component (B) and the component (C) to be blended can be 20 parts by mass or lower, can be 15 parts by mass or lower, and can be 10 parts by mass or lower. When a mixture of the component (A), the component (B) and the component (C) is used, there is an advantage in that even if the total amount to be blended is small (for example, even if the total amount is 10 parts by mass or lower with respect to 100 parts by mass of the total amount of component (A) to component (D)), high flame retardance can be achieved.
If necessary, a flame retardant other than the flame retardant composition of the present invention can be used in the thermoplastic resin composition of the present invention. That is, a compound other than the above-described component (A), component (B) and component (C) which can provide a flame retardance with a thermoplastic resin (hereinafter, referred to as “other flame retardant”) can also be used in the thermoplastic resin composition.
For example, if necessary, an organic-type flame retardant other than the phosphoramidate compounds or an inorganic-type flame retardant can be used. Examples of the organic-type flame retardant other than the phosphoramidate compounds include a halogen-based flame retardant, a phosphate-based flame retardant, and the like. Examples of the inorganic flame retardant include an antimony compound, metal hydroxide, and the like. Specific examples of the metal hydroxide include, for example, aluminum hydroxide (alumina hydrate), magnesium hydroxide, and the like. In addition, a metal oxide or metal salt can also be used as an other flame retardant. For example, zinc oxide, aluminum hypophosphite or tris(diethylphosphinic acid) aluminum can be preferably used.
However, in order to take advantage of the flame retardant of the present invention, it is preferable that an amount of the other flame retardant to be used is small. For example, the amount of the other flame retardant to be used is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, further preferably 5 parts by mass or less, still more preferably 1 part by mass or less with respect to 100 parts by mass of a thermoplastic resin. Further, for example, the amount of the other flame retardant to be used is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, further preferably 20 parts by mass or less, and still more preferably 10 parts by mass or less with respect to 100 parts by mass of the flame retardant composition of the present invention.
In one preferable embodiment, the thermoplastic resin of the present invention does not comprise a halogen-based flame retardant. That is, it does not comprise a compound which has a halogen atom and can provide a flame retardance to a thermoplastic resin.
In a particularly preferable embodiment, the other flame retardant is not mixed, and a flame retardant composition which consists of only component (A) and component (B) or a flame retardant composition which consists of only component (A), component (B) and component (C) is used.
The flame retardant of the present invention can achieve a high flame retardance and various performances which are required for general thermoplastic resin products even if it is not mixed with the other flame retardant. Therefore, if the intended thermoplastic resin product is not a product for a special use, then it is not necessary to mix the thermoplastic resin composition of the present invention with the other flame retardant.
Further, various additives other than components (A) to (C) may be blended in the flame retardant thermoplastic resin composition of the present invention depending on the properties which are desired for the resin composition and within a range in which the effect of the present invention is not deteriorated. For example, a flame retardant auxiliary agent, ultraviolet absorber, antioxidant other than hindered amine compounds, light stabilizer other than hindered amine compounds, coloring agent (for example, dye or pigment), surface modifier, antibacterial agent, insect repellent, antistatic agent, filler (for example, inorganic filler), reinforcing agent (for example, glass fiber reinforcing material), and the like can be added.
It should be noted that, a hindered amine compound generally has a function as an antioxidant or light stabilizer. However, in the present specification, a hindered amine compound is encompassed in the above-described component (B) and therefore is not encompassed in other additives.
The types and amount to be added of these additives are not particularly limited, and an additive which is generally used can be used in a range of the amount which is generally used. Specifically, for example, for each of these additives, the amount can be 0.01 parts by mass or more, 0.1 parts by mass or more, or 1 part by mass or more with respect to 100 parts by mass of a thermoplastic resin. Further, the amount can be 20 parts by mass or less, and can be 10 parts by mass or less, or 5 parts by mass or less with respect to 100 parts by mass of a thermoplastic resin.
However, the aforementioned additives, such as coloring agent, cross-linking agent, ultraviolet absorber, hydrolysis inhibitor, filler, reinforcing material, and the like, are not always required for the thermoplastic resin composition of the present invention. It is enough as long as these additives are used for a thermoplastic resin composition in a minimum required amount based on required performances for an intended thermoplastic resin product.
The operations of mixing and stirring at the time of preparing the flame retardant composition or preparing the flame retardant thermoplastic resin composition can be performed by using a conventional stirring device, for example, a various mill, Henschel mixer (FM mixer) or the like. If the various components can be uniformly mixed, the order of the addition does not matter. It is possible that all of the components are put into a stirring device at once and they are mixed and stirred. Alternatively, it is possible to add the phosphoramidate compound from a side feeder. In addition, it is possible that a masterbatch of a thermoplastic resin and the phosphoramidate compound is prepared in advance, and a required amount of the masterbatch is blended to a thermoplastic resin, making into a necessary amount of a flame retardant in accordance with the flame retardant standard of the final product, to obtain a flame retardant resin composition having a desired flame retardance.
In addition, it is also possible that when heat-melting molding of a thermoplastic resin (for example, injection molding or extrusion molding) is performed, a flame retardant is mixed with a thermoplastic resin to obtain a flame retardant resin composition.
The flame retardant thermoplastic resin composition of the present invention can be molded by any method which is known as a method of molding a thermoplastic resin. If a molding machine, a mold and the like which are suitable for the desired molded product are used, the desired molded product can be easily obtained. For example, various molded products such as automobile upholstery, packaging material, a material for electrical devices, a sheet or film for a building material, a material covering electric wire and the like can be molded.
The molded product which is obtained has an advantage that it has an excellent flame retardance and the performance of the thermoplastic resin is not significantly lowered.
The present invention is described in further details based on the following Examples. However, the present invention is not limited by the following Examples.
The resin and the additives were mixed in the ratios shown in Table 1, and flame retardant resin compositions were obtained.
The resin and additives which were used are as described below.
(1) Polypropylene resin: Prime Polypro (registered trademark) J-750HP made by Prime Polymer.
(2) Phosphoramidate 1: A cyclic phosphoramidate which was produced according to the procedure described in paragraph 0173 of U.S. Patent Application Laid-open Publication No. 2016/0244582. Pulverized product. Average particle size about 4 μm. A bicyclic phosphoramidate compound of formula (4). A phosphoramidate according to the present invention.
(3) Phosphoramidate 2: SP-703 made by Shikoku Chemicals, phosphoramidate for comparative examples.
(4) Melamine cyanurate: MC-4000 made by Nissan Chemical. Melamine cyanurate powder. Average particle diameter 12 μm.
(5) Hindered amine 1: Flamestab NOR-116 made by BASF Japan, Triazine derivative.
(5) Hindered amine 2: Tinuvin NOR-371 made by BASF Japan. A hindered amine compound of formula (ii):
wherein nb is 1 to 10.
(6) Hindered amine 3: Tinuvin XT 850 made by BASF Japan. A hindered amine compound.
(7) Stabilizer 1: Irganox B 561 made by BASF, a blend of 20% Irganox 1010, a hindered phenol-type thermal stabilizer and 80% Irgaphos 168, a phosphite process stabilizer.
A twin-screw kneading extruder (TEM-37BS made by Toshiba machine) was used to mix the resin and additives in the ratios shown in Table 1, and a kneading step was performed under setting of 180° C. The strand which was obtained from the extrusion axis was cooled in a water bath. Thereafter the strand was cut by a pelletizer to obtain pellets. The pellets were dried for 4 hours in a constant temperature dryer maintained at 80° C. The dried pellets were then molded at a molding temperature of 180° C. using an injection molding machine (FN2000: made by Nissei Plastic Industrial), and test pieces of a predetermined shape were produced.
The obtained test pieces were used to perform the tests as described below.
The flame retardance test was performed in accordance with the vertical test combustion method of “Test for flammability of plastic materials for parts in devices and appliances” of UL subject 94 (Underwrighters Laboratories Incorporated). Regarding the wall thickness of the test piece, 1.6 mm ( 1/16 inches) and 3.2 mm (⅛ inches) were used.
The measurement of oxygen indices (L.O.I) was performed in accordance with Japan Industrial Standard JIS K7201 (Test method of flammability based on oxygen index).
In order to check for bleed-out, when the above-described injection molding was performed, the presence/absence of adhesion of an additive to the mold and contamination were visually observed at the time of processing the resin. In order to further observe bleed-out from the molded products, test pieces having a wall thickness of 1.6 mm ( 1/16 inches) of UL Subject 94 obtained by the injection molding were prepared. The test pieces were left in a constant-temperature dryer maintained at 80° C. for 2 weeks, and the ratios of decrease were observed from the weight changes of the test pieces before and after the test. It should be noted that, regarding the weight change ratio, a difference between the weight of the test piece after the surface of the test piece was wiped with acetone after the test and the weight before the test was obtained and expressed as a percentage.
The results are shown in Table 1 and Table 2. It should be noted that the blending amounts in Table 1 and Table 2 are all based on parts by mass.
Not-V: The result did not fall within any of V-0, V-1, or V-2 of the UL-94 vertical burning test, and the flame reached the fixing clamp and the test piece was burned completely while dripping.
As shown in Table 1 and Table 2 above, from the results of Examples 1 to 7, when phosphoramidate 1 having the structure specified by the present invention was used in combination with a hindered amine compound, it was possible to increase the oxygen index values while it was possible to achieve flame retardance of V-2 in the UL94 vertical combustion test and it was possible to suppress bleed-out.
In particular, from the results of Examples 5 and 6, the flame retardant compositions of the present invention comprising the three components of the phosphoramidate 1, the hindered amine, and the melamine cyanurate was able to achieve V-2 flame retardance even when the amount of the addition was decreased to 10% by mass and it was possible to suppress bleed-out.
From Example 1 and Comparative Example 1, it was confirmed that even though the oxygen index values were at the same level, the composition in which component (B) was replaced with a stabilizer other than a hindered amine compound does not satisfy V-2 standard in the UL94 vertical combustion test.
From the results of Comparative Examples 1 and 2, it was confirmed that if phosphoramidate 1 was used without a hindered amine compound, it is impossible to achieve V-2 flame retardance.
From the results of Comparative Examples 3 to 4, when phosphoramidate 2 for comparison is used in combination with a hindered amine compound, then it was impossible to achieve both the flame retardance of V-2 and the bleed-out prevention. If the amount of the added phosphoramidate 2 for comparison is reduced, then it is impossible to satisfy the flame retardance of V-2, and conversely, if the added amount is increased, then bleed-out occurs.
From the results of Comparative Example 5, it was confirmed that the combination of a melamine cyanurate and a hindered amine alone cannot achieve the flame retardance resulting in V-2.
From the comparison of Examples 5 and 6 with Comparative Examples 3 and 4, it was confirmed that the thermoplastic resin containing phosphoramidate 2 for comparison has a disadvantage in that bleed-out already occurs during the molding process, while when phosphoramidate 1 of the present invention having a specific structure is used, no bleed-out occurs and there is no mold adhesion and contamination is generated by the additives.
According to the present invention, a flame retardant composition which can provide a flame retardance to a thermoplastic resin and does not substantially deteriorate a performance of the thermoplastic resin is provided. In addition, a flame retardant thermoplastic resin composition which uses the flame retardant composition is provided. The flame retardant composition and the flame retardant thermoplastic resin composition according to the present invention can be used in molded products such as an automobile upholstery, a packaging material, a material for electrical devices, a sheet or film for building materials, a material covering electric wire and the like.
The present invention has been exemplified so far with reference to the favorable embodiments of the present invention, but it should not be construed that the present invention is restricted by the embodiments. It is understood that the scope of the present invention should be construed only by the claims. It is understood that those who are skilled in the art can carry out an equivalent range based on the description of the present specification and technical common sense from the description of the specific favorable embodiments of the present invention. It is understood that the contents of the patents, patent applications and literatures cited in the present specification should be herein incorporated by reference, similarly to the case where the contents themselves are described specifically in the present specification.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2019-239539 | Dec 2019 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2020/048834 | 12/25/2020 | WO |
