CN112912429B

CN112912429B - Solid additive, resin composition, and method for producing same

Info

Publication number: CN112912429B
Application number: CN201980067965.3A
Authority: CN
Inventors: 立川友晴; 高野一史; 村濑裕明; 大北正信; 田渊英嗣; 绪方和幸; 山形宪一; 山根康之; 秋山穰慈
Original assignee: Osaka Gas Chemicals Co Ltd
Current assignee: Osaka Gas Chemicals Co Ltd
Priority date: 2018-10-26
Filing date: 2019-10-25
Publication date: 2023-03-28
Anticipated expiration: 2039-10-25
Also published as: KR20210080394A; JP7418342B2; WO2020085476A1; CN112912429A; TWI831854B; JPWO2020085476A1; TW202033645A

Abstract

As the solid additive to be added to the thermoplastic resin, when the CNT (a) is combined with the fluorene compound and at least a part of the surface of the CNT (a) is covered with the fluorene compound (B), the CNT can be uniformly dispersed in the thermoplastic resin and mechanical properties such as impact strength of the resin composition can be improved. The fluorene compound (B) may have a heteroatom-containing functional group via a hydrocarbon group bonded to the 9-position of fluorene.

Description

Solid additive, resin composition, and method for producing same

Technical Field

The present invention relates to a solid additive for a resin containing a carbon nanotube and a compound having a fluorene skeleton, a resin composition, and a method for producing the same.

Background

Since carbon nanotubes (hereinafter, sometimes referred to as "CNTs") are excellent in electrical conductivity, thermal stability, and mechanical properties, attempts have been made to improve the physical properties by kneading the carbon nanotubes with a thermoplastic resin. However, CNTs are difficult to uniformly disperse in a resin, and when they exist in the form of aggregates in the resin, mechanical properties such as impact strength and electrical conductivity may be reduced.

Japanese patent No. 6095761 (patent document 1) discloses a granular composition for producing a kneaded product by extrusion kneading, the granular composition comprising: a powdery thermoplastic resin such as Polycarbonate (PC), a carbon-based conductive material such as CNT, and a fluorene-based dispersant. The particulate composition is, for example, a composition in which CNTs are added to a powdery PC to which a small amount of a fluorene-based dispersant is added, and the CNTs are present so as to gradually decrease toward the inside of the PC.

Japanese patent laid-open publication No. 2010-111876 (patent document 2) discloses a composition comprising: a thermoplastic resin containing a compound having a 9,9-bisarylfluorene skeleton as a constituent monomer, another thermoplastic resin, and CNT. The composition is applied as a dispersion on a polyethylene terephthalate (PET) film to form a coating film in which CNTs are highly dispersed.

Japanese patent laid-open publication No. 2012-111680 (patent document 3) discloses a nanocarbon aqueous dispersion comprising: a water-soluble compound having 9,9-bis (substituted aryl) fluorene skeleton, nanocarbons such as CNT, and an aqueous solvent. The aqueous dispersion of nanocarbon was coated on a glass plate to form a dry film in which nanocarbon was isolated and dispersed at a high concentration.

Documents of the prior art

Patent document

Patent document 1: japanese patent No. 6095761

Patent document 2: japanese patent laid-open No. 2010-111876

Patent document 3: japanese patent laid-open publication No. 2012-111680

Disclosure of Invention

Problems to be solved by the invention

However, the particulate composition disclosed in patent document 1 has improved handling properties by reducing the volume of CNTs, and has improved conductivity and appearance of a resin composition to which the particulate composition is added, but has failed to achieve high dispersibility of CNTs, and has insufficient mechanical properties such as impact strength. The composition disclosed in patent document 2 and the aqueous dispersion disclosed in patent document 3 are only coating materials, and cannot improve the mechanical properties and conductivity of the resin molded article itself to be coated, and thus the applications are limited.

Accordingly, an object of the present invention is to provide a solid additive capable of uniformly dispersing CNTs in a thermoplastic resin and improving mechanical properties such as impact strength of the resin composition, a resin composition containing the solid additive, and methods for producing the solid additive and the resin composition.

Another object of the present invention is to provide a solid additive that can highly balance both electrical conductivity and mechanical properties of a resin composition, a resin composition containing the solid additive, and methods for producing the same.

It is still another object of the present invention to provide a solid additive which is excellent in workability and can satisfy both of electrical conductivity and mechanical properties of a resin composition, a resin composition containing the solid additive, and methods for producing the solid additive and the resin composition.

Means for solving the problems

The present inventors have conducted extensive studies in order to achieve the above-mentioned object, and as a result, have found that a solid additive which combines a CNT (a) and a fluorene compound (B) and coats or treats at least a part of the surface of the CNT (a) with the fluorene compound (B) can uniformly disperse the CNT in a thermoplastic resin and can improve mechanical properties such as impact strength of a resin composition, as a solid additive to be added to a thermoplastic resin, and have completed the present invention.

That is, the solid additive of the present invention is a solid additive (additive composition) to be added to a thermoplastic resin, and it comprises CNT (a) and a fluorene compound (B), and at least a part of the surface of the CNT (a) is covered or treated with the fluorene compound (B), and it can be said that the solid additive is a pre-dispersion or a mixture of the additive, or a composite of the CNT and the fluorene compound. The fluorene compound (B) may have a heteroatom-containing functional group via a hydrocarbon group bonded to the 9-position of fluorene.

The fluorene compound (B) may be a compound represented by the following formula (1).

[ solution 1]

(in the formula, wherein,

ring Z ¹ And Z ² Identical to or different from each other, represent an aromatic hydrocarbon ring,

R ¹ and R ² Identical to or different from each other, represent a substituent,

p1 and p2, which may be the same or different from each other, represent an integer of 0 or more,

X ¹ and X ² Identical to or different from each other, represent a heteroatom-containing functional group,

n1 and n2, which may be the same or different from each other, represent an integer of 1 or more,

R ³ represents a substituent group, and a pharmaceutically acceptable salt thereof,

k represents an integer of 0 to 8).

In the above formula (1), X ¹ And X ² Identical to or different from each other, are a group- [ (OA) ¹ ) _m1 -OH](in the formula, A) ¹ Represents an alkylene group, m1 represents an integer of 0 or more), and n1 and n2 may be 1.

The fluorene compound (B) may be a compound represented by the following formula (2).

[ solution 2]

/>

(in the formula, wherein,

A ² and A ³ Identical to or different from each other, represent an alkylene group,

X ¹ 、X ² 、R ³ and k is the same as described above. )

In the above formula (2), X ¹ And X ² Identical to or different from each other, may be a radical-COOR ⁴ (in the formula, R ⁴ Represents a hydrogen atom or an alkyl group).

The fluorene compound (B) may have an amorphous structure. The ratio of the fluorene compound (B) is about 5 to 200 parts by mass with respect to 100 parts by mass of the CNT (a). The solid additive may have a compressive strength of 1N or more. The solid additive may be an additive for adding to a thermoplastic resin to perform melt-kneading. The solid additive may be a conductive agent.

The present invention also includes a method for producing the solid additive by mixing the CNT (a) and the fluorene compound (B). In this production method, the CNT (a) and the fluorene compound (B) may be mixed in the presence of a solvent.

The present invention also includes a resin composition comprising a thermoplastic resin and the above solid additive. The proportion of the solid additive is about 0.1 to 20 parts by mass per 100 parts by mass of the thermoplastic resin. The thermoplastic resin may be a polycarbonate resin, and the polycarbonate resin composition may have a value of 10 ¹² Volume resistivity of not more than omega cm and 30kJ/m ² Charpy (Charpy) impact strength above.

The present invention also includes a method for producing the above resin composition by melt-kneading a thermoplastic resin and the above solid additive.

The present invention also includes a method of dispersing CNTs in a thermoplastic resin by adding the above solid additive to the thermoplastic resin. In addition, the present invention also includes the use of the above solid additive for dispersing CNTs in a thermoplastic resin.

It is specified that in the present description and claims there areWhen the number of carbon atoms of the substituent is represented by C ₁ 、C ₆ 、C ₁₀ Etc. For example, "C ₁ The "alkyl group" means an alkyl group having 1 carbon atom and "C _6-10 The "aryl group" refers to an aryl group having 6 to 10 carbon atoms. In the present specification and claims, the term "fluorene compound" refers to a compound having a fluorene ring as a main skeleton.

Effects of the invention

In the present invention, since the CNT and the fluorene compound are combined as the solid additive and at least a part of the surface of the CNT is covered with the fluorene compound, the CNT can be uniformly dispersed in the thermoplastic resin and the mechanical properties such as impact strength of the resin composition can be improved. In addition, by adjusting the proportion of the fluorene compound in the solid additive, the electrical conductivity and mechanical properties of the resin composition are improved. Further, since at least a part of the surface of the CNT is covered with the fluorene compound, the CNT is excellent in handling properties and can achieve both of electrical conductivity and mechanical properties of the resin composition.

Drawings

FIG. 1 is a Scanning Electron Microscope (SEM) photograph (magnification of 5000) of the solid additive obtained in example 3.

Fig. 2 is an SEM photograph (5000 ×) of Kumho CNT used in example 3.

FIG. 3 is an SEM photograph (magnification of 5000) of BPEF used in example 3.

FIG. 4 is an SEM photograph (magnification of 5000) of the solid additive obtained in example 4.

FIG. 5 is a DSC of the solid additive obtained in example 3.

FIG. 6 is a DSC chart of Kumho CNT used in example 4.

FIG. 7 is a DSC plot of BPEF as used in example 4.

FIG. 8 is an SEM photograph (magnification of 5000) of the solid additive obtained in example 8.

FIG. 9 is an SEM photograph (magnification of 5000) of FDP-m used in example 8.

FIG. 10 is a DSC of the solid additive obtained in example 8.

FIG. 11 is a DSC of FDP-m used in example 8.

FIG. 12 is an SEM photograph (magnification of 5000) of the solid additive obtained in example 12.

Fig. 13 is an SEM photograph (5000 ×) of BCF used in example 12.

FIG. 14 is a DSC of the solid additive obtained in example 12.

FIG. 15 is a DSC chart of BCF used in example 12.

FIG. 16 is an SEM photograph (magnification of 5000) of the solid additive obtained in example 16.

Fig. 17 is an SEM photograph (5000 x) of BNF used in example 16.

FIG. 18 is a DSC of the solid additive obtained in example 16.

FIG. 19 is a DSC of BNF used in example 16.

Detailed Description

The solid additive of the present invention comprises carbon nanotubes (a) and a fluorene compound (B).

[ carbon nanotubes (A) ]

The CNT (a) may be a carbon tube having a diameter of nanometer size (nanometer-scale carbon tube), and various CNTs commonly used may be used. The space in the tube of the CNT (a) may contain a metal (e.g., iron) therein.

As representative CNTs, there can be exemplified: an iron-carbon composite or the like comprising carbon nanotubes (a) and iron carbide or iron (b), wherein the carbon nanotubes (a) are at least one selected from the group consisting of single-layer or multi-layer carbon nanotubes (A1), amorphous nanoscale carbon tubes (A2), nanosheet carbon tubes (A3), nanosheet carbon tubes (A4), and nested multi-layer carbon nanotubes, and the iron carbide or iron (b) is composed of iron carbide or iron and fills the space in the tubes of the carbon nanotubes (a). These carbon nanotubes may be used alone or in combination of 2 or more.

The single-or multi-layered carbon nanotube (A1) is a hollow carbon substance in which graphite sheets (i.e., carbon atom planes of a graphite structure or graphene sheets) are closed in a tubular shape, the diameter of which is in the order of nanometers, and the wall structure has a graphite structure. Among the carbon nanotubes having such a structure, a carbon nanotube having a wall structure in which one graphite sheet is closed into a tubular shape is called a single-layer carbon nanotube, and a carbon nanotube having a structure in which a plurality of graphite sheets are respectively closed into tubular shapes and are nested is called a multi-layer carbon nanotube (a multi-layer carbon nanotube of a nested structure). The single-layer carbon nanotube and the multi-layer carbon nanotube can be used independently or in combination.

The size of the single-walled carbon nanotube may be 0.4 to 10nm in diameter (average diameter) and 1 to 500 μm in length (average length), preferably 0.7 to 5nm in diameter and 1 to 100 μm in length, more preferably 0.7 to 2nm in diameter and 1 to 20 μm in length.

Regarding the size of the multilayered carbon nanotube, the diameter (average diameter) may be 1 to 100nm and the length (average length) may be 1 to 500. Mu.m, preferably the diameter is 1 to 50nm and the length is 5 to 100. Mu.m, more preferably the diameter is 1 to 40nm and the length is 10 to 50 μm (particularly, the diameter is 5 to 20nm and the length is 20 to 30 μm).

The bulk density (knock method) of the multilayered carbon nanotube is, for example, 0.03 to 0.2g/cc, preferably 0.05 to 0.15g/cc, and more preferably 0.06 to 0.14g/cc.

Examples of the amorphous carbon nanotubes (A2) include: the nanotubes described in WO00/40509 (Japanese patent No. 3355442) are nano-sized carbon tubes having a main skeleton made of carbon, a diameter of 0.1 to 1000nm, and an amorphous structure, and are characterized by having a linear form, and in X-ray diffraction (incident X-ray: cuK. Alpha.), the planar spacing (d 002) of the carbon network plane (002) measured by the diffraction method is represented by

Above (in particular, be->

Above), the diffraction angle (2 θ) is 25.1 degrees or less (particularly, 24.1 degrees or less), and the half-value width of the 2 θ band is 3.2 degrees or more (particularly, 7.0 degrees or more).

Examples of the carbon nanotube (A3) having nanoplatelets include: a sheet-like graphite sheet is a carbon nanotube formed by assembling a plurality of sheets (usually a plurality of sheets) in a patchwork (patchwork) shape or a paper mask (paper mask) shape.

Examples of the iron-carbon composite (A4) include: an iron-carbon composite described in jp 2002-338220 a is an iron-carbon composite comprising (a) a carbon tube selected from a nanosheet carbon tube and a multilayered carbon nanotube having a nested structure and (b) iron carbide or iron, and the iron carbide or iron (b) is filled in the carbon tube (a) in a range of 10 to 90% of the space in the tube.

Among them, from the viewpoint of excellent balance between electrical conductivity and economical efficiency, an iron-carbon composite body composed of at least 1 type of carbon nanotube selected from among the multilayered carbon nanotube and the multilayered carbon nanotube having a nested structure, and iron carbide or iron is particularly preferable.

[ fluorene compound (B) ]

The fluorene compound (B) can improve the handling of the solid additive and the dispersibility of the CNT (a) in the thermoplastic resin by having a fluorene ring as a main skeleton and covering at least a part of the surface of the CNT (a).

The fluorene compound (B) may be fluorene (unsubstituted 9H-fluorene) or a compound having a hydrocarbon group at the 9-position of fluorene as long as it has a fluorene ring as a main skeleton, and is preferably a fluorene compound having a heteroatom-containing functional group via a hydrocarbon group bonded to the 9-position of fluorene, and more preferably a fluorene compound having a heteroatom-containing functional group via 2 hydrocarbon groups bonded to the 9,9-position of fluorene, from the viewpoint of improving dispersibility of CNTs in thermoplastic resins. Heteroatom-containing functional group and X described later ¹ And X ² Exemplary heteroatom-containing functional groups (including preferred embodiments) are the same and may be hydroxyl-containing groups or carboxyl-containing groups (including derivatives such as esters or salts of carboxyl groups). Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group, and examples of the hydrocarbon group for linking the heteroatom-containing functional group to the 9-position of fluorene include: alkylene such as methylene or ethylene, cycloalkylene such as cyclohexylene, arylene (arenediyl) such as phenylene or naphthylene, etc., preferably C _1-4 Alkylene radical, C _6-10 An arylene group.

Such a fluorene compound (B) may be specifically a compound represented by the above formula (1) or a compound represented by the above formula (2).

In the above formula (1), ring Z ¹ And Z ² The aromatic hydrocarbon ring includes a benzene ringAnd monocyclic aromatic hydrocarbon rings and polycyclic aromatic hydrocarbon rings. The monocyclic aromatic hydrocarbon ring and the polycyclic aromatic hydrocarbon ring may be used singly or in combination of 2 or more.

Examples of the polycyclic aromatic hydrocarbon ring include a fused polycyclic aromatic hydrocarbon ring (fused polycyclic hydrocarbon ring) and a ring-assembled aromatic hydrocarbon ring (ring-assembled aromatic hydrocarbon ring).

The fused polycyclic aromatic hydrocarbon ring includes a fused bicyclic aromatic hydrocarbon ring and a fused two-to four-cyclic aromatic hydrocarbon ring. Examples of the fused bicyclic aromatic hydrocarbon ring include a fused bicyclic C such as a naphthalene ring _10-16 Aromatic hydrocarbon rings, and the like.

Examples of the fused tricyclic aromatic hydrocarbon include fused two-to four-ring aromatic hydrocarbon rings such as an anthracene ring and a phenanthrene ring. These fused polycyclic aromatic hydrocarbon rings may be used alone or in combination of 2 or more. Among them, preferred are naphthalene rings and anthracene rings, and particularly preferred is a naphthalene ring.

The ring-aggregated aromatic hydrocarbon ring includes a biaryl ring, and the like. Examples of the biaryl ring include a biphenyl ring, a binaphthyl ring, a 1-phenylnaphthalene ring, a phenylnaphthalene ring such as a 2-phenylnaphthalene ring, and the like _6-12 Aromatic hydrocarbon rings, and the like. Examples of the bis-tri-aromatic hydrocarbon ring include bis-tri-C such as bis-tri-benzene ring _6-12 Aromatic hydrocarbon rings, and the like. These aromatic hydrocarbon rings may be used singly or in combination of 2 or more. Among them, preferred is the group C _6-10 An aromatic hydrocarbon ring, particularly preferably a biphenyl ring.

Ring Z ¹ And ring Z ² The rings may be the same or different, and are generally the same. In the illustrated ring Z ¹ And Z ² Among them, benzene ring, naphthalene ring and biphenyl ring are preferable, and benzene ring is particularly preferable.

Here, ring Z substituted at the 9-position of fluorene ¹ And Z ² The substitution position(s) is not particularly limited. For example, when ring Z ¹ And Z ² When it is a naphthalene ring, it corresponds to ring Z substituted at the 9-position of fluorene ¹ And Z ² The group of (B) may be 1-naphthyl, 2-naphthyl, etc.

As X ¹ And X ² Examples of the heteroatom-containing functional group include a functional group having at least one heteroatom selected from oxygen, sulfur and nitrogen atoms. Hetero atoms contained in such functional groupsThe number of (b) is not particularly limited, but may be usually 1 to 3, preferably 1 or 2.

Examples of the functional group include group- [ (OA) ¹ ) _m1 -Y ¹ ](in the formula, Y ¹ Is hydroxy, glycidoxy, amino, N-substituted amino or mercapto, A ¹ Is alkylene, m1 is an integer of 0 or more), a group- (CH) ₂ ) _m2 -COOR ⁴ (wherein R is ⁴ Hydrogen atom or alkyl group, and m2 is an integer of 0 or more), and the like.

In the group- [ (OA) ¹ ) _m1 -Y ¹ ]In as Y ¹ The N-substituted amino group of (1) can be exemplified by: n-monoalkylamino (N-mono C) groups such as methylamino and ethylamino _1-4 Alkylamino, etc.), N-monohydroxyalkylamino (N-monohydroxy C) such as hydroxyethylamino, etc _1-4 Alkylamino, etc.), and the like.

Alkylene radical A ¹ Including straight or branched chain alkylene groups. Examples of the linear alkylene group include C such as ethylene, trimethylene and tetramethylene _2-6 Alkylene groups, and the like. Among them, linear C is preferable _2-4 Alkylene, more preferably straight chain C _2-3 Alkylene, most preferably ethylene. Examples of the branched alkylene group include branched C groups such as propylene, 1,2-butanediyl and 1,3-butanediyl _3-6 Alkylene groups, and the like. Among them, preferred is branched C _3-4 Alkylene, particularly preferably propylene.

Represents an oxyalkylene group (OA) ¹ ) M1 of the number of repetitions (average molar number of addition) of (a) is 0 or more, and may be selected from the range of, for example, 0 to 15, preferably 0 to 10, and preferred ranges are, in order, as follows: 0 to 8, 0 to 5, 0 to 4, 0 to 3, 0 to 2, 0 or 1, most preferably 1. When m1 is 2 or more, the alkylene group A ¹ May be the same or different. In addition, alkylene groups A ¹ In the ring Z ¹ And Z ² May be the same or different.

In the group- (CH) ₂ ) _m2 -COOR ⁴ In (1) as R ⁴ Examples of the alkyl group include straight-chain or branched C groups such as methyl, ethyl, propyl, isopropyl, butyl and tert-butyl _1-6 Alkyl groups, and the like. Among them, C is preferred _1-4 Alkyl, particularly preferably C _1-2 An alkyl group. M2, which represents the number of repetitions of a methylene group, may be 0 or an integer of 1 or more, and is, for example, 0 to 6, preferably 0 to 4, more preferably 0 to 2, and still more preferably 0. m2 can usually be 0 or 1 to 2. When the number of repetition is an average molar number of addition, it can be selected from the above range.

Among them, the group X has a large effect of improving the dispersibility of the CNT (A) and is excellent in handling properties ¹ And X ² Preferably a group- [ (OA) ¹ ) _m1 -OH](in the formula, A) ¹ Is an alkylene group, m1 is an integer of 0 or more), more preferably a group- [ (OA) ¹ ) _m1 -OH](in the formula, A) ¹ Is ethylene or the like C _2-4 Alkylene group, m1 is an integer of 0 to 5), more preferably a group- [ (OA) ¹ ) _m1 -OH](in the formula, A) ¹ Is ethylene or the like C _2-3 Alkylene, m1 is 0 or 1), most preferably a group- [ (OA) ¹ ) _m1 -OH](in the formula, A) ¹ Is ethylene, and m1 is 1).

In the above formula (1), the ring Z represents ¹ And Z ² Of the above-substituted group X ¹ And X ² N1 and n2 in the number of (a) are each 1 or more, preferably 1 to 3, more preferably 1 or 2, and most preferably 1. The number of substitutions n1 may be the same as or different from the number of substitutions n 2. Radical X ¹ With the group X ² May be the same or different.

Group X ¹ And X ² Can be at ring Z ¹ And Z ² In a suitable position, e.g. when ring Z is substituted ¹ And Z ² In the case of a benzene ring, substitution at the 2-, 3-, 4-, preferably 3-and/or 4-position of the phenyl group is frequently made, when the ring Z is ¹ And Z ² In the case of a naphthalene ring, the substitution is often made at any position of 5 to 8 positions of the naphthalene group, for example, at the 1-position or 2-position of the naphthalene ring (substitution in the relation of 1-naphthyl or 2-naphthyl) with respect to the 9-position of fluorene, substitution is made in the relation of 1, 5, 2, 6 positions with respect to the substituted position, and particularly, when n1 and n2 are 1, the group X is substituted in the relation of 2, 6 positions ¹ And X ² Substitution is often performed. In addition, when n1 and n2 are 2 or moreIn the above, the substitution position is not particularly limited. Further, the aromatic hydrocarbon ring Z is condensed with the ring ¹ And Z ² In (1), the group X ¹ And X ² The substitution position(s) of (b) is not particularly limited, and may be, for example, a substitution on an aromatic hydrocarbon ring bonded at the 9-position of fluorene and/or an aromatic hydrocarbon ring adjacent to the aromatic hydrocarbon ring. For example, biphenyl ring Z ¹ And Z ² The 3-or 4-position of (A) may be bonded to the 9-position of the fluorene when the biphenyl ring Z is present ¹ And Z ² When the 3-position of (A) is bonded to the 9-position of fluorene, the group X ¹ And X ² The substitution position(s) of (b) may be any of the 2-, 4-, 5-, 6-, 2', 3', and 4' -positions, and preferably may be at the 6-position.

In the above formula (1), the substituent R ¹ And R ² May be a non-reactive group. As substituents R ¹ And R ² Examples thereof include: halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, and tert-butyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; aryl groups such as phenyl, methylphenyl (tolyl), dimethylphenyl (xylyl), biphenyl, and naphthyl; aralkyl groups such as benzyl and phenethyl; alkoxy groups such as methoxy, ethoxy, propoxy, n-butoxy, isobutoxy and tert-butoxy; aryloxy groups such as phenoxy group; cycloalkoxy groups such as cyclohexyloxy; aryloxy groups such as phenoxy group; aralkyloxy such as benzyloxy; alkylthio groups such as methylthio group; cycloalkylthio groups such as cyclohexylthio; arylthio groups such as thiophenoxy; aralkylthio groups such as benzylthio; acyl groups such as acetyl; a nitro group; a cyano group; and substituted amino groups such as methylamino groups. These substituents may be used alone or in combination of 2 or more.

These substituents R ¹ And R ² In (1), typically: a halogen atom; hydrocarbon groups such as alkyl, cycloalkyl, aryl, and aralkyl groups; an alkoxy group; an acyl group; a nitro group; a cyano group; substituted amino groups, and the like. These substituents R ¹ And R ² Among them, preferred is a linear or branched C _1-4 Alkyl, straight or branched C _1-4 The alkoxy group is particularly preferably a straight or branched C group such as a methyl group _1-3 An alkyl group. To illustrate, when the substituent R ¹ And R ² When it is aryl, substitutedRadical R ¹ And R ² Can be combined with ring Z ¹ And Z ² Together form the ring-assembled aromatic hydrocarbon ring described above. Substituent R ¹ With a substituent R ² May be the same or different.

Substituent R ¹ And R ² Can be based on the ring Z ¹ And Z ² The number of (b) is appropriately selected, and may be, for example, an integer of about 0 to 8, for example, 0 to 4, preferably 0 to 3, more preferably 0 to 2, and most preferably 0 or 1. In particular when p1 and p2 are 1, ring Z ¹ And Z ² Can be benzene ring, naphthalene ring or biphenyl ring, substituent R ¹ And R ² May be a methyl group.

As substituents R ³ Examples thereof include: a cyano group; halogen atoms such as fluorine atom, chlorine atom, and bromine atom; a carboxyl group; alkoxycarbonyl groups such as methoxycarbonyl group; alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, and tert-butyl; aryl groups such as phenyl and the like. Substituent R ³ May be a non-reactive group. These substituents may be used alone or in combination of 2 or more.

These substituents R ³ Among them, preferred is a carboxyl group, a linear or branched C _1-4 Alkyl radical, C _1-4 Alkoxy-carbonyl, cyano, halogen atom, particularly preferably C such as methyl _1-3 An alkyl group. The number of substitution k may be an integer selected from 0 to 8, and is, for example, 0 to 6, preferably 0 to 4, more preferably 0 to 2, further preferably 0 or 1, and most preferably 0. When the number of substitution k is 2 or more, the substituent R ³ May be the same as or different from each other. In addition, the substituent R ³ The substitution position(s) is not particularly limited, and may be 2-to 7-positions of the fluorene ring, for example, 2-, 3-and/or 7-positions.

In the above formula (2), A is ² And A ³ Examples of the alkylene group include: straight-chain or branched alkylene, e.g. methylene, ethylene, trimethylene, propylene, 2-ethylethylene, 2-methylpropane-1,3-diyl _1-8 An alkylene group. Preferred alkylene groups are straight or branched C _1-6 Alkylene groups, more preferably methylene, ethylene, trimethylene, propylene, ethylene, propylene, and mixtures thereof,Straight or branched C such as 2-methylpropane-1,3-diyl _1-4 An alkylene group.

As alkylene radicals A ² And A ³ Examples of the substituent(s) include aryl groups such as phenyl and cycloalkyl groups such as cyclohexyl.

Alkylene radical A ² And A ³ Is a linear or branched C such as ethylene or propylene _1-4 Alkylene groups are often the case. Alkylene having substituent(s) A ² And A ³ May be 1-phenylethylene, 1-phenylpropane-1,2-diyl, etc. Among them, preferred is C such as ethylene _1-3 An alkylene group. Alkylene radical A ² With alkylene radicals A ³ May be the same or different.

As the group X of the above formula (2) ¹ And X ² X is exemplified as the above formula (1) ¹ And X ² Exemplary groups. In the above-mentioned group X ¹ And X ² Of these, the group-COOR is preferred ⁴ (in the formula, R ⁴ Represents a hydrogen atom or an alkyl group). As the alkyl group, preferred is C such as methyl, ethyl, propyl, etc _1-3 Alkyl, more preferably C such as methyl _1-2 An alkyl group.

In the above formula (2), the substituent R ³ And the coefficient k thereof (including preferred embodiments) are respectively equal to R described in the above formula (1) ³ And k are the same.

Among them, preferred fluorene compounds are, from the viewpoint of high compatibility between conductivity and mechanical properties: the group X in the above formula (1) ¹ And X ² Is a group- [ (OA) _m1 -OH]A group X in the above formula (2) ¹ And X ² Is a group-COOR ⁴ The compound of (1). In particular, the compound represented by the formula (1) is easy to realize high conductivity, and the compound represented by the formula (2) can improve mechanical properties in a wide range of compounding ratio.

As the group X in the above formula (1) ¹ And X ² Is a group- [ (OA) _m1 -OH]Examples of the compound (1) include: 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (5-hydroxy-1-naphthyl) fluorene, 9,9-bis (6-hydroxy-2-naphthyl) fluorene and the like 9,9-bis (hydroxy C) _6-12 Aryl) fluorene; 9,9-bis (3,4-dihydroxyphenyl) fluorene, 9,9-Bis (di-or trihydroxy C) _6-12 Aryl) fluorene; 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, 9,9-bis (mono-or di-C) _1-4 Alkyl-hydroxy C _6-12 Aryl) fluorene; 9,9-bis (C) such as 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene and 9,9-bis (4-phenyl-3-hydroxyphenyl) fluorene _6-12 Aryl-hydroxy C _6-12 Aryl) fluorene; 9,9-bis [4- (2-hydroxyethoxy) phenyl]Fluorene, 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl]9,9-bis (hydroxy (poly) C) s, e.g., fluorene _2-4 alkoxy-C _6-12 Aryl) fluorene; 9,9-bis [ 3-methyl-4- (2-hydroxyethoxy) phenyl]Fluorene, etc. 9,9-bis (C) _1-4 Alkyl-hydroxy (poly) C _2-4 alkoxy-C _6-12 Aryl) fluorene; 9,9-bis [ 3-phenyl-4- (2-hydroxyethoxy) phenyl]Fluorene, 9,9-bis [ 4-phenyl-3- (2-hydroxyethoxy) phenyl]Fluorene, 9,9-bis (C) _6-12 Aryl-hydroxy (poly) C _2-4 alkoxy-C _6-12 Aryl) fluorene, and the like. These fluorene compounds are highly compatible in both conductivity and mechanical properties, and among them, 9,9-bis [4- (2-hydroxyethoxy) phenyl ] is preferable in applications requiring high conductivity]Fluorene, etc. 9,9-bis (hydroxy (poly) C _2-4 Alkoxy-phenyl) fluorene.

As the group X in the above formula (2) ¹ And X ² Is a group-COOR ⁴ Examples of the compound (1) include: 9,9-bis (carboxy C) such as 9,9-bis (2-carboxyethyl) fluorene and 9,9-bis (2-carboxypropyl) fluorene _2-6 Alkyl) fluorene; 5363 9,9-bis (C), such as 9,9-bis (2-methoxycarbonylethyl) fluorene, 9,9-bis (2-methoxycarbonylpropyl) fluorene and the like _1-3 Alkoxycarbonyl group C _2-6 Alkyl) fluorene, and the like. These compounds improve mechanical properties even in a small amount. Among them, 9,9-bis (C) such as 9,9-bis (2-methoxycarbonylethyl) fluorene is preferable in applications where high conductivity and high mechanical properties are required at the same time _1-2 Alkoxycarbonyl group C _2-4 Alkyl) fluorene.

These fluorene compounds (B) may be used alone or in combination of 2 or more. In the description, "(poly) alkoxy" is used in a sense including both alkoxy and polyalkoxy.

The proportion of the fluorene compound (B) is 1 to 200 parts by mass, preferably 3 to 150 parts by mass, and particularly preferably selected from a range of about 5 to 100 parts by mass, based on 100 parts by mass of the CNT (a).

The proportion of the fluorene compound (B) may be 50 parts by mass or less, preferably 1 to 40 parts by mass, and more preferably 3 to 30 parts by mass, based on 100 parts by mass of the CNT (a). When the fluorene compound (B) is blended in the CNT (a) in such a ratio, the impact strength can be remarkably improved by the fiber-reinforcing effect of the CNT (a) according to the uniform dispersibility of the CNT (a). Therefore, this ratio is particularly useful in applications requiring a high degree of impact strength.

The proportion of the fluorene compound (B) may be 30 parts by mass or more, for example, 35 to 100 parts by mass, preferably 40 to 80 parts by mass, and more preferably 40 to 60 parts by mass, based on 100 parts by mass of the CNT (a). When the fluorene compound (B) is blended in the CNTs (a) in such a ratio, the CNTs form a network in addition to the uniform dispersibility of the CNTs (a), and the electrical conductivity can be remarkably improved while maintaining the mechanical properties. Therefore, this ratio is particularly useful in applications requiring high conductivity. In particular when the fluorene compound (B) is a group X in the above formula (1) ¹ And X ² Is a group- [ (OA) _m1 -OH]A group X in the above formula (2) ¹ And X ² Is a group-COOR ⁴ When the fluorene compound is used in such a ratio, both conductivity and mechanical properties can be highly satisfied.

(characteristics of solid additive or additive composition)

In the present invention, since at least a part of the surface of the CNT (a) is covered or treated with the fluorene compound (B) (or since at least a part of the surface of the CNT (a) is in contact with the fluorene compound (B)), the dispersibility of the CNT (a) in the thermoplastic resin can be improved. In the present specification and claims, "CNT (a) having at least a part of the surface covered or treated with a fluorene compound (B)" may be referred to as a composite of CNT (a) and fluorene compound (B).

In the composite in which at least a part of the surface of the CNT (a) is covered with the fluorene compound (B), the coverage of the surface of the CNT (a) (the outer surface excluding the inner wall in the tube) may be 5 area% or more, and the preferable ranges are as follows: more than 10 area%, more than 20 area%, more than 30 area%, more than 50 area%, more than 80 area%, more than 90 area%, most preferably the entire surface coverage (entire surface coverage). When the coverage is too small, the dispersibility of the solid additive in the thermoplastic resin may be reduced. In the present specification and claims, the coverage of the surface of the CNT (a) with the fluorene compound (B) can be calculated by observing the surface of the CNT (a) in a predetermined region based on SEM or Transmission Electron Microscope (TEM) photographs.

In the composite, the average thickness of the coating film formed of the fluorene compound (B) may be 1nm or more, for example, 1 to 1000nm, preferably 3 to 800nm, and more preferably about 5 to 500 nm. When the thickness of the coating film is too thin, the dispersibility of the CNT (a) in the composition may be reduced.

In the present specification and claims, the thickness of the coating of the composite can be measured by a method of calculating the thickness of the coating in a predetermined region by observing the SEM or TEM photograph.

In the composite, the fluorene compound (B) and the CNT (a) are preferably not combined by strong chemical bonds such as covalent bonds, but combined by relatively moderate bonding such as pi-pi interaction (stacking), van der waals force, and hydrogen bonds. Presume that: when a solid additive which is compounded by relatively mild bonding such as pi-pi interaction is melt-kneaded into a thermoplastic resin, the fluorene compound (B) uniformly disperses CNTs (a) in the thermoplastic resin and has an appropriate degree of freedom with respect to CNTs (a), so that the conductivity of the thermoplastic resin can be improved without inhibiting the development of the conductivity of CNTs (a).

In the present specification and claims, the presence or absence of a covalent bond in the complex can be easily determined by a method of determining whether or not the fluorene compound (B) can be extracted with a solvent such as toluene.

In the solid additive of the present invention, the fluorene compound (B) preferably has an amorphous structure. The fluorene compound (B) may generally have a crystal structure in the state of the raw material at the stage before mixing with the CNT (a), but preferably has an amorphous structure among solid additives, and becomes an amorphous structure by being combined with the CNT (a), thereby generating a solid additive that can be uniformly dispersed in a thermoplastic resin.

In the present specification and claims, the crystal structure of the solid additive can be evaluated by a Differential Scanning Calorimetry (DSC) method, and specifically can be evaluated by the method described in the examples described later.

The solid additive of the present invention may contain a component (other component) other than the thermoplastic resin containing no fluorene in addition to the CNT (a) and the fluorene compound (B) as long as the effect of the present invention is not impaired, and the total proportion of the CNT (a) and the fluorene compound (B) in the solid additive may be 30 mass% or more, for example, 50 mass% or more, preferably 80 mass% or more, more preferably 90 mass% or more, and most preferably 100 mass% (only the CNT (a) and the fluorene compound (B)) from the viewpoint of improving the dispersibility of the solid dispersant in the thermoplastic resin.

Examples of other components include: thermoplastic resin, conductive agent, filler, stabilizer, colorant, flame retardant, etc. commonly used in addition to CNTs. The thermoplastic resin may be a thermoplastic resin of the resin composition described later, or may be a fluorene-free thermoplastic resin similar to the thermoplastic resin contained in the resin composition. These other components can be used alone or in combination of 2 or more. The total proportion of the other components in the solid additive may be 50% by mass or less, for example, 30% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less, and most preferably 5% by mass or less. When other components are contained, the proportion of the other components in the solid additive may be 0.1 to 50% by mass, for example, 1 to 10% by mass.

The solid additive of the present invention has high mechanical strength because the CNT (a) and the fluorene compound (B) are combined, and the compressive strength can be 1N or more, and the preferable ranges are as follows: 1.2 to 10N, 1.5 to 9N, 2 to 8N, 3 to 7N and 5 to 6.5N. When the compressive strength is too low, the operability may be reduced.

In the present specification and claims, the compressive strength of the solid additive can be measured by a method of calculating the compressive strength (N) as a point at which the solid additive collapses due to compression using a digital dynamometer manufactured by Imada, and specifically, can be measured by a method described in examples described later.

The bulk density of the solid additive of the invention is, for example, from 0.1 to 0.3g/m ³ Preferably 0.15 to 0.25g/m ³ . When the bulk density is too large, the solid additive may be difficult to uniformly disperse in the thermoplastic resin.

Note that, in the present specification and claims, the bulk density of the solid additive is determined by a value obtained by dividing the mass of the solid additive filled by the following method by the volume of the solid additive.

Using a measuring cylinder as a measuring vessel, a predetermined mass of the solid additive was charged, and then the bottom of the measuring cylinder was repeatedly dropped 20 times from a height of 1cm from the bottom surface. In the case where the change in volume occupied by the solid additive was visually observed, the drop was repeated 20 times from a height of 1cm, and the operation was terminated when no change in volume was confirmed.

The form of the solid additive is not particularly limited, and is usually in the form of particles, irregular particles, or the like, from the viewpoint of handling and the like. The average particle diameter is, for example, 0.5 to 20mm, preferably 1 to 15mm, and more preferably 1.5 to 10mm.

The solid additive (predispersion or mixture) of the present invention can impart high conductivity to the thermoplastic resin and thus can be preferably used as a conductive agent.

[ method for producing solid additive ]

The solid additive of the present invention can be obtained by mixing CNT (a) and fluorene compound (B). When the solid additive of the present invention further contains other components, the CNT (a) and the fluorene compound (B) may be mixed with other components.

The mixing method is not particularly limited, and mixing may be carried out by a conventional mixing method in the presence or absence of a solvent. When mixing is performed in the absence of a solvent, it is preferable to heat the mixture to a temperature of not less than the melting point of the fluorene compound (B) to perform melt kneading. Among these methods, a method of mixing in the presence of a solvent is preferred from the viewpoint of convenience and the like.

Examples of the solvent include: water; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, and cyclohexanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, ethyl propyl ketone, di-n-propyl ketone, diisopropyl ketone, and cyclohexanone; nitriles such as acetonitrile, propionitrile, and benzonitrile; cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve; amides such as formamide, acetamide, dimethylformamide, and dimethylacetamide; sulfoxides such as dimethyl sulfoxide; sulfolanes such as sulfolane; aliphatic hydrocarbons such as pentane, hexane, heptane and octane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; and halogenated hydrocarbons such as dichloromethane, dichloroethane, trichloroethylene, dichlorobenzene, and the like. These solvents may be used alone or in combination of 2 or more.

Among these solvents, water, alcohols, hydrocarbons, halogenated hydrocarbons, and the like are widely used, and from the viewpoint of easy production of a complex in which the surface of the CNT (a) is covered with the fluorene compound (B), a solvent in which the fluorene compound (B) is soluble is preferable, and from the viewpoint of workability and the like, an aqueous solvent is preferable.

The solvent in which the fluorene compound (B) can be dissolved can be appropriately selected depending on the kind of the fluorene compound (B), and examples thereof include: alcohols such as methanol, aliphatic hydrocarbons such as hexane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene, and halogenated hydrocarbons such as methylene chloride. Examples of the aqueous solvent include C such as water and methanol _1-3 Alkanols, and the like. Among them, aromatic hydrocarbons such as toluene, water, and C such as methanol are preferable _1-2 An alkanol, particularly preferably water.

The proportion of the solvent may be selected from a range of about 10 to 10000 parts by mass, for example, 100 to 1000 parts by mass, preferably 200 to 800 parts by mass, and more preferably 300 to 500 parts by mass, based on 100 parts by mass of the CNT (a). When the proportion of the solvent is too small, it may be difficult to manufacture the composite, whereas when the proportion of the solvent is too large, productivity may be lowered.

As the mixing method, a conventional method may be used, and: a method of mixing or kneading the CNT (a), the fluorene compound (B), and the solvent using an extruder such as a pelletizing extruder, a mixing roll, a kneader, or a mixer such as a banbury mixer; a method of immersing the CNT (a) in a solvent containing the fluorene compound (B), and the like. When an extruder is used, the CNT (a), the fluorene compound (B), and the solvent may be charged and mixed together, or the CNT (a) and the fluorene compound (B) may be mixed in advance, and then the solvent may be charged and mixed together. The peripheral speed of the screw in the extruder is, for example, 1 to 300 m/min, preferably 50 to 150 m/min. The mixing temperature is not particularly limited, and may be normal temperature.

The mixture obtained by these methods can be subjected to a drying treatment to distill off the solvent, thereby preparing a solid additive. The drying treatment may be natural drying, but a method of heating and/or reducing pressure is preferable from the viewpoint of productivity and the like.

As a method of heating, a conventional method, for example, a method using a static hot air dryer, a vacuum dryer, a rotary evaporator, a conical dryer, a hybrid dryer such as a Nauta (Nauta) dryer, or the like can be used. The heating temperature may be appropriately selected depending on the kind of the solvent, and is, for example, 40 to 300 ℃, preferably 60 to 180 ℃, and more preferably 80 to 160 ℃.

As the method of reducing the pressure, a conventional method such as a method using an oil pump, an oilless pump, an aspirator, or the like can be used. The pressure in the pressure reduction method is, for example, 0.00001 to 0.05MPa, preferably 0.00001 to 0.03MPa.

When a lump of the solid additive is obtained by using a mixer, the lump of the solid additive may be granulated by pulverization or the like in order to improve the handling properties.

[ resin composition ]

The resin composition of the present invention comprises a thermoplastic resin and the above solid additive. The thermoplastic resin may be a fluorene-free thermoplastic resin.

Such thermoplastic resins are not particularly limited, and include: poly alpha-C such as polyethylene, polypropylene, polymethylpentene _2-10 Olefin resins such as olefins, cyclic polyolefins such as cyclopentadiene resins and norbornene resins; vinyl resins such as polyvinyl chloride, polyvinylidene chloride and vinyl acetate resins; polystyrene, acrylonitrile-styrene resin, styrene-methyl methacrylate resin, ABS resinAromatic vinyl resins such as fats; acrylic resins such as homo-and copolymers of (meth) acrylic monomers such as polymethyl methacrylate and (meth) acrylic acid- (meth) acrylate, and methyl methacrylate-styrene copolymers; polycarbonate resins such as bisphenol a polycarbonate; poly C such as polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethanol terephthalate and polyethylene naphthalate _6-10 Aromatic acid C _2-10 Polyester resins such as alkylene glycol esters or copolyesters, or fluorene-containing polyesters, polyarylates, and liquid crystal polyesters; polyacetal resins such as polyoxymethylene; polyamide resins such as nylon 6, nylon 66, nylon 46, nylon 6T, and nylon MXD; sulfone resins such as polysulfone and polyethersulfone; phenylene ether resins such as polyphenylene ether and modified polyphenylene ether; thermoplastic elastomers such as styrene-based thermoplastic elastomers and olefin-based thermoplastic elastomers; fluorine resins such as polytetrafluoroethylene.

These thermoplastic resins may be used alone or in combination of 2 or more. Among these thermoplastic resins, polypropylene-based resins, polyamide-based resins, and polycarbonate-based resins are preferred, and polycarbonate-based resins are particularly preferred.

As the polycarbonate-based resin, a commonly used polycarbonate, for example, an aromatic polycarbonate based on a diphenol or a bisphenol, and the like can be used.

Examples of the bisphenols include: bis (hydroxyphenyl) alkanes, bis (hydroxyaryl) cycloalkanes, bis (hydroxyaryl) ethers, bis (hydroxyaryl) ketones, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, bis (hydroxyphenyl) thioethers, and the like.

Examples of bis (hydroxyphenyl) alkanes include: bis (hydroxyaryl) C.sub.C.sub.p.sub.f such as bis (4-hydroxyphenyl) methane (bisphenol F), 1,1-bis (4-hydroxyphenyl) ethane (bisphenol AD), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxytoluene) propane, 2,2-bis (4-hydroxyxylyl) propane, etc _1-6 Alkanes, and the like.

Examples of bis (hydroxyaryl) cycloalkanes include: bis (hydroxyaryl) C such as 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane _4-10 Cycloalkanes, and the like.

Examples of bis (hydroxyaryl) ethers include: bis (4-hydroxyphenyl) ether, and the like.

Examples of bis (hydroxyaryl) ketones are: 4,4' -bis (hydroxyphenyl) ketone, and the like.

Examples of bis (hydroxyphenyl) sulfones include: bis (4-hydroxyphenyl) sulfone (bisphenol S), and the like.

Examples of bis (hydroxyphenyl) sulfoxides include: bis (4-hydroxyphenyl) sulfoxide, and the like.

Examples of bis (hydroxyphenyl) sulfides include: bis (4-hydroxyphenyl) sulfide, and the like.

These bisphenols may be C _2-4 An alkylene oxide adduct. These bisphenols may be used alone or in combination of 2 or more. Among these bisphenols, bis (hydroxyaryl) C such as bisphenol A is preferred _1-6 An alkane.

The polycarbonate-series resin may be a polyester carbonate-series resin obtained by copolymerizing a dicarboxylic acid component (an aliphatic, alicyclic or aromatic dicarboxylic acid or an acid halide thereof, etc.). These polycarbonate-based resins may be used alone or in combination of 2 or more. The preferred polycarbonate resin is bis (hydroxyphenyl) C _1-6 The resin based on alkanes is, for example, a bisphenol A polycarbonate resin.

The proportion of the solid additive may be selected depending on the intended thermoplastic resin, and is, for example, 1 to 20 parts by mass, preferably 1.5 to 15 parts by mass, based on 100 parts by mass of the polycarbonate resin. When the proportion of the solid additive is too small, the effect of improving the electrical conductivity and mechanical properties may be reduced, whereas when the proportion of the solid additive is too large, the mechanical properties may be reduced.

The proportion of the CNT (a) is, for example, 0.1 to 15 parts by mass, preferably 0.3 to 10 parts by mass, based on 100 parts by mass of the thermoplastic resin. When the ratio of the CNTs is too small, the effect of improving the electrical conductivity and mechanical properties may be reduced, whereas when the ratio of the CNTs is too large, the mechanical properties may be reduced.

Unlike conventional resin compositions containing CNTs as a conductive agent, the resin composition of the present invention is a composite containing a fluorene compound (B) and CNTs (a) uniformly and finely dispersed in a thermoplastic resin. Therefore, the resin composition of the present invention can improve mechanical properties such as impact strength, and by adjusting the proportion of the fluorene compound (B) in the solid additive, it is possible to achieve both electrical conductivity and mechanical properties that cannot be achieved by conventional resin compositions.

That is, the resin composition of the present invention can also improve conductivity, and when the thermoplastic resin is a polycarbonate-based resin, the volume resistivity can be 10 ¹² Omega cm or less, e.g. 10 ¹¹ Omega cm or less, preferably 10 ¹⁰ Omega cm or less, more preferably 10 ⁸ Omega cm or less, most preferably 10 ⁷ Omega cm or less. In addition, the volume resistivity is, for example, 10 from the viewpoint of productivity and the like ² ～10 ¹² Ω · cm, preferably 10 ³ ～10 ¹⁰ Ω · cm, more preferably 10 ⁴ ～10 ⁸ Omega cm, most preferably 10 ⁵ ～10 ⁷ Ω·cm。

In the present specification and claims, the volume resistivity is measured by a resistivity meter ("Hiresta" or "Loresta") manufactured by mitsubishi chemical analysis.

The resin composition of the present invention is excellent in impact resistance, and when the thermoplastic resin is a polycarbonate-based resin, the Charpy impact strength may be 30kJ/m ² Above, for example, 40kJ/m ² Above, preferably 50kJ/m ² Above, more preferably 60kJ/m ² Above, most preferably 70kJ/m ² As described above. Further, from the viewpoint of productivity and the like, the Charpy impact strength is, for example, 30 to 120kJ/m ² Preferably 50 to 100kJ/m ² More preferably 60 to 90kJ/m ² Most preferably 70 to 85kJ/m ² . Further, in applications requiring high impact resistance, the Charpy impact strength may be 80kJ/m ² Above, for example, 80 to 90kJ/m ² 。

In the present specification and claims, the charpy impact strength can be measured according to JIS K7111, and specifically, can be measured by the method described in the examples described later.

The resin composition of the present invention has high flowability and excellent workability, and the flowability (MVR) of the resin composition is set to ISO1133[300 ℃,1.2kg load (11.8N)]For example, 3 to 20cm ³ 10 minutes, preferably 5 to 15cm ³ A time of 10 minutes, more preferably 8 to 12cm ³ 10 minutes.

In the resin composition, the form of the CNTs (a) and the fluorene compound (B) contained in the solid additive is not particularly limited, and the form before melt-kneading in which at least a part of the CNTs (a) and the fluorene compound (B) are combined may be maintained or may be changed by melt-kneading. When the change occurs, the CNT (a) and the fluorene compound (B) may be free in at least a part of the composite, and the CNT (a) and the fluorene compound (B) in a free state may also be composite. Among them, from the viewpoint of improving the conductivity of the resin composition, a state in which CNTs are uniformly dispersed by releasing a part of the composite is preferable. In any of the embodiments, in the present invention, the presence of the fluorene compound (B) allows the CNTs (a) to be uniformly and finely dispersed in the thermoplastic resin, thereby improving mechanical properties such as impact strength. Further, when the ratio of the fluorene compound (B) in the solid additive is adjusted, high conductivity and mechanical properties can be achieved at the same time, and by adjusting the ratio of the fluorene compound (B), conductivity can be further improved by high networking of CNTs.

The resin composition of the present invention may contain conventional additives in addition to the solid additives. As common additives, there may be exemplified: conductive agents other than CNTs, stabilizers, fillers, release agents, lubricants, antistatic agents, flame retardants, plasticizers, dispersants, flow control agents, leveling agents, antifoaming agents, surface modifiers, and hydrophobicity-improving agents. These additives may be used singly or in combination of 2 or more. The total amount of the additives is, for example, 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the thermoplastic resin.

The resin composition of the present invention can be produced by melt-kneading the thermoplastic resin and the solid additive by a conventional method. That is, the resin composition of the present invention can be obtained through the following steps: a compounding step of compounding the CNT (A) and the fluorene compound (B) by mixing them to prepare a solid additive; and a melt-kneading step of melt-kneading the thermoplastic resin and the obtained solid additive to prepare a resin composition.

In the melt kneading step, as a kneading method, there can be used: and a method using an extruder such as a mixing roll, a kneader, a Banbury mixer, a single-screw or twin-screw extruder, and the like. The conditions for the melt kneading may be appropriately selected depending on the kind of the thermoplastic resin, and a resin composition in which the solid additive containing the CNT (a) is uniformly and finely dispersed can be easily obtained by a conventional method. The melt-kneaded resin composition can be molded by a conventional molding method such as injection molding. The melt kneading and molding conditions are not particularly limited, and conventional conditions may be employed depending on the kind of the thermoplastic resin.

Examples

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The raw materials and evaluation methods used are as follows.

(use of raw materials)

Kumho CNT: multilayered carbon nanotube, "K-Nanos 100T" manufactured by Kumho Co., ltd "

Nanocyl CNT: multilayered carbon nanotube, NC7000 manufactured by Nanocyl "

And BPEF:9,9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene, osaka gas chemical Co., ltd

FDP-m:9,9-bis (2-methoxycarbonylethyl) fluorene, osaka gas chemical Co., ltd

BCF:9,9-bis (4-hydroxy-3-methylphenyl) fluorene, manufactured by Osaka gas chemical Co., ltd

BNF:9,9-bis (6-hydroxy-2-naphthyl) fluorene, osaka gas chemical Co., ltd

PC: bisphenol A type polycarbonate, mitsubishi engineering plastics corporation "Iipilon PC S-3000".

[ Crystal Structure ]

The crystal structure was evaluated by a Differential Scanning Calorimeter (DSC). The DSC was evaluated by using "EXTAR DSC6220" manufactured by Seiko Instruments as a device, placing the sample in an aluminum pan, and measuring the thermal change under a nitrogen atmosphere at a temperature rise rate of 10 ℃/min and a measurement temperature range of 30 to 280 ℃.

[ compressive Strength ]

The solid additives obtained in examples and comparative examples were measured for compressive strength (N) using a digital load cell manufactured by Imada. The measurement was performed 10 times in the vertical direction and the horizontal direction of the solid additive, and 6 values were obtained excluding the maximum 2 values and the minimum 2 values, and the average value of the 6 values was calculated.

[ volume resistivity (conductivity) ]

The resin compositions obtained in examples and comparative examples were measured for volume resistivity (Ω/□) by a resistivity meter ("Hiresta" or "Loresta") manufactured by mitsubishi chemical analysis and science.

[ Sharp impact Strength ]

The resin compositions obtained in examples and comparative examples were measured 10 times in accordance with JIS K7111 using a digital impact tester (manufactured by toyoyo Seiki Seisaku-Sho Ltd.), and the average of the 10 measurements was assumed to be the charpy impact strength (kJ/m) ² ). Note that, the notch shape: type a, pendulum energy: 0.5J.

Comparative example 1

Kumho CNT 400g and toluene 1600g were charged into a Henschel mixer (manufactured by Universe corporation), mixed at room temperature for 5 minutes, and then the resulting mixture was pelletized at room temperature using an extrusion pelletizer ("Disc cutter" manufactured by Dulton corporation). The granulated substance was dried at 180 ℃ under reduced pressure for 24 hours, thereby obtaining a solid additive.

Example 1

BPEF20 g is dissolved in methanol 1600g, further input Kumho CNT 400g, make the solution absorbed in Kumho CNT, then use the evaporator distillation to remove methanol, at 180 degrees C heating for 24 hours, thereby get the solid additive.

Example 2

A solid additive was obtained in the same manner as in example 1 except that the blending amount of BPEF was changed from 20g to 50 g.

Example 3

A solid additive was obtained in the same manner as in example 1 except that the blending amount of BPEF was changed from 20g to 100 g.

An SEM photograph (5000 ×) of the solid additive obtained in example 3 is shown in fig. 1. When compared with the SEM photograph (5000 times) of the CNT as the raw material shown in fig. 2 and the SEM photograph (5000 times) of the BPEF as the raw material shown in fig. 3, it can be observed in fig. 1 that the surface of the CNT is covered with the BPEF.

Example 4

Kumho CNT 400g and BPEF200g were put into a Henschel mixer (manufactured by Universe corporation), mixed at room temperature for 3 minutes, and then further added with water 1600g, and mixed at room temperature for 2 minutes. The resulting mixture was pelletized at room temperature using an extrusion pelletizer ("Disc cutter" manufactured by DULTON Co., ltd.). The granulated substance was dried at 180 ℃ under reduced pressure for 24 hours, thereby obtaining a solid additive.

An SEM photograph (5000 times) of the solid additive obtained in example 4 is shown in fig. 4. The coverage of the CNTs by BPEF was higher compared to the solid additive of example 3, and it was observed that BPEF covered almost the entire surface of the CNTs.

In addition, the DSC diagram of the resulting solid additive is shown in fig. 5. Meanwhile, a DSC diagram of CNT as a raw material is shown in fig. 6, and a DSC diagram of BPEF as a raw material is shown in fig. 7, but it can be confirmed that the peak observed in BPEF disappears and the solid additive obtained in example 4 has an amorphous structure.

The results of measuring the compressive strength of the solid additives obtained in comparative example 1 and examples 1 to 4 are shown in table 1.

[ Table 1]

As can be seen from the results of table 1, the solid additive of the example, which is a composite in which the surface of the CNT is covered with BPEF, has higher compressive strength than the solid additive of comparative example 1, which does not contain BPEF.

Example 5

A solution prepared by dissolving Kumho CNT 400g and FDP-m20g in methanol 1600g was put into a Henschel mixer (manufactured by Universe corporation), and the mixture was mixed at room temperature for 5 minutes. The resulting mixture was then granulated at room temperature using an extrusion granulator ("Disc cutter" manufactured by DULTON Co.). The granulated substance was dried at 90 ℃ under reduced pressure for 24 hours, thereby obtaining a solid additive.

Example 6

A solid additive was obtained in the same manner as in example 5, except that the blending amount of FDP-m was changed from 20g to 50 g.

Example 7

A solid additive was obtained in the same manner as in example 5, except that the blending amount of FDP-m was changed from 20g to 100 g.

Example 8

A solid additive was obtained in the same manner as in example 5, except that the blending amount of FDP-m was changed from 20g to 200 g.

An SEM photograph (5000 ×) of the solid additive obtained in example 8 is shown in fig. 8. When compared with the SEM photograph (5000X) of FDP-m as a starting material shown in FIG. 9, it can be observed in FIG. 8 that FDP-m covers almost the entire surface of CNT.

Fig. 10 shows a DSC diagram of the obtained solid additive. While a DSC chart of FDP-m as a raw material is also shown in FIG. 11, it was confirmed that the peak observed in FDP-m disappeared and the solid additive obtained in example 8 became an amorphous structure.

Example 9

A solid additive was obtained in the same manner as in example 5, except that FDP-m was changed to BCF.

Example 10

A solid additive was obtained in the same manner as in example 6, except that FDP-m was changed to BCF.

Example 11

A solid additive was obtained in the same manner as in example 7, except that FDP-m was changed to BCF.

Example 12

A solid additive was obtained in the same manner as in example 8, except that FDP-m was changed to BCF.

An SEM photograph (5000 ×) of the solid additive obtained in example 12 is shown in fig. 12. When compared with the SEM photograph (5000 times) of BCF as a raw material shown in fig. 13, it can be observed in fig. 12 that BCF covers almost the entire surface of CNT.

Fig. 14 shows a DSC diagram of the obtained solid additive. While fig. 15 also shows a DSC chart of BCF as a raw material, it was confirmed that the solid additive obtained in example 12 had an amorphous structure due to disappearance of the peak observed in BCF.

Example 13

A solid additive was obtained in the same manner as in example 5 except that FDP-m was changed to BNF.

Example 14

A solid additive was obtained in the same manner as in example 6, except that FDP-m was changed to BNF.

Example 15

A solid additive was obtained in the same manner as in example 7, except that FDP-m was changed to BNF.

Example 16

A solid additive was obtained in the same manner as in example 8, except that FDP-m was changed to BNF.

An SEM photograph (5000 ×) of the solid additive obtained in example 16 is shown in fig. 16. When compared with the SEM photograph (5000 x) of BNF as the raw material shown in fig. 17, BNF can be observed to cover almost the entire surface of CNT in fig. 16.

In addition, a DSC chart of the obtained solid additive is shown in fig. 18. Also, in fig. 19, a DSC diagram of BNF as a raw material is shown, but the peak observed in BNF of the solid additive obtained in example 16 disappeared and it was confirmed that the solid additive had an amorphous structure.

Comparative example 2

A resin composition (kneaded product or test piece) was obtained by adding 2 parts by mass of Nanocyl CNT to 100 parts by mass of PC and injection-molding the mixture using an injection molding machine ("NEX 50I II" electric high performance injection molding machine manufactured by Nichisu resin industries, ltd.) at a cylinder temperature of 290 ℃, a mold temperature of 90 ℃ and a filling rate of 20 mm/s.

Comparative example 3

In the case where no solid additive was prepared, nanocyl CNT 2 parts by mass and BPEF 1 parts by mass were added to PC 100 parts by mass, and injection molding was performed in the same manner as in comparative example 2 to obtain a resin composition.

Examples 17 to 32

The solid additives obtained in examples 1 to 16 were added to 100 parts by mass of PC so that the ratio of Kumho CNT was 2 parts by mass, and injection molding was performed in the same manner as in comparative example 2 to obtain a resin composition.

The results of measuring the volume resistivity and the Charpy impact strength of the resin compositions obtained in comparative examples 2 to 3 and examples 17 to 32 are shown in Table 2.

[ Table 2]

As is clear from the results in Table 2, the impact resistance of the injection-molded articles of examples was improved as compared with that of the injection-molded article of comparative example 3, and particularly, the injection-molded articles of examples 17, 18 and 21 to 25 showed 80kJ/m ² The impact resistance of the above-described height is superior to that of the injection-molded article of comparative example 2. On the other hand, the injection-molded articles of examples 20 and 24 had both high conductivity and impact resistance.

Industrial applicability

The resin composition containing the solid additive of the present invention can be used in various applications requiring mechanical properties such as electrical conductivity and impact strength, and for example, can be effectively used in the following applications: a transport and packaging material or a transport molded article for semiconductors and electric/electronic parts, a part of electric/electronic equipment such as Office Automation (OA) equipment, an automobile part for electrostatic painting, and the like.

Claims

1. A solid additive for addition to a thermoplastic resin, which comprises a carbon nanotube (A) and a fluorene compound (B), wherein the fluorene compound (B) has a hydroxyl-containing group or a carboxyl-containing group as a heteroatom-containing functional group via a hydrocarbon group bonded to the 9-position of fluorene, and at least a part of the surface of the carbon nanotube (A) is covered with the fluorene compound (B).

2. The solid additive according to claim 1, wherein the fluorene compound (B) is a compound represented by the following formula (1),

in the formula (I), the compound is shown in the specification,

k represents an integer of 0 to 8.

3. The solid additive as claimed in claim 2, wherein, in the above formula (1), X is ¹ And X ² Identical to or different from each other, are a group- [ (OA) ¹ ) _m1 -OH]In the formula, A ¹ Represents an alkylene group, and m1 represents an integer of 0 or more;

and n1 and n2 are 1.

4. The solid additive according to claim 1 or 2, wherein the fluorene compound (B) is a compound represented by the following formula (2),

in the formula (I), the compound is shown in the specification,

A ² and A ³ Are the same or different from each other, represent an alkylene group,

X ¹ 、X ² 、R ³ and k is as defined in formula (1) of claim 2.

5. The solid additive as claimed in claim 4, wherein, in the above formula (2), X ¹ And X ² Are identical to or different from each other and are a radical-COOR ⁴ In the formula, R ⁴ Represents a hydrogen atom or an alkyl group.

6. The solid additive according to claim 1 or 2, wherein the fluorene compound (B) has an amorphous structure.

7. The solid additive according to claim 1 or 2, wherein the ratio of the fluorene compound (B) is 5 to 200 parts by mass with respect to 100 parts by mass of the carbon nanotube (a).

8. The solid additive according to claim 1 or 2, which has a compressive strength of 1N or more.

9. The solid additive as claimed in claim 1 or 2, which is an additive for melt kneading for addition to a thermoplastic resin.

10. The solid additive of claim 1 or 2, which is a conductive agent.

11. The method for producing a solid additive as claimed in any one of claims 1 to 10, wherein the carbon nanotubes (A) and the fluorene compound (B) are mixed.

12. The production method according to claim 11, wherein the carbon nanotube (a) and the fluorene compound (B) are mixed in the presence of a solvent.

13. A resin composition comprising a thermoplastic resin and the solid additive according to any one of claims 1 to 10.

14. The resin composition according to claim 13, wherein the solid additive is contained in an amount of 0.1 to 20 parts by mass based on 100 parts by mass of the thermoplastic resin.

15. The resin composition according to claim 13 or 14, wherein the thermoplastic resin is a polycarbonate-series resin.

16. The resin composition of claim 15, having a volume resistivity of 10 ¹² Omega cm or less and a Charpy impact strength of 30kJ/m ² The above.

17. The method for producing a resin composition according to any one of claims 13 to 16, wherein the thermoplastic resin is melt-kneaded with the solid additive.