JP2007191645A - Modifier for thermoplastic resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a modifier for a thermoplastic resin, having excellent dispersibility in the thermoplastic resin, and used for improving mechanical characteristics, heat resistance and electric characteristics of the thermoplastic resin; to provide a thermoplastic resin composition containing the modifier; and to provide a molded article obtained by molding the composition, and having the excellent mechanical characteristics, heat resistance and electric characteristics. <P>SOLUTION: The modifier for the thermoplastic resin comprises a compound obtained by binding a (co)polymer having a specific repeating unit with fullerene and/or carbon nanotube. The thermoplastic resin composition contains the modifier in the thermoplastic resin. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a modifier for thermoplastic resins. More specifically, a modifier having excellent dispersibility in a thermoplastic resin, a thermoplastic resin composition containing the modifier, and heat resistance, mechanical properties, and electrical properties formed by molding the composition. It relates to a molded product that excels.

  In recent years, fullerenes and carbon nanotubes have been discovered, and their unique mechanical, electrical, and optical properties are expected to be applied to various products such as electrical and electronic equipment, automobiles, building materials, and parts of industrial machinery. .

  For example, it has been studied to disperse fullerene in a thermoplastic resin, and it is known that its mechanical strength and heat resistance are improved. (For example, refer to Patent Documents 1 and 2).

Japanese Patent Laid-Open No. 10-310709 JP 2004-182768 A

However, since fullerenes have strong cohesive forces, the mechanical dispersion method described in the above-described literature has a problem that dispersion into a thermoplastic resin is difficult and sufficient improvement in mechanical strength and heat resistance cannot be realized. On the other hand, in order to improve dispersibility in thermoplastic resins, studies have been made to modify fullerenes. For example, alkylene oxide modification (for example, see Patent Document 3), silicone modification (for example, Patent Document) according to the matrix resin to be used. 4), fluorine modification (see, for example, Patent Document 5), acrylate modification (see, for example, Patent Document 6), and the like have been proposed, but these modified fullerenes are still poorly compatible with thermoplastic resins. Dispersibility cannot be improved.
An object of the present invention is to provide a modifier for improving the mechanical, thermal and electrical properties of a thermoplastic resin and a thermoplastic resin composition containing the modifier.

JP 2003-246904 A Japanese Patent Application Laid-Open No. 08-295694 JP 09-141730 A JP-A-08-283199

As a result of intensive studies to solve the above problems, the present inventor has reached the present invention. That is, the present invention is a thermoplastic comprising a compound (C) formed by binding a (co) polymer (A) having a repeating unit represented by the following general formula (1) and fullerene and / or carbon nanotube (B). Resin modifier

^{-CR 1 R 2 -CR 3 R 4} - (1)

[Wherein R ¹ , R ² and R ³ independently represent H, methyl group or ethyl group, and R ⁴ represents H, methyl group, phenyl group, Cl or C (═O) —OR ⁵ (R ⁵ Represents an alkyl group having 1 to 30 carbon atoms. ]
A thermoplastic resin composition containing the modifier in a thermoplastic resin; and a molded article formed by molding the composition.

The modifier for thermoplastic resins of the present invention has the following effects.
(1) Excellent dispersibility in thermoplastic resin.
(2) To increase the dispersibility of fullerene and / or carbon nanotubes with respect to thermoplastic resins
(3) The thermoplastic resin composition containing the modifier is excellent in moldability, and the molded article is excellent in mechanical, thermal and electrical characteristics.

The (co) polymer (A) in the present invention has a repeating unit of the following general formula (1).

^{-CR 1 R 2 -CR 3 R 4} - (1)

In the formula, R ¹ , R ² and R ³ each independently represent H, a methyl group or an ethyl group, R ⁴ represents H, a methyl group, a phenyl group, Cl or C (═O) —OR ⁵ [R ⁵ represents An alkyl group having 1 to 30 carbon atoms (hereinafter abbreviated as C)].
Specific examples of (A) include polyolefins (polymers of C2-6 olefins such as ethylene, propylene, butylene or isobutylene), polystyrene, polyalkyl (C1-22) (meth) acrylates [eg methyl (meth) acrylates. , Ethyl (meth) acrylate or stearyl (meth) acrylate polymers] and copolymers thereof (eg, ethylene / propylene, ethylene / butylene, ethylene / methyl (meth) acrylate, ethylene / vinyl alcohol, ethylene / propylene / Butylene, styrene / propylene or styrene / methyl (meth) acrylate copolymer].
Among these, from the viewpoint of mechanical properties, polyolefin, polystyrene and copolymers thereof [ethylene / propylene, ethylene / butylene, ethylene / propylene / butylene or styrene / methyl (meth) acrylate copolymer], Particularly preferred are polyethylene, polypropylene and ethylene / propylene copolymers.

  Number average molecular weight of (A) [hereinafter abbreviated as Mn. The measurement is based on a gel permeation chromatography (GPC) method. ] Is preferably 500 to 50,000, more preferably 1,000 to 30,000 from the viewpoints of moldability and dispersibility.

The production method of (A) is not particularly limited. For example, the method (I) of polymerizing an ethylenically unsaturated group-containing monomer represented by the following general formula (2) in the presence of a polymerization initiator, the unsaturated A method (II) for thermally degrading a polymer obtained by polymerizing a group-containing monomer (for example, JP-B 43-9368, JP-B 44-29742, JP-B 6-70094, etc.) Can be mentioned. Among these, the method (II) is preferable because the molecular weight is adjusted, the number of double bonds contained is large, modification is easy, and a bond with (B) described later is easily formed.

CR ¹ R ² = CR ³ R ⁴ (2)

[Wherein R ¹ , R ² and R ³ independently represent H, methyl group or ethyl group, and R ⁴ represents H, methyl group, phenyl group, Cl or C (═O) —OR ⁵ (R ⁵ Represents a C1-30 alkyl group). ]

The average number of double bonds per molecule of (A) produced by the method (II) is not particularly limited, but is preferably 0.5 to 2.0, more preferably from the viewpoint of ease of modification. 0.9 to 1.6. Here, the average number of double bonds per molecule can be determined from the integrated value of the peak corresponding to the double bond obtained by nuclear magnetic resonance spectroscopy ( ¹ H-NMR method) and Mn in (A). it can.

Although the method of (I) is not specifically limited, For example, it can superpose | polymerize by various radical polymerization methods (for example, solution polymerization, block polymerization, and emulsion polymerization). Polymerization conditions are not particularly limited, and can be synthesized under general radical polymerization conditions. For example, in the case of solution polymerization, an ethylenically unsaturated group-containing monomer (or a mixture of two or more thereof) in a solvent (xylene, toluene, etc.) usually at 60 to 180 ° C., preferably 80 to 160 ° C. A polymerization initiator solution is dropped and allowed to react for 2 to 10 hours.
The amount of the solvent used is usually 5 to 90%, preferably 15 to 80%, based on the weight of the monomer. Moreover, a chain transfer agent can also be used if necessary.

Examples of the polymerization initiator include peroxides [hydrogen peroxide, benzoyl peroxide, di-t-butyl peroxide, lauroyl peroxide, dicumyl peroxide, 2,2-bis (4,4-di-t -Butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, di-t-butylperoxyhexahydroterephthalate, etc.] and azo compounds [azobisisobutyro Nitrile, azobisisovaleronitrile, etc.].
The amount of the polymerization initiator used is usually 10% or less, preferably 0.1 to 5%, based on the weight of the monomer.

Examples of the chain transfer agent include lauryl mercaptan, dodecyl mercaptan, diphenyl disulfide, and carbon tetrachloride.
The amount of chain transfer agent used is usually 10% or less, preferably 0.1 to 5%, based on the weight of the monomer.

The radical polymerization reaction can be carried out under normal pressure, reduced pressure, or increased pressure, but pressure is preferable from the viewpoint that the reaction temperature can be set high to shorten the reaction time.
The progress of the radical polymerization reaction can be judged by analysis of double bond equivalent and Mn by bromine number or the like, or analysis of residual monomer amount by gas chromatography or the like.
After completion of the reaction, it is preferable to remove the unreacted monomer and the polymerization initiator from the viewpoint of safety and odor. Examples of the removing method include a method of polymerizing an unreacted monomer by adding a polymerization initiator and a method of removing by distillation under reduced pressure. With respect to the polymerization initiator, a method in which the temperature is further increased (for example, 150 to 200 ° C.) for decomposition is used.

  In the case of bulk polymerization, a polymerization initiator (same as above) is added to an ethylenically unsaturated group-containing monomer (or a mixture of two or more thereof) usually at 0 to 150 ° C., preferably 10 to 130 ° C. React for 2-10 hours. If necessary, a chain transfer agent can also be used. The kind and amount of chain transfer agent used are the same as in solution polymerization.

In the case of emulsion polymerization, usually an ethylenically unsaturated group-containing monomer (or a mixture of two or more thereof), a polymerization initiator (same as above) and water at 0 to 150 ° C., preferably 50 to 100 ° C. An emulsifier is added or added dropwise and allowed to react for 2 to 10 hours. If necessary, a chain transfer agent can also be used. The kind and amount of chain transfer agent used are the same as in solution polymerization.
Examples of the emulsifier used in emulsion polymerization include nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants.

Nonionic surfactants include alkylene oxide (hereinafter abbreviated as AO) addition type nonionics, such as active hydrogen atom-containing compounds having a hydrophobic group (C8-24 or higher) [for example, saturated and unsaturated, higher Alcohols (C8-18), higher aliphatic amines (C8-24), higher fatty acids (C8-24) and phenolic compounds (C7-24): eg alkyl or alkenyl (eg dodecyl, stearyl, oleyl) alcohols and amines, alkanes Or alkenoic acid (eg laurin, stearin and oleic acid)] and (poly) oxyalkylene derivatives of alkyl or alkenylphenols [AO [C2-4, eg ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), Butylene Oki And combinations of two or more thereof, particularly EO] (1 to 500 mol or more) adduct (molecular weight 174 or more and Mn 30,000 or less), and polyalkylene glycol (for example, polyethylene glycol: molecular weight 150 or more and Mn6, 000 or less) higher fatty acid mono- and diesters];
Higher grades of polyhydric alcohols [divalent to octavalent or higher, such as ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol (hereinafter abbreviated as EG, GR, TMP, PE and SO, respectively), sorbitan and sucrose] (Poly) oxyalkylene derivatives of fatty acid (above) esters (above, molecular weight of 320 or more and Mn 30,000 or less, such as tween type nonionics);
(Alkanol) amide (poly) oxyalkylene derivative of higher fatty acid (above) (above, molecular weight of 330 or more and Mn of 30,000 or less);
A (poly) oxyalkylene derivative of a polyhydric alcohol (above) alkyl (C3-60) ether (above, a molecular weight of 180 or more and Mn 30,000 or less);
And polyoxypropylene polyols [polyoxypropylene derivatives of polyhydric alcohols (above) and polyamines (diamines and polyamines having 3-5 or more primary and / or secondary amino groups) such as polypropylene glycol and ethylenediamine PO adduct: Mn 500 to 5,000)] polyoxyethylene derivative (Mn 1,000 to 30,000) [pluronic and tetronic nonionics]; polyhydric alcohol (C3-60) type nonionics such as many Fatty acid (C8-20) esters of polyhydric alcohols (above), polyhydric alcohols (above) alkyl (C3-60) ethers, and higher fatty acids (above) alkanolamides;
In addition, amine oxide type nonionics, such as (hydroxy) alkyl (C10-18: dodecyl, stearyl, oleyl, 2-hydroxydodecyl, etc.) di (hydroxy) alkyl (C1-3: methyl, ethyl, 2-hydroxyethyl, etc.) Examples include amine oxides.

Anionic surfactants include carboxylic acids (salts) such as higher fatty acids (C8-24), ether carboxylic acids [higher alcohols (C8-18) or their AO adducts such as EO (1-10 mol) adducts. Carboxymethylates], and salts thereof;
Sulfate esters such as sulfates of the above higher alcohols or their AO adducts (alkyl and alkyl ether sulfates such as sodium lauryl sulfate), sulfated oils (natural unsaturated oils or unsaturated waxes) Neutralized salts), sulfated fatty acid esters (salts neutralized by sulphating lower alcohol esters of unsaturated fatty acids) and sulfated olefins (salts neutralized by sulphating C12-18 olefins);
Sulfonates, such as alkyl benzene sulfonates (eg sodium dodecylbenzene sulfonate), alkyl naphthalene sulfonates, dialkyl ester sulfosuccinates, α-olefin (C12-18) sulfonates and N-acyl-N-methyl taurines (Eg Igepon T type);
In addition, phosphate ester salts such as the above-mentioned higher alcohols or AO adducts thereof [eg EO (1 to 10 mol) adducts] or phosphate ester salts of alkyl (C4-60) phenol AO adducts (same as above) ( Alkyl, alkyl ether and alkylphenyl ether phosphate).

Cationic surfactants include quaternary ammonium salt-type cationics such as tetraalkylammonium salts (C11 to 100), such as alkyl (C8-18: lauryl, stearyl, etc.) trimethylammonium salts and dialkyl (C8-18: Decyl, octyl, etc.) dimethylammonium salts; trialkylbenzylammonium salts (C17-80), such as lauryldimethylbenzylammonium salt, stearylbenzyldimethylammonium salt and distearylbenzylmethylammonium salt;
Alkyl (C8-60) pyridinium salts, such as cetyl pyridinium salts;
(Poly) oxyalkylene (C2-4) (degree of polymerization 1-100 or higher) trialkylammonium salts (C12-100), such as polyoxyethylene lauryldimethylammonium salts; and acyl (C8-18) aminoalkyl (C2 -4) or acyl (C8-18) oxyalkyl (C2-4) tri [(hydroxy) alkyl (C1-4)] ammonium salts such as stearamide ethyl diethyl methyl ammonium salt (sapamine type quaternary ammonium salts) [these Salts include, for example, halides (eg, chloride and bromide), alkyl sulfates (eg, methosulfate) and organic acids (below)];
In addition, amine salt-type cationics: 1-3 primary amines [for example, higher aliphatic amines (C12-60: lauryl, stearyl and cetylamine, hardened tallow amine, rosinamine, etc.), aliphatic amines (C8-20) (poly) Oxyalkylene derivatives (above, EO adducts, etc.), and acylaminoalkyl or acyl (C8-18) oxyalkyldi (hydroxy) alkyl (above) amines (eg stearoyloxyethyl dihydroxyethylamine and stearamide ethyl diethylamine)] Inorganic acid (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and the like) salts and organic acid (C2-22: acetic acid, propion, laurin, olein, succinic acid, adipine and azelaic acid, benzoic acid, etc.) salts and the like.

Amphoteric surfactants include carboxylic acid (salt) type amphoterics such as amino acid type amphoterics such as alkyl (C8-18) aminopropionic acid (salt), and betaine type amphoterics such as alkyl. (Same as above) di (hydroxy) alkyl (above) betaines (eg alkyldimethylbetaine and alkyldihydroxyethylbetaine);
Sulfate ester (salt) type amphoterics, for example, alkyl (same as above) amine sulfates (salts), and hydroxyalkyl (C2-4: hydroxyethyl, etc.) imidazoline sulfates (salts);
Sulfonic acid (salt) type amphoterics, for example alkyl (same as above: pentadecyl, etc.) sulfotaurine, and imidazoline sulfonic acid (salt);
In addition, phosphate ester (salt) type amphoterics, for example, phosphate ester (salt) of glycerol higher fatty acid (above) ester and the like can be mentioned.

  Of these, nonionic and anionic surfactants are preferred from the viewpoint of the stability of the emulsion.

  The method (II) for thermally degrading the polymer is a high molecular weight polymer (Mn is usually 8,000 to 500,000, which is produced in advance by the method (I), preferably from the viewpoint of easy modification. Includes 10,000 to 300,000) by (1) continuous thermal degradation or (2) batch thermal degradation.

In the method (1), a high molecular weight polymer fed to a continuous tank at a constant flow rate (10 to 700 kg / hour) is usually 0.5 to 10 hours at 300 to 450 ° C. in the absence of a polymerization initiator. In addition, in the presence of a polymerization initiator, it is usually a method in which heat is continuously degraded at 180 to 300 ° C. for 0.5 to 10 hours, and the method (2) is a method for treating the high molecular weight in a closed reaction vessel. In the same manner as in the above (1), the polymer is thermally degraded under the same heat treatment conditions in the absence or presence of a polymerization initiator.
The amount of the polymerization initiator used is usually 0.01 to 10% based on the weight of the high molecular weight polymer, and preferably 0.1 to 1% from the viewpoint of molecular weight control.

  Among these methods, the method (1) is preferable from the viewpoint of moldability and dispersibility, and more preferable is a method in which heat degradation is continuously performed at 300 to 450 ° C. in the absence of a polymerization initiator. Is preferred.

Among the fullerenes and / or carbon nanotubes (B) in the present invention, the fullerene (B1) is a fullerene C ₃₅ , C ₆₀ , C ₇₀ , C ₇₆ , C ₈₂ , C ₈₄ , C ₉₀ , C ₉₅ , carboxyl group substitution. Fullerenes C ₆₀ and C ₇₀ , methoxycarbonyl group-substituted fullerenes C ₆₀ and C ₇₀ , hydrogenated fullerenes C ₆₀ and C ₇₀ , alkyl group-substituted fullerenes C ₆₀ and C _{70, and the} like.

(B1) is a known method [for example, the method for producing fullerene C ₃₆ is New Diamond. , Vol. 16, no. 2, 2000, p. 30-31, fullerenes C ₆₀ , C ₇₀ , C ₇₆ , C ₇₈ , C ₈₂ , C ₈₄ , C ₉₀ and C ₉₆ are prepared according to J. Phy. Chem. 94, 8634 (1990), Z. Phys. D, 40, 414 (1997) etc.].

  Among (B), the carbon nanotube (B2) is not particularly limited in terms of type and manufacturing method, but is formed of carbon and has a tube shape with a diameter of nanometer order. It has a structure in which hexagonal meshes that are formed are connected in a tube shape. Single-walled nanotubes with a single hexagonal tube structure (hereinafter abbreviated as SWNT), double-walled nanotubes with a hexagonal network tube (hereinafter abbreviated as DWNT), three or more layers Multiwall nanotubes (hereinafter abbreviated as MWNT) and the like are composed of the hexagonal mesh tubes. (B2) can be produced by a known method (for example, described in JP-A-6-157016, JP-A-6-280116, JP-A-10-203810, JP-A-11-11917). it can. Further, it is a manufacturing method using an arc discharge method, a laser evaporation method, a thermal decomposition method, or a plasma discharge described in “Basics of Carbon Nanotubes” (P23 to P57, Saito, Itoh, Corona Publishing, 1998). May be.

  In the product obtained by the above production method, (B1), amorphous carbon nanoparticles, graphite pieces and metal (catalyst) nanoparticles are mixed as by-products at the same time as (B2). When (B2) is used, it may be used in the state of the mixture or may be used after purification. As a purification method, (B1) may be extracted with an organic solvent (for example, toluene, hydrogen disulfide, benzene, chlorobenzene). In addition, the metal nanoparticles and the graphite pieces may be formed by selectively forming an intercalation compound, and sintering and insolubilizing at a low temperature.

  (B2) includes, in addition to SWNT, DWNT, MWNT, (B2) containing a metal, an inorganic substance or other organic substance, (B2) filled with carbon or other substance, (B2) A coil (spiral) or fibril can be used. Further, the diameter and length of the carbon nanotube are not particularly limited, but from the viewpoint of ease of production and function development, the number average diameter is preferably 1 to 20 nm, and the number average length is preferably 0.05 to 100 μm. It is.

(B) may be (B1) and (B2) each alone, a mixture of two or more of them, or a mixture of (B1) and (B2), but is preferable from the viewpoint of easy synthesis of (C). Is a mixture of (B1) and (B1) and (B2).
Mn of (B) is preferably 400 to 50,000, more preferably 700 to 30,000 from the viewpoints of moldability and dispersibility.

  The compound (C) in the present invention is obtained by bonding (A) and (B). At the time of the binding, (B) is usually modified to introduce a reactive functional group. Examples of the reactive functional group include an alkenyl group [C2-30], an organic acid (anhydride) group, a hydroxyl group, an epoxy group, and an amino group. The method for introducing the reactive functional group is not particularly limited. For example, the Diels-Alder reaction [J. Am. Chem. Soc, 114, 7301 (1992)], hydroxylation reaction [described in J. Chem. Soc., Chem. Commun., 1791 (1992)], epoxidation reaction [Science, 252, 548 (1991) and J Am. Chem. Soc, 114, 1103 (1992)] or addition reaction of amine [described in Angew. Chem. Int. Ed. Engl., 30, 1309 (1991)].

  Among the reactive functional groups, preferred are a hydroxyl group, an amino group, and an epoxy group, and more preferred are a hydroxyl group and an amino group having an active hydrogen atom, from the viewpoint of ease of bonding with (A).

The bond between (A) and (B) may be produced by directly radically polymerizing the terminal double bond of (A) and (B) prepared by the method of (II) above. From the viewpoint, (A) is preferably modified to introduce a functional group. Examples of the functional group to be introduced include an organic acid (anhydride) group, a hydroxyl group, an epoxy group, an isocyanate group, and an alkylsiloxane group. Among these, an organic acid (anhydride) group and an isocyanate group are preferable from the viewpoint of reactivity with (B).
The method for introducing the functional group is not particularly limited. For example, when (A) is produced by the method (I), a method of copolymerizing the functional group and a monomer having an ethylenically unsaturated double bond ( 1) In the case where (A) is produced by the above method (II), there is a method (2) in which a monomer having a functional group and an ethylenically unsaturated double bond is further reacted with (A) after the production. Can be mentioned. Of these, the method (2) is preferable because a functional group can be introduced at the molecular end.

  As the monomer having the functional group and the ethylenically unsaturated double bond, when the functional group is an organic acid group (anhydride), for example, a monobasic acid [C3 to 10, for example, (meth) acrylic Acid], and dibasic acids [C4-15, such as maleic acid (anhydride), fumaric acid, tetrahydrophthalic acid (anhydride), methyltetrahydrophthalic acid (anhydride), cyclopentadiene and maleic acid (anhydride) Diels-Alder reactant]; in the case of a hydroxyl group, C5 or more and Mn 3,000 or less, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, propenyl alcohol, and their AO (C2-4 ) 1-30 mol adduct; in the case of epoxy groups, C6-20, such as glycidyl (meth) acrylate, vinylglycol Diethyl ether, propenyl glycidyl ether; C3-20 for isocyanate groups, such as (meth) acryloylethyl isocyanate], vinyl isocyanate ethyl ether, propenyl isocyanate ethyl ether; and C9-20 for alkylsiloxane groups, such as (Meth) acryloylpropyltrimethylsilicon and (meth) acryloylpropyltriethylsilicon are mentioned.

The combination of the functional groups (A) and (B) is not particularly limited as long as they react with each other. For example, (A): organic acid group (anhydride) and (B): hydroxyl group, epoxy Group or amino group, (A): hydroxyl group and (B) organic acid group (anhydride) or epoxy group, (A): epoxy group and (B): hydroxyl group, organic acid group (anhydride) or amino group , (A): isocyanate group and (B): hydroxyl group or amino group, (A): alkylsiloxane group and (B): hydroxyl group, and the like.
Among these, from the viewpoint of reactivity, (A): organic acid group (anhydride) and (B): hydroxyl group, epoxy group or amino group, (A): isocyanate group and (B) hydroxyl group or amino group are preferred. More preferred is a combination of (A): an organic acid group (anhydride) and (B): a hydroxyl group or an epoxy group.

The reaction conditions for (A) and (B) are not particularly limited. For example, when (A) is an organic acid group (anhydride), the hydroxyl group is used at 60 to 180 ° C. for 0.5 to 10 hours. In the case of an isocyanate group, 0.5 to 10 hours at 20 to 140 ° C., and in the case of an alkylsiloxane group, 0.5 to 20 at 60 to 200 ° C. It can be produced by reacting for a time. During these reactions, an esterification catalyst (the reaction of the alkylsiloxane group is the same), an epoxidation catalyst, or a urethanization catalyst may be used.
Examples of the catalyst include polyester resin handbooks [published by Nikkan Kogyo Shimbun (1988)], epoxy resin handbooks [published by Nikkan Kogyo Shimbun (1987)] and polyurethane resin handbooks [published by Nikkan Kogyo Shimbun (1987)]. Things can be used. In the reaction, various organic solvents may be used. Although it does not specifically limit as an organic solvent, From a soluble viewpoint of (A) and (B), an aromatic hydrocarbon (xylene, toluene, etc.) is preferable. Although the usage-amount of an organic solvent is not specifically limited, Usually, it is 5-500% based on the total weight of (A) and (B).

  Of the combinations of (A) and (B), from the viewpoint of ease of production, (A) is preferably a reaction product (a2) of a low molecular weight polyolefin (a1) and an unsaturated organic acid (anhydride). ) And (B) has a hydroxyl group, and further, a reactive site is also present at the terminal. Therefore, it is preferable that (a1) is thermally degraded by the method (II).

  The ratio (weight ratio) between (A) and (B) is preferably 99/1 to 10/90, more preferably 97/3 to 40/60, from the viewpoint of dispersibility.

  Mn of (C) is usually 1,000 to 200,000, and preferably 2,000 to 100,000 from the viewpoint of ease of blending, dispersibility, and moldability described later.

The modifier for thermoplastic resins of the present invention comprises the above (C). The modifier is contained in the thermoplastic resin (D) to form a thermoplastic resin composition, and by molding this, a molded product having excellent mechanical, thermal and electrical characteristics can be obtained.
The amount of the modifier used is preferably from 0.5 to 900%, more preferably from 0.7 to 500%, particularly from the viewpoint of mechanical, thermal and electrical properties, based on the weight of (D). Preferably it is 1 to 100%.

  The thermoplastic resin (D) is not particularly limited as long as it can be kneaded with (C). For example, polyolefin (C2-6 olefin such as ethylene, propylene, butylene or isobutylene polymer) (D1), polystyrene (D2 ), Polyalkyl (C1-22) (meth) acrylate [for example, a polymer of methyl (meth) acrylate, ethyl (meth) acrylate or stearyl (meth) acrylate] (D3), and copolymers thereof [for example, ethylene / Propylene, ethylene / butylene, ethylene / methyl (meth) acrylate, ethylene / vinyl alcohol, ethylene / propylene / butylene, styrene / propylene or styrene / methyl (meth) acrylate copolymer] (D4).

  Among these (D), those having the same structure as (A) are preferable from the viewpoint of compatibility. For example, when (A) has ethylene as the main structural unit, (D) is, for example, polyethylene, ethylene-propylene copolymer, ethylene- (meth) acrylic acid copolymer, ethylene-vinyl alcohol copolymer, etc. When (A) has propylene as the main structural unit, polypropylene, propylene-ethylene copolymer, propylene- (meth) acrylic acid copolymer, and the like are preferable.

  Mn of (D) is usually 8,000 to 500,000, and preferably 10,000 to 300,000 from the viewpoint of ease of molding and mechanical properties.

  In the thermoplastic resin composition of the present invention, (C) can contain other fullerenes and / or carbon nanotubes (E) for the purpose of improving mechanical, thermal and electrical properties. (E) includes, in addition to the above-mentioned (B), an alkyl-modified product of (B) [production method is described in J. Am. Chem. Soc, 114, 7301 (1992)], AO modified product (manufacturing method described in Patent Document 3), silicone modified product (manufacturing method described in Patent Document 4), fluorine modified product (manufacturing method) Are described in Patent Document 5) and acrylate-modified products (the production method is described in Patent Document 3).

  In the production of the thermoplastic resin composition of the present invention, when (C), (D) and (E) are kneaded, (C) serves as a dispersant for (E) with respect to (D). The amount of (E) used is usually 0.1 to 200% based on the weight of (D), preferably 0.5 to 100% from the viewpoint of mechanical, thermal and electrical properties of the molded product. More preferably, it is 0.5 to 50%.

  In addition to (C), (D), and (E), the thermoplastic resin composition of the present invention includes a colorant (F1), a dispersant (F2), a release agent (F3), a slip according to the purpose. Containing at least one additive (F) selected from the group consisting of an agent (F4), an antioxidant (F5), an ultraviolet absorber (F6), a flame retardant (F7) and a filler (F8). it can. Examples of (F) include the following.

Examples of the colorant (F1) include the following.
(1) Azo pigments Insoluble monoazo pigments (toluidine red, permanent carmine FB, fast yellow G, etc.), insoluble disazo pigments (disazo yellow AAA, disazo orange PMP, etc.), azo lakes (soluble azo pigments) (lake red C, brilliant carmine) 6B, etc.), condensed azo pigments, chelate azo pigments, etc. (2) polycyclic pigments phthalocyanine blue, indanthrone blue, quinacridone red, dioxazine violet, etc. (4) Others Azine pigments (aniline black, etc.), daylight fluorescent pigments, nitroso pigments, nitro pigments, natural pigments, etc. (F1) is used based on the total weight of the composition Usually less than 50%, based on It is 0.1 to 30%.

  Examples of the dispersant (F2) include organic dispersants [polymer dispersants (Mn 2,000 to 500,000) and low molecular dispersants (molecular weight of 100 or more and less than Mn 2,000)] and inorganic dispersants.

  Examples of the polymer dispersant include naphthalene sulfonate [alkali metal (Na and K etc.) salts, ammonium salts, etc. The same applies to the salt below. ] Formalin condensate, polystyrene sulfonate, polyacrylate, poly (2-4) carboxylic acid (maleic acid / glycerin / monoallyl ether copolymer, etc.) salt, carboxymethyl cellulose (Mn 2,000 to 10,000) ) And polyvinyl alcohol (Mn 2,000 to 100,000).

The following are mentioned as a low molecular weight dispersing agent.
(1) Polyoxyalkylene type AO (C2-4) of aliphatic alcohol (C4-30), [alkyl (C1-30)] phenol, aliphatic (C4-30) amine and aliphatic (C4-30) amide 1-30 mol adducts As aliphatic alcohols, n-, i-, sec- and t-butanol, octanol, dodecanol etc .; (alkyl) phenols as phenol, methylphenol and nonylphenol etc .; as aliphatic amines , Laurylamine, methylstearylamine and the like; and aliphatic amides include stearic acid amide and the like.
(2) Polyhydric alcohol type monoester compound of C4-30 fatty acid (lauric acid, stearic acid, etc.) and polyhydric (2-6 or more) alcohols (eg GR, PE, SO and sorbitan) (3) Carvone Salt type C4-30 fatty acid (same as above) alkali metal (same as above) salt (4) sulfate ester type C4-30 aliphatic alcohol (same as above) and aliphatic alcohol AO (C2-4) 1) 30 mol adduct sulfate alkali metal (same as above) salts, etc.

(5) Sulfonate type [Alkyl (C1-30)] Phenol (same as above) sulfonate alkali metal (same as above) salt (6) Phosphate ester type C4-30 aliphatic alcohol (same as above) ) And fatty alcohol AO (C2-4) 1-30 mol adduct mono- or diphosphate salts [alkali metal (same as above) salts, quaternary ammonium salts, etc.]
(7) C1-30 aliphatic amines [primary (laurylamine, etc.), secondary (dibutylamine, etc.) and tertiary amine (dimethylstearylamine, etc.) hydrochloride, triethanolamine And C4-30 fatty acid (same as above) monoester inorganic acid (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.) salt (8) quaternary ammonium salt type C4-30 quaternary ammonium (butyltrimethylammonium, diethyl) Inorganic acid (same as above) salts of laurylmethylammonium, dimethyldistearylammonium and the like.

Examples of inorganic dispersants include alkali metal salts of polyphosphoric acid (same as above) and phosphoric acid dispersants (such as phosphoric acid, monoalkyl phosphate ester, dialkyl phosphate ester).
The amount of (F2) used is usually 5% or less, preferably 0.05 to 3%, based on the total weight of the composition of the present invention.

As the release agent (F3), lower alcohol (C1-6) (methanol, butanol, etc.), higher alcohol (C8-18) (octyl alcohol, hexadecyl alcohol, etc.), higher fatty acid (C10-20) (oleic acid) , Stearic acid, etc.), higher fatty acid esters (C11-30) (glycerin monolaurate), phosphate esters (tributyl phosphate, etc.), metal soaps (calcium stearate, aluminum stearate, etc.), polyethers [polyethylene glycol (hereinafter PEG) Abbreviation) (Mn200-10,000), polypropylene glycol (hereinafter abbreviated as PPG) (Mn200-10,000), etc.], silicone (dimethylsilicone oil, alkyl-modified silicone oil, fluorosilicone oil, etc.) and mineral oils Silica powder those dispersed in mineral oil) and the like.
The amount of (F3) used is usually 3% or less, preferably 0.01-2%, based on the total weight of the composition of the present invention.

Examples of slip agents (F4) include higher fatty acid esters (such as butyl stearate), higher fatty acid amides (such as ethylene bis stearic acid amide and oleic acid amide), metal soaps (such as calcium stearate and aluminum oleate), and wax [paraffin wax. And polyolefin wax (polyethylene wax, polypropylene wax, carboxyl group-containing polyethylene wax, etc.)] and silicone (for example, dimethyl silicone oil, alkyl-modified silicone oil and fluorosilicone oil).
The amount of (F4) used is usually 5% or less, preferably 0.01-2%, based on the total weight of the composition of the present invention.

Antioxidants (F5) include hindered phenol compounds [triethylene glycol-bis- [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis. [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,5-di- t-butyl-4-hydroxybenzylphosphonate diethyl ester] and amine compounds (n-butylamine, triethylamine, diethylaminomethyl methacrylate, etc.).
The amount of (F5) used is usually 3% or less, preferably 0.005 to 2%, based on the total weight of the composition of the present invention.

Examples of the ultraviolet absorber (F6) include benzotriazole compounds [2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2 -(3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, etc.], triazine compounds [ 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol], benzophenone (such as 2-hydroxy-4-n-octyloxybenzophenone), An oxalic acid anilide compound (2-ethoxy-2'-ethyl oxalic acid bisanilide etc.) is mentioned.
The amount of (F6) used is usually 3% or less, preferably 0.005 to 2%, based on the total weight of the composition of the present invention.

Examples of the flame retardant (F7) include organic flame retardants [phosphorus compounds (eg, tricresyl phosphate, cresyl diphenyl phosphate), bromine compounds (eg, tetrabromobisphenol A, decabromobiphenyl ether, etc.), chlorine compounds ( For example, chlorinated paraffin, anhydrous fetic acid, etc.)] and inorganic flame retardants [antimony trioxide, magnesium hydroxide, zinc borate, barium metaborate, aluminum hydroxide, red phosphorus, ammonium polyphosphate, etc.].
The amount of (F7) used is usually 15% or less, preferably 3 to 10%, based on the total weight of the composition of the present invention.

Although it does not specifically limit as a filler (F8), In order to obtain the molded article excellent in mechanical, thermal, an electrical property, and dimensional stability, it is fibrous, particulate form, plate shape, or hollow according to the objective. Can be selected.
Examples of fibrous fillers include glass fiber, asbestos fiber, carbon fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, and stainless steel, aluminum, titanium. Inorganic fibrous materials such as metal fibrous materials such as copper and brass. Particularly typical fibrous fillers are glass fibers or carbon fibers. High melting point organic fibrous materials such as polyamide, fluororesin, and acrylic resin can also be used.
Particulate fillers include carbon black, silica, quartz powder, glass beads, glass powder, oxalate (calcium oxalate, aluminum oxalate, kaolin, talc, clay, diatomaceous earth, wollastonite, etc.), metal Examples include oxides (iron oxide, titanium oxide, alumina, etc.), metal carbonates (calcium carbonate, magnesium carbonate, etc.), metal sulfates (calcium sulfate, barium sulfate, etc.), silicon carbide, silicon nitride, various metal powders, etc. It is done.
Examples of the plate filler include mica, glass flakes, various metal foils and the like.
Examples of the hollow filler include shirasu balloons, metal balloons, and glass balloons.
These fillers can be used alone or in combination of two or more.
The amount of (F8) used is usually 70% or less, preferably 0.1 to 50%, based on the total weight of the composition of the present invention.

As a method for producing the composition of the present invention, (C), (D) and, if necessary, (E), (F) a method of melting and mixing all together, (C) and optionally (E), a small amount of A method (master batch method) in which (D) is melt-kneaded to prepare a master batch, and then the remaining (D) and, if necessary, (F) is added to perform melt mixing.
Examples of the melt mixing apparatus include a batch mixer (Banbury mixer, kneader, etc.), a continuous mixer (FCM, KCM, NCM, CIM, etc.), a single screw extruder, a twin screw extruder, and the like.

  Examples of the molding method of the present invention include extrusion molding, injection molding, compression molding, transfer molding, stamping molding, blow molding, laminate molding, calender molding, foam molding, and the like. Can be produced.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these. The part in an Example shows a weight part and% shows weight%.

Example 1
In a glass reaction vessel equipped with a dropping funnel, a thermometer, a reflux condenser, and a stirring rod, 500 parts of an ethylene / 1-butene copolymer [trade name: Excelen FXCX5501, manufactured by Sumitomo Chemical Co., Ltd.] was charged under a nitrogen atmosphere. Then, thermal degradation was performed at 350 ° C. for 3 hours with stirring. Next, the thermally degraded product was cooled to 200 ° C. and then taken out to obtain a low molecular weight ethylene / 1-butene copolymer (a1-1). Mn of (a1-1) was measured at 3,000 [high temperature GPC: manufactured by Waters Co., Ltd., column PLgel MIX ED-B: manufactured by Polymer Laboratories Co., Ltd.]. same as below. The average number of double bonds was 1.3.
Next, 300 parts of (a1-1) and 19.6 parts of maleic anhydride were charged into a reaction vessel similar to the above, and uniformly dissolved at 200 ° C. in a nitrogen atmosphere, and then 1,1′-azobis (cyclohexane- A solution prepared by dissolving 1.8 parts of 1-carbonitrile in 10 parts of xylene was dropped from a dropping funnel and reacted for 1 hour. After the reaction, the system was depressurized while maintaining the temperature at 200 ° C., 5 mmHg, xylene was removed in 1 hour, then cooled to 160 ° C., and the maleic anhydride-modified low molecular weight ethylene / 1-butene copolymer (a2-1 ) Mn of (a2-1) was 4,000, and the acid value was 20.
In another similar reaction vessel, fullerene [trade name: mixed fullerene, C ₇₀ / C ₆₀ (weight ratio) = 37/100, manufactured by Frontier Carbon Co., Ltd. same as below. ] 50 parts and 500 parts of toluene were added, and 5 parts of 80% hydrogen peroxide was added dropwise with stirring in a nitrogen atmosphere at 40 ° C., reacted at 40 ° C. for 10 hours, and then aged at 100 ° C. for 2 hours. did. After the reaction, the reaction solution was cooled to 30 ° C., and the reaction solution was filtered with a filter paper. The filtrate was concentrated with an evaporator and the solid was dried to obtain hydroxyl group-modified fullerene (b1-1). The hydroxyl value of (b1-1) was 80.
Next, 100 parts of (a2-1), 37.6 parts of (b1-1), and 300 parts of xylene were charged into another similar reaction vessel, stirred under a nitrogen atmosphere at 120 ° C., and reacted for 5 hours. After the reaction, the reaction solution was cooled to 100 ° C., and the reaction solution was filtered with a filter paper. Then, the filtrate was concentrated with an evaporator and the solid was dried to obtain a modifier (c-1). Mn of (c-1) was 5,000.

Example 2
500 parts of polypropylene [trade name: Chisso Polypro K1011, manufactured by Chisso Co., Ltd.] was charged in the same reaction vessel as in Example 1, and thermal degradation was performed at 300 ° C. for 4 hours with stirring in a nitrogen atmosphere. Next, the thermally degraded product was cooled to 200 ° C. and then taken out to obtain a low molecular weight polypropylene (a1-2). Mn of (a1-2) was 5,000, and the average double bond number was 2.0.
Next, 100 parts of (a1-2) and 2 parts of maleic anhydride were charged into the same reaction vessel as in Example 1, and uniformly dissolved at 200 ° C. in a nitrogen atmosphere. Then, 1,1′-azobis (cyclohexane- A solution prepared by dissolving 0.8 part of 1-carbonitrile in 10 parts of xylene was dropped from a dropping funnel and reacted for 1 hour. After the reaction, the system was depressurized while maintaining the temperature at 200 ° C., 5 mmHg, xylene was removed in 1 hour, and then cooled to 160 ° C. to obtain maleic anhydride-modified low molecular weight polypropylene (a2-2). Mn of (a2-2) was 8,000, and the acid value was 19.
In another similar reaction vessel, 50 parts of fullerene and 500 parts of toluene were charged, and m-chloroperoxide benzoic acid was added dropwise with stirring in a nitrogen atmosphere at 110 ° C. and reacted at 110 ° C. for 2 hours. . After the reaction, the reaction solution was cooled to 30 ° C., and the reaction solution was filtered with a filter paper. Then, the filtrate was concentrated with an evaporator and the solid was dried to obtain an epoxy group-modified fullerene (b1-2). The epoxy value of (b1-2) was 149.
Next, 100 parts of (a2-2), 10 parts of (b1-2) and 100 parts of xylene were charged into another similar reaction vessel, and stirred at 145 ° C. in a nitrogen atmosphere and reacted for 10 hours. After the reaction, the reaction solution was cooled to 100 ° C., and the reaction solution was filtered with a filter paper. Then, the filtrate was concentrated with an evaporator and the solid was dried to obtain a modifier (c-2). Mn of (c-2) was 20,000.

Example 3
In a reaction vessel similar to that in Example 1, 100 parts of carbon nanotubes [trade name: amorphous carbon nanotubes, Osaka Gas Co., Ltd.] and 500 parts of xylene were charged and t-butyl was stirred at 140 ° C. in a nitrogen atmosphere. 2 parts of hydroperoxide [purity: 69%, trade name: Perbutyl H-69, manufactured by NOF Corporation] was added dropwise and reacted at 140 ° C. for 5 hours. After the reaction, the reaction solution was cooled to 30 ° C., and the reaction solution was filtered with a filter paper. Then, the filtrate was concentrated with an evaporator and the solid was dried to obtain hydroxyl group-modified carbon nanotubes (b2-1). The hydroxyl value of (b2-1) was 22.
In another similar reaction vessel, 100 parts of (a2-1), 100 parts of (b2-1), and 500 parts of xylene were charged, and a solution of 10 parts of AIBN and 50 parts of xylene was added dropwise with stirring under a nitrogen atmosphere. The reaction was carried out at 5 ° C for 5 hours. After the reaction, the reaction solution was cooled to 100 ° C., and the reaction solution was filtered with a filter paper. Then, the filtrate was concentrated with an evaporator and the solid was dried to obtain a modifier (c-3). Mn of (c-3) was 30,000.

Examples 4-10
According to the composition shown in Table 1, after melt-kneading in a twin screw extruder with a vent under the conditions of 240 ° C., 100 rpm, residence time 20 minutes, an injection molding machine [trade name: PS40E5ASE, Nissei Plastic Industry Co., Ltd. The product was molded at a cylinder temperature of 230 ° C. and a mold temperature of 40 ° C., and the heat resistance, mechanical properties, and electrical properties (surface resistivity) of the molded products were evaluated according to the following test methods. The results are shown in Table 1.

<Test method>
(1) Deflection temperature under load Using a test piece (150 × 15 × 3.2 mm), the deflection temperature under load was measured at a stress of 0.45 MPa in accordance with JIS K6911 5.35.
(2) Flexural modulus Using a test piece (100 × 10 × 3.2 mm), the flexural modulus was measured at a fulcrum distance of 60 mm in accordance with ASTM D790.
(3) Impact strength Impact strength was measured in accordance with ASTM D256 (with notch, 3.2 mm thickness) Method A.
(4) Surface resistivity The humidity of the test piece (100 × 100 × 2 mm) was adjusted for 48 hours in an atmosphere of 23 ° C. and 50% RH. The test piece was measured in an atmosphere of 23 ° C. and 50% RH with a super insulation meter [DSM-8103 manufactured by Toa Denpa Kogyo Co., Ltd. (electrode SME-8310 for flat plate sample)] according to [ASTM D257 (1984). ].

PEB: ethylene-1-butene copolymer [trade name: Excellen FXCX5501,
Sumitomo Chemical Co., Ltd.]
PP: Polypropylene [Product name: Chisso Polypro K1011, manufactured by Chisso Corporation]
PMMA: Polymethylmethacrylate [Product name: Acrypet VH, Mitsubishi Rayon Co., Ltd.
)]
FL: fullerene [trade name: mixed fullerene, C ₇₀ / C ₆₀ weight ratio = 37 /
100, made by Frontier Carbon Co., Ltd.]
CNT: Carbon nanotube [Product name: Amorphous carbon nanotube, Osaka
Gas Co., Ltd.]

Comparative Examples 1-5
According to the composition shown in Table 1, the heat resistance, mechanical properties, and insulation (electric properties) of the molded products were evaluated in the same manner as in the Examples. The results are shown in Table 1.

  From the results in Table 1, when compared with the same thermoplastic base resin, the examples had higher deflection temperatures under load, higher flexural modulus, impact strength, and surface specific resistance values, and heat resistance. It can be seen that both the mechanical characteristics and the electrical characteristics are excellent.

  A molded product formed by molding the thermoplastic resin composition containing the modifier of the present invention is excellent in mechanical properties, heat resistance, and electrical properties, so that it can be used in electrical and electronic equipment, automobiles, building materials, industrial machinery. It is extremely useful as a component.

Claims (7)

Modification for a thermoplastic resin comprising a (co) polymer (A) having a repeating unit represented by the following general formula (1) and a compound (C) formed by binding fullerene and / or carbon nanotube (B) Agent.

^{-CR 1 R 2 -CR 3 R 4} - (1)

[Wherein R ¹ , R ² and R ³ independently represent H, methyl group or ethyl group, and R ⁴ represents H, methyl group, phenyl group, Cl or C (═O) —OR ⁵ (R ⁵ Represents an alkyl group having 1 to 30 carbon atoms. ] The modifier according to claim 1, wherein the weight ratio of (A) to (B) is 99/1 to 10/90. A thermoplastic resin composition comprising the thermoplastic resin (D) containing the modifier according to claim 1 or 2. The composition according to claim 3, wherein the proportion of the modifier based on the weight of (D) is 0.5 to 900%. Furthermore, the composition of Claim 3 or 4 made to contain fullerene and / or a carbon nanotube (E). Furthermore, at least one additive (F) selected from the group consisting of a colorant, a dispersant, a release agent, a slip agent, an antioxidant, an ultraviolet absorber, a flame retardant and a filler is contained. The composition in any one of 3-5. A molded article formed by molding the composition according to claim 3.