JPS6245660A - Composite material composition - Google Patents

Abstract

PURPOSE:To form a magnetic composite material compsn. having excellent moldability, dimensional stability, mechanical properties, heat resistance, magnetic characteristics, etc., by mixing magnetic powder, a binder resin composed of a polymer compsn. and additives. CONSTITUTION:The titled compsn. is formed by mixing magnetic powder (A), a binder resin (B) composed of a polymer compsn. capable of forming an anisotropic melt phase and allowing melt processing to be conducted and at least one additive (C) selected from among surfactant, low-viscosity liquid oil substance and surface treating agent. Said binder resin is a polymer compsn. which exhibits optical anisotropy during melting and allows thermoplastic melt processing to be conducted. As the surface treating agent, titanate and silane coupling agents are preferred. The coupling agent must have a decomposition point of 270 deg.C or above, because the melt processing temp. of the compsn. is 300 deg.C or above.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides moldability, dimensional stability, mechanical properties, heat resistance,
The present invention relates to a magnetic composite material composition with excellent flame retardancy and magnetic properties.

[Conventional technology and problems]

At present, magnetic composite materials made of resin and magnetic substances have better mechanical properties, workability, and dimensional accuracy than the sintered magnets of -a, and have stable magnetic properties, so they can be used for various purposes. It is used in a variety of applications such as transformers, motors, and switches.

Examples of resins used include epoxy and phenol resins for thermosetting types, and polypropylene, ethylene-vinyl acetate copolymer, nylon, PBT, PPS, etc. for thermoplastic types. In general, the maximum energy product increases in proportion to the amount of magnetic material added, and thermosetting types are better in terms of molding process.
A larger amount of magnetic substance can be added than a thermoplastic resin, and the maximum energy product obtained is larger.However, such a thermosetting resin has difficulty in mass production as a composite magnetic material.

On the other hand, thermoplastic resins have the advantage of being mass-producible, but have the disadvantage of being poor in moldability and heat resistance.

[Means for solving problems]

In view of the above points, the present inventors conducted intensive research and found that when a polymer composition that forms an anisotropic melt phase that can be melt-processed is mixed with magnetic powder as a binder resin, a polymer that exhibits the above-mentioned melt singularity Even when the composition is melted and no external stress such as stretching is applied, that is, even in a static state, the polymer chains are highly oriented, resulting in an abnormally low melt viscosity and a large amount of magnetic material. It has been discovered that the magnetic composite material can be easily molded by injection molding, extrusion molding, compression molding, etc., and the resulting magnetic composite material has excellent properties such as dimensional stability, mechanical properties, heat resistance, and flame retardance. Ta. and,
A composite material composition based on this knowledge was first filed in a patent application in 1973.
The application was filed as No. 9-191368. However, subsequent research revealed that the above composition still had insufficient fluidity during melting, and as a result, the magnetic properties of the resulting molded products were somewhat problematic. There was also room for improvement in the mechanical properties of the molded products, particularly in the impact resistance. As a result of further research, the present inventors found that by adding a specific surface treatment agent to the above composition, the heat resistance and mechanical strength were further improved, and the fluidity when melted was improved. discovered that a composition with improved magnetic properties and mechanical strength could be obtained,
This led to the present invention.

That is, the present invention relates to a magnetic composite material composition formed by mixing magnetic powder, additives such as a surface treatment agent, and a binder resin consisting of a melt-processable polymer composition that forms an anisotropic melt phase. When using the binder resin of the present invention, a magnetic composite material composition containing a large amount of magnetic powder with a binder resin content of 95 double rings relative to the total amount of magnetic powder and binder resin can be easily melted and molded. As a result, a target product with excellent properties can be obtained. The preferable binder resin content is 5 to 50fiii
%, especially from 7 to 20% by weight.

The binder resin of the present invention is a thermoplastic melt-processable polymer composition that exhibits optical anisotropy when melted, and is generally classified as a thermotropic liquid crystal polymer.

Polymers that form such an anisotropic melt phase have a property in which polymer molecular chains are regularly arranged in parallel in a molten state. The state in which the molecules are arranged in this way is often called the liquid crystal state or the nematic phase of liquid crystal materials. Such polymers are generally elongated, oblate, and are made from monomers that are fairly rigid along the long axis of the molecule and have multiple chain extensions, usually in either coaxial or parallel relationships. Manufactured.

The nature of the anisotropic melt phase can be confirmed by conventional polarization testing using crossed polarizers. More specifically, the anisotropic melt phase can be confirmed by using a Leitz polarizing microscope and observing a sample placed on a Leitz hot stage at a magnification of 40 times under a nitrogen atmosphere.

The polymer is optically anisotropic. That is, it transmits light when examined between orthogonal polarizers. If the sample is optically anisotropic, polarized light will pass through it even if it is at rest.

Constituent components of the polymer that forms the anisotropic melt phase as described above include: - Consisting of one or more of aromatic dicarboxylic acids and alicyclic dicarboxylic acids - Aromatic diols, alicyclic diols, and aliphatic diols ■ Consisting of one or more aromatic hydroxycarboxylic acids ■ Consisting of one or more aromatic thiol carboxylic acids ■ One of aromatic dithiol, aromatic thiol phenol
Polyesters consisting of one or more of aromatic hydroxyamines and aromatic diamines, etc. Polyesters that form an anisotropic melt phase include polyesters consisting of ■)■ and ■■) Polyester consisting of only ■ Polyester consisting of ■) ■, ■ and ■ ■) Polythiol ester consisting only of ■ ■) Polythiol ester consisting of ■ and ■ ■) Polythiol ester consisting of ■ and ■ ■) ■ and ■ It is composed of a combination of polyester amide consisting of - I) polyester amide consisting of ■, ■, and polyester amide consisting of ■ and ■.

Furthermore, although it is not included in the above range of combinations of ingredients,
Polymers that form an anisotropic melt phase include aromatic polyazomethines, and specific examples of such polymers include poly trilo-2=methyl-1,4-phenylenenitrilomethylidine-1,4-phenylenemethylidine ) ; poly
Trilow 2-methyl-1,4-phenylenenitrilomethylidine-1,4-phenylenemethylidine); and Trilow 2-chloro-1,4-phenylenenitrilomethylidine-1,4-phenylenemethylidine) Can be mentioned.

Furthermore, although it is not included in the above range of combinations of ingredients,
Polyester carbonate is included as a polymer that forms an anisotropic melt phase. It may consist essentially of 4-oxybenzoyl units, dioxyphenyl units, dioxycarbonyl units and terephthaloyl units.

The compounds constituting the above-mentioned components (1) to (2) are listed below.

As the aromatic dicarboxylic acid, terephthalic acid, 4.4"
-diphenyldicarboxylic acid, 4.4"-triphenyldicarboxylic acid, 2,6-naphthalene dicarboxylic acid, diphenyl ether-4,4°-dicarboxylic acid, diphenoxyethane-4,4"-dicarboxylic acid, diphenoxybutane-4 , 4'-dicarboxylic acid, diphenylethane-4,4
"-dicarboxylic acid, isophthalic acid, diphenyl ether-3,3'-dicarboxylic acid, diphenoxyethane-3,
Aromatic dicarboxylic acids such as 3°-dicarboxylic acid, diphenylethane-3,3'-dicarboxylic acid, naphthalene-1,6-dicarboxylic acid, or chloroterephthalic acid, dichloroterephthalic acid, bromoterephthalic acid, methylterephthalic acid, Examples include alkyl, alkoxy or halogen substituted products of the aromatic dicarboxylic acids such as dimethyl terephthalic acid, ethyl terephthalic acid, methoxyterephthalic acid and ethoxyterephthalic acid.

Examples of alicyclic dicarboxylic acids include alicyclic dicarboxylic acids such as trans-1゜4-cyclohexanedicarboxylic acid, cis-1,4-cyclohexanedicarboxylic acid, and 1,3-cyclohexanedicarboxylic acid, or trans-1,4-( 1
-methyl)cyclohexanedicarboxylic acid, trans-1
, 4-(1-chloro)cyclohexanedicarboxylic acid, etc.
Examples include alkyl, alkoxy, or halogen-substituted products of the above alicyclic dicarboxylic acids.

Aromatic diols include hydroquinone, resorcinol, 4.4'-dihydroxydiphenyl, 4.4'-dihydroxytriphenyl, 2,6-naphthalenediol,
4.4'-dihydroxydiphenyl ether, bis(4
-hydroxyphenoxy)ethane, 3,3'-dihydroxydiphenyl, 3,3°-dihydroxydiphenyl ether, 1,6-naphthalenediol, 2,2-bis(
4-hydroxyphenyl)propane, 2,2-bis(4
Aromatic diols such as -hydroxyphenyl)methane or chlorohydroquinone, methylhydroquinone, 1
-Butylhydroquinone, phenylhydroquinone, methoxyhydroquinone, phenoxyhydroquinone:
Examples include alkyl, alkoxy or halogen substituted products of the above aromatic diols such as 4-chlorresorcin and 4-methylresorcin.

Examples of alicyclic diols include trans-1,4-cyclohexanediol, cis-1,4-cyclohexanediol, trans-1,4-cyclohexane dimetatool,
Alicyclic diols such as cis-1,4-cyclohexane dimetatool, trans-1,3-cyclohexanediol, cis-1,2-cyclohexanediol, trans-1,3-cyclohexane dimetatool, or trans-1 , 4-(1-methyl)cyclohexanediol,
Examples include alkyl, alkoxy or halogen substituted products of the above alicyclic diols such as trans-1,4-(1-chloro)cyclohexanediol.

As the aliphatic diol, ethylene glycol, 1.3
- Straight chain or branched aliphatic diols such as propanediol, 1,4-butanediol, neopentyl glycol and the like can be mentioned.

Examples of aromatic hydroxycarboxylic acids include 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, and 6-hydroxybenzoic acid.
Aromatic hydroxycarboxylic acids such as 2-naphthoic acid, 6-hyFC+xy-1-naphthoic acid, or 3-methyl-4
-Hydroxybenzoic acid, 3,5-dimethyl-4-hydroxybenzoic acid, 2,6-dimethyl-4-hydroxybenzoic acid, 3-methoxy-4-hydroxybenzoic acid, 3.5
-dimethoxy-4-hydroxybenzoic acid, 6-hydroxy-5-methyl-2-naphthoic acid, 6-hydroxy-5
-methoxy-2-naphthoic acid, 3-chloro-4-hydroxybenzoic acid, 2-chloro-4-hydroxybenzoic acid,
2,3-dichloro-4-hydroxybenzoic acid, 3,5-
Dichloro-4-hydroxybenzoic acid, 2,5-dichloro-4-hydroxybenzoic acid, 3-bromo-4-hydroxybenzoic acid, 6-hydroxy-5-chloro-2-naphthoic acid, 6-hydroxy-7-chloro 2-naphthoic acid,
Examples include alkyl, alkoxy or halogen substituted aromatic hydroxycarboxylic acids such as 6-hydroxy-5,7-dichloro-2-naphthoic acid.

Examples of aromatic mercaptocarboxylic acids include 4-mercaptobenzoic acid, 3-mercaptobenzoic acid, 6-mercapto-2-naphthoic acid, and 7-mercapto-2-naphthoic acid.

Examples of the aromatic dithiol include benzene-1,4-dithiol, benzene-1,3-dithiol, 2,6-naphthalene-dithiol, and 2,7-naphthalene-dithiol.

Examples of aromatic mercaptophenol include 4-mercaptophenol, 3-mercaptophenol, 6-mercaptophenol, and 7-mercaptophenol.

Aromatic hydroxyamine, aromatic diamine is 4-
Aminephenol, N-methyl-4-aminophenol, 1,4-phenylenediamine/N-methyl-1,4-
Phenyldiamine, N, N'-dimethyl-1,4-
Phenylenediamine/3-aminophenol, 3-methyl-4-aminophenol, 2-chloro-4-aminophenol, 4-amino-1-naphthol, 4-aminol 4°-hydroxydiphenyl, 4-amino-4' -Hydroxydiphenyl ether, 4-amino-4"-hydroxydiphenylmethane, 4-amino-4°-hydroxydiphenyl sulfide, 4.4'-diaminophenyl sulfide (thiodianiline), 4.4'-diaminodiphenylsulfone, 2.5- Diaminotoluene, 4.4
"-ethylene dianiline, 4.4°-diaminodiphenoxyethane, 4.4°-diaminodiphenylmethane (methylene dianiline), 4.4'-diaminodiphenyl ether (oxydianiline), and the like.

The above-mentioned polymers I) to ① consisting of each of the above components may or may not form an anisotropic melt phase depending on the constituent components, the composition ratio in the polymer, and the sea fence distribution, but they may or may not form an anisotropic melt phase. The polymer used is the above-mentioned poly'7-
It is limited to those that form an anisotropic melt phase.

Polyesters (N, n), III) and polyesteramides (3), which are polymers that form an anisotropic melt phase suitable for use in the present invention, have functional groups that form required repeating units by condensation. They can be produced by a variety of ester-forming methods that allow the reaction of organic monomer compounds that are For example, the functional groups of these organic monomer compounds may be carboxylic acid groups, hydroxyl groups, ester groups, acyloxy groups, acid halides, amine groups, and the like. The above organic monomer compounds can be reacted without the presence of a heat exchange fluid by a melt acidolysis method. In this method, the seven polymers are first heated together to form a molten solution of the reactants. As the reaction continues, solid polymer particles become suspended in the liquid. Vacuum may be applied to facilitate removal of by-product volatiles (eg acetic acid or water) during the final stage of condensation.

Slurry polymerization techniques can also be employed to form fully aromatic polyesters suitable for use in the present invention. In this process, a solid product is obtained in suspension in a heat exchange medium.

Regardless of whether the above-mentioned melt acidolysis method or slurry polymerization method is employed, the organic monomer reactant for inducing the fully aromatic polyester is in a modified form (i.e., lower (as an acyl ester). The lower acyl group preferably has about 2 to 4 carbon atoms. Preferably, an acetate ester of such an organic monomer reactant is subjected to the reaction.

Furthermore, representative examples of catalysts that can optionally be used in either the melt acidolysis method or the slurry method include dialkyltin oxides (e.g., dibutyltin oxide), diaryltin oxides, titanium dioxide, antimony dioxide, alkoxytitanium silicates, titanium alkoxides, Gaseous acid catalysts such as alkali and alkaline earth metal salts of carboxylic acids (eg, zinc acetate), Lewis (eg, BP, ``)'', hydrogen halides (eg, IIcI ''), and the like. The amount of catalyst used is generally about 0.001 to 1% by weight, especially about 0.01 to 0.2% by weight, based on the total weight of monomers.

Fully aromatic polymers suitable for use in the present invention tend to be substantially insoluble in common solvents and are therefore unsuitable for solution processing.

However, as previously mentioned, these polymers can be readily processed using conventional melt processing techniques. Particularly preferred fully aromatic polymers are somewhat soluble in pentafluorophenol.

Fully aromatic polyesters suitable for use in the present invention generally have a weight average molecular weight of about 2,000 to 200,000.
, preferably from about 10,000 to so,ooo, particularly preferably from about 20,000 to 25,000. On the other hand, suitable fully aromatic polyester amides generally have a molecular weight of about s, ooo to 50,000, preferably about 10,000.
~30,000, for example 15,000-17,000. Such molecular weight measurements can be carried out by gel permeation chromatography as well as other standard methods of measuring polymers that do not involve solution formation, such as quantification of end groups by infrared spectroscopy on compression molded films. Alternatively, the molecular weight can be measured using a light scattering method using a pentafluorophenol solution.

The fully aromatic polyesters and polyesteramides described above also yield 0.1% of pentafluorophenol at 60°C.
When dissolved at a weight percent concentration of at least about 2.0 d
! /g, for example from about 2.0 to 10.041 g.

Particularly preferred anisotropic melt phase forming polyesters for use in the present invention include repeating units containing naphthalene moieties such as 6-hydroxy-2-naphthoyl, 2,6-dihydroxynaphthalene and 2,6-dicarboxynaphthalene. It contains about 10 mol% or more. Preferred polyesteramides are those containing repeating units of the naphthalene moiety described above and a moiety consisting of 4-aminophenol or 1,4-phenylenediamine. Specifically, the details are as follows.

(1) A polyester consisting essentially of the following repeating units I and ■.

The polyester contains about 10 to 90 mole percent of units I and about 1
Contains 0 to 90 mol % of units (■). In one embodiment, Unit I is present in an amount of about 65-85 mol%, preferably about 70-80 mol% (eg, about 75 mol%). In another embodiment, the unit ■ is present in much lower concentrations of about 15-35 mole %, preferably about 20-30 mole %.

In addition, at least a portion of the hydrogen atoms bonded to the ring may optionally be selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, halogen, phenyl, substituted phenyl, and a combination thereof. It may be substituted with selected substituents.

(2) A polyester consisting essentially of the following repeating units I, ■ and ■.

This polyester contains about 30 to 70 mole % of units I. The polyester preferably has about 40 to 60
It contains about 20 to 30 mol % of units (2), about 20 to 30 mol % of units (2), and about 20 to 30 mol % of units (2). In addition, at least some of the hydrogen atoms bonded to the ring may optionally be
It may be substituted with a substituent selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, halogen, phenyl, substituted phenyl, and combinations thereof.

(3) Polyester consisting essentially of the following repeating units ■, ■, ■ and ■: (wherein R means methyl, chloro, bromo or a combination thereof, and is a substituent for the hydrogen atom on the aromatic ring. ), and about 20 to 60 mol% of unit I,
It contains about 5 to 18 mol % of units 1, about 5 to 35 mol % of units m, and about 20 to 40 mol % of units . The polyester preferably contains about 35 to 45 mole % units ■, about 10 to 15 mole % units ■, about 15 to 2
5 mol% unit■, and approximately 25-35 mol% unit■
Contains. However, the total molar concentration of units ■ and ■ is substantially equal to the molar concentration of unit ■.

In addition, at least some of the hydrogen atoms bonded to the ring are
Optionally, an alkyl group having 1 to 4 carbon atoms, 1 to 4 carbon atoms
may be substituted with a substituent selected from the group consisting of an alkoxy group, halogen, phenyl, substituted phenyl, and combinations thereof. This fully aromatic polyester was converted into pentafluorophenol by 0.3w at 60°C.
/v! At least 2.0411 g when dissolved in concentration
For example, it generally exhibits a logarithmic viscosity of 2.0 to 10.0 aj/g.

(4) Polyester consisting essentially of the following repeating units r, ■, ■ and ■: ■ General formula -EO-Ar-0) (wherein Ar means a divalent group containing at least one aromatic ring) ) dioxyaryl unit represented by the general formula (C-Ar'-C
) (wherein ^r' is a dicarboxyaryl unit represented by a small number (both mean a divalent group containing one aromatic ring), and about 20 to 40 mol% of unit 1, unit exceeding 10 mol% and not more than about 50 mol%, unit ■ exceeding 5 mol% and not more than about 30 mol%, and unit ■ 5 mol%
30 mole % or less. The polyester preferably contains about 20 to 30 mole percent (e.g., about 2
5 mol%) of unit I, about 25 to 40 mol% (e.g. about 3
5 mol%) unit ■, about 15 to 25 mol% (e.g. about 20
mol %) of the unit (2), and about 15 to 25 mol % (eg, about 20 mol %) of the unit (2). In addition, at least a portion of the hydrogen atoms bonded to the ring may optionally be a group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, halogen, phenyl, substituted phenyl, or a combination thereof. may be substituted with a substituent selected from.

Units ■ and ■ have a symmetrical arrangement on one or more aromatic rings in which the divalent bonds connecting these units to other units on either side within the polymer backbone (e.g., on a naphthalene ring) When present, they are preferably symmetrical in the sense that they are disposed apart from each other or on a diagonal ring. However, asymmetric units such as those derived from resorcinol and isophthalic acid can also be used.

The preferred dioxyaryl unit ■ is and the preferred dicarboxyaryl unit ■ is It is.

(5) Polyester consisting essentially of the following repeating units ■, ■ and ■: ■ With the general formula (0-Ar-0) (wherein Ar means a divalent group containing at least one aromatic ring) dioxyaryl unit shown (meaning a divalent group containing at least one aromatic ring), and about 10 to 90 mol% of unit I and 5 to 45 mol% of unit Contains 5 to 45 mol% of unit (2) by mol%. The polyester preferably contains about 20 to 80 mole % I units.

It contains about 10 to 40 mol % of units (2) and about 10 to 40 mol % of units (2). More preferably, the polyester has about 60 to 80 mole percent of units ■, about 10 to 2.0
It contains about 10 to 20 mole % of units (■) and about 10 to 20 mole % of units (2). In addition, at least a portion of the hydrogen atoms bonded to the ring may optionally be a group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, halogen, phenyl, substituted phenyl, or a combination thereof. may be substituted with a substituent selected from.

The preferred dioxyaryl unit ■ is and the preferred dicarboxyaryl unit ■ is It is.

(6) Polyester amide consisting essentially of the following repeating units I, ■, ■ and or divalent trans-cyclohexane group), ■ General formula Y-Ar-Z)
(In the formula, the total is a divalent group containing at least one aromatic ring, Y
means 0, NH or NR, Z means NH or NR, respectively, R means an alkyl group having 1 to 6 carbon atoms or an aryl group), IV-9 formula (0-Ar'-
0) (wherein Ar' means a divalent group containing at least one aromatic ring), and consists of about 10 to 90 mol% of unit I, about 5 to 45 mol% of unit It contains about 5 to 45 mol % of (1) and about 0 to 40 mol % of units (2). In addition, at least a portion of the hydrogen atoms bonded to the ring may optionally be a group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, halogen, phenyl, substituted phenyl, or a combination thereof. may be substituted with a substituent selected from.

Preferred dicarboxyaryl units (2) are, preferred units (2) are, and preferred dioxyaryl units (2) are.

Furthermore, the polymer forming the anisotropic melt phase of the present invention includes:
A part of one polymer chain is composed of polymer segments that form an anisotropic melt phase as explained above, and the remaining part is composed of thermoplastic resin segments that do not form an anisotropic melt phase. Also includes polymers.

As the magnetic substance used in the present invention, magnetic powder commonly used in magnetic composite materials can be used. For example, hard magnetic powders include hard ferrite such as strontium ferrite, rare earth cobalt, and alnico powders, and soft magnetic powders include Fe, Mn, Go, Ni, and Cu.
, soft ferrite made of metal oxides such as Zn+Mg, carbonyl iron, permalloy, sendust, and other powders. The average particle size of the magnetic powder is generally 0.5 to 2.0 μm for hard ferrite powder, 1 to 100 μm for rare earth cobalt powder, and 2 to 100 μm for soft ferrite powder and carbonyl powder.

However, the average particle diameter of the magnetic powder used in the present invention is not limited to the above numerical range.

The additives used in the present invention improve the wettability of the filler surface, and those commonly used in magnetic composite materials can be used, such as surfactants and low-viscosity/liquid oily substances. (silicone oil, mineral oil, other oils, etc.), and in particular, a so-called coupling agent, which is a surface treatment agent that modifies the surface by reacting with the filler surface, is suitable.

In the present invention, the surfactant primarily serves as a wetting agent. Here, the surfactant is a cationic type,
They can be classified into anionic, nonionic, and amphoteric types, and any of them can be used in the present invention.

As an anionic surfactant, Phosphate ester type M=, Na or (CJtO)nH M=+Na or (Cz)ItO), lH sulfonic acid type S03M RO5OIMM=K or Na Sulfate ester type RO(cz++no) -5O:IM etc.

As for the cation type, quaternary ammonium salt type imidacillin type amide amine type X-=NOff-, CH: +C00-+R (CJaO)
Examples include 1) z-, C) I:+5On-, and the like.

Nonionic types include alkyl ether, ester type RO (CzH40), 1H RCOO (CzHnO), polyoxyethylene sorbitan ester type CHz
CHCOOR Alkylamine type, alkylamide type, etc. are mentioned.

As a bisexual type betaine type R' RN”-CH2COO- Alanine type RNHCHzcOONa etc.

These surfactants are used in the same way as for normal thermoplastic resins, but considering thermal stability etc.
Anionic, nonionic and amphoteric surfactants are preferred, and nonionic surfactants are particularly preferred.

The surfactant is used in an amount of 0.1% to 5% by weight of the total weight including the resin.

Both silane and titanate coupling agents can be used, but they must have a decomposition temperature of 270° C. or higher. This is because the binder resin requires a melt processing temperature of 280'C or higher, and the composite material composition of the present invention requires a melt processing temperature of 300C or higher. In other words, a surface treatment agent with a decomposition temperature lower than 270°C will thermally decompose during melt processing, resulting in a decrease in the compatibility between the binder resin and the magnetic powder, resulting in poor moldability and mechanical properties, which are the characteristics of the present invention. In addition, the generation of decomposed gas causes foaming on the surface of the molded product.

Examples of silane cuff pulling agents include the following.

Amino-based N,N-dimethyl-p-aminophenyltrimethoxysilane, p-(N-β-(aminoethyl)-aminoethyl)phenethyltrimethoxysilane, p-(aminomethyl)phenethyltrimethoxysilane, N-phenyl −γ
-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane,
N-β-(aminoethyl)-T-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-β-(aminoethyl)-di-aminopropylmethyljethoxy silane,
Organosilicon compounds such as γ-aminopropyltrimethoxysilane, T-aminopropyltriethoxysilane, and polyaminosilane.

Vinyl-based vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, chloro-based 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane methacryloxy-based 3-methacryloxypropyltrimethoxysilane.

Further, particularly preferred camping agents have a decomposition temperature of 300
℃ or higher, the following epoxy-based and mercapto-based coupling agents may be mentioned.

Epoxy-based 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(
3,4-Epoxycyclohexyl)ethyltrimethoxysilane Mercapto-based 3-mercaptopropyltrimethoxysilane On the other hand, examples of titanate coupling agents having a decomposition temperature of 270°C or higher include the following.

Isopropyl triisostearoyl titanate, isopropyl trioctanoyl titanate, isopropyl diisostearoyl cumylphenyl titanate, isopropyl distearoyl methacryl titanate, isopropyl dimethacrylylisostearoyl titanate, isopropyl dodecylbenzenesulfonyl titanate, isopropyl diisostearoyl acrylic titanate, isopropyl isostearoyl Diacryl titanate, Isopropyl tri (dioctyl phosphate) titanate, Isopropyl tri n-stearoyl titanate, Isopropyl 4-aminobenzenesulfonyl di(dodecylbenzenesulfonyl) titanate, Isopropyl trimethacryl titanate, Isopropyl tricumylphenyl titanate, Isopropyl di(4-amino) benzoyl)isostearoyl titanate, isopropyltri(dioctylpyrophosphate)titanate, isopropyltriacryltitanate, isopropyltri(N,N-dimethyl-ethylamino)titanate, isopropyltri(dioctylpyrophosphate)titanate
(N-ethylamino-ethylamino) titanate, isopropyltrianthranyl titanate, isopropyloctylbutylpyrophosphate titanate, isopropyldi(butyl, methylpyrophosphate)titanate, tetraisoprovir di(dilaurylphosphite)
Titanate, tetraisoprobyl di(dioctyl phosphite) titanate, tetraoctyl di(ditridecyl phosphite) titanate, tetra(2,2-diallyloxymethyl-1-butoxy) di(di-tridecyl) phosphite titanate, diisostearoyl Oxyacetate titanate, isostearylmethacryloxyacetate titanate, isosteacoyl acrylicoxyacetate titanate, di(dioctylphosphate)oxyacetate titanate, 4-aminobenzenesulfonyldodecylbenzenesulfonyloxyacetate titanate, dimethacryloxyacetate titanate, dicumylfer rate oxyacetate titanate,
4-aminobenzoyl isostearoyloxyacetate titanate, di(dioctylpyrophosphate)oxyacetate titanate, diacryloxyacetate titanate, di(octyl, butylpyrophosphate)oxyacetate titanate, diisostearoylethylene titanate, isostearoylmethacrylethylene titanate, Di(dioctyl phosphate) ethylene titanate, 4-aminobenzenesulfonyldodecylbenzenesulfonyl ethylene titanate, dimethacrylic ethylene titanate, 4-aminobenzene isostearoyl ethylene titanate, di(dioctyl pyrophosphate) ethylene titanate, diacrylic ethylene titanate, dianthranyl ethylene titanate, di(butyl, methyl, pyrophosphate) ethylene titanate, etc.

The amount of these additives varies depending on the particle size, specific surface area, surface activity, etc. of the magnetic powder, but usually 100% of the magnetic powder is added.
0.01 to Lot parts, preferably 0.01 to parts by weight.
It is 1 to 5 parts by weight.

The composite material composition of the present invention is obtained by simultaneously charging and mixing a melt-processable polymer composition forming an anisotropic melt phase, a magnetic powder, and a surface additive into a mixer or kneader. As a pretreatment, additives such as a surface treatment agent are added to the magnetic powder to perform surface treatment (preferably. In order to achieve a more uniform surface treatment, the surface treatment agent may be mixed with methyl alcohol or ethyl alcohol. It may be used by diluting it with a lower alcohol such as or pH-adjusted water, and then drying it.

As a method for molding the magnetic composite material composition of the present invention, a general method for molding magnetic composite materials can be used. That is, conventionally, when the binder resin is a thermosetting resin or a thermoplastic resin, compression molding and injection molding are used, respectively. Also,
When magnetized after molding, it becomes an isotropic magnet, but in order to create an anisotropic magnet with strong anisotropy of magnetic properties, molding with an electromagnet that generates a magnetic field inside or outside the mold is required. Depending on the machine, a magnetic field forming method is used in which magnetization is performed at the same time as forming. In this method, the mold is made of a combination of a non-magnetic material that does not conduct magnetism and a general magnetic material in order to induce a magnetic field in a predetermined direction of the cavity. Generally, the magnetic field of the mold cavity is required to be 10.0000e or more.

The melt-processable polymer composition that forms an anisotropic melt phase used in the present invention includes: (1) other polymers that form an anisotropic melt phase, (2) thermoplastic resins that do not form an anisotropic melt phase, (2) It may contain one or more of the following: a thermosetting resin, (1) a low-molecular organic compound, and (2) an inorganic substance. Here, the polymer forming the anisotropic melt phase and the remaining portion in the composition may or may not be thermodynamically compatible.

Examples of the above thermoplastic resin (■) include polyethylene,
Polypropylene, polybutylene, polybutadiene, polyisoprene, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, polystyrene, acrylic resin, ABS
Resin, AS resin, BS resin, polyurethane, silicone resin, fluorine resin, polyacetal, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, aromatic polyester, polyamide, polyacrylonitrile, polyvinyl alcohol, polyvinyl ether, polyetherimide, polyamideimide, polyetheretherimide, polyetheretherketone,
These include polyether sulfone, polysulfone, polyphenylene sulfide, polyphenylene oxide, and the like.

Examples of the thermosetting resin (2) include phenol resins, epoxy resins, melamine resins, urea resins, unsaturated polyester resins, and alkyd resins.

Examples of the low-molecular-weight organic compounds mentioned in (1) above include substances added to general thermoplastic resins and thermosetting resins, such as stabilizers such as plasticizers, antioxidants, and ultraviolet absorbers;
Antistatic agents, flame retardants, colorants such as dyes and pigments, foaming agents,
Furthermore, divinyl compounds, crosslinking agents such as peroxides and vulcanizing agents, and low-molecular organic compounds used as lubricants for improving fluidity and mold release properties are also included.

Furthermore, the above-mentioned inorganic substances include, for example, substances added to general thermoplastic resins and thermosetting resins, such as general inorganic fibers such as glass fibers, carbon fibers, metal fibers, ceramic fibers, boron fibers, asbestos, etc. Powdered materials and carbonization such as calcium carbonate, highly dispersed silicic acid, alumina, aluminum hydroxide, talc powder, mica, glass flakes, glass peas, quartz powder, silica sand, various metal powders, carbon blank, barium sulfate, calcined gypsum, etc. Inorganic compounds such as silicon, alumina, boron nitride and silicon nitride,
Includes whiskers, metal whiskers, etc.

〔Example〕

Examples of the magnetic composite material composition of the present invention are shown below,
The present invention is not limited to these examples. In the examples, all parts represent parts by weight.

Examples 1 to 8 Strontium ferrite powder with an average particle size of 1.2 μm, rare earth cobalt with an average particle size of 4 μm, a binder resin consisting of a polymer that forms an anisotropic melt phase described later, various surface treatment agents, and surfactants. , and an oily substance were blended in the proportions shown in Table 1, and then melt extruded at 300°C to produce chips. This chip was injected into a cylinder at a temperature of 300℃, a mold temperature of 70℃, and an injection pressure of 800kg/cm.
A disk-shaped specimen having a diameter of 20 mm and a thickness of 51 cm was prepared by injection molding in a magnetic field with an applied magnetic field of 120,000 e, and the melting fluidity and magnetic properties of this specimen were measured. In addition, under the same molding conditions and without applying a magnetic field, the length was 63.6 mm and the width was 6 mm.
．． A test piece measuring 35 mm x 12.80 mm in thickness and a test piece measuring 130 mm in length x 13 mm in width x 6.4 mm in thickness were prepared, and the Izod impact strength and heat distortion temperature of each were measured. The results are shown in Table 2.

Comparative Examples 1 to 4 Experiments were conducted in the same manner as in the examples except that no surface treatment agent, surfactant, or oily substance was used. The results are shown in Table 2.

The polymers A, B, C, and D used as the binder resin and forming the anisotropic melt phase have the following structural units.

=60/20/10/10 =60/20/20 [ =70/30 [ =70/15/15] Specific manufacturing methods for the above resins A, B, C, and D are described below.

Resin A> 1081 parts by weight of 4-acetoxybenzoic acid, 460 parts by weight of 6-acetoxy-2-naphthoic acid, 166 parts by weight of isophthalic acid
194 parts by weight of 1,4-diacetoxybenzene were charged into a reactor equipped with a stirrer, a nitrogen inlet tube, and a distillation tube, and the mixture was heated to 260° C. under a nitrogen stream. While distilling acetic acid from the reactor, the mixture was vigorously stirred at 260°C for 2.5 hours and then at 280°C for 3 hours.

Furthermore, after raising the temperature to 320°C and stopping the introduction of nitrogen, the pressure inside the reactor was gradually reduced to 0.5 minutes after 15 minutes.
The temperature was lowered to 1 mmHg, and the mixture was stirred at this temperature and pressure for 1 hour.

The resulting polymer had an intrinsic viscosity of 5.0, measured in pentafluorophenol at 0.1% concentration by weight and 60°C.

<Resin B> 1081 parts by weight of 4-acetoxybenzoic acid, 489 parts by weight of 2,6-diacetoxothyphthalate, 332 parts by weight of terephthalic acid
The double star part was placed in a reactor equipped with a stirrer, a nitrogen inlet tube, and a distillation tube, and the mixture was heated to 250° C. under a nitrogen stream. 250'C while distilling acetic acid from the reactor.
The mixture was vigorously stirred at 280° C. for 2 hours and then at 280° C. for 2.5 hours.

Furthermore, after raising the temperature to 320°C and stopping the introduction of nitrogen, the pressure inside the reactor was gradually reduced to 0.30 minutes later.
The temperature was lowered to 2 nuaHg, and the mixture was stirred at this temperature and pressure for 1.5 hours.

The resulting polymer had an intrinsic viscosity of 2.5, measured in pentafluorophenol at 60'C at a concentration of 0.1% by weight.

<Resin C> 1261 parts by weight of 4-acetoxybenzoic acid and 691 parts by weight of 6-acetoxy-2-naphthoic acid were charged into a reactor equipped with a stirrer, a nitrogen introduction pipe and a distillation pipe, and the mixture was heated under a nitrogen stream. The mixture was heated to 250°C. 3 hours at 250'C, then 280'C while distilling acetic acid from the reactor.
The mixture was stirred vigorously for 2 hours. Further, the temperature was raised to 320° C., and after stopping the introduction of nitrogen, the pressure in the reactor was gradually reduced, and after 20 minutes, the pressure was lowered to Q, 1 mm, and the mixture was stirred at this temperature and pressure for 1 hour.

The resulting polymer had an intrinsic viscosity of 5.4, measured in pentafluorophenol at a concentration of 0.1% by weight at 60°C.

Resin D> 6-acetoxy-2-naphthoate Ill 612 parts by weight,
290 parts by weight of 4-acetoxyacetanilide, 249 parts by weight of terephthalic acid, and 0.4 parts by weight of sodium acetate were charged into a reactor equipped with a stirrer, a nitrogen introduction pipe and a distillation pipe,
The mixture was heated to 250°C under a stream of nitrogen. While distilling acetic acid from the reactor, the temperature was 250°C for 1 hour, then 3 hours.
The mixture was stirred vigorously at 00° C. for 3 hours. Furthermore, the temperature was increased to 340°.
After stopping the introduction of nitrogen, the pressure in the reactor was gradually reduced to 0.2 mmHg after 30 minutes, and the mixture was stirred at this temperature and pressure for 30 minutes.

The resulting polymer had an intrinsic viscosity of 3.9, measured in pentafluorophenol at a concentration of 0.1% by weight at 60°C.

Procedural master's letter (spontaneous) September 8, 1986

Claims (1)

[Scope of Claims] 1 (A) magnetic powder, (B) binder resin consisting of a melt-processable polymer composition forming an anisotropic melt phase, (C) surfactant, low viscosity, liquid oil. A composite material composition formed by mixing one or more additives selected from the group consisting of a substance and a surface treatment agent. 2. The composite material composition according to claim 1, wherein the surface treatment agent is a titanate-based or silane-based coupling agent. 3. The composite material composition according to claim 2, wherein the coupling agent has a decomposition temperature of 270°C or higher. 4. The composite material composition according to claim 2, wherein the silane coupling agent is an epoxy or thiol coupling agent. 5. The composite material composition according to claim 4, wherein the coupling agent has a decomposition temperature of 300°C or higher. 6 The coupling agent is 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)
The composite material composition according to claim 5, which is ethyltrimethoxysilane or 3-mercaptopropyltrimethoxysilane.