JP2012149243A - Resin composition for molding, and electronic component using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a carbon material-containing resin composition for molding, capable of enhancing the electrical and thermal conductivities without damaging flowability at molding or appearance after molding by favorable dispersion of the carbon material.SOLUTION: There is provided a resin composition for molding which contains a thermoplastic resin (A) and the carbon material (B) and is excellent in dispersibility of the carbon material and in flowability of the resin composition by using a polyimide resin dispersant (C).

Description

The present invention relates to a molding resin composition containing a carbon material.

  Thermoplastic resins are widely used in all industries because of their ease of production and molding. For example, a polyamide resin is used as a molding material for automobile fuel parts in pipes, connectors, filters, injection parts and the like. Aromatic polycarbonate resins are widely used in the fields of electronic equipment and automobiles such as personal computers, electronic equipment, liquid crystal televisions and the like, lamp covers, interior and exterior parts, and the like.

  In these applications for automobiles and electronic devices, conductivity and heat dissipation are required. In recent years, especially in electronic devices, the heat generated in electronic devices is efficiently dissipated to the outside by increasing the density of semiconductor packages and increasing the speed and integration of LSIs with higher performance, smaller size, and lighter weight. Measures to dissipate heat are a very important issue. In addition, automobiles are being made of various parts of resin from the viewpoint of weight reduction, and countermeasures against static electricity are indispensable particularly in automobile fuel piping and the like, and there is an increasing demand for conductive resins.

  As a method for improving the electrical conductivity and heat dissipation (thermal conductivity), for example, carbon materials such as graphite, carbon black, and carbon nanotubes are heated in place of metals such as copper, aluminum, and stainless steel having electrical conductivity. A method of mixing with a plastic resin has been actively studied. If these carbon materials are not filled at a high concentration, sufficient electrical conductivity and thermal conductivity cannot be obtained. On the other hand, if they are filled at a high concentration, the good fluidity inherent to thermoplastic resins. For example, a short shot at the rib portion at the time of injection molding or a short shot to the farthest gate portion at a mold having a large L / T may occur.

As a method for improving fluidity, there is a method of adding a low molecular weight lubricant such as a fatty acid metal salt (metal soap), a fatty acid amide, or a compound containing a carboxylic acid such as isophthalic acid or terephthalic acid. Therefore, decomposition and sublimation occur during thermoforming, which may cause a flow mark or silver streak on the surface of the molded product, which may deteriorate the appearance of the molded product.
On the other hand, the electroconductivity which melt-molds, after adding 0.1-5 weight% of pentaerythritol fatty acid ester to the composition containing a thermoplastic resin and carbon black, carrying out the dispersion | distribution process and pelletizing by melt-kneading previously. A composition is known (see, for example, Patent Document 1). Pentaerythritol fatty acid ester has superior heat resistance compared to fatty acid metal salts (metal soaps) and fatty acid amides, so it can improve fluidity without being decomposed or sublimated even during injection molding. A large amount of black can be added.

  However, when this type of fatty acid ester is added to a thermoplastic resin, it is essential to impart lubricity in order to improve fluidity, and the thermoplastic resin achieved by lowering the compatibility with the thermoplastic resin to some extent. Is effective, but as a result, the physical properties inherent in the resin may be reduced. In addition, there is a concern that the range of applicable resins is limited for the above reasons. Moreover, although it is superior in heat resistance as compared with fatty acid metal salts and fatty acid amides, it does not describe heat resistance at 250 ° C. or higher. When used in a resin that is processed and molded at a high temperature of 250 ° C. or higher, there is a possibility that the dispersibility of carbon black may not be sufficiently obtained, and the dispersant itself is thermally decomposed and poorly differentiated. There is a concern about the appearance defect occurring due to the surface.

JP 2008-143991 A JP 2002-322366 A

  The problem of the present invention is that, in a molding resin composition containing a carbon material, the carbon material is well dispersed, whereby the electrical conductivity and thermal conductivity can be improved, and the appearance after molding at the time of molding is An object of the present invention is to provide a molding resin composition that is not damaged.

  The present inventors have found that the above problem can be solved by using a dispersant capable of dispersing the carbon material, and as the dispersant, the polyimide resin dispersant can disperse the carbon material at a high concentration, It has been found that the appearance after molding is also good.

  In addition, when the polyimide resin dispersant is a branched polyimide dispersant, the present inventors not only can disperse the carbon material at a high concentration, but also do not impair the fluidity of the thermoplastic resin used as the molding resin. In addition, it has been found that thermoforming is possible and the appearance after molding is also good.

  That is, the present invention provides a molding resin composition comprising a thermoplastic resin (A), a carbon material (B), and a polyimide resin dispersant (C).

  The present invention also provides a molding resin composition comprising a thermoplastic resin (A), a carbon material (B), and a branched polyimide resin dispersant (C).

  The present invention also provides a molding resin composition in which the branched polyimide resin dispersant (C1) is a branched polyimide resin dispersant (C2) having an isocyanuric ring structure.

  Moreover, this invention provides the molded object formed by shape | molding the said resin composition for shaping | molding.

  Moreover, this invention is a method of improving the fluidity | liquidity of the resin composition containing a thermoplastic resin (A) and a carbon material (B), Comprising: A branched polyimide resin dispersing agent (C1) is made with respect to a carbon material (B). The present invention provides a method for improving fluidity, characterized by adding 0.1 to 50% by weight.

According to the present invention, a carbon material can be favorably dispersed in a thermoplastic resin, and a molded article having a good appearance after molding can be obtained while enhancing conductivity and thermal conductivity.
Moreover, an electronic material and a conductive material can be obtained by molding the molding resin composition of the present invention.
Moreover, according to this invention, the method of improving the fluidity | liquidity of the resin composition containing a thermoplastic resin (A) and a carbon material (B) can be provided.

  In the present invention, the polyimide resin dispersant (C) improves the dispersibility when the carbon material (B) is blended with the thermoplastic resin (A). In particular, the use of the branched polyimide resin dispersant (C1) is preferable because the fluidity of the resin composition is kept good, and the molding is performed well even when a high-concentration carbon material (B) is blended. . Furthermore, the branched polyimide resin dispersant (C2) having an isocyanuric ring structure is particularly preferable because it can withstand a high molding temperature due to the heat resistance derived from the isocyanuric ring structure.

(Thermoplastic resin (A))
The thermoplastic resin (A) used in the present invention is not basically limited, and a known molding resin can be used.
For example, polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, (meth) acrylic resins such as polymethyl methacrylate and polyethyl methacrylate, polystyrene, acrylonitrile-butadiene-styrene resin, acrylonitrile-acrylic rubber- Styrene resin, acrylonitrile-ethylene rubber-styrene resin, (meth) acrylic ester-styrene resin, styrene resin such as styrene-butadiene-styrene resin, ionomer resin, polyacrylonitrile, polyamide resin such as nylon, ethylene-vinyl acetate resin , Ethylene-acrylic acid resin, ethylene-ethyl acrylate resin, ethylene-vinyl alcohol resin, polyvinyl chloride Chlorine resins such as polyvinylidene chloride, fluorine resins such as polyvinyl fluoride and polyvinylidene fluoride, polycarbonate resins, modified polyphenylene ether resins, methylpentene resins, cellulose resins, etc., and olefin elastomers, vinyl chloride elastomers, styrene elastomers, Examples thereof include thermoplastic elastomers such as urethane elastomers, polyester elastomers, and polyamide elastomers, polyphenylene sulfide resins, polyether imide resins, polyether ether ketone resins, thermoplastic polyimide resins, and mixtures of two or more thereof.

(Carbon material (B))
Specific examples of the carbon material (B) used in the present invention include carbon black (B-1), carbon nanotube (B-2), and graphite (B-3).

(Carbon black (B-1))
In the present invention, carbon black (B-1) is obtained by pyrolysis or incomplete combustion of hydrocarbons such as oil and natural gas, and is a primary in which graphite described later forms a layer and is partially fused. It consists of aggregates composed of particles. Aggregates aggregate by a van der Waals force and become agglomerates, which makes it difficult to disperse. In general, the smaller the average primary particle size, the higher the blackness and the higher the coloring power. However, since the specific surface area is large, the interface between the carbon black and the resin increases and the viscosity also increases. Specifically, as carbon black (B-1) used in the present invention, furnace black manufactured by the furnace method, acetylene black manufactured by the acetylene method, thermal black manufactured by the thermal method, manufactured by the channel method Channel black, ketjen black and the like.
Among these, when high conductivity is imparted, it is preferable to use acetylene black or ketjen black because of high crystallinity or high structure. In addition, it is particularly preferable to use furnace black when giving high blackness and high coloring power. The particle diameter, specific surface area, pH, and oil absorption are not particularly limited, and the average particle diameter is preferably 8 to 200 nm, more preferably 13 to 100 nm, and the specific surface area is preferably 10 to 700 m 2 / g. Preferably, 20 to 240 m2 / g, pH is preferably 2 to 10.5, more preferably 7 to 9.5, and oil absorption is preferably 50 to 320 ml / 100 g, more preferably 70 to 180 ml / 100 g. .

  The surface of carbon black (B-1) may be modified with a functional group so as to increase the affinity with the resin as long as the properties of the composition of the present invention are not impaired. Functionalization may be performed with a carboxyl group or an amino group. Further, carbon black may be used after being pretreated with a coupling agent, and examples of the coupling agent include isocyanate compounds, organic silane compounds, organic titanate compounds, and epoxy compounds.

  The content of the carbon black (B-1) is preferably 0.01 to 50 parts by weight, more preferably 0.3 to 30 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A). When the content of carbon black (B-1) is too small, there are few interfaces between carbon black and resin in the molded product, and the effect of improving mechanical strength (tensile strength, impact) due to the interaction cannot be obtained sufficiently. On the other hand, if the amount is too large, the interface between the carbon black and the resin in the molded article increases, and the fluidity decreases due to the increase in viscosity due to the interaction, which may lead to poor appearance.

(Carbon nanotube (B-2))
The carbon nanotube (B-2) used in the present invention has a cylindrical shape formed by winding one surface of graphite, which will be described later, and a single-wall nanotube (SWNT) having a structure wound in one layer, 2 Examples include multi-wall nanotubes (MWNTs) wound with more than one layer, and any of them can be used. Among these, multiwall nanotubes having a diameter of 20 nm or less are preferable, and the length is not particularly limited, but is preferably 100 nm or more so that a conductive path formed by adjacent carbon nanotubes can be efficiently performed. .

The carbon nanotube (B-2) used in the present invention can be generally produced by a laser ablation method, an arc heat radiation CVD method, a plasma CVD method, a gas phase method, a combustion method, etc., but any carbon nanotube produced by any method can be used. I do not care.
Further, the surface and end of the multi-walled carbon nanotube may be modified with a functional group in order to increase the affinity with the resin as long as the properties of the composition of the present invention are not impaired. Functionalization may be performed with a carboxyl group or an amino group. Further, carbon nanotubes may be used after being pretreated with a coupling agent, and examples of such a coupling agent include isocyanate compounds, organic silane compounds, organic titanate compounds, and epoxy compounds.

  The content of the carbon nanotube (B-2) is preferably 0.01 to 30 parts by weight, more preferably 0.15 to 15 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A). If the content of the carbon nanotube (B-2) is too small, the amount of conductive paths formed when the carbon nanotubes in the molded product are adjacent to each other becomes insufficient, and preferable conductivity cannot be obtained. If the amount is too large, the interface between the carbon nanotubes and the resin in the molded article increases, and the fluidity decreases due to an increase in the viscosity due to the interaction, resulting in poor appearance.

(Graphite (B-3))
The graphite (B-3) used in the present invention is also called graphite and refers to a crystal having a crystal formed by carbon atoms forming a hexagonal network plane layer, and the layer surfaces are regularly stacked. Although an average particle diameter is not specifically limited, 0.1-1000 micrometers is preferable and 25-1000 micrometers is more preferable. If the average particle size is 0.1 μm or less, the extrusion stability during production of the resin composition is poor and the productivity is lowered, which is not preferable. When the average particle diameter exceeds 1000 μm, the appearance of the surface of the molded product is deteriorated, which is not preferable.

The apparent bulk specific gravity of graphite (B-3) used in the present invention is preferably 0.01 g / cc or more, more preferably 0.05 or more and g / cc, still more preferably 0.10 g / cc. An apparent bulk specific gravity of less than 0.01 g / cc is not preferable because the extrusion stability during production of the resin composition is poor and the productivity is lowered.
Moreover, you may grind | pulverize by the method of grind | pulverizing using various well-known grinders as needed.

Graphite (B-3) used in the present invention is a method of graphitizing by treating a general carbon material from petroleum at a high temperature of 3000 ° C. or higher. After pyrolyzing an organic gas, pressurizing at a high temperature of 3000 ° C. or higher. Or a graphite whisker method in which carbon black, boron-added carbon powder, or the like is heat-treated at around 3000 ° C. and vapor-grown, etc., but graphite produced by any method may be used.
Moreover, the graphite (B-3) used by this invention shall also contain the expanded graphite which has the shape expanded in bowl shape. For expanded graphite, natural graphite naturally produced as a mineral, or petroleum coke, petroleum pitch, amorphous carbon, etc. were heat-treated at 2000 ° C. or higher, and the orientation of irregularly arranged fine graphite crystals was artificially performed. Artificial graphite is immersed in concentrated sulfuric acid, concentrated nitric acid, etc., and further treated by adding an oxidizing agent such as hydrogen peroxide or hydrochloric acid to form a graphite intercalation compound, and then washed with water, and then rapidly at 800 to 1000 ° C. It is graphite obtained by heating. The surface of the expanded graphite is subjected to surface treatment such as epoxy treatment, urethane treatment, silane coupling treatment, oxidation treatment, etc. in order to increase the affinity with the resin as long as the properties of the composition of the present invention are not impaired. Also good.

  The content of the graphite (B-3) is preferably 0.1 to 80 parts by weight, more preferably 1 to 70 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A). If the content of graphite (B-3) is too small, there are few interfaces between graphite and resin in the molded product, and the mechanical strength (tensile strength, impact) improvement effect due to the interaction may not be sufficiently obtained. On the other hand, if the amount is too large, the interface between the carbon black and the resin in the molded article increases, and the fluidity may decrease due to the increase in viscosity due to the interaction, resulting in poor appearance.

(Polyimide resin dispersant (C))
The polyimide resin dispersant (C) used in the present invention is a dispersant having a polyimide resin skeleton and capable of dispersing a carbon material. Specifically, there is no special limitation as long as it is a polyimide resin having an imide bond in the repeating structural unit of the polymer main chain, a method of polyimidizing from polyamic acid by dehydration cyclization, a carboxy group and / or an acid anhydride group. It can be manufactured by a method of reacting a compound having an isocyanate group with a compound having an isocyanate group.
The polyimide resin dispersant (C) used in the present invention can be used as long as it is a polyimide resin having an imide bond, but is more preferably a branched polyimide resin dispersant (C1) having a branched structure in the molecule. .

(Branched polyimide resin dispersant (C1))
The branched polyimide resin dispersant (C1) having a branched structure used in the present invention is a repeating structural unit of a polymer main chain obtained by reacting a monomer composition that is a polyfunctional monomer having at least one trifunctional or higher functionality. The dispersant is a polyimide resin having an imide bond.

  Since the branched polyimide resin dispersant (C1) has a branched structure, it has high fluidity, and can improve the fluidity of the resin composition when blending a high-concentration carbon material into the resin composition. Therefore, it is preferable.

  In order to produce the branched polyimide resin dispersant (C1), it is sufficient that at least one polyfunctional monomer having three or more functionalities is contained in the monomer composition before the reaction. Examples of the trifunctional or higher polyfunctional monomer that can be used include a trifunctional or higher polyfunctional monomer having an isocyanate group, a trifunctional or higher polyfunctional monomer having an acid anhydride group, and a trifunctional or higher polyfunctional monomer having an amino group. Examples thereof include polyfunctional monomers having three or more functional groups having functional groups other than functional monomers, isocyanate groups, acid anhydride groups, and amino groups.

[Trifunctional or higher polyfunctional monomer having an isocyanate group]
The trifunctional or higher polyfunctional monomer having an isocyanate group may be a monomer having at least one isocyanate group and having a total of three or more functional groups, and may be a low molecular weight monomer or a high molecular weight macromonomer. There may be a trifunctional or higher polyfunctional monomer having one isocyanate group, a trifunctional or higher polyfunctional monomer having two isocyanate groups, a trifunctional or higher polyfunctional monomer having three isocyanate groups, an isocyanate group. And a polyfunctional monomer having 4 or more. Since isocyanate groups are highly reactive and easily react with other functional groups, among them, polyfunctional monomers whose functional groups are all isocyanate groups are preferred.

Specifically, examples of the polyfunctional monomer having three isocyanate groups include isocyanurates composed of trimers of diisocyanate compounds, that is, triisocyanate compounds containing one isocyanurate ring. Examples of the diisocyanurate compound constituting the isocyanurate include p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, Aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 3,3'-diethyldiphenyl-4,4'-diisocyanate, naphthalene diisocyanate; isophorone diisocyanate, Hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, lysine diisocyanate Aliphatic diisocyanate and the like can be mentioned.
Furthermore, if it is a polyisocyanate compound containing two isocyanurate rings consisting of a pentamer of a diisocyanate compound, it becomes a polyfunctional monomer having four isocyanurate groups, and 3 isocyanurate rings consisting of a dimer of a diisocyanate compound. If it is a polyisocyanate compound containing one, a polyfunctional monomer having a different number of functional groups can be prepared depending on the number of diisocyanates constituting the polyisocyanate, such as a polyfunctional monomer having five isocyanurate groups.

[Trifunctional or higher functional monomer having an acid anhydride group]
The trifunctional or higher polyfunctional monomer having an acid anhydride group may be any monomer having at least one acid anhydride group and having at least three functional groups. Even a low molecular weight monomer may have a high molecular weight. The above-mentioned macromonomer may be a polyfunctional monomer having three or more functional groups having one acid anhydride group, a polyfunctional monomer having three or more functional groups having two acid anhydride groups, and three acid anhydride groups. Examples thereof include a polyfunctional monomer having three or more functions and a polyfunctional monomer having four or more acid anhydride groups.
Further, since the acid anhydride group is derived from two carboxy groups, one acid anhydride group may be replaced with two carboxy groups.

Specifically, polycarboxylic acid monoanhydride derivatives and the like are exemplified as the trifunctional or higher functional monomer having one acid anhydride group.
Examples of the trifunctional or higher functional monomer having two acid anhydride groups include polycarboxylic acid dianhydride derivatives.
Examples of the polyfunctional monomer having three acid anhydride groups include polycarboxylic acid dianhydride derivatives.
Is mentioned.

[Trifunctional or higher functional monomer having an amino group]
The trifunctional or higher polyfunctional monomer having an amino group may be any monomer having at least one amino group and a total of three or more functional groups, including low molecular weight monomers and high molecular weight macromonomers. There may be a trifunctional or higher polyfunctional monomer having one amino group, a trifunctional or higher polyfunctional monomer having two amino groups, a trifunctional or higher polyfunctional monomer having three amino groups, an amino group And a polyfunctional monomer having 4 or more.

Specifically, monofunctional polyhydroxy derivatives, monoamino polycarboxy derivatives, and the like are listed as the trifunctional or higher polyfunctional monomers having one amino group.
Examples of the trifunctional or higher polyfunctional monomer having two amino groups include diaminopolyhydroxy derivatives and diaminopolycarboxy derivatives.
Examples of the polyfunctional monomer having three amino groups include a triamine derivative, a triaminopolyhydroxy derivative, and a triaminopolycarboxy derivative.
Examples of the polyfunctional monomer having 4 or more amino groups include tetraamine derivatives, tetraaminopolyhydroxy derivatives, and tetraaminopolycarboxy derivatives.
Is mentioned.

[Trifunctional or higher polyfunctional monomer having a functional group other than isocyanate group, acid anhydride group and amino group]
The trifunctional or higher polyfunctional monomer having a functional group other than an isocyanate group, an acid anhydride group or an amino group does not contain an isocyanate group, an acid anhydride group or an amino group in the molecule, and has three other functional groups. Any monomer may be used as long as it has the above-described properties, and it may be a low molecular weight monomer or a macromonomer.
Examples of functional groups other than isocyanate groups, acid anhydride groups, and amino groups include one or more selected from hydroxyl groups, carboxyl groups, vinyl groups, epoxy groups, aldehyde groups, thiol groups, sulfonic acid groups, azo groups, and the like. It is done.
Specific examples of polyfunctional monomers having three or more functional groups other than isocyanate groups, acid anhydride groups, and amino groups include polyhydroxy derivatives, polycarboxy derivatives, polyvinyl derivatives, polyepoxy derivatives, polyaldehyde derivatives, One or more selected from polythiol derivatives, polysulfonic acid derivatives, polyazo derivatives and the like can be mentioned.

(Branched polyimide resin dispersant (C2) having an isocyanurate ring structure)
Among the branched polyimide resins (C1) having the branched structure, a branched polyimide resin dispersant (C2) having an isocyanurate ring structure is particularly preferable. This is because the branched polyimide resin dispersant (C2) having an isocyanurate ring structure is derived from the isocyanurate ring and has improved heat resistance.
The branched polyimide resin dispersant (C2) having an isocyanurate ring structure includes a polyisocyanate compound (1a) having three or more isocyanate groups and an acid anhydride (1b) of a polycarboxylic acid having three or more carboxy groups. Obtained by reacting in an organic solvent,

(Polyisocyanate compound having three or more isocyanate groups (1a))
The polyisocyanate compound (1a) may be any known polyisocyanate compound having three or more isocyanate groups. For example, a diisocyanate compound is an isocyanuration catalyst such as a quaternary ammonium salt. Isocyanurate ring-containing polyisocyanate compounds obtained by isocyanurate formation in the presence or absence of, for example, isocyanurates consisting of trimers of diisocyanate compounds, isocyanurates consisting of pentamers, and heptamers Isocyanurates and the like, and mixtures of these isocyanurates are preferred because of their excellent heat resistance. Examples of the diisocyanate compound include p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate. , 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 3,3'-diethyldiphenyl-4,4'-diisocyanate, naphthalene diisocyanate and other aromatic diisocyanates; isophorone diisocyanate, hexamethylene diisocyanate, 4,4 Aliphatic diisocyanates such as' -dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, lysine diisocyanate And the like. Among these polyisocyanate compounds, isocyanurates composed of trimers of cycloaliphatic diisocyanate compounds, that is, triisocyanate compounds containing one isocyanurate ring are preferable. Of these, isophorone diisocyanate is particularly preferred.
The proportion of the polyisocyanate compound (1a) in the isocyanate component is preferably 30% by weight or more from the viewpoint of heat resistance. Furthermore, the polyimide resin can be easily produced, the heat resistance of the molding resin composition and the carbon material dispersant. In particular, those containing 50% by weight or more, for example 50 to 95% by weight, are preferred, and the branched polyimide resin dispersant having an isocyanurate ring structure having excellent solvent solubility as well as heat resistance of the molding resin composition When (C2) is obtained, it is preferable to use 100% by weight.
Examples of the isocyanate component other than the polyisocyanate compound include known and commonly used aromatic diisocyanates and acyclic aliphatic diisocyanates.

  Furthermore, as said polyisocyanate compound (1a), it is a thing containing 5-30 weight% of isocyanate groups with respect to the said polyisocyanate compound, and a branched polyimide resin dispersing agent with favorable solvent solubility is obtained. Among them, it is particularly preferable that it contains 10 to 20% by weight of an isocyanate group.

(Acid anhydride (1b) of polycarboxylic acid having 3 or more carboxy groups)
The acid anhydride (1b) of the polycarboxylic acid used in the method for producing the branched polyimide resin dispersant (C2) having the isocyanurate ring structure is an acid anhydride derived from a polycarboxylic acid having 3 or more carboxy groups. There is no particular limitation, and tricarboxylic acid anhydrides and tetracarboxylic acid anhydrides are particularly preferred. Examples of the acid anhydride of tricarboxylic acid include trimellitic anhydride and naphthalene-1,2,4-tricarboxylic acid anhydride. Examples of the acid anhydride of tetracarboxylic acid include pyromellitic dianhydride; benzophenone-3,4,3 ′, 4′-tetracarboxylic dianhydride, diphenyl ether-3,4,3 ′, 4′- Tetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, biphenyl-3,4.3 ', 4'-tetracarboxylic dianhydride, biphenyl-2,3,2 ', 3'-tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1, 8,4,5-tetracarboxylic dianhydride, decahydronaphthalene-1,8,4,5-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7- Hexahydronaphthalene-1,2,5 6-tetracarboxylic dianhydride; 2,6-dichloronaphthalene-1,8,4,5-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,8,4,5-tetracarboxylic acid dianhydride Anhydride, 2,3,6,7-tetrachloronaphthalene-1,8,4,5-tetracarboxylic dianhydride, phenanthrene-1,2,9,10-tetracarboxylic dianhydride, berylene-3 , 4,9,10-tetracarboxylic dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 1,1-bis ( 2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride 2,3-bis 3,4-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride And tetracarboxylic anhydride having a group. In addition to these dianhydrides, there are monoanhydrides as tetracarboxylic acid anhydrides, which can be used alone or in combination with dianhydrides. Examples of the monoanhydride include those obtained by opening one of the anhydride groups of the dianhydride with an alcohol or the like. Moreover, what hydrogenated the acid anhydride which has said aromatic ring can be used individually or together with the acid anhydride which has said aromatic ring. Examples of such a compound include cyclohexanetricarboxylic acid and its anhydride. The acid anhydride (1b) of the polycarboxylic acid may be used alone or in combination of two or more. If necessary, an aromatic dicarboxylic acid compound and / or an anhydride thereof may be used in combination as long as the effects of the present invention are exhibited. Among these, it is more preferable to use trimellitic anhydride or hydrogenated trimellitic anhydride.

(Other polyisocyanate compound component (1c))
In the branched polyimide resin dispersant (C2) having the isocyanurate ring structure, the polyisocyanate compound (1a) is used as a polyisocyanate compound component. If necessary, other polyisocyanate compounds (1c) These may be used alone or in combination of two or more.

  Among the polyisocyanate compounds (1c), diisocyanate compounds are preferable, and examples thereof include p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2, Aromatics such as 6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 3,3'-diethyldiphenyl-4,4'-diisocyanate, naphthalene diisocyanate Diisocyanates; isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornylene diisocyanate Sulfonates, aliphatic diisocyanates such as lysine diisocyanate. Of these, aliphatic diisocyanates are particularly preferred.

When the polyisocyanate compound (1c) is used in combination as the polyisocyanate component in the branched polyimide resin dispersant (C2) having the isocyanurate ring structure, the number of moles of isocyanate groups (n _ac ) in the polyisocyanate compound (1a) And the polyisocyanate compound (1c) in a range where the ratio (n _ac ) / (n _h ) of the number of moles (n _h ) of isocyanate groups in the polyisocyanate compound (1c) is 1.0 or more. However, it is preferable to use in the range which becomes 1.5-10.5 especially.

(Urethane prepolymer type polyisocyanate compound component (1e))
In the branched polyimide resin dispersant (C2) having the isocyanurate ring structure, the polyisocyanate compound (1a) or (1c) is used as the polyisocyanate compound component. You may use together urethane prepolymer type polyisocyanate (1e) which has an isocyanate group in the terminal obtained from (1a) and (1c) and a polyol compound (1d). In order to produce the urethane prepolymer type polyisocyanate (1e), the polyisocyanate compound (1a) or (1c) and a polyol compound (1d) described later may be reacted by a known and conventional method.

(Polyol compound (1d))
In the urethane prepolymer type polyisocyanate compound component (1e), the polyol compound (1d) is not particularly limited as long as it is a polyol compound having two or more hydroxyl groups in one molecule. A compound having ˜6 is preferable, and a diol compound is particularly preferable. Examples of the polyol compound (1c) include alkyl polyols, polyester polyols, polyether polyols, polycarbonate polyols, urethane polyols, silicon polyols, acrylic polyols, and epoxy polyols.

  The branched polyimide resin dispersant (C2) having an isocyanurate ring structure used in the present invention preferably has an isocyanurate ring concentration of 0.6 to 1.1 mmol / g (resin solids conversion). Within the above range, a branched polyimide resin dispersant (C2) having an isocyanurate ring structure having good heat resistance and fluidity and excellent carbon material dispersibility can be obtained.

(Production method of polyimide resin dispersant (C))
As a preferable production method of the polyimide resin dispersant (C), a known and usual method may be used, for example, by reacting a compound having a carboxy group and / or an acid anhydride group with a compound having an isocyanate group in an organic solvent, The method etc. which manufacture a polyimide resin dispersing agent (C) are mentioned.
Moreover, as a preferable manufacturing method of the branched polyimide resin dispersant (C2) having an isocyanurate ring structure, a polycarboxylic acid anhydride (1b) and a polyisocyanate compound (1a) are heated at a temperature of 50 to 250 in an organic solvent. A method of reacting at 1 ° C. for 1 to 30 hours is preferable.

  In the production method of the branched polyimide resin dispersant (C2) having the isocyanurate ring structure, since the reaction is easy to control, an acid anhydride having a carboxy group is contained as the acid anhydride (1b) of the polycarboxylic acid. A method of reacting with the polyisocyanate compound (1a) using a compound to be used is preferable.

Furthermore, in the branched polyimide resin dispersant (C2) production method having the isocyanurate ring structure, a branched polyimide resin dispersant (C2) having an isocyanurate ring structure having sufficient heat resistance, fluidity, and carbon material dispersibility. In order to obtain, the ratio of the total number of moles of carboxylic acid anhydride groups and carboxy groups (n _b ) in the acid anhydride (1b) to the number of moles of isocyanate groups (n _a ) in the polyisocyanate compound (1a) (N _b ) / (n _a ) is preferably 0.3 to 2.0, and particularly preferably 0.6 to 1.8.

  As the organic solvent used in the method for producing the branched polyimide resin dispersant (C2) having the isocyanurate ring structure, various polar organic solvents can be used, and in particular, the branch having the isocyanurate ring structure used in the present invention. A solvent capable of dissolving the polyimide resin dispersant (C2), which is a polar solvent containing no nitrogen atom and sulfur atom, for example, an ether solvent, an ester solvent, a ketone solvent, etc. is preferable, and an ether solvent is used. Particularly preferred.

  Various ether solvents can be used, such as ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether; polyethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether; ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether acetate. Polyethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate; Polypropylene glycol dialkyl ethers such as propylene glycol dimethyl ether; Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate; Dipropylene glycol monomethyl ether Polypropylene glycol monoalkyl ether acetates such as Le acetate, and the like. Among them, polyethylene glycol monoalkyl ether acetates, polypropylene glycol monoalkyl ether acetates are preferred.

  Examples of the ester solvent include ethyl acetate and butyl acetate, and examples of the ketone solvent include acetone, methyl ethyl ketone, and cyclohexanone.

  The amount of the organic solvent used in the method for producing the branched polyimide resin dispersant (C2) having the isocyanurate ring structure is uniform in the system and can be reacted at a suitable reaction rate. A range in which the content is 10 to 70% by weight is preferable, and a range in which the content is 20 to 60% by weight is particularly preferable.

[Acid value and molecular weight]
In the polyimide resin dispersant (C), the acid value is not particularly essential, but is preferably 30-140, more preferably 60-130.
Moreover, in a polyimide resin dispersing agent (C), a preferable molecular weight is 1000-10000 in a number average.

In the method for producing the polyimide resin dispersant (C), when the polyimide resin dispersant (C) is obtained by reacting a compound having a carboxy group and / or an acid anhydride group with a compound having an isocyanate group, the carboxy group In addition, the molecular weight and acid value of the resulting polyimide resin dispersant (C) can be adjusted by changing the weight ratio of the compound having an acid anhydride group and the compound having an isocyanate group. Further, an imidation catalyst or the like may be used in the reaction between the compound having a carboxy group and / or an acid anhydride group and the compound having an isocyanate group.
Moreover, an acid value can be adjusted by making the carboxy group and / or acid anhydride group of the terminal structure of the obtained polyimide resin react with the compound which reacts with these functional groups. Examples of the compound that reacts with a carboxy group and / or an acid anhydride group include an epoxy derivative, an amino derivative, a hydroxy derivative, an isocyanate derivative, etc. Among them, an epoxy derivative is excellent in reactivity, and no by-product is produced. preferable. A monofunctional compound is preferred because there is no significant increase in the molecular weight of the resin.

  In the method for producing the polyimide resin dispersant (C), an acid anhydride group and / or a carboxy group in a compound having a carboxy group and / or an acid anhydride group are present at the molecular end, but the acid anhydride group is present at the molecular end. When present, the ring may be opened using water or the like to generate a carboxylic acid.

(Molecular weight adjustment)
The molecular weight is adjusted by reacting the carboxyl group or acid anhydride group remaining at the terminal of the branched polyimide resin dispersant (C1) with a compound having two or more functional groups that react with these functional groups in the molecule. Can do. Examples of the compound having two or more functional groups that react with a carboxy group and / or an acid anhydride group in the molecule include polyepoxy derivatives, polyamino derivatives, polyhydroxy derivatives, polyisocyanate derivatives, and the like. Is preferable because it has excellent reactivity and no by-products.

(Measuring method)
About the polyimide dispersing agent (C) in this invention, a branching degree, the density | concentration of an isocyanurate ring, an acid value, and a number average molecular weight can be measured with the following method.

Branching degree: The branching degree can be calculated from the following equation.
In the synthesis of the polyimide dispersant, the monomer charge used for the synthesis is W (g),
When a tri- or higher functional monomer is M _a (a is an integer starting from 1), the charged mole number of M _a is x _a (mol), and the number of functional groups contributing to the reaction of M _a is n _a (n is 3 If it is an integer above, the following formula is obtained.

Branching degree (mol / g) = [(n ₁ −2) × x ₁ ] + [(n ₂ −2) × x ₂ ] + [(n ₃ −2) × x ₃ ]... / W
The symbols in the above formula are as follows.
W: Charge of all monomer raw materials used in the synthesis (g)
n: number of functional groups of tri- or higher functional monomer material used for synthesis x; number of moles of charged tri- or higher functional monomer material used for synthesis (mol)

1. Concentration of isocyanurate ring: 13C-NMR analysis [solvent: deuterated dimethyl sulfoxide (DMSO-d6)] and branched polyimide resin using a calibration curve from the spectral intensity of carbon atoms caused by the isocyanurate ring at 149 ppm The concentration (mmol) of the isocyanurate ring per 1 g of the dispersant (C1) is determined. In addition, the concentration of the imide ring can be similarly determined from the spectral intensity of the carbon atom resulting from the imide ring at 169 ppm by 13C-NMR analysis.

2. Acid value: Measured according to JIS K-5601-2-1.
A resin sample (1.0 g) was dissolved in a mixed solvent of acetone / water (9/1 volume ratio) so that the acid value of acid anhydride could also be measured, and 0.1 mol / l potassium hydroxide / The neutralization titration was performed with an ethanol solution.

3. Epoxy equivalent: Can be measured by perchloric acid-tetraethylammonium bromide titration method according to JIS K 7236 (2001). Specifically, about 1 g of brominated epoxy resin is weighed in a 50 milliliter (mL) Erlenmeyer flask to a weighing accuracy of 0.1 mg, added with 20 mL of chloroform, and dissolved by stirring with a magnetic stirrer. To this solution, 2 mL of acetic acid, 1 mL of tetraethylammonium bromide acetic acid solution (a solution in which 25 g of tetraethylammonium bromide was dissolved in 100 mL of acetic acid), and a crystal violet indicator solution (a solution in which 1 mg of crystal violet was dissolved in 10 mL of acetic acid) Two to three drops are added, titrated with a commercially available 0.1 mol / L perchloric acid acetic acid standard solution, and the end point of the titration is determined by calculating the epoxy equivalent according to the following equation as the time when the color begins to turn green.

Epoxy equivalent _{= (1000 × m) / [} (V 1 -V 0) × (1- (t-t s) / 1000) × c]
The symbols in the above formula are as follows.
m: Mass of the sample (g)
V ₁ : Amount of perchloric acid acetic acid solution consumed for titration to the end point in the blank test (mL)
V ₀ : Amount of perchloric acid acetic acid solution consumed for titration to end point in sample measurement (mL)
t: Temperature of the perchloric acid acetic acid solution during the test and blank test (° C)
t _s ; temperature of perchloric acid acetic acid solution during standardization (° C)
c: Concentration of the perchloric acid acetic acid solution (usually 0.1 mol / L)

3. Number average molecular weight: The number average molecular weight in terms of polystyrene is determined by gel permeation chromatography (GPC). The number average molecular weight and the weight average molecular weight of the polyester resin (A) were measured by gel conversion using a gel permeation chromatograph under the following conditions.
Measuring device: HLC-8220 manufactured by Tosoh Corporation
Column: Tosoh Co., Ltd. Guard column H _XL- H
+ Tosoh Corporation TSKgel G5000H _XL
+ Tosoh Corporation TSKgel G4000H _XL
+ Tosoh Corporation TSKgel G3000H _XL
+ Tosoh Corporation TSKgel G2000H _XL
Detector: RI (differential refractometer)
Data processing; Tosoh Corporation SC-8010
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran flow rate 1.0 ml / min standard; polystyrene sample; 0.4 wt% tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 μl).

(Resin composition for molding)
The molding resin composition of the present invention is essential to contain the thermoplastic resin (A), the carbon material (B), and the polyimide resin dispersant (C), but the effects of the present invention are impaired. A known additive may be added to the extent that it does not exist. For example, examples of the additive include an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, and an inorganic filler.
As an example of the antioxidant, an antioxidant composed of phenolic, phosphorus, sulfur, and lactone may be added alone or in combination to prevent heat deterioration during processing of the resin. When properties are required, a benzophenone-based, salicylate-based, benzotriazole-based, cyanoacrylate-based, or hindered amine-based compound may be used as an ultraviolet absorber or light stabilizer.

  Examples of the inorganic filler include calcium carbonate, talc, precipitated barium sulfate, mica, kaolin clay, hydrotalcite, diatomaceous earth, and metal oxides such as magnesium oxide and aluminum oxide. These additives may be used alone or in combination of two or more.

Moreover, you may add a coloring agent to the resin composition for shaping | molding in this invention. The addition amount of the colorant varies depending on the type of colorant and the target color tone, but is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, with respect to 100 parts by weight of the thermoplastic resin (A). It is.
The colorant to be used is not particularly limited, and conventional inorganic pigments, organic pigments and dyes used for coloring general thermoplastic resins can be used according to the intended design. For example, inorganic pigments such as titanium oxide, titanium yellow, iron oxide, complex oxide pigments, ultramarine, cobalt blue, chromium oxide, bismuth vanadate, carbon black, zinc oxide, calcium carbonate, barium sulfate, silica, talc; azo Pigments, phthalocyanine pigments, quinacridone pigments, dioxazine pigments, anthraquinone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, quinophthalone pigments, thioindigo pigments and diketopyrrolo Organic pigments such as pyrrole pigments; metal complex pigments and the like. In addition, it is preferable to use one or two dyes mainly selected from the group of oil-soluble dyes.

(Formulation method)
The molding resin composition of the present invention can be blended by a known method. For example, a thermoplastic resin (such as a kneader generally used in thermoplastic resins, such as a single or twin screw extruder, a continuous kneader such as an FCM or a kneader, or a batch kneader such as a Banbury mixer or a kneader). A polyimide resin dispersant (C) can be added while highly dispersing A) and the carbon material (B) to produce a conductive composition. It is also possible to produce a master batch by adding the carbon material (B) and the polyimide resin dispersant (C) at a high concentration, dilute with the thermoplastic resin (A), and use for molding.

(Molding method)
As a molding method of the molding resin composition of the present invention, a molding method generally used for thermoplastic resins can be adopted. Specific examples include press molding, injection molding, film, sheet molding, blow molding, profile extrusion molding, and spinning. Further, there is no problem in post-processing the sheet-formed sheet by vacuum forming or the like.

(Use When carbon black (B-1) is used as the carbon material)
The molded object which shape | molded the resin composition for shaping | molding of this invention can be used for various uses. In particular, when the branched polyimide dispersant (C1) is used, for example, in the molding resin composition using carbon black (B-1) as the carbon material (B), the branched polyimide dispersant (C1) is particularly preferable. Since the effect of improving the fluidity at the time of high-temperature melting of the molding resin composition is high, it can be used particularly useful for molding that requires fluidity at the time of high-temperature melting, such as injection molding, film, and sheet molding.
In the molding resin composition of the present invention, the amount of the polyimide resin dispersant (C) relative to the amount of carbon black (B-1) is preferably in the range of 0.1 to 50% by weight. In such a blend, carbon black (B-1) can be added up to 0.01 to 50% by weight relative to the thermoplastic resin (A), and the resulting molded body is carbon black (B-1). Because it is filled at a high concentration, the effects derived from carbon black can be demonstrated, and not only electronic components such as connectors, LED lamp covers, and casings, but also automobiles such as instrument panels, bumpers, door trims, lamp covers, and tubes around the engine It can be used for various applications such as members, or thin films such as design films, light shielding films, and solar battery back sheets.

  Since the carbon black (B-1) -containing resin composition of the present invention has good dispersibility of the carbon black (B-1), there are almost no carbon black (B-1) aggregates in the resin composition. In addition, since the flowability is good, the unraveling property is good, so that almost no black streaks due to poor loosening at the time of injection molding are observed, so that it can be used well as a molding resin composition.

(Applications When using carbon nanotube (B-2) as carbon material)
Moreover, the resin composition for shaping | molding which uses a carbon nanotube (B-2) as a carbon material (B) can be used for various uses. In particular, when the branched polyimide dispersant (C1) is used, since the effect of improving the fluidity and improving the dispersibility of the molding resin composition at high temperature melting is high, the low concentration carbon nanotube (B-2 ) It is preferable because high conductivity can be imparted by addition.
In the molding resin composition of the present invention, the amount of the polyimide resin dispersant (C) relative to the amount of carbon nanotubes (B-2) at this time is preferably in the range of 0.1 to 50% by weight.
→ The blending amount is different from CB and graphite. Unification is necessary because it is within the scope of claims.
The resulting molded body has good moldability due to the low concentration of carbon nanotubes (B-2) and can exhibit high electrical conductivity, and only electronic members such as IC trays, wafer cases, and electromagnetic shielding materials. In addition, it can be used for various applications such as a tube for an engine around an automobile, a fuel tank, and a heat dissipation sheet.

(Use When using graphite (B-3) as a carbon material)
Moreover, the resin composition for shaping | molding which uses graphite (B-3) as a carbon material (B) can be used for various uses. In particular, when the branched polyimide dispersant (C1) is used, it can be added at a high concentration because the molding resin composition has a high effect of improving fluidity and improving dispersibility at high temperature melting. Therefore, it is preferable.
In the molding resin composition of the present invention, the amount of the polyimide resin dispersant (C) relative to the amount of graphite (B-3) is preferably in the range of 0.1 to 50% by weight. In such a blend, graphite (B-3) can be added up to 0.1 to 80% by weight with respect to the thermoplastic resin (A), and the resulting molded body has a high concentration of graphite (B-3). In addition to electronic members such as power modules, housings, connectors, IC trays, wafer cases, electromagnetic shielding materials, automobile motor parts, sliding parts, etc. It can be used for various applications such as a heat dissipation sheet.

  Hereinafter, the present invention will be described with reference to examples. Unless otherwise specified, “parts” and “%” are based on weight.

(Synthesis Example 1) Polyimide resin dispersant-1
In a four-necked flask equipped with a stirrer, a thermometer and a condenser, 5958.0 g of diethylene glycol monoethyl ether acetate and an isocyanurate ring-containing polyisocyanate compound derived from isophorone diisocyanate (hereinafter abbreviated as IPDI-N. Isocyanate group). Content: 18.2%, content of isocyanurate ring-containing triisocyanate compound: 952) 2772 g (12 mol of isocyanate group) and trimellitic anhydride 1728.0 g (9 mol) were charged at 160 ° C. while stirring. The temperature was raised to. Foaming started vigorously from around 60 ° C., and the flask contents gradually became transparent. After reacting at 160 ° C. for 4 hours, it was confirmed in the infrared absorption spectrum (hereinafter abbreviated as IR) that the absorption of the isocyanate group at 2270 cm −1 disappeared, and a light yellow transparent polyimide resin was obtained. A solution of Dispersant-1 was obtained. The degree of branching of the polyimide resin dispersant-1 and the concentration of the isocyanurate ring were 1.0 mmol / g in terms of solid content, the acid value was 99 KOH mg / g in terms of solid content, and the molecular weight was 4300 in terms of polystyrene. It was. The concentration of the resin component was 40% by weight.

(Synthesis Example 2) Polyimide resin dispersant-2
In a flask equipped with a stirrer, a thermometer, and a condenser, 4628 g of EDGA (diethylene glycol monoethyl ether acetate), 2070 g of IPDI-N (9 mol of isocyanate group), and cyclohexane-1,3,4-tricarboxylic acid-3,4 -1386 g (7 mol) of anhydride was added and the temperature was raised to 140 ° C. The reaction proceeded with foaming. The reaction was carried out at this temperature for 8 hours. The system became a pale yellow liquid, and a solution of polyimide resin dispersant-2) was obtained. As a result of measuring the characteristic absorption in the infrared spectrum of the polyimide resin dispersant-2), 2270 cm ^−1, which is the characteristic absorption of the isocyanate group, completely disappeared, and the absorption of the imide group at 1780 cm ⁻¹ and 1720 cm ^−1. confirmed. The degree of branching and isocyanurate ring concentration of the polyimide resin dispersant-2) is 0.97 mmol / g in terms of solid content, the acid value is 122 KOHmg / g in terms of solid content, and the molecular weight is number average molecular weight 5800 in terms of polystyrene. there were. The concentration of the resin component was 40% by weight.

(Synthesis Example 3) Polyimide resin dispersant-3
In a four-necked flask equipped with a stirrer, a thermometer and a condenser, 2100.0 g of diethylene glycol monoethyl ether acetate, 890.6 g of IPDI-N (3.8 moles of isocyanate groups), and 509.4 g of trimellitic anhydride (2.65 mol) was added and the temperature was raised to 160 ° C. while stirring. Foaming started vigorously from around 60 ° C., and the flask contents gradually became transparent. After reacting at 160 ° C. for 4 hours, it was confirmed in the infrared absorption spectrum (hereinafter abbreviated as IR) that the absorption of the isocyanate group at 2270 cm −1 disappeared, and a light yellow transparent polyimide resin was obtained. Dispersant-3 solution was obtained. The degree of branching and isocyanurate ring concentration of the polyimide resin dispersant-3 were 1.0 mmol / g in terms of solid content, the acid value was 79 KOH mg / g in terms of solid content, and the molecular weight was a number average molecular weight of 4800 in terms of polystyrene. It was. The concentration of the resin component was 37% by weight.

(Synthesis Example 4) Polyimide resin dispersant-4
In a four-necked flask equipped with a stirrer, a thermometer and a condenser, 1320.0 g of diethylene glycol monoethyl ether acetate, 660.0 g of IPDI-N (2.8 mol of isocyanate group), and 544.2 g of trimellitic anhydride (2.83 mol) was charged and the temperature was raised to 160 ° C. while stirring. Foaming started vigorously from around 60 ° C., and the flask contents gradually became transparent. After reacting at 160 ° C. for 4 hours, it was confirmed in the infrared absorption spectrum (hereinafter abbreviated as IR) that the absorption of the isocyanate group at 2270 cm −1 disappeared, and a light yellow transparent polyimide resin was obtained. Dispersant-4 solution was obtained. The degree of branching and the isocyanurate ring concentration of the polyimide resin dispersant-4 were 0.87 mmol / g in terms of solid content, the acid value was 205 KOHmg / g in terms of solid content, and the molecular weight was 1300 in terms of polystyrene. It was. The concentration of the resin component was 45% by weight.

(Synthesis Example 5) Polyimide resin dispersant-5
In a four-necked flask equipped with a stirrer, a thermometer and a condenser, 5958.0 g of diethylene glycol monoethyl ether acetate and an isocyanurate ring-containing polyisocyanate compound derived from isophorone diisocyanate (hereinafter abbreviated as IPDI-N. Isocyanate group). Content: 18.2%, content of isocyanurate ring-containing triisocyanate compound: 952) 2772 g (12 mol of isocyanate groups) and 1843.2 g (9.6 mol) of trimellitic anhydride were charged and stirred. The temperature was raised to 160 ° C. Foaming started vigorously from around 60 ° C., and the flask contents gradually became transparent. After reacting at 160 ° C. for 4 hours, it was confirmed in the infrared absorption spectrum (hereinafter abbreviated as IR) that the absorption of the isocyanate group at 2270 cm −1 disappeared, and a light yellow transparent polyimide resin was obtained. A solution of Dispersant-5 was obtained. The degree of branching of the polyimide resin dispersant-5 and the concentration of the isocyanurate ring are 0.97 mmol / g in terms of solid content, the acid value is 120 KOHmg / g in terms of solid content, and the molecular weight is weight average molecular weight 4100 in terms of polystyrene. there were. The concentration of the resin component was 40% by weight.

(Synthesis Example 6) Polyimide resin dispersant-6
In a four-necked flask equipped with a stirrer, a thermometer and a condenser, 1000 g of branched polyimide resin solution (C1-5) (concentration 40 wt%, acid value 120 KOH mg / g in terms of solid content), 38.8 g of phenylglycidyl ether (0 .257 mol) and 0.44 g of triphenylphosphine were charged, and the temperature was raised to 150 ° C. while stirring. Then, after making it react at 150 degreeC for 5 hours, it confirmed that the epoxy equivalent in a solution was 30000 g / mol or more, and obtained the solution of the light yellow transparent polyimide resin dispersant-6. The degree of branching and the isocyanurate ring concentration of the polyimide resin dispersant-6 were 0.88 mmol / g in terms of solid content, the acid value was 82 KOH mg / g in terms of solid content, and the molecular weight was a number average molecular weight of 4500 in terms of polystyrene. It was. Moreover, the density | concentration of the resin part was 42.2 weight%.

(Synthesis Example 7) Polyimide resin dispersant-7
In a four-necked flask equipped with a stirrer, a thermometer and a condenser, 1000 g of branched polyimide resin solution (C1-5) (concentration 40 wt%, acid value 120 KOHmg / g in terms of solid content), 64.6 g of phenylglycidyl ether (0 .428 mol) and 0.46 g of triphenylphosphine were charged, and the temperature was raised to 150 ° C. while stirring. Then, after making it react at 150 degreeC for 5 hours, it confirmed that the epoxy equivalent in a solution was 30000 g / mol or more, and obtained the solution of the light yellow transparent polyimide resin dispersant-7. The degree of branching and the isocyanurate ring concentration of the polyimide resin dispersant-7 were 0.84 mmol / g in terms of solid content, the acid value was 58 KOH mg / g in terms of solid content, and the molecular weight was 4800 in terms of polystyrene. It was. Moreover, the density | concentration of the resin part was 44.4 weight%.

(Synthesis Example 8) Polyimide resin dispersant-8
In a four-necked flask equipped with a stirrer, a thermometer and a condenser, 2100.0 g of diethylene glycol monoethyl ether acetate, 890.6 g of IPDI-N (3.8 moles of isocyanate group), and 659.7 g of trimellitic anhydride (3.44 mol) was charged and the temperature was raised to 160 ° C. while stirring. Foaming started vigorously from around 60 ° C., and the flask contents gradually became transparent. After reacting at 160 ° C. for 4 hours, it was confirmed in the infrared absorption spectrum (hereinafter abbreviated as IR) that the absorption of the isocyanate group at 2270 cm −1 disappeared, and a light yellow transparent polyimide resin was obtained. Dispersant-8 solution was obtained. The degree of branching and the isocyanurate ring concentration of the polyimide resin dispersant-8 were 0.92 mmol / g in terms of solids, the acid value was 160 KOHmg / g in terms of solids, and the molecular weight was 3800 in terms of polystyrene. It was. Moreover, the density | concentration of the resin part was 39.9 weight%.

(Synthesis Example 9) Polyimide resin dispersant-9
In a four-necked flask equipped with a stirrer, a thermometer and a condenser, 213.5 g of diethylene glycol monoethyl ether acetate, 52.4 g of IPDI-N (0.225 mol of isocyanate group), and 25.0 g of isophorone diisocyanate (isocyanate) The number of moles of the group was 0.225 mol) and trimellitic anhydride 64.8 g (0.338 mol) were charged, and the temperature was raised to 160 ° C. while stirring. Foaming started vigorously from around 60 ° C., and the flask contents gradually became transparent. After reacting at 160 ° C. for 4 hours, it was confirmed in the infrared absorption spectrum (hereinafter abbreviated as IR) that the absorption of the isocyanate group at 2270 cm −1 disappeared, and a light yellow transparent polyimide resin was obtained. Dispersant-9) A solution was obtained. The degree of branching and isocyanurate ring concentration of the polyimide resin dispersant-9 was 0.61 mmol / g in terms of solid content, the acid value was 120 KOH mg / g in terms of solid content, and the molecular weight was 4100 in terms of polystyrene. It was. Moreover, the density | concentration of the resin part was 36.4 weight%.

(Synthesis Example 10) Polyimide resin dispersant-10
In a four-necked flask equipped with a stirrer, a thermometer, and a condenser, a polyimide resin dispersant 1-5 solution 1000 g (concentration 40 wt%, solid-state acid value 120 KOH mg / g), phenylglycidyl ether 129.2 g (0 .856 mol) and 0.52 g of triphenylphosphine were charged, and the temperature was raised to 150 ° C. while stirring. Then, after making it react at 150 degreeC for 5 hours, it confirmed that the epoxy equivalent in a solution was 30000 g / mol or more, and obtained the solution of the light yellow transparent polyimide resin dispersant-7. The degree of branching and the isocyanurate ring concentration of the polyimide resin dispersant-10 are 0.73 mmol / g in terms of solid content, the acid value is 5 KOH mg / g in terms of solid content, and the molecular weight is 5200 in weight average molecular weight in terms of polystyrene. there were. Moreover, the density | concentration of the resin part was 46.9 weight%.

(Synthesis Example 11) Polyimide resin dispersant-11
In a flask equipped with a stirrer, a thermometer and a condenser, 232.5 g of DMAC (dimethylacetamide), 6.28 g (0.036 mol) of TDI (tolylene diisocyanate), TODI (4,4′-diisocyanate-3,3) '-Dimethyl-1,1'-biphenyl) 37.8 g (0.143 mol), TMA (trimellitic anhydride) 29.1 g (0.151 mol) and BTDA (benzophenone-3,3', 4,4) ′ -Tetracarboxylic dianhydride) and 12.2 g (0.038 mol) were added, the temperature was raised to 150 ° C. over 2 hours, taking note of heat generation while stirring, and the reaction was carried out at this temperature for 5 hours. I let you. The reaction proceeded with the foaming of carbon dioxide, and the system became a brown transparent liquid. A solution of a polyimide resin dispersant-11 having a resin solid content of 25% having a viscosity at 25 ° C. of 2 Pa · s was obtained. The degree of branching of the polyimide resin dispersant-11 and the concentration of the isocyanurate ring were 0 mmol / g in terms of solid content, the acid value was 46 KOH mg / g in terms of solid content, and the molecular weight was 10000 in terms of polystyrene.

(Synthesis Example 12) Synthesis Example of Comparative Dispersant 1 In a reaction flask equipped with a thermometer, stirrer, nitrogen inlet, reflux tube and water separator, 112 parts of ε-caprolactone, 9.2 parts of n-caproic acid, and 0.1 part of tetrabutyl titanate was charged and stirred at 180 to 190 ° C. for 18 hours under a nitrogen stream to obtain a polyester intermediate. The acid value of the product was 36 KOHmg / g. Next, 96 parts of the above polyester intermediate and a dry polyethyleneimine having an average molecular weight of 600 (Epomin SP-006, Nippon Shokubai Chemical Industry) (in a reaction flask equipped with a thermometer, stirrer, nitrogen inlet, reflux pipe and water separator ( 4 parts) was prepared, and stirred at 120 ° C. for 8 hours under a nitrogen stream to obtain Comparative Dispersant 1 which is a polyester resin. The amine value of the obtained product was 15 mgKOH / g, and the weight average molecular weight was 5,500.

Evaluation of resin composition containing carbon black (B-1) (kneading with a twin screw extruder)
[Example 1]
The polyimide resin dispersant-1 solution (carboxylic acid terminal, acid value 99) obtained in Synthesis Example 1 was removed using an evaporator and then dried under the conditions of 180 ° C. and 12 hours using a vacuum dryer. Dry polyimide resin dispersant-1 was obtained. Next, the dried polyimide resin dispersant-1 was pulverized into a powder form using an absolute mill. The obtained polyimide resin dispersant-1 powder was 9% by weight, polyamide 6, and “NOVAmid 1010J” manufactured by DSM Japan Engineering Plastics Co., Ltd. (viscosity 118 ml / g (in accordance with ISO 307 standard, temperature 25 ° C. Measured at a polyamide resin concentration of 0.5% by weight in 96% by weight sulfuric acid.) 61% by weight and carbon black (B-1) as “BP800” manufactured by CABOT (particle diameter 17 nm, specific surface area 210 m 2 / g, oil absorption 68 ml / 100 g) was 30% by weight premixed with a Henschel mixer, and then a twin screw extruder “KZW-25” (cylinder diameter 25 mm, L / D = 45) manufactured by Technobel Co., Ltd. was used. Kneading was performed using a cylinder (die temperature: 260 ° C., screw rotation speed: 200 rpm, supply amount: 8 kg / h). The current value of the twin screw extruder was measured to measure the load applied to the screw, and a die having three 3 mm diameter holes was attached to the tip of the twin screw extruder to obtain a kneaded strand. The obtained strand was cooled with water and then cut through a pelletizer to obtain a molding resin composition (F-1) as a cylindrical pellet.
The molding resin composition (F-1) 1.7% by weight and polyamide 6 “Novamid 1010J” 98.3% by weight were mixed, and an injection molding machine “MS-55” manufactured by Toshiba Machine was used. Molding was performed under the conditions of 240 ° C., injection pressure 5 MPa, back pressure 1 MPa, mold temperature 60 ° C. to obtain a test piece (F-1-s).
The test piece (F-1-s) is cut to a size of 1 mm square, and IMC-1819-A type hot press machine with a 50 kN load cell manufactured by Imoto Seisakusho Co., Ltd. (set temperature 260 ° C., pressure 10 kg / cm 2, pressure holding) Time (1 minute) was used to form a film (F-1-f).

[Evaluation item]
The evaluation items were as follows.

[Load of extrusion]
9% by weight of the dried polyimide resin dispersant-1, 61% by weight of polyamide 6 “Novamid 1010J” and 30% by weight of carbon black “BP800” were premixed with a Henschel mixer, and then manufactured by Technobel Co., Ltd. When kneading by a cylinder (die temperature 260 ° C., screw rotation speed 200 rpm), supply rate 8 kg / h using a shaft extruder “KZW-25” (cylinder diameter 25 mm, L / D = 45) The current value of the shaft extruder was measured and used as an index of the extrusion load.

[Unsolvability]
The obtained film (F-1-f) was observed at a magnification of 100 times with an optical microscope OPTIPHOT-2 manufactured by Nikon Corporation, and the peptizability of the molding resin composition was evaluated. ○ When the area of less than 5% in the field of view is unresolved (black streaks), Δ when the area of 5% to 10% in the field of view (black lines) is recognized, and 10 in the field of view The case where unraveling defects (black streaks) were recognized in an area of% or more was marked as x. (A resin composition having poor fluidity is not completely dissolved in the resin under the injection conditions, and is observed as a black stripe pattern in the visual field.)

[Dispersibility]
The obtained film (F-1-f) was observed at a magnification of 100 with an optical microscope OPTIPHOT-2 manufactured by Nikon Corporation, and the maximum particle diameter of carbon black aggregated particles recognized in the field of view was measured. Dispersibility was evaluated.
A case where a carbon black aggregate diameter of 50 μm or more is not recognized in the field of view, a case where a carbon black aggregate of 50 μm to 100 μm is recognized Δ, a case where a carbon black aggregate of 100 μm or more is recognized is × did.

[viscosity]
Using a capillary flow meter (manufactured by Toyo Seiki Seisakusho), the viscosity of the molding resin composition (F-1) at a shear rate of 100 mm / min (Pa · s) at a set temperature of 250 ° C., a capillary diameter of 1 mm, and a capillary length of 10 mm. ) Was measured. The viscosity of the molding resin composition (F-1) was 90 Pa · s.

[Example 2]
The same operation was performed except that the polyimide resin dispersant-1 solution used in Example 1 was changed to the polyimide resin dispersant-2 solution (carboxylic acid terminal, acid value 122) obtained in Synthesis Example 2, and molding was performed. Resin composition (F-2), test piece (F-2-s), and film (F-2-f) were obtained. The viscosity of the molding resin composition (F-2) was 135 Pa · s.

Example 5
The same operation was performed except that the polyimide resin dispersant-1 solution used in Example 1 was changed to the polyimide resin dispersant-8 solution (carboxylic acid terminal, acid value 160) obtained in Synthesis Example 8, and molding was performed. Resin composition (F-5), test piece (F-5-s), and film (F-5-f) were obtained. The viscosity of the molding resin composition (F-5) was 102 Pa · s.

[Comparative Example 1]
In the production of the molding resin composition (F-1) in Example 1, the same operation was carried out except that the polyamide 6 was 70% by weight, the carbon black was 30% by weight, and the formulation did not contain a dispersant. A composition (H-1), a test piece (H-1-s), and a film (H-1-f) were obtained. The viscosity of the molding resin composition (H-1) was 204 Pa · s.

[Comparative Example 3]
Except that the polyimide resin dispersant-1 solution used in Example 1 was changed to the comparative dispersant 1 obtained in Synthesis Example 12, the same operation was performed to obtain a molding resin composition (H-3) and a test piece. (H-3-s) and a film (H-3-f) were obtained. The viscosity of the molding resin composition (H-3) was 148 Pa · s.

Example 3
The polyimide resin dispersant-1 solution (carboxylic acid terminal, acid value 99) obtained in Synthesis Example 1 was removed using an evaporator and then dried under the conditions of 180 ° C. and 12 hours using a vacuum dryer. Dry polyimide resin dispersant-1 was obtained. Next, the dried polyimide resin dispersant-1 was pulverized into a powder form using an absolute mill. The obtained polyimide resin dispersant-1 powder is 4.5 wt%, polyamide 9T, “Genesta N1000A” manufactured by Kuraray Co., Ltd. is 80.5 wt%, carbon black, “BP800” manufactured by CABOT (particles) After premixing 15% by weight of 17 nm in diameter, specific surface area 210 m 2 / g, oil absorption 68 ml / 100 g) with a Henschel mixer, a twin screw extruder “KZW-25” manufactured by Technobell Co., Ltd. (cylinder diameter 25 mm, L / L) D = 45) and kneaded in a cylinder (die temperature: 320 ° C., screw rotation speed: 200 rpm, supply amount: 8 kg / h). The current value of the twin screw extruder was measured during kneading, and the load on the screw was measured. A die having three 3 mm diameter holes was attached to the tip of the twin screw extruder to obtain a kneaded strand. The obtained strand was water-cooled and then cut through a pelletizer to obtain a molding resin composition (F-3) as a cylindrical pellet.
The molding resin composition (F-3) 3.3% by weight and polyamide 9T “Genesta N1000A” 96.7% by weight are mixed, and an injection molding machine “MS-55” manufactured by Toshiba Machine is used. Molding was performed under the conditions of 320 ° C., injection pressure 5 MPa, back pressure 1 MPa, mold temperature 80 ° C. to obtain a test piece (F-3-s).
The test piece (F-3-s) is cut to a size of 1 mm square, and IMC-1819-A type hot press machine with a 50 kN load cell manufactured by Imoto Seisakusho Co., Ltd. (set temperature 320 ° C., pressure 10 kg / cm 2, pressure holding) Time (1 minute) was used to form a film (F-3-f).

  The evaluation regarding the molding resin composition (F-3) and the film (F-3-f) is the evaluation regarding the molding resin composition (F-1) and the film (F-1-f) in Example 1. The same was done.

[Example 4]
The same operation was performed except that the polyimide resin dispersant-1 solution used in Example 3 was changed to a polyimide resin dispersant-3 solution, and a molding resin composition (F-4) and a test piece (F-4-) were obtained. s) and a film (F-4-f) was obtained.

[Comparative Example 2]
In the production of the molding resin composition (F-3) in Example 3, the same operation was carried out except that the polyamide 9T was 70% by weight, the carbon black was 30% by weight, and the formulation did not contain a dispersant. A composition (H-2), a test piece (H-2-s), and a film (H-2-f) were obtained.

Evaluation of resin composition containing carbon black (B-1) (kneading with a mixer)
[Example 6]
The polyimide resin dispersant-5 solution obtained in Synthesis Example 5 (carboxylic acid terminal, acid value 99) was removed by using an evaporator and then dried at 180 ° C. for 12 hours using a vacuum dryer. Dry polyimide resin dispersant-5 was obtained. Next, the dry polyimide resin dispersant-5 was pulverized into a powder form using an absolute mill. The resulting polyimide resin dispersant-5 powder is 9% by weight, polyamide 6 is 61% by weight of Nov Japan 10 Plastics manufactured by DM Japan Engineering Plastics, and carbon black is “BP800” by CBOT. After charging 30% by weight into a polypropylene container and premixing by hand blending, using an R-60 mixer mounted on a lab plast mill manufactured by Toyo Seiki Co., Ltd., the temperature in the tank is 250 ° C. and the rotor rotates. Several hundred r. p. The mixture was kneaded for 5 minutes under the conditions of m. The average torque value 5 minutes after the start of mixing was read, and the load applied to the rotor was measured. Moreover, the obtained kneaded material was scraped off with a spatula to obtain a molding resin composition (F-6).
8. 8% by weight of the molding resin composition (F-6) and 91.7% by weight of polyamide 6 “Novamid 1010J” were mixed, and the temperature in the tank was 250 ° C. and the rotational speed of the rotor was 100 r using a lab plast mill-mixer. . p. The mixture was kneaded again for 5 minutes under the conditions of m. The obtained kneaded material was scraped off with a spatula to obtain a test piece (F-6-s).
The test piece (F-6-s) is cut to a size of 1 mm square, and IMC-1819-A type hot press machine with a 50 kN load cell manufactured by Imoto Seisakusho Co., Ltd. (set temperature 260 ° C., pressure 10 kg / cm 2, pressure holding) Time (1 minute) was used to form a film (F-6-f).

[Evaluation item]
The evaluation items were as follows.

[Load during kneading]
9% by weight of the dried polyimide resin dispersant-5, 61% by weight of polyamide 6 “Novamid 1010J” and 30% by weight of carbon black “BP800” are charged into a polypropylene container and premixed by hand blending. Then, using an R-60 type mixer attached to a lab plast mill manufactured by Toyo Seiki Seisakusho Co., Ltd., the temperature in the tank was 250 ° C. and the rotor rotation speed was 100 r. p. The mixture was kneaded for 5 minutes under the conditions of m. The average torque value 5 minutes after the start of mixing was read, and the load applied to the rotor was measured.

[Unsolvability]
Evaluation similar to the method performed in Example 1 was performed.

[Dispersibility]
Evaluation similar to the method performed in Example 1 was performed.

Example 7
The same operation was performed except that the polyimide resin dispersant-5 solution used in Example 6 was changed to the polyimide resin dispersant-2 solution (carboxylic acid terminal, acid value 122) obtained in Synthesis Example 2, and molding was performed. Resin composition (F-7), test piece (F-7-s), and film (F-7-f) were obtained.

Example 8
The same operation was performed except that the polyimide resin dispersant-5 solution used in Example 6 was changed to the polyimide resin dispersant-6 solution (carboxylic acid terminal, acid value 82) obtained in Synthesis Example 6. Resin composition (F-8), test piece (F-8-s), and film (F-8-f) were obtained.

Example 9
The same procedure was followed except that the polyimide resin dispersant-5 solution used in Example 6 was changed to the polyimide resin dispersant-7 solution (carboxylic acid terminal, acid value 58) obtained in Synthesis Example 7. Resin composition (F-9), test piece (F-9-s), and film (F-9-f) were obtained.

Example 10
The same operation was performed except that the polyimide resin dispersant-5 solution used in Example 6 was changed to the polyimide resin dispersant-8 solution (carboxylic acid terminal, acid value 160) obtained in Synthesis Example 8. Resin composition (F-10), test piece (F-10-s), and film (F-10-f) were obtained.

Example 11
The same operation was performed except that the polyimide resin dispersant-5 solution used in Example 6 was changed to the polyimide resin dispersant-4 solution (carboxylic acid terminal, acid value 205) obtained in Synthesis Example 4. Resin composition (F-11), test piece (F-11-s), and film (F-11-f) were obtained.

Example 12
The same operation was performed except that the polyimide resin dispersant-5 solution used in Example 6 was changed to the polyimide resin dispersant-9 solution obtained in Synthesis Example 9 (carboxylic acid terminal, acid value 120). Resin composition (F-12), test piece (F-12-s), and film (F-12-f) were obtained.

Example 13
The same operation was performed except that the polyimide resin dispersant-5 solution used in Example 6 was changed to the polyimide resin dispersant-10 solution (carboxylic acid terminal, acid value 5) obtained in Synthesis Example 11. Resin composition (F-13), test piece (F-13-s), and film (F-13-f) were obtained.

Example 14
The same operation was performed except that the polyimide resin dispersant-5 solution used in Example 6 was changed to the polyimide resin dispersant-11 solution (carboxylic acid terminal, acid value 46) obtained in Synthesis Example 11. Resin composition (F-14), test piece (F-14-s), and film (F-14-f) were obtained.

[Comparative Example 4]
In Example 6, the same operation was carried out except that the polyamide 6 was 70% by weight, the carbon black was 30% by weight, and the compound was not mixed with a dispersant, and the molding resin composition (H-4) and test piece (H -4-s) and a film (H-4-f) were obtained.

[Comparative Example 5]
The same procedure was followed except that the polyimide resin dispersant-5 solution used in Example 6 was changed to Comparative Dispersant 1 which was the polyester resin obtained in Synthesis Example 12, and a molding resin composition (H-5 ), A test piece (H-5-s), and a film (H-5-f).

[Example 15]
The polyamide 6 resin “Novamid 1010J” used in Example 6 was changed to “Iupilon S3000” manufactured by Mitsubishi Engineering Plastics Co., Ltd., which is a polycarbonate resin, and the mixing conditions were 280 ° C. in the tank, the rotor rotation speed was 100 r. p. m, except that the mixing time was 5 minutes, the same operation was performed to obtain a molding resin composition (F-15), a test piece (F-15-s), and a film (F-15-f).

[Comparative Example 6]
In Example 15, the same operation was carried out except that the polycarbonate was 70% by weight and the carbon black was 30% by weight, and the mixture was not mixed with a dispersant, and the molding resin composition (H-6) and test piece (H- 6-s) and a film (H-6-f) were obtained.

[Comparative Example 7]
The same procedure was followed except that the polyimide resin dispersant-5 solution used in Example 15 was changed to Comparative Dispersant 1 which was the polyester resin obtained in Synthesis Example 12, and a molding resin composition (H-7 ), A test piece (H-7-s), and a film (H-7-f).

Evaluation of Resin Composition Containing Carbon Nanotube (B-2) [Example 16]
The polyimide resin dispersant-5 solution obtained in Synthesis Example 5 (carboxylic acid terminal, acid value 120) was removed by using an evaporator and then dried at 180 ° C. for 12 hours using a vacuum dryer. A dry polyimide resin dispersant 5 was obtained. Next, the dry polyimide resin dispersant-5 was pulverized into a powder form using an absolute mill. The obtained polyimide resin dispersant-5 powder is 1.5% by weight, polycarbonate resin, “Iupilon S3000” manufactured by Mitsubishi Engineering Plastics Co., Ltd. is 97% by weight, and carbon nanotube is “NC7000” (diameter 9.5 nm, 1.5 μm in length) 1.5 wt% was premixed with a Henschel mixer, and then a twin-screw extruder “TEX-30” (Cylinder diameter 30 mm, L / D = 52) was used and kneaded in a cylinder (die temperature 250 ° C., screw rotation speed 250 rpm), supply rate 10 kg / h). A die having three 3 mm diameter holes was attached to the tip of the twin screw extruder to obtain a kneaded strand. The obtained strand was cooled with water and then cut through a pelletizer to obtain a molding resin composition (F-16) as a cylindrical pellet.
The molding resin composition (F-16) was dried with a vacuum dryer at 120 ° C. for 8 hours, and then a cylinder set temperature of 300 ° C. and a back pressure of 1 MPa using an injection molding machine “MS-55” manufactured by Toshiba Machine. Molding was performed under the conditions of a temperature of 90 ° C., an injection speed of 15 mm / s, and 40 mm / s to obtain a flat test piece (F-16-s) having a major axis of 90 mm × minor axis of 50 mm × thickness of 3 mm.

[Evaluation item]
The evaluation items were as follows.

[Load during kneading]
After 1.5% by weight of the dried polyimide resin dispersant-5, 97% by weight of polycarbonate resin, and 1.5% by weight of carbon nanotubes were placed in a polypropylene container and premixed by hand blending, Using an R-60 type mixer attached to a laboratory plast mill manufactured by Toyo Seiki Seisakusho, the temperature in the tank was 250 ° C., and the rotor rotation speed was 100 r. p. The mixture was kneaded for 5 minutes under the conditions of m. The average torque value 5 minutes after the start of mixing was read, and the load applied to the rotor was measured.

[Conductivity]
For the surface of the obtained test piece (F-16-s) on the moving mold side, the surface resistance value at the center is determined by a resistivity meter Loresta EP MCP-T360 type (less than 10 ^ 6 Ω / cm2) manufactured by Mitsubishi Chemical. ), And Hiresta UP MCP-HT450 type (10 ^ 6Ω / cm2 or more).

[Surface appearance of flat plate]
The surface of the obtained test piece (F-16-s) on the moving mold side was evaluated by visual observation or the like for the presence of flow marks, silver streaks, coarse foreign matter, and surface stickiness.

[Comparative Example 8]
In the production of the molding resin composition (F-16) in Example 16, the same operation was performed except that the polycarbonate was 98.5% by weight, the carbon nanotube was 1.5% by weight, and the composition did not contain a dispersant. A molding resin composition (H-8) and a test piece (H-8-s) were obtained.

[Comparative Example 9]
The same procedure was followed except that the polyimide resin dispersant-5 solution used in Example 16 was changed to Comparative Dispersant 1 which was the polyester resin obtained in Synthesis Example 12, and a molding resin composition (H-9 ), A test piece (H-9-s) was obtained.

Example 17
In Example 16, the same operation was carried out except that the polyimide resin dispersant 5-powder was 2.0% by weight, the polycarbonate resin was 96% by weight, and the carbon nanotubes were 2.0% by weight. (H-17) and a test piece (H-17-s) were obtained.

[Comparative Example 10]
A resin composition for molding (H-10) and test were carried out in the same manner as in Example 17 except that polycarbonate was 98.0% by weight, carbon nanotubes were 2.0% by weight, and the formulation was free of dispersant. Piece (H-10-s).

[Comparative Example 11]
The same procedure was followed except that the polyimide resin dispersant-5 solution used in Example 17 was changed to Comparative Dispersant 1 which was the polyester resin obtained in Synthesis Example 12, and a molding resin composition (H-11) was obtained. ), A test piece (H-11-s) was obtained.

Evaluation of resin composition containing graphite (B-3) [Example 17]
The polyimide resin dispersant-5 solution obtained in Synthesis Example 5 (carboxylic acid terminal, acid value 99) was removed by using an evaporator and then dried at 180 ° C. for 12 hours using a vacuum dryer. Dry polyimide resin dispersant-5 was obtained. Next, the dry polyimide resin dispersant-5 was pulverized into a powder form using an absolute mill. The obtained polyimide resin dispersant-5 powder is 10% by mass and polyamide 6 is 40% by mass of NM Japan Engineering Plastics “NOVAmid 1010J”, and graphite is “SGP” manufactured by SEC Carbon Co., Ltd. -5 "(average particle size 5 μm) was charged into a polypropylene container 50 mass%, premixed by hand blending, and then an R-60 type mixer mounted on a lab plast mill manufactured by Toyo Seiki Seisakusho Co., Ltd. Used, tank temperature 250 ° C., rotor rotation speed 100 r. p. The mixture was kneaded for 5 minutes under the conditions of m. The average torque value 5 minutes after the start of mixing was read, and the load applied to the rotor was measured. Moreover, the obtained kneaded material was scraped off with a spatula to obtain a molding resin composition (F-17).
Press the resin composition for molding (F-17) using an IMC-1819-A type hot press machine with a 50 kN load cell (set temperature 260 ° C., pressure 10 kg / cm 2, pressure holding time 1 minute) manufactured by Imoto Seisakusho Co., Ltd. Molding was performed to obtain a sheet-like test piece (F-17-s) having a major axis of 110 mm, a minor axis of 70 mm, and a thickness of 2 mm.

[Evaluation item]
The evaluation items were as follows.

[Load during kneading]
10% by mass of a dried polyimide resin dispersant-5, 40% by mass of polyamide 6, and 50% by mass of graphite were charged into a polypropylene container, premixed by hand blending, and then manufactured by Toyo Seiki Seisakusho Co., Ltd. Using an R-60 type mixer attached to a lab plast mill, the temperature in the tank was 250 ° C., and the rotor rotation speed was 100 r. p. The mixture was kneaded for 5 minutes under the conditions of m. The average torque value 5 minutes after the start of mixing was read, and the load applied to the rotor was measured.

[Conductivity]
For the surface of the obtained test piece (F-17-s), the surface resistance value at the center is designated as a resistivity meter Loresta EP MCP-T360 (less than 10 ^ 6 Ω / cm2) manufactured by Mitsubishi Chemical, and Hiresta It was measured using Hiresta UP MCP-HT450 type (10 ^ 6Ω / cm2 or more).

[Thermal conductivity]
The obtained test piece (F-17-s) was subjected to quartz (thermal conductivity 1.418 W / mK (29 ° C.) heater current value 4 A ^ in the thin film sample measurement mode using QTM-500 manufactured by Kyoto Electronics Co., Ltd. 2), zirconia (heat conductivity 3.42 W / mK (28 ° C) heater current value 6A ^ 2), and mullite (heat conductivity 5.64W / mK (27 ° C) heater current value 9A ^ 2) Was measured as a standard sample.

The results of Examples and Comparative Examples are shown in Tables 1 to 6.

As described above, the molding resin composition using the polyimide dispersant is excellent in dispersibility. In particular, it can be said that the molding resin composition using the branched polyimide dispersant has an excellent viscosity reducing effect because the torque during extrusion and kneading is lower than that of the comparative example regardless of the weight average molecular weight. The concentration of the isocyanurate ring is preferably 0.6 mmol / g or more, particularly preferably 0.7 mmol / g or more.
The reason why such a dispersant has an effect on high fluidity and good dispersibility is not clear. However, based on the above results, the mutual relationship between the carboxy group at the end of the polyimide dispersant and the functional group at the surface of the carbon material and at the end. The action has an effect on good dispersibility, and the polyimide dispersant has a branched structure, and is expected to have an effect on high fluidity and good dispersibility by preventing reaggregation of carbon materials. Further, not only carbon black, but also carbon nanotubes and graphite have an effect on good fluidity, and a molded product having good conductivity, surface appearance, thermal conductivity and the like was obtained.

  In the molding resin composition containing the thermoplastic resin (A) and the carbon material (B), by using the polyimide resin dispersant (C), the carbon material is well dispersed and the conductivity and thermal conductivity are increased. It is possible to provide a molding resin composition that can be manufactured and has excellent dispersibility.

Claims (7)

A molding resin composition comprising a thermoplastic resin (A), a carbon material (B), and a polyimide resin dispersant (C). The molding resin composition according to claim 1, wherein the polyimide resin dispersant (C) is a branched polyimide resin dispersant (C1) having a branched structure. The molding resin composition according to claim 2, wherein the branched polyimide resin dispersant (C1) is a branched polyimide resin dispersant (C2) having an isocyanuric ring structure. The molding resin composition according to any one of claims 1 to 3, wherein the carbon material (B) is at least one of carbon black (B-1), carbon nanotube (B-2), and graphite (B-3). object. The molded object formed by shape | molding the molding resin composition in any one of Claim 1 to 4. The electronic member formed using the molded object of Claim 5. A method for improving the fluidity of a resin composition comprising a thermoplastic resin (A) and a carbon material (B), wherein the branched polyimide resin dispersant (C1) is added in an amount of 0.1 to 50 with respect to the carbon material (B). A method for improving fluidity, characterized by adding% by weight.