JP4344211B2 - Thermoplastic resin composition, film and substrate material - Google Patents

Description

  The present invention relates to a thermoplastic resin composition, and a film and a substrate material using the thermoplastic resin composition.

  In recent years, electronic devices (including electrical devices) have been rapidly improved in performance, functionality, and downsizing, and electronic components used in electronic devices are also strongly required to be downsized and lightened. . As a result, further improvements in physical properties such as heat resistance, mechanical strength, and electrical characteristics have been demanded for the materials of electronic components. For example, for semiconductor device packaging methods and wiring boards for mounting semiconductor devices. However, there is a demand for higher density, higher functionality, and higher performance. In addition, with the recent increase in environmental awareness, it is also required to provide low environmental impact such as excellent recyclability, no halogen elements, and the use of lead-free solder. Yes.

  Multilayer printed circuit boards used in electronic devices are composed of multiple layers of insulating substrates (interlayer insulating substrates). Conventionally, as this interlayer insulating substrate, for example, thermosetting resin impregnated with a thermosetting resin A curable resin prepreg, a film made of a thermosetting resin or a photocurable resin, and the like have been used. Even in the multilayer printed circuit board, the interlayer is required to be extremely thin for high density and thinning, and an interlayer insulating substrate using a thin glass cloth or an interlayer insulating substrate not using a glass cloth is required. It is said that.

  As such an interlayer insulating substrate, an interlayer insulating substrate made of a thermosetting resin material modified with rubber (elastomer) or acrylic resin, an interlayer insulating substrate made of a thermoplastic resin material containing a large amount of an inorganic filler, etc. For example, a varnish mainly composed of a high molecular weight epoxy polymer having a weight average molecular weight of 50,000 or more, a polyfunctional epoxy resin, a curing agent, and a crosslinking agent has a mean particle diameter of 0.8 to 5 μm. There is a method for producing a multilayer printed wiring board (multilayer insulating substrate) in which a fibrous inorganic filler is blended, applied to one or both sides of a support, and an epoxy adhesive film obtained by removing the solvent is used as an insulating layer. (For example, refer to Patent Document 1).

  However, the multilayer insulating substrate produced by the above-described manufacturing method sufficiently improves the mechanical properties such as mechanical strength by securing the interface area between the high molecular weight epoxy polymer or polyfunctional epoxy resin and the inorganic filler. Therefore, since it is necessary to add a large amount of inorganic filler, there are problems that processing problems such as an increase in the manufacturing process and complexity, and a problem that it is difficult to make the interlayer thin. There is.

  In addition, the interlayer insulation substrate using a thin glass cloth and the interlayer insulation substrate not using a glass cloth have problems such as insufficient heat resistance and dimensional stability, and are fragile and easily broken. There is a problem that many problems occur.

  Polyimide films, on the other hand, are superior in heat resistance, low temperature characteristics, chemical resistance, electrical characteristics, etc. among various plastic films. Widely used in the communications field.

However, the polyimide film does not sufficiently satisfy various required performances, and is required to have various performances depending on applications. In particular, as a material for electronic equipment, a polyimide film having a low water absorption rate (moisture absorption rate) is desired in order to cope with high functionality and downsizing. By reducing the water absorption rate (moisture absorption rate), it is possible to suppress problems such as a decrease in electrical characteristics such as dielectric constant due to water absorption (moisture absorption) and the occurrence of dimensional changes due to water absorption (moisture absorption) and expansion. In addition to lowering the water absorption rate (moisture absorption rate), for example, when considering the production of TAB tape, since it includes many processes that receive stress and processes that undergo temperature changes, the base film (base film) The polyimide film (organic insulating film) is required to have a small dimensional change due to stress and temperature change, that is, excellent in dimensional stability.

  As described above, as the performance of the TAB tape, the substrate film of the flexible printed circuit board, and the resin for the laminated board are increased due to high performance, high functionality, downsizing, etc., in addition to heat resistance, heat and water absorption (moisture absorption) It is desired that the dimensional change is small and the elastic modulus is high.

  Various attempts have been made to meet such demands. For example, a novel polyimide resin having a specific structure having a water absorption rate of 1.6% by weight or less and a hygroscopic expansion coefficient of 15 ppm or less, and this A polyimide film made of a polyimide resin is disclosed (for example, see Patent Document 2).

However, since the polyimide resin is a non-thermoplastic resin, a casting method is adopted when forming the polyimide film. As described above, in the case of a non-thermoplastic resin, there are a problem that molding by heat is difficult, a problem that equipment costs and manufacturing costs are high, and a problem that recycling is difficult. As described above, a polyimide film that sufficiently satisfies various required performances has not been put into practical use.
JP 2000-183539 A Japanese Patent Laid-Open No. 10-36506

  In view of the above problems and the present situation, the object of the present invention is a thermoplastic resin composition suitable for obtaining a molded article having low water absorption (hygroscopicity) and exhibiting excellent dimensional stability even under high temperature and high humidity, and An object of the present invention is to provide a film and a substrate material using the thermoplastic resin composition.

  As a result of intensive studies in order to achieve the above-mentioned problems, the present invention, etc., highly disperses the above-mentioned layered silicate in a thermoplastic resin by using a layered silicate organized by a specific imidazolium ion. As a result, it has been found that a molded article that has extremely low water absorption (hygroscopicity) and exhibits excellent dimensional stability even under high temperature and high humidity can be obtained, and the present invention has been completed.

That is, the thermoplastic resin composition according to the first aspect of the present invention (the present invention) is a layered silicate that is organized with imidazolium ions having a molecular weight of 200 or more with respect to 100 parts by weight of the thermoplastic resin. 45 parts by weight are contained, Lee Mi Dazo potassium ions, characterized in that a structure of the formula (1) wherein.

(In the formula, _one of R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ is a group having at least an aromatic ring, and at least one of R ₁ , R ₂ , and R ₃ is H Is a group other than
The thermoplastic resin composition according to the invention according to claim 2, the thermoplastic resin composition according to claim 1, the thermoplastic resin is a glass transition temperature of 0.99 ° C. or more and a solubility parameter of 42 0.0 (J / cm ³ ) ^1/2 or more.

The thermoplastic resin composition according to the invention described in claim 3 is the thermoplastic resin composition according to claim 1 or 2 , wherein the thermoplastic resin is a polyimide resin, a polyesterimide resin, a polyetherimide resin, or a polyether. It is at least one selected from the group consisting of ether ketone resins.

The thermoplastic resin composition according to the invention described in claim 4 is the thermoplastic resin composition according to any one of claims 1 to 3 , wherein the layered silicate is montmorillonite, hectorite, swellability. It is at least one selected from the group consisting of mica and vermiculite.

The thermoplastic resin composition according to claim 5 is the thermoplastic resin composition according to any one of claims 1 to 4 , wherein the layered silicate is obtained by a wide-angle X-ray diffraction measurement method. The measured average distance between layers of the (001) plane is 3 nm or more, and part or all of them are dispersed as a laminate of 5 layers or less.

A film according to the invention described in claim 6 (the present invention) is produced using the thermoplastic resin composition described in any one of claims 1 to 5 .

A substrate material according to the invention described in claim 7 (the present invention) is produced using the thermoplastic resin composition according to any one of claims 1 to 5 . Hereinafter, the present invention will be described in detail.

  The thermoplastic resin used in the thermoplastic resin composition of the present invention preferably has a glass transition temperature (Tg) of 150 ° C. or higher, more preferably 200 ° C. or higher, and still more preferably 220 ° C. or higher. In addition, the glass transition temperature said by this invention means the glass transition temperature measured based on JISK-7121 "Plastic transition temperature measuring method".

  If the glass transition temperature of the thermoplastic resin is less than 150 ° C., the molded article produced using the thermoplastic resin composition obtained has insufficient heat resistance, and the molded article is used as a substrate material, for example. In such a case, high-temperature physical properties, particularly lead-free solder heat resistance and dimensional stability against heating, may be insufficient.

In addition, the thermoplastic resin used in the thermoplastic resin composition of the present invention has a solubility parameter (
The SP value is preferably 42.0 (J / cm ³ ) ^1/2 or more, more preferably 46.2 (J / cm ³ ) ^1/2 or more, and further preferably 52.5 (J / Cm ³ ) ^1/2 or more. In addition, the solubility parameter said by this invention means the solubility parameter calculated | required using the calculation formula of Fedors. According to the Fedors equation, the solubility parameter is the square root of the sum of the molar cohesive energies of each atomic group divided by the volume, and indicates the polarity per unit volume. The greater the solubility parameter, the greater the solubility parameter. The polarity will be high.

When the solubility parameter of the thermoplastic resin is less than 42.0 (J / cm ³ ) ^1/2 , the polarity of the thermoplastic resin does not become sufficiently high, so that the layered silicate organized by imidazolium ions described later May not be sufficiently dispersed (nanodispersed) in the thermoplastic resin.

  The thermoplastic resin having such characteristics (glass transition temperature and solubility parameter) is not particularly limited. For example, polyester resins such as polybutylene terephthalate, polybutylene naphthalate, polyethylene terephthalate, and polyethylene naphthalate. , Polyamide resins such as polyamide 6, polyamide 66 and polyamide 12, polyamide imide resins, polyimide resins, polyester imide resins, polyether imide resins, polyether ether ketone resins, polyphenylene ether resins, modified polyphenylene ether resins, polybenzimidazole resins, etc. Among them, it is composed of a polyimide resin, a polyesterimide resin, a polyetherimide resin and a polyetheretherketone resin, which are excellent in heat resistance. At least one being more selective is preferably used. These thermoplastic resins may be used alone or in combination of two or more.

  The layered silicate used in the thermoplastic resin composition of the present invention means a silicate mineral having an exchangeable metal cation between crystal layers.

  The layered silicate is not particularly limited. For example, smectite clay minerals such as montmorillonite, hectorite, saponite, beidellite, stevensite, nontronite, and swelling mica (swelling mica) Among them, at least one selected from the group consisting of montmorillonite, hectorite, swellable mica and vermiculite is preferably used. . These layered silicates may be natural products or synthetic products. Moreover, these layered silicates may be used independently and 2 or more types may be used together.

  As the layered silicate, it is preferable to use one having a large shape anisotropy effect defined by the following relational expression. By using a layered silicate having a large shape anisotropy effect, the resulting thermoplastic resin composition, and thus the molded body, exhibits more excellent mechanical properties.

Shape anisotropy effect = area of crystal surface (A) / area of crystal surface (B) In the formula of crystal surface (A), the crystal surface (A) means the surface of the layer, and the crystal surface (B) means the side surface of the layer.

  The shape of the layered silicate is not particularly limited, but the average length of the crystal flakes obtained by crushing the aggregated structure is 0.01 to 3 μm, the thickness is 0.001 to 1 μm, and the aspect ratio is 20 to 500. More preferably, the average length is 0.05 to 2 μm, the thickness is 0.01 to 0.5 μm, and the aspect ratio is 50 to 200.

The exchangeable metal cation existing between the layered silicate crystal layers is an ion of a metal such as sodium or calcium existing on the surface of the layered silicate crystal, and these metal ions are other cations. Since it has a cation exchange property with an active substance, various cationic substances can be inserted (intercalated) or captured between the crystal layers of the layered silicate.

  The cation exchange capacity of the layered silicate is not particularly limited, but is preferably 50 to 200 milliequivalent / 100 g. When the cation exchange capacity of the layered silicate is less than 50 milliequivalents / 100 g, the amount of the cationic substance inserted or trapped between the crystal layers of the layered silicate due to the cation exchange is reduced, so that the crystal layer is not sufficiently separated If the cation exchange capacity of the layered silicate exceeds 200 milliequivalents / 100 g, the bonding force between the crystal layers of the layered silicate becomes too strong, and the crystal flakes may not be polarized (hydrophobized). May become difficult to peel.

  The layered silicate used in the thermoplastic resin composition of the present invention is organically (chemically modified) with imidazolium ions having a molecular weight of 200 or more. When the molecular weight is less than 200, the layer of the layered silicate that has been subjected to the organic treatment is not sufficiently spread and the peelability is deteriorated, so that it cannot be highly dispersed in the resin. In order to highly disperse the layered silicate in the resin, it is more preferably organicized with imidazolium ions having a molecular weight of 225 or higher, and organicized with imidazolium ions having a molecular weight of 250 or higher. Is more preferable.

  Furthermore, it is preferable that the imidazolium ion has a structure represented by Formula 1. By having a group having an aromatic ring in the side chain, the heat resistance of the organically treated layered silicate is improved, and it is hardly decomposed even at high temperature kneading with the resin and can be highly dispersed in the resin.

(In the formula, _one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ is a group having at least an aromatic ring, and at least one of R ₁ , R ₂ , R ₃ is H (Examples of the group having an aromatic ring include a group having a phenyl group or a benzyl group.)
By using the layered silicate that has been organized with the imidazolium ions, the layered silicate can be dispersed in a large amount in a highly dispersed state (nanodispersed state) in the thermoplastic resin. That is, when the layered silicate is not subjected to organicization suitable for the solvent used in producing the thermoplastic resin and / or the thermoplastic resin composition of the present invention, the layered silicate aggregates. It becomes easy and it becomes difficult to disperse the layered silicate in the thermoplastic resin in a large amount and in a highly dispersed state, but the layered silicate becomes difficult to aggregate by applying the above-mentioned organication to the layered silicate. The layered silicate can be dispersed in a large amount and in a highly dispersed state in the thermoplastic resin.

  The method for organizing the layered silicate with imidazolium ions is not particularly limited, and examples thereof include a cation exchange method using a cationic surfactant that can be ionized into the imidazolium ions.

Non-polarization between the crystal layers of the layered silicate by the cation exchange method with the above cationic surfactant (
By making it hydrophobic, the affinity between the thermoplastic resin (low polarity resin) and the layered silicate is increased even when a low polarity resin such as polyphenylene ether resin is used as the thermoplastic resin. The layered silicate can be dispersed in a large amount and in a highly dispersed state in the low polar resin).

The cationic surfactant capable of ionizing the imidazolium is not particularly limited, and examples thereof include 1,2-dimethyl-3-octylimidazolium salt and 1,2-dimethyl-3-decylimidazolium salt. 1,3-dibenzyl-2-phenylimidazolium, 1,3-dibenzyl-2-phenyl-4 (5) -methylimidazolium, 1-benzyl-
2-phenyl-4 (5) -methylimidazolium salt, 1-dodecyl-2-methyl-3-benzylimidazolium salt, 1-octyl-2-methyl-3-benzylimidazolium salt, 1-decyl-2- Methyl-3-benzylimidazolium salt, 1-decyl-2-phenyl-3-benzylimidazolium salt, 1-octyl-2-phenyl-3-benzylimidazolium salt, 1-butyl-4,5-diphenylimidazolium Salt, 1-octyl-4,5-diphenylimidazolium salt, 1-decyl-4,5-diphenylimidazolium salt, 1-benzyl-4,5-diphenylimidazolium salt, 1- (3-phthalimidopropyl)- 2-phenyl-3-benzylimidazolium salt, 1- (2-phenylethyl) -2-phenyl-3-benzylimidazoli Salt-free, and the like. These cationic surfactants that can be ionized into imidazolium ions may be used alone or in combination of two or more.

  The thermoplastic resin composition of the present invention needs to contain 0.5 to 45 parts by weight of a layered silicate organized by the imidazolium ion with respect to 100 parts by weight of the thermoplastic resin, Preferably it is 1-35 weight part, More preferably, it is 1.5-25 weight part.

  When the content of the layered silicate organized by the imidazolium ions with respect to 100 parts by weight of the thermoplastic resin is less than 0.5 parts by weight, the resulting thermoplastic resin composition and thus the molded layered silicate is contained. The effect of improving the high-temperature physical properties and the effect of reducing the water absorption (hygroscopicity) are insufficient, and conversely, the content of the layered silicate organized by the organic onium ions with respect to 100 parts by weight of the thermoplastic resin is 45% by weight. When the amount exceeds 50 parts, the density (specific gravity) of the resulting thermoplastic resin composition and thus the molded body becomes too high, and mechanical properties such as mechanical strength are also lowered, resulting in poor practicality.

  In the thermoplastic resin composition of the present invention, the layered silicate has an (001) plane average interlayer distance of 3 nm or more measured by a wide-angle X-ray diffraction measurement method, and part or all of the layered silicate is 5 It is preferable to be dispersed as a laminate having a layer or less, more preferably, the average interlayer distance is 3 to 5 nm, and part or all of the laminate is dispersed as a laminate having 5 layers or less. . In addition, the average interlayer distance of the layered silicate referred to in the present invention means the average interlayer distance when the layered silicate fine flaky crystal is used as a layer, and by X-ray diffraction peak and transmission electron microscope photography, That is, it can be calculated by a wide-angle X-ray diffraction measurement method. The dispersion state of the layered silicate is observed with a transmission electron microscope at a magnification of 50,000 to 100,000, and the total number of layers (X) and 5 of the layered silicate laminate that can be observed in a certain area. The number of layers (Y) of the laminated body dispersed as a laminated body of layers or less can be measured and calculated by the following calculation formula.

Dispersion ratio (%) of laminate of 5 layers or less = (Y / X) × 100
That the average interlayer distance of the layered silicate is 3 nm or more means that the interlayer of the layered silicate is cleaved to 3 nm or more, and part or all of the layered silicate is 5 layers or less. Dispersion as a laminate of the above means that part or all of the layered silicate laminate is widely dispersed in the thermoplastic resin composition, both of which are layered silicate layers. Means that the interaction is weakened.

  When the average interlayer distance of the layered silicate is 3 nm or more and a part or all of the layered silicate is dispersed as a laminate of 5 layers or less, the interface area between the thermoplastic resin and the layered silicate becomes sufficiently large. At the same time, the distance between the flaky crystals of the layered silicate becomes appropriate, and the resulting thermoplastic resin composition, and thus the mechanical properties, high-temperature properties, heat resistance, dimensional stability, etc. of the molded product are remarkably improved.

  Also, when the average interlayer distance of the layered silicate exceeds 5 nm, the crystallites of the layered silicate are separated into layers, and the interaction between the layers of the layered silicate becomes so weak that it can be almost ignored. The binding strength is weakened, and the resulting thermoplastic resin composition, and thus the molded article, may have insufficient dimensional stability, particularly at high temperatures.

  That part or all of the layered silicate is dispersed as a laminate of 5 layers or less, specifically, 10% or more of the layered silicate laminate is dispersed as a laminate of 5 layers or less. It means that it is preferable to be in a state of being, and more preferably 20% or more of the layered silicate laminate is dispersed as a laminate of 5 layers or less.

  The number of layers in the layered silicate laminate is preferably divided into 5 layers or less, more preferably 3 layers or less in order to sufficiently obtain the effect of dispersion of the layered silicate. It is that it is layered, more preferably it is divided into one layer.

  The thermoplastic resin composition of the present invention contains 0.5 to 45 parts by weight of a layered silicate organized by the organic onium ions with respect to 100 parts by weight of the thermoplastic resin, and the layered silicate has a wide angle. A thermoplastic resin having an average interlayer distance of (001) plane measured by X-ray diffractometry of 3 nm or more and part or all dispersed as a laminate of 5 layers or less. The interface area between the layered silicate and the layered silicate becomes sufficiently large, and the interaction between the thermoplastic resin and the surface of the layered silicate increases. As a result, the melt viscosity of the thermoplastic resin composition becomes moderately high and the moldability is improved, and the mechanical properties such as the elastic modulus are improved in a wide temperature range from room temperature to high temperature. Mechanical properties can be maintained even at high temperatures above the glass transition temperature or above the melting point, and the linear expansion coefficient at high temperatures can be kept low. Such an effect is that the layered silicate present in a highly dispersed state in the thermoplastic resin composition functions as a kind of pseudo-crosslinking point even at a high temperature not lower than the glass transition temperature or the melting point of the thermoplastic resin. It is thought that it is obtained by this.

  Further, since the distance between the lamellar crystals of the layered silicate is also appropriate, the lamellar crystals of the lamellar silicate move during combustion, and it becomes easy to form a sintered body that becomes a flame retardant coating. Since this sintered body is formed at an early stage during combustion, supply of oxygen from the outside world can be shut off, and combustible gas generated by combustion can be shut off. Therefore, the thermoplastic resin composition of the present invention, and thus the molded product, exhibits excellent flame retardancy.

  Further, in the thermoplastic resin composition of the present invention, since the layered silicate is highly dispersed in nanometer size, for example, a substrate material is prepared from the thermoplastic resin composition of the present invention, and this substrate material When drilling is performed with a laser such as a carbon dioxide laser, the thermoplastic resin component and the layered silicate component are simultaneously decomposed and evaporated, and the partially remaining layered silicate residue is only a few μm or less. Therefore, it can be easily removed by desmearing. Accordingly, it is possible to effectively prevent the occurrence of defective plating due to the layered silicate residue generated by drilling.

The method for producing the thermoplastic resin composition of the present invention is not particularly limited. For example, a monomer that is a raw material for the thermoplastic resin and a layered silicate are kneaded, and a polymerization reaction is performed in this state. A method for obtaining a thermoplastic resin, for example, a method for melt-kneading a thermoplastic resin and a layered silicate at room temperature or under heating using a kneader such as an extruder, a two-roller, a Banbury mixer, etc., and a thermoplastic resin A method of removing the solvent after kneading both in a solvent in which the layered silicate can be dissolved or dispersed may be used, and any production method may be adopted.

  Further, the method for dispersing the layered silicate more uniformly and finely in the thermoplastic resin is not particularly limited. For example, the foaming agent is obtained after kneading the thermoplastic resin and the layered silicate by a conventional method. A method of foaming a thermoplastic resin by using a method, a method of using a dispersant, and the like can be mentioned, and any dispersion method may be adopted. By adopting such a dispersion method, the layered silicate can be more uniformly and finely dispersed in the thermoplastic resin.

  The method in which the thermoplastic resin and the layered silicate are kneaded by a conventional method and then the thermoplastic resin is foamed using a foaming agent is a method in which the energy of foaming is utilized for the dispersion of the layered silicate.

  Although it does not specifically limit as said foaming agent, For example, a gaseous foaming agent, an easily volatile liquid foaming agent, a heat decomposable solid foaming agent etc. are mentioned. These foaming agents may be used independently and 2 or more types may be used together.

  The specific method of foaming the thermoplastic resin using a foaming agent after kneading the thermoplastic resin and the layered silicate by a conventional method is not particularly limited. For example, the thermoplastic resin and the layered material are used. A method for producing a foam by impregnating a thermoplastic resin composition comprising silicate with a gaseous foaming agent under high pressure and then vaporizing the gaseous foaming agent in the thermoplastic resin composition, lamellar silicic acid Examples include a method in which a thermally decomposable solid foaming agent is previously contained between the salt layers, and the thermally decomposable solid foaming agent is decomposed by heating to produce a foam. good.

  In the thermoplastic resin composition of the present invention, in addition to the thermoplastic resin which is an essential component and the layered silicate which is organized by the organic onium ions, as long as it does not impede the achievement of the object of the present invention. For example, inorganic fillers other than layered silicates, organic fillers, softeners (plasticizers), antioxidants (anti-aging agents), thermal stabilizers, light stabilizers, ultraviolet absorbers, viscosity modifiers, colorants In addition, one kind or two or more kinds of known various additives such as a lubricant, a flame retardant, an antistatic agent, and an organic solvent may be added.

  Next, the film and substrate material of the present invention are produced using the above-described thermoplastic resin composition of the present invention.

  The film forming (film forming) method of the present invention is not particularly limited, and examples thereof include various known film forming methods such as an extrusion method, an inflation method, and a casting method. May be taken. In addition, the film of the present invention may be subjected to a stretching treatment in the uniaxial direction or biaxial direction after the molding. Furthermore, the film of the present invention may have a single layer structure or a multilayer structure of two or more layers. When the film of the present invention has a multilayer structure, the forming (film forming) method is not particularly limited, and examples thereof include a multilayer extrusion laminating method and a multilayer coextrusion method. May be taken.

  The method for molding the substrate material of the present invention is not particularly limited, and examples thereof include various known molding methods such as an extrusion molding method, an injection molding method, a rolling molding method, and a casting molding method. Any molding method may be adopted.

  As described above, in the thermoplastic resin composition according to the first aspect of the present invention, the layered silicate organized by imidazolium ions having a molecular weight of 200 or more with respect to 100 parts by weight of the thermoplastic resin is 0. Since 5 to 45 parts by weight is blended, it is suitable for obtaining a molded article having low water absorption (hygroscopicity) and exhibiting excellent dimensional stability even under high temperature and high humidity. Therefore, the thermoplastic resin composition according to the invention described in claim 1 is suitably used as a molding material for molded articles for various industrial uses, including films and substrates.

When i Mi Dazo potassium ions has a structure according to formula (1) it is a layered silicate can be further large quantities and highly finely dispersed in the thermoplastic resin.

When the glass transition temperature of the thermoplastic resin is 150 ° C. or higher and the solubility parameter is 42.0 (J / cm ³ ) ^1/2 or higher, the polarity of the thermoplastic resin becomes sufficiently high, and imidazolium ions The affinity with the layered silicate that has been made organic is improved. Accordingly, the layered silicate can be further finely dispersed in the thermoplastic resin.

When the thermoplastic resin is at least one selected from the group consisting of polyimide resin, polyesterimide resin, polyether resin and polyetheretherketone resin, the polarity of the thermoplastic resin is sufficiently high, and thus imidazolium Layered silicates organized by ions can be even more finely dispersed.

Layer-like silicate, montmorillonite, hectorite, when at least one selected from the group consisting of swelling mica and vermiculite, are easily well organic treatment swellable in organic solvents.

  When the average interlayer distance of the (001) plane measured by the wide-angle X-ray diffractometry of the layered silicate is 3 nm or more and a part or all of them are dispersed as a laminate of 5 layers or less, Since the silicate is highly dispersed, the mechanical properties, heat resistance and dimensional stability of the molded article constituted by the thermoplastic resin composition according to the present invention can be improved more effectively.

  In addition, since the film and substrate material of the present invention are produced using the thermoplastic resin composition of the present invention, the water absorption (hygroscopicity) is low, and excellent dimensional stability even under high temperature and high humidity. It is expressed and is suitably used as a molded article for various industrial applications including electronic parts for electronic devices.

  The thermoplastic resin composition of the present invention is a layered silicate that is organized with an organic onium ion represented by the general formula (1) or the general formula (2) with respect to 100 parts by weight of the thermoplastic resin. Since ~ 45 parts by weight is contained, it is suitable for obtaining a molded article having low water absorption (hygroscopicity) and exhibiting excellent dimensional stability even under high temperature and high humidity.

In addition, the thermoplastic resin composition of the present invention is a polyimide resin having a glass transition temperature of 150 ° C. or higher and a solubility parameter of 42 (J / cm ³ ) ^1/2 or higher as the thermoplastic resin. By using at least one selected from the group consisting of polyetheretherketone resins, polyesterimide resins and polyetherimide resins and / or as the layered silicate, from montmorillonite, hectorite, swellable mica and vermiculite Using at least one selected from the group consisting of the above, the layered silicate was measured in a thermoplastic resin composition by wide-angle X-ray diffraction measurement, and the average interlayer distance on the (001) plane was 3n
The above-mentioned effect is more certain by making it partly or entirely dispersed as a laminate of 5 layers or less.

  Since the film and substrate material of the present invention are produced using the thermoplastic resin composition of the present invention, the water absorption (hygroscopicity) is low, and excellent dimensional stability is exhibited even under high temperature and high humidity. .

  In order to explain the present invention in more detail, examples are given below, but the present invention is not limited to these examples.

Example 1
Laboplast mill (Toyo Seiki, product number: 100C100) and 45 parts by weight of thermoplastic polyimide resin (trade name: “Aurum PD-450M”, manufactured by Mitsui Chemicals) and 1-dodecyl-2-methyl-3-benzylimidazo 5 parts by weight of mica treated with lithium chloride (manufactured by Shikoku Kasei Kogyo Co., Ltd.) was added and kneaded at 330 ° C. and 90 rpm for 15 minutes. The obtained kneaded product was sandwiched between upper and lower hot presses adjusted to 330 ° C. and pressed at a press pressure of 4.9 MPa for 75 seconds to prepare a polyimide resin sheet having a thickness of 100 μm.

(Example 2)
Laboplast mill (Toyo Seiki, product number: 100C100) and 45 parts by weight of thermoplastic polyimide resin (trade name: “Aurum PD-450M”, manufactured by Mitsui Chemicals) and 1-octyl-2-phenyl-3-benzylimidazo 5 parts by weight of mica treated with lithium chloride was added and kneaded at 330 ° C. and 90 rpm for 15 minutes. The obtained kneaded product was sandwiched between upper and lower hot presses adjusted to 330 ° C. and pressed at a press pressure of 4.9 MPa for 75 seconds to prepare a polyimide resin sheet having a thickness of 100 μm.

(Example 3)
Laboplast mill (Toyo Seiki, product number: 100C100) and 45 parts by weight of thermoplastic polyimide resin (trade name: “Aurum PD-450M”, manufactured by Mitsui Chemicals) and 1,3-benzyl-2-phenyl-4- 5 parts by weight of montmorillonite treated with methylimidazolium chloride was added and kneaded at 330 ° C. and 90 rpm for 15 minutes. The obtained kneaded product was sandwiched between upper and lower hot presses adjusted to 330 ° C. and pressed at a press pressure of 4.9 MPa for 75 seconds to prepare a polyimide resin sheet having a thickness of 100 μm.

(Comparative Example 1)
A plate having a thickness of 100 μm in the same manner as in Example 1 except that mica treated with 1-octyl-2-phenyl-3-benzylimidazolium chloride was not included in the thermoplastic resin composition. A molded body was produced.

(Comparative Example 2)
Instead of mica treated with 1-octyl-2-phenyl-3-benzylimidazolium chloride as a layered silicate, swellable synthetic mica (trade name: “Somasif ME”, which has not been organicized with organic onium ions) A plate-like molded body having a thickness of 100 μm was produced in the same manner as in Example 1 except that “−100” (manufactured by Coop Chemical Co., Ltd.) was used.

(Comparative Example 3)
Mica treated with dimethyldialkylammonium instead of mica treated with 1-octyl-2-phenyl-3-benzylimidazolium chloride in a thermoplastic resin composition (trade name: “Somasif MAE-100”, Corp. A film having a thickness of 100 μm was produced in the same manner as in Example 1 except that it was used.

(Comparative Example 4)
Instead of montmorillonite treated with 1,3-benzyl-2-phenyl-4-methylimidazolium chloride as a layered silicate, montmorillonite (“trade name CloisiteNa ⁺ ”, A plate-shaped molded article having a thickness of 100 μm was produced in the same manner as in Example 3 except that Southern Clay was used.

  The glass transition temperature of the thermoplastic resin used in Examples 1 to 3 and Comparative Examples 1 to 4 was measured according to JIS K-7121, and the solubility parameter was determined using the Fedors equation. The results are shown in Table 1.

  Moreover, using the plate-shaped molded body or film obtained in Examples 1 to 3 and Comparative Examples 2, 3, and 4, the average interlayer distance of the layered silicate and the dispersion ratio of the laminate of 5 layers or less are as follows: It was calculated by the method. The results are shown in Table 1.

[Average interlayer distance of layered silicate]
Using an X-ray diffractometer (trade name “RINT1100”, manufactured by Rigaku Corporation), 2θ of the diffraction peak obtained from diffraction of the laminated surface of the layered silicate in the plate-shaped molded body or film is measured, and the following The (001) plane distance d of the layered silicate was calculated from the black diffraction formula, and the obtained d was defined as the average interlayer distance (nm).

λ = 2 dsin θ
In the formula, λ is 0.154, and θ represents a diffraction angle.

[Dispersion ratio of laminate of 5 layers or less]
A plate-like molded product or film is observed with a transmission electron microscope (trade name “JEM-1200EXII”, manufactured by JEOL Ltd.) at a magnification of 100,000 times, and all layers of a layered silicate laminate that can be observed in a certain area The number (X) and the number of layers (Y) of the laminate dispersed as a laminate of 5 layers or less were measured, and the dispersion ratio (%) of the laminate of 5 layers or less was calculated by the following formula.

Dispersion ratio (%) of laminate of 5 layers or less = (Y / X) × 100
Furthermore, the performance ((1) water absorption, (2) humidity linear expansion coefficient) of the plate-like molded bodies or films obtained in Examples 1 to 3 and Comparative Examples 1 to 4 was measured by the following method. did. The results are shown in Table 1.

(1) Water absorption The plate-shaped molded body or film was cut into 3 cm × 5 cm to prepare test pieces, and the weight (W1) after drying at 80 ° C. for 5 hours was measured. Next, the test piece was immersed in water and allowed to stand in an atmosphere at 25 ° C. for 24 hours, then taken out, and the weight (W2) after carefully wiping off moisture with a waste was measured. % By weight) was calculated.

Water absorption (% by weight) = 100 × (W2−W1) / W1
(2) Humidity linear expansion coefficient The dimension (L1) after leaving a plate-shaped molded object or a film for 24 hours in a 50 degreeC-30% RH constant temperature and humidity chamber was measured. Subsequently, the dimension (L2) after leaving the said plate-shaped molded object or film for 24 hours in a 50 degreeC-80% RH constant temperature humidity chamber was measured, and the humidity linear expansion coefficient was computed by the following formula.

Humidity linear expansion coefficient (% RH- ¹ ) = (L2-L1) / L1 / (80-30)

  As is apparent from Table 1, the plate-like molded products or films of Examples 1 to 3 produced using the thermoplastic resin compositions of Examples 1 to 3 according to the present invention all have a water absorption rate. It has a low coefficient of linear expansion of humidity and exhibits excellent dimensional stability even under high temperature and high humidity.

  On the other hand, the thermoplastic resin composition of Comparative Example 1 that did not contain a layered silicate that was organized by organic onium ions, and a comparison that contained a layered silicate that was not organized by organic onium ions The thermoplastic resin compositions of Examples 2 and 4 and the plate-like molded articles of Comparative Examples 1 to 4 prepared using the thermoplastic resin composition of Comparative Example 3 that was organicized with an organic onium ion that is not an imidazolium ion Or all the films had a high water absorption rate, a large coefficient of linear expansion of humidity, and poor dimensional stability under high temperature and high humidity.

Claims (7)

It contains 0.5 to 45 parts by weight of a layered silicate organized by imidazolium ions having a molecular weight of 200 or more with respect to 100 parts by weight of the thermoplastic resin ,
A thermoplastic resin composition, wherein the imidazolium ion has a structure described by formula (1) .

(In the formula, _one of R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ is a group having at least an aromatic ring, and at least one of R ₁ , R ₂ , and R ₃ is H Is a group other than 2. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin has a glass transition temperature of 150 ° C. or higher and a solubility parameter of 42.0 (J / cm ³ ) ^1/2 or higher. object. The thermoplastic resin according to claim 1 or 2 , wherein the thermoplastic resin is at least one selected from the group consisting of a polyimide resin, a polyesterimide resin, a polyetherimide resin, and a polyetheretherketone resin. Composition. Layered silicate, montmorillonite, hectorite, thermoplastic resin according to any one of claims 1 to 3, characterized in that at least one kind selected from the group consisting of swelling mica and vermiculite Composition. The layered silicate has a (001) plane average interlayer distance of 3 nm or more measured by a wide-angle X-ray diffraction measurement method, and a part or all of the layered silicate is dispersed as a laminate of 5 layers or less. The thermoplastic resin composition according to any one of claims 1 to 4 . A film produced using the thermoplastic resin composition according to any one of claims 1 to 5 . A substrate material produced using the thermoplastic resin composition according to any one of claims 1 to 5 .