JP2005187727A - Polyimide resin composition, method for producing the same, its film and material for substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyimide resin composition having a low water absorbency and high dimensional stability and to provide a method for producing the same. <P>SOLUTION: The polyimide resin composition comprises a 100 pts. wt. polyimide resin, a 0.1-80 pts. wt. phyllosilicate derived to an organic compound by applying an organic onium ion and a 0.01-20 pts. wt. fatty acid. The method for producing the polyimide resin composition comprises first process to mix the organized phyllosilicate with a solvent, second process to add a fatty acid, third process to remove the solvent and fourth process to mix with a polyimide resin. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a polyimide resin composition in which a layered silicate is blended with a polyimide resin. More specifically, the polyimide resin composition is excellent in water absorption, dimensional stability, etc., and particularly exhibits excellent performance in water absorption. In addition, the present invention relates to a film and a substrate material using the polyimide resin composition.

  2. Description of the Related Art In recent years, high performance, high functionality, and downsizing of electronic devices are rapidly progressing, and there is an increasing demand for downsizing and weight reduction of electronic components used in electronic devices. Along with this, further improvements in various physical properties such as heat resistance, mechanical strength, and electrical characteristics are also demanded for materials of electronic components. For example, semiconductor device packaging methods and wiring boards on which semiconductor devices are mounted are also demanded to have higher density, higher functionality, and higher performance. Further, according to the recent increase in environmental awareness, low environmental load (recyclability, halogen-free content, use of lead-free solder) has been demanded.

  Multilayer printed circuit boards used in electronic devices are configured by laminating a plurality of insulating substrates. Conventionally, as this interlayer insulating substrate, for example, a glass cloth impregnated with a thermosetting resin is used. A film made of a curable resin prepreg, a thermosetting resin, or a photocurable resin has been used. Also in the multilayer printed circuit board, it is desired to make the interlayer insulating substrate extremely thin in order to achieve high density and thinning. Accordingly, there is a need for an interlayer insulating substrate using a thin glass cloth, and a thinner interlayer insulating substrate that does not use a glass cloth.

  Examples of such an interlayer insulating substrate include those made of rubber (elastomer), a thermosetting resin material modified with an acrylic resin, a thermoplastic resin material in which a large amount of an inorganic filler is blended, and the like. Are known. For example, in Patent Document 1 below, an inorganic filler having a predetermined particle size is blended in a varnish mainly composed of a high molecular weight epoxy polymer and a polyfunctional epoxy resin, and the insulating layer is applied to a support. A method of manufacturing a multi-layer insulating substrate that forms a substrate is disclosed.

  On the other hand, among various organic polymers, polyimide film is a material for electrical and electronic equipment due to its excellent heat resistance, low temperature characteristics, chemical resistance and electrical characteristics, and it is also widely used in the space / aerospace field and the electronic communication field. It is used.

  However, polyimide does not sufficiently satisfy the recent high required performance, and it is strongly required to have various performances depending on the application. In particular, for electronic materials, a polyimide having a low water absorption rate is desired in order to achieve high functionality and downsizing. By reducing the water absorption rate, it is possible to suppress problems such as a decrease in electrical characteristics such as a dielectric constant due to water absorption and a dimensional change due to hygroscopic expansion. In addition to water absorption, taking TAB tape as an example, there are many processes that undergo stress and processes that undergo temperature changes, and the organic insulating film as the base material has dimensional changes due to stress and temperature changes. It is strongly desired that the

  As described above, with high performance, high functionality, and downsizing, TAB tape, flexible printed circuit board base film, or laminated board resin material, in addition to heat resistance, changes in dimensions due to heat and water absorption. It is desired that the elastic modulus is small and the elastic modulus is high. However, a polyimide film that sufficiently satisfies these performances has not been obtained at present.

Patent Document 2 below discloses a method of developing low water absorption by defining the structure of polyimide. A polyimide composition containing a polyimide resin obtained by dehydrating and ring-closing a polyamic acid copolymer represented by a specific structure has been disclosed. By using a polyimide having a specific structure, low thermal expansion and low water absorption are disclosed. It is said that the rate and the low sound absorption expansibility are expressed.
JP 2000-183539 A Japanese Patent Laid-Open No. 10-36506

  In the multilayer insulating substrate produced by the manufacturing method described in Patent Document 1 described above, a large amount of inorganic filler is blended in order to sufficiently increase mechanical properties such as mechanical strength or reduce the linear expansion coefficient. Had to do. For this reason, there are problems in that a manufacturing defect such as an increase in the manufacturing process occurs and it is difficult to thin the interlayer. When a large amount of the inorganic filler is added, the interface between the resin and the inorganic filler is increased, and the resulting multilayer insulating substrate becomes brittle, which may cause cracks when subjected to a heat cycle.

  In addition, interlayer insulating substrates using thin glass cloth and thin interlayer insulating substrates that do not use glass cloth have insufficient heat resistance, dimensional stability, etc., and are brittle and easily broken, resulting in a decrease in yield in the manufacturing process. Tended to be.

  On the other hand, in the polyimide composition using the polyimide resin having a specific structure described in Patent Document 2 described above, it is described that low water absorption is expressed, but since it is a non-thermoplastic type polyimide, The film is formed by the rolling method. In the case of such a non-thermoplastic resin, the equipment cost and manufacturing cost have to be high. In addition, there is a problem that it is difficult to perform recycle use because it is difficult to form by heat.

  The object of the present invention is to provide a polyimide resin composition in which a layered silicate is dispersed in a polyimide resin in view of the current state of the prior art described above. An object of the present invention is to provide a polyimide resin composition having a sufficiently low rate and a method for producing the same.

  Another object of the present invention is to provide a film and substrate material comprising a polyimide resin composition having a low water absorption rate and linear expansion coefficient and suitable for thinning.

  As a result of earnestly examining the above problems, the inventors of the present application can lower the water absorption rate and the linear expansion coefficient of the polyimide resin composition by dispersing the layered silicate that has been organically treated in the polyimide resin at a nanoscale. The present invention has been found and the present invention has been made. That is, when the organic treatment and the treatment with fatty acid are used in combination with the layered silicate, the interlayer distance of the layered silicate is further increased, and the dispersibility in the polyimide resin can be greatly increased, thereby increasing the water absorption rate and the linearity. It has been found that the expansion rate can be further reduced.

  The polyimide resin composition of the present invention comprises 100 parts by weight of a polyimide resin, 0.1 to 80 parts by weight of a layered silicate that has been organicized with an organic onium ion, and 0.01 to 20 parts by weight of a fatty acid. And

In the polyimide resin composition according to the present invention, preferably, the layered silicate organized by the organic onium ions is further pretreated with the fatty acid.

  In the polyimide resin composition according to the present invention, the carbon number of the fatty acid is preferably in the range of 12-24.

  In the polyimide resin composition according to the present invention, the layered silicate is not particularly limited, but is preferably at least one selected from the group consisting of montmorillonite, hectorite, swellable mica and vermiculite.

  In the polyimide resin composition according to the present invention, preferably, an average interlayer distance of (001) plane measured by a wide-angle X-ray diffraction measurement method is 3 nm or more, and a laminate of a part or all of a layered silicate Is dispersed so that there are 5 layers or less.

  The method for producing a polyimide resin composition according to the present invention includes a first step of mixing an organically treated layered silicate with a solvent, a second step of adding a fatty acid after the first step, and removing the solvent. And a fourth step of further mixing the polyimide resin.

  The film and the substrate material according to the present invention are characterized by being configured using a polyimide resin composition configured according to the present invention.

  In the polyimide resin composition according to the present invention, 0.1 to 80 parts by weight of a layered silicate organized with an organic onium ion and 0.01 to 20 parts by weight of a fatty acid are blended with 100 parts by weight of the polyimide resin. Therefore, the layered silicate is treated with a fatty acid, and the layer of the layered silicate that has been organized is further expanded by the fatty acid treatment, so that the dispersibility of the lamellar crystals of the layered silicate in the polyimide resin can be improved. it can. As a result, a polyimide resin composition having a sufficiently low water absorption rate and linear expansion coefficient can be obtained. Therefore, since the water absorption rate and the linear expansion coefficient are sufficiently low, electrical characteristics such as dielectric constant due to water absorption are not easily reduced, and dimensional changes due to hygroscopic expansion are not likely to occur. A polyimide resin composition can be provided.

  In particular, when the layered silicate organized by the organic onium ion is previously treated with the fatty acid, the layer of the organized layered silicate is more reliably expanded by the fatty acid treatment. Therefore, the dispersibility of the lamellar silicate flake crystals in the polyimide resin can be further effectively improved.

  Moreover, when carbon number of a fatty acid exists in the range of 12-24, the dispersibility of a layered silicate can be improved much more effectively.

  In the present invention, since the organically layered silicate and fatty acid are blended in the above-mentioned specific ratio with respect to the polyimide resin, the obtained polyimide resin composition is preferably obtained by a wide-angle X-ray diffraction measurement method. The measured (001) plane average interlaminar distance is 3 nm or more, and some or all of the layered silicate laminates are dispersed in 5 layers or less. Therefore, since the layered silicate is highly dispersed, it is possible to provide a polyimide resin composition having a low water absorption rate and a low linear expansion coefficient.

In the production method according to the present invention, the organically treated layered silicate is first mixed with a solvent, and a fatty acid is added in the second step. And after removing a solvent in a 3rd process, a polyimide resin is mixed in a 4th process. Therefore, since the organically treated layered silicate is previously treated with a fatty acid and mixed with the polyimide resin, the layer of the layered silicate is highly dispersed in the obtained polyimide resin composition. Accordingly, it is possible to provide a polyimide resin composition having a small water absorption rate and a small linear expansion coefficient.

  The film and substrate material according to the present invention are configured using a polyimide resin composition configured according to the present invention. Therefore, the film and substrate material have a low water absorption rate and a sufficiently low linear expansion coefficient.

  Details of the present invention will be described below.

(Polyimide resin)
In the present invention, as the polyimide resin, any of a thermosetting polyimide resin and a thermoplastic polyimide resin can be used. In the case of a curable polyimide resin, the polyamic acid solution is obtained by removing the solvent and imidizing. The organically treated layered silicate may be previously treated with a fatty acid and added to the polyamic acid solution. Although the dispersion effect is reduced, a fatty acid may be added to the polyamic acid solution containing the organically modified layered silicate.

  In the case of thermoplastic polyimide, the layered silicate that has been organized in advance may be treated with a fatty acid in a solvent, or the fatty acid solution and the layered silicate may be dry blended with a Henschel mixer or the like. In order to effectively treat the layered silicate, a method of treating the layered silicate that has been organized in advance with a fatty acid in a solvent is desirable. This is because when the fatty acid is previously adsorbed on the layered silicate, evaporation due to heating is suppressed, and the dispersibility of the layered silicate in the thermoplastic polyimide can be improved.

  In addition, when a thermoplastic polyimide is used as the polyimide, the obtained polyimide resin composition is easily molded by heat.

(Layered silicate)
Examples of the layered silicate include smectite clay minerals such as montmorillonite, hectorite, saponite, beidellite, stevensite and nontronite, swelling mica, vermiculite, and halloysite. Among these, at least one selected from the group consisting of montmorillonite, hectorite, swellable mica, and vermiculite is preferably used. These layered silicates may be used alone or in combination of two or more.

  The crystal form of the layered silicate is not particularly limited, but the preferable lower limit of the average length is 0.01 μm, the upper limit is 3 μm, the preferable lower limit of the thickness is 0.0004 μm, the upper limit is 0.5 μm, and the preferable lower limit of the aspect ratio. The upper limit is 5000, the more preferable lower limit of the average length is 0.05 μm, the upper limit is 2 μm, the more preferable lower limit of the thickness is 0.0004 μm, the upper limit is 0.1 μm, and the more preferable lower limit of the aspect ratio is 50 The upper limit is 3000. The aspect ratio is a value represented by long side / short side.

  The layered silicate preferably has a large shape anisotropy effect defined by the following formula (1). By using a layered silicate having a large shape anisotropy effect, the resin obtained from the resin composition of the present invention has excellent mechanical properties.

Shape anisotropy effect = surface area of laminar crystal laminate surface / surface area of laminar crystal laminate surface
... Formula (1)
The exchangeable metal cation existing between the layers of the layered silicate means a metal ion such as sodium or calcium existing on the surface of the lamellar crystal of the layered silicate, and these metal ions are cations with the cationic substance. Since it has exchangeability, various substances having cationic properties can be inserted (intercalated) between the crystal layers of the layered silicate.

  Although it does not specifically limit as a cation exchange capacity | capacitance of the said layered silicate, A preferable minimum is 50 milliequivalent / 100g, and an upper limit is 200 milliequivalent / 100g. When the amount is less than 50 milliequivalents / 100 g, the amount of the cationic substance intercalated between the crystal layers of the layered silicate is reduced by cation exchange, so that the crystal layers are not sufficiently depolarized (hydrophobized). Sometimes. When it exceeds 200 milliequivalents / 100 g, the bonding force between the crystal layers of the layered silicate becomes too strong, and the crystal flakes may be difficult to peel off.

  The layered silicate is treated with organic onium ions. Examples of organic onium salts that generate such organic onium ions include quaternary ammonium salts, quaternary phosphonium salts, and imidazolium salts. From the viewpoint of heat resistance, quaternary phosphonium salts and imidazolium salts are preferably used.

The quaternary phosphonium salt is not particularly limited. For example, dodecyl triphenyl phosphonium salt, methyl triphenyl phosphonium salt, lauryl trimethyl phosphonium salt, stearyl trimethyl phosphonium salt, trioctyl phosphonium salt, distearyl dilyl dimethyl phosphonium salt, di Examples include stearyl dibenzylphosphonium salt. These quaternary phosphonium salts may be used alone or in combination of two or more.

  The imidazolium salt is not particularly limited, and examples thereof include dimethylbutylimidazolium salt, dimethyloctylimidazolium salt, dimethyldecylimidazolium salt, dimethyldodecylimidazolium salt, and dimethylhexadecylimidazolium salt. These imidazolium salts may be used alone or in combination of two or more.

  As the quaternary ammonium salt, a quaternary ammonium salt having an alkyl chain having 6 or more carbon atoms is preferably used because the crystal layer of the layered silicate can be sufficiently hydrophobized.

  The quaternary ammonium salt is not particularly limited. For example, trimethylalkylammonium salt, triethylalkylammonium salt, tributylalkylammonium salt, dimethyldialkylammonium salt, dibutyldialkylammonium salt, methylbenzyldialkylammonium salt, dibenzyldialkylammonium salt. , Trialkylmethylammonium salt, trialkylethylammonium salt, trialkylbutylammonium salt, quaternary ammonium salt having an aromatic ring, quaternary ammonium salt derived from aromatic amines such as trimethylphenylammonium, and two polyethylene glycol chains Dialkyl quaternary ammonium salt, dialkyl quaternary ammonium salt having two polypropylene glycol chains, polyethylene glycol chain One having trialkyl quaternary ammonium salt, trialkyl quaternary ammonium salt having one polypropylene glycol chain. Among them, lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, trioctyl methyl ammonium salt, distearyl dimethyl ammonium salt, di-cured tallow dimethyl ammonium salt, distearyl dibenzyl ammonium salt, N-polyoxyethylene-N-lauryl N, N-dimethylammonium salt and the like are preferred. These quaternary ammonium salts may be used alone or in combination of two or more.

When the resin composition of the present invention is produced using the above layered silicate, it is preferable that the dispersibility in the resin is improved by chemically modifying the layered silicate to increase the affinity with the resin. A large amount of layered silicate can be dispersed in the resin by such chemical treatment. If the layered silicate is not subjected to chemical modification suitable for the resin used in the present invention or the solvent used in the production of the resin composition of the present invention, the layered silicate tends to aggregate and be dispersed in large quantities. However, by applying a chemical modification suitable for the resin or solvent, the layered silicate can be dispersed in the resin without agglomeration even when added in an amount of 10 parts by weight or more. As said chemical modification, it can implement by the chemical modification method shown below, for example.

  The chemical modification method is also referred to as a cation exchange method using a cationic surfactant, and is a method in which cation exchange between layers of a layered silicate is performed with a cationic surfactant in advance to make it hydrophobic. By making the layers of the layered silicate hydrophobic in advance, the affinity between the layered silicate and the polyimide resin is increased, and the layered silicate can be uniformly finely dispersed.

  In the present invention, the organically modified layered silicate is treated with a fatty acid. The treatment with a fatty acid exhibits the following first to third effects.

  The first effect is that the layer of the organically treated layered silicate is further expanded by the fatty acid treatment. Therefore, it becomes easy for the polyimide resin to penetrate between layers, and the improvement of the dispersibility of the layered silicate and the adhesion of the interface between the layered silicate and the polyimide resin are expected. Since the organically treated layered silicate has basicity, acidic fatty acids are easily adsorbed.

  The second effect is that the dispersibility of the layered silicate which is an inorganic substance is enhanced by the presence of the fatty acid.

  The third effect is that the heat resistance of the layered silicate can be expected by adsorbing the fatty acid to the layered silicate. In particular, in the case of a thermoplastic polyimide resin, the melt-kneading temperature with the layered silicate is 300 ° C. or higher, so there is a concern that the organic compound cation-exchanged into the layered silicate will be decomposed. Therefore, it is thought that it is very effective to perform the treatment with the organic fatty acid.

  As described above, the layered silicate is dispersed in the polyimide resin to a higher degree, that is, the interlayer is in nanometer units by performing the treatment with the fatty acid in addition to the organic treatment on the layered silicate. Can do.

  Aliphatics used in the present invention are not particularly limited, but for example, formic acid, acetic acid, propionic acid, butyric acid, kilauric acid, caproic acid, heptanoic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid , Myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, castor oil fatty acid, isoheptanoic acid, isomyristic acid, isopalmitic acid, isostearic acid, isoarachin Saturated fatty acids such as acids, acrylic acid, crotonic acid, angelic acid, brentzuric acid, citronellic acid, undecylenic acid, Linderic acid, perfume acid, zomer phosphoric acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, castor oil Fatty acid, moroctic acid, gado Ynoic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosapentaenoic acid, unsaturated fatty acids such as docosahexaenoic acid. In addition, it is also possible to add coconut oil, palm kernel oil, beef tallow, wood wax, rice bran oil, olive oil, cottonseed oil, soybean oil, peanut oil, pork fat, fish oil, whale oil, flaxseed oil, castor oil containing fatty acids. Included in the range.

The carbon number of the fatty acid is preferably in the range of 12-24. If the carbon number is less than 12, even if adsorbed between the layers of the layered silicate, the effect of expanding the layer may not be sufficiently obtained. This is because the fatty acid has a large molecular size and may not be adsorbed between layers.

  The addition amount of the fatty acid can be generally determined from the specific surface area and the monomolecular coverage area of the fatty acid when the layered silicate is dispersed in the polyimide resin. However, the adsorption form of fatty acids on the layered silicate varies greatly depending on the concentration and pH of the solution. Therefore, what is necessary is just to adjust a fatty-acid addition amount so that it may become the optimal addition amount from which a desired physical property is obtained. When selecting the solvent for pretreating the layered silicate, a solvent that can satisfy both the satisfactory dispersion of the layered silicate and the dissolution of the fatty acid may be selected.

  The timing of adding the fatty acid in the production of the polyimide resin composition of the present invention is not particularly limited, but it is most desirable to add the fatty acid in a state where the layered silicate is dispersed in the solvent. That is, the organically treated layered silicate reaggregates even if it is once dispersed in the polyimide by shearing or the like, particularly when a melt molding method is used. This is because the layers are attracted to each other by mutual addition of layered silicates, and the distance between the layers is completely set to the nanometer level, and it is difficult to disperse the layers highly. Therefore, the inventors of the present application select a solvent in which the layer of the organically treated layered silicate is well delaminated, leave the layered silicate organically treated in the solvent in a delaminated state, add a fatty acid, We considered adsorption of fatty acids between layers of layered silicate.

  The adsorbed fatty acid plays a role of molecular repulsion and steric hindrance between the layered silicate layers, and functions to prevent reaggregation of the layered silicate. That is, a nanocomposite using polyimide in which layered silicate is nano-dispersed can be obtained. In particular, nanocomposites using thermoplastic polyimide resin have large polymer molecules and low mobility in melt-kneading, so the conventional method is such that the layered silicate is sufficiently high, that is, the interlayer is on the nanometer order. It was difficult to disperse. Moreover, there is a problem that once the layered silicate layers are dispersed on the nanometer order and then remelted, the layered silicate reaggregates. On the other hand, according to the present invention, as described above, by treatment with fatty acid, it is possible to obtain a nanocomposite in which the interlayer of the layered silicate is sufficiently widened and the interlayer distance is reliably in the order of nanometers. In addition, reaggregation of the layered silicate in the remelted state can be reliably suppressed. In the present specification, the nanocomposite refers to a composite material in which the layered silicate is highly dispersed so that the interlayer distance of the layered silicate is on the order of nanometers.

  Moreover, since the dispersibility of the layered silicate is enhanced by treating the layered silicate with a fatty acid, the water resistance of the nanocomposite using polyimide is also increased, and the linear expansion coefficient is lowered.

  In the resin composition of the present invention, the layered silicate has an average interlayer distance of (001) plane measured by a wide angle X-ray diffraction measurement method of 3 nm or more, and a part or all of the laminate is 5 layers. The dispersion is preferably as follows. The interfacial area between the resin and the layered silicate is sufficiently large because the layered silicate is dispersed such that the average interlayer distance is 3 nm or more and a part or all of the laminate is 5 layers or less. The distance between the flaky crystals of the layered silicate is large, and a sufficient improvement effect due to dispersion can be obtained in high-temperature properties, mechanical properties, heat resistance, dimensional stability, and the like.

  A preferable upper limit of the average interlayer distance is 5 nm. If it exceeds 5 nm, the lamellar silicate crystal flakes are separated into layers and the interaction becomes so weak that the interaction is negligible. Therefore, the binding strength at high temperatures becomes weak, and sufficient dimensional stability may not be obtained.

  In the present specification, the average interlayer distance of the layered silicate means the average distance between layers when the flaky crystal of the layered silicate is regarded as a layer, and X-ray diffraction peak and transmission electron microscope photography That is, it can be calculated by a wide-angle X-ray diffraction measurement method.

  Specifically, the layered silicate is dispersed so that the part or all of the laminate is 5 layers or less. Specifically, the interaction between the flaky crystals of the layered silicate is weakened and the flaky crystals This means that a part or all of the laminate is dispersed. Preferably, 10% or more of the layered silicate laminate is dispersed in 5 layers or less, and 20% or more of the layered silicate laminate is dispersed in 5 layers or less.

  In addition, the ratio of the layered silicate dispersed as a laminate of 5 layers or less is a layered silicic acid that can be observed in a fixed area by observing the resin composition at a magnification of 50,000 to 100,000 times with a transmission electron microscope. It can be calculated from the following formula (2) by measuring the total number of layers X of the salt laminate and the number Y of layers dispersed as a laminate of 5 or less layers.

Ratio of layered silicate dispersed as a laminate of 5 layers or less (%) = (Y / X) × 100
... Formula (2)
The number of layers in the layered silicate laminate is preferably 5 layers or less, more preferably 3 layers or less, and even more preferably 1 layer in order to obtain the effect of dispersion of the layered silicate. is there.

  In the polyimide resin composition according to the present invention, the average interlayer distance of the (001) plane of the layered silicate measured by the wide-angle X-ray diffraction measurement method is 3 nm or more, and a part or all of the laminate is five layers. It is desirable that the following layered silicate is dispersed. In that case, the area of the interface between the polyimide resin and the layered silicate is sufficiently large, the interaction between the resin and the surface of the layered silicate is increased, the melt viscosity is increased, and the moldability is improved. In addition, mechanical properties such as elastic modulus are enhanced over a wide temperature range from room temperature to high temperature, and the mechanical properties can be maintained even at high temperatures above the glass transition point Tg or the melting point of the resin. Moreover, the coefficient of linear expansion at high temperatures can be kept low. The reason why such an excellent effect is obtained is not clear, but even in the temperature range above the glass transition point Tg or the melting point, since the layered silicate is in a finely dispersed state, it acts as a kind of pseudo-crosslinking point. Therefore, it is considered that these excellent physical properties are expressed. On the other hand, since the distance between the lamellar crystals of the layered silicate, that is, the interlayer distance is also appropriate, the lamellar crystals of the lamellar silicate move during combustion, and it is easy to form a sintered body that becomes a flame retardant coating. Become. Since this sintered body is formed at an early stage during combustion, it not only blocks the supply of oxygen from the outside, but also blocks the combustible gas generated by the combustion. Therefore, the polyimide resin composition according to the present invention also exhibits excellent flame retardancy.

  Furthermore, in the polyimide resin composition according to the present invention, since the flaky crystals of the layered silicate are finely dispersed in a nanometer size, a film or a substrate material constituted by using the polyimide resin composition of the present invention, etc. When drilling is performed with a laser such as a carbon dioxide laser, the resin component and the layered silicate are simultaneously decomposed and evaporated. That is, the partially remaining layered silicate residue is only a small one of several μm or less and can be easily removed by desmearing. Therefore, the residue generated by the drilling process can be remarkably reduced, and the occurrence of defective plating can be effectively suppressed.

In the present invention, the blending ratio of the organically modified layered silicate subjected to the fatty acid treatment is preferably 0.1 to 80 parts by weight with respect to 100 parts by weight of the polyimide resin. If it is less than 0.1 part by weight, the effect of reducing the hygroscopicity and the linear expansion coefficient is not sufficient. When it exceeds 80 parts by weight, the density (specific gravity) of the resin composition of the present invention is increased, the mechanical strength is lowered, and the practicality is lowered. The more preferable lower limit of the mixing ratio of the layered silicate is 1 part by weight, and the upper limit is 50 parts by weight. If it is less than 1 part by weight, a sufficient high-temperature property improving effect may not be obtained when the polyimide resin composition of the present invention is thinly formed, and if it exceeds 50 parts by weight, moldability may be reduced. A more preferred lower limit is 1.5 parts by weight and an upper limit is 25 parts by weight. It is because it will become a problem in a mechanical physical property and process suitability by setting it as the range of 1.5-25 weight part.

  In the present invention, other fillers may be added in addition to the layered silicate. Such a filler may be either an inorganic filler or an organic filler. Examples of inorganic fillers include metals such as iron, copper, bronze, titanium, stainless steel, nickel, gold, silver, aluminum, lead, tungsten, carbon such as carbon black, graphite, activated carbon, carbon balloon, silica, silica Balloon, alumina, titanium oxide, iron oxide, zinc oxide, magnesium oxide, tin oxide, antimony oxide, beryllium oxide, barium ferrite, strontium ferrite and other inorganic oxides, aluminum hydroxide, magnesium hydroxide and other inorganic hydroxides, Inorganic carbonates such as calcium carbonate, magnesium carbonate and sodium hydrogen carbonate, inorganic sulfates such as calcium sulfate, talc, kaolin, fly ash, calcium silicate, glass, glass balloons and other inorganic silicates, calcium titanate, titanium Lead zirconate, aluminum nitride , Silicon carbide, heat-expandable vinylidene chloride particles, whiskers, and the like. In the organic system, wood flour, starch, organic pigments, polystyrene, nylon, polyolefins such as polyethylene and polypropylene, vinyl chloride, various elastomers, waste plastics and the like can be mentioned.

  As for the said filler, only 1 type may be added and 2 or more types may be added.

  Furthermore, in the polyimide resin composition according to the present invention, a reinforcing material may be added. Reinforcing materials include inorganic fibers such as glass fibers, carbon fibers and metal fibers, or aramid fibers, nylon fibers, jute fibers, kenaf fibers, bamboo fibers, polyethylene fibers, stretched polyethylene fibers, polypropylene fibers, stretched polypropylene fibers and other organic fibers. Is mentioned.

  Furthermore, in the polyimide resin composition according to the present invention, an antioxidant, a reinforcing material, a dispersant, a foaming agent, an antifoaming agent, a surfactant, a coupling agent, and thixotropic addition are provided within a range not impairing the object of the present invention. Various additives such as an agent, an antistatic agent, a molecular weight modifier, a polymer modifier, a flame retardant, a plasticizer, a pigment, a dye, a colorant, an elastomer, an ultraviolet absorber, and a release agent can be blended. .

  The method for producing the polyimide resin composition of the present invention is not particularly limited. Preferably, the organically treated layered silicate is mixed with a solvent having good dispersibility in the first step to disperse the layered silicate. The Next, in the second step, fatty acids are added. Thereby, the layered silicate organically treated with fatty acid is pretreated. Thereafter, the solvent is removed in the third step. Then, the layered silicate treated as described above is mixed with the polyimide resin in the fourth step. The manufacturing method which has the said 1st-4th process is a manufacturing method suitable for the manufacturing method of the polyimide resin composition which concerns on this invention, especially in the case of the polyimide resin composition using a thermoplastic polyimide resin. It is a suitable manufacturing method.

  Next, the effects of the present invention will be clarified by giving specific examples. In addition, this invention is not limited to a following example.

(Example 1)
The synthetic smectite treated with 1,2-dimethyl-3-decylimidazolium was mixed with ethanol as a solvent while stirring for 5 parts by weight, and the synthetic smectite treated with 1,2-dimethyl-3-decylimidazolium was mixed. An ethanol solution was obtained. After left standing for 1 day, 1 part by weight of stearic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed with ethanol. And after drying at 150 degreeC for 2 hours, it vacuum-dried and obtained the synthetic smectite processed with the fatty acid.

  Next, 90 parts by weight of thermoplastic polyimide (Mitsui Chemicals, Aurum PD-450M) and 10 parts by weight of the synthetic smectite processed as described above in a small extruder (manufactured by Nippon Steel Works, TEX30). Were extruded by melting and kneading at 330 ° C. under a nitrogen stream, and the extruded strand was pelletized by a pelletizer to obtain pellets of a resin composition. Next, the obtained resin composition pellets were pressed with a hot press in which the temperature of the upper mold and the lower mold was adjusted to 340 ° C. in a nitrogen stream, and rolled to produce a plate-shaped molded body having a thickness of 100 μm.

(Example 2)
Montmorillonite treated with 1,2-dimethyl-3-decylimidazolium was mixed with 5 parts by weight of ethanol as a solvent while stirring, and ethanol solution of montmorillonite treated with 1,2-dimethyl-3-decylimidazolium. Got. After being allowed to stand for 1 day, 1 part by weight of isostearic acid (manufactured by Nissan Chemical Industries, Ltd.) was mixed with ethanol, and allowed to stand for 1 day, followed by filtration. And after drying at 150 degreeC for 2 hours, vacuum drying was performed and the montmorillonite processed with the fatty acid was obtained.

  Next, in a small extruder (manufactured by Nippon Steel Works, TEX30), 90 parts by weight of thermoplastic polyimide (Mitsui Chemicals, Aurum PD-450M) and 10 parts by weight of montmorillonite treated as described above, This was melt-kneaded and extruded at 330 ° C. under a nitrogen stream, and the extruded strand was pelletized with a pelletizer to obtain resin composition pellets. Next, the obtained resin composition pellets were pressed with a hot press in which the temperature of the upper mold and the lower mold was adjusted to 340 ° C. in a nitrogen stream, and rolled to produce a plate-shaped molded body having a thickness of 100 μm.

(Example 3)
Synthetic smectite treated with N-hexadecyltri-N-butylphosphonium was mixed with 5 parts by weight of ethanol as a solvent with stirring, and an ethanol solution of synthetic smectite treated with N-hexadecyltri-N-butylphosphonium. Got. After left standing for 1 day, 1 part by weight of stearic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed with ethanol. And after drying at 150 degreeC for 2 hours, it vacuum-dried and obtained the synthetic smectite processed with the fatty acid.

  Next, in a small extruder (manufactured by Nippon Steel Works, TEX30), 90 parts by weight of thermoplastic polyimide (Mitsui Chemicals, Aurum PD-450M) and 10 parts by weight of smectite treated as described above, This was melt-kneaded and extruded at 330 ° C. under a nitrogen stream, and the extruded strand was pelletized with a pelletizer to obtain resin composition pellets. Next, the obtained resin composition pellets were pressed with a hot press in which the temperature of the upper mold and the lower mold was adjusted to 340 ° C. in a nitrogen stream, and rolled to produce a plate-shaped molded body having a thickness of 100 μm.

Example 4
5 parts by weight of montmorillonite treated with N-hexadecyltri-N-butylphosphonium was mixed with ethanol as a solvent while stirring to obtain an ethanol solution of montmorillonite treated with N-hexadecyltri-N-butylphosphonium. It was. After being allowed to stand for 1 day, 1 part by weight of isostearic acid (manufactured by Nissan Chemical Industries, Ltd.) was mixed with ethanol, and allowed to stand for 1 day, followed by filtration. And after drying at 150 degreeC for 2 hours, vacuum drying was performed and the montmorillonite processed with the fatty acid was obtained.

Next, in a small extruder (manufactured by Nippon Steel Works, TEX30), 90 parts by weight of thermoplastic polyimide (Mitsui Chemicals, Aurum PD-450M) and 10 parts by weight of montmorillonite treated as described above, This was melt-kneaded and extruded at 330 ° C. under a nitrogen stream, and the extruded strand was pelletized with a pelletizer to obtain resin composition pellets. Next, the obtained resin composition pellets were pressed with a hot press in which the temperature of the upper mold and the lower mold was adjusted to 340 ° C. in a nitrogen stream, and rolled to produce a plate-shaped molded body having a thickness of 100 μm.

(Comparative Example 1)
In a small extruder (Nippon Steel Works, TEX30), thermoplastic polyimide (Mitsui Chemicals, Aurum PD-450M) was melted and kneaded at 330 ° C under a nitrogen stream, and the extruded strand was pelletized. The pellet of the resin composition was obtained by pelletizing. Next, the obtained resin composition pellets were pressed with a hot press in which the temperature of the upper mold and the lower mold was adjusted to 340 ° C. in a nitrogen stream, and rolled to produce a plate-shaped molded body having a thickness of 100 μm.

(Comparative Example 2)
In a small extruder (Nippon Steel Works, TEX30), 90 parts by weight of thermoplastic polyimide (Mitsui Chemicals, Aurum PD-450M) and 10 parts by weight of synthetic smectite SWN (Coop Chemical Co., synthetic smectite) This was melt-kneaded and extruded at 330 ° C. under a nitrogen stream, and the extruded strand was pelletized with a pelletizer to obtain resin composition pellets. Next, the obtained resin composition pellets were pressed with a hot press in which the temperature of the upper mold and the lower mold was adjusted to 340 ° C. in a nitrogen stream, and rolled to produce a plate-shaped molded body having a thickness of 100 μm.

(Comparative Example 3)
Comparative Example 2 except that the layered silicate was changed to montmorillonite Na + (manufactured by Southern Clay)
In the same manner as described above, a plate-like molded body having a thickness of 100 μm made of the resin composition was produced.

(Comparative Example 4)
In a small extruder (Nippon Steel Works, TEX30), 90 parts by weight of thermoplastic polyimide (Mitsui Chemicals, Aurum PD-450M) and 1,2-dimethyl-3-decylimidazolium-treated synthesis 10 parts by weight of smectite was melt kneaded and extruded at 330 ° C. under a nitrogen stream, and the extruded strand was pelletized with a pelletizer to obtain pellets of a resin composition. Next, the obtained resin composition pellets were pressed with a hot press in which the temperature of the upper mold and the lower mold was adjusted to 340 ° C. in a nitrogen stream, and rolled to produce a plate-shaped molded body having a thickness of 100 μm.

(Comparative Example 5)
Montmorillonite 10 treated with 90 parts by weight of thermoplastic polyimide (Mitsui Chemicals, Aurum PD-450M) and N-hexadecyltri-N-butylphosphonium in a small extruder (manufactured by Nippon Steel Works, TEX30) Part by weight was melt kneaded and extruded at 330 ° C. under a nitrogen stream, and the extruded strand was pelletized with a pelletizer to obtain pellets of a resin composition. Next, the obtained resin composition pellets were pressed with a hot press in which the temperature of the upper mold and the lower mold was adjusted to 340 ° C. in a nitrogen stream, and rolled to produce a plate-shaped molded body having a thickness of 100 μm.

(1) Measurement of coefficient of thermal expansion A test piece cut to 3 mm × 25 mm by cutting a plate-like molded product was used as a TMA (Thermal Mechanical Analysis) apparatus (manufactured by Seiko Denshi, TMA / SS120C).
Was used, and the average linear expansion coefficient (hereinafter sometimes referred to as “CTE”) of 25 to 150 ° C. was measured in a tensile mode.

(2) Measurement of water absorption The test piece which made the plate-shaped molded object of thickness 100 micrometers into the strip shape of 3x5 cm was produced, and the weight (W1) after making it dry at 80 degreeC for 5 hours was measured. Next, the test piece was immersed in water, left for 24 hours in an atmosphere at 25 ° C., then taken out, and the weight (W2) after carefully wiping with a waste was measured. The water absorption was determined by the following formula.
Water absorption (%) = (W2−W1) / W1 × 100

(3) Average interlayer distance of layered silicate Using an X-ray diffractometer (RINT1100, manufactured by Rigaku Corporation), a diffraction peak obtained from diffraction of the layered surface of the layered silicate in a 2 mm thick plate-shaped body 2θ was measured, the (001) plane distance d of the layered silicate was calculated by the black diffraction formula of the following formula (X), and the obtained d was defined as the average interlayer distance (nm).

λ = 2 d sin θ: Formula (X)
In the above formula (X), λ is 0.154, and θ represents a diffraction angle.

(4) Ratio of layered silicate dispersed as a laminate of 5 layers or less A plate-shaped molded body having a thickness of 100 μm is observed with a transmission electron microscope at a magnification of 100,000 times. The total number of layers X in the laminate and the number Y of layered silicate dispersed in 5 layers or less are measured, and the ratio of the layered silicate dispersed as a laminate of 5 layers or less according to the following formula (XX) ( %) Was calculated.
Ratio of layered silicate dispersed as a laminate of 5 layers or less (%) = (Y / X) × 100
... Formula (XX)

(5) Measurement of dielectric constant A dielectric constant in the vicinity of a frequency of 1 MHz was measured using an impedance measuring instrument (HP 4291B, manufactured by HP).

Claims (8)

  A polyimide resin composition comprising 100 parts by weight of a polyimide resin, 0.1 to 80 parts by weight of a layered silicate organized by an organic onium ion, and 0.01 to 20 parts by weight of a fatty acid.   The polyimide resin composition according to claim 1, wherein the layered silicate organized by the organic onium ions is further pretreated with the fatty acid.   The polyimide resin composition according to claim 1 or 2, wherein the fatty acid has 12 to 24 carbon atoms.   The polyimide resin composition according to any one of claims 1 to 3, wherein the layered silicate is at least one selected from the group consisting of montmorillonite, hectorite, swellable mica, and vermiculite.   The average interlaminar distance of the (001) plane measured by wide-angle X-ray diffraction measurement method is 3 nm or more, and part or all of the layered silicate laminates are dispersed so as to be 5 layers or less. The polyimide resin composition according to any one of claims 1 to 4, wherein:   A first step of mixing the organically treated layered silicate with a solvent, a second step of adding a fatty acid after the first step, a third step of removing the solvent, and a polyimide resin are further mixed. It consists of a 4th process, The manufacturing method of the polyimide resin composition of any one of Claims 1-5 characterized by the above-mentioned.   It is comprised using the polyimide resin composition of any one of Claims 1-5, The film characterized by the above-mentioned. It is comprised using the polyimide resin composition of any one of Claims 1-5, The board | substrate material characterized by the above-mentioned.