JP2013010917A - Polyimide resin composition, thermosetting resin composition, gas barrier material, interlayer adhesive film for printed wiring board and method for producing polyimide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyimide resin composition that affords a cured product excellent in heat resistance and dimensional stability, an interlayer adhesive film obtained by using the thermosetting resin composition and a gas barrier material excellent in gas barrier properties.SOLUTION: The polyimide resin composition comprises a polyimide resin, which is obtained by polymerizing a polyisocyanate compound comprising a polyisocyanate compound having a biphenyl skeleton with an acid anhydride or polymerizing an acid anhydride comprising an acid anhydride having a biphenyl skeleton with a polyisocyanate compound, and an organized layered silicate, where the organized layered silicate includes dispersed particles having a minor axis within the range of 1-50 nm and an aspect ratio within the range of 10-500. The gas barrier material comprises the polyimide resin composition. The thermosetting resin composition comprises the polyimide resin composition. The interlayer adhesive film for a printed wiring board comprises a carrier film and a layer formed thereon of the thermosetting resin composition.

Description

  In the present invention, a thermosetting composition excellent in heat resistance, dimensional stability and moisture resistance can be obtained, and a semi-cured state (B-stage) is possible and the resin solution has excellent meltability during coating. Resin composition having a good B-stage semi-cured product, a thermosetting resin composition containing the polyimide resin composition, and an interlayer adhesion obtained using the thermosetting resin composition The present invention relates to a film and a method for producing the polyimide resin composition.

  In recent years, as electronic devices have become thinner and lighter, electronic components have become smaller and denser, and the design of the resin materials used in the electronic devices is in line with the various materials that make up electronic components. Further improvements in heat resistance, dimensional stability, moisture resistance, etc. are required. Specifically, in order to improve the wiring density, the circuit is three-dimensionalized (laminated) by laminating wiring boards. From now on, it is considered that the number of stacked layers will reach 10 or more. With the increase in the number of layers, if a circuit strain stress occurs due to the difference in expansion coefficient between the insulating layer and the copper foil, or if the resin material contains moisture, the conductive material such as copper or silver ionizes and so-called migration occurs. There was a problem that occurred and caused a short circuit between electrodes and circuits.

  In general, resin materials used as the above parts use epoxy resins with excellent thermal, mechanical, and electrical properties, but are required by market demands where technological innovation and environmental measures are steadily progressing. The characteristics are becoming more severe. Therefore, as a resin material replacing the epoxy resin, when the total amount of the acid component is 100 mol%, the total amount of the amine (isocyanate) component is 100 mol%, and the total of the acid component and the amine (isocyanate) component is 200 mol, It is disclosed that a polyimide resin in which a monomer having a biphenyl bond is copolymerized in an amount of 90 mol% or more and 200 mol% or less is excellent in heat resistance and dimensional stability and has a low hygroscopic property, so that it is used as an insulating layer ( For example, see Patent Document 1). However, the adhesion and linear expansion coefficient between the substrate and the polyimide resin in the B-stage state are not yet sufficient.

  It is also known to use a composite material (nanocomposite) in which inorganic fine particles having a particle size of 1 μm or less are dispersed in a resin aiming at low thermal expansion and improved heat resistance of the insulating layer. For example, as an example of a polyimide resin-based nanocomposite, montmorillonite (layered silicate) that has been organized with organic onium ions such as ammonium ion of aminododecanoic acid is derived from pyromellitic anhydride and 4,4-diaminodiphenyl ether. A polyimide film obtained by ring-closing a polyamic acid by mixing with a polyamic acid solution and heating at 300 ° C. for 2 hours is disclosed (for example, see Patent Document 2). However, even in the polyimide film disclosed in Patent Document 2, the coefficient of thermal expansion is not yet sufficiently low. In addition, the polyimide film disclosed in Patent Document 2 is completely cured, and it is not possible to obtain a polyimide resin that can be B-staged or a composition thereof.

Japanese Patent Laying-Open No. 2005-068226 Japanese Patent Laid-Open No. 4-033955

  An object of the present invention is to provide a polyimide resin composition capable of obtaining a cured product having excellent heat resistance, dimensional stability, and moisture resistance, a thermosetting resin composition containing the polyimide resin composition, and the thermosetting resin composition. It is providing the manufacturing method of the interlayer adhesive film obtained using this, and this polyimide resin composition.

  As a result of intensive studies, the present inventors have found that a polyimide resin having a biphenyl skeleton, which is generally produced by a production method called an isocyanate method, and an organic layered silicate, for example, a cation between layers of a layered silicate The cured product using the organic layered silicate ion-exchanged with organic onium ions and containing the organic layered silicate having a specific shape and size is resistant to heat, dimensional stability and moisture. It is excellent, the composition can be B-staged, the B-staged cured product is excellent in meltability and has good substrate adhesion, and the cured product (coating film) has a gas barrier property such as oxygen and water vapor ( The present inventors have found that the gas barrier properties are excellent and have completed the present invention.

  That is, the present invention relates to a polyisocyanate compound containing a polyisocyanate compound having a biphenyl skeleton and an acid anhydride, or an acid anhydride containing an acid anhydride having a biphenyl skeleton and a polyisocyanate compound, and a polyimide resin and an organic resin. A polyimide resin composition containing a layered silicate, wherein the organic layered silicate is a dispersed particle having a minor axis of 1 to 50 nm and an aspect ratio of 10 to 500. A resin composition is provided.

  The present invention also provides a thermosetting resin composition comprising the polyimide resin composition and an epoxy resin.

  Furthermore, this invention provides the interlayer adhesive film for printed wiring boards characterized by being obtained by apply | coating and drying the said thermosetting resin composition on a carrier film.

  Furthermore, this invention provides the gas barrier material characterized by containing the said thermosetting resin composition.

  Furthermore, the present invention provides an organic layered silicic acid comprising a polyisocyanate compound containing a polyisocyanate compound having a biphenyl skeleton and an acid anhydride, or an acid anhydride containing a polyisocyanate having a biphenyl skeleton and a polyisocyanate compound. Provided is a method for producing a polyimide resin composition, which is reacted in the presence of a salt and an organic solvent to obtain a composition comprising a polyimide resin having a biphenyl skeleton, an organic layered silicate, and an organic solvent. It is.

  ADVANTAGE OF THE INVENTION According to this invention, the thermosetting resin composition from which the hardened | cured material excellent in heat resistance, dimensional stability, and moisture resistance is obtained can be provided. In addition, the thermosetting resin composition can be B-staged, and the B-staged semi-cured product has excellent meltability and therefore has good adhesion to the substrate. In addition, the thermosetting resin composition of the present invention is excellent in gas barrier properties and can be suitably used as a gas barrier material. These performances can be used in various fields. Specifically, engine peripheral parts, sliding parts, HDD sliding parts, voice coils, electromagnetic coils, coating agents for various films, insulation coatings for electric wires, heat resistance such as cooking devices, insulation Applications requiring coating properties: Fiber-reinforced composite materials such as carbon fiber prepregs, printed wiring boards, semiconductor insulating materials, coverlays, surface protection layers such as solder resists, build-up materials, prepreg resins, flexible displays Insulating materials, organic TFT insulating layers, buffer coatings, semiconductor coatings such as Low-k, polymer waveguides, semiconductor encapsulants, adhesives such as underfill, etc. Applications: solar cells, lithium ion batteries, capacitors, Insulating layers such as electric double layer capacitors, electrode binders, materials for various energy industries such as separators; It can be used for endless belts such as transfer belts and fixing belts for laser printers, copiers, coating materials, conductive films, binders for heat dissipation films, alignment films for color filters, overcoat films, etc. Especially for insulating layers such as multilayer printed wiring boards It can be suitably used for solder resist. In addition, by using the interlayer adhesive film for printed wiring boards of the present invention, it is possible to obtain an insulating layer having a low coefficient of linear expansion of a cured product, which is adhered while being melted at a low temperature when crimping with a copper foil, and a multilayer printed wiring board In order to form the interlayer insulating layer, it is suitably used as an adhesive film.

  The polyimide resin used in the present invention is obtained by polymerizing a polyisocyanate compound containing a polyisocyanate compound having a biphenyl skeleton and an acid anhydride, or an acid anhydride containing an acid anhydride having a biphenyl skeleton and a polyisocyanate compound.

  Examples of the polyisocyanate compound having a biphenyl structure include 4,4′-diisocyanate-3,3′-dimethyl-1,1′-biphenyl, 4,4′-diisocyanate-3,3′-diethyl-1, 1'-biphenyl, 4,4'-diisocyanate-2,2'-dimethyl-1,1'-biphenyl, 4,4'-diisocyanate-2,2'-diethyl-1,1'-biphenyl, 4,4 Examples include '-diisocyanate-3,3'-ditrifluoromethyl-1,1'-biphenyl, 4,4'-diisocyanate-2,2'-ditrifluoromethyl-1,1'-biphenyl, and the like.

  The polyisocyanate compound can contain a polyisocyanate other than the polyisocyanate compound having a biphenyl skeleton. Examples of such compounds include aromatic polyisocyanates and aliphatic polyisocyanates other than polyisocyanate compounds having a biphenyl skeleton.

  Examples of the aromatic polyisocyanate other than the polyisocyanate compound having a biphenyl skeleton include p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6. -Tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 3,3'-diethyldiphenyl-4,4'-diisocyanate, m-xylene diisocyanate, p- Xylene diisocyanate, 1,3-bis (α, α-dimethylisocyanatomethyl) benzene, tetramethylxylylene diisocyanate, diphenylene ether-4,4'-diisocyanate and na Examples thereof include phthalene diisocyanate.

  Examples of the aliphatic polyisocyanate compound include hexamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylenemethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, and norbornene diisocyanate.

  As the polyisocyanate compound, it is also possible to use an isocyanate prepolymer obtained by reacting the polyisocyanate compound and various polyol components in advance with an excess of isocyanate groups.

  As an acid anhydride used with the polyisocyanate compound containing the polyisocyanate compound which has the said biphenyl skeleton, acid anhydrides other than this acid anhydride and acid anhydrides which have a biphenyl structure can be mentioned, for example.

  Examples of the acid anhydride having a biphenyl structure include biphenyl-3,3 ′, 4,4′-tetracarboxylic acid, biphenyl-2,3,3 ′, 4′-tetracarboxylic acid, and monoanhydrides thereof. Products, dianhydrides and the like, and these can be used alone or as a mixture of two or more.

  Examples of acid anhydrides other than acid anhydrides having a biphenyl structure include aromatic tricarboxylic acid anhydrides other than acid anhydrides having a biphenyl structure, alicyclic tricarboxylic acid anhydrides, and acid anhydrides having a biphenyl structure. Examples include tetracarboxylic acid anhydride. Examples of aromatic tricarboxylic acid anhydrides other than acid anhydrides having a biphenyl structure include trimellitic anhydride and naphthalene-1,2,4-tricarboxylic acid anhydride.

  As the alicyclic tricarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid anhydride-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic acid anhydride-3,5-anhydride, And cyclohexane-1,2,3-tricarboxylic acid anhydride-2,3-anhydride.

  Examples of the tetracarboxylic acid anhydride other than the acid anhydride having a biphenyl structure include pyromellitic dianhydride, benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride, diphenyl ether-3, 3 ', 4,4'-tetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene -1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4 5,8-teto Carboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic Acid dianhydride, phenanthrene-1,3,9,10-tetracarboxylic dianhydride, berylene-3,4,9,10-tetracarboxylic dianhydride, bis (2,3-dicarboxyphenyl) methane Dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxy) Phenyl) ethane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,3-bis (3,4-dicarboxyphenyl) propane dianhydride, bis (3,4 -Dicarboxyfe Le) sulfone dianhydride, bis (3,4-carboxyphenyl) ether dianhydride,

Ethylene glycol bisanhydro trimellitate, propylene glycol bis anhydro trimellitate, butanediol bis anhydro trimellitate, hexamethylene glycol bis anhydro trimellitate, polyethylene glycol bis anhydro trimellitate, polypropylene glycol bis an Hydrotrimellitate and other alkylene glycol bisanhydroxy trimellitate and the like can be mentioned.

  In the present invention, the dimensional stability of a cured product obtained by using a polyisocyanate compound having a biphenyl skeleton or an acid anhydride having a biphenyl skeleton so that the biphenyl skeleton in the polyimide resin composition is 20 to 40% by mass. In addition to the heat resistance and moisture resistance, the solvent solubility of the resulting polyimide resin composition and the meltability at low temperatures of the semi-cured product in which the imide resin composition is in a B-stage state are also excellent. A preferable thermosetting resin composition is obtained, and a polyisocyanate compound having a biphenyl skeleton or an acid anhydride having a biphenyl skeleton is used so that the biphenyl skeleton in the polyimide resin is 25 to 40% by mass. Is more preferable, and the biphenyl skeleton in the polyimide resin is 25 to 35% by mass. It is more preferable to use a polyisocyanate compound or an acid anhydride having a biphenyl skeleton having a biphenyl skeleton.

  The content of the biphenyl structure is such that the molecular weight is 152 in the case of the biphenyl structure having two bonding sites to the main chain of the polyimide resin of the present invention, and the molecular weight is 150 in the case of the biphenyl structure having four bonding sites. It can be calculated from the ratio of the biphenyl structure to the weight.

  The polyimide resin composition obtained in the present invention is preferable because a polyimide resin having a benzophenone structure exhibits more heat resistance and low linear expansion. The polyimide resin having a benzophenone structure can be obtained by using, for example, a polyisocyanate compound having a benzophenone structure or an acid anhydride having a benzophenone structure, and among them, an acid anhydride having a benzophenone structure is preferably used. . Examples of the acid anhydride having a benzophenone structure include benzophenone tetracarboxylic acid anhydride.

  The content of the benzophenone structure is preferably in the range of 1 to 30% by mass based on the mass of the polyimide resin because a cured product having excellent heat resistance and low linear expansion is obtained, and the range of 5 to 25% by mass is the synthetic stability. More preferable.

  The content of the benzophenone structure can be calculated from the ratio of the benzophenone structure to the total weight of the polyimide resin, with the molecular weight of the benzophenone structure having 4 bonding points to the polyimide resin main chain being 178.

  As the polyimide resin in the polyimide resin composition obtained in the present invention, a polyimide resin having a tolylene structure bonded to the main chain at the 2nd and 4th positions is preferable because it easily develops melt adhesion and low linear expansion. A polyimide resin composition having a tolylene structure bonded to the main chain at positions 2 and 4 can be obtained, for example, by using toluene diisocyanate as an essential component.

  The content of the tolylene structure bonded to the main chain at the 2nd and 4th positions is based on the ratio of the tolylene structure to the total weight of the polyimide resin, assuming that the molecular weight of the tolylene structure bonded at the 2nd and 4th positions to the polyimide resin main chain is 150. Can be calculated.

  The content of the tolylene structure bonded to the main chain at positions 2 and 4 in the polyimide resin is preferably in the range of 1 to 20% by mass because it is excellent in heat resistance and low linear expansion, and in the range of 2 to 14% by weight. It is more preferable because of excellent synthesis stability.

  Moreover, the polyimide resin composition of the present invention may have a branched structure in order to improve solvent solubility and compatibility with other resins. Examples of the branching method include polyisocyanate compounds such as triisocyanate polyisocyanate compounds having an isocyanurate ring that are isocyanurate bodies such as the diisocyanate compounds, burette bodies, adduct bodies, allophanate bodies, and polyisocyanates. Methylene polyphenyl polyisocyanate (crude MDI) or the like may be used.

  In the polyimide resin composition of the present invention, a polyisocyanate compound and a compound having an acid anhydride group are polymerized to produce a polyimide resin. The ratio (ma) / (mb) of the number of moles of isocyanate groups in the polyisocyanate compound (ma) and the total number of moles of non-hydroxyl groups and carboxyl groups in the compound having an acid anhydride group (mb) is expressed as the molecular weight. A ratio of 0.7 to 1.2 is preferable, and a ratio of 0.8 to 1.2 is more preferable because a polyimide resin from which a large polyimide resin can be easily obtained and a cured product having excellent mechanical properties is obtained. Moreover, since it is easy to obtain the polyimide resin which is excellent in storage stability, the (ma) / (mb) is more preferably in the range of 0.9 to 1.1. In addition, when using together carboxylic anhydrides, such as trimellitic anhydride, said (mb) is the total number of moles of a hydroxyl-free group and a carboxyl group in all the carboxylic anhydrides.

  The organically modified layered silicate used in the present invention is dispersed particles having a minor axis in the range of 1 to 50 nm and an aspect ratio in the range of 10 to 500. By using the organically modified layered silicate having such a shape, excellent effects of heat resistance, dimensional stability, and moisture resistance can be obtained. It is more preferable that the minor axis is in the range of 1 to 30 nm, and the aspect ratio is in the range of 10 to 300, since further excellent effects are exhibited.

  The “particle” in the present invention is a broad concept including true sphere, ellipse, plate, needle and the like.

  Among the organically modified layered silicates, it is preferable to use one having a high aspect ratio from the viewpoint of imparting moisture resistance and gas barrier properties as a partition effect to the obtained cured product. The partition effect means that the peeled organic layered silicate obstructs the diffusion path of the gas that has entered the coating film and increases the transmission path length. The gas barrier property refers to a gas barrier property such as oxygen, nitrogen, air, carbon dioxide, and water vapor. As the aspect ratio of the organically modified layered silicate, smectite clay mineral having an aspect ratio of about 50, montmorillonite having a value of about 100, swellable mica having an aspect ratio of about 150, etc. It is more preferable to use a modified one. The aspect ratio is the ratio of the major axis to the minor axis of the dispersed particles of the organically modified layered silicate that is generally a plate-like or needle-like substance.

  The organically modified layered silicate used in the present invention is a layered silicate that has been subjected to an ion exchange treatment with an organic agent. Here, “organization of layered silicate” in the present invention refers to ion exchange using a salt compound of an organic onium ion with an alkali metal and / or alkaline earth metal present between the layers of the layered silicate as an organic agent. It means that the surface of the layered silicate is made organic by the treatment. By making layered silicate organic, the interlayer distance is larger than layered silicate, and the layered silicate is easily peeled off by polymerization, and heat with excellent heat resistance, dimensional stability, and moisture resistance. A cured composition is obtained.

  The interlayer distance is preferably 1 nm or more because a thermosetting resin composition having excellent heat resistance, dimensional stability, and moisture resistance can be obtained. The upper limit of the interlayer distance is not particularly limited as long as the organically modified layered silicate is delaminated and uniformly dispersed in the thermosetting resin composition.

  The interlayer distance of the organic layered silicate in the present invention means the distance between the (001) planes of the flaky crystals of the organic layered silicate. The interlayer distance can be measured by X-ray diffraction. When the organic layered silicate having an interlayer distance of less than 1 nm is used, a polyisocyanate compound containing a polyisocyanate compound having a biphenyl skeleton between the layers and an acid anhydride, or an acid anhydride having a biphenyl skeleton is used. The acid anhydride containing the product and the polyisocyanate compound are sufficiently organized layered silicate, and the organic solvent is not sufficiently inserted, so the dispersion of the organized layered silicate in the thermosetting resin composition becomes uneven, As a result, the thermosetting resin composition obtained may not have the heat resistance, dimensional stability, moisture resistance, and gas barrier properties.

  The organic layered silicate organic agent content used in the present invention, that is, the organic group content in the organic onium ion is 10 to 60% by mass based on the mass of the organic layered silicate. Preferably, it is in the range of 15 to 55% by mass. The interlayer distance of the organically modified layered silicate is 1 nm or more by being 10 to 60% by mass, and a polyisocyanate compound containing a solvent or a polyisocyanate compound having a biphenyl skeleton between the organically modified layered silicate and an acid anhydride Or an acid anhydride containing an acid anhydride having a biphenyl skeleton and a polyisocyanate compound are easily inserted, and by polymerizing these, the layer of the organically modified layered silicate can be easily peeled off to obtain desired performance. it can. In addition, an organic agent or a polyisocyanate compound containing a polyisocyanate compound having a biphenyl skeleton and an acid anhydride within the above range, or an acid anhydride and a polyisocyanate compound containing an acid anhydride having a biphenyl skeleton, There is also an advantage that the compatibility and solubility are not easily deteriorated, the appearance is poor (unevenness, etc.) and the performance is difficult to stabilize.

The method for measuring the content of the organic agent in the organically modified layered silicate is preferably the following method. That is, the organic layered silicate is weighed with a precision balance to obtain a sample having a mass (A) g. After weighing, the sample is left in an electric furnace at about 800 ° C. for 3 hours to obtain a sample having a mass (B) g of its ash. The content of the organic agent can be obtained from the obtained two masses and the following formula.
Content of organic agent (% by mass) = [{(A) − (B)} / (A)] × 100

  The layered silicate used to obtain the organically modified layered silicate of the present invention comprises a layer composed of a combination of a SiO4 tetrahedral sheet structure composed of SiO2 chains and an octahedral sheet structure containing Al, Mg, Li, etc. Silicate (silicate) or clay mineral (clay) with exchangeable cations coordinated between layers. These silicates (silicates) or clay minerals (clays) are typified by smectite minerals, vermiculite, halloysite, and swellable mica. Specifically, examples of the smectite-based mineral include montmorillonite, hectorite, fluorine hectorite, saponite, beidellite, and stevensite. Examples of the swellable mica include Li-type fluorine teniolite, Na-type fluorine teniolite, and Na-type tetrasilicon. Examples include swellable synthetic mica such as fluorine mica and Li-type tetrasilicon fluorine mica. These layered silicates can be either natural products or synthetic products. The synthetic product can be produced, for example, by hydrothermal synthesis, melt synthesis, or solid reaction.

  Examples of the swellable synthetic mica include swellable synthetic mica obtained by heat-treating a mixture of talc and alkali silicofluoride, and a fine powder obtained by mixing talc with sodium silicofluoride and / or lithium silicofluoride is 600 to 1200 ° C. Those obtained by heat treatment are preferred. Specific examples of such swellable synthetic mica include swellable synthetic mica represented by the general formula (I).

［式中、（Ｎａ，Ｌｉ）_ａは層間にある配位数１２の陽イオン、Ｍｇ_{３．０−ｂ}は八面体シートを形成している配位数６の陽イオン、Ｓｉは四面体シートを形成している配位数４の陽イオンであり、（Ｆ_{２．０−ｃ}，ＯＨ_ｄ，Ｏ_ｅ）中のＦ、ＯＨ、Ｏは陰イオンとして八面体シートに存在する。なお、“，”は“及び／又は”を表す。また、ａ〜ｅの記号は下記の数値を表す。０．２≦ａ≦１．０；０≦ｂ≦０．５；ｃ＝ｄ＋２ｅ≦１．０；０≦ｄ≦１．０；０≦ｅ≦０．５］

[Wherein (Na, Li) _a is a cation with a coordination number of 12 between layers, Mg _3.0-b is a cation with a coordination number of 6 forming an octahedral sheet, and Si is a tetrahedral sheet. the coordination number 4 cation forming _the, present in an octahedral sheet _{(F 2.0-c, OH d} , O e) F in, OH, O as an anion. “,” Represents “and / or”. Moreover, the symbol of ae represents the following numerical value. 0.2 ≦ a ≦ 1.0; 0 ≦ b ≦ 0.5; c = d + 2e ≦ 1.0; 0 ≦ d ≦ 1.0; 0 ≦ e ≦ 0.5]

  The ion exchange capacity of organic onium ions to the layered silicate can be prepared by adding the organic onium ion salt compound to the layered silicate dispersed in the polar solvent and collecting the precipitated ion exchange compound. . Usually, this ion exchange reaction involves adding an organic onium ion salt at a ratio of 1.0 to 1.5 equivalents to 1 equivalent of the ion exchange capacity of the layered silicate, and exchanging almost all of the metal ions between the layers with organic onium ions. It is common to make it. However, the swellable layered silicate may contain 50 wt% or less of non-clay mineral, but the amount of non-clay mineral is preferably 10 wt% or less.

  Examples of the organic onium ion salt compounds include organic ammonium salts, organic phosphonium salts, organic sulfonium salts, and organic imidazolium salts. Of these, organic ammonium salts, organic phosphonium salts, and organic imidazolium salts are preferable, and organic ammonium salts and organic phosphonium salts are more preferable.

  Specifically, as the organic onium ion, the organic onium ion represented by the following general formula (II) sufficiently extends the interlayer distance of the layered silicate, and is a thermosetting resin excellent in heat resistance, dimensional stability, and moisture resistance. It is more preferable because a composition can be obtained.

上記オニウムイオンは原子Ｍのまわりに４個の官能基（Ｒ基）がついたイオンであり、本発明で使用する有機オニウムイオンは、前記式（ＩＩ）において、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４が、同一又は異なり、それぞれ炭化水素基、−Ａ−ＯＨ又は−Ａ−ＣＯＯＨを表すものである。Ｍは窒素原子またはリン原子を表す。

The onium ion is an ion having four functional groups (R groups) around the atom M, and the organic onium ion used in the present invention is represented by R ¹ , R ² , R ³ in the formula (II). And R ⁴ are the same or different and each represents a hydrocarbon group, -A-OH or -A-COOH. M represents a nitrogen atom or a phosphorus atom.

In the formula (I), examples of the hydrocarbon group represented by R ¹ , R ² , R ³ or R ⁴ include an alkyl group, an alkenyl group, an aryl group, an aralkyl group, and a polyalkylene ether group. Of these, an alkyl group or a polyalkylene ether group is more preferred.

  Among the alkyl groups, a linear or branched alkyl group having 1 to 40 carbon atoms is preferable, a linear or branched alkyl group having 1 to 25 carbon atoms is more preferable, and the number of carbon atoms is 2 More preferred are -20 linear or branched alkyl groups.

  Among the alkenyl groups, a linear or branched alkenyl group having 2 to 40 carbon atoms is preferable, and a linear or branched alkenyl group having 2 to 25 carbon atoms is more preferable.

  Examples of the alkenyl group include vinyl group, allyl group, 2-methylallyl group, 1-butenyl group, 2-butenyl group (crotyl group), and 3-butenyl group.

    Among the aryl groups, a linear or branched aryl group having 6 to 22 carbon atoms is preferable, and a linear or branched aryl group having 6 to 10 carbon atoms is more preferable.

  Examples of the aryl group include a phenyl group, a naphthyl group, and a tolyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, a vinylbenzyl group, and a naphthylmethyl group.

  Among the aralkyl groups, a linear or branched aralkyl group having 7 to 22 carbon atoms is preferable, and a linear or branched aralkyl group having 7 to 12 carbon atoms is more preferable.

  Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, Examples include decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, and octadecyl group.

  As the polyalkylene ether group, for example, those represented by the following general formula (II) can be used.

X- (RO) n-H (II)
(In the formula, R represents an alkylene group having 2 to 20 carbon atoms, n represents an integer having 1 to 20 carbon atoms, and X represents an ionic group.)

  Specific examples of R in the general formula (II) include an ethylene group, a propylene group, and an alkylene group derived from an ethylene-propylene copolymer. As the polyalkylene ether having an ionic group, two or more types having different polyalkylene ether chains may be used in combination.

In the formula (I), A in —A—OH or —A—COOH represented by R ¹ , R ² , R ³ or R ⁴ is a linking group and is not particularly limited. 35, preferably those having chain members of 2 to 21. Examples of the linking group usually include those having at least one structure among an aromatic group, an aliphatic group, and an ether bond, and a linear or branched alkylene group is preferable, and particularly a group having 2 to 30 carbon atoms. A range of linear or branched alkylene groups is preferred.

  Examples of the -A-OH include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, a hydroxyhexyl group, a hydroxyheptyl group, a hydroxyoctyl group, a hydroxynonyl group, and a hydroxydecyl group. .

  Examples of -A-COOH include carboxymethyl group, carboxyethyl group, carboxypropyl group, carboxybutyl group, carboxypentyl group, carboxyhexyl group, carboxyheptyl group, carboxyoctyl group, carboxynonyl group, and carboxydecyl group. .

Specific examples of the organic onium ion in the general formula (I) in which M is a nitrogen atom and at least one of R ^{1 to} R ⁴ is an alkyl group having 2 to 20 carbon atoms include, for example, tetraethylammonium, Quaternary ammonium having the same alkyl group such as tetrabutylammonium; trimethylalkyl such as trimethyloctylammonium, trimethyldecylammonium, trimethyldodecylammonium, trimethyltetradecylammonium, trimethylhexadecylammonium, trimethyloctadecylammonium, trimethylicosanylammonium Ammonium;

Triethylalkylammonium such as triethyldodecylammonium, triethyltetradecylammonium, triethylhexadecylammonium, triethyloctadecylammonium;

Tributyl alkyl ammonium such as tributyl dodecyl ammonium, tributyl tetradecyl ammonium, tributyl hexadecyl ammonium, tributyl octadecyl ammonium;

Dimethyl dialkyl ammonium such as dimethyl dioctyl ammonium, dimethyl didecyl ammonium, dimethyl ditetradecyl ammonium, dimethyl dihexadecyl ammonium, dimethyl dioctadecyl ammonium, dimethyl didodecyl ammonium;

Dimethyl dialkenyl ammonium such as dimethyl dioctadecenyl ammonium;

Diethyldialkylammonium such as diethyldidodecylammonium, diethylditetradecylammonium, diethyldihexadecylammonium, diethyldioctadecylammonium;

Dibutyl dialkyl ammonium such as dibutyl dioctyl ammonium, dibutyl didecyl ammonium, dibutyl didodecyl ammonium, dibutyl ditetradecyl ammonium, dibutyl dihexadecyl ammonium, dibutyl dioctadecyl ammonium;

Dibenzyldialkylammonium such as dibenzyldihexadecylammonium;

Trialkylmethylammonium such as trioctylmethylammonium, tridodecylmethylammonium, tritetradecylmethylammonium;

Trialkylethylammonium such as trioctylethylammonium, tridodecylethylammonium;

And trialkylbutylammonium such as trioctylbutylammonium and tridecylbutylammonium.

In the general formula (I), as the organic onium ion in which M is a phosphorus atom and at least one of R ^{1 to} R ⁴ is an alkyl group having 2 to 20 carbon atoms, the nitrogen atom of the ammonium ion is a phosphorus atom. Examples include phosphonium ions replaced with atoms.

In order to introduce the organic onium ion represented by the formula (I) between the layers of the layered silicate, a salt of the organic onium ion containing the ion is used. Examples of such a salt include Cl ⁻ and Br ^−. , I ⁻ , NO ₃ ⁻ , OH ⁻ , and a salt with an anion such as CH ₃ COO ⁻ .

Specific examples of the organic onium ion in the general formula (I) in which M is a phosphorus atom and at least one of R ^{1 to} R ⁴ is an alkyl group having 2 to 20 carbon atoms include tetraethylphosphonium bromide, tetra Butylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium iodide, tributyloctylphosphonium bromide, tributyldodecylphosphonium bromide, tributylhexadecylphosphonium bromide, trioctylethylphosphonium bromide, triethylbenzylphosphonium chloride, tributylmethylphosphonium iodide, tributylallyl Phosphonium bromide,

  Tributylbenzylphosphonium chloride, trioctylvinylbenzylphosphonium chloride, tributyl 2-methylallylphosphonium chloride, trioctyl2-methylallylphosphonium chloride, dimethyldioctadecylphosphonium chloride, dimethyldioctadecylphosphonium bromide, dimethyloctadecylbenzylphosphonium chloride, dimethyloctadecylbenzylphosphonium Bromide, tetraphenylphosphonium bromide, triphenylbenzylphosphonium chloride, triphenylmethylphosphonium bromide, triphenylbutylphosphonium bromide, bis (hydroxypropyl) octadecylisobutylphosphonium chloride, triphenylcarboxyethylphosphonium Bromide, may be mentioned triphenyl carboxypentyl phosphonium bromide and the like.

  A commercial item can also be used for the said organically modified layered silicate. Specific examples of commercially available organic layered silicates include, for example, the Somasif series manufactured by Corp Chemical Co., Ltd., for example, Somasif MAE, Somasif MTE, Somasif MEE, Somasif MPE, etc., Lucentite series, for example, Lucentite STN , Lucentite SPN and the like, Bengel series made by Hojun Co., Ltd., Sven series and the like.

  The organic layered silicate can also be expected to have an effect as a catalyst for synthesizing a polyimide resin.

  If the content of the organically modified layered silicate in the polyimide resin composition of the present invention is in the range of 1 to 30 parts by mass with respect to 100 parts by mass of the polyimide resin, the organicated layered silicic acid is contained in the polyimide resin composition. It is preferable because a cured coating film having a strength capable of uniformly dispersing salt and capable of producing a coating film and having heat resistance, low linear expansion property, and moisture resistance is obtained, and is in the range of 3 to 20 parts by mass. Is more preferable.

  In order to produce the polyimide resin composition of the present invention, for example, the polyimide resin, the organically modified layered silicate and an appropriate amount and kind of organic solvent are mixed, and the polyimide is obtained by applying a shearing force by a mechanical dispersion method. The organic layered silicate can be uniformly dispersed in the resin, and the organic layered silicate can be peeled off.

  The disperser that can be used for the mechanical dispersion method may be any apparatus that can apply a shearing force. For example, a widely known apparatus such as a stirrer, an emulsifier, a disperser, or a twin screw extruder is used. be able to. Specifically, batch emulsifiers such as a homogenizer (manufactured by IKA), polytron (manufactured by Kinematica), TK auto homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), Ebara Milder (manufactured by Ebara Corporation), TK Phil Mix, TK pipeline homomixer (manufactured by Koki Kogyo Kogyo Co., Ltd.), Apex mill (manufactured by Kotobuki Giken Kogyo Co., Ltd.), colloid mill (manufactured by Shinko Pantech Co., Ltd.), slasher, trigonal wet pulverizer (Mitsui Miike Chemical Co., Ltd.) Manufactured), ultrasonic homogenizer, and high-pressure homogenizer include nanomizer (manufactured by Nanomizer Co., Ltd.), static mixer, and the like.

  Although the polyimide resin composition of this invention can be manufactured also by a mechanical dispersion | distribution method as above-mentioned, it can manufacture preferably with the manufacturing method of the polyimide resin composition of this invention.

  That is, the method for producing the polyimide resin composition of the present invention comprises a polyisocyanate compound containing a polyisocyanate compound having a biphenyl skeleton and an acid anhydride, or an acid anhydride and polyisocyanate compound containing an acid anhydride having a biphenyl skeleton. Is reacted in the presence of an organic layered silicate and an organic solvent to obtain a composition containing a polyimide resin having a biphenyl skeleton, the organic layered silicate, and an organic solvent.

  When synthesizing the polyimide resin, the average particle diameter of the organic layered silicate present in the raw material of the polyimide resin is preferably 100 μm or less because it is easy to swell and disperse between the layers of the organic layered silicate due to the raw material monomer and organic solvent, 50 μm or less is more preferable, and 20 μm or less is preferable. When the organic layered silicate having the average particle diameter is used, the organic layered silicate is peeled off as the polymerization of the polyimide resin proceeds, and the organic layered silicate has an aspect ratio in the range of 1 to 50 nm in the short axis. Particles with a ratio in the range of 10-500. In addition, a polyisocyanate compound and acid anhydride containing a polyisocyanate compound having a biphenyl skeleton, or an acid anhydride and polyisocyanate compound containing an acid anhydride having a biphenyl skeleton are used as a raw material, resulting in a B-stage semi-curing The composition which can obtain a thing can be obtained.

  The method for producing the imide resin composition of the present invention includes, for example, charging the organically modified layered silicate, the polyisocyanate compound, and the compound having an acid anhydride group in a reaction vessel, and decarboxylation by heating while stirring. However, it can be obtained by a so-called isocyanate method in which polymerization proceeds.

  The reaction temperature is usually preferably in the range of 50 ° C. to 250 ° C., and a polyisocyanate compound containing a polyisocyanate compound having a biphenyl skeleton and an acid anhydride, or an acid containing an acid anhydride having a biphenyl skeleton. It is preferable to carry out at the temperature of 60 to 180 degreeC from a viewpoint of melt | dissolution of an anhydride and a polyisocyanate compound, reaction rate, and side reaction prevention.

  Polymerization is preferable because the storage stability of the polyimide resin composition obtained is improved until almost all isocyanate groups have reacted. Moreover, you may make it react by adding alcohol and a phenol compound with respect to the isocyanate group which remains a little.

  In the method for producing a polyimide resin of the present invention, the organic layered silicate used is one in which the cation between the layers of the layered silicate is ion-exchanged with the organic onium ion represented by the general formula (I). Is preferred.

式（１）中、Ｒ^１〜Ｒ^４の少なくとも一つはアルキル基またはポリアルキレンエーテル基である。Ｍは窒素原子またはリン原子を表す。

In formula (1), at least one of R ^{1 to} R ⁴ is an alkyl group or a polyalkylene ether group. M represents a nitrogen atom or a phosphorus atom.

  In addition, the organic group content in the organic onium ion is preferably 10 to 60% by mass, more preferably 15 to 55% by mass based on the mass of the organically modified layered silicate.

The alkyl group is preferably an alkyl group having 2 to 20 carbon atoms. The polyalkylene ether group is preferably a polyalkylene ether group having a structure represented by the following general formula (III).
X- (RO) n-H (...) (III)
(In the formula, R represents an alkylene group having 1 to 20 carbon atoms, n represents an integer in the range of 5 to 50, and X represents an ionic group.)

  In the manufacturing method of this invention, the said organically modified layered silicate is used in the polyimide resin composition by using the range of 1-30 mass parts with respect to 100 mass parts of said polyimide resin raw materials. It is preferable because a cured coating film having a strength capable of being uniformly dispersed and capable of producing a coating film and having heat resistance, low linear expansion property, and moisture resistance is obtained, and a range of 3 to 25 parts by mass is used. Is more preferable.

  Moreover, when manufacturing the polyimide resin composition of this invention, by using the polyisocyanate compound which has a biphenyl skeleton, or the acid anhydride which has a biphenyl skeleton so that the biphenyl skeleton of a polyimide resin may be in the range of 20-40 mass%. In addition to the dimensional stability, heat resistance, and moisture resistance of the resulting cured coating film, the solvent solubility of the resulting polyimide resin composition and the meltability of the semi-cured product with the polyimide resin composition in a B-stage state at low temperatures Therefore, a polyisocyanate compound having a biphenyl skeleton or biphenyl so that the biphenyl skeleton in the polyimide resin is 25 to 40% by mass is preferable. More preferably, an acid anhydride having a skeleton is used. Skeleton is more preferably used an acid anhydride having a polyisocyanate compound or a biphenyl skeleton having a biphenyl skeleton such that 25 to 35 wt%.

  In the method for producing a polyimide resin composition of the present invention, the resulting cured product exhibits heat resistance and low linear expansion by using a polyisocyanate compound having a benzophenone structure or an acid anhydride having a benzophenone structure. To preferred. Examples of the acid anhydride having a benzophenone structure include benzophenone tetracarboxylic acid anhydride.

  The content of the benzophenone structure is preferably in the range of 1 to 30% by mass based on the mass of the polyimide resin because a cured product having excellent heat resistance and low linear expansion is obtained, and the range of 5 to 25% by mass is the synthetic stability. More preferable.

  The content of the benzophenone structure can be calculated from the ratio of the benzophenone structure to the total weight of the polyimide resin, with the molecular weight of the benzophenone structure having 4 bonding points to the polyimide resin main chain being 178.

  In the method for producing a polyimide resin composition of the present invention, a cured product obtained by using a polyisocyanate compound having a tolylene structure or a diisocyanate having a tolylene structure easily exhibits melt adhesion and low linear expansion. preferable. A polyimide resin composition having a tolylene structure bonded to the main chain at positions 2 and 4 can be obtained, for example, by using toluene diisocyanate as an essential component.

  The use amount of the organically modified layered silicate includes the mass obtained by subtracting the amount of decarboxylation from the total amount of the polyisocyanate compound including the polyisocyanate compound having the biphenyl skeleton and the acid anhydride, or the acid anhydride having the biphenyl skeleton. Heat excellent in heat resistance, dimensional stability, moisture resistance, and gas barrier properties by using a range of 1 to 30 parts by mass with respect to the mass obtained by subtracting the decarboxylation amount from the total amount of the acid anhydride and the polyisocyanate compound. A curable resin composition is obtained, and it is more preferable to use a range of 3 to 20 parts by mass. Here, the decarboxylation amount referred to in the present invention refers to the amount of theoretical decarboxylation produced when the imide resin composition of the present invention is synthesized by the isocyanate method described later.

  If the manufacturing method of the polyimide resin composition of this invention uses an organic solvent, uniform polymerization can advance. Here, the organic solvent may be preliminarily present in the system before polymerization or may be introduced during the polymerization. In order to maintain an appropriate reaction rate, the ratio of the organic solvent in the system is the total amount of the polyisocyanate compound including the polyisocyanate compound having the biphenyl skeleton and the acid anhydride, or the acid having the biphenyl skeleton. Although it is 98 mass% or less of the total amount of the acid anhydride containing an anhydride and a polyisocyanate compound, it is more preferable that it is the range of 10-90 mass%, and the range of 20-80 mass% is still more preferable. As such an organic solvent, since a compound containing an isocyanate group is used as a raw material component, it does not have an active proton such as a hydroxyl group or an amino group, and the dispersibility and swelling property of the organically modified layered silicate are excellent. Polar organic solvents are preferred.

  Examples of the aprotic polar organic solvent include dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, and γ-butyrolactone. Among these, one or more solvents selected from the group consisting of dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone are preferable. In addition to the above solvents, ether solvents, ester solvents, ketone solvents, petroleum solvents and the like may be used as long as they are soluble. Various solvents may be used alone or in combination.

  Examples of the ether solvent that can be used in the present invention include ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol, and the like. Polyethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether; ethylene glycol monoalkyls such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate Ether ethers; polyethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol monobutyl ether acetate ;

Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether; dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol Polypropylene glycol dialkyl ethers such as propylene glycol dibutyl ether; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate; Polypropylene glycol monoalkyl ether acetate such as triglycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monobutyl ether acetate Dialkyl ethers of copolymerized polyether glycols such as low molecular weight ethylene-propylene copolymers; monoacetate monoalkyl ethers of copolymerized polyether glycols; alkyl esters of copolymerized polyether glycols; Examples include ether glycol monoalkyl esters and monoalkyl ethers. It is.

  Examples of the ester solvent include ethyl acetate and butyl acetate. Examples of the ketone solvent include acetone, methyl ethyl ketone, and cyclohexanone. In addition, as the petroleum solvent, it is also possible to use toluene, xylene, other high-boiling aromatic solvents, and aliphatic and alicyclic solvents such as hexane and cyclohexane.

  In addition, the organic layered silicate is appropriately added in advance for the purpose of promoting the swelling between the layers of the organic layered silicate with the organic solvent. A method, an organic solvent, or a polyisocyanate compound containing a polyisocyanate compound having a biphenyl skeleton and an acid anhydride, or an acid anhydride containing an acid anhydride having a biphenyl skeleton and a polyisocyanate compound between the layers of the organically modified layered silicate. For the purpose of promoting swelling, an organic solvent, an organic layered silicate and a polyisocyanate compound containing a polyisocyanate compound having a biphenyl skeleton and an acid anhydride, or an acid anhydride containing an acid anhydride having a biphenyl skeleton, and A method of preparing a polyisocyanate compound in advance, and the above organic formation by shearing by polymerization For the purpose of accelerating the peeling of the layered silicate, the polyisocyanate compound and acid anhydride containing the polyisocyanate compound having an organic solvent and the biphenyl skeleton, or the acid anhydride and polyisocyanate compound stirring containing the acid anhydride having the biphenyl skeleton Although the method of making it superpose | polymerize, making it decarboxylate by heating, performing the said, adding the said organically modified layered silicate in the middle, etc. are mentioned, The method will not be restrict | limited at all if it is in the range which does not impair this invention.

  The resin structure of the polyimide resin in the polyimide resin composition obtained in the present invention may have a linear structure, a polyimide resin having a branched structure, or both a linear structure and a branched structure. . Further, polyester-modified polyester imide or urethane-modified polyurethane imide may be used as the copolymer component.

  Preferred examples of the terminal functional group or terminal chemical structure of the polyimide resin in the polyimide resin composition obtained in the present invention include carboxylic acid, carboxylic acid anhydride, isocyanate group, amine group, and phenol. Since the polyimide resin of the present invention itself has good storage stability, solubility after blending with organic solvents and other resins, and storage stability, the terminal functional group is more preferably a chemical structure of carboxylic acid or its anhydride. . When the chemical structure of the terminal functional group is carboxylic acid or its anhydride, it becomes a polyimide resin composition with an acid value in the range of 1 to 200 in terms of solid content acid value, and it is a film or molding excellent in mechanical strength and dimensional stability. This is preferable because a product is obtained.

  The solution acid value of the polyimide resin solution in the polyimide resin composition obtained in the present invention is preferably in the range of 3 to 30 mgKOH / g. If it is within this range, it is preferable because a thermosetting composition having strength and dimensional stability of the film when cured is obtained, and if it is within the range of 5 to 25 mg KOH / g, transparency when cured. Is more preferable.

  By including an epoxy resin in the polyimide resin composition obtained by the production method of the present invention, the polyimide resin composition and the epoxy resin react to form a thermosetting resin composition. The epoxy resin preferably has two or more epoxy groups in the molecule. Examples of the epoxy resin include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol S type epoxy resin, and bisphenol F type epoxy resin; biphenyl type epoxy resin; naphthalene type epoxy resin; phenol novolac epoxy resin, cresol novolac type Epoxy resins, novolak type epoxy resins such as bisphenol type novolacs; epoxidized products of various dicyclopentadiene modified phenolic resins obtained by reacting dicyclopentadiene with various phenols; epoxy resins having a fluorene skeleton; 10- (2,5 -Dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide and the like, a phosphorus-containing epoxy resin; neopentyl glycol diglycol Aliphatic epoxy resins such as dil ether and 1,6-hexanediol diglycidyl ether; 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis- (3,4-epoxycyclohexyl) adipate, etc. Alicyclic epoxy resins; heterocycle-containing epoxy resins such as triglycidyl isocyanurate. Among them, a thermosetting composition is obtained in which one or more epoxy resins selected from the group consisting of bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, biphenyl type epoxy resins, and naphthalene type epoxy resins are obtained. It is preferable because it is excellent in meltability at low temperatures while being heat resistant and low linear expansion.

  The thermosetting composition is heat resistant by using at least one epoxy resin selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, and naphthalene type epoxy resin. , Has low linear expansion. Furthermore, the reason why the meltability at low temperature is excellent is that the chemical structure of biphenyl that the polyimide resin composition of the present invention has, the chemical structure of bisphenol A that the epoxy resin has, the chemical structure of bisphenol F, the chemical structure of biphenyl, naphthalene The compatibility with the chemical structure of each other is excellent, and the epoxy resin prevents the aggregation of the polyimide resin composition when melted, and at the same time, after the curing, each other interacts closely to form a dense cured state It is estimated that.

  The amount of the epoxy resin used is a thermosetting resin composition excellent in meltability at a low temperature that the mass composition ratio of the solid content of the polyimide resin composition and the epoxy resin is in the range of 90/10 to 30/70. It is preferable from the viewpoint of obtaining a product, and more preferably in the range of 80/20 to 50/50 because it has low linear expansion.

  Moreover, since the viscosity of an epoxy resin becomes a composition excellent in low-temperature meltability, an epoxy resin having a viscosity at 150 ° C. of 15 Pa · s or less is preferable, and an epoxy resin having a viscosity of 10 Pa · s or less is more preferable.

  As described above, the organically modified layered silicate nano-dispersed in the resin is excellent in transparency, heat resistance and dimensional stability, moisture resistance, etc. due to nano-effects such as dispersion effect, quantum size effect, and interface effect. A thermosetting composition is obtained, and a thermosetting resin composition that can be in a semi-cured state (B-staged) and has excellent meltability of the B-staged cured product is obtained.

  As a method for confirming the dispersion state of the organically modified layered silicate of the thermosetting resin composition, for example, a film obtained from the obtained polyimide resin composition or a film obtained from the thermosetting resin composition is cured by visible light. After embedding with resin, an ultra-thin section with a thickness of about 50 nm is prepared with an ultramicrotome, and organicized using photographs observed using a transmission microscope (JSM-1400, acceleration voltage 120 kV). The size of the particles derived from the layered silicate is measured, or the distribution state of the particles derived from the organically modified layered silicate is visually determined.

  In addition, as a method for confirming delamination of the organically modified layered silicate in the cured film, a film obtained from the obtained polyimide resin composition and a film obtained from the thermosetting resin composition are converted into an X-ray diffractometer (stock) This is confirmed by the fact that the absorption peak of the higher-order line derived from the organically modified layered silicate is no longer observed using the company Rigaku Corporation, TTRII). In particular, in the present invention, it was determined that delamination at a level at which the effect of the present invention was exhibited progressed due to the disappearance of the absorption peak derived from the (001) plane.

  From the viewpoint of heat resistance of the thermosetting composition of the polyimide resin composition obtained in the present invention and the thermosetting resin composition, the glass transition temperature is preferably 260 ° C. or higher, and more preferably in the range of 260 ° C. to 380 ° C. Here, the glass transition temperature referred to in the present invention refers to a cured product of a polyimide resin composition obtained according to JISK-7198 and / or a film obtained from a thermosetting resin composition. The storage elastic modulus (E ′) corresponding to the elasticity and the loss elastic modulus (E) corresponding to the viscosity measured at a measurement frequency of 1 Hz in the range of 20 ° C. to 400 ° C. using RSA-III manufactured by A Instruments Inc. The peak top temperature of the loss tangent (tan δ), which is a ratio to “)”.

  Boron compounds such as boric acid and / or boric acid esters can be used in combination with the thermosetting resin composition of the present invention. Examples of such compounds include boric acid; trialkyl such as trimethyl borate, triethyl borate, tributyl borate, tri-n-octyl borate, tri (triethylene glycol methyl ether) borate ester, tricyclohexyl borate, and trimenthyl borate. Linear aliphatic borate esters typified by borate esters; aromatic borate esters such as tri-o-cresyl borate, tri-m-cresyl borate, tri-p-cresyl borate, triphenyl borate, tri Boric acid esters containing two or more boron atoms such as (1,3-butanediol) biborate, tri (2-methyl-2,4-pentanediol) biborate, trioctylene glycol diborate, etc. and containing a cyclic structure ; Polyvinyl alcohol borate ester Xylene glycol anhydrous boric acid to.

  Furthermore, phosphorus compounds such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide can also be added to the thermosetting resin composition.

  For the purpose of obtaining a thermosetting resin composition having excellent storage stability as a compound other than an epoxy resin in the thermosetting resin composition of the present invention and a cured coating film having excellent dimensional stability. Boric acid and linear aliphatic borate esters can be preferably used. Among the linear aliphatic borate esters, trialkyl borate esters having 4 to 20 carbon atoms are preferable, and tributyl borate (tributyl borate) is particularly preferable.

  Other thermosetting resin components can be added to the thermosetting resin composition of the present invention. Specifically, a phenol compound, an isocyanate compound, a silicate, an alkoxysilane compound, a melamine resin, etc. are mentioned, for example.

  Preferred examples of the phenol compound include, for example, bisphenol compounds having two or more phenolic hydroxyl groups in one molecule such as bisphenol A, bisphenol F, and bisphenol S; hydroquinone, 4,4′-biphenol, 3,3′- 1 phenolic hydroxyl group such as dimethyl-4,4′biphenol, 3,3 ′, 5,5′-tetramethylbiphenol, 2,4-naphthalenediol, 2,5-naphthalenediol, 2,6-naphthalenediol A compound having two or more in the molecule, a phenol compound containing a phosphorus atom such as 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide; a phenol novolac resin; Cresol novolac resin, t-butylphenol Borac resin, dicyclopentagencresol novolak resin, dicyclopentagen phenol novolak resin, xylylene-modified phenol novolak resin, naphthol novolak resin, trisphenol novolak resin, tetrakisphenol novolak resin, bisphenol A novolak resin, poly-p-vinylphenol Examples thereof include novolak type phenol resins such as resins and phenol aralkyl resins. These phenol resins can be used alone or in combination of two or more. Among them, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide is obtained at a low temperature while the resulting cured product has high heat resistance, flame retardancy, and low linear expansion. It is preferable because it becomes a thermosetting composition having excellent meltability.

  Examples of the isocyanate compound include aromatic isocyanate compounds, aliphatic isocyanate compounds, and alicyclic isocyanate compounds. Preferably, a polyisocyanate compound having two or more isocyanate groups in one molecule is preferable. A blocked isocyanate compound can also be used.

  Examples of the alkylalkoxysilane include alkyltrialkoxysilane and dialkyldialkoxysilane.

  Examples of the alkyltrialkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, Examples thereof include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, and phenyltributoxysilane.

  Examples of the dialkyl dialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldibutoxysilane, and diphenyldimethoxy. Silane, diphenyldiethoxysilane, diphenyldipropoxysilane, diphenyldibutoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methylethyldipropoxysilane, methylethyldibutoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane , Methylphenyldipropoxysilane, methylphenyldibutoxysilane, trimethylmethoxysilane, trimethyl ether Kishishiran, triethyl silane, triethyl silane, triphenyl methoxy silane, triphenyl ethoxy silane, and the like.

  Moreover, the condensate of alkyl alkoxysilane can also be used, for example, the condensate of the above-mentioned alkyl trialkoxysilane, the condensate of dialkyl dialkoxysilane, etc. are mentioned.

  As the melamine resin, for example, an alkoxylated melamine resin obtained by reacting a part or all of a methylol product obtained by reaction of a triazine ring-containing amino compound such as melamine or benzoguanamine with formaldehyde is used with an alcohol compound. be able to. As the alcohol compound used here, a lower alcohol having about 1 to 4 carbon atoms can be used. Specifically, a methoxymethylolated melamine resin, a butylated methylolated melamine resin, or the like can be used. The molecular structure may be completely alkoxylated, a methylol group may remain, or an imino group may remain.

  This alkoxylated melamine resin, in the thermosetting resin composition of the present invention, has the effect of preventing precipitation with time when boric acid and / or boric acid esters are added in addition to the improvement of heat resistance and physical properties as a crosslinking component. Yes, it improves the stability as a thermosetting resin composition.

  As the resin structure of the alkoxylated melamine resin, a methoxymethylolated melamine resin is preferable because of compatibility with the polyimide resin composition and good curability at the time of curing, and more preferably a methoxylation rate of 80% or more. A methoxymethylolated melamine resin is more preferred.

  Further, the resin structure may be a polynuclear substance by self-condensation. The degree of polymerization at this time is preferably in the range of about 1 to 5 and more preferably in the range of about 1.2 to 3 in terms of compatibility and stability.

  The alkoxylated melamine resin having a number average molecular weight in the range of 100 to 10,000 can be used. Preferably, the range of 300 to 2000 as the number average molecular weight is preferable in terms of compatibility with the polyimide resin composition and curability at the time of curing, and the range of 400 to 1000 is more preferable as the number average molecular weight.

  As the alkoxylated melamine resin, even if melamine, benzoguanamine, formalin and alcohol are simultaneously charged and reacted, melamine or benzoguanamine and formalin are reacted in advance to obtain a methylolated melamine compound and then alkoxylated with the alcohol compound. May be.

  Specific examples of commercially available alkoxylated melamine resins include, for example, product Cymel 300, 301, 303, and 305 manufactured by Nippon Cytec Industries, as methoxymethylolated melamine resins. Examples of the methylol group-containing methoxymethylolated melamine resin include product Cymel 370 and 771 manufactured by Nippon Cytec Industries. Examples of the imino group-containing methoxylated melamine resin include commercial Cymel 325, 327, 701, 703, and 712 manufactured by Mitsui Cytec Co., Ltd. Examples of the methoxylated butoxylated melamine resin include product Cymel 232, 235, 236, 238, 266, 267, 285 manufactured by Nippon Cytec Industries. Examples of the butoxylated melamine resin include product Uban 20SE60 manufactured by Nippon Cytec Industries.

  As the usage-amount of the said alkoxylated melamine resin, since it is excellent in a mechanical physical property and heat resistance, the range of 1-80 mass parts with respect to a total of 100 mass of the said polyimide resin (A) and a boron compound (B), Preferably The range of 1-50 mass parts and the range of 1-30 mass parts are preferable.

  Further, the thermosetting resin composition of the present invention includes a binder resin such as polyester, phenoxy resin, PPS resin, PPE resin, polyarylene resin, phenol resin, melamine resin, alkoxysilane curing agent, polybasic acid anhydride, cyanate compound. Curing such as curing agents or reactive compounds such as melamine, dicyandiamide, guanamine and derivatives thereof, imidazoles, amines, phenols having one hydroxyl group, organic phosphines, phosphonium salts, quaternary ammonium salts, photocationic catalysts, etc. It is also possible to add a defoaming agent, leveling agent, slip agent, wetting improver, anti-settling agent, flame retardant, antioxidant, ultraviolet absorber, etc. as a catalyst, curing accelerator, further filler, and other additives .

  As the thermosetting resin composition of the present invention, when the composition is cured, the linear expansion coefficient of the cured composition is preferably 50 ppm / K or less, and the thermosetting composition having 40 ppm / K or less is dimensionally stable. Is more preferable.

  In addition, various fillers, organic pigments, inorganic pigments, extender pigments, rust inhibitors, and the like can be appropriately added to the thermosetting resin composition of the present invention as necessary. These may be used alone or in combination of two or more.

  Examples of the filler include barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica, and alumina. It is done.

  As the filler, those having various particle sizes can be used, and the filler can be added within a range not impairing the performance of the thermosetting composition of the present invention. Such an appropriate addition amount is in the range of about 5 to 80% by mass, and it is preferable to use it after uniformly dispersing. As a dispersion method, it is possible to carry out dispersion by a known roll, bead mill, high-speed dispersion, or the like, and the particle surface may be surface-modified with a dispersion treatment agent in advance.

  Examples of the organic pigment include azo pigments; copper phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, and quinacridone pigments.

  Examples of the inorganic pigment include chromates such as chrome lead, zinc chromate and molybdate orange; ferrocyanides such as bitumen, titanium oxide, zinc white, bengara, iron oxide; metal oxides such as chromium carbide green, Cadmium yellow, cadmium red; metal sulfides such as mercury sulfide; selenides; sulfates such as lead sulfate; silicates such as ultramarine; carbonates, cobalt biored; phosphates such as manganese purple; aluminum powder, zinc dust Metal powders such as brass powder, magnesium powder, iron powder, copper powder and nickel powder; carbon black and the like.

  In addition, any of other coloring, rust prevention, and extender pigments can be used. These may be used alone or in combination of two or more.

  The thermosetting resin composition of the present invention can be dried or cured by heating in the range of 100 to 300 ° C. after coating or molding.

  The substrate used in the method for forming the coating film can be used without any particular limitation. Examples of the substrate include plastic, metal, wood, glass, inorganic material, and composite materials thereof.

  The interlayer adhesive film for printed wiring boards of the present invention is characterized by having a layer formed of a thermosetting resin composition on a carrier film. Such an adhesive film can illustrate the form of the film (adhesive film) which consists of a layer (A layer) and a support body film (B layer) of the thermosetting resin composition of this invention, for example.

  The adhesive film is prepared according to various methods, for example, by preparing a resin varnish obtained by dissolving the thermosetting resin composition of the present invention in an organic solvent, applying the resin varnish to a support film, and heating or blowing hot air. It can manufacture by drying an organic solvent and forming a resin composition layer.

  The support film (B layer) serves as a support when the adhesive film is produced, and is finally peeled off or removed in the production of the printed board. Examples of the support film include polyolefins such as polyethylene and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyesters such as polyethylene naphthalate, polycarbonate, and release paper and copper foil. The metal foil etc. can be mentioned. In addition, when using copper foil as a support body film, it can remove by etching with etching liquid, such as ferric chloride and cupric chloride. The support film may be subjected to a release treatment in addition to a mat treatment and a corona treatment, but it is more preferable that the release treatment is performed in consideration of releasability. Although the thickness of a support film is not specifically limited, Usually, it is 10-150 micrometers, Preferably it is used in 25-50 micrometers.

  Organic solvents for preparing the varnish include, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, cellosolve, butyl Examples thereof include carbitols such as carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and gamma butyrolactone. Two or more organic solvents may be used in combination.

  The drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the resin composition is usually 5% by mass or less, preferably 3% by mass or less. Specific drying conditions vary depending on the curability of the resin composition and the amount of the organic solvent in the varnish. For example, in a varnish containing an organic solvent in the range of 30 to 60% by mass, it is usually 3 to 80 to 120 ° C. It can be dried for about 13 minutes. Those skilled in the art can appropriately set suitable drying conditions by simple experiments.

  The thickness of the resin composition layer (A layer) can usually be in the range of 5 to 500 μm. The preferred range of the thickness of the A layer varies depending on the use of the adhesive film, and when used for manufacturing a multilayer flexible circuit board by the build-up method, the thickness of the conductor layer forming the circuit is usually 5 to 70 μm. The thickness of the A layer corresponding to the layer is preferably in the range of 10 to 100 μm.

  The A layer may be protected with a protective film. By protecting with a protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The protective film is peeled off during lamination. As the protective film, the same material as the support film can be used. Although the thickness of a protective film is not specifically limited, Preferably it is the range of 1-40 micrometers.

  The adhesive film obtained using the thermosetting resin composition of the present invention can be suitably used particularly for the production of a multilayer printed board. Below, the method to manufacture a printed circuit board is demonstrated. The adhesive film obtained by using the thermosetting resin composition of the present invention can be suitably laminated on a printed board with a vacuum laminator. The printed circuit board used here is mainly a conductor layer patterned on one or both sides of a substrate such as a fiber reinforced prepreg such as an epoxy substrate or a glass epoxy substrate, a polyester substrate, a polyimide substrate, a polyamideimide substrate, or a liquid crystal polymer substrate. (Circuit) As a matter of course, a multilayer printed circuit board in which a circuit and an insulating layer are alternately formed and a circuit is formed on one side or both sides can be used for further multilayering. In addition, from the viewpoint of adhesion of the insulating layer to the circuit board, the surface of the circuit should have been previously roughened with a surface treatment agent such as hydrogen peroxide / sulfuric acid or MEC Etch Bond (MEC Co., Ltd.). preferable.

  Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nichigo Morton, a vacuum pressurizing laminator manufactured by Meiki Seisakusho, a roll dry coater manufactured by Hitachi Techno Engineering Co., Ltd., Hitachi AIC ( A vacuum laminator manufactured by Co., Ltd. can be mentioned.

In the lamination, when the adhesive film has a protective film, the protective film is removed, and then the adhesive film is pressure-bonded to the circuit board while being pressurized and heated. The laminating conditions include pre-heating the adhesive film and the circuit board as required, laminating at a pressure of preferably 70 to 140 ° C., a pressure of pressure of preferably 1 to 11 kgf / cm ² and laminating under a reduced pressure of an air pressure of 20 mmHg or less. preferable. The laminating method may be a batch method or a continuous method using a roll.

  After laminating the adhesive film on the circuit board, it is cooled to around room temperature and the support film is peeled off. Next, the thermosetting resin composition laminated on the circuit board is cured by heating. The conditions for heat curing are usually selected in the range of 150 to 220 ° C. for 20 to 180 minutes, more preferably in the range of 160 to 200 ° C. for 30 to 120 minutes. When the support film has a release layer or a release layer such as silicon, the support film can be peeled after the thermosetting resin composition is heat-cured or after heat-curing and punching.

  After the insulating layer, which is a cured product of the thermosetting resin composition, is formed, the via holes and through holes are formed by drilling the circuit board as necessary using a method such as drilling, laser, plasma, or a combination thereof. May be. In particular, drilling with a laser such as a carbon dioxide laser or a YAG laser is generally used.

  Next, surface treatment of the insulating layer (cured product of the thermosetting resin composition) is performed. The surface treatment can employ a method used in a desmear process, and can be performed in a form that also serves as a desmear process. As a chemical used in the desmear process, an oxidizing agent is generally used. Examples of the oxidizing agent include permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid, and the like. Preferably, an alkaline permanganate solution (for example, potassium permanganate, sodium hydroxide aqueous solution of sodium permanganate), which is an oxidizer widely used for roughening the insulating layer in the production of multilayer printed wiring boards by the build-up method. It is preferable to carry out the treatment using A treatment with a swelling agent can also be performed before the treatment with the oxidizing agent. Further, after the treatment with an oxidizing agent, neutralization treatment with a reducing agent is usually performed.

  After the surface treatment, a conductor layer is formed by plating on the surface of the insulating layer. The conductor layer can be formed by a method combining electroless plating and electrolytic plating. Alternatively, a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating. After the conductor layer is formed, the peel strength of the conductor layer can be further improved and stabilized by annealing at 150 to 200 ° C. for 20 to 90 minutes.

  As a method for forming a circuit by patterning the conductor layer, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used. In the case of the subtractive method, the thickness of the electroless copper plating layer is in the range of 0.1 to 3 μm, preferably in the range of 0.3 to 2 μm. An electroplating layer (panel plating layer) is formed thereon with a thickness in the range of 3 to 35 μm, preferably in the range of 5 to 20 μm, and then an etching resist is formed to etch ferric chloride, cupric chloride, etc. After forming the conductor pattern by etching with a liquid, the circuit board can be obtained by removing the etching resist. In the case of the semi-additive method, after forming the electroless copper plating layer in the range of 0.1 to 3 μm, preferably 0.3 to 2 μm, the pattern resist is formed. Then, the circuit board can be obtained by peeling after electrolytic copper plating.

  A film in which the support film is replaced with a heat-resistant resin layer (heat-resistant resin film), that is, a film comprising the thermosetting composition layer (A layer) and the heat-resistant resin layer (C layer) of the present invention is a flexible circuit board. Can be used as a base film. A film comprising the thermosetting resin composition layer (A layer), the heat-resistant resin layer (C layer) and the copper foil (D layer) of the present invention can be used as a base film of a flexible circuit board as well. In this case, the base film has a layer structure in the order of A layer, C layer, and D layer. In the base film as described above, the heat resistant resin layer is not peeled off and constitutes a part of the flexible circuit board.

  A film in which an insulating layer (A ′ layer) made of a cured product of the thermosetting resin composition of the present invention is formed on a heat-resistant resin layer (C layer) can be used as a base film for a single-sided flexible circuit board. Moreover, it consists of a film having a layer structure in the order of A ′ layer, C layer and A ′ layer, and A ′ layer, C layer and copper foil (D layer). Similarly, a film having a layer structure can be used as a base film for a double-sided flexible circuit board.

  Examples of the heat-resistant resin used for the heat-resistant resin layer include a polyimide resin, an aramid resin, a polyamideimide resin, and a liquid crystal polymer. In particular, a polyimide resin and a polyamideimide resin are preferable. Moreover, on the characteristic used for a flexible circuit board, the breaking strength is 100 MPa or more, the breaking elongation is 5% or more, the thermal expansion coefficient between 20 and 150 ° C. is 40 ppm or less, and the glass transition temperature is 200 ° C. or more or the decomposition temperature is 300 ° C. It is preferable to use the above heat resistant resin.

  As the heat-resistant resin satisfying such characteristics, a heat-resistant resin that is commercially available in the form of a film can be suitably used. For example, a polyimide film “Upilex-S” manufactured by Ube Industries, Ltd., Toray DuPont Co., Ltd. ) Polyimide film "Kapton", Kaneka Chemical Co., Ltd. polyimide film "Apical", Teijin Advanced Films Ltd. "Aramika", Kuraray Co., Ltd. liquid crystal polymer film "Bexstar", Sumitomo Bakelite Co., Ltd. A polyether ether ketone film “Sumilite FS-1100C” and the like are known.

  The thickness of the heat resistant resin layer is usually in the range of 2 to 150 μm, preferably in the range of 10 to 50 μm. As the heat-resistant resin layer (C layer), a surface-treated layer may be used. Examples of the surface treatment include dry treatment such as mat treatment, corona discharge treatment and plasma treatment, chemical treatment such as solvent treatment, acid treatment and alkali treatment, sand blast treatment and mechanical polishing treatment. In particular, from the viewpoint of adhesion to the A layer, it is preferable that plasma treatment is performed.

  A base film for a single-sided flexible circuit board comprising an insulating layer (A ′ layer) and a heat-resistant resin layer (C layer) can be produced as follows. First, similarly to the adhesive film described above, a resin varnish prepared by dissolving the thermosetting resin composition of the present invention in an organic solvent is prepared, and this resin varnish is applied on a heat-resistant resin film, and heated or blown with hot air or the like. The organic solvent is dried to form a thermosetting resin composition layer. Conditions such as the organic solvent and drying conditions are the same as those for the adhesive film. The thickness of the resin composition layer is preferably in the range of 5 to 15 μm.

  Next, the thermosetting resin composition layer is dried by heating to form an insulating layer of the thermosetting resin composition. The conditions for heat curing are usually selected in the range of 150 to 220 ° C. for 20 to 180 minutes, more preferably in the range of 160 to 200 ° C. for 30 to 120 minutes.

  The production of a base film of a double-sided flexible circuit board film consisting of three layers of an insulating layer (A ′ layer), a heat-resistant resin layer (C) layer and a copper foil (D layer) is made of a heat-resistant resin layer (C layer) and copper foil. A resin composition may be formed on a copper-clad laminated film made of (D layer) and manufactured in the same manner as described above. Examples of the copper-clad laminated film include a cast method two-layer CCL (Copper-clad laminate), a sputtering method two-layer CCL, a laminate method two-layer CCL, and a three-layer CCL. The thickness of the copper foil is preferably 12 μm or 18 μm.

  Commercially available two-layer CCL includes Espanex SC (manufactured by Nippon Steel Chemical Co., Ltd.), Neoprex I <CM>, Neoprex I <LM> (Mitsui Chemicals), S'PERFLEX (Sumitomo Metal Mining Co., Ltd.) Nikaflex F-50VC1 (manufactured by Nikkan Kogyo Co., Ltd.) and the like are mentioned as the commercially available three-layer CCL.

  The production of a base film for a double-sided flexible circuit board film comprising three layers of an insulating layer (A ′ layer), a heat-resistant resin layer (C layer) and an insulating layer (A ′ layer) can be carried out as follows. First, in the same manner as the adhesive film described above, a resin varnish prepared by dissolving the thermosetting resin composition of the present invention in an organic solvent is prepared, and this resin varnish is applied onto a support film, and organic by heating or hot air blowing, etc. The solvent is dried to form a resin composition layer. Conditions such as the organic solvent and drying conditions are the same as those for the adhesive film. The thickness of the resin composition layer is preferably in the range of 5 to 15 μm.

  Next, this adhesive film is laminated on both surfaces of the heat resistant resin film. Lamination conditions are the same as described above. Moreover, if the resin composition layer is previously provided on one side of the heat-resistant film, the lamination may be only on one side. Next, the resin composition layer is cured by heating to form an insulating layer that is a layer of the resin composition. The conditions for heat curing are usually selected in the range of 150 to 220 ° C. for 20 to 180 minutes, more preferably in the range of 160 to 200 ° C. for 30 to 120 minutes.

  A method for producing a flexible circuit board from the base film for the flexible circuit board will be described. In the case of a base film composed of an A ′ layer, a C layer, and an A ′ layer, first, after heat curing, a circuit board is drilled by a method such as drilling, laser, or plasma to form a through hole for conduction on both sides. . In the case of a base film composed of an A ′ layer, a C layer, and a D layer, holes are formed by the same method to form via holes. In particular, drilling with a laser such as a carbon dioxide laser or a YAG laser is generally used.

  Next, a surface treatment of the insulating layer (resin composition layer) is performed. About surface treatment, it is the same as that of the case of the adhesive film mentioned above. After the surface treatment, a conductor layer is formed by plating on the surface of the insulating layer. The formation of the conductor layer by plating is the same as in the case of the adhesive film described above. After the conductor layer is formed, the peel strength of the conductor layer can be further improved and stabilized by annealing at 150 to 200 ° C. for 20 to 90 minutes.

  Next, the conductor layer is patterned to form a circuit to obtain a flexible circuit board. When a base film composed of an A layer, a C layer, and a D layer is used, a circuit is also formed on the copper foil that is the D layer. As a circuit formation method, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used. Details are the same as in the case of the adhesive film described above.

  The single-sided or double-sided flexible circuit board obtained in this way can be produced as a multilayer flexible circuit board by using the adhesive film of the present invention, for example, as described above.

  The resin composition of the present invention is also useful as a material for forming a stress relaxation layer between a semiconductor and a substrate substrate. For example, in the same manner as described above, all or part of the uppermost insulating layer of the substrate substrate is formed by the adhesive film obtained by using the resin composition of the present invention, and the resin is connected by connecting the semiconductor. A semiconductor device in which a semiconductor and a substrate substrate are bonded via a cured product of the composition can be manufactured. In this case, the thickness of the resin composition layer of the adhesive film is appropriately selected within a range of 10 to 1000 μm. The resin composition of the present invention can form a conductor layer by plating, and a circuit pattern can also be produced by simply forming a conductor layer by plating on an insulating layer for stress relaxation provided on a substrate substrate. Is possible.

  The cured product of the thermosetting resin composition of the present invention is also excellent in gas barrier properties. Therefore, it can be used as a coating material for packaging materials containing foods and pharmaceuticals. In addition, it can be used in fields other than packaging materials, for example, fields requiring gas barrier properties such as liquid crystal display elements, solar cells, electromagnetic wave shields, touch panels, EL substrates, color filters, and the like.

  EXAMPLES Next, an Example is shown and this invention is demonstrated further in detail. Unless otherwise specified, “parts” and “%” are based on weight.

Synthesis Example 1 Preparation of Organized Layered Silicate (C-1) 13.5 g of talc finely pulverized with a ball mill to an average particle diameter of 2 μm and 2.5 g of sodium silicofluoride having an average particle diameter of 2 μm Stir and mix for 2 minutes, put in a magnetic crucible, cover, hold in an electric furnace at 800 ° C. for 2 hours, synthesis with 12.3-mm gap in the air and cation exchange capacity of 120 meq / 100 g Fluorine mica was obtained. Further, 20 g of synthetic fluorine mica was dispersed in 1000 mL of tap water, and 300 mL of an aqueous solution in which 9.7 g of trioctylmethylammonium chloride (1.0 times the cation exchange capacity of synthetic fluorine mica) was dissolved was added and stirred. The reaction was allowed to proceed for 2 hours at room temperature. Next, the reaction product was separated into solid and liquid, washed with water, dried, pulverized and passed through a 280 mesh sieve to obtain about 22 g of organically modified layered silicate A.

Synthesis Example 2 Preparation of Organized Layered Silicate (C-2) Using 20 g of the synthetic fluorine mica obtained in Synthesis Example 1, 11.5 g of trioctylethylphosphonium bromide (1.0 cation exchange capacity of the synthetic fluorine mica) 300 ml of an aqueous solution in which 2 times the amount was dissolved was added and reacted at room temperature for 2 hours with stirring. Next, the reaction product was separated into solid and liquid, washed with water, dried, pulverized and passed through a 280 mesh sieve to obtain about 24 g of organically modified layered silicate B.

Synthesis Example 3 Preparation of Organized Layered Silicate (C-3) 10 g of montmorillonite having a cation exchange capacity of 11.5 meq / 100 g was dispersed in 1000 mL of distilled water and stirred at room temperature for 24 hours. The obtained suspension was heated to 70 ° C., 4.7 g of N-lauryl diethanolamine (hereinafter referred to as LEA) (1.5 times the cation exchange capacity of montmorillonite) and 100 mL of pure water and hydrochloric acid (concentration: (36.0%) A solution prepared by adding 2.22 mL and dissolving at 70 ° C. was added and stirred for 1 hour. The obtained suspension was filtered, washed three times with pure water and ethanol (volume ratio 1: 1), the resulting mass was pulverized in a mortar, passed through a 280 mesh sieve, and the organically modified layered silicate About 12 g of C was obtained.

  Table 1 shows the interlayer distance of the organically modified layered silicate obtained in Synthesis Examples 1 to 3 and the content of the organic compound. The interlayer distance and the amount of organic compound were measured according to the following methods.

[Measurement of interlayer distance of organically modified layered silicate]
Using an X-ray diffractometer (manufactured by Rigaku Co., Ltd., TTRII), 2θ of the (001) plane obtained by diffraction of the laminated surface of the following four types of organic layered silicate was measured, and Bragg's formula (λ = 2d · sin θ) was used to calculate the surface spacing. Here, λ = 1.54, d indicates the interplanar spacing of the organically modified layered silicate, and θ indicates the diffraction angle. The obtained d was defined as the interlayer distance.

[Measurement of Organizing Layered Silicate Organizer Content]
The obtained organically modified layered silicate was weighed with a precision balance (A), allowed to stand in an electric furnace at about 800 ° C. for 3 hours, and left to stand, and the ash content was weighed (B). The content of the organic agent was obtained from the obtained two masses and the following formula.
Content of organic agent (% by mass) = [{(A) − (B)} / (A)] × 100

Synthesis Example 4 Synthesis of Organized Clay-Containing Polyimide Resin Composition (A-1) 297 g of dimethylacetamide (hereinafter abbreviated as “DMAc”) and tolylene diisocyanate (hereinafter referred to as “hereinafter abbreviated as DMAc”) were added to a 4-neck flask equipped with a stirrer, a thermometer and a condenser. , Abbreviated as TDI), and 48.6 g (0. 46 mol) of 4,4′-diisocyanate-3,3′-dimethyl-1,1′-biphenyl (hereinafter abbreviated as TODI). 184 mol) and trimellitic anhydride (hereinafter abbreviated as TMAn) 37.2 g (0.194 mol), benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride (hereinafter referred to as BTDAn) 15.6 g (0.048 mol) was charged, and the raw materials were dissolved at 55 ° C. while stirring. After dissolution of the raw material, 5 g (5 phr with respect to the amount obtained by subtracting the amount of decarboxylation from the total amount of TDI, TODI, TMAn, and BTDAn) was added. After 0.5 hours, the temperature was raised to 100 ° C. over 0.5 hours, and then polymerized at this temperature for 3.5 hours, and an isocyanate bond-derived peak (about 2365 cm −1) disappeared by infrared absorption spectrum measurement. I confirmed that. During this time, the polymerization proceeded with the foaming of carbon dioxide. Then, after heating up to 150 degreeC over 1 hour, it superposed | polymerized for 5 hours. The obtained polyimide resin solution had an E-type viscosity (25 ° C.) of 4.1 Pa · s, a solid content of 25.7% by mass, and a solution acid value of 10.1 (KOH mg / g). This is abbreviated as a polyimide resin composition (A-1). According to the observation with an electron microscope (5,000 times) in the polyimide resin composition (A-1), the minor axis of the organically modified layered silicate was 30 nm on average and the aspect ratio was 50.

Synthesis example 5 (same as above)
9.9 g of organic layered silicate (C-2) instead of organic layered silicate (C-1) (based on the total amount of TDI, TODI, TMAn and BTDAn minus the amount of decarboxylation) A polyimide resin composition was polymerized in the same manner as in Synthesis Example 4 except that 10 phr) was added. The solution of the obtained polyimide resin composition (resin composition in which the polyimide resin is dissolved in DMAc) has an E-type viscosity (25 ° C.) of 15.9 Pa · s, a resin solid content of 27.0% by mass, a solution acid The value was 8.9 (KOHmg / g). This is abbreviated as a polyimide resin composition (A-2). According to the observation with an electron microscope (5000 times) in the polyimide resin composition (A-2), the minor axis of the organically modified layered silicate was 20 nm on average and the aspect ratio was 80.

Synthesis example 6 (same as above)
14.9 g of organic layered silicate (C-3) instead of organic layered silicate (C-1) (based on the total amount of TDI, TODI, TMAn and BTDAn minus the amount of decarboxylation) A polyimide resin composition was polymerized in the same manner as in Synthesis Example 4 except that 15 phr) was added. The resulting polyimide resin composition solution (resin composition in which the polyimide resin is dissolved in DMAc) has an E-type viscosity (25 ° C.) of 21.2 Pa · s, a resin solid content of 21.4 mass%, and a solution acid. The value was 8.2 (KOHmg / g). This is abbreviated as a polyimide resin composition (A-3). According to the observation with an electron microscope (5000 times) in the polyimide resin composition (A-3), the minor axis of the organically modified layered silicate was 50 nm on average and the aspect ratio was 30.

Synthesis example 7 (same as above)
In a four-necked flask equipped with a stirrer, a thermometer, and a condenser, 213.2 g of dimethylformamide (hereinafter abbreviated as DMF) and 6.3 g (0.036 mol) of tolylene diisocyanate (hereinafter abbreviated as TDI) 3,4′-diisocyanate-3,3′-dimethyl-1,1′-biphenyl (hereinafter abbreviated as TODI) 37.8 g (0.143 mol), trimellitic anhydride (hereinafter abbreviated as TMAn) 29.0 g (0.151 mol) and 12.2 g (0.038 mol) of benzophenone-3,3 ′, 4,4′-tetracarboxylic dianhydride (hereinafter abbreviated as BTDAn) While stirring, the temperature was raised to 100 ° C. over 1 hour and polymerized for 3 hours. After 3 hours, it was confirmed by infrared absorption spectrum measurement that an isocyanate bond-derived peak (about 2365 cm −1) disappeared, and the temperature was raised to 150 ° C. over 1 hour to polymerize for 5 hours. The obtained polyimide resin solution obtained a polyimide resin having an E-type viscosity (25 ° C.) of 1.3 Pa · s, a resin solid content of 27.5 mass%, and a solution acid value of 13.0 (KOHmg / g). .

  100 g of this polyimide resin, 11.5 g of DMAc, and 9.9 g of organic layered silicate (C-1) (based on the total amount of TDI, TODI, TMAn and BTDAn minus the amount of decarboxylation) 10 phr) was added and melt-mixed at 120 ° C. for 6 hours, and further melt-mixed using an ultrasonic homogenizer for 30 minutes. The solution of the obtained polyimide resin composition (resin composition in which the polyimide resin is dissolved in DMAc) has an E-type viscosity (25 ° C.) of 3.8 Pa · s, a resin solid content of 26.5% by mass, and a solution acid. The value was 10.6 (KOH mg / g). This is abbreviated as a polyimide resin composition (A-4). According to the observation with an electron microscope (5000 times) in the polyimide resin composition (A-4), the minor axis of the organically modified layered silicate was 50 nm on average and the aspect ratio was 20.

[Infrared absorption spectrum measurement]
The polyimide resin compositions (A-1) to (A-4) were applied to a KBr plate and measured using an infrared absorption spectrum apparatus (FTIR-6100, manufactured by JASCO Corp.). As a result, 2270 cm −1, which is the characteristic absorption of the isocyanate group, disappeared completely, and imide ring-derived characteristic absorption was confirmed at 725 cm −1, 1780 cm −1 and 1720 cm −1.

  The raw materials of the polyimide resin compositions (A-1) to (A-5) obtained in Synthesis Examples 4 to 7 and their amounts, the content of the biphenyl skeleton, the logarithmic viscosity, and the solution acid value are shown in Table 2. Show. The viscosity and solution acid value were measured according to the following methods.

[Measurement of viscosity]
The viscosity at 25 ° C. of the polyimide resin composition was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., model: TV-22).
[Measurement of solution acid value]
About 3 to 5 g of the polyimide resin composition was weighed into a 100 ml Erlenmeyer flask, and 30 mL of DMAc was added and dissolved. To this, a few drops of phenolphthalein solution as an indicator was added and titrated with a 0.1 mol / L potassium hydroxide / acetone solution, and the solution acid value of the polyimide resin composition was calculated from the following formula.
Acid value = V × F × 5.61 / S
V: Amount of use of 0.1 mol / L potassium hydroxide / alcohol solution (mL)
F: Potency of 0.1 mol / L potassium hydroxide / alcohol solution S: Amount of sample collected (g)

Synthesis Example 8 (Synthesis of comparative polyimide resin)
A 4-necked flask equipped with a stirrer, thermometer and condenser was charged with 76.8 g of trimellitic anhydride, 88.8 g of isophorone diisocyanate, 0.44 g of sodium methoxide, and 140 g of γ-butyrolactone for about 30 minutes while stirring. The temperature was raised to 190 ° C. Thereafter, the mixture was stirred at 190 ° C. for 5 hours, cooled to 150 ° C., and diluted with 724 g of N-methyl-2-pyrrolidone. The obtained polyimide resin solution (resin composition in which the polyimide resin was dissolved in DMAc) had a logarithmic viscosity of 1.26 dl / g, a resin solid content of 26.5% by mass, and a solution acid value of 15 (KOHmg / g )Met. This is abbreviated as a polyimide resin composition (a-1).

Examples 1 to 6 and Comparative Example 1
The thermosetting resin compositions (P-1) to (P-5) of the present invention were obtained at the blending composition ratios shown in Tables 3 and 4. Using the obtained thermosetting resin composition, the meltability of the B-staged semi-cured composition, and the heat resistance, dimensional stability, moisture resistance, and gas barrier properties of the cured product of the thermosetting resin composition Evaluation was performed according to the following measurement method. The evaluation results are shown in Tables 3 and 4.

-Evaluation of meltability Preparation of adhesive film The thermosetting composition was uniformly coated on an PET film (thickness 125 μm) with an applicator so that the thickness of the resin composition layer after drying was 25 μm, and dried at 100 ° C. for 5 minutes. An adhesive film was obtained.

2. Melt adhesion test of adhesive film The above adhesive film is placed on an electrolytic copper foil (thickness 18 μm, surface roughness: M surface Rz 7.4 μm, S surface Ra 0.21 μm) previously heated to 120 ° C. so that the resin surface is in contact with copper Superposition and hot pressing for 1 minute under a pressure of 1 MPa. Thereafter, the PET film was peeled off, and the resin composition was further cured by heating at 200 ° C. for 60 minutes. The test piece was subjected to a tape peeling test according to JIS K 5400 8.5.2 (adhesive cross-cut tape method), and the melt adhesion was evaluated according to the following five-stage evaluation criteria.

5: The resin melted without applying pressure was sufficiently spread and adhered to the surface of the electrolytic copper foil, and after the main curing, the tape was peeled off and the area of the defective portion was less than 5% with respect to the test execution area.
Melt bonding is possible at a pressure of 4: 1 MPa, and after the main curing, the tape is peeled off and the area of the defect portion is less than 5% with respect to the test execution area.
It can be melt-bonded at a pressure of 3: 1 MPa, and after the main curing, the tape is peeled off so that the area of the defective portion is 5% or more with respect to the test execution area.
Although partly melt bonded at a pressure of 2: 1 MPa, the area of the melt bonded part is less than 50%.
No melt adhesion at a pressure of 1: 1 MPa.

3. Evaluation of heat resistance, moisture resistance and dimensional stability of thermosetting composition Evaluation of heat resistance of the cured product of the thermosetting resin composition was performed by measuring a glass transition temperature and performing a solder reflow test. The dimensional stability was evaluated by measuring the linear expansion coefficient of the cured product.

<Method for producing measurement specimen>
The thermosetting resin composition was coated on a mirror surface aluminum substrate so that the film thickness of the coating film obtained after curing was 30 μm. Next, using a hot air dryer, the coated plate was thermally cured at 50 ° C. for 30 minutes, 100 ° C. for 30 minutes, and 200 ° C. for 60 minutes to produce a film of a thermosetting composition.

<Method for evaluating heat resistance>
According to JIS K-7198, using a dynamic viscometer (hereinafter abbreviated as DMA, RSAII manufactured by Rheometrics Co., Ltd.), the cured film was heated at a rate of 2 ° C./min, a measurement frequency of 1 Hz, and a measurement temperature. It measured in the range of 30 degreeC-400 degreeC. The peak maximum value of loss tangent in the obtained DMA curve was defined as the glass transition temperature.

The heat resistance was also evaluated by conducting a solder reflow resistance test. After the film was cut into 10 mm × 50 mm, it was immersed in a solder bath heated to 260 ° C. for 180 seconds, and the state was visually observed.
Judgment criteria: ○ No change
× Blistering or cracking

<Method for evaluating dimensional stability>
Evaluation was performed by measuring the linear expansion coefficient. Using a thermomechanical analyzer TMA-60 / 60H manufactured by Shimadzu Corporation, measurement was performed by the TMA (Thermal Mechanical Analysis) method under the conditions of a sample length of 10 mm, a heating rate of 10 ° C./min, and a load of 30 mN. The linear expansion coefficient was calculated as an average value in the range of 20 ° C to 200 ° C.

<Method for evaluating moisture resistance>
A test piece similar to the solder reflow resistance test was subjected to a pressure cooker test under the conditions of 121 ° C., 100% RH, 2 atm, and 2 hours. The thermosetting composition after the pressure cooker test was visually inspected for defects such as cracks, cracks, discoloration, and cloudiness.

<Gas barrier property evaluation method>
1. Preparation method of cured coating film The thermosetting resin composition was coated on a mirror-finished aluminum substrate so that the film thickness of the coating film obtained after curing was 30 μm. Next, using a hot air dryer, the coated plate was thermally cured at 50 ° C. for 30 minutes, 100 ° C. for 30 minutes, and 200 ° C. for 60 minutes to produce a film of a thermosetting composition. The film of the obtained thermosetting composition was cut into a circle having a diameter of about 8 cm.

2. Measurement Method of Oxygen Permeability Oxygen permeability was measured by a differential pressure method according to JIS K7126-1 using a gas permeability meter (Deltaperm manufactured by Technolox) at 30 ° C.

3. Method for measuring water vapor permeability Water vapor permeability was measured by a differential pressure method according to JIS K7126-1 under the condition of 40 ° C and 90% RH using a gas permeability meter (Deltaperm manufactured by Technolox).

Footnotes of Table 3 to Table 4 E-1: Naphthalene type epoxy resin manufactured by DIC Corporation Epicron HP-4710 (epoxy equivalent 173 g / eq)
E-2: Bisphenol A type liquid epoxy resin manufactured by DIC Corporation Epicron 850-S (epoxy equivalent 188 g / eq)

Claims (22)

  A polyisocyanate compound containing a polyisocyanate compound having a biphenyl skeleton and an acid anhydride, or a polyimide resin obtained by polymerizing an acid anhydride containing an acid anhydride having a biphenyl skeleton and a polyisocyanate compound, and an organic layered silicate A polyimide resin composition comprising: a dispersed resin having a minor axis of 1 to 50 nm and an aspect ratio of 10 to 500.   The polyimide resin composition according to claim 1, wherein the organically modified layered silicate is a particle having a minor axis of 1 to 30 nm and an aspect ratio of 10 to 300.   The polyimide resin composition according to claim 1, wherein the polyimide resin is a polyimid resin obtained by using a polyisocyanate compound having a biphenyl skeleton or an acid anhydride having a biphenyl skeleton so that the biphenyl skeleton is 20 to 40% by mass. .   The polyimide resin composition according to claim 1, wherein the polyimide resin is a polyimide resin obtained by using a polyisocyanate compound having a benzophenone structure or an acid anhydride having a benzophenone structure.   The polyimide resin composition according to claim 4, wherein the polyimide resin is a polyimide resin obtained by using a polyisocyanate compound having a tolylene structure or a diisocyanate having a tolylene structure. In the organic layered silicate, a cation between the layers of the layered silicate is ion-exchanged with an organic onium ion represented by the following general formula (1), and the organic group content in the organic onium ion is The polyimide resin composition according to claim 1, which is 10 to 60% by mass based on the mass of the organically modified layered silicate.

In formula (1), at least one of R ^{1 to} R ⁴ is an alkyl group or a polyalkylene ether group. M represents a nitrogen atom or a phosphorus atom.   The polyimide resin composition according to claim 6, wherein the alkyl group is an alkyl group having 2 to 20 carbon atoms. The polyimide resin composition according to claim 6, wherein the polyalkylene ether group is a polyalkylene ether group having a structure represented by the following general formula (III).
X- (RO) n-H (...) (III)
(In the formula, R represents an alkylene group having 1 to 20 carbon atoms, n represents an integer in the range of 5 to 50, and X represents an ionic group.)   The polyimide resin composition according to claim 1, wherein the content of the organically modified layered silicate is 1 to 30 parts by mass with respect to 100 parts by mass of the polyimide resin.   A thermosetting resin composition comprising the polyimide resin composition according to any one of claims 1 to 9 and an epoxy resin.   The thermosetting resin composition according to claim 10, wherein the content of the organically modified layered silicate is 1 to 30 parts by mass with respect to 100 parts by mass of the resin content in the thermosetting resin composition.   An interlayer adhesive film for printed wiring boards, comprising a layer formed of the thermosetting resin composition according to claim 10 or 11 on a carrier film.   A gas barrier material comprising the polyimide resin composition according to claim 1.   Presence of an organic layered silicate and an organic solvent comprising a polyisocyanate compound containing a polyisocyanate compound having a biphenyl skeleton and an acid anhydride, or an acid anhydride containing a polyisocyanate having a biphenyl skeleton and a polyisocyanate compound. The manufacturing method of the polyimide resin composition characterized by making it react under and obtaining the composition containing the polyimide resin which has biphenyl frame | skeleton, organic-ized layered silicate, and the organic solvent. In the organic layered silicate, a cation between the layers of the layered silicate is ion-exchanged with an organic onium ion represented by the following general formula (1), and the organic group content in the organic onium ion is The method for producing a polyimide resin composition according to claim 14, wherein the content is 10 to 60% by mass based on the mass of the organically modified layered silicate.

In formula (1), at least one of R ^{1 to} R ⁴ is an alkyl group or a polyalkylene ether group. M represents a nitrogen atom or a phosphorus atom.   The method for producing a polyimide resin composition according to claim 15, wherein the alkyl group is an alkyl group having 2 to 20 carbon atoms. The method for producing a polyimide resin composition according to claim 15, wherein the polyalkylene ether group is a polyalkylene ether group having a structure represented by the following general formula (III).
X- (RO) n-H (...) (III)
(In the formula, R represents an alkylene group having 1 to 20 carbon atoms, n represents an integer in the range of 5 to 50, and X represents an ionic group.)   The manufacturing method of the polyimide resin composition of Claim 14 using 1-30 mass parts of said organically modified layered silicate with respect to 100 mass parts of raw materials of a polyimide resin.   The manufacturing method of the polyimide resin composition of Claim 14 using the polyisocyanate compound which has a biphenyl skeleton, or the acid anhydride which has a biphenyl skeleton so that the biphenyl skeleton in the said polyimide resin may be 20-40 mass%.   Furthermore, the manufacturing method of the polyimide resin composition of Claim 14 using the polyisocyanate compound which has a benzophenone structure, or the acid anhydride which has a benzophenone structure.   Furthermore, the manufacturing method of the polyimide resin composition of Claim 19 using the polyisocyanate compound which has a tolylene structure, or the diisocyanate which has a tolylene structure.   The method for producing a polyimide resin composition according to any one of claims 14 to 21, wherein at least one solvent selected from the group consisting of dimethylformamide, dimethylacetamide and N-methyl-2-pyrrolidone is used as the organic solvent.