JP5010124B2 - Thermoplastic resin composition, sheet, copper foil with resin, printed circuit board, and prepreg - Google Patents

Description

The present invention, mechanical properties, dimensional stability, heat resistance, excellent flame retardancy, a thermoplastic resin composition particularly excellent in high temperature properties, shea over preparative, tree fat copper foil, the PCB and prepreg about the.

  2. Description of the Related Art In recent years, electronic devices with high performance, high functionality, and miniaturization are rapidly progressing, and there is an increasing demand for miniaturization and weight reduction of electronic components used in electronic devices. As a result, further improvements in physical properties such as heat resistance, mechanical strength, and electrical characteristics have been demanded for the materials of electronic components. For example, for semiconductor device packaging methods and wiring boards for mounting semiconductor devices. However, higher density, higher functionality, and higher performance are required.

  Multilayer printed circuit boards used in electronic devices are composed of a plurality of insulating substrates, and conventionally, as this interlayer insulating substrate, for example, a thermosetting resin prepreg in which a glass cloth is impregnated with a thermosetting resin, Films made of thermosetting resins or photocurable resins have been used. Even in the multilayer printed circuit board, it is desired to make the interlayer extremely thin for high density and thinning, and an interlayer insulating board using a thin glass cloth or an interlayer insulating board not using a glass cloth is required. ing. As such an interlayer insulating substrate, for example, those made of rubber (elastomer), thermosetting resin material modified with acrylic resin, thermoplastic resin material containing a large amount of inorganic filler, etc. are known. In Patent Document 1 below, an inorganic filler having a predetermined particle size is blended in a varnish mainly composed of a high molecular weight epoxy polymer and a polyfunctional epoxy resin, and applied to a support to form an insulating layer. A method for manufacturing a multilayer insulating substrate is disclosed.

  However, in the multilayer insulating substrate produced by the above production method, in order to sufficiently improve the mechanical properties such as mechanical strength by securing the interface area between the inorganic filler and the high molecular weight epoxy polymer or polyfunctional epoxy resin. In addition, it is necessary to add a large amount of an inorganic filler, which causes problems in processing such as an increase in the manufacturing process and difficulty in thinning the interlayer.

  In addition, interlayer insulation substrates that use thin glass cloth and interlayer insulation substrates that do not use glass cloth have problems such as insufficient heat resistance and dimensional stability. There was a problem that often occurred.

  The multilayer printed circuit board is manufactured by a build-up method for obtaining a multilayer laminate by repeating circuit formation and lamination on a layer, a batch lamination method for laminating layers on which circuits are formed, or the like. In any manufacturing method, since the number of processes is large, the quality of the material greatly affects the yield, and the process includes a plating process, a curing process, a solder reflow process, and the like. , Heat resistance and dimensional stability at high temperatures are required. Specifically, for example, resistance to acids, alkalis, and organic solvents; low moisture absorption that affects electrical characteristics; dimensional stability at high temperatures and after heating that affects high-precision circuit connections between upper and lower layers; Heat resistance up to 260 ° C required for mounting with lead-free solder; copper migration that affects connection reliability is unlikely to occur.

  For example, build-up boards and printed multilayer boards used in IC packages may be subject to high-temperature conditions due to heat generation, and it is required to maintain high reliability even in such an environment. If it is large, there is a problem that peeling occurs from a metal wiring such as copper forming a circuit, causing a short circuit or disconnection. In addition, even in a flexible multilayer substrate that has recently attracted attention as a thin substrate, the thermal dimensional change between the adhesive layer that bonds single-layer flexible substrates to each other, the polyimide film that forms the flexible substrate, and the metal wiring such as copper that forms the circuit If the difference is large, the same problem occurs.

  Patent Document 1 below discloses a technique for improving high-temperature physical properties by using an epoxy resin having excellent heat resistance and an inorganic compound in combination, but the effect of improving physical properties at a temperature higher than the glass transition temperature is disclosed. Almost no effect is seen, and the effect of improvement is small even at temperatures below the glass transition temperature. In addition, no improvement in hygroscopicity or solvent resistance can be expected.

  Conventionally, a method using an inorganic filler has been known as a method for reducing the linear expansion coefficient at a temperature lower than the glass transition temperature, but it has not been compatible with high-temperature treatment such as solder reflow. In recent years, lead-free solder has been used in consideration of the environment, and the temperature of the solder reflow process has further increased. Therefore, even if a resin with high heat resistance is used, the wire above the glass transition temperature is used. There was a problem that the expansion rate was large and problems occurred during high temperature treatment.

  In recent years, the progress of semiconductor packaging technology has been remarkable. Among them, TAB (Tape Automated Bonding) can easily form multi-pins because conductor patterns can be formed at an extremely high density, and wires can be used for bonding. Since it is possible to wire-connect the entire lead to a semiconductor element at one time without using it, development of a high-density mounting technology is being actively promoted.

  There are two types of TAB tapes, a two-layer structure and a three-layer structure, but a three-layer structure (hereinafter abbreviated as three-layer TAB) generally bonds a conductive foil such as copper foil and a heat-resistant resin film. Even if a resin film having excellent characteristics such as heat resistance and chemical resistance is used, it has an adhesive layer that is inferior in heat resistance, so that the characteristics could not be fully utilized.

  On the other hand, in general, a two-layer structure TAB (hereinafter abbreviated as two-layer TAB) is excellent in heat resistance as a TAB because it does not have an adhesive layer in the base film, but is practically used because of its difficulty in production. There were few things.

  Polyimide film, among various organic polymers, has excellent heat resistance, low temperature characteristics, chemical resistance, electrical characteristics, etc., and is used as a material for electrical and electronic equipment. Widely used.

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

  As described above, with high performance, high functionality, and downsizing, TAB tapes, flexible printed circuit board base films, and laminated board resins have less dimensional change due to heat and water absorption besides heat resistance. It is desired that the elastic modulus is high. However, a polyimide film that sufficiently satisfies these performances has not been obtained at present.

  Speaking of polyimide film, the product name “Kapton” manufactured by Toray DuPont Co., Ltd., the product name “Upilex” manufactured by Ube Industries, Ltd., and the product name “Apical” manufactured by Kaneka Chemical Co., Ltd. A polyimide film such as is used. Although these films have high heat resistance, they are decomposed before reaching the softening temperature, so that the films are formed by a solution casting method. In addition, the equipment cost and the manufacturing cost are increased, and further, there is a problem that it is difficult to perform molding by heat.

  On the other hand, in recent years, with the progress of optical communication technology, it has been demanded that optical communication devices be connected at low cost. Therefore, attention has been paid to optical communication materials made of polymer materials. However, when a conventional polymer material is used as an optical communication material, there are various problems.

  The polymer material for optical communication is required to have low loss, excellent heat resistance, a low coefficient of thermal linear expansion, low moisture permeability, and easy control of the refractive index.

  Note that low loss means that the propagation loss is small because the polymer material has almost no absorption band in the wavelength band used for optical communication.

  In the following Patent Document 2, a polymer optical communication material formed on a substrate such as silicon having a coefficient of thermal expansion close to 10 times the coefficient of thermal expansion of a semiconductor or metal material and having a low coefficient of thermal expansion. However, stress may be applied to cause polarization dependency of the optical communication material, warpage of the optical communication material and the substrate, or the edge of the polymer optical communication material may peel off from the substrate. Are listed.

  Patent Document 3 describes a problem that a fiber strand protrudes from a jacket due to a difference in thermal expansion coefficient between the fiber strand (quartz glass) and a resin case, or a crack occurs in the fiber strand due to stress concentration. ing.

  Further, in Patent Document 4, when the optical waveguide substrate and the optical fiber are connected using an adhesive, if the difference in thermal expansion between the optical waveguide substrate and the connection component is large, a positional shift due to thermal expansion occurs, and a stable optical It is described that connection with a waveguide cannot be realized.

  With respect to moisture permeability, in Patent Document 3, when water vapor penetrates into the hollow case, condensation occurs on the surface of the optical element or the fiber strand, causing corrosion of the optical element or causing crack growth to proceed. There is a problem that the wire is broken, and it is described that these factors, together with thermal expansion, comprehensively reduce the reliability of optical communication parts using polymer materials. In addition, if the hygroscopic property is high, light absorption due to the O—H bond of moisture is likely to occur, and from this reason, a material having low hygroscopic property is required.

  With regard to heat resistance, when optical communication is introduced to terminal equipment, conversion from optical signals to electrical signals or conversion from electrical signals to optical signals is required. A polymeric material will be used. Accordingly, the polymer material for optical communication needs to have heat resistance against the process temperature at the time of manufacturing the printed circuit board and heat resistance from the electric circuit at the time of use. Non-Patent Document 1 describes solder heat resistance as a required characteristic.

  As described above, materials that satisfy physical properties such as transparency, heat resistance, low linear expansion coefficient, and low hygroscopicity are desired as optical communication materials.

  On the other hand, Patent Document 5 below describes that a fluorinated polyimide having a rigid skeleton achieves a low coefficient of thermal expansion.

  Patent Document 6 below discloses a polymer optical waveguide comprising a core layer and a clad layer surrounding the core layer, the polymer optical waveguide having a second clad layer having a thermal expansion coefficient smaller than that of the clad layer outside the clad layer. Is disclosed. Here, it is said that by making the polymers constituting the cladding layer and the second cladding layer different, the thermal expansion coefficient of the second cladding layer can be made relatively low, and the difference in thermal expansion coefficient from the electric / optical element can be reduced. It is shown.

  Further, in Patent Document 2 below, the end face of the optical communication material is sealed with a resin so that the resin adheres the insulating film forming the optical communication material and air, and the peeling at the end where stress concentrates. It is stated that it can be prevented.

  Patent Document 7 below describes that the thermal expansion coefficient can be lowered by using a polyimide film having a specific structure as the resin for the optical waveguide.

  The fluorinated polyimide described in Patent Document 5 below is inferior in transparency to other types of fluorinated polyimide, has a high refractive index of 1.647, and is used as a material constituting a clad layer of an optical communication material. It was not appropriate.

  On the other hand, in the optical waveguide resin containing the particles described in Patent Document 6 below, it has been suggested that the low linear expansion coefficient and the transparency may be compatible. A large amount of particles must be added. Therefore, when a large amount of particles are added, it is difficult to achieve sufficient transparency. Further, when a large amount of particles are contained, there is a problem that the resin composition becomes brittle. In addition, when a large amount of particles are added, the hydrophilicity increases and the hygroscopicity may increase.

  Further, in the configuration described in Patent Document 2 below, the number of manufacturing processes increases, and an increase in cost is inevitable.

  On the other hand, when a polyimide-based film having a specific structure described in Patent Document 7 is used as an optical waveguide resin, it is difficult to achieve low hygroscopicity, although the thermal expansion coefficient can be lowered, and the cost is still high. I had to stay high.

Therefore, the optical circuit forming material is also excellent in transparency, heat resistance, low linear expansion coefficient and low hygroscopicity, and it has been difficult to realize a material capable of realizing particularly high transparency.
JP 2000-183539 A JP 2001-183539 A WO98 / 45741 JP-A-9-152522 Japanese Patent No. 2843314 JP 2001-108854 A JP 2001-4850 A Hitachi Technical Report No. 37 (July 2001), pp. 7-16

In view of the above situation, mechanical properties, dimensional stability, heat resistance, excellent flame retardancy, a thermoplastic resin composition particularly excellent in high temperature properties, shea over preparative, tree fat-coated copper foil, flop it is an object to provide a PC board and a prepreg.

The present invention relates to a thermoplastic resin composition containing 100 parts by weight of a thermoplastic resin and an inorganic compound 0.1 to 65 parts by weight comprising a thermoplastic polyimide, the inorganic compound, a heterocyclic quaternary ammonium ion comprising a layered silicate containing from 10 ° C. higher than the glass transition temperature of the thermoplastic resin composition, average coefficient of linear expansion up to a temperature higher 50 ° C. than the glass transition temperature of the thermoplastic resin composition ([alpha] 2) is It is a thermoplastic resin composition which is 3.0 × 10 ⁻³ [° C. ⁻¹ ] or less. Hereinafter, in the present invention, the resin composition refers to a thermoplastic resin composition.

  The present invention is described in detail below.

The resin composition of the present invention has an average coefficient of linear expansion (from 10 ° C. higher than the glass transition temperature of the resin composition (hereinafter also referred to as Tg) to 50 ° C. higher than the glass transition temperature of the resin composition ( Hereinafter, also referred to as α2) is 3.0 × 10 ⁻³ [° C. ⁻¹ ] or less. When the temperature is 3.0 × 10 ⁻³ [° C. ⁻¹ ] or less, the resin material comprising the resin composition of the present invention has a small dimensional change when heat-treated at a high temperature, and is bonded to a copper foil or the like. There is no warping or peeling due to the difference in shrinkage rate. Preferably, it is 1.0 × 10 ⁻³ [° C. ⁻¹ ] or less, more preferably 8.0 × 10 ⁻⁴ [° C. ⁻¹ ] or less, and further preferably 5.0 × 10 ⁻⁴ [° C. ^{−. 1} ] The following.

  The average linear expansion coefficient can be measured by a method according to JIS K7197. For example, a test of about 3 mm × 15 mm using a TMA (Thermal Mechanical Analysis) apparatus (manufactured by Seiko Denshi, TMA / SS120C). It can be determined by heating the piece at a heating rate of 5 ° C./min.

  In the resin composition of the present invention, α2 is an average linear expansion coefficient (hereinafter also referred to as α1) from a temperature 50 ° C. lower than the Tg of the resin composition to a temperature 10 ° C. lower than the glass transition temperature of the resin composition. It is preferable that the average coefficient of linear expansion ratio (α2 / α1) obtained by dividing by () is 70 or less. When it is 70 or less, the resin material comprising the resin composition of the present invention has a small dimensional change in the vicinity of Tg and does not cause wrinkles or warpage in the vicinity of Tg when used as a laminated material or a laminated material. More preferably, it is 15 or less, More preferably, it is 10 or less, Most preferably, it is 5 or less.

The resin composition of the present invention has an average linear expansion coefficient at 50 to 100 ° C. of 4.5 × 10 ⁻⁵ [° C. ⁻¹ ] or less and an average linear expansion coefficient at 200 to 240 ° C. of 7 ×. It is preferably 10 ⁻⁵ [° C. ⁻¹ ] or less. The average linear expansion coefficient at 50 to 100 ° C. is 4.5 × 10 ⁻⁵ [° C. ⁻¹ ] or less, and the average linear expansion coefficient at 200 to 240 ° C. is 7 × 10 ⁻⁵ [° C. ⁻¹ ]. The resin material comprising the resin composition of the present invention is suitable for an electronic material or the like that requires a small amount of dimensional change under normal use conditions and requires precise accuracy. Even in a manufacturing process or the like in which the high temperature treatment is performed, no warping or peeling occurs. The average linear expansion coefficient at 50 to 100 ° C. is more preferably 4.0 × 10 ⁻⁵ [° C. ⁻¹ ] or less, and still more preferably 3.5 × 10 ⁻⁵ [° C. ⁻¹ ] or less. The average linear expansion coefficient at 200 to 240 ° C. is more preferably 6.5 × 10 ⁻⁵ [° C. ⁻¹ ] or less, and further preferably 5.5 × 10 ⁻⁵ [° C. ⁻¹ ] or less.

  In the resin composition of the present invention, the average linear expansion coefficient ratio (1) obtained by dividing the average linear expansion coefficient at 150 to 200 ° C. by the average linear expansion coefficient at 50 to 100 ° C. is 2.0 or less. In addition, the average linear expansion coefficient ratio (2) obtained by dividing the average linear expansion coefficient at 250 to 300 ° C. by the average linear expansion coefficient at 50 to 100 ° C. is preferably 20 or less. When the average linear expansion coefficient ratio (1) is 2.0 or less and the average linear expansion coefficient ratio (2) is 20 or less, the resin material comprising the resin composition of the present invention has dimensional stability against heating. Therefore, even in a manufacturing process or the like in which high-temperature processing such as reflow of lead-free solder is performed, warping or peeling does not occur, and it is suitable for applications that are used at high temperatures. The average linear expansion coefficient ratio (1) is more preferably 1.5 or less, and still more preferably 1.2 or less. The average linear expansion coefficient (2) is more preferably 15 or less, still more preferably 10 or less.

  In the resin composition of the present invention, the amount of change in length when a resin piece made of the resin composition is heated from 25 ° C. to 300 ° C. is divided by the length of the resin piece made of the resin composition at 25 ° C. It is preferable that the change rate obtained in this way is 7% or less. When it is 7% or less, the resin material comprising the resin composition of the present invention has good dimensional stability with respect to temperature, and even when laminated with other materials or laminated, There is no warping or peeling. More preferably, it is 6% or less, More preferably, it is 5% or less.

  The resin composition of the present invention preferably has an average linear expansion coefficient ratio (3) represented by the following formula (1) of 1.5 or less.

  When the average linear expansion coefficient ratio (3) is 1.5 or less, the resin material comprising the resin composition of the present invention has good dimensional stability, and even when laminated with other materials or pasted together. No warping or peeling during manufacturing and use. More preferably, it is 1.4 or less, More preferably, it is 1.3 or less.

  The resin composition of the present invention has an average linear expansion coefficient (α2) of a resin composition from a temperature 10 ° C. higher than the glass transition temperature of the resin composition to a temperature 50 ° C. higher than the glass transition temperature of the resin composition. The improvement rate obtained by dividing by the average coefficient of linear expansion of the resin from a temperature 10 ° C. higher than the glass transition temperature of the resin to a temperature 50 ° C. higher than the glass transition temperature of the resin is 0.50 or less. Preferably there is. If it is 0.50 or less, the resin material comprising the resin composition of the present invention has sufficiently improved high-temperature properties due to the inorganic compound, and causes problems in the manufacturing process for high-temperature treatment and use at high temperatures. There is nothing. More preferably, it is 0.35 or less, More preferably, it is 0.25 or less.

  Since the resin composition of the present invention has a low average linear expansion coefficient at a high temperature above the glass transition temperature as described above, the high temperature physical properties such as dimensional stability at a high temperature are improved, and the plating process, curing process, lead It can be used for a resin material that does not warp or peel off even in a high-temperature treatment step such as a free solder reflow step.

  The resin composition of the present invention preferably has a tensile modulus of 6 GPa or more and a dielectric constant at 1 MHz of 3.3 or less. When the resin composition of the present invention is used as a TAB tape, if the tensile elastic modulus is less than 6 GPa, it is necessary to increase the thickness in order to ensure the required strength, and it becomes impossible to produce a small TAB. If the dielectric constant at 1 MHz is larger than 3.3, it is necessary to increase the thickness in order to ensure sufficient reliability, and it may be impossible to manufacture a small TAB.

The resin composition of the present invention preferably has a water absorption rate of 1.0% or less and a humidity linear expansion coefficient of 1.5 × 10 ⁻⁵ [% RH ⁻¹ ] or less. If the water absorption rate exceeds 1.0%, when a substrate is produced using the resin composition of the present invention, dimensional changes occur during absolutely dry and water absorption, which makes fine wiring difficult and cannot be miniaturized. There is. More preferably, it is 0.7% or less, More preferably, it is 0.3% or less. When the linear expansion coefficient of humidity exceeds 1.5 × 10 ⁻⁵ [% RH ⁻¹ ], the resulting substrate may be warped, and the copper foil may be peeled off due to the difference in the change rate of the copper foil. More preferably, it is 1.2 × 10 ⁻⁵ [% RH ⁻¹ ] or less, and further preferably 1.0 × 10 ⁻⁵ [% RH ⁻¹ ] or less.

  The resin composition of the present invention preferably has a water absorption of 1.0% or less, a dielectric constant at 1 MHz of 3.3 or less, and a dielectric constant after water absorption of 3.4 or less. If the electrical characteristics change greatly due to water absorption, the reliability may not be maintained, and the material may explode in the manufacturing process such as solder reflow and the yield may decrease.

In addition, the said water absorption is the weight W1 when it dries at 80 degreeC for 5 hours about the test piece which made the film of thickness 50-100 micrometers into a 3x5 cm strip shape, and is immersed in water, and is 24 at 25 degreeC. It is a value obtained by measuring the weight W2 when the surface is thoroughly wiped off after standing for a period of time and calculated by the following formula.
Water absorption (%) = (W2−W1) / W1 × 100

  The resin composition of the present invention preferably has a glass transition temperature of 100 ° C. or higher. When the glass transition temperature is 100 ° C. or higher, when the resin composition of the present invention is used for a substrate or the like, high-temperature properties, particularly lead-free soldering heat resistance and dimensional stability against heating are improved. More preferably, it is 140 degreeC or more, More preferably, it is 200 degreeC or more.

  The resin composition of the present invention preferably has a glass transition temperature of 100 ° C. or higher and a dielectric constant at 1 MHz of 3.3 or lower. Since the glass transition temperature is 100 ° C. or higher and the dielectric constant at 1 MHz is 3.3 or lower, the resin material comprising the resin composition of the present invention has high-temperature properties, particularly lead-free solder heat resistance and The dimensional stability against heating is improved, high reliability required for an electronic material can be obtained, and the transmission speed necessary for an electronic material can be obtained even in the transmission speed of a signal in a high frequency region. The glass transition temperature is more preferably 140 ° C. or higher, and further preferably 200 ° C. or higher. The dielectric constant of 1 MHz is more preferably 3.2 or less, and still more preferably 3.0 or less.

  The resin composition of the present invention has the above-described excellent high-temperature physical properties, and contains a thermoplastic resin and an inorganic compound.

  Examples of the thermoplastic resin include polyphenylene ether resin; functional group-modified polyphenylene ether resin; polyphenylene ether resin or functional group-modified polyphenylene ether resin; and polystyrene resin and other polyphenylene ether resins or functional group-modified polyphenylene. Mixtures of thermoplastic resins compatible with ether resins; Alicyclic hydrocarbon resins; Thermoplastic polyimide resins; Polyether ether ketone resins; Polyether sulfone resins; Polyamide imide resins; Polyester imide resins; Resin; Polystyrene resin; Polyamide resin; Polyvinyl acetal resin; Polyvinyl alcohol resin; Polyvinyl acetate resin; Poly (meth) acrylate resin; Polyoxymethylene resin; Polyetherimide resins; thermoplastic polybenzimidazole resins. Among them, polyphenylene ether resins, functional group-modified polyphenylene ether resins, polyphenylene ether resins or mixtures of functional group-modified polyphenylene ether resins and polystyrene resins, alicyclic hydrocarbon resins, thermoplastic polyimide resins, polyether ethers A ketone resin, a polyesterimide resin, a polyetherimide resin, a thermoplastic polybenzimidazole resin, or the like is preferably used. These thermoplastic resins may be used independently and 2 or more types may be used together. In addition, in this specification, (meth) acryl means acryl or methacryl.

  The polyphenylene ether resin is a polyphenylene ether homopolymer or polyphenylene ether copolymer composed of repeating units represented by the following formula (2).

  In said formula (2), R1, R2, R3, and R4 represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, or an alkoxyl group. These alkyl group, aralkyl group, aryl group and alkoxyl group may each be substituted with a functional group.

  Examples of the polyphenylene ether homopolymer include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, and poly (2,6 -Diethyl-1,4-phenylene) ether, poly (2-ethyl-6-n-propyl-1,4-phenylene) ether, poly (2,6-di-n-propyl-1,4-phenylene) ether Poly (2-ethyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-) 1,4-phenylene) ether and the like.

  Examples of the polyphenylene ether copolymer include a copolymer partially containing an alkyl trisubstituted phenol such as 2,3,6-trimethylphenol in the repeating unit of the polyphenylene ether homopolymer, and these polyphenylene ethers. Examples of the copolymer further include a copolymer obtained by graft copolymerization of one or more styrene monomers such as styrene, α-methylstyrene, and vinyl toluene. These polyphenylene ether resins may be used alone or in combination of two or more kinds having different compositions, components, molecular weights and the like.

  Examples of the functional group-modified polyphenylene ether resin include those obtained by modifying the polyphenylene ether resin with one or more functional groups such as a maleic anhydride group, a glycidyl group, an amino group, and an allyl group. Can be mentioned. These functional group-modified polyphenylene ether resins may be used alone or in combination of two or more. When the polyphenylene ether resin modified with the functional group is used as a thermoplastic resin, the mechanical properties, heat resistance, dimensional stability, etc. of the resin composition of the present invention can be further improved by a crosslinking reaction.

  Examples of the mixture of the polyphenylene ether resin or the functional group-modified polyphenylene ether resin and the polystyrene resin include the polyphenylene ether resin or the functional group-modified polyphenylene ether resin, a styrene homopolymer; styrene, α- Examples thereof include copolymers with one or more styrene monomers such as methyl styrene, ethyl styrene, t-butyl styrene and vinyl toluene; and mixtures with polystyrene resins such as styrene elastomers.

  The said polystyrene resin may be used independently and 2 or more types may be used together. Moreover, these polyphenylene ether resins or a mixture of functional group-modified polyphenylene ether resin and polystyrene resin may be used alone or in combination of two or more.

  The alicyclic hydrocarbon resin is a hydrocarbon resin having a cyclic hydrocarbon group in a polymer chain, and examples thereof include a cyclic olefin, that is, a norbornene monomer homopolymer or copolymer. These alicyclic hydrocarbon resins may be used alone or in combination of two or more.

  Examples of the cyclic olefin include norbornene, methanooctahydronaphthalene, dimethanooctahydronaphthalene, dimethanododecahydroanthracene, dimethanodecahydroanthracene, trimethanododecahydroanthracene, dicyclopentadiene, 2,3-dihydrocyclopentadiene. , Methanooctahydrobenzoindene, dimethanooctahydrobenzoindene, methanodecahydrobenzoindene, dimethanodecahydrobenzoindene, methanooctahydrofluorene, dimethanooctahydrofluorene, substituted products thereof and the like. These cyclic olefins may be used independently and 2 or more types may be used together.

  Examples of the substituent in the substituent such as norbornene include known hydrocarbon groups and polar groups such as an alkyl group, an alkylidene group, an aryl group, a cyano group, an alkoxycarbonyl group, a pyridyl group, and a halogen atom. These substituents may be used alone or in combination of two or more.

  Examples of the substituent such as norbornene include 5-methyl-2-norbornene, 5,5-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, and 5-ethylidene-2. -Norbornene, 5-methoxycarbonyl-2-norbornene, 5-cyano-2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, 5-phenyl-2-norbornene, 5-phenyl-5-methyl-2 -Norbornene and the like. These substituents such as norbornene may be used alone or in combination of two or more.

  Examples of commercially available alicyclic hydrocarbon resins include a trade name “Arton” series manufactured by JSR Corporation and a product name “Zeonor” series manufactured by Nippon Zeon Co., Ltd.

  Examples of the thermoplastic polyimide resin include a polyetherimide resin having an imide bond and an ether bond in the molecular main chain, a polyamideimide resin having an imide bond and an amide bond in the molecular main chain, and a molecular main chain. Examples thereof include a polyesterimide resin having an imide bond and an ester bond. Moreover, it does not specifically limit as a raw material to be used, For example, pyromellitic anhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid Dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, ethylene glycol bis (anhydrotrimethate) (5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2) , 5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione and the like, and 4,4′-bis (3-aminophenol) Alkoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] sulfone, 1,3-bis (4-aminophenoxy) benzene and diamine and 4,4'-diaminodiphenyl ether.

  These thermoplastic polyimide resins may be used independently and 2 or more types may be used together. As what is marketed among the said thermoplastic polyimide resins, the brand name "Aurum" series by Mitsui Chemicals, etc. are mentioned, for example.

  Examples of the polyether ether ketone resin include those obtained by polycondensation of dihalogenobenzophenone and hydroquinone. As what is marketed among the said polyetheretherketone resin, the brand name "Victrex PEEK" by ICI, etc. are mentioned, for example.

  Examples of the thermoplastic polybenzimidazole resin include those obtained by polycondensation of dioctadecyl terephthalaldoimine and 3,3'-diaminobenzidine. As what is marketed, the brand name "cerazole" series etc. by Clariant Japan are mentioned, for example.

The thermoplastic resin preferably has a solubility parameter (SP value) determined by using the Fedors formula of 42 [J / cm ³ ] ^1/2 or more. According to the Fedors calculation formula, the SP value is the square root of the sum of the molar aggregation energy of each atomic group divided by the volume, and indicates the polarity per unit volume. Since the SP value is 42 [J / cm ³ ] ^1/2 or more, it has a large polarity, so it has good compatibility with chemically treated inorganic compounds such as layered silicates, and layered silicates are used as inorganic compounds. Even if it is used, the interlayer of the layered silicate can be spread and dispersed one by one. More preferably, it is 46.2 [J / cm ³ ] ^1/2 or more, and further preferably 52.5 [J / cm ³ ] ^1/2 or more.

Examples of the resin having an SP value of 42 [J / m ³ ] ^1/2 or more include polyester resins such as polybutylene terephthalate, polybutylene naphthalate, polyethylene terephthalate, and polyethylene naphthalate, polyamide 6, polyamide 66, and polyamide. 12 polyamide resin, polyamideimide resin, polyimide resin, polyesterimide resin, polyetherimide resin, polyetheretherketone resin, polyphenylene ether resin, modified polyphenylene ether resin, polybenzimidazole resin and the like.

  The thermoplastic resin preferably has a 10% weight loss temperature of 400 ° C. or higher when thermogravimetric measurement is performed in a nitrogen atmosphere. By being 400 degreeC or more, the resin material which consists of a resin composition of this invention does not generate | occur | produce outgas in high temperature processing processes, such as a reflow process of lead-free solder, and becomes a suitable electronic material. More preferably, it is 450 degreeC or more, More preferably, it is 500 degreeC or more. Examples of the resin having a 10% weight loss temperature of 400 ° C. or higher in thermogravimetry in a nitrogen atmosphere include polyether ether ketone resins, polyether imide resins, polyamide imide resins, and thermoplastic polyimide resins. .

  The resin composition of the present invention contains an inorganic compound.

  Examples of the inorganic compound include layered silicates, talc, silica, alumina, glass beads and the like, and among them, layered silicates are preferably used in order to improve high temperature physical properties. In the present specification, the layered silicate means a layered silicate mineral having an exchangeable metal cation between layers, and may be a natural product or a synthetic product.

  When a particularly high tensile elastic modulus is required, it is preferable to contain a layered silicate and a whisker as the inorganic compound. Although it is known that when a whisker is added to a resin, the elastic modulus is improved, the resin composition containing the whisker so that a high tensile elastic modulus can be achieved has a problem that the moldability deteriorates. In the resin composition of the present invention, by using a layered silicate and whisker as an inorganic compound, a sufficient improvement in elastic modulus can be obtained even with a small amount of whisker.

  When the whisker is blended with the layered silicate as an inorganic compound, the whisker is preferably 25 to 95% by weight in 100% by weight of the inorganic compound. If the amount is less than 25% by weight, the effect of adding the whisker is not sufficient, and if it exceeds 95% by weight, the effect of adding the layered silicate may not be sufficient.

  In particular, when a low water absorption rate is required, it is preferable to contain a layered silicate and silica as an inorganic compound. The silica is not particularly limited, and examples thereof include Aerosil manufactured by Nippon Aerosil Co., Ltd. By using layered silicate and silica together as an inorganic compound, the hygroscopicity of the polymer material obtained from the resin composition of the present invention can be effectively reduced. It is known that when silica is added to the resin, the water absorption rate is improved. However, the resin composition containing silica so as to achieve a low water absorption rate has a problem that physical properties such as tensile strength are lowered. . In the resin composition of the present invention, by using a layered silicate and silica in combination as an inorganic compound, a sufficient water absorption reduction effect can be obtained even with a small amount of silica. The proportion of silica in the inorganic compound is preferably in the range of 25 to 95% by weight. If it is less than 25% by weight, the effect of blending silica with layered silicate is not sufficient, and if it exceeds 95% by weight, the effect of adding layered silicate may be impaired.

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

  The crystal shape of the layered silicate is not particularly limited, but the preferable lower limit of the average length is 0.01 μm, the upper limit is 3 μm, the preferable lower limit of the thickness is 0.001 μm, the upper limit is 1 μm, and the preferable lower limit of the aspect ratio is 20 μm. The upper limit is 500, the more preferred lower limit of the average length is 0.05 μm, the upper limit is 2 μm, the more preferred lower limit of the thickness is 0.01 μm, the upper limit is 0.5 μm, the more preferred lower limit of the aspect ratio is 50, the upper limit Is 200.

  The layered silicate preferably has a large shape anisotropy effect defined by the following formula (3A). By using a layered silicate having a large shape anisotropy effect, the resin obtained from the resin composition of the present invention has excellent mechanical properties.

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

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

  When the resin composition of the present invention is produced using a layered silicate as the inorganic compound, the dispersibility in the resin is improved by chemically modifying the layered silicate to increase the affinity with the resin. Preferably, a large amount of layered silicate can be dispersed in the resin by such chemical treatment. If the layered silicate is not subjected to chemical modification suitable for the resin used in the present invention or the solvent used in the production of the resin composition of the present invention, the layered silicate tends to aggregate and be dispersed in large quantities. However, by applying a chemical modification suitable for the resin or solvent, the layered silicate can be dispersed in the resin without agglomeration even when added in an amount of 10 parts by weight or more. As said chemical modification, it can implement by the chemical modification (1) method-chemical modification (6) method shown below, for example. These chemical modification methods may be used alone or in combination of two or more.

  The chemical modification (1) method is also referred to as a cation exchange method using a cationic surfactant. Specifically, when the resin composition of the present invention is obtained using a low polar resin such as a polyphenylene ether resin, a layered silicic acid is used in advance. In this method, cation exchange is performed between the salt layers with a cationic surfactant to make it hydrophobic. By making the layers of the layered silicate hydrophobic in advance, the affinity between the layered silicate and the low polarity resin is increased, and the layered silicate can be finely dispersed in the low polarity resin more uniformly.

  The cationic surfactant is not particularly limited, and examples thereof include quaternary ammonium salts and quaternary phosphonium salts. Of these, alkyl ammonium ions, aromatic quaternary ammonium ions, or heterocyclic quaternary ammonium ions having 6 or more carbon atoms are preferably used because the crystal layers of the layered silicate can be sufficiently hydrophobized. In particular, when a thermoplastic polyimide resin, polyesterimide resin, or polyetherimide resin is used as the thermoplastic resin, aromatic quaternary ammonium ions or heterocyclic quaternary ammonium ions are preferred.

  The quaternary ammonium salt is not particularly limited. For example, trimethylalkylammonium salt, triethylalkylammonium salt, tributylalkylammonium salt, dimethyldialkylammonium salt, dibutyldialkylammonium salt, methylbenzyldialkylammonium salt, dibenzyldialkylammonium salt. , Trialkylmethylammonium salt, trialkylethylammonium salt, trialkylbutylammonium salt; benzylmethyl {2- [2- (p-1,1,3,3-tetramethylbutylphenoxy) ethoxy] ethyl} ammonium chloride A quaternary ammonium salt having an aromatic ring such as: a quaternary ammonium salt derived from an aromatic amine such as trimethylphenylammonium; an alkylpyridinium salt, an imidazoli A quaternary ammonium salt having a heterocyclic ring such as a dimethyl salt; a dialkyl quaternary ammonium salt having two polyethylene glycol chains, a dialkyl quaternary ammonium salt having two polypropylene glycol chains, and a trialkyl quaternary having one polyethylene glycol chain Examples include ammonium salts and trialkyl quaternary ammonium salts having one polypropylene glycol chain. Among them, lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, trioctyl methyl ammonium salt, distearyl dimethyl ammonium salt, di-cured tallow dimethyl ammonium salt, distearyl dibenzyl ammonium salt, N-polyoxyethylene-N-lauryl-N N-dimethylammonium salt and the like are preferred. These quaternary ammonium salts may be used alone or in combination of two or more.

  The quaternary phosphonium salt is not particularly limited. For example, dodecyltriphenylphosphonium salt, methyltriphenylphosphonium salt, lauryltrimethylphosphonium salt, stearyltrimethylphosphonium salt, trioctylmethylphosphonium salt, distearyldimethylphosphonium salt, distearyl And dibenzylphosphonium salts. These quaternary phosphonium salts may be used alone or in combination of two or more.

  In the chemical modification (2) method, a hydroxyl group present on the crystal surface of the organically modified layered silicate chemically treated by the chemical modification (1) method has a chemical affinity with a functional group or a hydroxyl group capable of chemically bonding to the hydroxyl group. This is a method of chemical treatment with a compound having at least one functional group having a large molecular weight at the molecular end.

  The functional group capable of chemically bonding to the hydroxyl group or the functional group having a large chemical affinity with the hydroxyl group is not particularly limited, and examples thereof include an alkoxy group, a glycidyl group, a carboxyl group (including dibasic acid anhydrides), A hydroxyl group, an isocyanate group, an aldehyde group, etc. are mentioned.

  The compound having a functional group capable of chemically bonding to the hydroxyl group or the compound having a functional group having a large chemical affinity with the hydroxyl group is not particularly limited. For example, a silane compound, titanate compound, or glycidyl compound having the functional group. , Carboxylic acids, alcohols and the like. These compounds may be used independently and 2 or more types may be used together.

  The silane compound is not particularly limited, and examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, and γ-amino. Propyldimethylmethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyldimethylethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, hexyltrimethoxysilane, hexyltri Ethoxysilane, N-β- (aminoethyl) γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) γ-aminopropyltriethoxysilane, N-β- (aminoethyl) γ- Minopropylmethyldimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltri An ethoxysilane etc. are mentioned. These silane compounds may be used independently and 2 or more types may be used together.

In the chemical modification (3) method, the hydroxyl group present on the crystal surface of the organically modified layered silicate chemically treated by the chemical modification (1) method has a functional group capable of chemically bonding to the hydroxyl group or a chemical affinity with the hydroxyl group. This is a chemical treatment method using a large functional group and a compound having at least one reactive functional group at the molecular end.
The chemical modification (4) method is a method in which the crystal surface of the organically modified layered silicate chemically treated by the chemical modification (1) method is chemically treated with a compound having an anionic surface activity.

  The compound having an anionic surface activity is not particularly limited as long as the layered silicate can be chemically treated by ionic interaction. For example, sodium laurate, sodium stearate, sodium oleate, higher alcohol sulfate ester salt , Secondary higher alcohol sulfates, unsaturated alcohol sulfates and the like. These compounds may be used independently and 2 or more types may be used together.

  The chemical modification (5) method is a method of chemically treating a compound having one or more reactive functional groups in addition to the anion site in the molecular chain among the compounds having anionic surface activity.

  In the chemical modification (6) method, an organically modified layered silicate chemically treated by any one of the chemical modification (1) method to the chemical modification (5) method is further used, for example, maleic anhydride-modified polyphenylene ether resin. This is a method using a resin having a functional group capable of reacting with the layered silicate.

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

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

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

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

  In addition, the ratio of the layered silicate dispersed as a laminate of 5 layers or less is a layered silicic acid that can be observed in a fixed area by observing the resin composition at a magnification of 50,000 to 100,000 times with a transmission electron microscope. It can be calculated from the following formula (4) by measuring the total number of layers X of the salt laminate and the number of layers Y of the laminate dispersed as a laminate of 5 layers or less.

  The number of layers in the layered silicate laminate is preferably 5 layers or less, more preferably 3 layers or less, and even more preferably 1 layer in order to obtain the effect of dispersion of the layered silicate. is there.

  The resin composition of the present invention uses a layered silicate as the inorganic compound, has an average interlayer distance of (001) plane measured by wide-angle X-ray diffraction measurement method of 3 nm or more, and part or all of the laminate When the layered silicate is 5 layers or less, the interface area between the resin and the layered silicate becomes sufficiently large, and the interaction between the resin and the surface of the layered silicate increases. In addition to increasing melt viscosity and improving moldability, mechanical properties such as elastic modulus are improved over a wide temperature range from room temperature to high temperature, and mechanical properties are maintained even at high temperatures above the Tg or melting point of the resin. And the coefficient of linear expansion at high temperatures can be kept low. The reason for this is not clear, but it is considered that even in the temperature range above Tg or the melting point, these physical properties are manifested because the finely dispersed layered silicate acts as a kind of pseudo-crosslinking point. On the other hand, since the distance between the lamellar crystals of the layered silicate is also appropriate, the lamellar crystals of the lamellar silicate move during combustion, and it becomes easy to form a sintered body that becomes a flame retardant coating. Since this sintered body is formed at an early stage during combustion, not only the supply of oxygen from the outside world but also the flammable gas generated by the combustion can be blocked, and the resin composition of the present invention The product exhibits excellent flame retardancy.

  Furthermore, in the resin composition of the present invention, since the layered silicate is finely dispersed in a nanometer size, when a perforation process is performed on the substrate or the like made of the resin composition of the present invention by a laser such as a carbon dioxide laser, The resin component and the layered silicate component are simultaneously decomposed and evaporated, and the partially remaining layered silicate residue is only a small one of several μm or less and can be easily removed by desmearing. Thereby, it is possible to prevent the occurrence of defective plating due to the residue generated by the drilling process.

  The method for dispersing the layered silicate in the resin is not particularly limited, for example, a method using an organically modified layered silicate, a method of foaming the resin with a foaming agent after mixing the resin and the layered silicate by a conventional method, Examples thereof include a method using a dispersant. By using these dispersion methods, the layered silicate can be more uniformly and finely dispersed in the resin.

  In the method in which the resin and the layered silicate are mixed by a conventional method and the resin is foamed with a foaming agent, the energy of foaming is used for the dispersion of the layered silicate.

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

  The method of foaming the resin with a foaming agent after mixing the resin and the layered silicate by a conventional method is not particularly limited. For example, a gaseous foaming agent is added to a resin composition comprising the resin and the layered silicate under high pressure. A method in which the gaseous foaming agent is vaporized in the resin composition to form a foam after impregnation with the above-mentioned method; a thermally decomposable foaming agent is previously contained between the layers of the layered silicate, and the thermally decomposable foaming agent And a method of decomposing the foam by heating to form a foam.

  The minimum of the compounding quantity with respect to 100 weight part of said thermoplastic resins of the said inorganic compound is 0.1 weight part, and an upper limit is 65 weight part. If it is less than 0.1 parts by weight, the effect of improving high-temperature properties and hygroscopicity is reduced. If it exceeds 65 parts by weight, the density (specific gravity) of the resin composition of the present invention will increase, and the mechanical strength will also decrease, making it impractical. The preferred lower limit is 1 part by weight and the upper limit is 60 parts by weight. When the amount is less than 1 part by weight, a sufficient effect of improving high-temperature physical properties may not be obtained when the resin composition of the present invention is thinly molded. If it exceeds 60 parts by weight, the moldability may deteriorate. A more preferred lower limit is 1.5 parts by weight and an upper limit is 50 parts by weight. When the amount is 1.5 to 50 parts by weight, there is no problem in terms of mechanical properties and process suitability, and sufficient flame retardancy is obtained.

  In the resin composition of the present invention, when a layered silicate is used as the inorganic compound, the lower limit of the amount of the layered silicate is preferably 0.5 parts by weight, and the upper limit is preferably 50 parts by weight. If it is less than 0.5 parts by weight, the effect of improving high-temperature properties and hygroscopicity may be reduced. If it exceeds 50 parts by weight, the density (specific gravity) of the resin composition of the present invention is increased, and the mechanical strength is also decreased, so that it may be impractical. A more preferred lower limit is 1 part by weight and an upper limit is 45 parts by weight. If it is less than 1 weight, sufficient improvement of the high-temperature properties may not be obtained when the resin composition of the present invention is thinly molded. If it exceeds 45 parts by weight, the dispersibility of the layered silicate may deteriorate. A more preferred lower limit is 1.5 parts by weight, and an upper limit is 40 parts by weight. When the amount is 1.5 to 40 parts by weight, there is no region causing problems in process suitability, sufficiently low water absorption is obtained, and the effect of reducing the average linear expansion coefficient is sufficiently obtained even in both the α1 and α2 regions. It is done.

  The resin composition of the present invention preferably further contains a flame retardant that does not contain a halogen-based composition. It should be noted that a trace amount of halogen may be mixed due to the manufacturing process of the flame retardant.

  The flame retardant is not particularly limited. For example, metal hydroxide such as aluminum hydroxide, magnesium hydroxide, dawsonite, calcium aluminate, dihydrate gypsum, calcium hydroxide; metal oxide; red phosphorus or polyphosphoric acid Phosphorus compounds such as ammonium; Nitrogen compounds such as melamine, melamine cyanurate, melamine isocyanurate, melamine phosphate and melamine derivatives obtained by surface treatment thereof; fluororesins; silicone oils; layered double water such as hydrotalcite Japanese products: silicone-acrylic composite rubber and the like. Of these, metal hydroxides and melamine derivatives are preferred. Among the metal hydroxides, magnesium hydroxide and aluminum hydroxide are particularly preferable, and these may be subjected to surface treatment with various surface treatment agents. The surface treatment agent is not particularly limited, and examples thereof include a silane coupling agent, a titanate coupling agent, a PVA surface treatment agent, and an epoxy surface treatment agent. These flame retardants may be used alone or in combination of two or more.

  When a metal hydroxide is used as the flame retardant, the lower limit of the preferable blending amount of the metal hydroxide with respect to 100 parts by weight of the thermoplastic resin is 0.1 part by weight, and the upper limit is 100 parts by weight. If it is less than 0.1 part by weight, the flame retarding effect may not be sufficiently obtained. If it exceeds 100 parts by weight, the density (specific gravity) of the resin composition of the present invention may become too high, resulting in poor practicality and extremely low flexibility and elongation. A more preferred lower limit is 5 parts by weight and an upper limit is 80 parts by weight. When it is less than 5 parts by weight, a sufficient flame retarding effect may not be obtained when the resin composition of the present invention is thinly molded. If it exceeds 80 parts by weight, the defect rate due to blistering or the like may increase in the step of performing high temperature treatment. A more preferred lower limit is 10 parts by weight and an upper limit is 70 parts by weight. When the amount is in the range of 10 to 70 parts by weight, there is no region causing problems in mechanical properties, electrical properties, process suitability, etc., and sufficient flame retardancy is exhibited.

  When a melamine derivative is used as the flame retardant, the lower limit of the preferred blending amount of the melamine derivative with respect to 100 parts by weight of the thermoplastic resin is 0.1 part by weight, and the upper limit is 100 parts by weight. If it is less than 0.1 part by weight, the flame retarding effect may not be sufficiently obtained. If it exceeds 100 parts by weight, mechanical properties such as flexibility and elongation may be extremely lowered. A more preferred lower limit is 5 parts by weight and an upper limit is 70 parts by weight. If it is less than 5 parts by weight, a sufficient flame retarding effect may not be obtained when the insulating substrate is thinned. If it exceeds 70 parts by weight, mechanical properties such as flexibility and elongation may be extremely lowered. A more preferred lower limit is 10 parts by weight and an upper limit is 50 parts by weight. When the amount is in the range of 10 to 50 parts by weight, there is no region causing problems in mechanical properties, electrical properties, process suitability, etc., and sufficient flame retardancy is exhibited.

  The resin composition of the present invention includes, as necessary, thermoplastic elastomers, crosslinked rubber, oligomers, nucleating agents, oxidizers, and the like for the purpose of modifying the properties within a range that does not hinder achievement of the present invention. Additives such as inhibitors (anti-aging agents), heat stabilizers, light stabilizers, UV absorbers, lubricants, flame retardant aids, antistatic agents, antifogging agents, fillers, softeners, plasticizers, colorants, etc. May be blended. These may be used alone or in combination of two or more.

  The thermoplastic elastomers are not particularly limited, and examples thereof include styrene elastomers, olefin elastomers, urethane elastomers, and polyester elastomers. In order to enhance the compatibility with the resin, these thermoplastic elastomers may be functional group-modified. These thermoplastic elastomers may be used alone or in combination of two or more.

  The crosslinked rubber is not particularly limited, and examples thereof include isoprene rubber, butadiene rubber, 1,2-polybutadiene, styrene-butadiene rubber, nitrile rubber, butyl rubber, ethylene-propylene rubber, silicone rubber, and urethane rubber. In order to enhance the compatibility with the resin, it is preferable that these crosslinked rubbers are functional group-modified. The functional group-modified crosslinked rubber is not particularly limited, and examples thereof include epoxy-modified butadiene rubber and epoxy-modified nitrile rubber. These crosslinked rubbers may be used alone or in combination of two or more.

  The oligomers are not particularly limited, and examples thereof include maleic anhydride-modified polyethylene oligomers. These oligomers may be used independently and 2 or more types may be used together.

  The method for producing the resin composition of the present invention is not particularly limited. For example, each predetermined amount of a resin and an inorganic compound, and each predetermined amount of one or more additives blended as necessary, Direct kneading method of directly blending and kneading at normal temperature or under heating, and a method of removing the solvent after mixing in a solvent; previously blending a predetermined amount or more of an inorganic compound in the resin or a resin other than the resin Then, a master batch kneaded is prepared, and this master batch, the remainder of the predetermined amount of the resin, and each predetermined amount of one or more additives to be blended as necessary are at room temperature or heated. Below, the masterbatch method etc. which knead | mix or mix in a solvent are mentioned.

  In the master batch method, a master batch in which an inorganic compound is blended with the resin or a resin other than the resin, and a master batch dilution resin containing the resin used when the master batch is diluted to a predetermined inorganic compound concentration The compositions may be the same composition or different compositions.

  The masterbatch is not particularly limited. For example, at least one resin selected from the group consisting of a polyamide resin, a polyphenylene ether resin, a polyether sulfone resin, and a polyester resin, in which an inorganic compound can be easily dispersed, is used. It is preferable to contain. Although it does not specifically limit as said resin composition for masterbatch dilution, For example, at least 1 sort (s) selected from the group which consists of a thermoplastic polyimide resin excellent in the high temperature physical property, polyetheretherketone resin, thermoplastic polybenzoimidazole resin It is preferable to contain this resin.

  Although the compounding quantity of the inorganic compound in the said masterbatch is not specifically limited, The preferable minimum with respect to 100 weight part of resin is 1 weight part, and an upper limit is 500 weight part. When the amount is less than 1 part by weight, the convenience as a master batch that can be diluted to an arbitrary concentration is reduced. If it exceeds 500 parts by weight, the dispersibility in the master batch itself, and particularly the dispersibility of the inorganic compound when diluted to a predetermined blending amount by the master batch dilution resin composition may deteriorate. A more preferred lower limit is 5 parts by weight and an upper limit is 300 parts by weight.

  Further, for example, by using an inorganic compound containing a polymerization catalyst (polymerization initiator) such as a transition metal complex, a thermoplastic resin monomer and an inorganic compound are kneaded, and the above monomer is polymerized, thereby thermoplastic resin. You may use the method of performing simultaneously superposition | polymerization and manufacture of a resin composition collectively.

  The method for kneading the mixture in the method for producing the resin composition of the present invention is not particularly limited, and examples thereof include a method for kneading using a kneader such as an extruder, two rolls, and a Banbury mixer.

  The resin composition of the present invention is a combination of a resin and an inorganic compound, and has a low linear expansion coefficient at a high temperature due to an increase in Tg and heat-resistant deformation temperature due to molecular chain restraint. Excellent mechanical properties and transparency.

  Furthermore, gas molecules are much easier to diffuse in the resin than inorganic compounds, and when diffusing in the resin, the gas molecules diffuse while bypassing the inorganic compound, so the gas barrier properties are also improved. Similarly, barrier properties against other than gas molecules are improved, and solvent resistance, hygroscopicity, water absorption and the like are improved. Thereby, for example, copper migration from a copper circuit in a multilayer printed wiring board can be suppressed. Furthermore, it is possible to suppress the occurrence of defects such as defective plating due to bleed-out of trace additives in the resin on the surface.

In the resin composition of the present invention, if layered silicate is used as the inorganic compound, excellent mechanical properties can be obtained without adding a large amount, and thus a thin insulating substrate can be obtained. Density and thickness can be reduced. In addition, improvement in dimensional stability based on a nucleation effect of layered silicate in crystal formation and a swelling suppression effect accompanying improvement in moisture resistance, and the like have been attempted. Furthermore, since a sintered body made of layered silicate is formed at the time of combustion, the shape of the combustion residue is maintained, the shape does not collapse after the combustion, the spread of fire can be prevented, and excellent flame retardancy is exhibited.
Moreover, in the resin composition of this invention, if a non-halogen flame retardant is used, it is possible to achieve both high mechanical properties and high flame retardancy while considering the environment.

  The use of the resin composition of the present invention is not particularly limited. For example, a core layer or a build-up layer of a multilayer substrate is formed by processing in a suitable solvent or by forming into a film. It is suitably used for substrate materials, sheets, laminates, copper foils with resin, copper-clad laminates, TAB tapes, printed boards, prepregs, varnishes and the like. Substrate materials, sheets, laminates, resin-coated copper foils, copper-clad laminates, TAB tapes, printed boards, prepregs, and adhesive sheets using the resin composition of the present invention are also one aspect of the present invention. .

  The molding method is not particularly limited. For example, an extrusion molding method in which an extruder is melted and kneaded and then extruded and formed into a film using a T-die or a circular die; dissolved in a solvent such as an organic solvent or Casting molding method in which the material is dispersed and then cast into a film shape; in a varnish obtained by dissolving or dispersing in a solvent such as an organic solvent, a cloth-like or non-woven fabric made of an inorganic material such as glass or an organic polymer Examples include a dipping molding method in which a substrate is dipped to form a film. Among these, the extrusion molding method is suitable for reducing the thickness of the multilayer substrate. In addition, it does not specifically limit as a base material used in the said dipping molding method, For example, a glass cloth, an aramid fiber, a polyparaphenylene benzoxazole fiber etc. are mentioned.

  The substrate material, sheet, laminate, copper foil with resin, copper-clad laminate, TAB tape, printed circuit board, prepreg, adhesive sheet and optical circuit forming material of the present invention are composed of the resin composition of the present invention. Therefore, it is excellent in high temperature physical properties, dimensional stability, solvent resistance, moisture resistance and barrier properties, and can be obtained with a high yield even when manufactured through multiple processes. In the present specification, the sheet includes a film-like sheet having no self-supporting property. In addition, in order to improve the sliding of these sheets, the surface may be embossed.

  In the case of a thermoplastic resin, not only the equipment and the manufacturing cost are reduced, but also the above-mentioned processing can be performed at the same time as the sheet is formed, or it can be post-processed by a simple method and is excellent in formability. Moreover, it can be reused by melting, and has the advantage of reducing the environmental load.

  In addition, the resin composition of the present invention has a low linear expansion coefficient, heat resistance, low water absorption, and high transparency because the layered silicate is finely dispersed in a nanometer size in the thermoplastic resin. Can also be realized. Therefore, the resin composition of the present invention can be suitably used as an optical circuit forming material such as an optical package forming material, an optical waveguide material, a connecting material, and a sealing material.

  According to the present invention, a resin composition, a substrate material, a sheet, a laminate, a resin-coated copper foil, a copper-clad, excellent in mechanical properties, dimensional stability, heat resistance, flame retardancy, etc., and particularly excellent in high-temperature properties. A laminate, a TAB tape, a printed board, a prepreg, an adhesive sheet, and an optical circuit forming material can be provided.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

( Reference Example 1)
In a small extruder (manufactured by Nippon Steel Works, TEX30), 100 parts by weight of modified polyphenylene ether resin (Asahi Kasei Kogyo Co., Ltd., Zylon (PKL) X9102) as a thermoplastic resin, distearyldimethyl quaternary ammonium as a layered silicate Feeding 30 parts by weight of swellable fluorine mica (Somasif MAE-100, manufactured by Co-op Chemical Co., Ltd.) that has been organically treated with salt, melted and kneaded at 290 ° C. and extruded into a strand, and the extruded strand was pulverized by a pelletizer. A master batch was prepared by pelletizing. Next, 100 parts by weight of a polyimide resin (Mitsui Chemicals, Aurum PD-450) as a thermoplastic resin and 9.5 parts by weight of the obtained master batch were fed into a small extruder (manufactured by Nippon Steel Works, TEX30). Then, the mixture was melt-kneaded and extruded at 420 ° C. under a nitrogen stream, and the extruded strand was pelletized with a pelletizer to obtain pellets made of the resin composition. Subsequently, the pellets made of the resin composition were rolled by pressing them with a hot press adjusted to 420 ° C. in the up and down directions under a nitrogen stream, and a plate-like molded body having a thickness of 2 mm and 100 μm made of the resin composition. Was made.

( Reference Example 2)
In a small extruder (manufactured by Nippon Steel Works, TEX30), 100 parts by weight of modified polyphenylene ether resin (Asahi Kasei Kogyo Co., Ltd., Zylon (PKL) X9102) as a thermoplastic resin, distearyldimethyl quaternary ammonium as a layered silicate Feeding 30 parts by weight of swellable fluorine mica (Somasif MAE-100, manufactured by Co-op Chemical Co., Ltd.) that has been organically treated with salt, melted and kneaded at 280 ° C., extruded into a strand, and the extruded strand was pulverized by a pelletizer. A master batch was prepared by pelletizing. Next, 100 parts by weight of polyetheretherketone as a thermoplastic resin and 9.5 parts by weight of the obtained master batch were fed into a small extruder (manufactured by Nippon Steel Works, TEX30) and melted at 400 ° C. in a nitrogen stream. The pellets made of the resin composition were obtained by kneading and extruding, and pelletizing the extruded strand with a pelletizer. Subsequently, the pellets made of the resin composition were rolled by pressing them with a hot press adjusted to 400 ° C. in the upper and lower directions under a nitrogen stream, and a plate-like molded body having a thickness of 2 mm and 100 μm made of the resin composition. Was made.

( Reference Example 3)
66.12 parts by weight of bis [4- (3-aminophenoxy) phenyl] sulfone is weighed into a 500 ml separable flask, 370 parts by weight of dehydrated N-methylpyrrolidone is added, and after purging with nitrogen, the mixture is stirred at 150 rpm for about 30 minutes. did. Subsequently, 33.72 parts by weight of pyromellitic anhydride and 40 parts by weight of dehydrated N-methylpyrrolidone were added and stirred at 150 rpm for 1 hour. Subsequently, 253.2 parts by weight of N-methylpyrrolidone solution containing 7.9% synthetic hectorite (manufactured by Corp Chemical Co., Lucentite STN), 0.001 part by weight of aniline, and 40 parts by weight of dehydrated N-methylpyrrolidone at 600 rpm. Stirring was performed for 4 hours to obtain a clay-containing polyamic acid solution.

  The obtained polyamic acid solution was heated to a high temperature to dilute most of the solvent into a film, and then heated to a higher temperature to cause the reaction to proceed to imidization. A master batch of clay-containing polyimide was obtained. Next, 100 parts by weight of a thermoplastic resin (trade name “Aurum PD-450” (manufactured by Sankyo Chemical Co., Ltd.)) and 43 parts by weight of the obtained master batch were put into a small extruder (manufactured by Nippon Steel Works, TEX30), and nitrogen was added. The mixture was melt-kneaded and extruded at 420 ° C. under an air stream, and the extruded strand was pelletized with a pelletizer to obtain pellets of the resin composition. It pressed and rolled with the hot press each temperature-controlled at 400 degreeC, and produced the plate-shaped molded object of thickness 2mm and 100 micrometers.

(Example 1 )
47.24 parts by weight of 1,3-bis (4-aminophenoxy) benzene (Wako Pure Chemical Industries, Ltd.) was weighed in a 500 ml separable flask, and 370 parts by weight of dehydrated N-methylpyrrolidone (Wako Pure Chemical Industries, Ltd.) was added. After adding and replacing with nitrogen, the mixture was stirred at 150 rpm for about 30 minutes. Next, 52.60 parts by weight of 3,3′4,4′-benzophenonetetracarboxylic dianhydride (manufactured by Daicel Chemical Industries, BTDA-BFS-06) and 40 parts by weight of dehydrated N-methylpyrrolidone were added, and 150 rpm For 1 hour. Subsequently, 253.2 parts by weight of 3.9% synthetic mica (1,2-dimethyl-3-N-decyl-imidazolium-treated synthetic mica) -containing N-methylpyrrolidone solution, aniline (manufactured by Wako Pure Chemical Industries), 0. 002 parts by weight and 40 parts by weight of dehydrated N-methylpyrrolidone were stirred at 600 rpm for 4 hours to obtain a clay-containing polyamic acid solution. The resulting polyamic acid solution was solvent dried and imidized to obtain a clay-containing polyimide master batch. Next, 100 parts by weight of Aurum (Mitsui Chemicals, PD-450) as a thermoplastic resin and 25 parts by weight of the obtained master batch were put into a small extruder (manufactured by Nippon Steel Works, TEX30). The resin composition pellets were obtained by melting and kneading at 420 ° C. and extruding, and pelletizing the extruded strands with a pelletizer. Next, the obtained pellets of the resin composition were pressed and rolled with a hot press adjusted to 400 ° C. above and below under a nitrogen stream, and 2 mm and 100 μm thick plate-like molded bodies were produced.

( Reference Example 4 )
66.12 parts by weight of bis [4- (3-aminophenoxy) phenyl] sulfone is weighed into a 500 mL separable flask, 370 parts by weight of dehydrated dimethylformamide (DMF) is added, and after purging with nitrogen, the mixture is stirred at 150 rpm for about 30 minutes. did. Subsequently, 33.72 parts by weight of pyromellitic anhydride and 40 parts by weight of dehydrated dimethylformamide (DMF) were added and stirred at 150 rpm for 1 hour. Subsequently, 253.2 parts by weight of DMF solution containing 7.9% synthetic hectorite (manufactured by Corp Chemical Co., Lucentite STN), 0.001 part by weight of aniline, and 40 parts by weight of dehydrated DMF were stirred at 600 rpm for 4 hours. A containing polyamic acid solution was obtained.

  The resulting polyamic acid solution was dried with a solvent and imidized to obtain a clay-containing polyimide master batch. Next, in a small extruder (Nippon Steel Works, TEX30), 100 parts by weight of Aurum (Mitsui Chemicals, PD-450) as a thermoplastic resin, 17.6 parts by weight of the obtained master batch, aluminum borate whisker 10 parts by weight (manufactured by Shikoku Kasei Kogyo Co., Ltd.) was charged, melt kneaded and extruded at 420 ° C. under a nitrogen stream, and pellets of the extruded strands were obtained by pelletizing with a pelletizer. Next, the obtained pellets of the resin composition were pressed and rolled with a hot press adjusted to 400 ° C. above and below under a nitrogen stream, and 2 mm and 100 μm thick plate-like molded bodies were produced.

( Reference Example 5 )
47.24 parts by weight of 1,3-bis (4-aminophenoxy) benzene was weighed into a 500 mL separable flask, 370 parts by weight of dehydrated N-methylpyrrolidone (NMP) was added, and after substitution with nitrogen, about 30 at 150 rpm. Stir for minutes. Subsequently, 52.60 parts by weight of 3,3′4,4′-benzophenonetetracarboxylic dianhydride and 40 parts by weight of dehydrated NMP were added and stirred at 150 rpm for 1 hour. Subsequently, 253.2 parts by weight of NMP solution containing 3.9% synthetic mica (manufactured by Coop Chemical Co., Somasifu MPE), 0.002 parts by weight of aniline, and 40 parts by weight of dehydrated NMP were stirred at 600 rpm for 4 hours to contain clay. A polyamic acid solution was obtained.

  The resulting polyamic acid solution was dried with a solvent and imidized to obtain a clay-containing polyimide master batch. Then, in a small extruder (Nippon Steel Works, TEX30), 100 parts by weight of Aurum (Mitsui Chemicals, PD-450) as a thermoplastic resin, 25 parts by weight of the master batch obtained, silicon carbide whisker (Toyo Carbon Co., Ltd.) 8 parts by weight were charged, melt-kneaded and extruded at 420 ° C. under a nitrogen stream, and the extruded strand was pelletized with a pelletizer to obtain pellets of the resin composition. Next, the obtained pellets of the resin composition were pressed and rolled with a hot press adjusted to 400 ° C. above and below under a nitrogen stream, and 2 mm and 100 μm thick plate-like molded bodies were produced.

( Reference Example 6 )
In a small extruder (manufactured by Nippon Steel Works, TEX30), 100 parts by weight of Aurum (made by Mitsui Chemicals, PD-450M) as thermoplastic resin, 3 parts by weight of synthetic mica (manufactured by Corp Chemical, Somasif MPE), nitrogen The mixture was melt kneaded and extruded at 330 ° C. under an air stream, and the extruded strand was pelletized with a pelletizer to obtain resin composition pellets. Next, the obtained pellets of the resin composition were pressed and rolled with a hot press adjusted to 340 ° C. in the upper and lower directions under a nitrogen stream to produce a plate-like molded body having a thickness of 2 mm and 100 μm.

(Example 2 )
In a small extruder (Nippon Steel Works, TEX30), 100 parts by weight of Aurum (Mitsui Chemicals, PD-450) as a thermoplastic resin, synthetic mica (1,2-dimethyl-3-N-decyl-imidazo) (Thrium-treated synthetic mica) 3 parts by weight, 15 parts by weight of silica (manufactured by Admatechs, SO-E5) are charged, melt-kneaded and extruded at 420 ° C. under a nitrogen stream, and the extruded strand is pelletized by a pelletizer. Thus, pellets of the resin composition were obtained. Next, the obtained pellets of the resin composition were pressed and rolled with a hot press adjusted to 400 ° C. above and below under a nitrogen stream, and 2 mm and 100 μm thick plate-like molded bodies were produced.

( Reference Example 7 )
After weighing 92.3 g of isobornyl acrylate into a 500 ml flask and adding 77.0 g of a dimethylformamide (DMF) solution containing 10% by weight of synthetic hectorite (Corp Chemical, Lucentite STN) to this flask. Stirring was performed for 1 hour to obtain a clay-containing isobornyl acrylate solution. Subsequently, DMF was distilled off from the clay-containing isobornyl acrylate solution obtained in an oven stream at 80 ° C. to obtain clay-containing isobornyl acrylate. 0.9 g of a photopolymerization initiator (Irgacure 651, manufactured by Ciba Specialty Chemical Co., Ltd.) was added to the resulting clay-containing isobornyl acrylate to obtain a uniform state, and then ultraviolet rays at 365 nm were applied at an illuminance of 1 mW / cm ² . Irradiated for 1 minute, and further heat-pressed at 160 ° C. to produce a plate-like molded body having a thickness of 2 mm and a thickness of 100 μm made of the resin composition.

( Reference Example 8 )
92.3 g of methyl methacrylate was weighed into a 1000 ml flask, 77.0 g of methyl ethyl ketone (MEK) solution containing 10% by weight of synthetic hectorite (manufactured by Corp Chemical, Lucentite STN) and 200 g of MEK were added to the flask. The mixture was stirred at 80 ° C. Then, an AIBN solution consisting of 2.5 g of azoisobutyronitrile (AIBN) and 100 ml of MEK was added in 20 ml portions every 5 hours to a flask that was stirred at 80 ° C. in a hot water bath. , Held at 80 ° C. for a further 2 hours after the last addition. MEK was distilled off from the resulting reaction mixture by heating and drying under reduced pressure, followed by hot pressing at 160 ° C. to produce a plate-like molded body having a thickness of 2 mm and a thickness of 100 μm made of the resin composition.

(Comparative Example 1)
Except that no swellable fluorine mica (manufactured by Co-op Chemical Co., Ltd., Somasif MAE-100) was blended, a resin composition and a plate-like molding having a thickness of 2 mm and 100 μm comprising the resin composition were the same as in Reference Example 1. The body was made.

(Comparative Example 2)
Except that no swellable fluorine mica (manufactured by Co-op Chemical Co., Ltd., Somasif MAE-100) was blended, a resin composition and a plate-like molding having a thickness of 2 mm and 100 μm comprising the resin composition were the same as in Reference Example 2. The body was made.

(Comparative Example 3)
Except that synthetic hectorite (Coop Chemical Co., Lucentite STN) was not blended, a resin composition, and a plate-shaped molded article having a thickness of 2 mm and 100 μm made of the resin composition were used in the same manner as in Reference Example 3. Produced.

(Comparative Example 4)
A resin composition and a thickness of 2 mm made of the resin composition were the same as in Example 1 except that synthetic mica (1,2-dimethyl-3-N-decyl-imidazolium-treated synthetic mica) was not blended. And the 100-micrometer plate-shaped molded object was produced.

(Comparative Example 5)
Except that synthetic hectorite (Coop Chemical Co., Lucentite STN) was not blended, a resin composition and a plate-shaped molded article having a thickness of 2 mm and 100 μm comprising the resin composition were obtained in the same manner as in Reference Example 4. Produced.

(Comparative Example 6)
A resin composition and a plate-like molded article having a thickness of 2 mm and 100 μm made of the resin composition were prepared in the same manner as in Reference Example 5 except that synthetic mica (manufactured by Co-op Chemical Co., Ltd., Somasif MPE) was not blended. .

(Comparative Example 7)
A resin composition and a plate-like molded article having a thickness of 2 mm and 100 μm made of the resin composition were prepared in the same manner as in Reference Example 6 except that synthetic mica (manufactured by Co-op Chemical Co., Ltd., Somasif MPE) was not blended. .

(Comparative Example 8)
A resin composition and a thickness of 2 mm comprising the resin composition were the same as in Example 2 except that synthetic mica (1,2-dimethyl-3-N-decyl-imidazolium-treated synthetic mica) was not blended. And the 100-micrometer plate-shaped molded object was produced.

(Comparative Example 9)
Except that the blending amount of silica (manufactured by Admatechs, SO-E5) was changed to 60 parts by weight, and synthetic mica (1,2-dimethyl-3-N-decyl-imidazolium-treated synthetic mica) was not blended Produced a resin composition and a plate-shaped molded article having a thickness of 2 mm and 100 μm comprising the resin composition in the same manner as in Example 2 .

(Comparative Example 10)
0.9 g of a photopolymerization initiator (Ibusacure 651, manufactured by Ciba Specialty Chemicals) was added to 92.3 g of isobornyl acrylate to obtain a uniform state, and then irradiated with 365 nm ultraviolet rays at an illuminance of 1 mW / cm ² for 10 minutes. Further, hot pressing was performed at 160 ° C. to prepare a plate-like molded body having a thickness of 2 mm and 100 μm made of the resin composition.

<Evaluation>
The performance of the plate-shaped molded bodies produced in Examples 1 and 2, Reference Examples 1 to 8 and Comparative Examples 1 to 10 was evaluated for the following items. In addition, about the plate-shaped molded object produced in Reference Examples 4 and 5 and Comparative Examples 5 and 6, the elastic modulus was also evaluated. The results are shown in Tables 1 and 2.

(1) Measurement of coefficient of thermal expansion A test piece cut to 3 mm × 25 mm by cutting a plate-shaped molded body was heated at a rate of 5 ° C. using a TMA (Thermal Mechanical Analysis) apparatus (manufactured by Seiko Denshi, TMA / SS120C). The average linear expansion coefficient (hereinafter sometimes referred to as “CTE”) was measured, and the following items were evaluated.

The average linear expansion coefficient (α2) [° C. ⁻¹ ] at a temperature 10 ° C. to 50 ° C. higher than the glass transition temperature of the resin composition.

  The average linear expansion coefficient (α2) at a temperature 10 ° C. to 50 ° C. higher than the glass transition temperature of the resin composition is 50 ° C. to 10 ° C. lower than the glass transition temperature of the resin composition. Average linear expansion coefficient ratio (α2 / α1) obtained by dividing by (α1).

· 50-100 average linear expansion coefficient at ° C. [° C. ^-1] and 200 to 240 average coefficient of linear expansion at ℃ [℃ ^-1].

  -Average linear expansion coefficient ratio (1) obtained by dividing the average linear expansion coefficient at 150 to 200 ° C by the average linear expansion coefficient at 50 to 100 ° C, and the average linear expansion coefficient at 250 to 300 ° C Is an average linear expansion coefficient ratio (2) obtained by dividing by the average linear expansion coefficient at 50 to 100 ° C.

  A rate of change (%) obtained by dividing the amount of change in length when the plate-shaped molded body was heated from 25 ° C. to 300 ° C. by the length of the plate-shaped molded body at 25 ° C.

  -Average linear expansion coefficient ratio (3) represented by said Formula (1).

  The average linear expansion coefficient at a temperature 10 ° C. to 50 ° C. higher than the Tg of the resin composition is 10 ° C. to 50 ° C. higher than the Tg of the resin composition prepared in the comparative example corresponding to each example. The improvement rate obtained by dividing by the average linear expansion coefficient.

(2) Average interlayer distance of layered silicate Using an X-ray diffractometer (RINT1100, manufactured by Rigaku Corporation), a diffraction peak obtained from diffraction of the layered surface of the layered silicate in a 2 mm thick plate-shaped body. 2θ was measured, the (001) plane spacing d of the layered silicate was calculated from the black diffraction formula of the following formula (5), and the obtained d was defined as the average interlayer distance (nm).

λ = 2 dsin θ (5)
In the above formula (5), λ is 0.154, and θ represents the diffraction angle.

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

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

(5) Measurement of humidity coefficient of linear expansion The dimension (L1) after leaving a plate-shaped molded article having a thickness of 100 μm in a constant temperature and humidity chamber at 50 ° C. and 30% Rh for 24 hours was measured. Subsequently, the dimension (L2) after leaving a plate-shaped molded object for 24 hours in a constant temperature and humidity chamber of 50 degreeC80% Rh was measured. The coefficient of linear thermal expansion was determined by the following formula.
Humidity coefficient of linear expansion [% RH-1] = (L2-L1) / L1 / (80-30)

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

(7) Measurement of elastic modulus Measurement was performed by a method according to JIS K 6301.

(8) Measurement of solubility parameter It calculated with the formula of Fedors.

(9) Measurement of heating 10% weight loss temperature After 5 to 10 mg of sample was dried at 150 ° C. for 5 hours, it was measured using a TG / DTA apparatus (Seiko Electronics Co., Ltd., TG / DTA320) under the following measurement conditions. did.

Measurement temperature: 25-600 ° C
Temperature increase rate: 10 ° C / min
Nitrogen gas: 200 ml / min

Claims (20)

A thermoplastic resin composition comprising 100 parts by weight of a thermoplastic resin and an inorganic compound 0.1 to 65 parts by weight comprising a thermoplastic polyimide,
The inorganic compound includes a layered silicate containing a heterocyclic quaternary ammonium ion,
From 10 ° C. higher than the glass transition temperature of the thermoplastic resin composition, average coefficient of linear expansion of up to 50 ° C. higher than the glass transition temperature of the thermoplastic resin composition ([alpha] 2) is 3.0 × 10 ^-3 [ C < ^-1 >] or less, The thermoplastic resin composition characterized by the above-mentioned. From 10 ° C. higher than the glass transition temperature of the thermoplastic resin composition, average coefficient of linear expansion of up to 50 ° C. higher than the glass transition temperature of the thermoplastic resin composition ([alpha] 2) is 1.0 × 10 ^-3 [ The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is not higher than [° C. ⁻¹ ]. Glass from 10 ° C. higher than the glass transition temperature of the thermoplastic resin composition, average coefficient of linear expansion up to a temperature higher 50 ° C. than the glass transition temperature of the thermoplastic resin composition ([alpha] 2), the thermoplastic resin composition Average linear expansion coefficient ratio (α2 / α1) obtained by dividing by an average linear expansion coefficient (α1) from a temperature 50 ° C. lower than the transition temperature to a temperature lower by 10 ° C. than the glass transition temperature of the thermoplastic resin composition The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is 70 or less. Glass from 10 ° C. higher than the glass transition temperature of the thermoplastic resin composition, average coefficient of linear expansion up to a temperature higher 50 ° C. than the glass transition temperature of the thermoplastic resin composition ([alpha] 2), the thermoplastic resin composition Average linear expansion coefficient ratio (α2 / α1) obtained by dividing by an average linear expansion coefficient (α1) from a temperature 50 ° C. lower than the transition temperature to a temperature lower by 10 ° C. than the glass transition temperature of the thermoplastic resin composition The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is 15 or less. The average linear expansion coefficient at 50 to 100 ° C. is 4.5 × 10 ⁻⁵ [° C. ⁻¹ ] or less, and the average linear expansion coefficient at 200 to 240 ° C. is 7 × 10 ⁻⁵ [° C. ⁻¹ ]. It is the following, The thermoplastic resin composition of any one of Claims 1-4 characterized by the above-mentioned. The average linear expansion coefficient ratio (1) obtained by dividing the average linear expansion coefficient at 150 to 200 ° C. by the average linear expansion coefficient at 50 to 100 ° C. is 2.0 or less, and 250 to 300 ° C. 6. The average linear expansion coefficient ratio (2) obtained by dividing the average linear expansion coefficient by the average linear expansion coefficient at 50 to 100 [deg.] C. is 20 or less. 2. The thermoplastic resin composition according to item 1. The amount of change in length when a resin piece made of a thermoplastic resin composition was heated from 25 ° C. to 300 ° C. was obtained by dividing the amount of change in length of the resin piece made of a thermoplastic resin composition at 25 ° C. Change rate is 7% or less, The thermoplastic resin composition of any one of Claims 1-6 characterized by the above-mentioned. From 10 ° C. higher than the glass transition temperature of the thermoplastic resin composition, the average coefficient of linear expansion of the thermoplastic resin composition to a temperature 50 ° C. than the glass transition temperature of the thermoplastic resin composition, the glass of the resin The improvement rate obtained by dividing by the average linear expansion coefficient of the resin from a temperature 10 ° C. higher than the transition temperature to a temperature higher by 50 ° C. than the glass transition temperature of the resin is 0.50 or less. The thermoplastic resin composition according to any one of claims 1 to 7. A glass transition temperature is 100 degreeC or more, The thermoplastic resin composition of any one of Claims 1-8 characterized by the above-mentioned. The thermoplastic resin includes a polyphenylene ether resin, a functional group-modified polyphenylene ether resin, a polyphenylene ether resin or a mixture of a functional group-modified polyphenylene ether resin and a polystyrene resin, an alicyclic hydrocarbon resin, and a polyether ether ketone resin. Thermoplastic according to any one of claims 1 to 9, comprising at least one selected from the group consisting of a polyesterimide resin, a polyetherimide resin, and a thermoplastic polybenzimidazole resin . Resin composition. The thermoplastic resin composition according to any one of claims 1 to 10, comprising 50 parts by weight or less of the layered silicate with respect to 100 parts by weight of the thermoplastic resin. The thermoplastic resin composition according to any one of claims 1 to 11, comprising 0.5 parts by weight or more of the layered silicate with respect to 100 parts by weight of the thermoplastic resin. The thermoplastic resin composition according to any one of claims 1 to 12, wherein the inorganic compound is a layered silicate. The thermoplastic resin composition according to any one of claims 1 to 12, wherein the inorganic compound comprises at least one of whiskers and / or silica and a layered silicate. 15. The thermoplastic resin according to claim 1, wherein the layered silicate is at least one selected from the group consisting of montmorillonite, hectorite, swellable mica, and vermiculite. Composition. An average interlayer distance of (001) plane measured by wide-angle X-ray diffraction measurement method is 3 nm or more, and a layered silicate in which some or all of the laminates are 5 layers or less is dispersed. The thermoplastic resin composition according to any one of claims 1 to 15. The sheet | seat characterized by using the thermoplastic resin composition of any one of Claims 1-16. A resin-coated copper foil comprising the thermoplastic resin composition according to any one of claims 1 to 16. A printed circuit board comprising the thermoplastic resin composition according to claim 1. A prepreg comprising the thermoplastic resin composition according to any one of claims 1 to 16.