JP2007056233A - Thermosetting resin composition and use thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin composition excellent in adhesivity, processability and heat resistance and further resin flowability and dielectric characteristic in a GHz band, hardly causing defects due to entanglement of bubbles or foaming, and capable of being suitably used for the manufacture of circuit boards or the like, and to provide typical use technologies thereof. <P>SOLUTION: This thermosetting resin composition comprises (A) a polyimide resin component, (B) an epoxy resin component, (C) an epoxy curing agent component and (D) a defoaming agent component. Thereby the thermosetting resin composition and the hardened resin after curing hardly cause defects due to entanglement of bubbles or foaming, and can exhibit well-balanced good characteristics such as adhesivity, processability, heat resistance, resin flowability and dielectric characteristics in a GHz band. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a thermosetting resin composition and use thereof, and particularly includes a polyimide resin component, an epoxy resin component, an epoxy curing agent component, and an antifoaming agent as essential components. The present invention relates to a typical use such as a thermosetting resin composition that can be suitably used for production of a circuit board such as an up circuit board, and a laminate, a circuit board, and the like using the same.

  In order to improve the information processing capability in electronic devices, in recent years, the frequency of electrical signals that transmit circuits on wiring boards used in electronic devices has been increased. For this reason, it is desirable to maintain the electrical reliability of the wiring (circuit) substrate even when the frequency of the electrical signal is increased, and to suppress a decrease in the transmission speed of the electrical signal in the circuit and the loss of the electrical signal.

  By the way, an insulating layer such as a protective film for protecting the wiring board or circuit or an interlayer insulating film for ensuring insulation between layers in the multilayer wiring board is usually formed on the circuit board. Is done. Since the insulating layers such as the protective film and the interlayer insulating film are provided on the wiring board, in addition to the insulating properties, adhesiveness for bonding to the wiring board is also required.

  In particular, when a multilayer printed circuit board is manufactured by laminating a flexible printed circuit board (FPC), a build-up circuit board, etc., the substrates are bonded and fixed together by the interlayer insulating film, and at the same time, The insulating film material fills the space between the circuit wirings to fix the wirings. For this reason, the interlayer insulating film is required to have fluidity enough to fill the space between the circuit wirings together with excellent adhesion to the substrate or the like. Therefore, the insulating layers such as the protective film and the interlayer insulating film are formed using an adhesive material having adhesiveness and resin fluidity.

  When an insulating layer is formed using the adhesive material, the adhesive material (insulating layer) has a characteristic that at least (1) high reliability of the wiring board can be obtained in a GHz (gigahertz) band. Furthermore, (2) it is desirable to have a characteristic that does not adversely affect the transmission of electrical signals. Thereby, as described above, the information processing capability of the electronic device can be improved by increasing the frequency of the electrical signal.

  Here, conventionally, an epoxy adhesive material or a thermoplastic polyimide adhesive material is generally used as the adhesive material used for the wiring board.

  The above-mentioned epoxy-based adhesive material is excellent in workability such as bonding between adherends under low temperature and low pressure conditions and embedding between circuit wiring lines, and excellent adhesion to adherends. Yes.

  The thermoplastic polyimide-based adhesive material has excellent heat resistance such as low thermal expansion below the glass transition temperature of the polyimide resin and high thermal decomposition temperature.

  Furthermore, Patent Document 1 discloses a technique using a film adhesive formed by mixing a polyimide resin, an epoxy compound, and a compound having an active hydrogen group capable of reacting with the epoxy compound.

The film adhesive obtained by this technique enables adhesion between adherends in a short time at a low temperature and also enables heat resistance reliability at a high temperature to be obtained.
JP-A-8-27430 (Publication date: January 30, 1996)

    However, the above-mentioned conventional adhesive material has a problem that its various characteristics are still insufficient for using it for the purpose of manufacturing a wiring board corresponding to the high frequency of electric signals. Specifically, first, in the general epoxy adhesive material, the cured resin (epoxy resin) after curing has a dielectric constant of 4 or more in the GHz band and a dielectric loss tangent of 0.02 or more. Therefore, good dielectric properties cannot be obtained. In contrast, the thermoplastic polyimide-based adhesive material has a dielectric constant of 3.5 or less and a dielectric loss tangent of 0.02 or less in a cured resin (thermoplastic polyimide-based resin) after curing. Excellent dielectric properties. On the other hand, in order to adhere the adherends to each other using the thermoplastic polyimide-based adhesive material, the adherends need to be bonded under high temperature and high pressure conditions, so that the workability is not sufficient. The film adhesive disclosed in Patent Document 1 is a mixture of a polyimide resin and an epoxy compound, and can be bonded at a lower temperature than using a polyimide resin alone, and uses a polyimide resin. As a result, the heat-resistant reliability at high temperatures is superior to that of epoxy-based materials, and it is expected as a material suitable for the production of wiring boards that can cope with higher frequency electrical signals.

  The film adhesive is produced by dissolving each component in a solvent to prepare a resin solution, applying the resin solution to a substrate such as a polyimide film, and drying.

  However, the viscosity of the solution containing the polyimide resin tends to be high, for example, the polyimide resin has a lower affinity or solubility with the solvent than the epoxy resin. For this reason, it is difficult to produce a film with few defects because it tends to bite bubbles during application and drying of the film, or bubbles due to volatilization of the solvent. In addition, as a method for preventing the generation of bubbles due to bubble entrapment or solvent volatilization, there are methods such as diluting a solution and loosening drying conditions. However, a large amount of solvent tends to remain in the film adhesive. If a large amount of the solvent remains, in the manufacture of the circuit board, the solder reflow process tends to cause swelling due to the volatilization of the solvent, that is, the solder heat resistance is impaired.

  Patent Document 1 does not describe bubble entrapment, foaming, or swelling during the production of a film adhesive or a circuit board. Moreover, there is no description about the amount of volatile components, such as a solvent contained in a film adhesive, or solder heat resistance.

Therefore, the film adhesive disclosed in Patent Document 1 has not been realized as a material suitable for manufacturing a wiring board corresponding to high frequency electrical signals.
Therefore, in order to improve the information processing capability of electronic equipment by increasing the frequency of electrical signals, the insulating layer has (i) adhesiveness, (ii) workability and handleability, (iii) heat resistance, (iv In addition to having sufficient resin fluidity, (v) a cured resin after curing is required to exhibit a low dielectric constant and a low dielectric loss tangent even in the GHz band and exhibit sufficient dielectric properties. Therefore, in order to form the said insulating layer, development of the adhesive material which makes the various characteristics of said (i)-(v) sufficient is anticipated.

  The present invention has been made in order to solve the above-described conventional problems, and its purpose is to reduce defects due to entrapment or foaming of a foam, and to provide a circuit board such as a flexible printed wiring board or a build-up circuit board. It is providing the thermosetting resin composition which can be used suitably for manufacture etc., and its typical utilization technique.

  As a result of intensive studies in view of the above problems, the present inventors have made polyimide resin, epoxy resin, and epoxy curing agent as essential components, and further include a defoaming agent, so that the adhesive material and the insulating layer can be foamed. There are few defects and residual volatile components due to dents and foams, and (i) adhesion to adherends such as circuit boards, (ii) processability and handleability that enables adhesion at low temperatures, (iii) thermal expansion and In addition to excellent heat resistance related to thermal decomposition, (iv) the fluidity of the resin necessary for embedding the circuit is specifically improved, and (v) the dielectric constant and dielectric loss tangent of the GHz band in the cured resin after curing. It has been found that the dielectric properties can be lowered and the dielectric properties are excellent, and the present invention has been completed.

  That is, the thermosetting resin composition according to the present invention includes (A) a polyimide resin component containing at least one polyimide resin component and at least one epoxy resin (B) in order to solve the above problems. It comprises at least an epoxy resin component, at least one epoxy curing agent (C) an epoxy curing agent component, and at least one antifoaming agent (D) an antifoaming component. Yes.

  In the said thermosetting resin composition, the weight mixing represented by the weight of the said (D) antifoamer component with respect to the total weight of (A) polyimide resin component, (B) epoxy resin component, and (C) epoxy hardener component. The ratio (D) / [(A) + (B) + (C)] is preferably 0.0001 or more and 0.01 or less.

  In the said thermosetting resin composition, it is preferable that (D) antifoamer component is a silicone type antifoamer.

  In the thermosetting resin composition, the weight mixing ratio (A) / [(() represented by the weight of the (A) polyimide resin component with respect to the total weight of the (B) epoxy resin component and the (C) epoxy curing agent component. B) + (C)] is also preferably in the range of 0.4 to 2.0.

  Moreover, in the said thermosetting resin composition, at least 1 type of polyimide resin contained in (A) polyimide resin component is general formula (1).

（式中、Ｘ_１は、−Ｏ−，−ＣＯ−，−Ｏ−Ｘ_２−Ｏ−，及び，−ＣＯＯ−Ｘ_２−ＯＣＯ−からなる群より選択される２価基であり、Ｘ_２は２価の有機基を表す）で表される構造を有する酸二無水物を少なくとも１種含んでなる酸二無水物成分と、少なくとも１種のジアミンを含んでなるジアミン成分とを反応させて得られるものであることが好ましい。

_{(Wherein, X} 1 is, -O -, - CO -, - O-X 2 -O-, and a divalent radical selected from the group consisting of _-COO-X 2 -OCO-, _{X 2} Represents a divalent organic group), and an acid dianhydride component comprising at least one acid dianhydride having a structure represented by: and a diamine component comprising at least one diamine are reacted. It is preferable to be obtained.

  Moreover, it is preferable that the said thermosetting resin composition contains the (E) inorganic filler component containing at least 1 type of inorganic filler.

  The present invention also includes a semi-cured resin film containing the thermosetting resin composition of the present invention. In the resin film, the amount of volatile components in the resin film is preferably 10% or less of the total resin film weight.

  Furthermore, the present invention includes a laminate comprising at least one resin layer formed using the thermosetting resin composition, and a circuit board using the thermosetting resin composition.

  Further, the present invention provides a laminate comprising a thermoplastic resin layer containing at least one thermoplastic resin formed on both sides or one side of the resin layer, which is formed by using the thermosetting resin composition. In addition, a circuit board using the laminate is also included. The thermoplastic resin layer has a general formula (2)

（但し、式中のＺ_１は同一であっても異なっていてもよく、アルキレン基またはフェニレン基であり、Ｚ_２は同一であっても異なっていてもよく、アルキル基、フェニル基またはフェノキシ基であり、ｈは１以上３０以下の整数を表す）で表わされる構造を有する熱可塑性ポリイミド樹脂であることが好ましい。

(However, Z ₁ in the formula may be the same or different, and is an alkylene group or a phenylene group; Z ₂ may be the same or different; an alkyl group, a phenyl group, or a phenoxy group; And h represents an integer of 1 or more and 30 or less, and is preferably a thermoplastic polyimide resin having a structure represented by:

  As described above, the thermosetting resin composition according to the present invention comprises (A) a polyimide resin component, (B) an epoxy resin component, (C) an epoxy curing agent component, and (D) an antifoaming component. Is included. Thereby, a thermosetting resin composition with few defects and residual volatile components due to foam entrapment and foaming can be obtained as the adhesive material and the insulating layer. In addition, (i) adhesion to an adherend such as a circuit board, (ii) processability and handleability that enables adhesion at low temperature, and (iii) resin fluidity necessary for embedding a circuit are conventional polyimides. It can improve rather than the resin composition which consists of resin and an epoxy resin, and can provide the outstanding thermosetting resin composition. Moreover, since the thermosetting resin composition of this invention can be hardened | cured by heating, it can improve the heat resistance regarding (iv) thermal expansion and thermal decomposition of resin. Moreover, in the cured resin obtained by curing, the dielectric constant and dielectric loss tangent in the GHz band can be made much lower than the resin composition made of epoxy resin by using the polyimide resin. ) A thermosetting resin composition having excellent dielectric properties can be provided.

  Therefore, by using the thermosetting resin composition according to the present invention, compared with conventional resin compositions and thermosetting resin compositions, such as dielectric properties, fluidity, heat resistance, adhesiveness, workability, etc. There is an effect that various characteristics can be realized in a well-balanced manner. In particular, since there are few defects such as bubbles in the film and there are few residual volatile components, it has excellent solder heat resistance. Therefore, flexible prints that require solder heat resistance, low dielectric constant in the GHz band, and low dielectric loss tangent. The effect that it can be used suitably for manufacture of a wiring board, a buildup circuit board, or a laminated body is also produced.

  One embodiment of the present invention will be described in detail below, but the present invention is not limited to the following description.

In the present embodiment, the present invention is described in detail in the order of the outline of the thermosetting resin composition according to the present invention, each component of the thermosetting resin composition, and the use of the thermosetting resin composition. explain.
(I) Thermosetting resin composition according to the present invention The thermosetting resin composition according to the present invention is used for a circuit board such as a flexible printed wiring board or a build-up circuit board, and the circuit board or the circuit board is used. It is used as a protective material for protecting a patterned circuit or an interlayer insulating material for ensuring insulation between layers in a multilayer circuit board.

  The thermosetting resin composition of the present invention comprises (A) a polyimide resin component containing at least one polyimide resin, (B) an epoxy resin component containing at least one epoxy resin, and at least one epoxy curing agent. (C) an epoxy curing agent component, and (D) an antifoaming agent component including at least one kind of antifoaming agent, and (E) an inorganic filler or (F) other as described later. Ingredients may be included. Each component (essential component) of the components (A) to (D) only needs to contain at least one substance classified into each component. In the present invention, among these components, since it contains an antifoaming agent, there are few film defects such as bubbles and residual volatile components with respect to the resin film containing the thermosetting resin composition, Various characteristics such as i) adhesiveness, (ii) workability and handleability, (iii) heat resistance, (iv) resin flowability, and (v) dielectric properties can be provided in a sufficient and balanced manner. In particular, it is possible to prevent blistering and the like in the IR reflow process, that is, improve solder resistance, by reducing film defects and reducing residual volatile components remaining in the film. As a result, the properties of the thermosetting resin composition as an adhesive material can be improved, and the properties of the cured resin as an insulating layer can be improved. In the present invention, a low dielectric constant and a low dielectric loss tangent in the GHz (gigahertz) band are referred to as excellent dielectric characteristics.

<Composition 1: Thermosetting resin composition 1: Mixing ratio of components (A) to (D)>
The mixing ratio of the components (A) to (D) is defined by the weight ratio. In the thermosetting resin composition according to the present invention, when the weights of the components (A) to (D) mixed in the thermosetting resin composition are represented by symbols (A) to (D), Weight mixing ratio of the (D) antifoam component to the total weight (A) + (B) + (C) of the (A) polyimide resin component, (B) epoxy resin component and (C) epoxy curing agent component ( D) / [(A) + (B) + (C)] is preferably within a predetermined range. Specifically, the lower limit of the weight mixing ratio (D) / [(A) + (B) + (C)] may be 0.0001 or more, and preferably 0.0005 or more. On the other hand, the upper limit of the weight mixing ratio (D) / [(A) + (B) + (C)] may be 0.01 or less, and is preferably 0.005 or less. Therefore, a preferable range of the weight mixing ratio is in the range of 0.0001 to 0.01.

  The weight mixing ratio is less than 0.0001, that is, the content of (A) polyimide resin, (B) epoxy resin component, and (C) epoxy curing agent component contained in the thermosetting resin composition ((A ) + (B) + (C)) becomes relatively larger than the content of (D) antifoaming agent component, the defoaming action by the antifoaming agent is lost, and the resin film with few defects and residual volatilization It may be difficult to obtain a resin film with few components.

  On the other hand, the weight mixing ratio exceeds 0.01, that is, the content of (D) antifoam component contained in the thermosetting resin composition is (A) polyimide resin component and (B) epoxy. If the resin component and the content of the (C) epoxy curing agent component ((A) + (B) + (C)) are relatively large, a large amount of antifoaming agent will be present on the surface, and metal In some cases, the adhesion to the resin may deteriorate.

<Composition 2: Thermosetting resin composition: Mixing ratio of components (A) to (C)>
In the present invention, by defining the mixing ratio of at least the components (A) to (C) within a specific range, the obtained thermosetting resin composition and the cured resin after curing (i) Various characteristics such as adhesiveness, (ii) workability and handleability, (iii) heat resistance, (iv) resin flowability, and (v) dielectric properties can be provided in a sufficient and balanced manner. As a result, the properties of the thermosetting resin composition as an adhesive material can be improved, and the properties of the cured resin as an insulating layer can be improved. In the present invention, a low dielectric constant and a low dielectric loss tangent in the GHz (gigahertz) band are referred to as excellent dielectric characteristics.

  The mixing ratio of the components (A) to (C) is defined by a weight ratio. In the thermosetting resin composition according to the present invention, when the weights of the components (A) to (C) mixed in the thermosetting resin composition are represented by symbols (A) to (C), Weight mixing ratio of the above (A) polyimide resin component to the total weight (B) + (C) of the (B) epoxy resin component and (C) epoxy curing agent component (A) / [(B) + (C) ] Is preferably within a predetermined range.

  Specifically, the lower limit of the weight mixing ratio (A) / [(B) + (C)] may be 0.4 or more, and is preferably 0.5 or more. On the other hand, the upper limit of the weight mixing ratio (A) / [(B) + (C)] may be 2.0 or less, and is preferably 1.5 or less. Therefore, the preferable range of the weight mixing ratio is in the range of 0.4 to 2.0.

  The mass mixing ratio is less than 0.4, that is, the content of (B) epoxy resin component and (C) epoxy curing agent component contained in the thermosetting resin composition ((B) + (C) ) Is relatively large compared to the content of (A) polyimide resin component, (iii) heat resistance and (iv) resin fluidity are improved, but (v) dielectric properties cannot be made sufficient There is. That is, in the cured resin sheet, it may be difficult to achieve a low dielectric constant and a low dielectric loss tangent (excellent dielectric characteristics) in the GHz (gigahertz) band.

  Here, the excellent dielectric characteristics will be described more specifically. A cured resin can be obtained by heating the heat-resistant resin composition at 150 ° C. to 250 ° C. for 1 to 5 hours. In this cured resin, the dielectric constant is 3 at a frequency of 1 to 10 GHz. When the dielectric loss tangent is 0.02 or less, excellent dielectric characteristics are realized. If the dielectric constant and the dielectric loss tangent are within the above ranges, even when the thermosetting resin composition according to the present invention is used as a protective material for a circuit board or an interlayer insulating material, the electrical insulation of the circuit board is ensured. It is possible to ensure and reduce the signal transmission speed and signal loss of the circuit on the circuit board, so that it is possible to provide a highly reliable circuit board.

  On the other hand, the weight mixing ratio exceeds 2.0, that is, the content of the (A) polyimide resin component contained in the thermosetting resin composition is (B) epoxy resin component and (C) epoxy. When the content is relatively large compared to the content of the curing agent component ((B) + (C)), (v) the dielectric properties can be improved, but (i) adhesiveness, (ii) workability, Handling properties and (iv) resin fluidity may decrease. That is, when the weight mixing ratio exceeds 2.0, the cured resin after curing can obtain excellent dielectric characteristics in the GHz band. However, in the thermosetting resin composition before curing, the adhesiveness between the thermosetting resin composition and the conductor or the circuit board, and the workability when the thermosetting resin composition is bonded to the conductor or the circuit board. In particular, the circuit embedding property may be greatly impaired due to a decrease in resin fluidity.

<Characteristics of thermosetting resin composition>
The thermosetting resin composition according to the present invention includes the components (A) to (D) as essential components.
Moreover, it is preferable to prescribe | regulate the mixing ratio of each component of (A)-(D), weight ratio, or molar ratio. The specific characteristic in this thermosetting resin composition is not specifically limited.

(II) Components of the thermosetting resin composition according to the present invention Next, the components (A) to (D) used in the present invention, (E) inorganic filler, and (F) other components. Will be described more specifically.

(II-1) (A) Polyimide resin component The (A) polyimide resin component used by this invention should just contain at least 1 type of polyimide resin. The thermosetting resin composition according to the present invention is provided with sufficient heat resistance by containing this (A) polyimide resin component, and has excellent flex resistance and excellent resistance to the cured resin after curing. Mechanical properties and chemical resistance can be imparted, and excellent dielectric properties can also be imparted.

  The polyimide resin used as the (A) polyimide resin component in the present invention is not particularly limited, but is preferably a soluble polyimide resin that dissolves in an organic solvent. Here, the soluble polyimide resin refers to a polyimide resin that dissolves in an organic solvent in an amount of 1% by weight or more in a temperature range of 15 ° C to 100 ° C. Examples of the organic solvent include ether solvents such as dioxane, dioxolane and tetrahydrofuran; acetamide solvents such as N, N-dimethylformamide and N, N-diethylacetamide; formamide solvents such as N, N-diethylformamide and the like. Examples of the solvent include at least one solvent selected from N, N-dimethylacetamide; pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone. These solvent may use only 1 type and may use it combining 2 or more types by arbitrary ratios.

  If the said soluble polyimide resin is used, when thermosetting the thermosetting resin composition concerning this invention, the process for high temperature and a long time is not required. Therefore, the epoxy resin component (B) described later can be cured efficiently. That is, in the present invention, it is preferable to use a soluble polyimide resin as one of the (A) polyimide resin components in terms of (ii) improving workability and handleability.

  The said polyimide resin can be manufactured by a conventionally well-known method. Specifically, for example, it can be obtained by chemically or thermally imidizing polyamic acid (polyamic acid) which is a precursor material of polyimide resin. Hereinafter, a method for producing a polyimide resin from a polyamic acid by imidization will be described in detail.

<Production (synthesis) method of polyamic acid>
The polyamic acid contains, as monomer raw materials, an (A-1) acid dianhydride component containing at least one acid dianhydride and a (A-2) diamine component containing at least one diamine in an organic solvent. It can synthesize | combine by making it react with. At this time, the total amount of the (A-1) acid dianhydride component and the total amount of the (A-2) diamine component are mixed so as to be substantially equimolar. Accordingly, when two or more compounds are used as (A-1) acid dianhydride component and (A-2) diamine component, respectively, the molar ratio of the total amount of plural diamines and the molar ratio of the total amount of plural acid dianhydrides Are adjusted so as to be substantially equimolar, a polyamic acid copolymer can be obtained.

  The (A-1) acid anhydride component and (A-2) diamine component referred to here are monomer raw materials for synthesizing polyamic acid, which is a precursor of polyimide resin, and are thermosetting according to the present invention. It goes without saying that the component is different from the amine-based curing agent component and the acid anhydride-based curing agent component that can be used as the epoxy curing agent component of the conductive resin composition. For the convenience of explanation, in order to clearly distinguish from (C) the components of the thermosetting resin composition such as the epoxy curing agent component, the monomer raw material components of the polyamic acid are represented by “(A-1) monomeric acid dianhydride, respectively. “Component” and “(A-2) Monomer diamine component”.

  The method of reacting the (A-1) monomeric acid dianhydride component and the (A-2) monomer diamine component is not particularly limited, but a typical method is (A-2) monomer diamine. A solution obtained by dissolving a polyamic acid in an organic solvent by dissolving the components in an organic solvent and then adding and mixing the monomer acid dianhydride component (hereinafter referred to as a polyamic acid solution). The method of obtaining is mentioned. Here, “dissolved” means a state in which the solvent completely dissolves the solute and a state in which the solute is uniformly dispersed or diffused in the solvent and is substantially in a dissolved state. Shall be included.

  The addition of the (A-1) monomeric dianhydride component and the (A-2) monomer diamine component is not limited to the above order, and those skilled in the art can appropriately change the addition method. Can be modified / modified. For example, (A-1) a monomer acid dianhydride component may be first dissolved or dispersed in an organic solvent, and then (A-2) a monomer diamine component may be added. Alternatively, first, an appropriate amount of the (A-2) monomer diamine component is added to the organic solvent, and then the amount of the (A-1) monomer that is excessive relative to the total amount of the added (A-2) monomer diamine component. It may be a method of adding an acid dianhydride component and then adding (A-1) a monomer diamine component in an amount corresponding to the excess amount of (A-1) monomeric acid dianhydride.

  The reaction conditions (polyamide acid synthesis conditions) of the above (A-1) monomeric acid dianhydride component and (A-2) monomeric diamine component are not particularly limited, and the acid dianhydride that is a monomer raw material and Any conditions may be used as long as the diamine can be polymerized. However, among the reaction conditions, the reaction temperature is preferably 80 ° C. or lower, and more preferably in the range of 0 to 50 ° C. Moreover, what is necessary is just to set reaction time arbitrarily in the range of 30 minutes-50 hours. If the reaction temperature and reaction time are within these ranges, the polyamic acid can be efficiently synthesized.

  The organic solvent used for the synthesis of the polyamic acid is not particularly limited as long as it is an organic polar solvent. However, it is preferable to select an organic solvent that is a good solvent for the polyamic acid and has a boiling point as low as possible. When such an organic solvent is used, (1) the viscosity of the reaction solution increases when the monomer raw material components (A-1) and (A-2) are subjected to a polymerization reaction (during synthesis of polyamic acid). This is preferable in terms of the production process from the viewpoint of making it easy to stir and suppressing (2) easy drying of the resulting polyimide resin.

  Specific examples of the organic solvent include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide; formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide; N, N-dimethylacetamide and N, Acetamide solvents such as N-diethylacetamide; Pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone; Phenol, o-cresol, m-cresol, p-cresol, xylenol, halogenated phenol And phenol solvents such as catechol; hexamethylphosphoramide, γ-butyrolactone, and the like. These solvent may use only 1 type and may use it combining 2 or more types by arbitrary ratios. Furthermore, you may use it combining aromatic hydrocarbons, such as xylene or toluene, with respect to the said organic solvent as needed.

<(A-1) Monomer acid dianhydride component>
The (A-1) monomeric acid dianhydride component as the monomer raw material used for the synthesis of the polyamic acid is not particularly limited, and in particular, the polyimide resin finally obtained has solubility in various organic solvents. A known acid dianhydride can be used as long as various properties such as heat resistance and compatibility with the other essential components (B) and (C) can be realized. Of these, aromatic tetracarboxylic dianhydrides are preferred. In particular, the aromatic tetracarboxylic dianhydride has the following general formula (1)

（ただし、式中、Ｘ₁ は、−Ｏ−，−ＣＯ−，−Ｏ−Ｘ₂−Ｏ−，および，−ＣＯＯ−Ｘ₂−ＯＣＯ−からなる群より選択される２価基であり、Ｘ₂は２価の有機基を表す）で表される構造を有する化合物であることが好ましい。このような構造を有する酸二無水物は、１種のみを用いてもよく、２種以上を任意の割合で組み合わせて用いてもよい。

(Wherein, X ₁ is a divalent group selected from the group consisting of —O—, —CO—, —O—X ₂ —O—, and —COO—X ₂ —OCO—, X ₂ is preferably a compound having a structure represented by: Only one type of acid dianhydride having such a structure may be used, or two or more types may be used in combination at any ratio.

In the acid dianhydride having the structure represented by the general formula (1) (referred to as “acid dianhydride of the formula (1)” for convenience of explanation), the thermosetting resin composition finally obtained X ₁ in the general formula (1) is —O—X ₂ —O— or —COO—X ₂ —OCO— because the dielectric properties and heat resistance of the product and the cured resin can be made excellent. Preferably there is. Here, X ₂ is a group of formulas (1-1) shown below.

から選択される２価の芳香族有機基、または、次に示す一般式（１−２）

Or a divalent aromatic organic group selected from the following general formula (1-2)

（ただし、式中、Ｘ₃ は、−Ｃ_pＨ_2p−，−Ｃ(＝Ｏ)−，−ＳＯ₂−，−Ｏ−，および，−Ｓ−からなる群より選択される２価基であり、ｐは１以上５以下の整数である）で表される構造を有する２価の芳香族有機基の何れかであることが好ましい。

( _Wherein X ₃ is a divalent group selected from the group consisting of —C _p H _2p —, —C (═O) —, —SO ₂ —, —O—, and —S—). And p is an integer of 1 or more and 5 or less) and is preferably any one of divalent aromatic organic groups having a structure represented by:

  Among the above aromatic tetracarboxylic dianhydrides, it is particularly preferable to use 4,4 '-(4,4'-isopropylidenediphenoxy) bisphthalic dianhydride represented by the following structural formula.

この４，４’−（４，４’−イソプロピリデンジフェノキシ）ビスフタル酸二無水物は、得られるポリアミド酸やポリイミド樹脂に対して、各種の有機溶媒に対する溶解性、耐熱性、（Ｂ）エポキシ樹脂成分及び（Ｃ）エポキシ硬化剤成分との相溶性、誘電特性等の諸特性を十分なものにできるとともに、各諸特性のバランスも良好なものとすることができる。また、（Ａ−１）モノマー酸二無水物成分として用いる化合物としては入手しやすいという利点もある。

This 4,4 ′-(4,4′-isopropylidenediphenoxy) bisphthalic dianhydride has solubility in various organic solvents, heat resistance and (B) epoxy for the resulting polyamic acid and polyimide resin. Various characteristics such as compatibility with the resin component and the (C) epoxy curing agent component, dielectric characteristics, and the like can be made sufficient, and the balance of the various characteristics can also be made good. In addition, (A-1) the compound used as the monomeric acid dianhydride component has an advantage that it is easily available.

  As the (A-1) monomeric acid dianhydride component, a plurality of types of compounds (acid dianhydrides) can be used. Therefore, in the present invention, as the at least one acid dianhydride, the above general formula (1 An acid dianhydride having a structure represented by) may be used. That is, as the (A-1) monomeric acid dianhydride component, it is sufficient that at least one acid dianhydride of the above-described formula (1) is contained, and two or more kinds are in any proportion as necessary. In addition, an acid dianhydride other than the acid dianhydride of the above formula (1) (hereinafter, other acid dianhydrides) may be included.

  The content of the acid dianhydride of the above formula (1) in the monomer acid dianhydride component (A-1), that is, the ratio of the acid dianhydride of the formula (1) in all the acid dianhydrides is: It is preferable that it is 50 mol% or more when all the acid dianhydride components are 100 mol%. If the content of the acid dianhydride of formula (1) is 50 mol% or more, the resulting polyamic acid and polyimide resin have solubility in various organic solvents, (B) epoxy resin component and (C) epoxy curing Various properties such as compatibility with the agent component and dielectric properties can be made excellent.

  Among the above-mentioned (A-1) monomeric acid dianhydride components, other acid dianhydrides are not particularly limited, but are aromatic having a structure other than the structure represented by the general formula (1). Tetracarboxylic dianhydride can be preferably used. Specifically, for example, pyromellitic dianhydride [1,2,4,5-benzenetetracarboxylic dianhydride], 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3 , 3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) ) Diphenylpropanoic dianhydride, 4,4′-hexafluoroisopropylidene diphthalic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4 ′ -Biphenylte Rakarubon dianhydride, 4,4'-oxydiphthalic anhydride, mention may be made of p- phenylene phthalic anhydrides. These other acid dianhydrides may be used alone or in combination of two or more at any ratio.

<(A-2) Monomer diamine component>
The monomer diamine component (A-2) as a monomer raw material used for synthesizing the polyamic acid is not particularly limited, and in particular, the polyimide resin finally obtained has solubility and heat resistance in various organic solvents. If various properties such as solder heat resistance, PCT resistance, low water absorption, and thermoplasticity can be sufficiently realized, a known diamine can be used. Of these, aromatic diamines are preferred. In particular, the aromatic diamine includes 1,3-phenylenediamine, phenylenediamine such as 1,2-phenylenediamine, and the following general formula (3):

（ただし、式中、Ｙ₁ は同一であっても異なっていてもよく、−Ｃ(＝Ｏ)−，−ＳＯ₂−，−Ｏ−，−Ｓ−，−(ＣＨ₂)m−，−ＮＨＣＯ−，−Ｃ(ＣＨ₃)₂−，−Ｃ(ＣＦ₃)₂−，および，−Ｃ(＝Ｏ)Ｏ−からなる群より選択される２価基、または、直接結合を表し、Ｒ₂は同一であっても異なっていてもよく、水素原子、ハロゲン原子、または、炭素数１〜４のアルキル基を表し、ｍ，ｎは、同一であっても異なっていてもよく、１以上５以下の整数である）で表される構造を有する化合物であることが好ましい。なお、ここでいう直接結合とは、２つのベンゼン環のそれぞれに含まれる炭素が直接結合することによって、２つのベンゼン環が結合していることを指す。

(In the formula, Y ₁ may be the same or different, and —C (═O) —, —SO ₂ —, —O—, —S—, — (CH ₂ ) m—, — _{NHCO -, - C (CH 3} ) 2 -, - C (CF 3) 2 -, and, -C (= O) 2 divalent group selected from the group consisting of O-, or a direct bond, R ₂ may be the same or different and each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms, and m and n may be the same or different, and one or more It is preferably a compound having a structure represented by: Note that the direct bond referred to here means that two benzene rings are bonded to each other by directly bonding carbon contained in each of the two benzene rings.

  Specific examples of the diamine having the structure represented by the general formula (3) (referred to as “diamine of formula (3)” for convenience of description) include, for example, bis [4- (3-aminophenoxy). ) Phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-amino) Phenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, 1,2-bis [4- (4-aminophenoxy) phenyl] ethane, 2,2-bis [4- Bis [((3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] butane, etc. A Nophenoxy) phenyl] alkanes; 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- ( Bis [(aminophenoxy) phenyl] fluoroalkanes such as 4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane; 1,3-bis (3-aminophenoxy) benzene; Bis (aminophenoxy) benzene compounds such as 1,4-bis (3-aminophenoxy) benzene, 1,4′-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl Bis (aminophenoxy) such as bis [4- (3-aminophenoxy) phenyl] ketone and bis [4- (4-aminophenoxy) phenyl] ketone Bis [(aminophenoxy) phenyl] sulfide compounds such as bis [4- (3-aminophenoxy) phenyl] sulfide and bis [4- (4-aminophenoxy) phenyl] sulfide; bis [4 -(3-Aminophenoxy) phenyl] sulfone, bis [(aminophenoxy) phenyl] sulfone compounds such as bis [4- (4-aminophenoxy) phenyl] sulfone; bis [4- (3-aminophenoxy) phenyl] Ethers, bis [(aminophenoxy) phenyl] ether compounds such as bis [4- (4-aminophenoxy) phenyl] ether; 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1, Bis [(aminophene) such as 3-bis [4- (3-aminophenoxy) benzoyl] benzene Noxy) benzoyl] benzene compounds; bis [4,4′-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether, and the like (Aminophenoxy) benzoyl] diphenyl ether compounds; 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone and other benzophenone compounds; 4,4′-bis [4 (Phenoxy) phenylsulfone compounds such as-(4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone and bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] sulfone; 1,4 -Bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1, - bis [4- (4-aminophenoxy)-.alpha., alpha-dimethylbenzyl] bis benzene [(aminophenoxy) dimethylbenzene] benzene-based compounds; and the like. These diamines of the formula (3) may be used alone or in combination of two or more at an arbitrary ratio.

  Among the diamines of the above formula (3), the following general formula (3-1)

（ただし、式中、Ｙ₁ は同一であっても異なっていてもよく、−Ｃ(＝Ｏ)−，−ＳＯ₂−，−Ｏ−，−Ｓ−，−(ＣＨ₂)m−，−ＮＨＣＯ−，−Ｃ(ＣＨ₃)₂−，−Ｃ(ＣＦ₃)₂−および−Ｃ(＝Ｏ)Ｏ−からなる群より選択される２価基、または、直接結合を表し、Ｒ_２は同一であっても異なっていてもよく、水素原子、ハロゲン原子、または、炭素数１〜４のアルキル基を表し、ｍ，ｎは同一であっても異なっていてもよく１以上５以下の整数である）で表される構造を有するジアミン、すなわちメタ位にアミノ基を有するジアミンをより好ましく用いることができる。式（３）のジアミンがメタ位にアミノ基を有していれば、パラ位にアミノ基を有するジアミンを用いた場合よりも、得られるポリイミド樹脂において各種の有機溶媒に対する溶解性に優れたものとすることができる。

(In the formula, Y ₁ may be the same or different, and —C (═O) —, —SO ₂ —, —O—, —S—, — (CH ₂ ) m—, — Represents a divalent group selected from the group consisting of NHCO-, -C (CH ₃ ) _2- , -C (CF ₃ ) ₂ -and -C (= O) O-, or a direct bond, and R ₂ represents They may be the same or different and each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms, and m and n may be the same or different and are integers of 1 or more and 5 or less. And a diamine having an amino group at the meta position can be more preferably used. If the diamine of formula (3) has an amino group at the meta position, the resulting polyimide resin has better solubility in various organic solvents than when a diamine having an amino group at the para position is used. It can be.

  Specific examples of the diamine having the structure represented by the general formula (3-1) (referred to as “meta-position diamine” for the sake of convenience) include, for example, the above-described examples of the diamine of the formula (3). 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, 2,2-bis [4 -(3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3) -aminophenoxy] phenyl] butane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1 , 1,3,3,3-hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, bis [4- (3-aminophenoxy) phenyl ] Bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, 1,4-bis [ 4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 4,4′-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether, etc. Can be mentioned. These meta diamines may be used alone or in combination of two or more at any ratio.

  Of these, it is particularly preferable to use 1,3-bis (3-aminophenoxy) benzene as the meta-position diamine. If the 1,3-bis (3-aminophenoxy) benzene is used, the final thermosetting resin composition has excellent solubility in various organic solvents, solder heat resistance, and PCT resistance. It becomes possible.

  Further, the diamine contained in the monomer diamine component (A-2) is a diamine having a hydroxyl group (—OH) and / or a carboxyl group (—COOH) (for convenience of explanation, from —OH that is common in structure to “hydroxydiamine”. For example). If this hydroxydiamine is used, a hydroxyl group and / or a carboxyl group can be introduced into the resulting polyimide resin.

  When at least one of a hydroxyl group and a carboxyl group is introduced into the polyimide resin, curing of the epoxy resin component (B) described later can be promoted in the thermosetting resin composition. Therefore, when hardening a thermosetting resin composition, it becomes possible to perform the thermosetting of the (B) epoxy resin component at low temperature or for a short time. Furthermore, since the (B) epoxy resin component reacts with a hydroxyl group or a carboxyl group, the polyimide resins are cross-linked via the epoxy resin. Therefore, in the cured resin after curing, the molecular structure is strengthened.

  Therefore, by using the above hydroxydiamine to obtain a polyimide resin into which a hydroxyl group and / or a carboxyl group have been introduced, the thermosetting resin composition and the cured resin finally obtained have heat resistance, solder heat resistance, Various characteristics such as PCT resistance can be further improved.

  The hydroxydiamine is not particularly limited as long as it has at least one of a hydroxyl group and a carboxyl group in its structure. Specifically, for example, diaminophenol compounds such as 2,4-diaminophenol; diaminobiphenyl compounds such as 3,3′-dihydroxy-4,4′-diaminobiphenyl; 3,3′-diamino-4, 4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-2,2'-dihydroxybiphenyl, 4,4'-diamino-2,2 ', 5 Hydroxybiphenyl compounds such as 5′-tetrahydroxybiphenyl; 3,3′-diamino-4,4′-dihydroxydiphenylmethane, 4,4′-diamino-3,3′-dihydroxydiphenylmethane, 4,4′-diamino -2,2'-dihydroxydiphenylmethane, 2,2-bis [3-amino-4-hydroxyphenyl] propane 2,2-bis [4-amino-3-hydroxyphenyl] propane, 2,2-bis [3-amino-4-hydroxyphenyl] hexafluoropropane, 4,4′-diamino-2,2 ′, 5 Hydroxydiphenylalkanes such as 5′-tetrahydroxydiphenylmethane; 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 4,4′-diamino-3,3′-dihydroxydiphenyl ether, 4,4′-diamino- Hydroxydiphenyl ether compounds such as 2,2′-dihydroxydiphenyl ether and 4,4′-diamino-2,2 ′, 5,5′-tetrahydroxydiphenyl ether; 3,3′-diamino-4,4′-dihydroxydiphenylsulfone 4,4'-diamino-3,3'-dihydroxydiphenylsulfo Diphenylsulfone compounds such as 4,4′-diamino-2,2′-dihydroxydiphenylsulfone, 4,4′-diamino-2,2 ′, 5,5′-tetrahydroxydiphenylsulfone; Bis [(hydroxyphenyl) phenyl] alkanes such as [4- (4-amino-3-hydroxyphenoxy) phenyl] propane; Bis such as 4,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl (Hydroxyphenoxy) biphenyl compounds; bis [(hydroxyphenoxy) phenyl] sulfone compounds such as 2,2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl] sulfone; 3,5-diaminobenzoic acid Diaminobenzoic acids such as acids; 3,3′-diamino-4,4′-dicarboxybiphenyl, 4,4′-dia Carboxy such as Mino-3,3′-dicarboxybiphenyl, 4,4′-diamino-2,2′-dicarboxybiphenyl, 4,4′-diamino-2,2 ′, 5,5′-tetracarboxybiphenyl, etc. Biphenyl compounds; 3,3′-diamino-4,4′-dicarboxydiphenylmethane, 4,4′-diamino-3,3′-dihydroxydiphenylmethane, 4,4′-diamino-2,2′-dihydroxy Diphenylmethane, 2,2-bis [4-amino-3-carboxyphenyl] propane, 2,2-bis [3-amino-4-carboxyphenyl] hexafluoropropane, 4,4′-diamino-2,2 ′, Carboxydiphenylalkanes such as carboxydiphenylmethane such as 5,5′-tetracarboxydiphenylmethane; -4,4'-dicarboxydiphenyl ether, 4,4'-diamino-3,3'-dicarboxydiphenyl ether, 4,4'-diamino-2,2'-dicarboxydiphenyl ether, 4,4'-diamino-2 Carboxydiphenyl ether compounds such as 2,2 ', 5,5'-tetracarboxydiphenyl ether; 3,3'-diamino-4,4'-dicarboxydiphenylsulfone, 4,4'-diamino-3,3'-dicarboxy Diphenyl sulfone compounds such as diphenyl sulfone, 4,4′-diamino-2,2′-dicarboxydiphenyl sulfone, 4,4′-diamino-2,2 ′, 5,5′-tetracarboxydiphenyl sulfone; Bis [((2-bis [4- (4-amino-3-carboxyphenoxy) phenyl] propane) and the like Ruboxyphenyl) phenyl] alkanes; bis (hydroxyphenoxy) biphenyl compounds such as 4,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl; 2,2-bis [4- (4- Bis [(carboxyphenoxy) phenyl] sulfone compounds such as amino-3-carboxyphenoxy) phenyl] sulfone; and the like. These hydroxydiamines may be used alone or in combination of two or more at any ratio.

  Among the above-mentioned compounds, it is particularly preferable to use 3,3′-dihydroxy-4,4′-diaminobiphenyl represented by the following structural formula as the hydroxydiamine.

３，３’−ジヒドロキシ−４，４’−ジアミノビフェニルを（Ａ−２）モノマージアミン成分に含めることで、得られる熱硬化性樹脂組成物および硬化樹脂に対して、良好な半田耐熱性やＰＣＴ耐性を与えることが可能となる。

By including 3,3′-dihydroxy-4,4′-diaminobiphenyl in the (A-2) monomer diamine component, good solder heat resistance and PCT are obtained for the resulting thermosetting resin composition and cured resin. It becomes possible to give tolerance.

  Thus, the (A-2) monomer diamine component contains at least one diamine of the above formula (3) (particularly a meta-position diamine), and further contains at least one hydroxydiamine. It is preferable. Moreover, even when the diamine of Formula (3) is not included, it is preferable that at least one hydroxydiamine is included. That is, in the present invention, it is preferable that the (A-2) monomer diamine component contains at least one diamine and / or hydroxydiamine of the formula (3). Thereby, more excellent solder heat resistance and PCT resistance can be obtained with respect to the obtained thermosetting resin composition and cured resin.

  The content of the diamine of the above formula (3) in the monomer diamine component (A-2), that is, the ratio of the diamine of the formula (3) in all diamines is 60 when all diamine components are 100 mol%. It is preferable to be from mol% to 99 mol%. Similarly, the content of the hydroxydiamine in the monomer diamine component (A-2), that is, the ratio of hydroxydiamine in all diamines is 1 mol% or more and 40 mol when all diamine components are 100 mol%. % Or less is preferable. When the content of each diamine deviates from the above range, the resulting thermosetting resin composition and cured resin tend to impair the solubility in various organic solvents, solder heat resistance, and PCT resistance.

  In addition, what is necessary is just to combine each said diamine in each arbitrary ratio, and when using together the diamine of the said Formula (3) and hydroxydiamine, what is necessary is just to contain each within the said range.

  Furthermore, the (A-2) monomer diamine component may contain a diamine other than the diamine of formula (3) and hydroxydiamine (referred to as “other diamine” for convenience of description). (A-2) Other diamines contained in the monomer diamine component are not particularly limited, but aromatic diamines can be preferably used.

  Specific examples of the aromatic diamine include m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, and bis (3-aminophenyl) sulfide. , (3-aminophenyl) (4-aminophenyl) sulfide, bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfoxide, (3-aminophenyl) (4-aminophenyl) sulfoxide, bis (3 -Aminophenyl) sulfone, (3-aminophenyl) (4-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'- Diaminodiphenylmethane, 3,4'-diaminodiphenylmeta 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, bis [4- (3-aminophenoxy) phenyl] sulfoxide, bis [4 -(Aminophenoxy) phenyl] sulfoxide and the like can be mentioned.

  These other diamines may be used alone or in combination of two or more in any ratio. Moreover, it is preferable that content of the other diamine in (A-2) monomer diamine component is less than 10 mol% when all the diamine components are 100 mol%.

<Imidization of polyamic acid>
The above (A-1) monomeric acid dianhydride component and (A-2) monomeric diamine component are mixed and stirred in an organic solvent as described in the above section <Production (synthesis) method of polyamic acid>. As a result, a polyamic acid solution is obtained. A soluble polyimide resin can be obtained by imidizing the polyamic acid in the polyamic acid solution. Specific examples of imidization performed at this time include (1) thermal method, (2) chemical method, and (3) vacuum imidization method. By these methods, polyamic acid is dehydrated and cyclized to obtain a polyimide resin.

  The above (1) thermal method is a method in which the polyamic acid solution is heat-treated to perform dehydration and cyclization, and the specific steps thereof are not particularly limited. For example, imidization is performed by heat treatment of the polyamic acid solution. A process such as advancing the reaction and simultaneously evaporating the solvent can be mentioned. By this thermal method, a solid polyimide resin can be obtained. In addition, although the conditions of the said heat processing are not specifically limited, It is preferable to heat at the temperature of 300 degrees C or less for the time of the range of about 5 minutes-20 minutes.

  The above (2) chemical method is a method of dehydrating and ring-closing polyamic acid using a dehydrating agent, and the specific process is not particularly limited. A method of performing a dehydration reaction and evaporation of an organic solvent by adding a dehydrating agent and a catalyst that are more than the stoichiometric amount can be mentioned. By this chemical method, a solid polyimide resin can be obtained.

  Examples of the dehydrating agent include aliphatic acid anhydrides such as acetic anhydride; aromatic acid anhydrides such as benzoic anhydride; carbodiimides such as N, N′-dicyclohexylcarbodiimide and N, N′-diisopropylcarbodiimide. Can do. Examples of the catalyst include aliphatic tertiary amines such as triethylamine; aromatic tertiary amines such as dimethylaniline; heterocyclic groups such as pyridine, α-picoline, β-picoline, γ-picoline, and isoquinoline. Tertiary amines; and the like.

  In addition, it is preferable that the temperature condition at the time of (2) dehydration ring closure by a chemical method is 100 degrees C or less, and it is preferable to carry out reaction time within the range of about 1 minute-50 hours. The evaporation of the organic solvent is preferably performed at a temperature of 200 ° C. or less for a time in the range of about 5 minutes to 120 minutes.

  Further, the (3) vacuum imidization method is a method of imidizing polyamic acid by heat treatment under reduced pressure, and the specific steps thereof are not particularly limited. The heating condition may be in the range of 80 to 400 ° C., but in order to perform imidization and dehydration efficiently, the temperature is more preferably 100 ° C. or more, and further preferably 120 ° C. or more. Here, the maximum temperature in the heat treatment is preferably set to be equal to or lower than the thermal decomposition temperature of the polyimide resin, and is usually set within a temperature range of about 150 ° C. to 350 ° C., which is a complete temperature of imidization. The pressure condition is preferably low pressure. Specifically, it is preferably within a range of 0.001 to 0.9 atmosphere, more preferably within a range of 0.001 to 0.8 atmosphere, and a range of 0.001 to 0.7 atmosphere. More preferably, it is within.

  According to the above (3) vacuum imidization method, water produced by imidization can be positively removed out of the system, so that hydrolysis of polyamic acid can be suppressed. As a result, a high molecular weight polyimide resin can be obtained. Furthermore, if this method is used, one-side ring-opened product or both-side ring-opened products existing as impurities in the acid dianhydride that is a raw material of the polyamic acid can be closed, so that the molecular weight of the polyimide resin is further improved. can do.

  In the imidation methods (1) to (3) described above, the case of evaporating the solvent has been described as an example. However, the imidization method is not limited to this, and the solvent need not be evaporated. . Specifically, for example, a method of adding a polyimide resin solution obtained by the imidization method of the above (1) and (2) to a poor solvent and precipitating the polyimide resin can be mentioned. In this method, the unreacted monomer (acid dianhydride / diamine) contained in the polyimide resin solution is removed for purification. If this is dried, a higher quality solid polyimide resin can be obtained.

  The poor solvent used in this method is not particularly limited as long as it is well mixed with the solvent of the polyimide resin solution, but the polyimide resin is a solvent that is difficult to dissolve. Specific examples include acetone, methanol, ethanol, isopropanol, benzene, methyl cellosolve (registered trademark), and methyl ethyl ketone. These poor solvents may use only 1 type and may use it combining 2 or more types by arbitrary ratios.

(II-2) (B) Epoxy Resin Component The (B) epoxy resin component used in the present invention only needs to contain at least one epoxy resin. The thermosetting resin composition according to the present invention can impart good resin fluidity to the thermosetting resin composition by containing this (B) epoxy resin component, and is also a cured resin after curing. Good heat resistance and insulation can be imparted. Moreover, the favorable adhesiveness with respect to conductors and circuit boards, such as metal foil, can be provided by containing (B) an epoxy resin component.

  The epoxy resin is not particularly limited. Specifically, for example, bisphenol type epoxy resin, bisphenol A novolac type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, alkylphenol novolac type epoxy resin, and the like. , Epoxy resins such as polyglycol type epoxy resins, cycloaliphatic epoxy resins, cresol novolac type epoxy resins, glycidylamine type epoxy resins, naphthalene type epoxy resins, urethane modified epoxy resins, rubber modified epoxy resins, epoxy modified polysiloxanes; These halogenated epoxy resins; crystalline epoxy resins having a melting point; These epoxy resins may be used alone or in combination of two or more at any ratio.

  Among these epoxy resins, an epoxy resin having at least one aromatic ring and / or aliphatic ring in a molecular chain, a bisphenol novolac type epoxy resin having a bisphenol novolak skeleton, a biphenyl type epoxy resin having a biphenyl skeleton, and a naphthalene skeleton A naphthalene type epoxy resin and a crystalline epoxy resin having a melting point are more preferably used. These epoxy resins are easily available and have excellent compatibility with (A) and (C). Moreover, while being able to provide favorable resin fluidity | liquidity with respect to the thermosetting resin composition obtained, the outstanding heat resistance and insulation can be provided with respect to the cured resin after hardening.

  Among the epoxy resins described above, the following group of formulas (4)

（ただし、式中、ｑ，ｒ，ｓは同一であっても異なっていてもよく、任意の整数を表す）
又は一般式（５）

(In the formula, q, r, and s may be the same or different, and represent an arbitrary integer.)
Or general formula (5)

（但し、表中Ｒ_１は同一であっても異なっていてもよく、水素または炭素数が１〜４以下のアルキル基であり、aは０以上１０００以下の整数を表す）で表されるエポキシ樹脂をより一層好ましく用いることができる。これらエポキシ樹脂を用いれば、熱硬化性樹脂組成物および硬化樹脂に対して、誘電特性、耐熱性、回路埋め込み性等の諸特性を付与することができる上に、これら諸特性のバランスを良好なものとすることができる。

(However, in the table, R ₁ may be the same or different and is hydrogen or an alkyl group having 1 to 4 carbon atoms, and a represents an integer of 0 to 1000) Resins can be used more preferably. If these epoxy resins are used, various properties such as dielectric properties, heat resistance and circuit embedding properties can be imparted to the thermosetting resin composition and the cured resin, and a good balance of these properties can be obtained. Can be.

  In addition, it is preferable that the epoxy resin used as (B) epoxy resin component is a high purity epoxy resin, even if it is any epoxy resin mentioned above. In the thermosetting resin composition and the cured resin thus obtained, highly reliable electrical insulation can be realized. In the present invention, the high purity standard is the concentration of halogen or alkali metal contained in the epoxy resin. Specifically, the concentration of halogen or alkali metal contained in the epoxy resin is preferably 25 ppm or less, more preferably 15 ppm or less when extracted under the conditions of 120 ° C. and 2 atm. . If the content concentration of halogen or alkali metal is higher than 25 ppm, reliability of electrical insulation may be impaired in the cured resin after curing.

  In addition, the epoxy resin used as the epoxy resin component (B) is any epoxy resin described above, and the lower limit of the epoxy value (also referred to as epoxy equivalent) is preferably 150 or more, and is 170 or more. More preferably, it is most preferably 190 or more. The upper limit value of the epoxy value of the epoxy resin is preferably 700 or less, more preferably 500 or less, and most preferably 300 or less. Therefore, it is preferable that the epoxy value of the epoxy resin used as the (B) epoxy resin component is in the range of 150 to 700.

  If the epoxy value of the epoxy resin is less than 150, the dielectric properties may be impaired because the number of polar groups in the cured resin after curing increases. That is, the dielectric constant and dielectric loss tangent of the cured resin are increased. On the other hand, when the epoxy value exceeds 700, the crosslink density in the cured resin is lowered, so that the heat resistance may be impaired.

(II-3) (C) Epoxy Curing Agent Component The (C) epoxy curing agent component used in the present invention only needs to contain at least one epoxy curing agent. The epoxy curing agent may be a compound containing a group capable of reacting with an epoxy group contained in the epoxy resin, and examples thereof include a phenol resin curing agent, an amine curing agent, and an acid anhydride curing agent. be able to.

  The thermosetting resin composition according to the present invention can impart good resin fluidity to the thermosetting resin composition by containing this (C) epoxy curing agent component and cure after curing. Good heat resistance can be imparted to the resin. In addition, when the thermosetting resin composition is cured by containing the (C) epoxy curing agent component, the above-described (B) epoxy resin component can be efficiently cured.

  (C) Epoxy curing agent used in the present invention is a phenol resin curing agent or amine in terms of easy to obtain a cured product having excellent heat resistance and dielectric properties, easy control of processing temperature, and availability. A system curing agent can be preferably used.

  The phenolic resin-based curing agent that can be used in the present invention is not particularly limited, and examples thereof include phenol novolac type phenol resins, cresol novolac type phenol resins, bisphenol A novolac type phenol resins, and biphenol cresol novolac type phenol resins. , Cresol melamine copolymer phenol resin, naphthol / cresol copolymer phenol resin, and the like. Among the above phenol resins, it is preferable to use a phenol resin having at least one aromatic ring and / or aliphatic ring in the molecular chain. Thereby, compatibility with (A) polyimide resin component and (B) epoxy resin component can be obtained, and excellent heat resistance is imparted to a cured resin obtained by curing a thermosetting resin composition. Can do.

  As a phenol resin having at least one aromatic ring and / or aliphatic ring in the molecular chain,

（但し、式中のＲ_５およびＲ_６は、それぞれ独立して水素あるいは、炭素数１〜４にアルキル基であり、ｂ，ｃ，ｄ，ｅは、任意の整数を表す）にて表される構造を有する化合物群から選択される少なくとも１種のフェノール樹脂が好ましい。

(Wherein R ₅ and R ₆ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, and b, c, d, and e represent any integer) At least one phenol resin selected from the group of compounds having a structure is preferred.

  What is necessary is just to use combining 1 type (s) or 2 or more types in the arbitrary ratio among the said phenol resins.

  The phenol resin preferably has a lower limit of hydroxyl value (also referred to as hydroxyl equivalent) of 90 or more, more preferably 95 or more, and most preferably 100 or more. The upper limit of the hydroxyl value of the phenol resin is preferably 300 or less, more preferably 200 or less, and most preferably 150 or less.

If the hydroxyl value of the phenol resin is less than 90, the dielectric properties may be impaired because the number of polar groups in the cured resin obtained by curing the thermosetting resin composition increases.
That is, the cured resin may have a high dielectric constant and dielectric loss tangent. On the other hand, when the hydroxyl value exceeds 200, the crosslink density in the cured resin is lowered, so that the heat resistance may be impaired.

  The amine-based curing agent that can be used in the present invention is not particularly limited. For example, monoamines such as aniline, benzylamine, and aminohexane; used for the production of the above-described polyamic acid (A-2). ) Various diamines mentioned in the monomer diamine component; polyamines such as diethylenetriamine, tetraethylenepentamine, and pentaethylenehexamine; Among these amines, (B) the amine component is preferably an aromatic diamine, preferably contains an aromatic diamine having a molecular weight of 300 or more, and has a molecular weight of 300 or more and 600 or less. It is more preferable that the aromatic diamine is contained. Thereby, favorable heat resistance and dielectric properties can be given to the cured resin after curing.

When the aromatic diamine has a molecular weight of less than 300, the cured resin after curing has a large number of polar groups contained in the structure, which may impair dielectric properties. That is, the cured resin may have a high dielectric constant and dielectric loss tangent. On the other hand, when the molecular weight exceeds 600, the crosslink density in the cured resin is lowered, so that the heat resistance may be impaired.

  The aromatic diamine is not particularly limited. Specifically, for example, [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [4- (3-aminophenoxy) Phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, 1,2-bis [4- (4 -Aminophenoxy) phenyl] ethane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [ Bis [(aminophenoxy) phenyl] alkanes such as 4- (3-aminophenoxy) phenyl] butane; 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3 Bis [(aminophenoxy) phenyl] such as 3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane Fluoroalkanes; bis (aminophenoxy) benzene compounds such as 4,4′-bis (4-aminophenoxy) biphenyl; bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4- Bis (aminophenoxy) ketone compounds such as aminophenoxy) phenyl] ketone; bis [((aminophenoxy) phenyl] sulfide, bis [(4- (4-aminophenoxy) phenyl] sulfide, etc. Aminophenoxy) phenyl] sulfide compounds; bis [4- (3-aminophenoxy) phenyl] sulfone, bi Bis [(aminophenoxy) phenyl] sulfone compounds such as [4- (4-aminophenoxy) phenyl] sulfone; bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) Bis [(aminophenoxy) phenyl] ether compounds such as phenyl] ether; 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) Bis [(aminophenoxy) benzoyl] benzene compounds such as benzoyl] benzene; 4,4′-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [3- (3-amino Bis [(aminophenoxy) benzoyl] diphenyl ether such as phenoxy) benzoyl] diphenyl ether Ter compounds; benzophenone compounds such as 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone; 4,4′-bis [4- (4-amino- (phenoxy) phenylsulfone compounds such as α, α-dimethylbenzyl) phenoxy] diphenylsulfone and bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] sulfone; 1,4-bis [4- ( Bis [(aminophenoxy) dimethylbenzene] benzene such as 4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene And the like. These diamines may be used alone or in combination of two or more at any ratio.

  Among these, in particular, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3- (3-Aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3 3,3-hexafluoropropane, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, Bis [4- (4-aminophenoxy) phenyl] ether can be more preferably used.

  These compounds are not only preferable from the viewpoint of easy handling and availability such as being easily dissolved in a solvent, but also by containing these compounds in an amine-based curing agent, they are resistant to a cured resin after curing (glass Various properties such as a high transition temperature) and dielectric properties can be made excellent.

(II-4) (D) Antifoaming component (D) The antifoaming component used in the present invention only needs to contain at least one antifoaming agent. An antifoamer will not be specifically limited if it is a compound which has a defoaming effect | action in a resin solution. Here, the antifoaming agent will be specifically described. An antifoaming agent refers to an additive that breaks down the foam film by partially penetrating the foam surface when the foam is generated or entrained and partially lowers the surface tension.

  Specific examples include silicone antifoaming agents, acrylic antifoaming agents, vinyl antifoaming agents, and fluorosilicone oils. These antifoaming agents may use only 1 type and may use it combining 2 or more types by arbitrary ratios.

Among these antifoaming agents, it is preferable to use a silicone-based antifoaming agent from the viewpoint of excellent heat resistance and antifoaming action, availability, and the like.
(E) Inorganic filler It is preferable to contain an inorganic filler (filler) component in order to improve the characteristics of the cured resin, particularly to further reduce the thermal expansion coefficient. The inorganic filler used as the inorganic filler component is not particularly limited, and specific examples include inorganic fillers such as titanium oxide, calcium carbonate, alumina, and silica, and organic fillers such as acrylic resins and silicone resins. It is done.

  In particular, it can reduce the thermal expansion coefficient of the cured resin by being able to be filled at a high concentration, and even when melted in the process of curing from the B-stage state, it does not hinder the fluidity of the molten resin composition, and melt viscosity It is particularly preferable to use spherical fused silica from the viewpoints of avoiding the increase in the thickness and excellent dielectric characteristics.

(II-5) (F) Other components The thermosetting resin composition according to the present invention includes (F) other components other than the components (A) to (E) as necessary. It may be. (F) Other components are not particularly limited, but specific examples include (F-1) a curing accelerator and (F-2) a thermosetting component other than an epoxy resin. it can.

<(F-1) Curing accelerator>
The (F-1) curing accelerator is not particularly limited. Specifically, for example, phosphine compounds such as triphenylphosphine; trimethylamine, triethylamine, triphenylamine, trimethanolamine, trimethylamine, Amine compounds such as ethanolamine and tetraethanolamine; borate compounds such as 1,8-diaza-bicyclo [5,4,0] -7-undecenium tetraphenylborate; imidazole, 2-ethylimidazole, 2- Ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4 -Methylimidazole Imidazoles such as 2-methylimidazoline, 2-ethylimidazoline, 2-isopropylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2,4-dimethylimidazoline, 2-phenyl-4-methylimidazoline, etc. 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')]- Examples thereof include azine-based imidazoles such as ethyl-s-triazine and 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine. These curing accelerators may be used alone or in combination of two or more at any ratio.

  Among these compounds, triphenylphosphine, triethylamine, triphenylamine, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2 from the viewpoint of excellent circuit embedding property, availability, solvent solubility, and the like. , 4-Diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine is more preferably used.

  The amount (mixing ratio) of these curing accelerators is not particularly limited, as long as it is an amount that can accelerate the reaction between the epoxy resin component and the curing agent and does not impair the dielectric properties of the cured resin. In general, however, it is preferable to use within the range of 0.01 to 10 parts by weight when the total amount of the (B) epoxy resin component is 100 parts by weight.

<(F-2) Thermosetting component other than epoxy resin>
Although it does not specifically limit as said (F-2) thermosetting component, Specifically, for example, bismaleimide resin, bisallyl nadiimide resin, acrylic resin, methacryl resin, hydrosilyl cured resin, allyl cured Thermosetting resin such as resin and unsaturated polyester resin; Side chain reactive group type thermosetting having reactive groups such as allyl group, vinyl group, alkoxysilyl group, hydrosilyl group at the side chain or terminal of polymer chain Polymer; etc. can be used. These thermosetting components may be used alone or in combination of two or more at any ratio. By adding these thermosetting components, various properties such as adhesion, heat resistance, and workability can be improved in the resulting thermosetting resin composition and the cured resin after curing.

  The amount (mixing ratio) of the thermosetting component is not particularly limited as long as it is an amount that can exhibit various characteristics improving effects and does not impair the dielectric properties of the cured resin. .

(III) Use of the thermosetting resin composition according to the present invention The thermosetting resin composition according to the present invention can be suitably used for various applications, among them, a flexible printed wiring board and a build-up circuit board. It can be suitably used as a material for a circuit board. Specifically, it is preferably used as a protective material for protecting the circuit board or a patterned circuit on the circuit board, an interlayer insulating material for ensuring insulation between layers in a multilayer circuit board, or the like. it can.

<Resin solution>
Although the form in the case of utilizing the thermosetting resin composition concerning this invention is not specifically limited, For example, it can use as a resin solution (varnish). The method for preparing the resin solution is not particularly limited, and the thermosetting resin composition according to the present invention may be added to an appropriate solvent and stirred. Alternatively, the components (A) to (F) described above may be dissolved in an appropriate solvent to prepare solutions for each component, and these may be mixed. The solution according to component at this time may contain only each component of (A)-(F), and may contain two or more types of components. Moreover, even if it is the same component, when using multiple types of compounds, you may prepare a solution about each. For example, when two types of polyimide resins are used as the (A) polyimide resin component, the respective polyimide resins may be prepared and mixed as a solution.

  The solvent that can be used for the resin solution is not particularly limited as long as it is a solvent that can dissolve each component of the thermosetting resin composition or (A) to (F), but the boiling point is 150 ° C. The following solvents are preferable. Specifically, for example, cyclic ethers such as tetrahydrofuran, dioxolane and dioxane; ethers such as chain ethers such as ethylene glycol dimethyl ether, triglyme, diethylene glycol, ethyl cellosolve and methyl cellosolve; and the like are preferably used. In addition, a mixed solvent obtained by mixing these ethers with toluene, xylenes, glycols, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, cyclic siloxane, chain siloxane, etc. is also preferably used. Can do. These solvent may use only 1 type and may use it combining 2 or more types by arbitrary ratios.

<Resin sheet>
Moreover, the thermosetting resin composition concerning this invention can be used as a resin sheet by shape | molding in advance into a sheet form. The configuration of the resin sheet is not particularly limited, and specifically, for example, a single-layer sheet composed solely of a thermosetting resin composition, or the above thermosetting resin composition on one or both sides of a film substrate. Examples of the laminate include a two-layer sheet or a three-layer sheet provided with a resin layer, and a multilayer sheet obtained by alternately laminating a resin layer composed of a film base material and a thermosetting resin composition. Therefore, the present invention includes not only a thermosetting resin composition but also a laminate comprising at least one resin layer formed using the thermosetting resin composition.

  The method for molding the resin sheet is not particularly limited. Usually, the resin solution is cast or coated on the surface of the film substrate (support), and then the resin solution is dried to form a film. What is necessary is just to shape | mold. In this resin sheet, the thermosetting resin composition is in a semi-cured state (B stage state). Therefore, if the semi-cured resin sheet is peeled from the support, the single-layer sheet can be obtained. Moreover, if the resin sheet is not peeled off, a two-layer sheet comprising a film substrate and a resin layer of a thermosetting resin composition can be obtained.

  Furthermore, if a resin solution is cast or applied on both surfaces of the film substrate, and then the resin solution is dried, a three-layer sheet comprising the film substrate and the resin layers on both surfaces thereof can be obtained. Moreover, the said multilayer sheet can be manufactured by repeating the process of casting or apply | coating the said resin solution on the surface of the said film base material, and drying a resin solution after that.

  The kind of film base material used as said support body is not specifically limited, A well-known thermosetting resin composition can be used suitably. Moreover, when manufacturing a single layer sheet, you may use support bodies other than a film base material. Examples of such a support include a drum and an endless belt.

When the thermosetting resin composition according to the present invention is used as a resin sheet, whether it is used as a single layer sheet or a laminate, the thickness of the resin layer (a layer made of the thermosetting resin composition) is It is not particularly limited. The thickness of the resin layer may be set to an appropriate thickness depending on the purpose of use.
In addition, it is preferable that the amount of volatile components contained in the semi-cured resin film containing the thermosetting resin composition of the present invention is 10% or less of the total resin film weight. The amount of volatile components in the present invention indicates the ratio of the weight decreased in the range of 300 ° C. or less to the total resin film weight when measured by a thermogravimetric apparatus (TGA). That is, when the total resin film weight is W1, and the weight reduced at 300 ° C. or less is W2, the volatile content (%) = W2 ÷ W1 * 100 is shown.

  If the amount of volatile components exceeds 10 wt%, the amount of gas generated during the IR reflow process increases, and the gas causes the resin film and metal layer made of the thermosetting resin composition of the present invention to swell in other resin layers. Will occur. That is, solder heat resistance is impaired.

Furthermore, the thermosetting resin composition according to the present invention may impregnate the resin solution (varnish) in various fibers such as glass cloth, glass mat, aromatic polyamide fiber cloth, and aromatic polyamide fiber mat. it can. A fiber-reinforced resin sheet can be obtained by semi-curing the thermosetting resin composition impregnated in the fibers.
<Laminated body containing thermoplastic resin layer>
When forming a laminate comprising the thermosetting resin composition of the present invention, the adhesion of the laminate with a metal layer, metal foil or resin film, improvement of heat resistance, or mechanical strength of the laminate For the purpose of improvement, a thermoplastic resin layer containing at least one thermoplastic resin can be formed on both sides or one side of a resin layer formed of a resin composition containing a thermosetting resin composition.

  The thermoplastic resin is not particularly limited. Specific examples include thermoplastic polyamide resins, thermoplastic polyimide resins, polyester resins, polycarbonate resins, polyphenylene sulfide resins, polyether ether ketone resins, and alicyclic polymer resins. A thermoplastic polyimide resin can be preferably used in terms of excellent balance of properties such as heat resistance, mechanical strength, and adhesion to a metal layer or metal foil. In particular, the general formula (2) is excellent in terms of adhesion to a metal layer or a metal foil.

（但し、式中のＺ_１は同一であっても異なっていてもよく、アルキレン基またはフェニレン基であり、Ｚ_２は同一であっても異なっていてもよく、アルキル基、フェニル基またはフェノキシ基であり、ｈは１以上３０以下の整数を表す）で表わされる構造を有する熱可塑性ポリイミド樹脂をより好ましく用いることができる。

(However, Z ₁ in the formula may be the same or different, and is an alkylene group or a phenylene group; Z ₂ may be the same or different; an alkyl group, a phenyl group, or a phenoxy group; And h represents an integer of 1 or more and 30 or less. A thermoplastic polyimide resin having a structure represented by

  The thermoplastic polyimide resin having the structure represented by the general formula (2) can be produced according to the (A) polyamic acid production (synthesis) method and the imidization method described in the description of the polyimide resin component. I can do it. That is, a polyamic acid and a polyimide can be produced using (A-1) monomeric acid dianhydride or (A-2) monomeric diamine component having the structure of the general formula (2).

<Metal layer-containing laminate>
Moreover, the laminated body concerning this invention can also obtain the laminated body (metal layer containing laminated body) containing a metal layer, if not a resin film etc. but metals, such as copper and aluminum, are used as the said film base material. The configuration of the metal layer-containing laminate is not particularly limited as long as it is a laminate including one or more resin layers and metal layers each made of a thermosetting resin composition. Moreover, the resin layer may be provided only on one side of the metal layer or on both sides. Furthermore, you may laminate | stack a metal layer and a resin layer alternately.

  As described above, the metal layer-containing laminate can be produced by casting or coating a resin solution on the surface of the metal layer and drying the resin solution, but is not limited thereto. . For example, it can also be manufactured by laminating a metal foil on the surface of the resin layer in a single-layer sheet or a two-layer sheet obtained by the method described above. Moreover, it can also manufacture by forming a metal layer on the surface of the resin layer in a single layer sheet or a 2 layer sheet | seat by methods, such as chemical plating and sputtering.

<Circuit board>
Furthermore, in the metal layer-containing laminate, if the metal layer is formed of a metal that can be used as a conductor of a circuit board, an etching process is performed on the metal layer to obtain a circuit having a desired pattern (pattern Circuit) can also be formed. That is, a circuit board can also be obtained by forming a pattern circuit in the metal layer of the metal layer-containing laminate according to the present invention. Therefore, the present invention includes a circuit board using the thermosetting resin composition.

  The etching method is not particularly limited, and a known metal etching method using a dry film resist or a liquid resist can be suitably used. Moreover, if the resin layer which is a support substrate has flexibility after hardening, it can be set as a flexible printed wiring board. Furthermore, in order to protect the pattern circuit formed by the etching process, the semi-cured resin sheet (sheet-like thermosetting resin composition) can be laminated. Further, a build-up circuit board having a multilayer structure can be manufactured by laminating a resin layer (a metal layer-containing laminate having a two-layer structure) on which a pattern circuit is formed.

  When the resin layer is in a semi-cured state, it has an appropriate fluidity. Therefore, by performing thermocompression treatment such as hot press treatment, laminating treatment (thermal laminating treatment), and hot roll laminating treatment, it is possible to satisfactorily embed the space between pattern circuits with a resin (thermosetting resin composition). .

  Although the processing temperature in the said thermocompression bonding process is not specifically limited, It is preferable that it exists in the range of 50 degreeC or more and 200 degrees C or less, It is more preferable that it exists in the range of 60 degreeC or more and 180 degrees C or less, 80 degreeC. It is preferably within the range of 130 ° C. or lower. If the treatment temperature exceeds 200 ° C., the resin layer may be cured during the thermocompression treatment. On the other hand, when the treatment temperature is less than 50 ° C., the fluidity of the resin layer is low, and it may be difficult to embed the pattern circuit.

  The resin layer provided on the pattern circuit becomes a protective material for protecting the pattern circuit or an interlayer insulating material in a multilayer circuit board. Therefore, after embedding the pattern circuit, it is preferable to completely cure by performing exposure processing, heat curing, and the like. The specific method of exposure treatment or heat curing is not particularly limited, and may be performed under conditions that allow the resin layer, that is, the thermosetting resin composition, to be sufficiently cured.

  In the case of curing the resin layer (thermosetting resin composition), in order to sufficiently advance the curing reaction of the epoxy resin component (B), after the metal layer and the resin layer are bonded together, post heat treatment is performed. It is preferable to implement. The conditions for the post heat treatment are not particularly limited, but it is preferable to perform the heat treatment for 10 minutes to 3 hours under temperature conditions in the range of 150 ° C. to 200 ° C.

  Thus, the laminated body and circuit board concerning this invention are equipped with the resin layer containing the thermosetting resin composition mentioned above. Therefore, the laminated body and the resin layer of the circuit board can give a good balance of various properties such as adhesiveness, workability / handleability, heat resistance, resin fluidity, and dielectric properties, and are particularly excellent in solder resistance. ing. Thereby, it becomes possible to manufacture a high quality laminated body and a circuit board suitably. In particular, when the laminate and the circuit board have a circuit or the like, the electrical reliability of each circuit can be ensured, and a decrease in signal transmission speed and signal loss in each circuit can be suppressed.

  The present invention will be described more specifically based on examples, but the present invention is not limited to this. Those skilled in the art can make various changes, modifications, and alterations without departing from the scope of the present invention. In addition, when using the thermosetting resin composition concerning this invention as a resin sheet, the lamination property, defect observation, solder heat resistance, and the amount of volatile components were evaluated or computed as follows. In addition, the dielectric properties and glass transition temperature of a cured resin sheet (cured resin) obtained by heating and curing the resin sheet were measured and evaluated as follows.

[Laminating properties]
Glass epoxy substrate FR-4 (product number: MCL-E-67, manufactured by Hitachi Chemical Co., Ltd.) having a circuit formed with a height of 18 μm, a circuit width of 50 μm, and a distance between circuits of 50 μm; copper foil Resin sheet with a PET film (50 μm thickness) so as to come into contact with the glossy surface of the circuit forming surface and copper foil (Product No .: BHY22BT, manufactured by Japan Energy Co., Ltd.) ) Was laminated so that the resin sheet side was in contact with the substrate side, and laminated using a vacuum laminator MVLP-IIA type (product number, manufactured by Meiki Seisakusho) under the following conditions to obtain a laminate. The PET film was peeled off from the obtained laminate, and the surface thereof was visually observed using an optical microscope (50 times magnification) to confirm the presence or absence of bubbles between the circuits. The stacking property when the encroachment of bubbles between the circuits (the portion where the resin does not enter between the circuits) is not confirmed is accepted (O), and the laminating property when the entrapment of bubbles is confirmed is rejected ( Evaluation was carried out as x).

[Solder heat resistance]
After the desmear treatment is applied to the above sample for evaluating laminateability, a sample is formed by forming an 18 μm thick copper layer on the resin film surface on electroless copper plating and electrolytic copper plating, and a sample for evaluating solder heat resistance It was.
The desmear treatment conditions are shown in Table 1, and the electroless copper plating conditions are shown in Table 2. The electrolytic copper plating was pre-cleaned in 10% sulfuric acid for 30 seconds and then plated at room temperature for 40 minutes. Current density is 2A / dm ^2. The thickness of the electrolytic copper film was 18 μm. After electrolytic copper plating, it was dried by heating in a hot air oven at 180 ° C./30 minutes.

半田耐熱性の評価は、上記方法により作製した試料を用い、ＩＲリフロー（商品番号；ＦＴ０４、ＣＩＦ製）を使用して下記条件にて３回加熱処理することにより行った。
評価試料サイズ：１５ｍｍ×３０ｍｍ
設定条件：（ＪＥＤＥＣ Ｌｅｖｅｌ３に準拠した条件）
Ｐ０：１００℃／０．２ｍｉｎ
Ｐ１：１６５℃／１．３ｍｉｎ
Ｐ２：２００℃／１．３ｍｉｎ
加熱後の試料を目視観察し、膨れが発生している場合を不合格（×）。膨れがない場合を合格（○）とした。

Evaluation of solder heat resistance was performed by using the sample prepared by the above method and performing heat treatment three times under the following conditions using IR reflow (product number; FT04, manufactured by CIF).
Evaluation sample size: 15 mm x 30 mm
Setting conditions: (Conditions based on JEDEC Level3)
P0: 100 ° C./0.2 min
P1: 165 ° C / 1.3min
P2: 200 ° C / 1.3min
When the sample after heating is visually observed and blistering occurs, it is rejected (x). The case where there was no blistering was determined to be a pass (◯).

[Calculation of amount of volatile components in resin sheet]
Using a mass spectrometer (product number: TGA50, manufactured by Shimadzu Corporation), the resin sheet was placed in a sample container, and the change in weight was measured under the following conditions. The weight reduced within the range of 100 ° C. to 300 ° C. was calculated as a ratio to the weight of the resin sheet before the weight change, and was defined as the amount of volatile components.
Measurement temperature range: 15 ° C-350 ° C
Temperature increase rate: 20 ° C./min Measurement atmosphere: Nitrogen, flow rate 50 mL / min Sample container: Aluminum [Observation of defects such as foaming of resin sheet (before and after curing)]
The surface of the resin sheet or laminate including the thermosetting resin composition of the present invention was observed with an optical microscope (product BM2-UMA, number: Olympus, magnification 50 times), and the case where foaming occurred was rejected ( X), and the case where there was no pass was marked as (O). The observed range was 50 mm × 50 mm.

[Dielectric properties]
Using a cavity resonator perturbation method complex dielectric constant evaluation apparatus (trade name, manufactured by Kanto Electronics Application Development Co., Ltd.), the dielectric constant and dielectric loss tangent of the cured resin sheet were measured under the following conditions.
Measurement frequency: 3GHz, 5GHz, 10GHz,
Measurement temperature: 22 ° C to 24 ° C
Measurement humidity: 45% to 55%
Measurement sample: Resin sheet left for 24 hours under the above measurement temperature and humidity conditions [Glass transition temperature]
Using DMS-200 (product number, manufactured by Seiko Denshi Kogyo Co., Ltd.), the measurement length (measurement jig interval) is 20 mm, and the storage elastic modulus (ε ′) of the cured resin sheet is measured under the following conditions. The inflection point of the storage elastic modulus (ε ′) was defined as the glass transition temperature (° C.).
Measurement atmosphere: Dry air atmosphere Measurement temperature: 20 ° C to 400 ° C
Measurement sample: cured resin sheet slit to 9 mm width and 40 mm length [Synthesis example 1 of polyimide resin]
In a glass flask having a volume of 2000 ml, 0.95 equivalent of 1,3-bis (3-aminophenoxy) benzene (APB) and 0.05 equivalent of 3,3′-dihydroxy-4,4 in dimethylformamide (DMF). '-Diaminobiphenyl (manufactured by Wakayama Seika Kogyo Co., Ltd.) was charged and stirred to dissolve in a nitrogen atmosphere to obtain a DMF solution. Subsequently, the inside of the flask was placed under a nitrogen atmosphere, and the DMF solution was stirred while being cooled with ice water, and 1 equivalent of 4,4 ′-(4,4′-isopropylidenediphenoxy) bisphthalic anhydride (IPBP, GE) was added. Then, the polyamic acid solution was obtained by further stirring for 3 hours. In addition, the usage-amount of the said DMF was set so that the preparation density | concentration of the monomer of APB, 3,3'- dihydroxy-4,4'-diaminobiphenyl and IPBP might be 30 weight%.

  By transferring 300 g of the polyamic acid solution to a vat coated with a fluororesin and heating in a vacuum oven under reduced pressure for 3 hours under the conditions of 200 ° C. and 5 mmHg (about 0.007 atm, about 5.65 hPa). The polyimide resin 1 was obtained.

[Polyimide resin synthesis example 2]
A polyimide having a structure represented by the general formula (2) was synthesized as follows.
In a glass flask having a volume of 2000 ml, 37 g (0.05 mol) of KF8010 manufactured by Shin-Etsu Chemical Co., Ltd., 21 g (0.10 mol) of 4,4′-diaminodiphenyl ether, and DMF were added and dissolved while stirring. 78 g (0.15 mol) of 4,4 ′-(4,4′-isopropylidenediphenoxy) bisphthalic anhydride was added and stirred for about 1 hour to obtain a DMF solution of 30% polyamic acid with a solid content concentration of 30%.
By transferring 300 g of the polyamic acid solution to a vat coated with a fluororesin and heating in a vacuum oven under reduced pressure for 3 hours under the conditions of 200 ° C. and 5 mmHg (about 0.007 atm, about 5.65 hPa). The polyimide resin 2 was obtained.

[Formation example A of laminate]
Polyimide resin 2 was dissolved in dioxolane to obtain a polyimide resin solution (A). The solid content concentration was 15% by weight.

  The above solution was cast on the surface of a 125 μm-thick PET film (trade name Therapy HP, manufactured by Toyo Metallizing Co., Ltd.) as a support so that the layer thickness of polyimide resin 2 after drying was 2 to 3 μm. . Then, it was heat-dried at a temperature of 60 ° C. for 1 minute in a hot air oven to obtain a laminate A in which a layer made of polyimide resin 2 was formed on a PET film.

[Example 1]
Each component shown below was dissolved in dioxolane so as to have a mixing ratio shown in Table 3 to obtain a resin solution (varnish) as a thermosetting resin composition according to the present invention.
(A) Polyimide resin component: Polyimide resin 1 obtained by the above synthesis example
(B) Epoxy resin component: naphthalene type epoxy resin (trade name: NC7000L, epoxy value = 228 g / eq, manufactured by Nippon Kayaku Co., Ltd.)
(C) Epoxy curing agent component: naphthol / cresol copolymer type phenol resin (trade name: NC30, hydroxyl value = 126 g / eq, manufactured by Gunei Chemical Co., Ltd.)
(D) Antifoam component: Silicone defoamer (trade name; KS603, manufactured by Shin-Etsu Chemical Co., Ltd.) (E) Imidazole component: 2,4-diamino-6- [2′-undecylimidazolyl- ( 1 ′)]-Ethyl-s-triazine (trade name: Curesol C11Z-A, manufactured by Shikoku Chemicals Co., Ltd.)
The obtained resin solution was cast on the surface of the layer made of the polyimide resin 2 of the laminate A obtained in the formation example A of the laminate. Thereafter, it is heated and dried in a hot air oven at 60 ° C., 80 ° C., 100 ° C., 120 ° C. and 140 ° C. for 2 minutes each, and a polyimide resin layer based on a PET film / thermosetting of the present invention. A resin sheet (two layers) as a resin layer was obtained.

  The obtained resin sheet was used in a state where the PET film was not peeled off, and the defect observation of the resin sheet and the evaluation of the lamination were performed. Moreover, after performing desmear, electroless copper plating, and electrolytic copper plating on the sample used in the evaluation of the laminate property, the solder heat resistance was evaluated. The results are shown in Table 4. Moreover, the two-layer sheet (resin sheet before heat-curing) was obtained by peeling and removing the PET film from the resin sheet with PET film. The thickness of the obtained resin sheet was 50 μm. The amount of volatile components of the obtained resin sheet was evaluated. The results are shown in Table 4.

  Next, using 18 μm rolled copper foil (trade name: BHY-22B-T, manufactured by Japan Energy Co., Ltd.), the resin sheet is sandwiched so as to be in contact with the roughened copper foil surface of the rolled copper foil. It is. Then, the copper foil laminated body (metal layer containing laminated body) of the structure which pinched | interposed the resin sheet with the rolled copper foil was obtained by heat-pressing for 1 hour on conditions of temperature 180 degreeC and pressure 3MPa. The copper foil of the obtained copper foil laminate was removed by etching to obtain a cured resin sheet. The dielectric properties and glass transition temperature of the obtained cured resin sheet were measured. The results are shown in Table 5.

(Example 2)
A resin sheet (before heat curing) and a cured resin sheet obtained by curing the resin sheet in the same manner as in Example 1 except that the components (A) to (E) were mixed in the ratios shown in Table 3. Got.

  The obtained resin sheet was evaluated for defect observation, solder heat resistance fluidity, laminating property, and volatile component amount, and the cured resin sheet was evaluated for dielectric properties and glass transition temperature. The results are shown in Tables 4 and 5.

〔比較例１〕
（Ａ）〜（Ｅ）の各成分を表３に示す比率で混合した以外は、実施例１と同様の手法で、樹脂シート（加熱硬化前）、当該樹脂シートを硬化させてなる硬化樹脂シートを得た。得られた樹脂シートについて、欠陥観察、積層性、半田耐熱性、揮発成分量を評価し、硬化樹脂シートについて、誘電特性、ガラス転移温度を評価した。その結果を表４および表５に示す。

[Comparative Example 1]
A resin sheet (before heat curing) and a cured resin sheet obtained by curing the resin sheet in the same manner as in Example 1 except that the components (A) to (E) were mixed in the ratios shown in Table 3. Got. The obtained resin sheet was evaluated for defect observation, lamination property, solder heat resistance, and volatile component amount, and the cured resin sheet was evaluated for dielectric properties and glass transition temperature. The results are shown in Tables 4 and 5.

  As apparent from the above results, the thermosetting resin composition according to the present invention contains (A) a polyimide resin component, (B) an epoxy resin component, and (C) an epoxy curing agent component, and (D) By including an antifoam component, the resin has (i) adhesiveness, (ii) processability and handleability, (iii) resin flowability, (iv) heat resistance, and (v) dielectric properties. It can be seen that it can be realized in a sufficient and balanced manner.

  The present invention is not limited to the configurations described above, and various modifications can be made within the scope of the claims, and technical means disclosed in different embodiments and examples can be used. Embodiments obtained by appropriate combinations are also included in the technical scope of the present invention.

  As described above, the thermosetting resin composition according to the present invention has sufficient (i) adhesiveness, (ii) workability and handleability, (iii) heat resistance, and (iv) resin flowability. In addition, (v) the cured resin after curing exhibits a low dielectric constant and a low dielectric loss tangent even in the GHz band, and can exhibit sufficient dielectric properties. Therefore, it can be suitably used for manufacturing circuit boards such as flexible printed wiring boards and build-up circuit boards. Therefore, the present invention can be suitably used not only in the material processing industry such as resin compositions and adhesives and various chemical industries, but also in the industrial field of various electronic components.

Claims (12)

  (A) a polyimide resin component comprising at least one polyimide resin, (B) an epoxy resin component comprising at least one epoxy resin, and (C) an epoxy curing agent component comprising at least one epoxy curing agent, A thermosetting resin composition comprising (D) an antifoaming agent component containing at least one antifoaming agent. Weight mixing ratio (D) / [(A) expressed by the weight of the (D) antifoaming agent component to the total weight of the (A) polyimide resin component, (B) epoxy resin component and (C) epoxy curing agent component The thermosetting resin composition according to claim 1, wherein + (B) + (C)] is 0.0001 or more and 0.01 or less. The thermosetting resin composition according to claim 1, wherein the antifoaming component (D) is a silicone-based antifoaming agent.   The weight mixing ratio (A) / [(B) + (C)] represented by the weight of the (A) polyimide resin component with respect to the total weight of the (B) epoxy resin component and (C) epoxy curing agent component is: The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition is in a range of 0.4 to 2.0. The at least one polyimide resin contained in the (A) polyimide resin component is represented by the general formula (1).

_{(Wherein, X} 1 is, -O -, - CO -, - O-X 2 -O-, and a divalent radical selected from the group consisting of _-COO-X 2 -OCO-, _{X 2} Represents a divalent organic group), and an acid dianhydride component comprising at least one acid dianhydride having a structure represented by: and a diamine component comprising at least one diamine are reacted. The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition is obtained. The thermosetting resin composition according to claim 1, further comprising (E) an inorganic filler component including at least one inorganic filler.   A semi-cured resin film comprising the thermosetting resin composition according to claim 1.   The resin film according to claim 7, wherein an amount of a volatile component in the resin film is 10% or less of a total resin film weight.   A laminate comprising at least one resin layer formed of the thermosetting resin composition according to any one of claims 1 to 6.   A thermoplastic resin layer containing at least one kind of thermoplastic resin is formed on both sides or one side of the resin layer formed by the thermosetting resin composition according to any one of claims 1 to 6. Laminated body. The at least one thermoplastic resin contained in the thermoplastic resin layer is represented by the general formula (2).

(However, Z ₁ in the formula may be the same or different, and is an alkylene group or a phenylene group; Z ₂ may be the same or different; an alkyl group, a phenyl group, or a phenoxy group; And h is a thermoplastic polyimide resin having a structure represented by the following formula.   A circuit board comprising a resin layer formed of the thermosetting resin composition according to claim 1.