WO2023127523A1

WO2023127523A1 - Resin composition, multilayer sheet, prepreg, cured product, substrate with cured product, and electronic device

Info

Publication number: WO2023127523A1
Application number: PCT/JP2022/046199
Authority: WO
Inventors: 豪阪口; 裕士曽根田; 勇貴宇佐
Original assignee: 東洋インキＳｃホールディングス株式会社; トーヨーケム株式会社
Priority date: 2021-12-27
Filing date: 2022-12-15
Publication date: 2023-07-06
Also published as: JP2023097050A; TWI832614B; JP7196275B1; TW202325799A; JP2023097359A

Abstract

The present invention provides a resin composition which has substrate processing adequacy including embeddability into substrate relief patterns, heat cycle resistance and plating solution resistance, and which enables the achievement of a cured product that has excellent long-term heat resistance and excellent bending strength. The above is achieved by means of a resin composition which contains a polyimide resin (A), a curable compound (B) and a thermally conductive filler (C), wherein: a cured product of this resin composition has a Tg of 140°C to 400°C; the polyimide resin (A) has a residue X²d that is derived from a dimer diamine and/or a dimer diisocyanate, while having a total average number of functional groups selected from among an amino group, an acid anhydride group and a maleimide group of 1 or less (including 0); the temperature and Mw at which the storage elastic modulus G' of the polyimide resin (A) is 1.0 × 10⁷ Pa are within specific ranges; and the curable compound (B) is selected from the group consisting of an epoxy compound (b1) and the like.

Description

Resin compositions, laminate sheets, prepregs, cured products, substrates with cured products, and electronic devices

The present disclosure relates to resin compositions, laminated sheets and prepregs. Further, the present invention relates to a cured product obtained from the resin composition, a substrate with a cured product containing the cured product formed by curing the resin composition, and an electronic device mounted with the substrate with the cured product.

Materials obtained by curing resin compositions are used in various parts of electronic components. For example, a multilayer printed wiring board has an interlayer insulating layer formed between a plurality of conductor layers. Also, a prepreg obtained by impregnating glass cloth or the like with a resin composition is used as an insulating layer covering a conductor layer of a printed wiring board. Also, an insulating sealing resin is used in a semiconductor package.

A composition containing a resin component, a curing component, and an inorganic filler component is disclosed as such a resin composition. For example, Patent Document 1 discloses a composition containing an epoxy compound, a curing agent, silica and a polyimide having a dimer structure, and Patent Document 2 discloses a specific amount of an N-alkylbis Compositions are disclosed that include a maleimide compound or the like, an epoxy compound, an inorganic filler, and a specific curing agent. Further, Patent Document 3 discloses a resin composition containing a thermosetting resin, an inorganic filler, a specific amount of an organic filler and an adhesive softening agent. Furthermore, Patent Document 4 discloses a resin composition for forming an insulating layer containing a specific amount of an epoxy resin, a specific amount of a maleimide compound having a specific structure, a specific amount of an active ester compound, and an inorganic filler. .

Patent Document 5 discloses a polyimide adhesive composition containing a polyimide resin, a thermosetting resin, a flame retardant, and an organic solvent obtained by reacting diamines containing specific amounts of aromatic tetracarboxylic acids and dimer diamine. ing. Further, Patent Document 6 discloses a resin material containing a cyclohexane ring, a maleimide compound having a dimer structure, a polyimide resin having a dimer structure, an epoxy compound, an active ester compound and an inorganic filler. Furthermore, Patent Document 7 discloses a resin composition containing a thermosetting resin, an inorganic filler, a specific amount of an organic filler and a tacky softening agent. Further, in Patent Document 8, the problem is to provide a polyimide-based adhesive that has a low B-stage loss elastic modulus and provides an adhesive layer with good heat-resistant adhesiveness and low dielectric properties. A polyimide adhesive containing an organic solvent is disclosed. Further, in Patent Document 8, the problem is to provide a polyimide-based adhesive that has a low B-stage loss elastic modulus and provides an adhesive layer with good heat-resistant adhesiveness and low dielectric properties. A polyimide adhesive containing an organic solvent is disclosed.

WO2018/062404 WO2019/189466 JP 2020-158704 A JP 2020-186392 A JP 2013-199645 A Japanese Patent Application Laid-Open No. 2021-25052 JP 2020-158704 A JP 2016-191049 A

With the advancement of electronic equipment, there is an increasing demand for high reliability of the electronic components built into the equipment. There is a demand for resin compositions that are excellent in substrate processing suitability during the production of printed wiring boards and the like. Specifically, when an insulating layer made of a resin composition is formed on a substrate on which an uneven pattern such as wiring is formed, there is a demand for a material that is excellent in filling the uneven shape. In addition, a cured product obtained by curing the resin composition is required to have excellent plating resistance (alkali resistance, acid resistance). Furthermore, there is a need for heat cycle resistant materials that can withstand high temperature processes such as solder reflow processes. In addition, the market demands materials that have both long-term heat resistance and bending strength.

The present disclosure has been made in view of the above background. It is an object of the present invention to provide a resin composition which is excellent in terms of strength, a laminated sheet, a prepreg, a cured product, a substrate with the cured product, and an electronic device which are formed using the resin composition.

As a result of extensive studies, the present inventors have found that the following aspects can solve the problems of the present disclosure, and have completed the present disclosure.
[1]: A resin composition containing a polyimide resin (A), a curable compound (B) and a thermally conductive filler (C),
The polyimide resin (A) has residues X ² d derived from dimer diamine and/or dimer diisocyanate, and the total average number of functional groups selected from amino groups, acid anhydride groups and maleimide groups is 0. is less than or equal to 1 including
The temperature at which the polyimide resin (A) has a storage modulus G' of 1.0×10 ⁷ Pa is in the range of −30 to 90° C., and the polyimide resin (A) has a weight average molecular weight of 10,000 to 100. ,000, and
The curable compound (B) is one or two selected from the group consisting of an epoxy compound (b1), a cyanate ester compound (b2), a maleimide compound (b3), a polyphenylene ether compound (b4) and a nadimide compound (b5). and
A resin composition having a glass transition temperature of 140 to 400° C. in a cured product obtained by curing treatment.
[2]: The polyimide resin (A) has the general formula (1):

(X ¹ is independently a tetravalent tetracarboxylic acid residue for each repeating unit, X ² is independently a divalent organic group for each repeating unit, and the X ¹ and the imide bond are bonded to each other. form two imide rings.)
Having a repeating unit of the structure represented by
^[ ^_ 1].
[3]: The resin composition according to [1] or [2], further comprising a heat stabilizer (D).
[4]: The resin according to any one of [1] to [3], wherein 1 to 40% by mass of the polyimide resin (A) is blended in 100% by mass of the non-volatile components of the resin composition. Composition.
[5]: The resin composition according to any one of [1] to [4], which contains an epoxy compound (b1) as the curable compound (B) and further contains an active ester compound.
[6]: A laminated sheet comprising a substrate and a resin composition layer formed on the substrate and formed of the resin composition according to any one of [1] to [5].
[7]: A prepreg in which a substrate is impregnated with the resin composition according to any one of [1] to [5].
[8]: A cured product obtained from the resin composition according to any one of [1] to [5].
[9]: A substrate with a cured product, comprising a cured product formed by curing the resin composition according to any one of [1] to [5].
[10]: An electronic device equipped with the substrate with a cured product according to [9].

According to the present disclosure, a resin composition that is excellent in substrate processing suitability (embedding property in substrate unevenness, heat cycle resistance, plating solution resistance), and whose cured product has excellent long-term heat resistance and excellent bending strength, and the resin An excellent effect is obtained that a laminate sheet, a prepreg, a cured product, a substrate with the cured product, and an electronic device formed using the composition can be provided.

The present disclosure will be described in detail below. It goes without saying that other embodiments are also included in the scope of the present disclosure as long as they match the gist of the present disclosure. In addition, in this specification, the numerical range specified using "-" shall include the numerical values described before and after "-" as the range of lower and upper values. Moreover, in this specification, the terms "film" and "sheet" have the same meaning and are not distinguished by thickness. In addition, unless otherwise noted, the various components appearing in the present specification may be used singly or in combination of two or more. Numerical values described in this specification refer to values obtained by methods described in [Examples] below.

1. Resin Composition The resin composition according to the present embodiment (hereinafter also referred to as the present composition) contains a polyimide resin (A), a curable compound (B) and a thermally conductive filler (C). The polyimide resin (A) has a residue X ² d (hereinafter also referred to as a dimer structure) derived from dimer diamine and/or dimer diisocyanate. In addition, the polyimide resin (A) has an average total number of functional groups selected from amino groups, acid anhydride groups and maleimide groups of 1 or less, including 0. The temperature at which the polyimide resin (A) has a storage elastic modulus G′ of 1.0×10 ⁷ Pa is in the range of −30 to 90° C., and the weight average molecular weight (hereinafter also referred to as Mw) is 10. , 000 to 100,000. Polyimide resin (A) can be used alone or in combination of two or more.

The curable compound (B) includes an epoxy compound (b1), a cyanate ester compound (b2), a maleimide compound (b3), a polyphenylene ether compound (b4) and a nadimide compound (b5) (hereinafter also referred to as (b1) to (b5) is one or two or more selected from the group consisting of The composition has a glass transition temperature (hereinafter also referred to as Tg) of 140 to 400° C. when cured.

The average functional group number is the total average functional group number of functional groups selected from amino groups, acid anhydride groups and maleimide groups per molecule of the polyimide resin (A), and is the raw material used for synthesizing the polyimide resin (A). It can be determined from the charging ratio of the components. The total average number of functional groups being 0 means that the polyimide resin (A) does not have any groups among amino groups, acid anhydride groups and maleimide groups. The total average number of functional groups of 1 or less means that the total number of functional groups of amino groups, acid anhydride groups and maleimide groups is 1 or less on average in one molecule of the polyimide resin (A).

In this specification, the term "cured product" refers to curing by forming a three-dimensional crosslinked structure through curing, and refers to a state in which the curing reaction does not proceed substantially even after further curing. Curing treatment causes the curable compound (B) to crosslink with each other, the curable compound (B) and the polyimide resin (A) to crosslink, and the curable compound (B) to crosslink with other components. , and an embodiment in which these are arbitrarily combined. As curing treatment, heat curing treatment and photocuring treatment can be exemplified. When using a thermoreactive group, heat treatment is usually performed, and when using a photoreactive group, light irradiation treatment is usually performed. Curing conditions vary depending on the composition, but when a thermoreactive group is used, a cured product can be obtained, for example, by treating at 180° C. for about 60 minutes. Similarly, when a photoreactive group is used, a cured product can be obtained by, for example, irradiating actinic rays (for example, 365 nm) in such a light amount as to allow the cross-linking reaction to proceed sufficiently. In addition, when the present composition is molded into a desired shape such as a sheet, a part of the composition may undergo a curing reaction, but the state in which the composition can be cured by further curing treatment is not included in the cured product. At the stage of the resin composition, it may be in a B-stage state in which a part of the components are semi-cured.

Since the present composition has the above structure, it is possible to provide a resin composition that is highly suitable for substrate processing, having excellent embedding properties in substrate irregularities, excellent heat cycle resistance and plating solution resistance in the substrate processing process. The main reason is that the polyimide resin (A) having high flexibility and Mw in a specific range is blended into the resin composition that has a relatively high glass transition temperature when cured, and the polyimide resin By making the total average number of functional groups of amino groups, acid anhydride groups and maleimide groups of (A) 1 or less including 0, it is possible to increase the fluidity before curing and bring out the stress relaxation effect after curing. It is thought that it depends on what has been done.

In addition, since the composition has the above structure, the cured product thereof has excellent long-term heat resistance. The main reason for this is that a thermally conductive filler (C) is added as a compounding component of the resin composition that has a relatively high glass transition temperature when cured, and furthermore, it has a dimer structure and high planarity. It is believed that this is due to the combination of the polyimide resin (A) having the above structure and having an imide group and excellent heat resistance.

Furthermore, since the present composition has the above constitution, the bending strength of the cured product is excellent. The main reason is that the resin composition, which has a relatively high glass transition temperature when cured, has a hydrocarbon chain or ring structure, a dimer structure with little interaction between molecular chains, and a moderate It is believed that this is due to the addition of the polyimide resin (A) having flexibility (having a storage elastic modulus within the above specific range) and having Mw within the above specific range. By blending such a polyimide resin (A) with the curable compound (B) that becomes rigid when cured, stress relaxation is imparted to the cured product, and the curable compound (B) and the thermally conductive filler (C) It is considered that the fracture toughness could be imparted to the composition containing Each component of the present composition and the production method are described in detail below.

1-1. Polyimide resin (A)
Polyimide resin (A) has residues X ² d derived from dimer diamine and/or dimer diisocyanate. Also, the polyimide resin (A) should have an average total functional group number of 1 or less including 0, of functional groups selected from amino groups, acid anhydride groups and maleimide groups. Furthermore, the polyimide resin (A) has a storage modulus G′ of 1.0×10 ⁷ Pa at a temperature of −30 to 90° C. and an Mw in the range of 10,000 to 100,000. .

A dimer diamine can be obtained, for example, by converting the carboxy group of a dimer acid into an amino group. A dimer diisocyanate is obtained, for example, by converting a carboxy group of a dimer acid into an isocyanate group. Here, the dimer acid refers to a dimer of unsaturated aliphatic carboxylic acid or a hydrogenated product thereof. For example, natural fatty acids such as soybean oil fatty acid, tall oil fatty acid, rapeseed oil fatty acid, or linolenic acid, linoleic acid, oleic acid, erucic acid, myristoleic acid, palmitoleic acid, sapienic acid, elaidic acid, stearolic acid, vaccenic acid , gadoleic acid, eicosenoic acid, brassic acid, nervonic acid, eicosadienoic acid, docosadienoic acid, pinolenic acid, eleostearic acid, mead acid, dihomo-γ-linolenic acid, eicosatrienoic acid, stearidonic acid, arachidonic acid, eicosa Unsaturated fatty acids such as tetraenoic acid, cetoleic acid, adrenic acid, boseopentaenoic acid, osponded acid, sardine acid, tetracosapentaenoic acid, eicosapentaenoic acid, docosahexaenoic acid and nisinic acid can be dimerized to obtain dimer acids. can. Unsaturated bonds may be optionally hydrogenated to reduce the degree of unsaturation. Dimer diamine and dimer diisocyanate with a lowered degree of unsaturation are preferable in terms of oxidation resistance (particularly coloration at high temperatures) and suppression of gelation during synthesis.

The dimer acid is preferably a compound having 20 to 60 carbon atoms, more preferably a compound having 24 to 56 carbon atoms, still more preferably a compound having 28 to 48 carbon atoms, and even more preferably a compound having 36 to 44 carbon atoms. A dicarboxylic acid compound having a branched structure obtained by Diels-Alder reaction of a fatty acid is preferred. The branched structure is preferably an aliphatic chain and a ring structure, more preferably a ring structure. The ring structure is preferably one or more aromatic rings or an alicyclic structure, more preferably an alicyclic structure. When there are two ring structures, the two rings may be independent or continuous. A dimer diamine and a dimer diisocyanate can use 1 type or multiple types of compounds. The alicyclic structure may have one or more double bonds in the ring, or may have no double bonds. Methods for converting the carboxy group of the dimer acid to an amino group include, for example, a method of amidating the carboxylic acid, aminating it by Hoffmann rearrangement, and further distilling and purifying it. A method for converting a carboxy group of a dimer acid into a diisocyanate group includes, for example, a method of isocyanating a carboxylic acid by Curtius rearrangement.

The amino group in the dimer diamine or the isocyanate group in the dimer diisocyanate may be directly bonded to the ring structure, but from the viewpoint of improving solubility and flexibility, the amino group is bonded to the ring via an aliphatic chain. It is preferably attached to the structure. The number of carbon atoms between the amino group or isocyanate group and the ring structure is preferably 2-25. Suitable examples of aliphatic chains include chain hydrocarbon groups such as alkylene groups. A suitable example is a compound in which the two amino groups or isocyanate groups are each bonded to a ring structure via an alkylene group.

Specific examples of dimer acid (polybasic acid) for obtaining dimer diamine or dimer diisocyanate include the following chemical formulas (d1) to (d4). These are examples, and the dimer acid is not limited to the structures below.

The dimer diamine and dimer diisocyanate are preferably compounds having 20 to 60 carbon atoms, more preferably compounds having 24 to 56 carbon atoms, still more preferably compounds having 28 to 48 carbon atoms, and even more preferably compounds having 36 to 44 carbon atoms. Such a carbon number is preferable from the viewpoint of availability.

Commercial products of dimer diamine include, for example, "Priamine 1071", "Priamine 1073", "Priamine 1074", and "Priamine 1075" manufactured by Croda Japan, and "Versamin 551" manufactured by BASF Japan.

As a result of extensive studies by the present inventors, it was found that the total number of functional groups of an amino group, an acid anhydride group and a maleimide group in one molecule of the polyimide resin (A) is 1 or less on average, thereby improving substrate processing suitability. It turned out to work well. The total average number of functional groups of amino groups, acid anhydride groups and maleimide groups in the polyimide resin (A) is 1 or less (including 0), so that the polyimide resin (A) has a crosslinked structure via these groups. Structures taken inside can be suppressed. In other words, the average number of bonds between the polyimide resin (A) and the curable compound (B) via these groups can be reduced to one or less. As a result, the fluidity is increased at the stage before the curing treatment, and the embedding of the wiring formed on the substrate into the unevenness of the circuit board, etc. is excellent, while stress relaxation of the polyimide resin (A) after the curing treatment. It can improve the properties and dispersibility, and effectively improve the plating solution resistance and long-term heat resistance of the cured product. From the viewpoint of further improving substrate processability, in addition to an amino group, an acid anhydride group and a maleimide group, as a group that makes the total average number of functional groups in one molecule of the polyimide resin (A) 1 or less (including 0), more preferably contain a carboxy group. That is, it is more preferable that the total average functional group number of functional groups selected from amino groups, acid anhydride groups, carboxy groups and maleimide groups is 1 or less, including 0. The average number of functional groups in this case is the total average number of functional groups selected from amino groups, acid anhydride groups, carboxy groups and maleimide groups per molecule of the polyimide resin (A).

When the epoxy compound (b1) is used as the curable compound (B), the high reactivity of the epoxy group facilitates the formation of crosslinks before the curing treatment. According to the present composition, the total functional groups of amino groups, acid anhydride groups and maleimide groups (hereinafter also referred to as amino groups, etc.) in one molecule of the polyimide resin (A) are 1 or less on average, It is possible to suppress the cross-linking reaction in the stage before the curing treatment, and effectively improve the poor embedding of the wiring formed on the substrate into the unevenness of the circuit board. On the other hand, a cyanate ester compound (b2), a maleimide compound (b3), a polyphenylene ether compound (b4) and/or a nadimide compound (b5) having lower reactivity than the epoxy compound (b1) is used as the curable compound (B). In this case, the acid anhydride group, amino, etc. of the polyimide resin (A) tend to remain in the cured product after curing. According to the present composition, the total functional groups of amino groups, acid anhydride groups and maleimide groups in one molecule of the polyimide resin (A) is 1 or less on average, so that the number of amino groups, etc. remaining after curing can be reduced, and plating solution resistance such as acid resistance is excellent. Furthermore, according to the present composition, by setting the number of functional groups of the maleimide group in the above range, the increase in the crosslink density around the crosslinked site of the polyimide resin (A) is suppressed, and the stress of the polyimide resin (A) is relieved. It is possible to appropriately maintain the properties and maintain good heat cycle resistance of the cured product.

The polyimide resin (A) has a storage modulus G′ of 1.0×10 ⁷ Pa at a temperature of -30 to 90°C. By setting it as this range, a polyimide resin (A) with high flexibility can be obtained. From the viewpoint of bending strength and long-term heat resistance, it is more preferable that the temperature at which the storage elastic modulus G' becomes 1.0×10 ⁷ Pa is in any of 30 to 80°C, and any of 30 to 70°C. More preferably, there is a temperature at which the storage modulus G' is 1.0×10 ⁷ Pa.

By containing the thermally conductive filler (C), a molded article having excellent heat dissipation can be obtained. On the other hand, the formation of voids is not a big problem when forming a coating film, but when producing a prepreg, inclusion of the thermally conductive filler (C) makes voids more likely to occur. This problem becomes more likely to occur as the temperature decreases and as the content of the thermally conductive filler (C) increases. As a result of repeated studies by the present inventors, it was found that by containing a polyimide resin (A) having a storage elastic modulus G′ of 1.0×10 ⁷ Pa at a temperature of −30° C. or more and less than 30° C., heat conduction It was found that the generation of voids can be more effectively suppressed even when a prepreg is formed using a resin composition containing the reactive filler (C). In other words, it is considered that the use of the polyimide resin (A), which has low elasticity in the low-temperature range, enabled effective filling of the voids during the preparation of the prepreg even at relatively low drying temperatures. From the viewpoint of lowering the drying temperature of the prepreg, a polyimide resin (A) having a storage modulus G′ of 1.0×10 ⁷ Pa is preferably −15° C. or more and less than 27° C., −5° C. or more, It is more preferably less than 27°C. By reducing the drying temperature, the environmental load can be reduced. The drying temperature here is not the temperature for making a cured product, but the temperature for removing the volatile components of the resin composition, including the B stage where the resin composition is partly cured. obtain. Here, "drying temperature" refers to a temperature higher than the boiling point of the volatile component and at which voids do not occur.

The polyimide resin (A) having a storage elastic modulus G′ of 1.0×10 ⁷ Pa at a temperature of −30 to 90° C. can be adjusted by adjusting the type of the monomer that becomes the repeating structural unit and the Mw. . Specifically, by combining a monomer having flexibility such as a dimer structure as a monomer with a structure having an aliphatic (including an alicyclic skeleton), the storage elastic modulus G′ tends to decrease, Conversely, when a structure in which an imide structure is directly bonded to a highly planar aromatic skeleton is combined, the storage elastic modulus G' tends to increase. Moreover, the storage elastic modulus G' tends to decrease by decreasing the Mw. A rigid polyimide resin such as a polyimide resin composed of pyromellitic anhydride and diaminobiphenyl has a storage modulus G′ at 90° C. of approximately 1.0×10 ⁹ , and a flexible polyimide resin such as a dimer diamine and 1 ,2,4,5-Cyclohexanetetracarboxylic dianhydride has a storage elastic modulus G' at 90° C. of about 1.0×10 ⁵ .

The Mw of the polyimide resin (A) is 10,000 to 100,000. When it is 10,000 or more, even if the content of the thermally conductive filler (C) in the cured product is increased, good adhesion to other members can be maintained, and a high-quality cured product can be provided. Moreover, long-term heat resistance can be improved by making it 100,000 or less. A more preferred range is 15,000 to 80,000, and an even more preferred range is 20,000 to 75,000.

The amount of the polyimide resin (A) is arbitrary, but in order to increase the bending strength of the cured product and to improve the substrate processability (especially heat cycle resistance), the non-volatile component of the composition ( It is preferably contained in an amount of 1 to 40% by mass based on 100% by mass (solid content). The range is more preferably 7 to 27% by mass, and even more preferably 9 to 19% by mass.

As the polyimide resin (A), general formula (1):

(X ¹ is independently a tetravalent organic group for each repeating unit, X ² is independently a divalent organic group for each repeating unit, and X ¹ and an imide bond are bonded to form two forming an imide ring.) is preferred. Specific examples of ^X1 include a tetracarboxylic acid residue, and specific examples of ^X2 include a diamine residue and a diisocyanate residue.

As used herein, the term "tetracarboxylic acid residue" refers to tetracarboxylic acids and tetracarboxylic acid derivatives such as tetracarboxylic dianhydrides and tetracarboxylic acid diesters (hereinafter referred to as "tetracarboxylic acids"). It refers to the group to do. A "diamine residue" is a group derived from a diamine (a diamine compound), and a "diisocyanate residue" is a residue derived from a diisocyanate (a diisocyanate compound).

The "imido bond" is composed of one nitrogen atom and two carbonyl bonds (C=O), and the imide bond and part of X ¹ in formula (1) are bonded to each other to form an imide ring. . An "imide ring" is a ring having an imide bond, and the number of elements forming one ring is 4 or more and 7 or less. Preferably 5 or 6. The imide ring may be fused with another ring. In addition, the "acid anhydride group" means a group represented by -C(=O)-OC(=O)-, and the "acid anhydride ring" is an acid anhydride group and a carbon element. refers to a ring formed by combining

The polyimide resin (A) may or may not have reactive functional groups with respect to the curable compound (B). Examples of reactive functional groups include the above-described amino group, acid anhydride group, carboxy group, maleimide group, and phenolic hydroxyl group. When using a polyimide resin (A) that does not have a reactive functional group, a crosslinked structure with the curable compound (B) is not formed, but the resin composition having a relatively high glass transition temperature when cured. By blending the polyimide resin (A), which has high flexibility and Mw within a specific range, as a blending component, it is believed that the fluidity before curing can be enhanced and the stress relaxation effect after curing can be elicited. In addition, the polyimide resin (A) having a phenolic hydroxyl group enhances the interaction between the aromatic ring having a phenolic hydroxyl group and the imide ring, and combines a dimer-derived flexible structure to increase fluidity before curing. , it is thought that the stress relaxation effect after curing can be elicited.

A phenolic hydroxyl group refers to a hydroxyl group directly bonded to an aromatic ring. Preferred examples of aromatic rings include benzene ring, naphthalene ring and pyridine ring. A phenolic hydroxyl group can be introduced into any one of a molecular chain terminal, a side group, and a side chain, or can be combined arbitrarily. The term "molecular chain end" refers to a terminal portion of repeating structural units constituting the molecular chain of the polyimide resin (A), or a non-repeating structure linked to the terminal end.

The phenolic hydroxyl value of the polyimide resin (A) is preferably 1 to 50 mgKOH/g. Within this range, the crosslink density can be made appropriate, and substrate processability, particularly plating solution resistance (alkali resistance and acid resistance) can be more effectively improved. Moreover, by setting it as the said phenolic hydroxyl value, a crosslink density can be made suitable and a stress relaxation effect can be brought out. The phenolic hydroxyl value is more preferably 3 to 40 mgKOH/g, still more preferably 10 to 30 mgKOH/g. The phenolic hydroxyl value can be adjusted by adjusting the amount of the monomer having a phenolic hydroxyl group to be charged, the introduction rate of the phenolic hydroxyl group to the molecular chain end, and/or the introduction rate of the phenolic hydroxyl group to the side chain.

In order to introduce a phenolic hydroxyl group at the molecular chain end of the polyimide resin (A), after synthesizing an acid anhydride-terminated polyimide resin, an amine compound having a phenolic hydroxyl group represented by the general formula (3) is further reacted. A method can be exemplified. A phenolic hydroxyl group may be introduced by a similar method in place of the acid anhydride-terminated polyimide resin with a carboxylic acid-terminated polyimide resin.

Ar in the general formula (3) is an aromatic group which may have a substituent. Examples of substituents include alkyl groups having 1 to 10 carbon atoms, fluoroalkyl groups and halogen atoms. The same applies to Ar and substituents in general formulas (4) and (5) described later.

Further, after synthesizing an amino group-terminated polyimide resin, an acid anhydride compound having a phenolic hydroxyl group represented by the general formula (4), or a carboxylic acid compound having a phenolic hydroxyl group represented by the general formula (5) A method of further reacting to introduce a phenolic hydroxyl group at the terminal can be exemplified.

Specific examples of general formula (3) include 3-aminophenol, 4-aminophenol, 4-amino-o-cresol, 5-amino-o-cresol, 4-amino-2,3-xylenol, 4-amino- 2,5-xylenol, 4-amino-2,6-xylenol, 4-amino-1-naphthol, 5-amino-2-naphthol, 6-amino-1-naphthol, 4-amino-2,6-diphenylphenol can be exemplified. Specific examples of general formula (4) include 3-hydroxyphthalic anhydride and 4-hydroxyphthalic anhydride. Moreover, salicylic acid and oxybenzoic acid can be exemplified as specific examples of general formula (5). In the general formulas (3) and (4), one hydroxyl group is exemplified, but a compound in which two or more hydroxyl groups are bonded to Ar may be used.

A polyimide resin (A) having a phenolic hydroxyl group that satisfies at least one of the following (i) and (ii) is suitable from the viewpoint of effectively improving the substrate processing suitability of the cured product, particularly the heat cycle resistance.
(i) It has a phenolic hydroxyl group at the molecular chain end, and a nitrogen atom forming an imide ring derived from monoamine is bonded to the meta-position or ortho-position of the aromatic ring having the phenolic hydroxyl group.
(ii) having a phenolic hydroxyl group at the molecular chain end, having an aliphatic group directly connected to the aromatic ring having the phenolic hydroxyl group, and a nitrogen atom forming a monoamine-derived imide ring bound to the aliphatic group; do.
As a result of extensive studies by the present inventors, it has been found that the structure around the phenolic hydroxyl group at the end of the molecular chain has a large effect on stress relaxation because it is the structure around the cross-linking point. By having the structure (i) in which the positions of the hydroxyl group and the amino group are in the ortho or meta position, the interaction between the imide ring and another imide ring is reduced, and the stress relaxation property is considered to be improved. In addition, by having the structure (ii) in which the amino group is not directly connected to the aromatic ring but bonded through the aliphatic group, the interaction between the imide ring and another imide ring is reduced, resulting in stress relaxation. is expected to improve.

In order to obtain a molecular chain end that satisfies the above (i) and (ii), as a monoamine compound having a phenolic hydroxyl group used for terminal blocking of an acid anhydride group-terminated polyimide resin or a carboxyl group-terminated polyimide resin, the following compounds are used. I can give an example. Namely, m-aminophenol, o-aminophenol, 2-amino-5-ethylphenol, 2-(1-aminoethyl)phenol, 3-(2-aminoethyl)phenol, 4-(2-aminoethyl)phenol , 2-(2-aminoethyl)phenol, 2-(2-aminomethyl)phenol, 3-(2-aminomethyl)phenol, 2-(2-aminomethyl)phenol, 3-(2-aminomethyl)phenol , 4-(2-aminopropyl)phenol and the like.

The functional groups at the ends of the molecular chains of the polyimide resin (A) can be substantially all phenolic hydroxyl groups. In addition to phenolic hydroxyl group ends, molecular chain ends having no functional group may also be included. In addition to the phenolic hydroxyl group end, it may also have a molecular chain end having another functional group (acid anhydride group, etc.).

The polyimide resin (A) having a molecular chain end having no functional group and a phenolic hydroxyl group end is, for example, an amine compound of general formula (3) and a monoamine compound for end blocking for acid anhydride-terminated polyimide. It is obtained by mixing at a ratio and carrying out a terminal blocking reaction. Further, a terminal blocking reaction is performed by mixing a compound represented by general formulas (4) and/or (5) and an acid anhydride compound and/or a carboxylic acid compound for terminal blocking in a specific ratio with respect to an amine-terminated polyimide. may be obtained by According to these methods, the amount of phenolic hydroxyl groups at the ends of the molecular chains of the polyimide resin (A) can be easily adjusted.

Monoamine compounds for terminal blocking include, for example, aliphatic amines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine and dibutylamine; Alicyclic amines such as amines and dicyclohexylamine; aromatic amines such as aniline, toluidine, diphenylamine and naphthylamine, and any mixture thereof.

Acid anhydrides for terminal blocking include phthalic anhydride, 2,2′-biphenyldicarboxylic anhydride, 1,2-naphthalenedicarboxylic anhydride, 2,3-naphthalenedicarboxylic anhydride, and 1,8-naphthalene. dicarboxylic anhydride, 1,2-anthracenedicarboxylic anhydride, 2,3-anthracenedicarboxylic anhydride, L9-anthracenedicarboxylic anhydride and the like. Examples of the carboxylic acid having no phenolic hydroxyl group include carboxylic acids having a structure obtained by removing the phenolic hydroxyl group from the above carboxylic acid having a phenolic hydroxyl group.

The polyimide resin (A) having a phenolic hydroxyl group terminal and another functional group terminal is, for example, an acid anhydride terminal polyimide, an amine compound of general formula (3) and a monoamine compound having another functional group at a specific ratio. It is obtained by mixing with and performing a terminal blocking reaction. Similarly, in the amine-terminated polyimide, the compounds of the general formulas (4) and/or (5) and an acid anhydride compound and/or a carboxylic acid compound having other functional groups are mixed at a specific ratio to conduct a terminal blocking reaction. obtained by doing According to this method, the amounts of phenolic hydroxyl groups and other functional groups at the molecular chain ends of the polyimide resin (A) can be adjusted. Other functional groups are not particularly limited. Examples include a nitro group and a cyano group.

If the other functional group is an acid anhydride group, after synthesizing an acid anhydride-terminated polyimide, react with an amine compound having a phenolic hydroxyl group at a portion of the terminal to convert a portion of the acid anhydride terminal to a phenolic hydroxyl group. can be converted to Similarly, when the other functional group is an amino group, after synthesizing an amino group-terminated polyimide, it is synthesized by a method of reacting a compound having one acid anhydride group having a phenolic hydroxyl group at a portion of the terminal. good too.

In the above, an example of synthesizing a polyimide resin and then reacting a compound as a molecular chain end was given. A polyimide resin (A) may be synthesized. According to this method, the synthesis process can be simplified.

From the viewpoint of improving the plating solution resistance (alkali resistance, acid resistance), the ratio of the phenolic hydroxyl value to the total functional group value (total) is preferably 50 to 100%, more preferably 70 to 100%. is more preferred. By introducing a phenolic hydroxyl group into the polyimide resin (A), the internal stress relaxation of the polyimide resin (A) having a dimer-derived flexible structure is enhanced while enhancing the interaction between the aromatic ring having the phenolic hydroxyl group and the imide ring. can be performed more effectively. If it does not contain phenolic hydroxyl groups, the total average amount of functional groups of amino groups, acid anhydride groups and maleimide groups should be small from the viewpoint of improving plating solution resistance (alkali resistance and acid resistance). is desirable, and it is more desirable that the total average amount of functional groups of carboxy groups, amino groups, acid anhydride groups and maleimide groups is small. Specifically, the total average amount of functional groups of amino groups, acid anhydride groups and maleimide groups is preferably 0.5 or less, including 0, and more preferably 0.3 or less, including 0. . Further, in the case of the polyimide resin (A) containing a carboxy group, the total average amount of functional groups of the carboxy group, amino group, acid anhydride group and maleimide group is preferably 0.5 or less, including 0. It is more preferably 0.3 or less including 0.

In order to introduce phenolic hydroxyl groups into the side chains and/or side groups of the polyimide resin (A), there is a method using organic compounds such as diamines and diisocyanates having phenolic hydroxyl groups and/or tetracarboxylic acids having phenolic hydroxyl groups. preferred. Moreover, after synthesizing the polyimide resin, a compound having a phenolic hydroxyl group may be introduced into the side chain.

Suitable examples of diamines having a phenolic hydroxyl group include bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl) Propane, bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxy)biphenyl, 2,2'-ditrifluoromethyl-5 ,5'-dihydroxyl-4,4'-diaminobiphenyl, bis(3-amino-4-hydroxyphenyl)fluorene, 2,2'-bis(trifluoromethyl)-5,5'-dihydroxybenzidine, etc. family diamines. Also, a substituent may be introduced at any position of these compounds.

A diamine represented by the following general formula (6) may also be used.

wherein R ¹ represents a direct bond or a group containing carbon, hydrogen, oxygen, nitrogen, sulfur, or halogen. The group is, for example, a divalent hydrocarbon group having 1 to 30 carbon atoms or a divalent hydrocarbon group having 1 to 30 carbon atoms in which some or all of the hydrogen atoms are substituted by halogen atoms, -(C= O)-, -SO ₂ -, -O-, -S-, -NH-(C=O)-, -(C=O)-O-, a group represented by the following general formula (7) and the following A group represented by the general formula (8) can be mentioned. In the formula, r and s each independently represent an integer of 1 to 20, and ^R2 represents a hydrogen atom or a methyl group.

Diamines represented by general formula (6) include, for example, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, 2,2-bis (3-amino-4-hydroxyphenyl)hexafluoropropane, 4,4'-diamino-3,3'-dihydroxybisphenyl and the like.

Suitable examples of tetracarboxylic acids having a phenolic hydroxyl group include compounds having a hydroxyl group as a substituent of the aromatic group of the aromatic tetracarboxylic acids described later.

Among these, a diamine containing a phenolic hydroxyl group that satisfies at least one of the following (iii) and (iv) is preferable from the viewpoint of more effectively improving the plating solution resistance.
(iii) part of X ² in general formula (1) is a diamine residue X ² f containing a phenolic hydroxyl group, and the aromatic ring having the phenolic hydroxyl group is derived from a diamine that forms the imide ring; Nitrogen atoms bond.
(iv) part of X ² in general formula (1) is a diamine residue X ² f having a phenolic hydroxyl group, having an aliphatic group directly linked to an aromatic ring having the phenolic hydroxyl group, A nitrogen atom derived from the diamine forming the imide ring is bonded to the aliphatic group.
By having a phenolic hydroxyl group that satisfies at least one of the above (iii) and (iv), the plating solution resistance of the cured product of the present composition can be more effectively enhanced. By making the cross-linking point with the curable compound (B) a side group of the polyimide resin (A), a cross-linked structure can be effectively formed.

Suitable examples of the diamine satisfying the above (iii) or (iv) include the following general formulas (9) and (10). In formula (9), n is an integer of 1-10.

X ¹ in general formula (1) is, as described above, a tetravalent tetracarboxylic acid residue that may have an independent structure for each repeating unit. The tetracarboxylic acids used in the polymerization for obtaining ^X1 are not particularly limited. As tetracarboxylic acids, aromatic tetracarboxylic acids containing an aromatic group, aliphatic tetracarboxylic acids containing an aliphatic group, and tetracarboxylic acids containing an aromatic group and an aliphatic group are preferably used. In addition, an aliphatic group is a hydrocarbon group, and refers to a chain, a branched chain, a ring (alicyclic structure), or a combination thereof. The aliphatic group may contain unsaturated bonds. Aliphatic groups may also contain heteroatoms such as nitrogen, oxygen, sulfur, selenium, fluorine, chlorine, bromine, and the like. Tetracarboxylic acids may be used alone or in combination of two or more. Moreover, the examples of the above monomers may optionally have a substituent. Examples of substituents include alkyl groups, halogen atoms, nitro groups, and cyano groups.

Examples of aromatic tetracarboxylic acids include pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and 2,3′,3,4′-biphenyltetracarboxylic dianhydride. , 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, diphthalic anhydride represented by the following general formula (11) I can give an example.

X ⁵ in the formula is an organic group optionally having a divalent substituent (eg, a hydrocarbon group having 1 to 10 carbon atoms), —O—, —CO—, —SO ₂ —, —S— , -SO ₂ -, -CONH-, -COO-, or -OCO-, -C(CF ₃ ) ₂ -, -COO-Z-OCO-, -O-Ph-C(CH ₃ ) ₂ -Ph- A connecting group such as O- is shown. Examples of Z include -C ₆ H ₄ -, -(CH ₂ ) _n -, and -CH ₂ -CH(-O-C(=O)-CH ₃ )-CH ₂ -. These may contain substituents. An alkyl group, a halogen, a carbonyl group, etc. can be illustrated as said substituent. The same applies to tetracarboxylic acids described later. Specific examples include 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′ -diphenylsulfonetetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 2,2-bis[4-(3,4-di Carboxyphenoxy)phenyl]propane dianhydride, p-phenylenebis(trimellitic acid monoester acid anhydride), and ethylene glycol bisanhydrotrimellitate can be exemplified.

The structure of X ¹ in the general formula (1) of the polyimide resin (A) is not limited, but while adjusting the storage elastic modulus, the stress relaxation effect synergistically with the dimer structure is brought out, and the substrate processability is improved. Specifically, from the viewpoint of further improving bending strength and heat cycle resistance, it is preferable that X ¹ a having an aliphatic group is included. X ¹ a may have an aliphatic group and may contain an aromatic group.

Tetracarboxylic acids having an aliphatic group include a chain hydrocarbon structure and/or an alicyclic hydrocarbon structure that may contain an aromatic group. A "chain hydrocarbon structure" is a linear hydrocarbon structure and/or branched hydrocarbon structure that may have an unsaturated bond. In addition, the "alicyclic hydrocarbon structure" is an alicyclic hydrocarbon which may have an unsaturated bond, and may be monocyclic or polycyclic. These may contain substituents.

Specific examples of tetracarboxylic acids having an aliphatic group include 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-pentanetetracarboxylic acid, and 1,2,4,5-pentanetetracarboxylic acid. Acids, tetracarboxylic acid dianhydrides having a chain hydrocarbon structure such as 1,2,3,4-hexanetetracarboxylic acid and 1,2,5,6-hexanetetracarboxylic acid can be exemplified.
In addition, cyclobutane-1,2,3,4-tetracarboxylic acid, cyclopentane-1,2,3,4-tetracarboxylic acid, cyclohexane-1,2,3,4-tetracarboxylic acid, cyclohexane-1,2 , 4,5-tetracarboxylic acid, 1-carboxymethyl-2,3,5-cyclopentanetricarboxylic acid, 3-carboxymethyl-1,2,4-cyclopentanetricarboxylic acid, rel-dicyclohexyl-3,3′, 4,4′-tetracarboxylic acid, tricyclo[4.2.2.02,5]dec-9-ene-3,4,7,8-tetracarboxylic acid, 5-carboxymethylbicyclo[2.2.1 ]heptane-2,3,6-tricarboxylic acid, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic acid, bicyclo[2.2.2]oct-7-ene-2, 3,6,7-tetracarboxylic acid, bicyclo[3.3.0]octane-2,4,6,7-tetracarboxylic acid, 7,8-diphenylbicyclo[2.2.2]oct-7-ene -2,3,5,6-tetracarboxylic acid, 4,8-diphenyl-1,5-diazabicyclooctane-2,3,6,7-tetracarboxylic acid, 9-oxatricyclo[4.2. 1.02,5]nonane-3,4,7,8-tetracarboxylic acid, 9,14-dioxopentacyclo[8.2.11,11.14,7.02,10.03,8]tetradecane -cyclo, bicyclo, tricyclotetracarboxylic acids such as 5,6,12,13-tetracarboxylic acid; spiro ring-containing such as 2,8-dioxaspiro[4.5]decane-1,3,7,9-terotone Tetracarboxylic acid; 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 1,3,3a,4,5,9b-hexahydro-5 ( Tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3, Examples include tetracarboxylic dianhydrides having an alicyclic hydrocarbon structure such as 4-tetrahydronaphthalene-1,2-dicarboxylic anhydride.

Among X ¹ a having an aliphatic group, it is preferable to have a structure S that satisfies at least one of the following (I) and (II) from the viewpoint of exerting stress relaxation more effectively.
(I) At least one of the carbon atoms in X ¹ constituting the imide ring is directly linked to at least one of the carbon atoms in X ¹ constituting the other imide ring.
(II) At least one of the carbons in the X ¹ constituting each of the two imide rings independently has a structure directly linked to an aliphatic structure, and contains an aliphatic structure that is one of the constituent elements , satisfies either
As specific examples satisfying the above (I), chemical formulas (Ia) to (Id) can be exemplified. The chemical formulas (Ib) to (Id) are also compounds satisfying the above (II). * in the formula indicates the bonding site with the imide group.

As specific examples satisfying the above (II), chemical formulas (II-a) to (II-v) can be exemplified.

Examples of X ¹ a having a structure S in which the carbon in X ¹ forming the imide ring is directly linked to a chain hydrocarbon structure that is an aliphatic structure are represented by chemical formulas (II-a) and (II-v). can be exemplified. As an example of X ¹ a having a structure S in which the carbon in X ¹ forming the imide ring contains an alicyclic hydrocarbon structure among the aliphatic structures serving as one of the constituent elements, the chemical formula (II-b) The represented compound can be exemplified. Further, the carbon of X ¹ forming one imide ring is directly connected to the alicyclic hydrocarbon structure in the aliphatic structure, and the carbon in X ¹ forming the other imide ring is one of the constituent elements. Chemical formula (II-c) can be exemplified as an example of X ¹ a having a structure S containing an alicyclic hydrocarbon structure among the aliphatic structures. The two imide rings may each independently satisfy at least one of (I) and (II) above, and may contain an aromatic ring as shown in chemical formula (II-d).

The ratio of X ¹ a having an aliphatic group is preferably 60 to 100 mol%, more preferably 75 to 100 mol%, with respect to 100 mol% of X ¹ constituting the polyimide resin (A). A preferred range is 85 to 100 mol %. By using 60 to 100 mol % of X ¹ a having an aliphatic group, the heat cycle resistance (substrate processing suitability) becomes more excellent. The ratio of X ¹ a having an aliphatic group is, among the raw material monomers used when synthesizing the polyimide resin (A), the total monomers to be X ¹ residues 100 mol% with respect to the aliphatic group It can be determined from the content ratio (mol %) of the monomer in which X ¹ a is a residue. In general, in 100 mol% of the monomer which is a tetracarboxylic acid used in the polymerization of the polyimide resin (A), by setting the charging rate of the monomer containing X ¹ a having an aliphatic group to 60 to 100 mol% , the ratio of the constituent components derived from the monomers of the polyimide resin (A).

X ² in general formula (1) is, as described above, a divalent organic group which may have an independent structure for each repeating unit. Preferred examples of organic compounds used for polymerization to obtain ^X2 include diamines and diisocyanates, as described above. At least part of X ² is residue X ² d derived from dimer diamine and/or dimer diisocyanate.

The ratio of X ² d having a dimer structure is preferably 60 to 100 mol % when the entire X ² constituting the polyimide resin (A) is taken as 100 mol %. By setting this range, the packing of the polyimide resin (A) is moderately inhibited, the dispersibility with the curable compound (B) and the thermally conductive filler (C) is effectively increased, and the substrate processability and bending strength can have both in good balance. A more preferred range is 75 to 100 mol %, and a still more preferred range is 85 to 100 mol %. The proportion of X ² d having a dimer structure is, among the raw material monomers used when synthesizing the polyimide resin (A), X ² having a dimer structure with respect to 100 mol% of all monomers that become X ² residues It can be determined from the content (mol%) of the monomer in which d is the residue.

In X ² in the general formula (1) of the polyimide resin (A), the other diamine that becomes a monomer of X ² other than the monomer forming the residue X ² d having a dimer structure described above is particularly Not limited. Specifically, an optionally substituted aliphatic group (a chain hydrocarbon structure and/or an alicyclic hydrocarbon structure that may contain an unsaturated bond), an aromatic ring and these There is a diamine compound that is an arbitrary combination of

Specific examples of diamines other than dimer structures include 1,4-diaminobenzene, 1,3-diaminobenzene, 1,2-diaminobenzene, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,3-diamino naphthalene, 2,6-diaminotoluene, 2,4-diaminotoluene, 3,4-diaminotoluene, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4 '-diamino-1,2-diphenylethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 3,3'-diamino Aromatic diamines such as benzophenone and 3,3'-diaminodiphenylsulfone; ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,9- Aliphatic diamines such as nonanediamine, 1,12-dodecamethylenediamine, metaxylenediamine; isophoronediamine, norbornanediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4' - Alicyclic diamines such as diaminodicyclohexylmethane and piperazine.

Also, bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4 -hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxy)biphenyl, 2,2'-ditrifluoromethyl-5,5'-dihydroxyl-4, Diamines having a phenolic hydroxyl group such as 4'-diaminobiphenyl, bis(3-amino-4-hydroxyphenyl)fluorene, and 2,2'-bis(trifluoromethyl)-5,5'-dihydroxybenzidine can be mentioned. Any substituent may be introduced at any position of the diamine.

The polyimide resin (A) may contain residues derived from monomers other than ^X1 residue and ^X2 residue within the scope of the present disclosure. For example, a polyamine compound having 3 or more amino groups may be used. Examples of polyamine compounds having three or more amino groups include 1,2,4-triaminobenzene and 3,4,4'-triaminodiphenyl ether.

The polyimide resin (A) can be produced by various known methods. A specific example is a method of cyclizing a polyamic acid resin or polyamic acid ester resin, which is a polyimide precursor, by heating to convert it into an imide group. A method for synthesizing a polyamic acid resin includes, for example, a method of reacting a tetracarboxylic dianhydride and a diamine. More specifically, a monomer containing a tetracarboxylic dianhydride and a diamine is dissolved in a solvent and stirred at a temperature of, for example, 60 to 120° C. for 0.1 to 2 hours to polymerize the polyimide precursor. Polyamic acid resin can be produced.

In the polyimide resin (A), a method in which the total average functional group number of functional groups selected from amino groups, acid anhydride groups and maleimide groups is 1 or less including 0, the number of terminal functional groups is increased by the reaction of a monofunctional compound. A method of adjustment is preferred. Amino groups and acid anhydride groups can be introduced from monomers. A maleimide group can be obtained by a method of introducing a maleimide group-containing compound into a molecular chain terminal or a side chain, or a method of reacting a terminal amine compound with maleic anhydride. When introducing a maleimide group or a phenolic hydroxyl group, they may be introduced at the stage of synthesizing the polyamic acid resin, or may be introduced after obtaining the polyimide resin. The same is true when passing through a polyamic acid ester resin, which will be described later. Amino groups, acid anhydride groups and maleimide groups may be introduced into side chains or side groups. A phenolic hydroxyl group may be similarly introduced into a side chain or side group. When introducing these functional groups into side chains and side groups, a method of using a compound having these functional groups as a monomer for polymerizing the polyimide resin (A), a polyimide resin precursor, or a polyimide resin was synthesized. Later, there is a method of introducing a phenolic hydroxyl group into a side chain or side group.

Polyamic acid ester resin synthesis methods include obtaining a diester with a tetracarboxylic dianhydride and an alcohol and then reacting it with a diamine in the presence of a condensing agent, or obtaining a diester with a tetracarboxylic dianhydride and an alcohol. Then, the remaining dicarboxylic acid is acid chlorided and reacted with a diamine. A method of reacting a tetracarboxylic dianhydride and a diisocyanate to obtain a polyimide precursor and subsequently obtaining a polyimide resin is also suitable.

Organic solvents used for polymerization include, for example, N-methyl-2-pyrrolidone (NMP), 2-butanone, dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc). , N,N-diethylacetamide, hexamethylphosphoramide, N-methylcaprolactam, dimethyl sulfate, cyclohexanone, dioxane, tetrahydrofuran, diglyme, triglyme and cresol. A solvent is used individually or in combination of 2 or more types. Aromatic hydrocarbons such as xylene and toluene can also be used in combination.

The method of imidizing a polyimide precursor to obtain a polyimide resin is not particularly limited, but a method of heating in a solvent at a temperature of 80 to 400° C. for 0.5 to 50 hours can be exemplified. At this time, a catalyst and/or a dehydrating agent may be used as necessary.

Examples of reaction catalysts include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, and heterocyclic tertiary amines such as pyridine, picoline and isoquinoline. Examples of dehydrating agents include aliphatic acid anhydrides such as acetic anhydride and aromatic acid anhydrides such as benzoic anhydride.

The imidization rate (imido ring formation rate) is not limited, but from the viewpoint of effectively exhibiting the effects of alkali resistance and acid resistance (plating solution resistance), it is preferably 80% or more, and 90% or more. is more preferable, and 95 to 100% is even more preferable. The imidization rate can be determined by NMR, IR analysis, or the like.

1-2. Curable compound (B)
Curable compound (B) is one or more selected from the group consisting of epoxy compound (b1), cyanate ester compound (b2), maleimide compound (b3), polyphenylene ether compound (b4) and nadimide compound (b5). . The epoxy compound (b1) may be used in combination with an active ester compound. The curable compound (B) can be used singly or in combination of two or more regardless of whether the resin is the same or different. Curing agents other than those described above and curing accelerators may also be used in combination.

It is preferable to use 10 to 98% by mass of the curable compound (B), more preferably -30 to 90% by mass, in 100% by mass of the components excluding the thermally conductive filler (C) and the solvent in the present composition. , more preferably 45 to 85% by mass. For the average number of functional groups of the curable compound (B), the average number of functional groups is calculated for each curable compound (B) having the same skeleton.

From the viewpoint of more effectively improving long-term heat resistance, among (b1) to (b5), a combined system of a cyanate ester compound (b2) and a maleimide compound (b3), a maleimide compound (b3) and a polyphenylene ether compound (b4) ) is preferred. Further, from the viewpoint of more effectively improving the bending strength, a combined system of the maleimide compound (b3) and the nadimide compound (b5) is suitable.

Epoxy compound (b1) refers to a curable resin having an epoxy group. The epoxy compound (b1) is preferably used in combination with an active ester compound. The active ester compound is a compound that has one or more ester groups that react with epoxy groups in one molecule and that cures the epoxy resin. Examples of commercially available active ester compounds include "HPC-8000-65T", "EXB9416-70BK" and "EXB8100-65T" manufactured by DIC.

By using an active ester compound, an ester group is generated by the reaction between the epoxy compound (b1) and the active ester compound. Therefore, the polarity can be made lower than in the case of using a phenol-based curing agent. As a result, compatibility between the dimer structure of the polyimide resin (A) and the epoxy compound (b1) can be effectively enhanced.

Specific examples of the epoxy compound (b1) include glycidyl ether-type epoxy resins; Epoxy resins; glycidyl ester-type epoxy resins such as diglycidyl phthalate, diglycidyl hexahydrophthalate, or diglycidyl tetrahydrophthalate; cyclic) epoxy resin; bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin can be exemplified. Also, cresol novolak type epoxy resin, phenol novolak type epoxy resin, α-naphthol novolak type epoxy resin, bisphenol A type novolak type epoxy resin, dicyclopentadiene type epoxy resin, tetrabromobisphenol A type epoxy resin, brominated phenol novolak type epoxy resin. Epoxy resin can be exemplified.

The cyanate ester compound (b2) refers to a curable resin having a cyanate group. Examples of the cyanate ester compound (b2) include bisphenol A-type cyanate ester resin, bisphenol F-type cyanate ester resin, bisphenol E-type cyanate ester resin, bisphenol S-type cyanate ester resin, bisphenol sulfide-type cyanate ester resin, and phenylene ether-type cyanate ester resin. , naphthylene ether type cyanate ester resin, biphenyl type cyanate ester resin, tetramethylbiphenyl type cyanate ester resin, polyhydroxynaphthalene type cyanate ester resin, phenol novolac type cyanate ester resin, cresol novolac type cyanate ester resin, triphenylmethane type cyanate Ester resin, tetraphenylethane type cyanate ester resin, dicyclopentadiene-phenol addition reaction type cyanate ester resin, phenol aralkyl type cyanate ester resin, naphthol novolak type cyanate ester resin, naphthol aralkyl type cyanate ester resin, naphthol-phenol cocondensed novolak type cyanate ester resins, naphthol-cresol cocondensed novolak type cyanate ester resins, aromatic hydrocarbon formaldehyde resin-modified phenol resin type cyanate ester resins, biphenyl-modified novolac type cyanate ester resins, anthracene type cyanate ester resins, and the like.

Commercial products of cyanate ester compound (b2), phenol novolac type cyanate ester resin (“PT-30” and “PT-60” manufactured by Lonza Japan), prepolymer trimerized bisphenol type cyanate ester resin (Lonza Japan ("BA-230S", "BA-3000S", "BTP-1000S" and "BTP-6020S"), etc. may be used.

The maleimide compound (b3) refers to a curable resin having a maleimide group. The type of maleimide compound (b3) is not particularly limited. From the viewpoint of long-term heat resistance, the average number of maleimide groups is preferably 1.5 to 4, more preferably 2 or more.

Although the Mw of the maleimide compound (b3) is not particularly limited, it is preferably 100 or more, more preferably 150 or more, from the viewpoint of suppressing volatilization during drying. Although the upper limit of Mw is not particularly limited, it is 8,000 or less, more preferably 5,000 or less in consideration of availability.

Examples of the maleimide compound (b3) include polyfunctional maleimides obtained by reacting a polyfunctional amine with maleic anhydride. Polyfunctional amines include isophoronediamine, dicyclohexylmethane-4,4'-diamine, and Jeffamine D-230, HK-511, D-400, and XTJ- having terminal aminated polypropylene glycol skeletons manufactured by Huntsman Corporation. 582, D-2000, XTJ-578, XTJ-509, XTJ-510, T-403, T-5000, XTJ-500 with a terminally aminated ethylene glycol backbone, XTJ-501, XTJ-502, XTJ-504, XTJ-511, XTJ-512, XTJ-590 XTJ-542, XTJ-533, XTJ-536, XTJ-548, XTJ-559, etc. having a terminal aminated polytetramethylene glycol backbone.

Examples of maleimide compounds (b3) include 4,4′-diphenylmethanebismaleimide, m-phenylenebismaleimide, p-phenylenebismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, bis-(3 -ethyl-5-methyl-4-maleimidophenyl)methane, 4-methyl-1,3-phenylenebismaleimide, N,N'-ethylenedimaleimide, N,N'-hexamethylenedimaleimide, bis(4-maleimide phenyl)ether, bis(4-maleimidophenyl)sulfone, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, bisphenol A diphenyletherbismaleimide, etc. with two maleimide groups in the molecule biphenyl aralkyl type maleimide, polyphenylmethane maleimide (CAS NO: 67784-74-1, a reaction product of a polymer composed of formaldehyde and aniline and maleic anhydride), N,N'-(toluene-2,6-diyl ) bismaleimide, 4,4′-diphenyl ether bismaleimide, 4,4′-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, N , N'-ethylenebismaleimide, N,N'-trimethylenebismaleimide, N,N'-propylenebismaleimide, N,N'-tetramethylenebismaleimide, N,N'-pentamethylenebismaleimide, N,N '-(1,3-pentanediyl)bis(maleimide), N,N'-hexamethylenebismaleimide, N,N'-(1,7-heptanediyl)bismaleimide, N,N'-(1,8- octanediyl)bismaleimide, N,N'-(1,9-notanediyl)bismaleimide, N,N'-(1,10-decanediyl)bismaleimide, N,N'-(1,11-undecanediyl)bismaleimide Maleimide, N,N'-(1,12-dodecanediyl)bismaleimide, N,N'-[(1,4-phenylene)bismethylene]bismaleimide, N,N'-[(1,2-phenylene)bismethylene] bismaleimide, N,N'-[(1,3-phenylene)bismethylene]bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, N,N'-[(methylimino)bis (4,1-phenylene)]bismaleimide, N,N'-(2-hydroxypropane-1,3-diylbisiminobiscarbonylbisethylene)bismaleimide, N,N'-(dithiobisethylene)bismaleimide, N,N'-[hexamethylenebis(iminocarbonylmethylene)]bismaleimide, N,N'-carbonylbis(1,4-phenylene)bismaleimide, N,N',N''-[nitrilotris(ethylene) ]trismaleimide, N,N',N''-[nitrilotris(4,1-phenylene)]trismaleimide, N,N'-[p-phenylenebis(oxy-p-phenylene)]bismaleimide, N, N'-[methylenebis(oxy)bis(2-methyl-1,4-phenylene)]bismaleimide, N,N'-[methylenebis(oxy-p-phenylene)]bis(maleimide)N,N'-[ dimethylsilylenebis[(4,1-phenylene)(1,3,4,-oxadiazole-5,2-diyl)(4,1-phenylene)]]bismaleimide, N,N'-[(1, 3-phenylene)bisoxybis(3,1-phenylene)]bismaleimide, 1,1′-[3′-oxospiro[9H-xanthene-9,1′(3′H)-isobenzofuran]-3,6-diyl ] Bis(1H-pyrrole-2,5-dione), N,N′-(3,3′-dichlorobiphenyl-4,4′-diyl)bismaleimide, N,N′-(3,3′-dimethyl biphenyl-4,4′-diyl)bismaleimide, N,N′-(3,3′-dimethoxybiphenyl-4,4′-diyl)bismaleimide, N,N′-[methylenebis(2-ethyl-4, 1-phenylene)]bismaleimide, N,N'-[methylenebis(2,6-diethyl-4,1-phenylene)]bismaleimide, N,N'-[methylenebis(2-bromo-6-ethyl-4, 1-phenylene)]bismaleimide, N,N'-[methylenebis(2-methyl-4,1-phenylene)]bismaleimide, N,N'-[ethylenebis(oxyethylene)]bismaleimide, N,N' -[sulfonylbis(4,1-phenylene)bis(oxy)bis(4,1-phenylene)]bismaleimide, N,N'-[naphthalene-2,7-diylbis(oxy)bis(4,1-phenylene )] bismaleimide, N,N'-[p-phenylenebis(oxy-p-phenylene)]bismaleimide, N,N'-[(1,3-phenylene)bisoxybis(3,1-phenylene)]bismaleimide , N,N′-(3,6,9-trioxaundecane-1,11-diyl)bismaleimide, N,N′-[isopropylidenebis[p-phenyleneoxycarbonyl(m-phenylene)]]bismaleimide , N,N'-[isopropylidenebis[p-phenyleneoxycarbonyl (p-phenylene)]]bismaleimide, N,N'-[isopropylidenebis[(2,6-dichlorobenzene-4,1-diyl) oxycarbonyl(p-phenylene)]]bismaleimide, N,N'-[(phenylimino)bis(4,1-phenylene)]bismaleimide, N,N'-[azobis(4,1-phenylene)]bis Maleimide, N,N'-[1,3,4-oxadiazole-2,5-diylbis(4,1-phenylene)]bismaleimide, 2,6-bis[4-(maleimido-N-yl) Phenoxy]benzonitrile, N,N'-[1,3,4-oxadiazole-2,5-diylbis(3,1-phenylene)]bismaleimide, N,N'-[bis[9-oxo-9H -9-phospha(V)-10-oxaphenanthren-9-yl]methylenebis(p-phenylene)]bismaleimide, N,N'-[hexafluoroisopropylidenebis[p-phenyleneoxycarbonyl(m-phenylene)] ] bismaleimide, N,N'-[carbonylbis[(4,1-phenylene)thio(4,1-phenylene)]]bismaleimide, N,N'-carbonylbis(p-phenyleneoxy p-phenylene)bis maleimide, N,N'-[5-tert-butyl-1,3-phenylenebis[(1,3,4-oxadiazol-5,2-diyl)(4,1-phenylene)]]bismaleimide, N,N'-[cyclohexylidenebis(4,1-phenylene)]bismaleimide, N,N'-[methylenebis(oxy)bis(2-methyl-1,4-phenylene)]bismaleimide, N,N '-[5-[2-[5-(dimethylamino)-1-naphthylsulfonylamino]ethylcarbamoyl]-1,3-phenylene]bismaleimide, N,N'-(oxybisethylene)bismaleimide, N, N'-[dithiobis(m-phenylene)]bismaleimide, N,N'-(3,6,9-trioxaundecane-1,11-diyl)bismaleimide, N,N'-(ethylenebis-p- phenylene) bismaleimide, Designer Molecules BMI-689, BMI-1500, BMI-1700, BMI-3000, BMI-5000, BMI-9000, JFE Chemical Co. ODA-BMI, BAFBMI and other polyfunctional maleimides. be able to.

When the maleimide compound (b3) is crosslinked by radicals, a radical polymerization initiator can be added. Specifically, azo compounds and organic peroxides can be exemplified. A polymerization initiator is used alone or in combination of two or more.
Azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis(2-methylbutyronitrile), 1,1′-azobis(cyclohexane 1-carbonitrile), 2,2 '-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4 , 4′-azobis(4-cyanovaleric acid), 2,2′-azobis(2-hydroxymethylpropionitrile), 2,2′-azobis[2-(2-imidazolin-2-yl)propane] can be exemplified.
Organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl) peroxydicarbonate. , t-butyl peroxy 2-ethylhexanoate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl Peroxide can be exemplified.

The polyphenylene ether compound (b4) has a repeating unit having a structure represented by the following general formula (14) and contains a curable functional group.

R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), an optionally substituted alkyl group ( Linear or branched compounds with 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, heptyl group, and cyclohexyl group. cyclic compounds), optionally substituted alkoxy groups (C1-C6 alkoxy groups such as methoxy, ethoxy, butoxy, and propoxy groups), optionally substituted aryl Examples include groups (phenyl group, naphthyl group, etc.), optionally substituted amino groups, carboxy groups, nitro groups, cyano groups, and the like.

From the viewpoint of long-term heat resistance, the polyphenylene ether compound (b4) preferably has an average number of curable functional groups of 1 to 10, more preferably 2 or more.

Although the Mw of the polyphenylene ether compound (b4) is not particularly limited, it is preferably 200 or more, more preferably 500 or more, from the viewpoint of bending strength. Although the upper limit of Mw is not particularly limited, it is 10,000 or less in consideration of availability and the like.

Specific examples of the polyphenylene ether compound (b4) include poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2,6-dimethyl-1,4-phenylene ether), poly(2- methyl-6-phenyl-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether), 2,6-dimethylphenol and other phenols (e.g., 2,3,6- trimethylphenol, 2-methyl-6-butylphenol, etc.). In addition, polyphenylene ether copolymers obtained by coupling 2,6-dimethylphenol with biphenols or bisphenols, poly(2,6-dimethyl-1,4-phenylene ether), and the like are added to bisphenols and trisphenols. A polyphenylene ether having a linear or branched structure obtained by heating in a solvent such as toluene in the presence of a phenol compound and an organic peroxide such as the above to cause a redistribution reaction.

The nadimide compound (b5) is not particularly limited as long as it has two or more nadimide groups in the molecule. Suitable examples of the nadimide compound (b5) include compounds having a structure represented by the following general formula (15).

R ²¹ is an optionally substituted alkylene group having 1 to 20 carbon atoms (eg, an alkylene group such as a methylene group, ethylene group, propylene group, butylene group, pentylene group, heptylene group), cyclohexylene; alicyclic groups such as groups, phenylene groups, biphenylene groups, naphthylene groups, and groups consisting of any combination thereof. ^R22 and ^R23 are curable functional groups such as allyl groups or (meth)acrylate groups.

Commercially available products include "BANI-M" and "BANI-X" from Maruzen Petrochemical Co., Ltd.

1-3. Thermally conductive filler (C)
The thermally conductive filler (C) is a compound that imparts thermal conductivity to the cured product of the present composition. From the viewpoint of thermal conductivity, the thermally conductive filler preferably has a thermal conductivity of 0.5 W/(m K) or more, more preferably 1.0 W/(m K) or more. It is more preferably 1.5 W/(m·K) or more. As the thermally conductive filler (C), a thermally conductive inorganic filler and a thermally conductive organic-inorganic hybrid filler can be used. The content of the thermally conductive filler (C) may be appropriately adjusted depending on the application, and is usually 5 to 95% by mass with respect to 100% by mass of non-volatile components in the present composition. The shape of the thermally conductive filler (C) is not particularly limited. For example, spherical, powdery, fibrous, acicular, scaly and the like can be mentioned. By using a plurality of types of thermally conductive fillers having different particle sizes and shapes, the thermally conductive filler (C) can be highly filled in some cases. A heat conductive filler (C) is used individually by 1 type or in combination of 2 or more types.

Specific examples of thermally conductive inorganic fillers include alumina, aluminum hydroxide, zirconium hydroxide, barium hydroxide, calcium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, magnesium sulfate, oxide Titanium, tin oxide, aluminum oxide, magnesium oxide, zirconium oxide, calcium oxide, magnesium oxide, zinc oxide, molybdenum oxide, antimony oxide, nickel oxide, calcium silicate, beryllia, calcium titanate, silicon carbide, silicon nitride, aluminum nitride , metal compounds such as boron nitride, titanium white, zinc borate, aluminum borate; talc; clay; mica; glass fiber, kaolin, hydrotalcite, wollastonite, xonotlite, calcium hydrogen phosphate, calcium phosphate, glass flakes, Metal oxides and metal nitrides such as hydrated glass and sepiolite; hydrated metal compounds; fused crushed silica, fused spherical silica, crystalline silica, non-crystalline silica, secondary aggregated silica, finely divided silica, hollow silica, porous Examples include silica-based fillers such as silica; nitride-based fillers such as silicon carbide, silicon nitride, titanium carbide, and diamond; and carbon-based fillers.
Among these, alumina, aluminum oxide, aluminum nitride, and boron nitride are more preferable, and alumina and boron nitride are particularly preferable from the viewpoint of effectively increasing long-term heat resistance.

Specific examples of thermally conductive organic-inorganic hybrid fillers include fillers obtained by coating the surface of the inorganic fillers listed above with a resin or dispersant. As a method for coating the surface of the thermally conductive inorganic filler with a resin or a dispersant, a known method can be applied. In this case, the inorganic filler is preferably exposed in order to effectively bring out the thermal conductivity of the thermally conductive inorganic filler. The surface of the thermally conductive inorganic filler can be surface-treated with, for example, a silane-, titanate-, or aluminate-based coupling agent. The surface treatment can enhance the dispersibility of the thermally conductive filler in the binder component. It is also possible to increase the interfacial adhesive strength between the binder component and the thermally conductive filler.

Silane coupling agents include γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane. Aminosilanes such as methoxysilane and γ-ureidopropyltriethoxysilane; epoxysilane; mercaptosilane such as 3-mercaptopropyltrimethoxysilane; p-styryltrimethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyl Examples include vinylsilanes such as trimethoxysilane.

Titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tri(N-aminoethyl/aminoethyl) titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(ditridecyl)phosphite titanate, bis( dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate)ethylene titanate, diisopropylbis(dioctylphosphate)titanate, tetraisopropylbis(dioctylphosphite)titanate, tetraoctylbis(ditridecylphosphite)titanate and the like.

A mode in which the surface of the thermally conductive inorganic filler is coated with a fluororesin is also suitable. From the viewpoint of maintaining good thermal conductivity, it is preferable that the thermally conductive inorganic fillers are exposed at the portions where the thermally conductive inorganic fillers are in contact with each other.

The method of adding the thermally conductive filler (C) is not particularly limited, and conventionally known methods can be used. Preferred examples include a method of adding the filler to the polymerization reaction solution before or during the polymerization of the polyimide resin (A), a method of kneading the filler into the polyimide resin (A) using a triple roll or the like, and preparing a dispersion containing the filler. and a method of mixing this with the polyimide resin (A). Further, in order to disperse the filler well and stabilize the dispersed state, dispersants, thickeners and the like may be used as long as they do not affect the physical properties of the resin composition.

1-4. Thermal stabilizer (D)
The present composition can optionally contain a heat stabilizer (D). The heat stabilizer (D) may be a compound having an ultraviolet absorption function, a radical scavenging function, a peroxide decomposition function, or a flame retardant function. Phenolic compounds such as resin hindered phenol; hindered amine, phosphorus, sulfur, benzotriazole, benzophenone, hydroxylamine, salicylate, and triazine compounds. Also, metal hydrates and halogen compounds can be exemplified. Known ultraviolet absorbers, antioxidants and flame retardants can be used. The heat stabilizer (D) can be used alone or in combination of two or more. Including the heat stabilizer (D) can improve the substrate processability in addition to the long-term heat resistance. When the heat stabilizer (D) is used, the content thereof is, for example, 0.1 to 5% by mass in 100% by mass of the composition excluding the thermally conductive filler (C) and the solvent.

Hindered phenol compounds include, for example, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H ,5H)-trione, 1,1,3-tris-(2′-methyl-4′-hydroxy-5′-t-butylphenyl)-butane, 4,4′-butylidene-bis-(2-t- butyl-5-methylphenol), 3-(3,5-di-t-butyl-4-hydroxyphenyl)stearylpropionate, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxy Phenyl)propionate, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10 -tetraoxaspiro[5.5]undecane, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3,5 -tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2′-methylenebis (6-t-butyl-4-ethylphenol), 2,2′ thiodiethylbis-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis(3, 5-di-t-butyl-4-hydroxy-hydrocinnamamide), i-octyl 3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,6-bis(dodecylthiomethyl )-o-cresol, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4,6-bis(octylthiomethyl)-o-cresol, bis[3-(3 -methyl-4-hydroxy-5-t-butylphenyl)propionic acid]ethylenebisoxybisethylene, 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate , 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2,2′-thio-bis-(6 -t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,6-di-t-butyl-4-nonylphenol, 2,2′-isobutylidene-bis-(4,6 -dimethyl-phenol), 2,2′-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol, etc. mentioned.

Commercially available products are Adekastab AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330 manufactured by ADEKA, KEMINOX101, 179, 76, 9425 manufactured by Chemipro, manufactured by BASF. IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565, Cyanox CY-1790, CY-2777 manufactured by Sun Chemical Co., and the like.

Hindered amine compounds include, for example, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6-tetramethyl -4-piperidyl) 1,2,3,4-butane tetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl) -4-piperidyl) sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2, 2,6,6-tetramethyl-4-piperidyl methacrylate, a polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[ [6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino] -hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and 3,5,5 -ester of trimethylhexanoic acid, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}- 1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-decanedioate piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane, bis(1,2,2,6,6-pentamethyl-4-pyliperidyl)[[3,5-bis(1,1 dimethylethyl )-4-hydroxyphenyl]methyl]butylmalonate methyl 1,2,2,6,6-pentamethyl-4-pyriperidyl sebacate, poly[[6-morpholino-s-triazine-2,4-diyl] -[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 2,2,6 ,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid esters, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine , 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide and the like.

Commercially available products are ADEKA's Adekastab LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA- 402F, LA-502XP, KAMISTAB29, 62, 77, 94 manufactured by Chemipro Kasei Co., Ltd., Tinuvin249 manufactured by BASF, TINUVIN111FDL, 123, 144, 292, 5100, Cyasorb UV-3346 manufactured by Sun Chemical Co., UV-3529, UV-3853, etc. mentioned.

The phosphorus-based compound is not particularly limited as long as it contains a phosphorus atom, and may be an inorganic compound or an organic compound. Examples of inorganic phosphorus compounds include red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate and ammonium polyphosphate; inorganic nitrogen-containing phosphorus compounds such as amide phosphoric acid; phosphoric acid; phosphine oxide; Examples of organic phosphorus compounds include di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite, 2,2′-methylenebis(4 ,6-di-t-butylphenyl)2-ethylhexyl phosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra(C12-C15 alkyl)-4, 4′-Isopropylidenediphenyldiphosphite, diphenylmono(2-ethylhexyl)phosphite, diphenylisodecylphosphite, tris(isodecyl)phosphite, triphenylphosphite, tetrakis(2,4-di-t-butylphenyl )-4,4-biphenyldiphosphonate, tris(tridecyl)phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi(tridecyl)phosphite, diphenylisooctylphosphite, diphenyltridecylphosphite, 4 , 4′ isopropylidenediphenol alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl) phosphite, di(2,4-di-t-butylphenyl) pentaerythritol diphosphite, di(nonylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1,1 , 3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, sodium bis(4-t- butylphenyl)phosphite, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, ethylbisphosphite (2,4-di-tert-butyl-6-methylphenyl) and the like.

Commercially available products are Adekastab PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, TPP manufactured by ADEKA, IRGAFOS168 manufactured by BASF, HostanoxP-EPQ manufactured by Clariant Chemicals, and manufactured by Sanko. HCA etc. are mentioned.

Sulfur compounds include, for example, 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], 3,3′-thiobis ditridecyl propionate, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, 2,4-bis[(laurylthio)methyl]-o-cresol and the like.

Commercially available products include Adekastab AO-412S and AO-503 manufactured by ADEKA, and KEMINOXPLS manufactured by Chemipro Kasei.

1-5. Other Optional Components The composition may be solventless or may contain a solvent. Solvents include toluene, xylene, methyl ethyl ketone, N,N-dimethylformamide, methyl isobutyl ketone, N-methyl-pyrrolidone, acetone, methanol, ethanol, butanol, 2-propanol, 2-methoxyethanol, 2-ethoxyethanol, 1 -Methoxy-2-propanol, 2-acetoxy-1-methoxypropane, n-hexane, cyclohexane, cyclohexanone and mixtures thereof.

A fluorine-based filler may be used from the viewpoint of more effectively exhibiting a low dielectric constant. Examples of fluorine-based fillers include PTFE, PVDF (a vinylidene fluoride polymer having a linear structure in which CF2 and CH2 are alternately bonded), NEOFLON FEP (tetrafluoroethylene-hexafluoropropylene copolymer: tetrafluoroethylene- propylene hexafluoride copolymer resin), PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer: perfluoroalkoxy resin), NEOFLON ETFE (tetrafluoroethylene-ethylene copolymer), ECTFE (polychlorotrifluoroethylene : Trifluoroethylene chloride resin) and the like can be exemplified.

Furthermore, additives can be included within the scope of the present disclosure. For example, a polyimide resin that does not correspond to the polyimide resin (A) and/or a curable compound that does not correspond to the curable compound (B) may be used. Also, any thermoplastic resin can be used. A catalyst may also be included as an optional component to accelerate the curing process. Suitable examples of catalysts include imidazole-based, amine-based, and phosphorus-based catalysts. Furthermore, dyes, pigments (e.g., carbon black), polymerization inhibitors, antifoaming agents, leveling agents, ion scavengers, moisturizing agents, viscosity modifiers, preservatives, antibacterial agents, antistatic agents, antiblocking agents, ultraviolet rays Absorbents, infrared absorbents, electromagnetic wave shielding agents and the like can be mentioned.

1-6. Properties of Resin Composition and Cured Product The glass transition temperature of the cured product obtained by curing the present composition is in the range of 140 to 400°C. More preferably, it is 200 to 300°C. When the glass transition temperature is 140°C or higher, long-term heat resistance can be enhanced. On the other hand, when the glass transition temperature is 400° C. or lower, a certain degree of flexibility can be imparted, and the stress relaxation effect of the polyimide resin (A) can be brought out.

2. Method for Producing Resin Composition The present composition is obtained by blending each compounding component. An imidized polyimide resin (A) is used as a compounding component instead of a polyimide precursor. A solvent can be used as appropriate for blending. The solid content concentration can be, for example, 20 to 60% by mass. Since the polyimide resin (A) has a dimer structure, it can be easily dissolved in various organic solvents.

The composition can be in the form of powder, film, sheet, plate, pellet, paste or liquid, for example. A liquid or paste resin composition can be easily obtained by adjusting the viscosity using a solvent. Moreover, a film-like, sheet-like, or plate-like resin composition can be formed, for example, by applying a liquid or paste resin composition and drying it. Further, the powdery or pellet-like resin composition can be obtained, for example, by pulverizing or cutting the film-like resin composition into a desired size.

3. Resin Composition Layer, Laminated Sheet, and Prepreg The present composition can be suitably used as a resin composition layer. In addition, the present composition can be suitably used for laminated sheet applications including a base material and a resin composition layer formed of the present composition provided on the base material. Since the resin composition layer exhibits excellent adhesiveness after curing treatment, it is suitable for bonding with various materials (resin layer, metal layer, inorganic layer such as ITO, composite layer, etc.). For example, it is suitable as an adhesive sheet for copper clad laminates (CCL), and as a bonding material between electronic circuit boards and electronic components.

For example, a coating liquid (varnish) of the present composition containing a solvent is applied to one side of the release film, and a liquid medium such as an organic solvent is removed and dried at 40 to 150 ° C., for example, to form a resin composition layer (adhesive sheet) is obtained. By laminating another release film on the surface of the obtained adhesive sheet, a laminated sheet that is an adhesive sheet with a double-sided release film is obtained. By laminating the release film on both sides, surface contamination of the adhesive sheet can be prevented. The adhesive sheet can be isolated by peeling off the release film. The two release films can be of the same type or of different types. By using release films with different release properties, the strength of the release force can be adjusted, making it easier to peel off in order. Alternatively, a laminate sheet having an adhesive sheet (resin composition layer) may be obtained by coating a substrate other than the releasable substrate with the coating liquid.

Base materials include resin materials such as polyimide film, polyethylene film, polycarbonate, polyethylene, liquid crystal polymer, phenolic resin, and aramid resin; metal materials such as copper, aluminum, and stainless steel; inorganic materials such as ITO, glass, silicon, and silicon carbide. and composite materials in which these are arbitrarily combined can be exemplified. According to the present composition, the soft polyimide resin (A) having a storage elastic modulus G′ of 1.0×10 ⁷ Pa at a temperature between −30° C. and 90° C. provides excellent adhesion to various substrates. In addition, it is excellent in moldability.

Examples of coating methods include known methods such as comma coating, knife coating, die coating, lip coating, roll coating, curtain coating, bar coating, gravure printing, flexographic printing, screen printing, dip coating, spray coating, and spin coating. can be selected. The thickness of the adhesive sheet after drying is preferably 5 to 500 μm, more preferably 10 to 100 μm, in order to exhibit sufficient adhesiveness and from the viewpoint of ease of handling.

The composition can be suitably used for forming a prepreg obtained by impregnating a base material with the composition. A prepreg can be produced, for example, by impregnating a fibrous base material with the present composition, then heating and drying the resin composition for semi-curing (B-staging). The amount of solid matter adhered to the fiber base material of the resin composition is preferably 20 to 90% by mass in terms of the content of the resin composition after drying relative to the prepreg. It is more preferably 30 to 80% by mass, still more preferably 40 to 70% by mass. For example, after impregnating or coating a fiber base material with the present composition so that the solid content adhesion amount of the resin composition in the prepreg is 20 to 90% by mass, for example, 1 to 30 at a temperature of 40 to 250 ° C. It can be manufactured by heating and drying for minutes and semi-curing (to B stage).

As the fiber base material, known materials can be used without limitation, but organic fibers, inorganic fibers and glass fibers can be exemplified. Examples of organic fibers include polyimide, polyester, tetrafluoroethylene, and wholly aromatic polyamide. Examples of inorganic fibers include carbon fibers. Examples of glass fibers include E-glass cloth, D-glass cloth, S-glass cloth, Q-glass cloth, NE-glass cloth, L-glass cloth, T-glass cloth, spherical glass cloth, and low dielectric glass cloth. Among these, E-glass cloth, T-glass cloth, S-glass cloth, Q-glass cloth and organic fibers are preferable from the viewpoint of low coefficient of thermal expansion. The fiber base material may be used singly or in combination of two or more.

The shape of the fiber base material can be appropriately selected according to the intended use and performance. Specific examples include woven fabrics, non-woven fabrics, robinks, chopped strand mats and surfacing mats. Plain weave, Nanako weave, and twill weave can be exemplified as the weave method of the woven fabric. It can be arbitrarily selected and designed according to desired characteristics. The thickness of the fibrous substrate can range, for example, from about 0.01 to 1.0 mm. From the viewpoint of thinning, the thickness is preferably 500 μm or less, more preferably 300 μm or less.

If necessary, the fiber base material can be surface-treated with a silane coupling agent or the like in order to bring out the desired properties, or can be mechanically opened. In addition, corona treatment or plasma treatment may be performed. The surface treatment of the silane coupling agent includes aminosilane coupling treatment, vinylsilane coupling treatment, cationic silane coupling treatment, epoxysilane coupling treatment, and the like.

The method of impregnating the fiber base material with the resin composition is not particularly limited, but examples include alcohols, ethers, acetals, ketones, esters, alcohol esters, ketone alcohols, ether alcohols, ketone ethers, A method of preparing a varnish of a resin composition using an organic solvent such as ketone esters or ester ethers and immersing a fiber base material in the varnish, a method of applying or spraying the varnish on the fiber base material, a method of spreading the varnish on the fiber base material, A method of laminating both sides of a base material with a film made of a resin composition can be used.

Furthermore, the resin composition layer and the like formed from the present composition are suitable for insulating layers, underfill materials, adhesive materials, and the like of semiconductor chip packages. It is also suitable for use as a composition for copper-clad laminates, a bonding sheet for wiring board formation, and a cover coat for flexible substrates.

4. Method for Producing Cured Product A cured product can be obtained by subjecting the present composition to a curing treatment. When it contains a thermosetting compound, it is usually cured by heat curing treatment, and when it contains a photocurable compound, it is usually cured by light irradiation treatment. For example, a method of molding the resin composition into a desired shape such as a sheet and curing treatment can be exemplified. A molded body such as a sheet of the resin composition can be easily obtained by coating the resin composition containing a solvent and drying it. Then, the molded product is cured to form a cured product. The molding and curing may be performed at the same time. A sheet-shaped cured product is also referred to as a cured layer.

The temperature for heat curing may be appropriately selected according to the type of the curable compound (B). For example, a method of heat treatment at a temperature of 150 to 300° C. for 30 to 180 minutes can be exemplified. In the case of photocuring treatment, actinic rays may be irradiated at an intensity sufficient for curing. At the time of curing, pressure can be applied for thermocompression bonding (for example, 5 MPa) as needed. By the curing treatment, a crosslinked structure is formed in the present composition to obtain a three-dimensionally crosslinked cured product.

5. Cured product and substrate with cured product The cured product obtained from this composition has excellent long-term heat resistance, bending strength, and substrate processability during the manufacturing process. It is suitable as a cured product of various parts or a substrate with a cured product containing this cured product.
A metal-clad laminate is obtained, for example, through a process of forming an insulating layer using the present composition and laminating the insulating layer and a metal layer. Adhesive sheets and prepregs formed from the present composition can be suitably used for this insulating layer. For example, a metal-clad laminate can be obtained by laminating a metal layer and a prepreg formed using the present composition and then performing a curing treatment step by thermocompression bonding. A known method can be used for the thermocompression bonding step. For example, hot pressing is performed at a temperature of 120 to 250° C. and a pressure of 0.5 to 10 MPa for 0.5 to 5 hours.

The laminate structure of the metal-clad laminate includes a two-layer laminate of metal layer/hardened layer, a multilayer laminate of metal layer/hardened layer/metal layer, or metal layer/hardened layer/metal layer/hardened layer. A metal-clad laminate having a multi-layer structure in which metal layers or the like are alternately laminated can be exemplified. The laminate may also contain an insulating layer other than the cured layer formed from the present composition. Moreover, in order to adjust the thickness of the cured layer, a plurality of prepregs or the like may be stacked and cured. Also, a conductive layer other than a metal layer may be laminated.

For example, a metal-clad laminate having a layer structure of metal layer/hardening layer/metal layer is obtained by forming a circuit pattern on the metal layers formed on both main surfaces of the hardening layer, thereby producing a circuit board having a circuit pattern layer. can be obtained. Through-holes and vias may be formed in the cured layer using a laser or the like. A build-up process may be performed on the core substrate to stack insulating hardened layers and form vias to form multiple layers. A circuit board can be obtained, for example, by forming a desired circuit pattern on a metal layer of a metal-clad laminate by a subtractive method, or by forming a desired circuit pattern on one or both sides of an insulating layer by an additive method. can.

A copper foil or the like is used as the metal layer. A copper clad laminate includes a step of performing electrolytic copper plating on the copper foil surface, removing the resist layer, and then etching with an alkaline plating solution. The present composition is suitable for copper-clad laminates because it is excellent in substrate processability such as plating solution resistance. Furthermore, since the cured product is excellent in bending strength and long-term heat resistance, a substrate with a cured product containing a cured product formed by curing the composition can be used in a wide range of applications under various environments.

A printed wiring board is produced, for example, by processing the copper foil of a copper-clad laminate by etching or the like, forming a signal circuit or the like, and bonding a substrate and a cover film together via an adhesive sheet, followed by a curing treatment process, etc. can be manufactured. Alternatively, for example, a flexible printed wiring board can be produced by forming a conductive pattern on an insulating flexible film, forming a protective film thereon via the present adhesive sheet, and performing thermocompression bonding. Examples of the flexible film include polyester, polyimide, liquid crystal polymer, and PTFE film. The conductive pattern can be exemplified by a method of forming by printing technology, and a method by sputtering or plating.

For the cured layer of the present composition formed on one or both sides of the printed wiring board, openings may be provided by drilling or laser processing, and vias may be formed by filling with a conductive agent. A circuit layer can also be formed on the cured layer of the present composition. The cured product of the present composition has excellent plating resistance and is therefore suitable for producing multilayer printed wiring boards. A printed wiring board formed using the present composition has excellent workability and excellent long-term heat resistance and bending strength, and is therefore suitable for various electronic devices such as smartphones and tablet terminals.

Since the polyimide resin (A) of this composition has excellent electrical insulation, a cured product with excellent insulation can be provided by using an insulating material for the curable compound (B) and the thermally conductive filler (C). For example, it is suitably used as a material for forming an insulating layer on a circuit board (including a coverlay layer of a printed wiring board, an interlayer insulating layer of a built-up board, a bonding sheet, etc.). Moreover, by using a conductive material in a filler such as the thermally conductive filler (C), it can be used as a conductive member of an electronic component. Examples of electronic components include power modules such as power semiconductor devices, LEDs, and inverter devices.

Furthermore, since the cured product of this composition contains a thermally conductive filler (C), it can be applied to general applications that require heat dissipation. For example, by utilizing the moldability of the resin composition, it can be suitably used as a heat radiating component having a desired shape. In particular, it is useful as a heat-dissipating adhesive or heat-dissipating sheet for electronic devices (smartphones, doublet terminals, etc.) that cannot be equipped with a fan or heat sink due to its lightness, thinness, shortness and size, and battery exterior materials. Moreover, the cured product of the present composition is suitable as an adhesive layer between a heating element and a heat sink, or as a heat spreader. It can also be applied as a heat dissipation layer covering one or more electronic components mounted on a substrate.

Hereinafter, the present disclosure will be described more specifically by way of examples. The disclosure is not limited to the following examples. Unless otherwise specified, "%" and "parts" are based on mass.

(i) Measurement of weight-average molecular weight (Mw) Mw was measured using a GPC (gel permeation chromatograph) “GPC-101” manufactured by Showa Denko KK. THF (tetrahydrofuran) was used as the solvent, and two "KF-805L" columns (manufactured by Showa Denko Co., Ltd.: GPC column: 8 mm ID×300 mm size) connected in series were used. The conditions were a sample concentration of 1% by mass, a flow rate of 1.0 mL/min, a pressure of 3.8 MPa, and a column temperature of 40° C. Mw was determined in terms of polystyrene. Data analysis was performed by calculating the calibration curve, molecular weight and peak area using the manufacturer's built-in software, and determining the Mw with the retention time range of 17.9 to 30.0 minutes as the analysis target.

(ii) Measurement of acid value The acid value was measured according to JIS K0070. Specifically, about 1 g of a sample (polyimide resin (A)) is accurately weighed into a stoppered Erlenmeyer flask, and dissolved by adding 100 mL of cyclohexanone solvent. Phenolphthalein test solution was added to this as an indicator, titration was carried out with a 0.1N alcoholic potassium hydroxide solution, and the end point was when the indicator maintained a light red color for 30 seconds. The acid value was determined by the following formula.
Acid value (mgKOH/g) = (5.611 x a x F)/S
however,
S: Sample collection amount (g)
a: consumption of 0.1N alcoholic potassium hydroxide solution (mL)
F: Titer of 0.1N alcoholic potassium hydroxide solution

(iii) Measurement of phenolic hydroxyl value The phenolic hydroxyl value was measured according to JIS K0070. The phenolic hydroxyl value is the amount (mg) of potassium hydroxide required to neutralize the acetic acid bound to the phenolic hydroxyl group when the phenolic hydroxyl group contained in 1 g of the polyimide resin (A) is acetylated. is represented by When calculating the phenolic hydroxyl value of the polyimide resin (A), it was calculated in consideration of the acid value as shown in the following formula. Specifically, about 1 g of a sample (polyimide resin (A)) is accurately weighed into a stoppered Erlenmeyer flask, and dissolved by adding 100 mL of cyclohexanone solvent. Exactly 5 mL of an acetylating agent (a solution of 25 g of acetic anhydride dissolved in pyridine to a volume of 100 mL) was further added and stirred for about 1 hour. To this, phenolphthalein test solution is added as an indicator and maintained for 30 seconds. The solution is then titrated with 0.5N alcoholic potassium hydroxide solution until it turns pink. The phenolic hydroxyl value was determined by the following formula.
Phenolic hydroxyl value (mgKOH/g) = [{(ba) x F x 28.05}/S] + D
however,
S: Sample collection amount (g)
a: consumption of 0.5N alcoholic potassium hydroxide solution (mL)
b: Consumption (mL) of 0.5N alcoholic potassium hydroxide solution in blank experiment
F: Potency of 0.5N alcoholic potassium hydroxide solution D: Acid value (mgKOH/g)
The value of b can be determined by titrating 5 mL of the acetylating agent (a solution of 25 g of acetic anhydride dissolved in pyridine to a volume of 100 mL) with a 0.5N alcoholic potassium hydroxide solution.

(iv) Measurement of acid anhydride group value About 1 g of a sample (polyimide resin (A)) was accurately weighed into a stoppered Erlenmeyer flask and dissolved by adding 100 mL of 1,4-dioxane solvent. 10 mL of a mixed solution of octylamine, 1,4-dioxane, and water (mixing ratio (mass) is 1.49/800/80), which is larger than the amount of acid anhydride groups in the sample, is added and stirred for 15 minutes, and the acid reacted with anhydride groups. Thereafter, excess octylamine was titrated with a mixed solution of 0.02M perchloric acid and 1,4-dioxane. In addition, 10 mL of a mixed solution of octylamine, 1,4-dioxane and water (mixing ratio (mass): 1.49/800/80) to which no sample was added was also measured as a blank. The acid anhydride value was obtained by the following formula (unit: mgKOH/g)
Acid anhydride value (mgKOH/g) = 0.02 x (BA) x F x 56.11/S
B: Blank titration volume (mL)
A: Titration volume of sample (mL)
S: Sample collection amount (g)
F: 0.02 mol/L perchloric acid titer

(v) Measurement of amine value About 1 g of a sample (polyimide resin (A)) is accurately weighed into a stoppered Erlenmeyer flask, and dissolved in 100 mL of cyclohexanone solvent. A few drops of an indicator prepared by mixing a solution of 0.20 g of Methyl Orange dissolved in 50 mL of distilled water and a solution of 0.28 g of Xylene Cyanol FF dissolved in 50 mL of methanol were added. Hold for seconds. Then titrate with 0.1N alcoholic hydrochloric acid solution until the solution turns blue-grey. The amine value was determined by the following formula.
Amine value (mgKOH/g) = (5.611 x a x F)/S
however,
S: Sample collection amount (g)
a: consumption of 0.1N alcoholic hydrochloric acid solution (mL)
F: Titer of 0.1N alcoholic hydrochloric acid solution

(vi) Measurement of temperature at which storage elastic modulus G' becomes 1.0×10 ⁷ Pa A resin sheet having a thickness of 25 μm was obtained by coating on a heat-resistant release film using a doctor blade having a gap of 10 mil and drying at 130° C. for 10 minutes. The obtained resin sheet was peeled off from the heavy release film, and the storage modulus and Tg of the resin sheet were measured with a dynamic viscoelasticity measuring device "DVA200" (manufactured by IT Keisoku Kogyo Co., Ltd.).
After cooling the resin sheet to 0° C., the resin sheet was heated to 300° C. at a heating rate of 10° C./min. was confirmed to be 1.0×10 ⁷ Pa.
Heating rate: 10°C/min
Measurement frequency: 10Hz
Length between grips: 10 mm
Width: 5mm

<Synthesis of polyimide resin>
[Synthesis Example 1]
200 g of cyclohexanone was added to a 1 L separable flask equipped with a stirring bar equipped with an oil bath while introducing nitrogen gas, and 149.4 g of dimer diamine (PRIAMINE 1075) as a diamine and 4.7 g of m-aminophenol as a monoamine compound were stirred. Subsequently, 67.3 g of 1,2,4,5-cyclohexanetetracarboxylic dianhydride was added as a tetracarboxylic acid and stirred at room temperature for 30 minutes. After heating this to 100° C. and stirring for 3 hours, the oil bath was removed and the temperature was returned to room temperature to obtain a varnish-like polyimide precursor. Thereafter, while removing distilled water out of the system using a Dean-Stark trap, the mixture was heated at 170° C. for 10 hours for imidization to obtain a polyimide resin P1.

[Synthesis Examples 2 to 32, Comparative Synthesis Examples 1 to 8]
Polyimide resins P2 to P32 and N1 to N8 were obtained in the same manner as in Synthesis Example 1, except that the monomers and amounts were changed as shown in Tables 1 to 4.
Abbreviations in Tables 1 to 4 are shown below.
DM1: 1,2,4,5-cyclohexanetetracarboxylic dianhydride DM2: 1,2,3,4-butanetetracarboxylic dianhydride DM3: 4,4'-(4,4'-isopropylidenedi phenoxy)diphthalic anhydride DM4: 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride DM5: 5-(2, 5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride DM6: X-22-168B (manufactured by Shin-Etsu Chemical Co., Ltd., siloxane-type tetracarboxylic dianhydride, molecular weight 2960)
MM1: maleic anhydride MM2: phthalic anhydride DA1: Priamine 1075 (dimer diamine, manufactured by Croda Japan)
DA2: 4,4'-(hexafluoroisopropylidene)bis(2-aminophenol)
DA3: 1,12-dodecanediamine DA4: KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd., siloxane diamine, molecular weight 850)
DA5: D-2000 (manufactured by HUNTSMAN, polypropylene glycol type polyether diamine, molecular weight 2000)
MA1: m-aminophenol MA2: o-aminophenol MA3: p-aminophenol MA4: 4-hydroxyphenethylamine (tyramine)
MA5: 1-aminodecane

Tables 1 to 4 show the blending amount (parts by mass), the phenolic hydroxyl group (PhOH) value, acid anhydride group value, amine value, maleimide value, and total functional group value of the obtained polyimide resin. Also shown are the mol % of the X ¹ a residue relative to 100 mol % of the X ¹ residue and the mol % of the X ² d residue relative to 100 mol % of the X ² residue. In addition, the Mw of the polyimide resin (A), the temperature at which the storage elastic modulus G' is 1.0 × 10 ⁷ Pa, the amino group in the polyimide resin (A), the functional group selected from the acid anhydride group and the maleimide group indicates the total average functional group number of In addition, the value of the maleimide value was calculated from the charged amount used for synthesizing the polyimide resin (A). In addition, the total functional group value in this example is the total functional group value of phenolic hydroxyl value + acid anhydride group value + amine group value + maleimide value. When a carboxy group is included, the carboxy value may be added to the above formula.

[Example 1]
<<Preparation of resin composition (varnish)>>
100 parts of the polyimide resin (P1) of Synthesis Example 1 in terms of solid content, 80 parts each of (B)-1 and (B)-2 as the curable compound (B), and a thermally conductive filler (C)- 260 parts of 1 are charged in a container, a mixed solvent (toluene: MEK = 9: 1 (mass ratio)) is added so that the concentration of non-volatile components is 50%, and the varnish according to Example 1 is stirred for 10 minutes with a disper. got

<<Production of prepreg 1>>
Next, a glass cloth (#2116 type, WEA116E, E glass manufactured by Nitto Boseki Co., Ltd.) was impregnated with the obtained varnish so that the mass ratio of the glass cloth: non-volatile resin composition was 2:3. After that, the prepreg 1 according to Example 1 was obtained by drying by heating at 140° C. for about 5 minutes.

<<Production of prepreg 2>>
A prepreg 2 according to Example 1 was obtained in the same manner as in the prepreg production 1, except that the heat drying temperature and time were changed to 120° C. for 5 minutes.

<Production of copper-clad laminate>
The obtained prepreg 1 and three layers of copper foil with a thickness of 35 μm were laminated, and hot-pressed under the conditions of 250° C., 3.0 MPa, and 120 minutes. A copper-clad laminate according to Example 1 was obtained by arranging them. And the evaluation mentioned later was performed. Table 5 shows the results.

[Examples 2 to 55, Comparative Examples 1 to 15]
Varnishes according to Examples 2 to 48, 50 to 53, and Comparative Examples 1 to 15 were prepared in the same manner as in Example 1 except that the ingredients and amounts were changed to those shown in Tables 5 to 9. Prepreg 1 , prepreg 2 was obtained. In addition, with respect to Examples 49, 54, and 55, instead of prepreg 1, an adhesive sheet, which is a resin composition layer obtained in the <<manufacture of adhesive sheet>> described later, was used, and copper clad was obtained in the same manner. A laminate was obtained. Each evaluation result is shown in Tables 4-9.

<<Manufacture of adhesive sheets, etc.>>
The varnishes of Examples 49, 54, and 55 were each coated with a 50 μm thick heavy release film (polyethylene terephthalate (PET) coated with a heavy release agent) using a doctor blade so that the thickness after drying was 50 μm. ) film) and dried at 100° C. for 2 minutes. Then, it was cooled to room temperature to obtain an adhesive sheet with a single-sided release film. Next, the adhesive sheet surface of the obtained adhesive sheet with a single-sided release film is superimposed on a 50 μm thick light release film (PET film coated with a light release agent), and from the heavy release film / adhesive sheet / light release film A laminated sheet with a double-sided release film was obtained. The obtained adhesive sheet and three layers of copper foil with a thickness of 35 μm were laminated, and hot-pressed under the conditions of 250° C., 3.0 MPa, and 120 minutes. A copper-clad laminate was obtained by arranging.

Materials used in Examples and Comparative Examples are shown below.
(Curable compound (B))
(B)-1: Epoxy compound (b1), XD-1000 (manufactured by Nippon Kayaku Co., Ltd., dicyclopentadiene type epoxy, polyfunctional, functional group equivalent 252 g/eq.)
(B)-2: cyanate ester compound (b2), BAD (manufactured by Mitsubishi Gas Chemical Company, bisphenol A type cyanate ester, bifunctional, functional group equivalent weight 139 g/eq)
(B)-3: Maleimide compound (b3), BMI-3000 (manufactured by Daiwa Kasei Kogyo Co., Ltd., bisphenol A diphenyl ether bismaleimide, difunctional, functional group equivalent 285.3 g/eq.)
(B)-4: Polyphenylene ether compound (b4), Noryl (registered trademark) SA9000 (manufactured by SABIC, methacrylate group-containing polyphenylene ether, bifunctional, functional group equivalent: 850 g/eq.)
(B)-5: Nadimide compound (b5), BANI-M (manufactured by Maruzen Petrochemical Co., Ltd., bisallyl nadimide, difunctional)
(B)-6: Active ester compound, HPC-8000-65T (manufactured by SABIC, active ester compound)
(B) -7: Phenolic resin, H-4 (manufactured by Meiwa Kasei Co., Ltd.)
(B)-8: dodecanedioic acid dihydrazide (thermally conductive filler (C))
(C)-1: AO-509 (manufactured by Admatechs, alumina)
(C)-2: SP-2 (manufactured by Denka, boron nitride)
(C)-3: SC2050-MB (manufactured by Admatechs, silica)
(C)-4: FZO-50 (manufactured by Ishihara Sangyo Co., Ltd., zinc oxide)
(Heat stabilizer (D))
(D)-1:2 pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] ("IRGANOX1010" manufactured by BASF)
(D)-2: TT-LX (1-[N,N-bis(2-ethylhexyl)aminomethyl]methylbenzotriazole)
(D)-3: bis(2-allylphenoxy)phosphazene

(vii) Measurement of Tg of cured product of resin composition Using a doctor blade with a gap of 10 mil on a heat-resistant release film, apply the varnish according to each example and dry at 130 ° C. for 10 minutes. Thus, a resin composition layer having a thickness of 25 μm was obtained. The obtained resin composition layer was peeled off from the heavy release film and heat-treated at 250° C. for 60 minutes to obtain a cured layer. For the obtained cured layer, using the same dynamic viscoelasticity measuring device as in (vi), under the same conditions of temperature increase rate, measurement frequency, length between grips, and width, at a temperature range of -50 to 400 ° C. Loss tangent (tan δ) was measured, and Tg was measured by the same method as above.

α. Bending strength The obtained copper-clad laminate was cut into a piece having a width of 40 mm and a length of 25 mm. On a plane parallel to the horizontal plane, two support members made of metal and having rounded ends were placed at a distance (23.7 mm) shorter than the length of the test piece. The specimen was placed on the support members so that the longitudinal center of the specimen overlapped the center of the spacing between the two support members. Subsequently, from above the center of the test piece, a pressurizing tool made of metal and having a rounded tip was pressed against the central portion of the test piece to apply force to the test piece. The speed at which the force was applied to the test piece was 1.0 mm/min. The force was continued to be applied to the specimen and ended when the specimen broke. The bending strength in terms of 1.6 mm thickness was calculated based on the distance between support members (distance between fulcrums), the width of the test piece, the thickness of the test piece, and the force applied when the test piece broke.
A: 400 N/mm ² or more.
B: 300 N/mm ² or more and less than 400 N/mm ² .
C: 200 N/mm ² or more and less than 300 N/mm ² .
D: 150 N/mm ² or more and less than 200 N/mm ² .
E: 100 N/mm ² or more and less than 150 N/mm ² .
F: Less than 100 N/ ^mm2 . Not practical.

β. Substrate processing suitability A printed wiring board for evaluation was produced according to the following method, and a series of tests of embeddability, heat cycle resistance, and plating solution resistance were conducted. After that, the printed wiring board for evaluation was cut, and the exposed cross section was observed with an optical microscope at a magnification of 100 times.

<Preparation of printed wiring board for evaluation (embeddability test in copper circuit)>
A glass cloth-based epoxy resin copper-clad laminate having L/S=25 μm/25 μm and two types of circuit patterns having copper thicknesses of 25 μm and 50 μm, respectively, was prepared as an inner layer circuit board. The prepregs according to the examples and comparative examples (hereinafter referred to as each example) were heat-pressed on both sides under the conditions of 250° C., 3.0 MPa, and 120 minutes, and then copper foil was placed on the outermost layers on both sides. A printed wiring board for evaluation was obtained. In Examples 49, 54 and 55, printed wiring boards for evaluation were obtained in the same manner using the obtained adhesive sheets.

<Heat cycle test>
The printed wiring board for evaluation was put into a thermal shock device ("TSE-11-A", manufactured by Espec Co., Ltd.), and exposed to high temperature: 125 ° C. for 15 minutes, low temperature exposure: -50 ° C., 15 minutes. A predetermined number of alternating exposures were performed.

<Plating solution resistance test>
The printed wiring board for evaluation after the above heat cycle test was subjected to the following acidic plating test, then washed with pure water and dried. After that, using the same sample, the following alkaline plating test was carried out.
[I. Acid plating test]
The adhesive sheet with the double-sided release film was cut into a size of 65 mm×65 mm, and the light release film was peeled off. Then, the adhesive sheet surface exposed by peeling was combined with a two-layer CCL [ESPANEX MC18-25-00FRM] copper surface manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. and laminated at 90 ° C., followed by 180 ° C. and 2.0 MPa. The crimping process was performed for 60 minutes under the conditions. Finally, the heavy release film was peeled off to prepare a test piece for evaluation. For this test piece, the light release film was peeled off from the adhesive sheet with the double-sided release film, and the exposed adhesive sheet surface was subjected to electroless nickel treatment according to the following procedures and conditions hn.
h. Acid degreasing step: immersion in ICP Clean S-135K (manufactured by Okuno Chemical Industry Co., Ltd.) at 40° C. for 4 minutes.
i. Soft etching step: immersion in sodium persulfate at 30°C for 1 minute.
j. Desmutting step: immersion in sulfuric acid at 25°C for 1 minute.
k. Pre-dip step: immersion in hydrochloric acid at 25° C. for 30 seconds.
l. Activation step: Immerse in ICP Accela (manufactured by Okuno Chemical Industry Co., Ltd.) at 30°C for 1 minute.
m. Post-dipping step: Immerse in sulfuric acid at 25°C for 1 minute.
n. Electroless nickel plating process: immersed in IP Nicolon FPF (manufactured by Okuno Chemical Industry Co., Ltd.) at 85°C for 20 minutes.
[II. Alkaline Plating Test]
A test piece for evaluation was prepared in the same manner as the acid plating test, and the test piece was subjected to electroless nickel treatment according to the following procedures and conditions of sw.
s. Alkaline degreasing step: Immersed in an alkaline degreasing agent (50 g/L aqueous solution of A-SCREEN A-220 (trade name) manufactured by Okuno Pharmaceutical Co., Ltd.) at 50°C for 5 minutes.
t. Etching process: immersion at 67° C. for 10 minutes in an aqueous solution containing 400 g/L of chromic anhydride and 400 g/L of 98% sulfuric acid.
u. Activation step: immersion in an aqueous solution containing 20 mL/L of 98% sulfuric acid at 25°C for 2 minutes.
v. Imparting catalytic activity: Immerse in a catalyst activating solution (manufactured by Okuno Chemical Industry Co., Ltd., an aqueous solution containing 10 mL/L of TSP Activator Conc (trade name)) at 25°C for 2 minutes.
w. Electroless nickel plating process: Ammonia alkali type autocatalytic electroless nickel plating solution (manufactured by Okuno Chemical Industry Co., Ltd., chemical nickel A (trade name) 160 mL / L, chemical nickel B (trade name) pH 9 containing 160 mL / L solution) at 40°C for 5 minutes.

The samples subjected to the above series of tests were evaluated according to the following criteria. Incidentally, the term "defective appearance" refers to the occurrence of peeling from the substrate surface, voids, and the like.
A: No appearance defects after completion of the embedding test in a copper circuit with a thickness of 50 μm, the heat cycle test of 5000 times, and the plating solution resistance test.
B: Although it does not correspond to A above, there is no appearance defect after the embedding test in a copper circuit with a thickness of 50 μm, the heat cycle test of 1000 times, and the plating solution resistance test.
C: Not applicable to the above A and B, but no appearance defects after completion of the embedding test in a copper circuit with a thickness of 50 μm, the heat cycle test of 200 times, and the plating solution resistance test.
D: Although it does not correspond to the above A to C, there is no appearance defect after completion of the embedding test in a copper circuit with a thickness of 25 μm, the heat cycle test of 200 times, and the plating solution resistance test.
E: Although it does not correspond to the above A to D, there is no appearance defect after the embedding test in a copper circuit with a thickness of 25 μm, the heat cycle test of 50 times, and the plating solution resistance test.
F: Not applicable to any of the above A to E. Not practical.

γ. Long-term heat resistance The prepreg or adhesive sheet prepared in each example is cut into a width of 40 mm and a length of 25 mm, and the cut sample is heated and pressed under the conditions of 250 ° C., 3.0 MPa, and 120 minutes to obtain a cured product. Tg was measured. Subsequently, this cured product was stored in an air atmosphere at 250° C. for 1000 hours in a hot air oven, and the Tg after storage was measured. Long-term heat resistance was evaluated from the degree of decrease in Tg after storage relative to Tg before storage.
A: less than 5% reduction.
B: Decrease width of 5% or more and less than 8%.
C: Reduction width of 8% or more and less than 10%.
D: Reduction range of 10% or more and less than 15%.
E: Reduction range of 15% or more and less than 20%.
F: Decrease width of 20% or more. Not practical.

δ. Manufacturability of Prepregs 1 and 2 The prepregs 1 and 2 of each example were cut, and the exposed cross section was observed with a scanning electron microscope (SEM) at a magnification of 5000 times. In addition, the void means a crack having a size of 0.1 μm or more.
A: No voids were observed when dried at 120°C for about 5 minutes and when dried at 140°C for about 5 minutes.
B: Although voids were observed when dried at 120°C for about 5 minutes, no voids were observed when dried at 140°C for about 5 minutes.

A resin composition containing a polyimide resin in which the total average number of functional groups of amino groups, acid anhydride groups and maleimide groups per molecule exceeds 1 was inferior in substrate processability as shown in Comparative Examples 1 to 3. . Moreover, the resin composition using the polyimide resin at which the storage modulus G′ becomes 1.0×10 ⁷ Pa at a temperature exceeding 90° C. was inferior in flexural strength as shown in Comparative Examples 4 and 5. Moreover, as shown in Comparative Example 6, the resin composition using a polyimide resin having an Mw of less than 10,000 was inferior in substrate processability. Furthermore, the resin composition using a polyimide resin having an Mw exceeding 100,000 was inferior in long-term heat resistance as shown in Comparative Example 7. On the other hand, Examples 1 to 55 according to the present disclosure have substrate processing suitability that combines embeddability into substrate unevenness, heat cycle resistance, and plating solution resistance, and the cured product has excellent long-term heat resistance and bending strength. I was able to confirm that it is excellent.

This application claims priority based on Japanese Patent Application No. 2021-213179 filed on December 27, 2021, and the entire disclosure thereof is incorporated herein.

Claims

A resin composition containing a polyimide resin (A), a curable compound (B) and a thermally conductive filler (C),
The polyimide resin (A) has residues X 2 d derived from dimer diamine and/or dimer diisocyanate, and the total average number of functional groups selected from amino groups, acid anhydride groups and maleimide groups is 0. is less than or equal to 1 including
The temperature at which the polyimide resin (A) has a storage modulus G' of 1.0×10 7 Pa is in the range of −30 to 90° C., and the polyimide resin (A) has a weight average molecular weight of 10,000 to 100. ,000, and
The curable compound (B) is one or two selected from the group consisting of an epoxy compound (b1), a cyanate ester compound (b2), a maleimide compound (b3), a polyphenylene ether compound (b4) and a nadimide compound (b5). and
A resin composition having a glass transition temperature of 140 to 400° C. in a cured product obtained by curing treatment.
The polyimide resin (A) has the general formula (1):

(X 1 is independently a tetravalent tetracarboxylic acid residue for each repeating unit, X 2 is independently a divalent organic group for each repeating unit, and the X 1 and the imide bond are bonded to each other. form two imide rings.)
Having a repeating unit of the structure represented by
The claim characterized by having 60 to 100 mol% of the residue X 2d derived from the dimer diamine and/or dimer diisocyanate when the entire X 2 constituting the polyimide resin (A) is 100 mol%. Item 1. The resin composition according to item 1.
The resin composition according to claim 1 or 2, further comprising a heat stabilizer (D).
The resin composition according to claim 1 or 2, characterized in that 1 to 40% by mass of the polyimide resin (A) is blended in 100% by mass of the non-volatile components of the resin composition.
3. The resin composition according to claim 1 or 2, which contains an epoxy compound (b1) as the curable compound (B) and further contains an active ester compound.
A laminated sheet comprising a substrate and a resin composition layer formed of the resin composition according to any one of claims 1 to 5 provided on the substrate.
A prepreg in which a base material is impregnated with the resin composition according to any one of claims 1 to 5.
A cured product obtained from the resin composition according to any one of claims 1 to 5.
A substrate with a cured product, comprising a cured product formed by curing the resin composition according to any one of claims 1 to 5.
An electronic device equipped with the substrate with a cured product according to claim 9.