TW202323387A - Thermosetting compositions, adhesive sheets, printed wiring boards, and electronic devices - Google Patents

Abstract

A heat-curable composition comprising: a polyimide resin (A) which has a repeating unit of general formula (1), has a phenolic hydroxyl group, and has a storage modulus G' of 1.0*107 Pa at a temperature of 0-90 DEG C, at least some of the X2 moieties having residues X2d derived from a dimer diamine, etc.; and a crosslinking agent (B) having two or more functional groups. The crosslinking agent (B) includes one or more compounds selected from the group consisting of epoxidized compounds (b1), cyanate ester compounds (b2), etc., these compounds being contained in an amount of 0.5-10 parts by mass per 100 parts by mass of the polyimide resin (A).

Description

Thermosetting composition, adhesive sheet, printed wiring board and electronic equipment

The present invention relates to a thermosetting composition containing polyimide resin. In addition, the present invention relates to an adhesive sheet including a thermosetting composition, and a printed wiring board and electronic equipment formed using the adhesive sheet.

Since polyimide resins are excellent in heat resistance and chemical resistance, they are widely used in a wide range of fields including the electrical insulation field and the electronic field. For example, Patent Document 1 discloses a method of forming a coating film from a thermosetting ink composition containing an amide acid having a specific structure by inkjet coating, and curing it to obtain a polyimide membrane. In addition, Patent Document 2 discloses a polyimide-based adhesive comprising a terminal-modified polyimide, a crosslinking agent, and an organic solvent. A reaction product of an acid anhydride group-terminated polyimide, which is a reaction product of a monomer group including an aromatic tetracarboxylic anhydride and a dimer diamine, and a primary monoamine is used for the terminal-modified polyimide.

Patent Document 3 discloses a polyimide-based adhesive composition comprising a polyimide resin obtained by reacting aromatic tetracarboxylic acids and diamines containing a specific amount of dimer diamine, heat Hardening resins, flame retardants, and organic solvents. In addition, a polyimide-based adhesive composition using a polyimide resin in which chain extension is further performed by diamines containing a specific amount of dimer diamine in the polyimide resin is disclosed. . Patent Document 4 discloses a resin film containing polyimide obtained by reacting a tetracarboxylic anhydride component and a diamine component having a dimer structure, and exhibiting specific dielectric properties. A resin composition is disclosed in Patent Document 5, which includes a polyimide resin, an epoxy resin, and a hardener that can harden the epoxy group. The polyimide resin contains aliphatic, alicyclic and/or An aromatic tetracarboxylic acid residue, and a diamine residue including dimer diamine. A polyimide resin is disclosed in Patent Document 6, which is an imide compound of a polyamide acid resin. The polyamide acid resin is an aminophenol compound, an aliphatic diamine compound, a tetrabasic acid diamine The reaction product of an anhydride and an aromatic diamine-based compound, and has amine groups at both ends. In addition, a resin composition including an end-modified polyimide resin obtained by using the polyimide resin is disclosed. Patent Document 7 discloses a curable resin composition containing a curable resin and a curing agent (including an imide oligomer). In addition, it is described that the Tg of the curable resin composition is preferably 0°C or more and less than 25°C, and after curing is preferably 100°C or more and less than 250°C. [Prior art literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2013-032501 [Patent Document 2] Japanese Patent Laid-Open No. 2016-191049 [Patent Document 3] Japanese Patent Laid-Open No. 2013-199645 [Patent Document 4] Japanese Patent Laid-Open No. 2020-056011 [Patent Document 5] Japanese Patent Laid-Open No. 2015-117278 [Patent Document 6] International Publication No. 2020/189354 [Patent Document 7] International Publication No. 2019/188436

[Problem to be Solved by the Invention] When exposed to an alkaline aqueous solution or an acid solution in a plating process during electronic component manufacture, there is a problem that floating or peeling easily occurs between members. For example, in the thermosetting ink composition containing amide acid disclosed in Patent Document 1, since polyamide acid which is a polyimide precursor is used, there is a problem of low storage stability. In addition, since this ink composition uses polyamic acid with a high acid value, there are problems such as insufficient plating solution resistance. In addition, the polyimide-based adhesive disclosed in Patent Document 2 or Patent Document 3 has insufficient alkali resistance, and there is a problem that the adhesive layer tends to peel off when exposed to an aqueous alkali solution.

On the other hand, with the popularization of electronic devices such as smartphones and tablet terminals in recent years, reliability in a wide temperature range is required. In particular, it is required to exhibit high insulation reliability against extreme temperature changes (hereinafter, insulation reliability after a thermal cycle test). For example, in the polyimide-based adhesive disclosed in Patent Document 2, ion migration is likely to occur under voltage application after a heat cycle test, and a short circuit is likely to occur, resulting in a problem in insulation reliability. In the polyimide-containing resin film disclosed in Patent Document 4 or the resin composition disclosed in Patent Document 5, there is also a problem in terms of insulation reliability after a heat cycle test.

Furthermore, with the development of high-speed and large-capacity wireless communication in recent years, liquid crystal polymer (LCP (Liquid Crystal Polymer)) substrates with low dielectric properties have attracted attention, and compatibility with LCP substrates is being sought in the market. Good material. However, in the lamination step of temporary bonding of the LCP substrate and the thermosetting sheet, there is a problem that temporary bonding defects are likely to occur. For example, in the polyimide resin composition disclosed in Patent Document 6, there is a problem of insufficient lamination properties with respect to an LCP substrate. In addition, as electronic devices such as smartphones and tablet terminals become thinner, excellent bendability is required.

The present invention is made in view of the above-mentioned background, and its object is to provide an excellent lamination property to the LCP base material, which is excellent in plating solution resistance (alkali resistance and acid resistance) by curing the composition, and bendable. Thermosetting composition of cured product which is also excellent in performance and excellent in insulation reliability after thermal cycle test, adhesive sheet, printed wiring board and electronic equipment formed using the adhesive sheet. [Means to solve the problem]

（X ¹於每個重複單元分別獨立地為四價四羧酸殘基，X ²於每個重複單元分別獨立地為二價有機基，所述X ¹與醯亞胺鍵相互鍵結而形成兩個醯亞胺環） 所述X ²的至少一部分為源自二聚物二胺及/或二聚物二異氰酸酯的殘基X ²d， 聚醯亞胺樹脂（A）中儲存彈性係數G'成為1.0×10 ⁷Pa的溫度處於0℃～90℃中的任一溫度， 交聯劑（B）包含選自由含環氧基的化合物（b1）、氰酸酯酯化合物（b2）、含異氰酸酯基的化合物（b3）、金屬螯合化合物（b4）、含碳二醯亞胺基的化合物（b5）及含馬來醯亞胺基的化合物（b6）所組成的群組中的一種以上， 相對於聚醯亞胺樹脂（A）100質量份，含環氧基的化合物（b1）、氰酸酯酯化合物（b2）、含異氰酸酯基的化合物（b3）、金屬螯合化合物（b4）、含碳二醯亞胺基的化合物（b5）及含馬來醯亞胺基的化合物（b6）的合計含量為0.5質量份～10質量份。 [2]：如[1]所述的熱硬化性組成物，其特徵在於，於180℃、60分鐘的條件下熱硬化後的玻璃轉移溫度為0℃～70℃。 [3]：如[1]或[2]所述的熱硬化性組成物，包含滿足以下的（i）～（iv）中的至少任一者的酚性羥基作為所述酚性羥基。 （i）於分子鏈末端具有酚性羥基，於具有該酚性羥基的芳香環的間位或鄰位鍵結有形成源自單胺的醯亞胺環的氮原子。 （ii）於分子鏈末端具有酚性羥基，具有與具有該酚性羥基的芳香環直接鍵結的脂肪族基，於該脂肪族基鍵結有形成源自單胺的醯亞胺環的氮原子。 （iii）所述X ²的一部分為具有酚性羥基的二胺殘基X ²f，於具有該酚性羥基的芳香環鍵結有形成源自二胺的醯亞胺環的氮原子。 （iv）所述X ²的一部分為具有酚性羥基的二胺殘基X ²f，具有與具有該酚性羥基的芳香環直接鍵結的脂肪族基，於該脂肪族基鍵結有形成源自二胺的醯亞胺環的氮原子。 [4]：如[1]至[3]中任一項所述的熱硬化性組成物，其特徵在於，聚醯亞胺樹脂（A）中的所述X ¹的至少一部分為具有脂肪族基的X ¹a，相對於該X ¹100莫耳%，具有60莫耳%～100莫耳%的所述X ¹a。 [5]：如[1]至[4]中任一項所述的熱硬化性組成物，其特徵在於，相對於不揮發成分100質量%，包含0.1質量%～10質量%的紫外線吸收劑（C）。 [6]：如[1]至[5]中任一項所述的熱硬化性組成物，其特徵在於，相對於不揮發成分100質量%，包含3質量%～60質量%的填料（D）。 [7]：一種接著片，包含如[1]至[6]中任一項所述的熱硬化性組成物。 [8]：一種印刷配線板，使用如[7]所述的接著片而形成。 [9]：一種電子機器，具有如[8]所述的印刷配線板。 [發明的效果] As a result of diligent research, the present inventors found that the problems of the present invention can be solved in the following aspects, and completed the present invention. [1]: A thermosetting composition comprising a polyimide resin (A) and a crosslinking agent (B) having two or more functional groups. In the thermosetting composition, the polyimide resin (A) a repeating unit having a structure represented by the general formula (1), and having a phenolic hydroxyl group, [Chem. 1]

(X ¹ is independently a tetravalent tetracarboxylic acid residue in each repeating unit, and X ² is independently a divalent organic group in each repeating unit, and the X ¹ and an imide bond are bonded to each other to form Two imide rings) At least a part of X ² is the residue X ² d derived from dimer diamine and/or dimer diisocyanate, storage elastic coefficient G in polyimide resin (A) 'The temperature at which 1.0×10 7 Pa becomes 1.0×10 ⁷ Pa is at any temperature between 0°C and 90°C, and the crosslinking agent (B) contains an epoxy group-containing compound (b1), a cyanate ester compound (b2), a compound containing One or more of the group consisting of isocyanate group-containing compound (b3), metal chelate compound (b4), carbodiimide group-containing compound (b5) and maleimide group-containing compound (b6) , per 100 parts by mass of polyimide resin (A), epoxy group-containing compound (b1), cyanate ester compound (b2), isocyanate group-containing compound (b3), metal chelate compound (b4) The total content of the carbodiimide group-containing compound (b5) and the maleimide group-containing compound (b6) is 0.5 to 10 parts by mass. [2]: The thermosetting composition according to [1], wherein the glass transition temperature after thermosetting at 180°C for 60 minutes is 0°C to 70°C. [3]: The thermosetting composition according to [1] or [2], which contains, as the phenolic hydroxyl group, a phenolic hydroxyl group that satisfies at least one of the following (i) to (iv). (i) It has a phenolic hydroxyl group at the end of the molecular chain, and a nitrogen atom forming an imide ring derived from a monoamine is bonded to the meta-position or ortho-position of the aromatic ring having the phenolic hydroxyl group. (ii) Has a phenolic hydroxyl group at the end of the molecular chain, has an aliphatic group directly bonded to an aromatic ring having the phenolic hydroxyl group, and has bonded to the aliphatic group a nitrogen forming an imide ring derived from a monoamine atom. (iii) A part of X ² is a diamine residue X ² f having a phenolic hydroxyl group, and a nitrogen atom forming an imide ring derived from a diamine is bonded to an aromatic ring having the phenolic hydroxyl group. (iv) A part of the X ² is a diamine residue X ² f having a phenolic hydroxyl group, has an aliphatic group directly bonded to an aromatic ring having the phenolic hydroxyl group, and forms a bond to the aliphatic group. A nitrogen atom derived from an imide ring of a diamine. [4]: The thermosetting composition according to any one of [1] to [3], wherein at least a part of the X ¹ in the polyimide resin (A) has an aliphatic The base X ¹ a has 60 mol % to 100 mol % of said X ¹ a relative to 100 mol % of said X ¹ . [5]: The thermosetting composition according to any one of [1] to [4], which contains 0.1% by mass to 10% by mass of an ultraviolet absorber based on 100% by mass of non-volatile components (C). [6]: The thermosetting composition according to any one of [1] to [5], which contains 3% by mass to 60% by mass of filler (D ). [7]: An adhesive sheet comprising the thermosetting composition according to any one of [1] to [6]. [8]: A printed wiring board formed using the adhesive sheet described in [7]. [9]: An electronic machine having the printed wiring board as described in [8]. [Effect of the invention]

According to the present invention, the following excellent effects can be achieved: it is possible to provide an LCP substrate with excellent lamination properties, excellent plating solution resistance (alkali resistance and acid resistance) obtained by curing the composition, and thermal cycle resistance. A cured thermosetting composition having excellent insulation reliability after a test, an adhesive sheet, a printed wiring board and an electronic device formed using the adhesive sheet.

Hereinafter, the present invention will be described in detail. Furthermore, as long as it conforms to the gist of the present invention, other embodiments are also included in the scope of the present invention. In addition, the numerical range specified using "-" in this specification shall be the range which includes the numerical value described before and after "-" as a lower limit and an upper limit. In addition, "film" and "sheet" have the same meaning in this specification, and are not distinguished by thickness. In addition, unless otherwise noted, each of the various components appearing in this specification may be independently used alone or in combination of two or more. The numerical value described in this specification means the value obtained by the method described in the [Example] mentioned later.

式（1）中的X ¹於每個重複單元分別獨立地為四價四羧酸殘基，X ²於每個重複單元分別獨立地表示二價有機基。X ¹與醯亞胺鍵相互鍵結而形成兩個醯亞胺環。所述X ²的至少一部分為源自二聚物二胺及/或二聚物二異氰酸酯的殘基X ²d（以下，亦稱為二聚物結構）。 1. Thermosetting composition The thermosetting composition of this embodiment (hereinafter, also referred to as this composition) contains a polyimide resin (A) and a crosslinking agent (B) having two or more functional groups . The polyimide resin (A) has a repeating unit of a structure represented by the following general formula (1), and has a phenolic hydroxyl group. [Chem 2]

X ¹ in the formula (1) is independently a tetravalent tetracarboxylic acid residue for each repeating unit, and X ² independently represents a divalent organic group for each repeating unit. X ¹ and the imide bond are mutually bonded to form two imide rings. At least a part of the X ² is a residue X ² d derived from dimer diamine and/or dimer diisocyanate (hereinafter also referred to as a dimer structure).

In this specification, the so-called "tetracarboxylic acid residue" refers to tetracarboxylic acid derivatives derived from tetracarboxylic acid, tetracarboxylic dianhydride, and tetracarboxylic diester (hereinafter, these are referred to as "tetracarboxylic acid residues"). ”), the term “organic group” in the formula (1) refers to a group derived from an organic compound having a functional group reactive with tetracarboxylic acids. The imide bond is obtained by reaction of tetracarboxylic acids with the organic compound. As a preferable example of the said organic compound, a diamine and a diisocyanate can be illustrated.

The so-called "imide bond" is assumed to include one nitrogen atom and two carbonyl bonds (C=O), and the imide bond is bonded to a part of X ¹ in formula (1) to form an imide ring. The "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 it is 5 or 6. The imide ring can be condensed with other rings. In addition, the "acid anhydride group" means a group represented by -C(=O)-OC(=O)-, and the "acid anhydride ring" means a ring formed by bonding an acid anhydride group to a carbon element.

The crosslinking agent (B) is selected from compounds containing epoxy groups (b1), cyanate ester compounds (b2), compounds containing isocyanate groups (b3), metal chelate compounds (b4), carbodiamide-containing compounds One or more species selected from the group consisting of an amino group-containing compound (b5) and a maleimide group-containing compound (b6) (hereinafter also referred to as (b1) to (b6)). The total content of (b1) to (b6) is 0.5 to 10 parts by mass relative to 100 parts by mass of the polyimide resin (A). Here, the term "thermosetting composition" refers to a composition that includes a thermosetting resin and is cured by forming a three-dimensional crosslinked structure of the resin through heat curing treatment. In addition, the term "cured product" in this specification refers to a state cured to such an extent that the curing reaction does not substantially proceed even if it is further heated. When the thermosetting composition is molded into a desired shape such as a sheet, part of it can undergo a curing reaction, but the state that can be cured by further heating is not included in the cured product described here. In the stage of the thermosetting composition, it may be in a B-stage state where a part of the components are semi-hardened.

Previously, LCP substrates were prone to temporary poor lamination, and a composition that could be laminated at low temperature and in a short time was required. Since this composition has such a structure, it is excellent in lamination property to LCP base material. This is considered to be due to the effect of using a highly flexible resin with a storage modulus G' of 1.0×10 ⁷ Pa at any temperature between 0°C and 90°C, the effect of the affinity of the phenolic hydroxyl group for the LCP substrate, And the synergistic effect brought about by the high wettability of the dimer structure. It is possible to provide a thermosetting composition, and a thermosetting sheet formed of this composition has an excellent performance with respect to an LCP substrate, for example, even at a low temperature of about 90°C to 100°C x a heating time of about 60 seconds to 120 seconds. lamination.

In addition, since this composition has the above structure, a cured product having excellent alkali resistance and acid resistance (hereinafter, also collectively referred to as plating solution resistance) can be obtained. In addition, the alkali resistance and acid resistance in this specification refer to the tolerance with respect to the evaluation described in the Example mentioned later. In particular, a polyimide resin (A) having a dimer structure, having a storage elastic coefficient G' of 1.0×10 ⁷ Pa within the above-mentioned specific range, and introducing a phenolic hydroxyl group can significantly improve Improve the plating solution resistance of hardened products. It is considered that by including any one of (b1) to (b6) as the crosslinking agent (B), crosslinking can be formed between the phenolic hydroxyl group of the polyimide resin (A) and the crosslinking agent (B). Linked structure, the effect brought about by the interaction between the aromatic ring of the phenolic hydroxyl group near the crosslink and the imide ring of the polyimide resin (A). In addition, it is considered to be an effect of constructing a strong cross-linked structure by cross-linking the phenolic hydroxyl group of the polyimide resin (A) with the cross-linking agent (B). Furthermore, the reactive functional group in the polyimide resin (A) is crosslinked with the crosslinking agent (B) by thermosetting, but a part of it may remain as a reactive functional group without being crosslinked. . When the remaining functional group is a phenolic hydroxyl group, acid resistance and alkali resistance can be improved, for example, compared with the case where an acid anhydride group, a carboxyl group, and/or an amine group remain. In addition, even when an acid anhydride group, a carboxyl group, and/or an amine group are used together with a phenolic hydroxyl group, the remaining amount of carboxyl groups and the like can be further reduced, so the effect of improving acid resistance and alkali resistance can be expected.

Furthermore, since this composition has the said structure, the hardened|cured material which is excellent in insulation reliability also after a heat cycle test can be obtained. By using the polyimide resin (A) which satisfies the condition of the storage elastic coefficient G' and further has a dimer structure with less interaction between molecular chains having a hydrocarbon chain or ring structure, it is possible to moderately hinder The encapsulation around the imide ring with high planarity achieves both uniform dispersion of the imide ring and flexibility. By blending a relatively small amount of the specific crosslinking agent (B) into this polyimide resin (A), in the cured product of this composition, it is possible to alleviate the occurrence of rapid temperature changes during thermal cycles. stress, thereby inhibiting the generation of cracks, etc. As a result, it is considered that excellent insulation reliability can be achieved also after the thermal cycle test.

This composition is preferably used as various sheets or films typified by, for example, a thermosetting adhesive sheet and a thermosetting cover sheet. These can be used by using other substrates or layers and the laminated layer formed from this composition. As the lamination method, known methods can be applied without limitation. For example, there are coating methods and lamination methods. The lamination method is excellent in terms of simplicity. Hereinafter, each component and the manufacturing method of this composition are demonstrated.

1-1. Polyimide resin (A) As mentioned above, polyimide resin (A) has the repeating unit of the structure represented by the said General formula (1), and has a phenolic hydroxyl group. The position of the phenolic hydroxyl group of the polyimide resin (A) is not particularly limited. The temperature at which the storage modulus G' becomes 1.0×10 ⁷ Pa in the polyimide resin (A) is any one of 0°C to 90°C. A resin whose storage modulus G' satisfies the above conditions softens at a low temperature to improve fluidity, thereby improving wettability to the substrate, but has the problem that resistance to a plating solution tends to deteriorate compared to conventional ones. As a result of repeated studies by the inventors of the present invention, it was found that the above-mentioned resistance to plating can be solved by using this composition of the polyimide resin (A) having a phenolic hydroxyl group on the basis of the storage elastic coefficient under the above conditions. liquid problem. The polyimide resin (A) may be used alone or in combination of two or more.

1-1-a. X ¹ in the general formula (1) As described above, X ¹ in the general formula (1) is a tetravalent tetracarboxylic acid residue that may have an independent structure for each repeating unit. Tetracarboxylic acids used for polymerization to obtain ^X1 are not particularly limited. As tetracarboxylic acids, aromatic tetracarboxylic acids containing aromatic groups, aliphatic tetracarboxylic acids containing aliphatic groups, and tetracarboxylic acids containing aromatic groups and aliphatic groups can be preferably used. Heteroatoms such as nitrogen, oxygen, sulfur, selenium, fluorine, chlorine, bromine, etc. may also be included in ^X1 . Tetracarboxylic acids may be used alone or in combination of two or more. In addition, examples of the monomers may suitably have substituents. As a substituent, an alkyl group, a halogen atom, a nitro group, a cyano group etc. can be illustrated.

式中的X ⁵表示二價的可具有取代基的有機基（例如碳數1～10的烴基）、-O-、-CO-、-SO ₂-、-S-、-SO ₂-、-CONH-、-COO-、或-OCO-、-C(CF ₃) ₂-、-COO-Z-OCO-、-O-Ph-C(CH ₃) ₂-Ph-O-等連結基。所述Z例如可例示：-C ₆H ₄-、-(CH ₂) _n-、-CH ₂-CH(-O-C(=O)-CH ₃)-CH ₂-。該些亦可包含取代基。作為所述取代基，可例示：烷基、鹵素、羰基等。於後述的四羧酸中亦相同。作為具體例，可例示：3,3',4,4'-二苯甲酮四羧酸二酐、3,3',4,4'-聯苯四羧酸二酐、3,3',4,4'-二苯基碸四羧酸二酐、4,4'-氧基二鄰苯二甲酸酐、4,4'-(六氟亞異丙基)二鄰苯二甲酸酐、2,2-雙〔4-(3,4-二羧基苯氧基)苯基〕丙烷二酐、對苯雙(偏苯三甲酸單酯酸酐)、乙二醇雙脫水偏苯三酸酯。 Examples of aromatic tetracarboxylic acids include: pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 2,3',3,4'-biphenyltetracarboxylic dianhydride , 3,3',4,4'-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, the following Diphthalic dianhydride represented by the general formula (2). [chemical 3]

X ⁵ in the formula represents a divalent organic group that may have substituents (such as a hydrocarbon group with 1 to 10 carbons), -O-, -CO-, -SO ₂ -, -S-, -SO ₂ -, - Linking groups such as CONH-, -COO-, or -OCO-, -C(CF ₃ ) ₂ -, -COO-Z-OCO-, -O-Ph-C(CH ₃ ) ₂ -Ph-O-. Z can be exemplified, for example, -C ₆ H ₄ -, -(CH ₂ ) _n -, -CH ₂ -CH(-OC(=O)-CH ₃ )-CH ₂ -. These may also contain substituents. As said substituent, an alkyl group, a halogen, a carbonyl group etc. can be illustrated. The same applies to tetracarboxylic acids described later. As specific examples, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-Diphenyl tetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 2 , 2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, terephthalic bis(trimellitic acid monoester anhydride), ethylene glycol dianhydro trimellitate.

From the viewpoint of effectively improving the laminability of the LCP base material at low temperature and further improving the insulation reliability after thermal cycles, at least a part of ^X1 in the general formula (1) is preferably set to have fat Group X ¹ a. In addition, X ^1a may have an aliphatic group, and may contain an aromatic group.

As tetracarboxylic acids which have an aliphatic group, there exist a chain hydrocarbon structure and/or alicyclic hydrocarbon structure which may contain an aromatic group. The "chain hydrocarbon structure" is a linear hydrocarbon structure and/or a branched hydrocarbon structure which 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 also contain substituents.

Specific examples of tetracarboxylic acids having an aliphatic group include: 1,2,3,4-butane tetracarboxylic acid, 1,2,3,4-pentane tetracarboxylic acid, 1,2,4, Tetracarboxylic dianhydrides having a chain hydrocarbon structure such as 5-pentanetetracarboxylic acid, 1,2,3,4-hexanetetracarboxylic acid, and 1,2,5,6-hexanetetracarboxylic acid. In addition, cyclobutane-1,2,3,4-tetracarboxylic acid, cyclopentane-1,2,3,4-tetracarboxylic acid, cyclohexane-1,2,3,4-tetracarboxylic acid, cyclohexane-1,2,3,4-tetracarboxylic acid, Carboxylic 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[4.2.2.0 ^2,5 ]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-bis Phenylbicyclo[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[4.2.1.0 ^2,5 ]nonane-3,4,7,8-tetracarboxylic acid, 9,14-dioxopentacyclo[8.2.1 ^{1 ,11} .1 ^4,7 .0 ^2,10 .0 ^3,8 ]tetradecane-5,6,12,13-tetracarboxylic acid and other cyclic, bicyclic, tricyclic tetracarboxylic acids; 2,8-di Oxaspiro[4.5]decane-1,3,7,9-tetraketone and other spiro-containing tetracarboxylic acids; 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-ring Hexene-1,2-dicarboxylic anhydride, 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furyl)naphtho[1,2 -c]furan-1,3-dione, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, etc. have Tetracarboxylic dianhydride of alicyclic hydrocarbon structure.

From the viewpoint of more effectively improving the lamination property to the LCP substrate at low temperature, X ¹ a having an aliphatic group preferably has a structure satisfying at least one of the following (I) and (II) S. (I) At least one of the carbons in X ¹ , that is, X ¹ a constituting the imide ring in the general formula (1), and at least one of the carbons in X ¹ a constituting the other imide ring are directly bonded to each other. (II) At least one of the carbons in each of the two imide rings constituting the general formula (1), X ¹ , that is, X ¹ a, independently satisfies a direct bond with a chain hydrocarbon structure or an alicyclic hydrocarbon structure, and any one of the constituent elements of the alicyclic hydrocarbon structure. Specific examples satisfying the above (I) include chemical formula (Ia) to chemical formula (Id). In addition, chemical formula (Ib) to chemical formula (Id) are also compounds satisfying the aforementioned (II). In the formula, * represents a bonding site with an imide group. [chemical 4]

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

[chemical 5]

Examples of X ¹ a having a structure S in which carbons in X ¹ a forming an imide ring are directly bonded to a chain hydrocarbon structure include compounds represented by chemical formula (II-a). Examples of X ¹ a having a structure S in which carbon in X ¹ forming an imide ring becomes one of constituent elements of an alicyclic hydrocarbon structure include compounds represented by chemical formula (II-b). In addition, as a configuration in which the carbon of X ¹ a forming one of the imide rings is directly bonded to the alicyclic hydrocarbon structure, and the carbon in X ¹ a forming the other imide ring becomes an alicyclic hydrocarbon structure The chemical formula (II-c) can be illustrated as an example of X ¹ a of the structure S which is one of the elements. In addition, the two imide rings each independently satisfy at least one of (I) and (II), and may include an aromatic ring as represented by the chemical formula (II-d).

The ratio of X ¹ a having an aliphatic group to 100 mol % of X ¹ constituting the polyimide resin (A) is preferably 60 mol % to 100 mol %, more preferably 75 mol % % to 100 mol%, and a more preferable range is 85 mol% to 100 mol%. By using 60 mol % to 100 mol % of X ¹ a having an aliphatic group, the lamination property to LCP becomes more excellent. The ratio of X ¹ a having an aliphatic group can be determined from 100 mol% of all monomers that become X ¹ residues in the raw material monomers used for synthesizing the polyimide resin (A). X ¹ a of the aliphatic group was obtained from the content rate (mole %) of the monomeric body of the residue. Usually, the ratio of the monomers used in the synthesis is equal to the ratio of the structure in the resin.

1-1-b. X ² in the general formula (1) As described above, X ² in the general formula (1) is a divalent organic group that may have an independent structure for each repeating unit. As a preferable example of the organic compound used for the polymerization to obtain ^X2 , diamine and diisocyanate can be illustrated as mentioned above. At least a part of X ² is a residue X ² d derived from dimer diamine and/or dimer diisocyanate.

Dimeric diamines are obtainable, for example, by converting the carboxyl groups of dimer acids into amine groups. In addition, a dimer diisocyanate can be obtained, for example, by converting the carboxyl group of a dimer acid into an isocyanate group. The term "dimer acid" here refers to a dimer of an 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, and unsaturated fatty acids such as linoleic acid, linoleic acid, oleic acid, and erucic acid obtained by dimerization can be used. Dimer acid is obtained. The degree of unsaturation can also be reduced by hydrogenation of unsaturated bonds if desired. A dimer diamine and a dimer diisocyanate having a reduced degree of unsaturation are preferable in terms of oxidation resistance (especially coloring in a high-temperature range) and inhibition 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, particularly preferably a compound having 36 to 44 carbon atoms. Preferably, it is a dicarboxylic acid compound having a branched structure in which a fatty acid undergoes a Diels-Alder reaction. 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 than two aromatic rings or alicyclic structures, more preferably an alicyclic structure. When there are two ring structures, the two rings may be independent or continuous. One or more kinds of compounds can be used for dimer diamine and dimer diisocyanate. The alicyclic structure may have one or more double bonds in the ring, or may not have a double bond. The method of converting the carboxyl group of a dimer acid into an amine group includes, for example, amidation of a carboxylic acid, followed by amination by Hofmann rearrangement (Hofmann rearrangement), followed by distillation and purification. Moreover, as a method of converting the carboxyl group of a dimer acid into a diisocyanate group, the method of performing isocyanation from a carboxylic acid by Curtius rearrangement is mentioned, for example.

The amine 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 amine group is preferably The family chain is bonded to the ring structure. The carbon number between the amine group or the isocyanate group and the ring structure is preferably 2-25. As a preferable example of an aliphatic chain, chain hydrocarbon groups, such as an alkylene group, can be illustrated. As a preferred example, a compound in which the two amine groups or isocyanate groups are respectively bonded to a ring structure via an alkylene group can be exemplified.

In addition, as a specific example of the dimer acid (polyacid) for obtaining dimer diamine or dimer diisocyanate, following chemical formula (d1) - chemical formula (d4) are mentioned. These are examples, and the dimer acid is not limited to the following structure.

[化7]

[化8]

[化9]

[chemical 6]

[chemical 7]

[chemical 8]

[chemical 9]

The dimer diamine and the dimer diisocyanate are preferably compounds with 20 to 60 carbon atoms, more preferably compounds with 24 to 56 carbon atoms, further preferably 28 to 48 carbon atoms, further preferably 36 carbon atoms ~44 compounds. The above carbon number is preferable from the viewpoint of ease of acquisition.

Examples of commercially available dimer diamines include "Priamine 1071", "Priamine 1073" and "Priamine" manufactured by Croda Japan. Priamine 1074", "Priamine 1075", or "Versamine 551" manufactured by BASF Japan.

The ratio of the monomeric form of the residue X ² d which is a dimer structure is preferably 80% by mass to 100% by mass relative to 100% by mass of the monomeric form of the residue X ² . By setting it as 80 mass % or more, the lamination property with respect to the LCP base material at low temperature becomes more excellent. The more preferable range is 83% by mass to 100% by mass, and the more preferable range is 85% by mass to 100% by mass. The ratio of X ² d having a dimer structure can be determined from 100% by mass of all monomers that become X ² residues in the raw material monomers used for synthesizing the polyimide resin (A). X ² d of the dimer structure was obtained from the content (mass %) of the monomeric body of the residue. Usually, the ratio of the monomers used in the synthesis is equal to the ratio of the structure in the resin.

As X ² in the general formula (1), a diamine having a phenolic hydroxyl group described later can be exemplified. In addition, diamines other than diamines that form a monomer of residue X ² d and diamines having a phenolic hydroxyl group can be used suitably. For example, diamine compounds which may have substituents, aliphatic groups (chain hydrocarbon structures and/or alicyclic hydrocarbon structures which may contain unsaturated bonds), aromatic rings, and any combinations thereof are exemplified.

Examples of other diamines include: 1,4-diaminobenzene, 1,3-diaminobenzene, 1,2-diaminobenzene, 1,5-diaminonaphthalene, 1,8-diamino Naphthalene, 2,3-diaminonaphthalene, 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'-diaminodiphenylmethane, 3, Aromatic diamines such as 3'-diaminobenzophenone and 3,3'-diaminodiphenylphenone; ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, 1 , 6-hexamethylenediamine, 1,7-heptanediamine, 1,9-nonanediamine, 1,12-dodecamethylenediamine, m-xylenediamine and other aliphatic diamines; isophorone Diamine, norbornanediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-diaminodicyclohexyl Alicyclic diamines such as methane and piperazine, etc.

1-1-c. Phenolic hydroxyl As mentioned above, polyimide resin (A) has a phenolic hydroxyl group. The phenolic hydroxyl group refers to a hydroxyl group directly bonded to an aromatic ring. As a preferable example of an aromatic ring, a benzene ring, a naphthalene ring, and a pyridine ring can be illustrated. The phenolic hydroxyl group can be introduced into the molecular chain terminal of the polyimide resin (A), or can be introduced into the side chain or side group of the main chain skeleton. The phenolic hydroxyl groups can be combined arbitrarily except for being introduced into any of molecular chain terminals, side groups, and side chains. In addition, the term "molecular chain terminal" refers to a non-repeating structure located at the terminal or linked to the terminal among the repeating structural units constituting the molecular chain of the polyimide resin (A).

The phenolic hydroxyl value of the polyimide resin (A) is preferably from 1 mgKOH/g to 30 mgKOH/g. By setting it as this range, a crosslink density can be made appropriate, and plating solution resistance (alkali resistance and acid resistance) can be improved more effectively. In addition, by setting the phenolic hydroxyl group value as described above, the crosslink density can be made appropriate to exhibit a stress relaxation effect, and the insulation reliability after a thermal cycle test can be more effectively improved. The phenolic hydroxyl value is more preferably from 3 mgKOH/g to 20 mgKOH/g, and still more preferably from 5 mgKOH/g to 15 mgKOH/g. The phenolic hydroxyl value can be adjusted by the loading amount of the monomer having a phenolic hydroxyl group, the introduction rate of the phenolic hydroxyl group into the molecular chain terminal, and/or the introduction rate of the phenolic hydroxyl group into the side chain.

As a preferred example of the polyimide resin (A), it is possible to enumerate: a polyimide resin ( A); all or part of the functional groups at the end of the molecular chain are phenolic hydroxyl groups and polyimide resins (A) that also have phenolic hydroxyl groups at the side groups/side chains; the end of the molecular chain is capped and the side groups are Or a polyimide resin (A) having a phenolic hydroxyl group in a side chain; a polyimide resin (A) having a molecular chain end as another functional group such as an acid anhydride group and having a phenolic hydroxyl group in a side group or a side chain. Among them, from the viewpoint of plating solution resistance, polyimide resin (A) in which substantially all the functional groups at the molecular chain ends are phenolic hydroxyl groups, and the molecular chain ends include phenolic hydroxyl groups and A polyimide resin (A) having no functional group at the molecular chain end. The polyimide resin (A) may also have other functional groups such as acid anhydride groups, amine groups, and carboxyl groups at molecular chain terminals, side groups, and/or side chains within the range not departing from the gist of the present invention. When an acid anhydride group is included, the acid anhydride group value is preferably at most 15 mgKOH/g, more preferably at most 10 mgKOH/g, and still more preferably at most 5 mgKOH/g, from the viewpoint of plating solution resistance. When an amine group is included, the amine value is preferably 15 mgKOH/g or less, more preferably 10 mgKOH/g or less, and still more preferably 5 mgKOH/g or less from the viewpoint of plating solution resistance.

通式（3）中的Ar為可具有取代基的芳香族基。作為取代基，可例示碳數1～10的烷基或氟烷基、鹵素原子。除通式（3）中的胺基與芳香族基直接鍵結的化合物以外，經由脂肪族基而與芳香族基鍵結的化合物亦較佳。對於後述的通式（4）、通式（5）的Ar及取代基亦相同。 1-1-c1. Molecular chain end In order to introduce phenolic hydroxyl groups at the molecular chain end of polyimide resin (A), the following method can be exemplified: After synthesizing an anhydride-terminated polyimide resin, make the general formula (3) The indicated amine compound having a phenolic hydroxyl group is further reacted. It is also possible to replace the acid anhydride-terminated polyimide resin with the carboxylic acid-terminated polyimide resin, and use the same method to introduce phenolic hydroxyl groups. [chemical 10]

Ar in the general formula (3) is an aromatic group which may have a substituent. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, and a halogen atom. In addition to the compound in which the amine group and the aromatic group in general formula (3) are directly bonded, the compound which bonded to the aromatic group via an aliphatic group is also preferable. The same applies to Ar and substituents in general formula (4) and general formula (5) described later.

In addition, the following method can be exemplified: after synthesizing an amino-terminated polyimide resin, an acid anhydride compound having a phenolic hydroxyl group represented by the general formula (4) or an acid anhydride compound having a phenolic hydroxyl group represented by the general formula (5) can be exemplified. The carboxylic acid compound is further reacted to introduce a phenolic hydroxyl group at the terminal.

[化12]

[chemical 11]

[chemical 12]

Specific examples of the 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-Naphthalene Phenol, 6-amino-1-naphthol, 4-amino-2,6-diphenylphenol. Specific examples of the general formula (4) include 3-hydroxyphthalic anhydride, 4-hydroxyphthalic anhydride, and the like. In addition, salicylic acid and hydroxybenzoic acid can be illustrated as specific examples of the general formula (5). In the general formulas (3) to (4), an example in which one hydroxyl group is used is given, but a compound in which two or more hydroxyl groups are bonded to Ar may also be used.

From the viewpoint of more effectively improving the insulation reliability after the thermal cycle test of the cured product, polyimide having a phenolic hydroxyl group satisfying at least one of the following (i) and (ii) is preferable Resin (A). (i) It has a phenolic hydroxyl group at the end of the molecular chain, and a nitrogen atom forming an imide ring derived from a monoamine is bonded to the meta-position or ortho-position of the aromatic ring having the phenolic hydroxyl group. (ii) Has a phenolic hydroxyl group at the end of the molecular chain, has an aliphatic group directly bonded to an aromatic ring having the phenolic hydroxyl group, and has bonded to the aliphatic group a nitrogen forming an imide ring derived from a monoamine atom. By having the phenolic hydroxyl group satisfying at least one of (i) and (ii), the insulation reliability of the cured product of the present composition after the thermal cycle test can be more effectively improved. As a result of intensive studies by the inventors of the present invention, it has been found that the structure around the phenolic hydroxyl group at the end of the molecular chain is a structure around the crosslinking point, and thus has a large influence on stress relaxation. It is considered that 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 other imide rings is reduced, and the stress relaxation property is improved. In addition, it is considered that by having the structure (ii) in which the amine group is not directly bonded to the aromatic ring but is bonded via the aliphatic group, the interaction between the imide ring and other imide rings is reduced and the stress relaxation property is improved.

In order to obtain a molecular chain terminal satisfying the above (i) and (ii), as a monoamine compound having a phenolic hydroxyl group used in the capping of an acid anhydride group-terminated polyimide resin or a carboxyl-terminated polyimide resin, Examples: 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.

Substantially all of the functional groups at the molecular chain terminals of the polyimide resin (A) may be phenolic hydroxyl groups. Moreover, it may contain the molecular chain terminal which does not have a functional group other than a phenolic hydroxyl terminal. In addition, molecular chain terminals having other functional groups (acid anhydride group, etc.) may be contained in addition to the phenolic hydroxyl terminal.

The polyimide resin (A) having a molecular chain terminal without a functional group and a phenolic hydroxyl terminal can be obtained by, for example, mixing an amine compound of the general formula (3) and a non-functional polyimide at a specific ratio with respect to an anhydride-terminated polyimide. A monoamine compound having a phenolic hydroxyl group is obtained by capping. In addition, it is also possible to mix the compound of the general formula (4) and/or the general formula (5), the acid anhydride compound and/or the carboxylic acid compound not having a phenolic hydroxyl group in a specific ratio with respect to the amine-terminated polyimide and Obtained by capping reaction. According to these methods, the amount of the phenolic hydroxyl group at the molecular chain terminal of the polyimide resin (A) can be easily adjusted.

Examples of monoamine compounds that do not have a phenolic hydroxyl group include methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, Aliphatic amines such as amine, diethylamine, dipropylamine and dibutylamine; cycloaliphatic amines such as cyclohexylamine and dicyclohexylamine; aromatics such as aniline, toluidine, diphenylamine and naphthylamine amines, and any mixtures of these.

Examples of acid anhydrides not having a phenolic hydroxyl group include: phthalic anhydride, 2,2'-biphenyl dicarboxylic anhydride, 1,2-naphthalene dicarboxylic anhydride, 2,3-naphthalene dicarboxylic anhydride, 1,8 -Naphthalene dicarboxylic anhydride, 1,2-anthracene dicarboxylic anhydride, 2,3-anthracene dicarboxylic anhydride, L9-anthracene dicarboxylic anhydride, etc. As a carboxylic acid which does not have a phenolic hydroxyl group, the carboxylic acid which has the structure which removed the phenolic hydroxyl group from the said carboxylic acid which has a phenolic hydroxyl group is mentioned.

The polyimide resin (A) having a phenolic hydroxyl end and other functional group ends can be obtained by, for example, mixing an amine compound of the general formula (3) and a polyimide having other functional groups at a specific ratio relative to an anhydride-terminated polyimide. Monoamine compound, and to obtain by capping reaction. Similarly, amine-terminated polyimides are capped by mixing compounds of general formula (4) and/or general formula (5) with acid anhydride compounds and/or carboxylic acid compounds having other functional groups in a specific ratio. response to get. According to this method, the amount of the phenolic hydroxyl group and other functional groups at the molecular chain terminal of the polyimide resin (A) can be adjusted. Other functional groups are not particularly limited. For example, a nitro group and a cyano group can be illustrated.

When the other functional group is an acid anhydride group, after synthesizing the anhydride-terminated polyimide, an amine compound having a phenolic hydroxyl group at a part of the terminal may be reacted to convert a part of the anhydride terminal into a phenolic hydroxyl group. Similarly, when the other functional group is an amine group, it can also be synthesized by reacting a compound having a phenolic hydroxyl group at a part of the end and an acid anhydride group after synthesizing an amine-terminated polyimide.

In the description, an example is given in which polyimide resin is synthesized and then reacted with a compound set at the end of the molecular chain. The compounds are mixed together and polymerized to synthesize the polyimide resin (A). According to this method, simplification of the synthesis steps can be achieved.

From the viewpoint of making the insulation reliability after the heat cycle test and the plating solution resistance (alkali resistance, acid resistance) more excellent, relative to the functional group at the end of the molecular chain of the polyimide resin (A) 100 Mole %, the molecular chain terminal having a phenolic hydroxyl group is preferably 50 mole % to 100 mole %, more preferably 70 mole % to 100 mole %. By introducing a phenolic hydroxyl group into the molecular chain terminal of the polyimide resin (A), the crosslinking density with the crosslinking agent (B) can be made appropriate and the stress relaxation effect can be effectively exhibited. As a result, it is considered that the insulation reliability after the thermal cycle test can be maintained well.

1-1-c2. Side chain, side group In order to introduce phenolic hydroxyl groups into the side chains and/or side groups of the polyimide resin (A), it is preferable to use organic compounds such as diamines and diisocyanates having phenolic hydroxyl groups and/or tetracarboxylic compounds having phenolic hydroxyl groups. acid method. In addition, after synthesizing the polyimide resin, a compound having a phenolic hydroxyl group may be introduced into the side chain. In the case of introducing a phenolic hydroxyl group into the side chain, the phenolic hydroxyl group value of the side chain can be appropriately designed, but from the viewpoint of more effectively exhibiting plating solution resistance and insulation reliability after thermal cycles, it is preferable It is 1 mgKOH/g～5 mgKOH/g.

Preferable examples of diamines having phenolic hydroxyl groups include bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)pyridine, bis( 3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amine base-4-hydroxy)biphenyl, 2,2'-bis-trifluoromethyl-5,5'-dihydroxy-4,4'-diaminobiphenyl, bis(3-amino-4-hydroxy Aromatic diamines such as phenyl)fluorene and 2,2'-bis(trifluoromethyl)-5,5'-dihydroxybenzidine. In addition, a substituent may be introduced at an arbitrary position of these compounds.

Moreover, the diamine represented by following general formula (6) can also be used. [chemical 13]

In the formula, R ¹ represents a direct bond, or a group comprising carbon, hydrogen, oxygen, nitrogen, sulfur, or halogen. Such groups include, for example, a divalent hydrocarbon group with 1 to 30 carbons or a divalent hydrocarbon group with 1 to 30 carbons in which a part or all of the hydrogen is substituted with a halogen atom, -(C=O)-, -SO ₂ -, - O-, -S-, -NH-(C=O)-, -(C=O)-O-, groups represented by the following general formula (7) and groups represented by the following general formula (8) . In the formula, r and s each independently represent an integer of 1 to 20, and R ² represents a hydrogen atom or a methyl group.

[chemical 14]

[chemical 15]

Examples of the diamine represented by the general formula (6) include: 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, etc.

As a preferable example of the tetracarboxylic acid which has a phenolic hydroxyl group, the compound which has a hydroxyl group in the substituent of the aromatic group of the aromatic tetracarboxylic acid mentioned later can be illustrated.

Among these, diamine containing a phenolic hydroxyl group satisfying at least any one of the following (iii) and (iv) is preferable from the viewpoint of more effectively improving plating solution resistance. (iii) A part of X ² in the general formula (1) is a diamine residue X ² f containing a phenolic hydroxyl group, and an aromatic ring having the phenolic hydroxyl group is bonded with a compound derived from the formation of the imide ring. Nitrogen atoms of diamines. (iv) A part of X ² in the general formula (1) is a diamine residue X ² f having a phenolic hydroxyl group, which has an aliphatic group directly bonded to an aromatic ring having the phenolic hydroxyl group, and in the aliphatic The group is bonded to a nitrogen atom derived from a diamine forming the imide ring. By having a phenolic hydroxyl group satisfying at least one of (iii) or (iv), the cured product of this composition can be more effectively improved in plating solution resistance and insulation reliability after thermal cycles. By setting the crosslinking point with the crosslinking agent (B) as a side group of the polyimide resin (A), a crosslinked structure can be effectively formed.

The following general formula (9) and general formula (10) are mentioned as a preferable example of the diamine which satisfies said (iii) or (iv). In formula (9), n is an integer of 1-10. [chemical 16]

[chemical 17]

1-1-d. Other monomers In the range not departing from the gist of the present invention, the polyimide resin (A) may contain monomers other than residues ^X1 and ^X2 . residues. For example, polyamine compounds having three or more amine groups can also be used. Examples of the polyamine compound having three or more amino groups include 1,2,4-triaminobenzene and 3,4,4'-triaminodiphenyl ether.

1-1-e. Production method of polyimide resin (A) Polyimide resin (A) can be manufactured by various well-known methods. As a specific example, a method of cyclizing a polyamic acid resin or a polyamic acid ester resin as a polyimide precursor by heating to convert it into an imide group is mentioned. As a synthetic method of polyamic acid resin, there exists the method of making tetracarboxylic dianhydride and diamine react, for example. More specifically, it can be produced by dissolving a monomer comprising tetracarboxylic dianhydride and diamine in a solvent, for example, stirring at a temperature of 60°C to 120°C for 0.1 hour to 2 hours, and polymerizing it. Polyamide resins that are precursors of polyimides. The equivalent ratio (molar ratio) of tetracarboxylic acids and diamine etc. is 0.7-1.3, for example, Preferably it is 0.8-1.2. In addition, a method of obtaining a polyimide precursor by reacting tetracarboxylic dianhydride and diisocyanate to obtain a polyimide resin is also preferred.

In the case of introducing a phenolic hydroxyl group at a molecular chain terminal, it may be introduced at the stage of synthesizing the polyamide resin, or may be introduced after obtaining the polyimide resin. The same applies to the polyamide ester resin described later. In the case of introducing a phenolic hydroxyl group into a side chain or a side group, there is a method of using a compound having a phenolic hydroxyl group in the monomer for polymerizing the polyimide resin (A), and synthesizing the polyimide resin A method of introducing phenolic hydroxyl groups into side chains or side groups after precursors or polyimide resins.

The synthesis method of polyamide ester resin can be exemplified by the following method: the method of obtaining a diester by tetracarboxylic dianhydride and alcohol and then reacting with diamine in the presence of a condensing agent, or by tetracarboxylic dianhydride and alcohol The diester is obtained followed by acyl chlorination of the remaining dicarboxylic acid and reaction with a diamine.

Examples of organic solvents used for polymerization include N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone, NMP), 2-butanone, and dimethyl sulfoxide (DMSO). , N,N-dimethylformamide (N,N-dimethyl formamide, DMF), N,N-dimethylacetamide (N,N-dimethyl acetamide, DMAc), N,N-diethyl Acetamide, Hexamethylphosphamide, N-Methylcaprolactam, Dimethyl Sulfate, Cyclohexanone, Dioxane, Tetrahydrofuran, Diethylene glycol dimethyl ether, Triethylene glycol dimethyl ether , cresol. A solvent can be used individually or in combination of 2 or more types. Aromatic hydrocarbons such as xylene and toluene can also be used together.

The method of imidating the polyimide precursor to obtain the polyimide resin is not particularly limited, and a method of heating in a solvent, for example, at a temperature of 80° C. to 400° C. for 0.5 hours to 50 hours is exemplified. At this time, a catalyst and/or a dehydrating agent may be used as needed. Examples of the reaction catalyst include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, heterocyclic tertiary amines such as pyridine, picoline, and isoquinoline, and the like. Moreover, as a dehydrating agent, aliphatic acid anhydrides, such as acetic anhydride, and aromatic acid anhydrides, such as benzoic anhydride, can be illustrated, for example.

The imidization rate (formation rate of imide ring) is not limited, but it is preferably 80% or more, more preferably It is more than 90%, more preferably 95% to 100%. The imidization ratio can be determined by nuclear magnetic resonance (Nuclear Magnetic Resonance, NMR) or infrared (InfraRed, IR) analysis.

1-1-f. Properties of polyimide resin (A) The temperature at which the storage modulus G' of the polyimide resin (A) becomes 1.0×10 ⁷ Pa is any temperature between 0°C and 90°C . From the viewpoint of making the plating solution resistance more excellent, the temperature at which the storage modulus G' becomes 1.0×10 ⁷ Pa is more preferably any temperature between 30°C and 80°C, and more preferably between 30°C and 70°C. ℃. In addition, from the viewpoint of making the flexibility more excellent, the temperature at which the storage modulus G' becomes 1.0×10 ⁷ Pa is preferably any temperature between 0°C and less than 30°C, more preferably 10°C Any temperature above and below 25°C. The compounding amount of the polyimide resin (A) is arbitrary, but in order to make the lamination to the LCP substrate more excellent, it is preferable to contain 50% by mass to 98% by mass.

Storage modulus G' of 1.0×10 ⁷ Pa Polyimide resin (A) at any temperature between 0°C and 90°C can be adjusted according to the type of monomer that is a repeating structural unit and Mw . Specifically, by combining a flexible monomer such as a dimer structure as a monomer with an aliphatic (including alicyclic skeleton) structure, the storage elastic coefficient G' tends to decrease, On the contrary, when the structure in which the imide structure is directly bonded to the highly planar aromatic skeleton is combined, the storage modulus G' tends to increase. In addition, by reducing Mw, the storage modulus G' tends to decrease. In addition to the above, it is also effective to combine the method of setting the acid anhydride group equivalent of tetracarboxylic acids to about 80 to 300 and the ratio of dimer diamine in the diamine component to 60 mol % to 100. Mole% method. In addition, since the acid anhydride group of tetracarboxylic acid may ring-open by moisture, when measuring an acid anhydride group equivalent, it measures after drying a sample suitably. Rigid polyimide resins, such as polyimide resins containing pyromellitic acid and diaminobiphenyl, have a storage elastic coefficient G' of about 1.0×10 ⁹ at 90°C, and soft polyimide resins For example, the storage elastic coefficient G' at 90° C. of polyimide resin comprising dimer diamine and 1,2,4,5-cyclohexanetetracarboxylic dianhydride is about 1.0×10 ⁵ .

The weight average molecular weight (Mw) of the polyimide resin (A) is not particularly limited, but is preferably 15,000 or more, more preferably 2 More than ten thousand. The upper limit of Mw is not particularly limited, but is preferably 1 million, more preferably 100,000, and still more preferably 80,000, from the viewpoint of ease of handling of the solution viscosity.

1-2. Crosslinking agent (B) The crosslinking agent (B) is a compound that forms a crosslinked structure by thermosetting treatment, and has two or more crosslinkable functional groups. The crosslinking agent (B) is selected from compounds containing epoxy groups (b1), cyanate ester compounds (b2), compounds containing isocyanate groups (b3), metal chelate compounds (b4), carbodiamide-containing compounds One or more species selected from the group consisting of an amino group-containing compound (b5) and a maleimide group-containing compound (b6). (b1) to (b6) may be used alone or in combination of two or more. As long as the above (b1) to (b6) are contained, other crosslinking agents may be used in combination within a range not departing from the gist of the present invention. By including any one of (b1) to (b6) as a crosslinking agent (B), a crosslinking structure can be formed between the phenolic hydroxyl group of the polyimide resin (A) and the crosslinking agent (B) . A crosslinked structure of crosslinking agents (B) may be included in the cured product.

The total content of (b1) to (b6) of the crosslinking agent (B) is 0.5 to 10 parts by mass relative to 100 parts by mass of the polyimide resin (A). The total content of (b1) to (b6) in the crosslinking agent (B) is more preferably 1 to 8 parts by mass, still more preferably 2 to 6 parts by mass, particularly preferably 3 to 5 parts by mass. The crosslinking agent (B) may be a low-molecular compound or a high-molecular compound. In addition, in the metal chelate compound (b4) mentioned later, the number of objects which can coordinate bond is made into the number of functional groups. For example, in the case of a metal chelate compound containing Al, Ti, and Zr, it becomes a trifunctional component. In addition, regarding the average number of functional groups of the crosslinking agent (B), it is assumed that the average number of functional groups is calculated for each crosslinking agent (B) of the same skeleton.

In 100% by mass of the crosslinking agent (B), it is preferable to include (b1) to (b6) in a total of 30% by mass to 100% by mass, more preferably to contain a total of 50% by mass to 100% by mass of (b1 )~(b6).

From the viewpoint of well-balanced improvement of lamination with LCP base material, resistance to plating solution, insulation reliability after thermal cycle test, and laser processability after curing, epoxy group-containing Compound (b1) alone, or a combination of epoxy group-containing compound (b1) and any one or more of (b2) to (b6). Moreover, it is also preferable that it is a combination in which the crosslinking reaction of the crosslinking agent (B) which is combined performs a crosslinking reaction.

1-2-a. Epoxy group-containing compound (b1) The epoxy group-containing compound (b1) is not particularly limited as long as it is a compound having two or more epoxy groups in the molecule. Among epoxy group-containing compounds (b1), compounds having an epoxy group having an average number of functional groups of 3 or more are preferred. As the epoxy group-containing compound (b1), for example, a glycidyl ether type epoxy resin, a glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin, or a cycloaliphatic (alicyclic type) epoxy resin can be used. Resins and other epoxy resins.

Examples of the difunctional epoxy group-containing compound (b1) include diglycidyl phthalate, diglycidyl hexahydrophthalate, or diglycidyl tetrahydrophthalate. Glycidyl ester type epoxy resin; cycloaliphatic (alicyclic type) epoxy resin such as epoxycyclohexylmethyl-epoxycyclohexane carboxylate or bis(epoxycyclohexyl)adipate. Moreover, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin can be illustrated.

Examples of the epoxy group-containing compound (b1) having an average number of functional groups of 3 or more include tris(glycidyloxyphenyl)methane, tetrakis(glycidyloxyphenyl)ethane, glycidylamine-type epoxy Resins such as tetraglycidyldiaminodiphenylmethane, triglycidyl p-aminophenol, triglycidyl m-aminophenol, or tetraglycidyl m-xylylenediamine, sorbitol polyglycidol Ether etc.

In addition, cresol novolak-type epoxy resins, phenol novolac-type epoxy resins, α-naphthol novolac-type epoxy resins, bisphenol A novolac-type epoxy resins, dicyclopentadiene-type Epoxy group-containing compounds (b1), such as epoxy resins, tetrabromobisphenol A-type epoxy resins, and brominated phenol novolak-type epoxy resins.

As the epoxy group-containing compound (b1), these compounds may be used alone or in combination of two or more. From the viewpoint of high adhesion, it is preferable to use bisphenol A type epoxy resin, cresol novolak type epoxy resin, phenol novolak type epoxy resin, tris(glycidyloxyphenyl)methane, tetra (glycidyloxyphenyl)ethane, or tetraglycidyl m-xylylenediamine.

1-2-b. Cyanate ester compound (b2) The cyanate ester compound (b2) means a compound having two or more cyanate groups. Specific examples include: 2,2-bis(4-cyanate phenyl)propane (bisphenol A type cyanate resin), bis(3,5-dimethyl-4-cyanate phenyl) ) methane, 2,2-bis(4-cyanate phenyl) ethane, etc., or aromatic cyanate ester compounds such as derivatives thereof. These may be used alone or in combination of two or more.

1-2-c. Isocyanate group-containing compound (b3) The isocyanate group-containing compound (b3) is not particularly limited as long as it has two or more isocyanate groups in the molecule.

As an isocyanate group-containing compound having two isocyanate groups in one molecule, specifically, 1,3-phenylene diisocyanate, 4,4'-diphenylene diisocyanate, 1,4-phenylene diisocyanate, Phenyl diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-toluene diisocyanate, 2,4,6-tri Isocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4',4''-triphenylmethane triisocyanate and other aromatic diisocyanates Isocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylidene diisocyanate, 2,3-butylene diisocyanate, 1 , 3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and other aliphatic diisocyanates, ω,ω'-diisocyanate-1,3- Dimethylbenzene, ω,ω'-diisocyanate-1,4-dimethylbenzene, ω,ω'-diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylene diisocyanate , 1,3-tetramethylxylene diisocyanate and other araliphatic diisocyanates, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate [alias: isophorone diisocyanate], 1, 3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane Alkane diisocyanate, 4,4'-methylene bis(cyclohexyl isocyanate), 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, etc. Cyclic diisocyanates.

In addition, examples of isocyanate group-containing compounds having three isocyanate groups in one molecule include aliphatic polyisocyanates such as aromatic polyisocyanate and lysine triisocyanate, araliphatic polyisocyanate, alicyclic polyisocyanate, and the like. , and examples thereof include trimethylolpropane adducts of diisocyanates described above, biurets obtained by reacting with water, and trimers having isocyanurate rings.

As an isocyanate group-containing compound, a block containing isocyanate group protected by ε-caprolactam or methyl ethyl ketone (methyl ethyl ketone, MEK) oxime, etc. in the various exemplified isocyanate group-containing compounds can also be used. Isocyanate-based compounds. Specifically, the isocyanate group of the isocyanate group-containing compound is treated with ε-caprolactam, methyl ethyl ketone (hereinafter referred to as MEK) oxime, cyclohexanone oxime, pyrazole, phenol, etc. Block-derived compounds, etc. Especially in the case of using a hexamethylene diisocyanate trimer having an isocyanurate ring and being blocked by MEK oxime or pyrazole in the present invention, due to the It is excellent in adhesive strength and heat resistance. Moreover, it is preferable to have three or more isocyanate groups from a heat resistant viewpoint.

1-2-d. Metal chelate compound (b4) The metal chelate compound (b4) is an organometallic compound containing metal and organic matter, and reacts with the reactive functional group of the polyimide resin (A) or the crosslinkable functional group of the crosslinking agent (B) to form a crosslinking compound. linked compounds. The type of organometallic compound is not particularly limited, and examples thereof include organoaluminum compounds, organotitanium compounds, and organozirconium compounds. In addition, the bond between the metal and the organic substance may also be a metal-oxygen bond, and is not limited to a metal-carbon bond. Furthermore, from the viewpoint of heat resistance, it is preferable that the number of functional groups (the number of objects capable of coordinate bonding) is 3 or more.

The organoaluminum compound is preferably an aluminum metal chelate compound. Aluminum metal chelate compounds, for example, include aluminum ethyl acetylacetate diisopropoxide, tris(ethyl acetylacetate) aluminum, alkyl acetylacetate aluminum diisopropoxide, monoacetylpyruvate bis( Aluminum ethylacetate, aluminum tris(acetate), aluminum bis(ethylacetate) monoacetate, aluminum di-n-butanol monomethylacetate, diisobutanol monomethylacetate Aluminum acetylacetate, aluminum di-second-butanol monomethylacetyl acetate, aluminum isopropoxide, mono-second butoxyaluminum diisopropoxide, aluminum second butoxide, aluminum ethoxide, and the like.

The organotitanium compound is preferably a titanium metal chelate compound. Titanium metal chelate compounds include, for example: titanium acetylacetonate, titanium tetraacetylacetonate, titanium ethylacetate, titanium octane glycolate, titanium ethylacetate, 1,3-propanedioxybis Titanium (Ethyl Acetyl Acetate), Titanium Polyacetyl Acetyl Pyruvate, Tetraisopropyl Titanate, Tetra-N-Butyl Titanate, Butyl Titanate Dimer, Tetraoctyl Titanate, Tri-pentyl titanate, tetra-tert-butyl titanate, tetrastearyl titanate, titanium isostearate, tri-n-butoxytitanium monostearate, di-isopropoxy titanium distearate, titanium stearate, di-isopropoxytitanium diisostearate, (2-n-butoxycarbonylbenzoyloxy)tributoxytitanium, etc. The organic zirconium compound is preferably a zirconium metal chelate compound. Zirconium metal chelate compounds, for example, include: zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, bis(ethylacetylacetate) zirconium monobutoxyacetylacetonate, dibutoxybis( Zirconium ethyl acetylacetate, zirconium tetraacetylpyruvate, n-propyl zirconate, n-butyl zirconate, zirconium stearate, zirconium octoate, etc. Among these, organic titanium compounds and organic zirconium compounds are preferable in terms of thermosetting reactivity.

1-2-e. Carbodiimide group-containing compound (b5) The carbodiimide group-containing compound (b5) is not particularly limited as long as it has two or more carbodiimide groups in the molecule. Examples of carbodiimide group-containing compounds include: Carbodilite V-01, V-03, V-05, V-07, V-09 (Nisshinbo Chemical Co., Ltd.), cyclic Carbodiimide (Teijin Co., Ltd.), etc. From the viewpoint of heat resistance, those having a carbodiimide group with an average functional group number of 3 or more in one molecule are preferred.

1-2-f. Compounds containing maleimide groups (b6) The maleimide group-containing compound (b6) is not particularly limited as long as it has two or more maleimide groups in the molecule, but it is more preferable that the average number of functional groups is 3 or more. Specific examples include o-phenylene bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, 4-methyl-1,3- Phenylbismaleimide, N,N'-(toluene-2,6-diyl)bismaleimide, 4,4'-diphenylmethane bismaleimide, bisphenol A Diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4,4'- Diphenyl ether bismaleimide, 4,4'-diphenyl bismaleimide, 1,3-bis(3-maleimidephenoxy)benzene, 1,3- Bis(4-maleimidephenoxy)benzene, polyphenylmethanemaleimide (Chinese Academy of Sciences (CAS) number (NO): 67784-74-1, containing formaldehyde and aniline The reaction product of polymers with maleic anhydride), N,N'-ethylenebismaleimide, N,N'-trimethylenebismaleimide, N,N'-propylidene Bismaleimide, N,N'-Tetramethylenebismaleimide, N,N'-Pentamethylenebismaleimide, N,N'-(1,3-pentane Alkanediyl)bis(maleimide), N,N'-hexamethylenebismaleimide, N,N'-(1,7-pentanediyl)bismaleimide , N,N'-(1,8-octanediyl)bismaleimide, N,N'-(1,9-nonanediyl)bismaleimide, N,N'- (1,10-decanediyl)bismaleimide, N,N'-(1,11-undecanediyl)bismaleimide, N,N'-(1,12- dodecanediyl)bismaleimide, N,N'-[(1,4-phenylene)bismethylene]bismaleimide, N,N'-[(1,2 -Phenylylene)bismethylene]bismaleimide, N,N'-[(1,3-phenylene)bismethylene]bismaleimide, 1,6'-bismaleimide Maleimide-(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''-[nitrotris(ethylenyl)]trimaleimide, N,N',N''-[nitrotris(4, 1-phenylene)]trimaleimide, N,N'-[p-phenylenebis(oxy-p-phenylene)]bismaleimide, N,N'-[methylene Bis(oxy)bis(2-methyl-1,4-phenylene)]bismaleimide, N,N'-[methylenebis(oxy-p-phenylene)]bis (maleimide), N,N'-[dimethylsilanebis[(4,1-phenylene)(1,3,4-oxadiazole-5,2-diyl)( 4,1-phenylene)]]bismaleimide, N,N'-[(1,3-phenylene)dioxybis(3,1-phenylene)]bismaleimide Imine, 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' -Dimethylbiphenyl-4,4'-diyl)bismaleimide, N,N'-(3,3'-dimethoxybiphenyl-4,4'-diyl)bismaleimide Laimide, 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'-[ethylenylbis (oxyethylenyl)]bismaleimide, N,N'-[sulfonylbis(4,1-phenylene)bis(oxy)bis(4,1-phenylene)]bis Maleimide, N,N'-[naphthalene-2,7-diylbis(oxy)bis(4,1-phenylene)]bismaleimide, N,N'-[para Phenylbis(oxy-p-phenylene)]bismaleimide, N,N'-[(1,3-phenylene)dioxybis(3,1-phenylene)] Bismaleimide, N,N'-(3,6,9-trioxaundecane-1,11-diyl)bismaleimide, N,N'-[isopropylidene Bis[p-phenyleneoxycarbonyl(m-phenylene)]]bismaleimide, N,N'-[isopropylidene bis[p-phenyleneoxycarbonyl(p-phenylene)] ]bismaleimide, N,N'-[isopropylidenebis[(2,6-dichlorobenzene-4,1-diyl)oxycarbonyl(p-phenylene)]]bismaleimide Imide, N,N'-[(phenylimino)bis(4,1-phenylene)]bismaleimide, N,N'-[azobis(4,1- Phenyl)]bismaleimide, N,N'-[1,3,4-oxadiazole-2,5-diylbis(4,1-phenylene)]bismaleimide , 2,6-bis[4-(maleimide-N-yl)phenoxy]benzonitrile, N,N'-[1,3,4-oxadiazole-2,5-diylbis (3,1-phenylene)]bismaleimide, N,N'-[bis[9-oxo-9H-9-phosphora(V)-10-oxaphenanthrene-9-yl] Methylenebis(p-phenylene)]bismaleimide, N,N'-[hexafluoroisopropylidene bis[p-phenyleneoxycarbonyl(m-phenylene)]]bismaleimide Imide, N,N'-[carbonylbis[(4,1-phenylene)thio(4,1-phenylene)]]bismaleimide, N,N'-carbonylbis( p-phenyleneoxy-p-phenylene)bismaleimide, N,N'-[5-tert-butyl-1,3-phenylenebis[(1,3,4-oxadiazole -5,2-diyl)(4,1-phenylene)]]bismaleimide, N,N'-[cyclohexylene bis(4,1-phenylene)]bismaleimide Imine, N,N'-[methylenebis(oxy)bis(2-methyl-1,4-phenylene)]bismaleimide, N,N'-[5-[2 -[5-(Dimethylamino)-1-naphthylsulfonylamino]ethylaminoformyl]-1,3-phenylene]bismaleimide, N,N'- (Oxybisethylenyl)bismaleimide, N,N'-[dithiobis(m-phenylene)]bismaleimide, N,N'-(3,6,9 -trioxaundecane-1,11-diyl)bismaleimide, N,N'-(ethylenylbis-p-phenylene)bismaleimide, artificial molecule (Designer Molecules ) BMI-689, BMI-1500, BMI-1700, BMI-3000, BMI-5000, BMI-9000, ODA-BMI, BAFBMI and other polyfunctional maleimides manufactured by JFE CHEMICAL .

Moreover, the polyfunctional maleimide obtained by making polyfunctional amine and maleic anhydride react can be mentioned. Examples of polyfunctional amines include: isophoronediamine; dicyclohexylmethane-4,4'-diamine; Gif having a terminal aminated polypropylene glycol skeleton manufactured by Huntsman Corporation. Amine (Jeffamine) D-230, HK-511, D-400, XTJ-582, D-2000, XTJ-578, XTJ-509, XTJ-510, T-403, T-5000; XTJ-500, XTJ-501, XTJ-502, XTJ-504, XTJ-511, XTJ-512, XTJ-590 with diol skeleton; XTJ-542, XTJ-533, XTJ-536, XTJ-548, XTJ-559, etc.

When the maleimide group-containing compound (b6) is crosslinked by radicals, a radical polymerization initiator may be added. Specifically, an azo compound and an organic peroxide can be illustrated. The polymerization initiator can be used singly or in combination of two or more kinds. Examples of 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-methyl propionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2 -hydroxymethylpropionitrile), 2,2'-azobis[2-(2-imidazolin-2-yl)propane]. Examples of organic peroxides include: benzoyl peroxide, tert-butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, peroxide Bis(2-ethoxyethyl) dicarbonate, tert-butyl peroxy 2-ethylhexanoate, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, (3, 5,5-trimethylhexyl) peroxide, diacryl peroxide, diacetyl peroxide.

The crosslinking agent (B) is preferably used in combination with at least any one of the epoxy group-containing compound (b1) and the compound (b2) to compound (b7). In particular, it is preferable to use an epoxy group-containing compound (b1) and an isocyanate group-containing compound (b3) in combination, and to use an epoxy group-containing A compound (b1) containing a carbodiimide group and a compound (b5) containing a carbodiimide group, and an epoxy group-containing compound (b1) and a compound (b6) containing a maleimide group are used in combination. In addition, from the viewpoint of improving plating solution resistance and migration after thermal cycles, it is preferable to use an epoxy group-containing compound (b1) and a cyanate ester compound (b2) in combination, and to use an epoxy group-containing compound (b1) in combination. Compound (b1) and metal chelate compound (b4).

1-3. UV absorber (C) This composition may contain an ultraviolet absorber (C) as an optional component. The ultraviolet absorber functions to absorb ultraviolet rays and convert light energy of ultraviolet rays into heat energy. In the case of using ultraviolet (Ultraviolet, UV) laser light when forming the through holes of the hardened layer formed by curing a thermosetting sheet such as an adhesive sheet formed of this composition, the adhesive sheet can be adjusted by adding an ultraviolet absorber Or the energy applied by the hardened layer. As a result, laser processability can be improved. The ultraviolet absorber (C) is preferably contained in 0.1 mass % - 10 mass % in 100 mass % of this composition, More preferably, it is contained in 0.1 mass % - 5 mass %. In addition, various wavelengths (ultraviolet light, infrared light, etc.) can be selected for the laser light irradiation on the adhesive sheet or the cured material layer according to the application. In addition, a plurality of laser beams may be irradiated as needed.

Examples of the type of ultraviolet absorber (C) include benzophenone-based, benzotriazole-based, triazine-based, salicylate-based, cyanoacrylate-based, and the like. In addition, zinc oxide can also be used. UV absorber (C) can be used with or without surface treatment. Specifically, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-octyloxydiphenone, Benzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-n-octadecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone Ketone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 2-hydroxy-5-chlorobenzophenone, 2,4-dihydroxybenzophenone, 2,2'-di Hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone , poly-4-(2-acryloxyethoxy)-2-hydroxybenzophenone, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy -5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-dimethylphenyl)benzotriazole, 2-(2-methyl-4-hydroxyphenyl ) benzotriazole, 2-(2-hydroxy-3-methyl-5-tert-butylphenyl) benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl ) benzotriazole, 2-(2-hydroxy-3,5-dimethylphenyl)-5-methoxybenzotriazole, 2-(2-hydroxy-3-tert-butyl-5- Methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)-5-chlorobenzotriazole, 2-[4,6-bis(2, 4-Dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)phenol, 2-(4,6-diphenyl-1,3,5-tri Oxyzin-2-yl)-5-(hexyloxy)phenol, phenyl salicylate, p-octylphenyl salicylate, ethyl 2-cyano-3,3-diphenylacrylate, 2-cyano 2-ethylhexyl-3,3-diphenylacrylate, 2,2-bis{[2-cyano-3,3-diphenylacryloxy]methyl}propane-1,3 -Diyl-bis(2-cyano-3,3-diphenylacrylate) and the like.

1-4. Filler (D) The present composition may contain a filler (D) as an optional component. From the viewpoint of improving the plating solution resistance of this composition, the insulation reliability after a thermal cycle test, and the lamination property to LCP, it is preferable to contain 3% by mass to 60% by mass in 100% by mass of this composition % filler (D), more preferably 5% by mass to 40% by mass. By setting the amount of filler (D) to 3% by mass or more, the occurrence of cracks or peeling can be effectively suppressed against the stress caused by the rapid temperature change during the thermal cycle test. In addition, by including a specified amount or more The components that are not easily attacked by the plating solution can improve the resistance to the plating solution. In addition, with respect to the stress caused by the rapid temperature change during the thermal cycle test, the occurrence of cracks or peeling is effectively suppressed, thereby preventing moisture from entering the cracked or peeled part, thereby improving insulation reliability. On the other hand, by making the amount of the filler (D) 60% by mass or less, the ratio of the resin component that adheres to the adherend becomes higher, and the lamination property to the LCP substrate becomes more excellent.

The shape of the filler (D) is not particularly limited. For example, spherical shape, powdery shape, fibrous shape, needle shape, scale shape etc. are mentioned. Specific examples of the filler (D) include: fluorine filler: polytetrafluoroethylene powder or its modified product, tetrafluoroethylene-perfluoroalkyl vinyl ether powder, tetrafluoroethylene-ethylene powder, tetrafluoroethylene-hexafluoroethylene powder, Fluoropropylene powder, tetrafluoroethylene-vinylidene fluoride powder, tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether powder, polychlorotrifluoroethylene powder, chlorotrifluoroethylene-ethylene powder, chlorotrifluoroethylene - Vinylidene fluoride powder, polyvinylidene fluoride powder, polyvinylidene fluoride based powder. In addition, polyethylene powder, polyacrylate powder, epoxy resin powder, polyamide powder, polyimide powder, polyurethane powder, liquid crystal polymer beads, polysiloxane powder, etc., And polymer fillers such as silicone, acrylic, styrene butadiene rubber, butadiene rubber and other multi-layer core-shell structures; melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, polyphosphoric acid Ammonium, Ammonium Ammonium Phosphate, Ammonium Ammonium Polyphosphate, Ammonium Phosphate Formate, Ammonium Phosphate and other (poly)phosphate compounds, Organic Phosphate Compounds, Phosphazene Compounds, Phosphonic Acid Compounds, Aluminum diethylphosphinate, aluminum methylethylphosphinate, aluminum diphenylphosphinate, aluminum ethylbutylphosphinate, aluminum methylbutylphosphinate, aluminum polyethylenephosphinate, etc. Phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, phosphoramide compounds and other phosphorus fillers; benzoguanamine, melamine, melam, melem, melon ( Melon), melamine cyanurate, cyanuric acid compound, isocyanuric acid compound, triazole compound, tetrazole compound, diazo compound, urea and other nitrogen-based fillers; crystalline silica, amorphous Silicon, hollow silica, porous silica, mica, talc, kaolin, clay, hydrotalcite, wollastonite, xonotlite, silicon nitride, boron nitride, aluminum nitride, hydrogen phosphate Calcium, calcium phosphate, glass flakes, hydrated glass, calcium titanate, sepiolite, magnesium sulfate, aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, barium hydroxide, calcium hydroxide, titanium oxide, tin oxide, aluminum oxide , magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, antimony oxide, nickel oxide, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, zinc borate, aluminum borate and other inorganic fillers.

When applying the hardened layer formed by this composition to the insulating layer of a high-capacity high-speed substrate, liquid crystal polymers, fluororesins, modified polyphenylene ethers, glass spheres as glass hollow bodies, and soot hollow bodies can be exemplified , white balloon, calcium carbonate, talc, mixtures of these.

From the viewpoint of impact absorption, it is preferable to use fluorine filler, boron nitride, liquid crystal polymer, and silicon dioxide. The filler (D) may be used alone or in combination.

The method of adding the filler (D) is not particularly limited, and a previously known method can be used. Preferable examples include: a method of adding to the polymerization reaction solution before or during the polymerization of the polyimide resin (A), a method of kneading the filler in the polyimide resin (A) using a three-roll machine, A method of preparing a dispersion containing a filler and mixing it into the polyimide resin (A), etc. In addition, in order to disperse the filler well and stabilize the dispersed state, a dispersant, a thickener, and the like may be used within a range that does not affect the physical properties of the thermosetting resin composition.

1-5. Other optional ingredients This composition may contain various additives in the range which does not deviate from the summary of this invention. For example, a polyimide resin other than the polyimide resin (A) may also be used. In addition, arbitrary thermoplastic resins may be used. In addition, a catalyst may be contained as an optional component in order to promote the crosslinking of the phenolic hydroxyl group in the polyimide resin (A) and the crosslinking agent (B). Preferable examples of the catalyst include imidazole-based, amine-based, and phosphorus-based catalysts. Furthermore, dyes, pigments (for example, carbon black), flame retardants, antioxidants, polymerization inhibitors, defoamers, leveling agents, ion traps, humectants, viscosity regulators, preservatives, antibacterial agents, Antistatic agent, anti-blocking agent, ultraviolet absorber, infrared absorber, electromagnetic wave shielding agent, etc.

1-6. Characteristics of thermosetting composition From the viewpoint of insulation reliability after a thermal cycle test, the composition preferably has a glass transition temperature after thermal hardening at 180°C for 60 minutes in the range of 0°C to 70°C. More preferably, it is 10°C to 60°C. Since the glass transition temperature is 0° C. or higher, the crosslinked structure in the composition does not collapse significantly even against extreme ambient temperature cycles, and metal ions generated from electrodes that cause short circuits can be suppressed. The flow, thus excellent insulation reliability characteristics. On the other hand, since the glass transition temperature is 70° C. or lower, a certain degree of flexibility can be imparted to the present composition, and peeling can be suppressed by relieving stress against the expansion and contraction of the adherend during extreme environmental temperature cycles. , thereby suppressing a short circuit caused by moisture or the like flowing in from the gap generated by the peeling. In addition, the said hardening conditions are the hardening conditions for estimating the Tg at the time of hardening process of this composition, and are not limited to the hardening conditions of the hardened|cured material which consists of this composition at all.

2. Manufacturing method of thermosetting composition This composition is obtained by blending each blended component. Instead of using a polyimide precursor, an imidized polyimide resin (A) was used as a compounding component. When preparing, a solvent can be used appropriately. The solid content concentration can be set to, for example, 20% by mass to 60% by mass. According to the polyimide resin (A) of this embodiment, since it has a dimer structure, it can dissolve easily in various organic solvents.

The present composition can be prepared, for example, in the form of powder, film, sheet, plate, granule, paste or liquid. A liquid or pasty thermosetting composition can be easily obtained by adjusting the viscosity using a solvent. In addition, a film-like, sheet-like, or plate-like thermosetting composition can be formed, for example, by applying a liquid or paste-like thermosetting composition and drying it. In addition, a powdery or granular thermosetting composition can be obtained, for example, by pulverizing or breaking the film-like thermosetting composition into desired sizes.

The adhesive sheet is obtained by, for example, applying a coating solution of the present composition containing a solvent to one side of a release film, removing a liquid medium such as an organic solvent, and drying at, for example, 40°C to 150°C. An adhesive sheet with release films on both sides can be obtained by laminating another release film on the surface of the obtained adhesive sheet. By laminating both sides with a release film, surface contamination of the adhesive sheet can be prevented. The adhesive sheet can be separated by peeling off the release film. The two release films may be of the same type or of different types. By using the peeling film which differs in releasability, since strength and weakness can be given to peeling force, it peels off sequentially easily. In addition, it is also possible to directly apply the coating liquid on the substrate to form an adhesive sheet.

Examples of substrates include: polyimide film, polyethylene film, polycarbonate, polyethylene, liquid crystal polymer, phenolic resin, aramid resin, and other resin materials; metal materials such as copper, aluminum, and stainless steel; indium tin oxide (Indium Tin Oxide, ITO), glass, silicon, silicon carbide and other inorganic materials and composite materials made of these arbitrary combinations. According to this composition, by storing the flexible polyimide resin (A) whose modulus of elasticity G' becomes 1.0×10 ⁷ Pa at any temperature between 0°C and 90°C, not only the adhesion to various substrates Excellent properties and formability.

As the coating method, for example, chipping wheel coating, knife coating, die coating, lip coating, roll coating, curtain coating, bar coating, gravure printing, flexo printing, screen printing, dip coating can be selected. Known methods such as cloth, spray coating, spin coating, etc.

In order to exhibit sufficient adhesiveness and in terms of ease of handling, the thickness of the adhesive sheet after drying is preferably 5 μm to 500 μm, more preferably 10 μm to 100 μm.

3. Manufacturing method of hardened product A cured product is obtained by subjecting this composition to thermal curing treatment. For example, a method of molding a thermosetting composition into a desired shape such as a sheet and performing thermosetting treatment can be exemplified. A molded body such as a sheet of a thermosetting composition can be easily obtained by applying a thermosetting composition containing a solvent and drying it. Then, a cured product is formed by thermally curing the molded body. The timing of forming and hardening may be at the same time. Furthermore, the flaky one among the cured products is also referred to as a hardened layer.

The thermosetting temperature may be appropriately selected according to the type of the crosslinking agent (B). For example, a method of performing a heat treatment at a temperature of 150° C. to 230° C. for 30 minutes to 180 minutes can be illustrated. During thermal hardening, pressure may be applied for thermocompression bonding (for example, 5 MPa) if necessary. A cross-linked structure is formed in this composition by thermal hardening treatment, so as to obtain a three-dimensional cross-linked hardened product.

4. Application of thermosetting composition and cured product, etc. This composition has excellent lamination properties with LCP substrates, so it is suitable as an adhesive sheet for flexible printed wiring boards requiring low dielectric properties. It shows excellent adhesiveness after hardening, so it is suitable as an adhesive sheet and bonding material for bonding various materials (resin layer, metal layer, inorganic layer such as ITO, composite layer, etc.). For example, it is suitable as a bonding material of components such as an adhesive sheet of a copper-clad laminate, an electronic circuit board, and an electronic component. In copper-clad laminates (CCL: Copper Clad Laminate), there are steps of electrolytic copper plating on the surface of the copper foil, etching with a plating solution such as alkali after removing the resist layer, but according to this hardening It is excellent in resistance to plating solution, so it is suitable as an adhesive sheet for copper-clad laminates. Furthermore, since this cured product is excellent in laser processability, it is suitable for the use which forms openings, such as a via-hole and a pattern. In addition, it can also be used as an adhesive layer of a carrier tape of a TBA tape or a COF tape.

In addition, since the polyimide resin (A) of this composition is excellent in electrical insulation, a cured product excellent in insulation can be provided. For example, it can be preferably used as an insulating layer forming material on a circuit board (including a cover layer of a printed wiring board, an interlayer insulating layer of a build-up board, etc., a bonding sheet, etc.), and the like. Moreover, it can be suitably applied to the insulating member of an electronic component. Electronic components, such as power semiconductor devices, light emitting diodes (Light Emitting Diode, LED), inverter devices and other power modules, can be preferably used for substrates, insulating layers of semiconductor chip packages, underfill materials, and adhesive materials. wait. In addition, it can be used for thermosetting compositions for copper-clad laminates, bonding sheets for forming wiring boards, overcoat layers for flexible substrates, prepregs, and the like.

By preparing a conductive filler as the filler (D), it can be used as a conductive adhesive sheet. Furthermore, by using a thermally conductive filler as the filler (D), it can be applied to all applications requiring heat dissipation. For example, the formability of the resin composition can be used preferably as a heat dissipation part of a desired shape. In particular, it can be effectively used as a heat-dissipating adhesive material or heat-dissipating sheet for electronic devices (smart phones, tablet terminals, etc.) and battery packaging materials that cannot be equipped with fans or heat sinks in order to make them thinner and smaller. In addition, the cured product of this composition is preferably used as an adhesive layer between a heating element and a heat sink or as a heat spreader. In addition, it can be used as a heat dissipation layer covering one or more types of electronic components mounted on a substrate.

5. Printed wiring board Since the adhesive sheet containing this composition has the said characteristic, it can be used suitably for manufacture of a printed wiring board. The adhesive sheet functions as a cured layer that exhibits adhesiveness by thermosetting. Moreover, since the cured layer which is the cured product of the thermosetting sheet formed from this composition is excellent in insulation, it can be suitably used as a protective film or an interlayer insulating layer in a printed wiring board. Since the thermosetting sheet containing this composition uses the highly flexible polyimide resin (A), it can be laminated at low temperature and in a short time. Therefore, it is preferable for bonding to a liquid crystal polymer (LCP) substrate having excellent low dielectric properties.

The printed wiring board can be manufactured, for example, by processing the copper foil in the copper-clad laminate board by etching, bonding the substrate obtained by forming the signal circuit, etc. Hardened for bonding. Moreover, the flexible printed wiring board can be manufactured through the process of forming a conductor pattern on an insulating flexible film, forming a protective film thereon via this adhesive sheet, and performing thermocompression bonding, for example. Examples of the flexible film include polyester, polyimide, liquid crystal polymer, and polytetrafluoroethylene (PTFE) films. The conductive pattern can be exemplified by a method formed by a printing technique, a method by sputtering, or plating.

It is also possible to form an opening by drilling or laser processing to the hardened layer of this composition formed on one or both sides of the printed wiring board, and fill it with a conductive agent to form a via hole. In addition, a circuit layer can also be formed on the interlayer insulating layer which is a cured product of the present composition. Since the hardened|cured material of this composition is excellent in plating resistance, it is preferable for manufacture of a multilayer printed wiring board. Furthermore, by having a cross-linked structure of the highly flexible polyimide resin (A) via the phenolic hydroxyl group and the cross-linking agent (B), the residual stress can be suppressed to be low, and the insulation after the thermal cycle test is reliable excellent. Since the printed wiring board formed using this composition is excellent in insulation reliability in a wide temperature range, it is suitable for various electronic devices, such as a smartphone and a tablet terminal. [Example]

Hereinafter, the present invention will be described more specifically by means of examples. The present invention is not limited to the following examples unless the gist is exceeded. Unless otherwise specified, "%" and "parts" are used as mass standards.

(i) Determination of weight average molecular weight (Mw) For the measurement of Mw, a gel permeation chromatography (Gel Permeation Chromatograph, GPC) "GPC-101" manufactured by Showa Denko Co., Ltd. was used. The solvent was tetrahydrofuran (THF), and as a column, two "KF-805L" (manufactured by Showa Denko: GPC column: 8 mmID x 300 mm size) connected in series were used. It was carried out under the conditions of sample concentration of 1% by mass, flow rate of 1.0 mL/min, pressure of 3.8 MPa, and column temperature of 40°C. The determination of Mw was carried out in terms of polystyrene. For data analysis, a calibration curve, molecular weight, and peak area were calculated using the manufacturer's built-in software, and Mw was obtained by setting the retention time range of 17.9 minutes to 30.0 minutes as the analysis object.

(ii) Determination of acid value The acid value is measured in accordance with Japanese Industrial Standards (JIS) K0070. Specifically, about 1 g of a sample (polyimide resin (A)) was precisely weighed in a co-embedded Erlenmeyer flask, and dissolved by adding 100 mL of a cyclohexanone solvent. A phenolphthalein test solution was added thereto as an indicator, and titrated with a 0.1 N alcoholic potassium hydroxide solution, and the point at which the indicator remained light red for 30 seconds was set as the end point. The acid value was calculated|required by the following formula. Acid value (mgKOH/g)=(5.611×a×F)/S in, S: Amount of sample taken (g) a: Consumption of 0.1 N alcoholic potassium hydroxide solution (mL) F: titer of 0.1 N alcoholic potassium hydroxide solution

(iii) Determination of phenolic hydroxyl value The phenolic hydroxyl value is measured in accordance with JIS K0070. The amount of potassium hydroxide required to neutralize the acetic acid bonded to the phenolic hydroxyl group when the phenolic hydroxyl group is acetylated from the phenolic hydroxyl group contained in 1 g of polyimide resin (A) (mg )express. When calculating the phenolic hydroxyl value of a polyimide resin (A), it calculates considering an acid value as shown in the following formula. Specifically, about 1 g of a sample (polyimide resin (A)) was precisely weighed in a co-embedded Erlenmeyer flask, and dissolved by adding 100 mL of a cyclohexanone solvent. Furthermore, 5 mL of an acetylating agent (25 g of acetic anhydride was dissolved in pyridine to make a solution with a capacity of 100 mL) was accurately added, and stirred for about 1 hour. Phenolphthalein test solution was added thereto as an indicator and continued for 30 seconds. Afterwards, titrate with 0.5 N alcoholic potassium hydroxide solution until the solution turns light red. The phenolic hydroxyl value is calculated|required by the following formula. Phenolic hydroxyl value (mgKOH/g)=[{(b-a)×F×28.05}/S]+D in, S: Amount of sample taken (g) a: Consumption of 0.5 N alcoholic potassium hydroxide solution (mL) b: Consumption of 0.5 N alcoholic potassium hydroxide solution in blank experiment (mL) F: titer of 0.5 N alcoholic potassium hydroxide solution D: acid value (mgKOH/g) The side chain phenolic hydroxyl value was calculated from the loading rate of the monomer used in the synthesis of the polyimide resin (A) relative to the obtained phenolic hydroxyl value. In addition, the terminal phenolic hydroxyl value is set to a value obtained by subtracting the side chain phenolic hydroxyl value from the phenolic hydroxyl value obtained by experiment. In addition, the value of b was determined by titrating 5 mL of an acetylating agent (25 g of acetic anhydride was dissolved in pyridine to make a solution with a capacity of 100 mL) with a 0.5 N alcoholic potassium hydroxide solution.

(iv) Determination of amine value About 1 g of the sample (polyimide resin (A)) was accurately measured in a co-embedded Erlenmeyer flask, and dissolved by adding 100 mL of cyclohexanone solvent. Add 2 or 3 drops of a liquid obtained by dissolving 0.20 g of Methyl Orange in 50 mL of distilled water and 0.28 g of Xylene Cyanol FF in 50 mL of methanol. Prepare the indicator by mixing the resulting liquid and hold for 30 seconds. Afterwards, titrate with 0.1 N alcoholic hydrochloric acid solution until the solution turns blue-gray. The amine value was calculated|required by the following formula. Amine value (mgKOH/g)=(5.611×a×F)/S in, S: Amount of sample taken (g) a: Consumption of 0.1 N alcoholic hydrochloric acid solution (mL) F: titer of 0.1 N alcoholic hydrochloric acid solution

(v) Determination of acid anhydride base value About 1 g of the sample (polyimide resin (A)) was accurately measured in a co-embedded Erlenmeyer flask, and dissolved by adding 100 mL of 1,4-dioxane solvent. Add 10 mL of a mixed solution of octylamine, 1,4-dioxane, and water (the mass mixing ratio is 1.49/800/80) that is more than the amount of acid anhydride groups in the sample, and stir for 15 minutes to make it Reacts with anhydride groups. Thereafter, excess octylamine was titrated with a mixed solution of 0.02 M perchloric acid and 1,4-dioxane. In addition, 10 mL of a mixed solution of octylamine, 1,4-dioxane, and water (mixing ratio by mass: 1.49/800/80) to which no sample was added was also measured as a control. The acid anhydride value was obtained by the following formula (unit: mgKOH/g). Anhydride value (mgKOH/g)=0.02×(B-A)×F×56.11/S B: titer of control (mL) A: Titration of sample (mL) S: Amount of sample taken (g) F: The titer of 0.02 mol/L perchloric acid

(vi) Measurement of storage modulus G' and Tg of polyimide resin (A) The polyimide resin (A) of each synthesis example was dissolved in cyclohexanone so that the non-volatile content became 35%, Make polyimide resin varnish. Using a doctor blade with a gap of 10 mil, the varnish was applied on a heat-resistant release film, and dried at 130° C. for 10 minutes, thereby obtaining a resin sheet with a thickness of 25 μm. The obtained resin sheet was peeled off from the self-weight release film, and the storage elastic coefficient and Tg of the resin sheet were measured using a dynamic viscoelasticity measuring device "DVA200" (manufactured by IT Measurement & Control Co., Ltd.). Regarding the storage elastic coefficient, after cooling the resin sheet to 0°C, the temperature was raised to 300°C at a heating rate of 10°C/min, the viscoelasticity was measured at a vibration frequency of 10 Hz, and the length between chucks: 10 mm, and the storage elastic coefficient G' was measured at a temperature of 1.0×10 ⁷ Pa. In addition, let the peak temperature of the tan δ diagram be Tg. Heating rate: 10°C/min Measurement frequency: 10 Hz Length between clamps: 10 mm Width: 5 mm

(vii) Measurement of Tg when the thermosetting composition is heat-treated at 180°C for 60 minutes A polyimide resin sheet was obtained by the same method as the above (vi) for the coating liquid (thermosetting composition) of each Example and the comparative example mentioned later. Next, the polyimide resin sheet was heat-treated at 180° C. for 60 minutes to obtain a hardened sheet. For the obtained hardened sheet, use the same dynamic viscoelasticity measuring device as in (vi), and set the heating rate, measurement frequency, length between chucks, and width under the same conditions, and perform the test at a temperature range of -50°C to 200°C. The loss tangent (tan δ) was measured, and Tg was measured using the same method as described.

＜Synthesis of polyimide resin＞ [Synthesis Example 1] Polyimide resin (P1) In a 1 L separable flask with a stirring bar including an oil bath, 200 g of cyclohexanone was added while introducing nitrogen gas, and dimer diamine (PRIAMINE (PRIAMINE) as a diamine was added while stirring. ) 1075) 149.8 g, 4.7 g of m-aminophenol as a monoamine compound, and then 67.3 g of 1,2,4,5-cyclohexanetetracarboxylic dianhydride as tetracarboxylic dianhydride, at room temperature Stir for 30 minutes. After raising the temperature to 100° C. and stirring for 3 hours, the oil bath was removed and returned to room temperature to obtain a varnish-like polyimide precursor. Thereafter, while removing distilled water from the system using a Dean-Stark separator, heating was performed at 170°C for 10 hours to imidize the polyimide resin. (P1). Table 1 shows the Mw, Tg, and functional group valence of the obtained polyimide resin, respectively.

[Synthesis Example 2 to Synthesis Example 25, Comparative Synthesis Example 1 to Comparative Synthesis Example 5] Polyimide Resin (P2) to Polyimide Resin (P30) Except having used the monomer described in Table 1 - Table 3, polyimide resin P2 - polyimide resin P30 were obtained by the method similar to synthesis example 1. The contents of abbreviations such as Table 1 are shown below. TA1: 1,2,4,5-cyclohexanetetracarboxylic dianhydride, anhydride group equivalent weight 112.1 g/eq. TA2: 1,2,3,4-butanetetracarboxylic dianhydride, anhydride group equivalent weight 99.1 g/eq. TA3: 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride, anhydride group equivalent weight 260.2 g/eq. TA4: 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, anhydride group equivalent weight 150.1 g/eq. DA1: Priamine 1075 (dipolymer diamine) DA2: 4,4'-(hexafluoroisopropylidene)bis(2-aminophenol) DA3: 1,12-Dodecanediamine DA4: D-2000 (polyether diamine manufactured by Huntsman, molecular weight 2000) MA1: m-aminophenol MA2: o-aminophenol MA3: p-Aminophenol MA4: 4-Hydroxyphenethylamine (tyramide)

Table 1 and Table 2 show the compounding amount (parts by mass) of the polyimide resin in each synthesis example, the acid anhydride valency and phenolic hydroxyl group (hereinafter also referred to as PhOH) of the obtained polyimide resin. Valence (side chain PhOH value, terminal PhOH value), amine value, Mw, PhOH value/all functional groups, etc. In addition, the mole % of the ^X1 a residue relative to 100 mole % of the ^X1 residue is shown relative to 100 mass % of the monomer (charged amount) for obtaining the ^X2 residue The mass % of the monomer (charged amount) used to obtain X ² d. In addition, all functional group valences in this specification mean the total functional group valence of amine group value+acid anhydride group value+phenolic hydroxyl group value.

[Table 1] Table 1 Synthesis example 1 2 3 4 5 6 7 8 9 10 P1 P2 P3 P4 P5 P6 P7 P8 P9 P10 Tetracarboxylic acids [parts by mass] TA1 67.3 67.3 67.3 67.3 67.3 67.3 67.3 0.0 0.0 53.8 TA2 0.0 0.0 0.0 0.0 0.0 0.0 0.0 59.4 59.4 0.0 TA3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 31.2 TA4 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 TA5 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Organic compound [parts by mass] DA1 149.8 149.8 149.8 149.8 149.8 149.8 145.0 149.8 145.0 148.2 DA2 0.0 0.0 0.0 0.0 0.0 0.0 3.3 0.0 3.3 0.0 DA3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 DA4 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Monoamine compound [parts by mass] MA1 4.7 0.0 0.0 0.0 6.7 11.8 4.7 4.6 4.6 5.1 MA2 0.0 0.0 4.7 0.0 0.0 0.0 0.0 0.0 0.0 0.0 MA3 0.0 0.0 0.0 4.7 0.0 0.0 0.0 0.0 0.0 0.0 MA4 0.0 5.9 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Functional base price Terminal anhydride value [mgKOH/g] 0.0 0.0 0.0 0.0 3.4 6.7 0.0 0.0 0.0 0.0 Terminal PhOH value [mgKOH/g] 11.5 11.5 11.5 11.5 8.0 4.5 11.5 11.6 11.6 11.5 Side chain PhOH value [mgKOH/g] 0.0 0.0 0.0 0.0 0.0 0.0 4.5 0.0 4.7 0.0 Terminal + side chain PhOH value [mgKOH/g] 11.5 11.5 11.5 11.5 8.0 4.5 16.0 11.6 16.2 11.5 Amine value [mgKOH/g] 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 PhOH value / all functional base values [%] 100.0 100.0 100.0 100.0 70.0 40.0 100.0 100.0 100.0 100.0 All functional groups [mgKOH/g] 11.5 11.5 11.5 11.5 11.5 11.2 16.0 11.6 16.2 11.5 Weight average molecular weight [Mw] 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 (X ¹ a)/X ¹ [mol%] 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 80.0 Obtained monomer of x ² d residues/acquired monomer of X ² residues [mass %] 100.0 100.0 100.0 100.0 100.0 100.0 97.8 100.0 97.8 100.0 Monomer of x ² d residues obtained/monomer of X ² residues obtained [mol %] 100.0 100.0 100.0 100.0 100.0 100.0 96.8 100.0 96.8 100.0 PhOH groups/all functional groups [mol%] 100.0 100.0 100.0 100.0 70.0 40.0 100.0 100.0 100.0 100.0

[Table 2] Table 2 Synthesis example 11 12 13 14 15 16 17 18 19 20 P11 P12 P13 P14 P15 P16 P17 P18 P19 P20 Tetracarboxylic acids [parts by mass] TA1 53.8 33.6 33.6 0.0 0.0 67.3 67.3 67.3 67.3 67.3 TA2 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 TA3 31.2 78.1 78.1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 TA4 0.0 0.0 0.0 90.1 90.1 0.0 0.0 0.0 0.0 0.0 TA5 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Organic compound [parts by mass] DA1 143.4 146.6 143.4 148.2 143.4 135.3 128.9 148.2 151.4 135.3 DA2 3.3 0.0 3.3 0.0 3.3 0.0 3.3 3.3 3.3 9.9 DA3 0.0 0.0 0.0 0.0 0.0 5.4 5.4 0.0 0.0 0.0 DA4 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Monoamine compound [parts by mass] MA1 5.1 5.7 5.6 5.2 5.2 4.6 4.5 3.2 1.9 0.0 MA2 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 MA3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 MA4 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Functional base price Terminal anhydride value [mgKOH/g] 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 11.8 Terminal PhOH value [mgKOH/g] 11.5 11.4 11.5 11.4 11.4 11.6 11.6 7.7 4.7 0.0 Side chain PhOH value [mgKOH/g] 4.1 0.0 4.0 0.0 3.5 0.0 4.7 4.5 4.6 15.5 Terminal + side chain PhOH value [mgKOH/g] 15.6 11.4 15.5 11.4 14.9 11.6 16.3 12.3 9.3 15.5 Amine value [mgKOH/g] 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 PhOH value / all functional base values [%] 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 56.8 All functional groups [mgKOH/g] 15.6 11.4 15.5 11.4 14.9 11.6 16.3 12.3 9.3 27.3 Weight average molecular weight [Mw] 20000 20000 20000 20000 20000 20000 20000 30000 50000 20000 (X ¹ a)/X ¹ [mol%] 80.0 50.0 50.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Obtained monomer of x ² d residues/acquired monomer of X ² residues [mass %] 97.8 100.0 97.8 100.0 97.8 96.2 93.7 97.8 97.9 93.2 Monomer of x ² d residues obtained/monomer of X ² residues obtained [mol %] 96.7 100.0 96.7 100.0 96.7 90.3 87.0 96.8 96.9 90.3 PhOH groups/all functional groups [mol%] 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 56.8

[table 3] table 3 Synthesis example Comparative Synthesis Example twenty one twenty two twenty three twenty four 25 1 2 3 4 5 P21 P22 P23 P24 P25 P26 P27 P28 P29 P30 Tetracarboxylic acids [parts by mass] TA1 67.3 67.3 0.0 67.3 67.3 67.3 67.3 67.3 67.3 67.3 TA2 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 TA3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 TA4 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 TA5 0.0 0.0 79.3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Organic compound [parts by mass] DA1 138.5 106.3 149.8 142.0 134.5 141.8 174.0 0.0 75.7 82.2 DA2 3.3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 DA3 0.0 16.8 0.0 0.0 0.0 0.0 0.0 57.7 28.3 13.9 DA4 0.0 0.0 0.0 27.8 55.7 0.0 0.0 0.0 0.0 111.3 Monoamine compound [parts by mass] MA1 7.6 3.7 4.7 4.7 4.7 0.0 0.0 2.7 3.7 4.7 MA2 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 MA3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 MA4 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Functional base price Terminal anhydride value [mgKOH/g] 0.0 0.0 0.0 0.0 0.0 19.5 0.0 0.0 0.0 0.0 Terminal PhOH value [mgKOH/g] 19.0 10.5 10.9 10.5 10.9 0.0 0.0 12.0 11.7 10.9 Side chain PhOH value [mgKOH/g] 4.4 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Terminal + side chain PhOH value [mgKOH/g] 23.3 10.5 10.9 10.5 10.9 0.0 0.0 12.0 11.7 10.9 Amine value [mgKOH/g] 0.0 0.0 0.0 0.0 0.0 0.0 11.8 0.0 0.0 0.0 PhOH value / all functional base values [%] 100.0 100.0 100.0 100.0 100.0 0.0 0.0 100.0 100.0 100.0 All functional groups [mgKOH/g] 23.3 10.5 10.9 10.5 10.9 19.5 11.8 12.0 11.7 10.9 Weight average molecular weight [Mw] 12000 22000 21000 22000 21000 12000 20000 20000 20000 25000 (X ¹ a)/X ¹ [mol%] 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Obtained monomer of x ² d residues/acquired monomer of X ² residues [mass %] 97.7 86.3 100.0 83.6 70.7 100.0 100.0 0.0 72.8 39.6 Monomer of x ² d residues obtained/monomer of X ² residues obtained [mol %] 96.6 70.2 100.0 95.0 90.0 100.0 100.0 0.0 50.0 55.0 PhOH groups/all functional groups [mol%] 100.0 100.0 100.0 100.0 100.0 0.0 0.0 100.0 100.0 100.0

Details of materials used in Examples and Comparative Examples are shown below. (Crosslinking agent (B)) (B)-1: Epoxy group-containing compound (b1), Denacol EX-614B (manufactured by Nagase Chemtex Co., Ltd., sorbitol polyglycidyl ether, tetrafunctional, functional group Equivalent 173 g/eq.) (B)-2: epoxy group-containing compound (b1-2), jER828 (manufactured by Mitsubishi Chemical Corporation, bisphenol A epoxy, difunctional, functional group equivalent weight 188 g/eq.) (B)-3: Cyanate ester compound (b2), BAD (manufactured by Mitsubishi Gas Chemical Co., Ltd., bisphenol A type cyanate, difunctional, functional group equivalent weight 139) (B)-4: Isocyanate group-containing compound (b3), Duranate TKA-100 (manufactured by Asahi Kasei Co., Ltd., isocyanurate type isocyanate compound, trifunctional, functional group equivalent: 180 g/eq. ) (B)-5: Metal chelate compound (b4), Orgatix ZC-150 (manufactured by Matsumoto Fine Chemical Co., Ltd., organic zirconia compound, tetrafunctional, functional group equivalent weight 122 g/eq.) (B)-6: Carbodiimide group-containing compound (b5), Carbodilite V-05 (manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide group-containing compound, trifunctional or higher, functional group Equivalent: 262 g/eq.) (B)-7: Maleimide group-containing compound (b6), BMI-3000 (manufactured by Daiwa Kasei Kogyo Co., Ltd., bisphenol A diphenyl ether bismaleimide, difunctional, functional group equivalent weight 285.3 g/eq.) (B)-8: (b7), N-12 (dihydrazine dodecanedioate)

(Ultraviolet absorber (C)) (C)-1: Tinuvin 326 (manufactured by BASF Japan, benzotriazole-containing compound) (Filler (D)) (D)-1 : SC2050-MB (manufactured by Admatechs, silicon dioxide, average particle size D ₅₀ ; 0.5 μm) (D)-2: SP-2 (manufactured by Denka, boron nitride, Average particle diameter D ₅₀ ; 4.0 μm) (D)-3: Exolit OP935 (manufactured by Clariant, aluminum phosphinate, average particle diameter D ₅₀ ; 2.5 μm) (D )-4: KT-300 (manufactured by Kitamura Co., Ltd., fluorine-based filler, average particle diameter D ₅₀ ; 10.0 μm) (D)-5: E101-S (manufactured by Sumitomo Chemical Co., Ltd., liquid crystal polymer, average particle diameter D ₅₀ ; 17.5 μm)

[Example 1] ＜＜Manufacture of Coating Solution＞＞ In terms of solid content, 100 parts of the polyimide resin (P1) of Synthesis Example 1, 5 parts of the crosslinking agent ((B)-1), 7.0 parts (5.0% by mass relative to the non-volatile components) ) UV absorber (C)-1, 28.0 parts (20.0% by mass relative to the non-volatile content) of the filler (D)-1 were placed in a container, and mixed so that the non-volatile content concentration became 30%. A solvent (toluene:MEK=9:1 (mass ratio)) was stirred with a disperser for 10 minutes to obtain a coating liquid.

＜＜Manufacture of adhesive sheet＞＞ Using a doctor blade, apply the obtained coating solution evenly on a heavy release film (polyethylene terephthalate coated with a heavy release agent) with a thickness of 50 μm so that the thickness after drying becomes 25 μm. terephthalate, PET) film) and dried at 100°C for 2 minutes. Thereafter, it was cooled to room temperature to obtain an adhesive sheet with a release film on one side. Next, the adhesive surface of the obtained adhesive resin sheet with a release film on one side was superimposed on a light release film (polyethylene terephthalate (PET) film coated with a light release agent) with a thickness of 50 μm. , so as to obtain the adhesive sheet with release film on both sides including heavy release film/adhesive sheet/light release film. Then, the evaluation described later was performed. The results are shown in Table 3.

[Example 2 to Example 59, Comparative Example 1 to Comparative Example 9] The coating liquids of Examples 2 to 59 and Comparative Examples 1 to 9 were prepared in the same manner as in Example 1 except that the formulation components and formulation amounts described in Tables 4 to 8 were changed to obtain Adhesive sheet with release film on both sides. Each evaluation result is also shown in Table 4 - Table 8 together. In addition, the blank column in a table|surface means not adding.

α. Lamination with LCP substrate The light release film is peeled off from the adhesive sheet with release film on both sides, and the exposed adhesive sheet is bonded to LCP side of a single-sided copper-clad laminate (manufactured by Kuraray Co., Ltd., vecstar (registered trademark) FCCL Fxx-05012) in which a 50 μm LCP film and a 12 μm copper foil are laminated . In addition, the vacuum lamination conditions were a heating temperature of 90° C., a vacuum time of 60 seconds, a vacuum reaching pressure of 2 hPa, a pressure of 0.4 MPa, and a pressurization time of 60 seconds. Then, the heavy release film is peeled off, and the copper foil side of the second single-sided copper-clad laminate is bonded to the exposed bonding sheet surface by using a vacuum laminator to make copper foil/LCP film/bonding sheet/LCP Sample α for evaluation of laminated structure of film/copper foil.

A test piece with a width of 100 mm and a length of 100 mm was cut out from the evaluation sample α, and stored in an environment of 23° C. and a relative humidity of 50% for 24 hours or more. Then, in an environment of 23° C. and a relative humidity of 50%, a 90° tearing peel test was performed at a tensile speed of 50 mm/min, and the bonding strength (N/cm) was measured. A: 2 N/cm or more. The results are extremely good. B: 1 N/cm or more and less than 2 N/cm. The result is good. C: 0.5 N/cm to less than 1 N/cm. within the practical range. D: Less than 0.5 N/cm. Can't be practical.

β. Plating solution resistance of cured product The plating solution resistance of the cured product was evaluated based on the appearance of each test piece after performing the plating tests I and II described later. [I. Acid Plating Test] The adhesive sheet with release film on both sides was cut into a size of 65 mm×65 mm, and the light release film was peeled off. Then, the bonded side exposed due to peeling was laminated at 90°C with the two-layer CCL [ESPANEX (ESPANEX) MC18-25-00FRM] copper surface manufactured by Nippon Steel and Sumikin Chemical Co., Ltd., and then at 180°C. Crimping treatment for 60 minutes under the conditions of 2.0 MPa and 2.0 °C. 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 release film on both sides, and the exposed adhesive sheet surface was subjected to electroless nickel treatment according to the procedures and conditions of the following a to g. a. Acid degreasing step: immerse in ICP clecn S-135K (manufactured by Okuno Pharmaceutical Co., Ltd.) at 40° C. for 4 minutes. b. Microetching step: immerse in sodium persulfate at 30° C. for 1 minute. c. Ash removal step: immerse in sulfuric acid at 25°C for 1 minute. d. Pre-dipping step: dipping in hydrochloric acid at 25°C for 30 seconds. e. Activation step: immerse in ICP AXELA (manufactured by Okuno Pharmaceutical Co., Ltd.) at 30°C for 1 minute. f. Post-dipping step: dipping in sulfuric acid at 25° C. for 1 minute. g. Electroless nickel plating step: dipping in 85° C. IP Nicoron FPF (manufactured by Okuno Pharmaceutical Co., Ltd.) for 20 minutes. [II. Alkaline plating test] A test piece for evaluation was prepared by the same method as the acid plating test, and the electroless nickel treatment was performed on the test piece according to the procedures and conditions of the following s to w. s. Alkaline degreasing step: immerse in an alkaline degreasing agent (50 g/L aqueous solution of ace-clean A-220 (trade name) manufactured by Okuno Pharmaceutical Co., Ltd.) at 50° C. for 5 minutes. t. Etching treatment step: dip in an aqueous solution containing 400 g/L of chromic anhydride and 400 g/L of 98% sulfuric acid at 67° C. for 10 minutes. u. Activation step: immerse in an aqueous solution containing 20 mL/L of 98% sulfuric acid at 25°C for 2 minutes. v. Imparting catalyst activity: immerse in a 25° C. catalyst activation solution (an aqueous solution containing 10 mL/L of TSP activator conc (trade name) manufactured by Okuno Pharmaceutical Co., Ltd.) for 2 minutes. w. Electroless nickel plating step: in ammonia alkali type self-catalytic electroless nickel plating solution (containing chemical nickel A (trade name) 160 mL/L manufactured by Okuno Pharmaceutical Industry Co., Ltd., chemical nickel B ( brand name) in 160 mL/L of an aqueous solution with a pH of 9) at 40°C for 5 minutes.

The appearance of the test piece for evaluation subjected to the treatment of I was visually observed to confirm the presence or absence of abnormalities such as expansion and peeling of the adhesive layer after curing. Then, those without abnormalities then repeated the step I three times. The test piece for evaluation of II was also tested in the same manner. In this test, the resistance of the hardened layer to the plating solution is evaluated by the appearance, and the resistance is evaluated by the repetition times of a to g. A: In any of the test pieces I and II, there was no defect in appearance after the third immersion. extremely good. B: In any of the test pieces I and II, there was no defect in appearance before the second immersion, but a defect in appearance occurred in either test piece after the third immersion. good. C: In any of the test pieces I and II, there was no defect in appearance before the first immersion, but a defect in appearance occurred in any test piece after the second immersion. There is no problem practically. D: In any of the test pieces of I and II, appearance defects occurred during the first immersion. Can't be practical.

γ. Insulation reliability after heat cycle test of cured product The evaluation method will be described with reference to FIGS. 1 to 4 . The laminated body of the copper foil with a thickness of 12 μm and the polyimide film with a thickness of 25 μm is etched, and the comb-shaped signal wiring 2 for the cathode electrode including the cathode electrode connection point 2' is formed on the polyimide film 1 respectively. Comb-shaped signal wiring 3 for the anode electrode including the anode electrode connection point 3' (refer to FIG. 1 ). Line/space is set to 0.05 mm/0.05 mm. Next, on the surface on which the comb-shaped signal wiring 2 for cathode electrodes and the comb-shaped signal wiring 3 for anode electrodes were formed, the light release film of the adhesive sheet with release films on both sides was peeled off, and the adhesive sheet was attached. At this time, the vicinity of the cathode electrode connection point 2' and the vicinity of the anode electrode connection point 3' are exposed. Then, bonding is carried out using a vacuum laminator. Thereafter, the heavy release film is peeled off to expose the adhesive sheet 4 (see FIG. 2 ). On the bonding sheet 4, the insulating layer 5b of the single-sided copper-clad laminate (MC18-25-00FRM) 5 of the two-layer structure of the insulating layer 5b and the copper layer 5a is connected to the bonding sheet 4, using a vacuum layer The press is followed. Then, it was thermally cured by hot pressing at 180° C. for 1 hour at 2 MPa to form a hardened layer 4 ′ of the adhesive sheet 4 to obtain a laminate γ for evaluation (see FIGS. 3 and 4 ).

Next, heat cycle treatment was performed on the evaluation laminate γ. The evaluation laminate γ was placed in a thermal shock device ("TSE-11-A", manufactured by Espec Corporation), exposed to high temperature: 125°C for 15 minutes, and exposed to low temperature: -50°C for 15 minutes 200 alternate exposures were carried out under certain exposure conditions.

After that, for the evaluation laminate γ that was taken out, connect the anode electrode to the anode electrode connection point 3' and the cathode electrode to the cathode electrode connection point 2' in an environment of 85°C-85%RH (relative humidity). , and then the applied voltage of 50 V was continued for 1000 hours. Then, the change in resistance value until 1000 hours elapsed was continuously measured. Furthermore, the so-called "leak touch" means that there is insulation breakdown caused by a short circuit, and the resistance drops momentarily to allow current to flow. In the absence of leakage contact, the insulation will not be reduced. The evaluation criteria are as follows. A: The resistance value after 1000 hours was 1×10 ¹⁰ Ω or more, and there was no leakage contact. extremely good. B: The resistance value after 1000 hours has passed is 1×10 ⁸ Ω or more and less than 1×10 ¹⁰ Ω, and there is no leakage contact. good. C: Does not meet A and B, the resistance value after 1000 hours has passed is 1×10 ⁷ Ω or more, and the leakage current contact is one time or less. There is no problem practically. D: Does not correspond to A to C. Can't be practical.

δ. Laser processability of hardened layer The method of evaluating the laser processability of the hardened layer of the adhesive sheet will be described with reference to FIG. 5 . A double-sided copper-clad laminate 10 is formed by peeling off the peeling film from the adhesive sheet with a release film on both sides, and bonding the exposed adhesive sheet to a 50 μm polyimide film 12 on both sides with a 12 μm copper foil 11 on both sides. One side of the copper foil 11. Then, the heavy release film was peeled off, and the polyimide film of the single-sided copper-clad laminate 20 obtained by laminating the polyimide film 22 of 50 μm and the copper foil 21 of 12 μm was similarly laminated using a vacuum laminator. The 22 sides are then connected to the four sides of the exposed bonding sheet. Afterwards, it was heat-cured by hot pressing at 180°C, 1 hour, and 2 MPa to obtain a hardened layer 4'/polyimide film with copper foil 11/polyimide film 12/copper foil 11/adhesive sheet Evaluation sample δ of the laminated structure of the amine film 22 /copper foil 21 .

For the evaluation sample δ, a UV-YAG laser (Model (Model) 5330, manufactured by ESI Corporation) was used to irradiate the laser from the copper foil 21 side of the single-sided copper-clad laminate 20 to process blind holes with a diameter of 150 μm. Up to the boundary between the hardened layer 4 ′ of the bonding sheet and the double-sided copper-clad laminate 10 (see FIG. 5 ). Next, observe the cross section of the blind hole portion 30 with a laser microscope (VK-X100 manufactured by Keyence Corporation) at a magnification of about 20 times to 500 times, and measure the hardened layer 4' of the thermosetting adhesive sheet. The maximum length of the side etching 31 (horizontally cut to above the designed opening diameter) is produced. The evaluation criteria are as follows. A: 5 μm or less. The results are extremely good. B: More than 5 μm and 7 μm or less. The result is good. C: More than 7 μm and 10 μm or less. within the practical range. D: More than 10 μm. Can't be practical.

ω. Flexibility of hardened layer The adhesive sheet with release film on both sides of each Example and Comparative Example was cut into a size of 65 mm×65 mm, and the light release film was peeled off. Then, the exposed adhesive sheet was laminated at 90°C on a printed wiring board (a comb-shaped pattern of copper circuits formed on polyimide (conductor pattern width/space width=50 μm/50 μm, conductor Thickness of 12 μm, polyimide thickness of 25 μm)), and then peel off the heavy release film on the opposite side of the adhesive sheet, at 90 ° C on the polyimide film with a thickness of 25 μm [Toray DuPont ( Co., Ltd.) by laminating "Kapton (Kapton) 100H"] to produce a polyimide film/resin sheet/printed wiring board (comb-shaped pattern of copper circuits formed on polyimide) three-layer membrane. Next, pressure bonding treatment was performed for 30 minutes under the conditions of 160° C. and 1.0 MPa. Furthermore, this test piece was thermosetted at 160 degreeC for 2 hours, and the test piece for evaluation was produced. The test piece for evaluation was bent 180 degrees so that the polyimide film surface was on the outside (bending so that one side of the test piece faced and the other side faced with a gap), and placed on the polyimide film arranged on the upper side. A load of 1 kg was applied to the amine film for 10 seconds, and thereafter, the test piece for evaluation was returned to its original flat state. Set it to One Bend Count. The presence or absence of cracks at the bent portion of the adhesive sheet was observed using a microscope "VHX-900" manufactured by Keyence Co., Ltd., and the number of times until cracks occurred was evaluated according to the following criteria. A: No cracks can be seen even after bending twenty times. The results are extremely good. B: No cracks were seen even after bending ten times. Cracks occurred up to twenty times. The result is good. C: No cracks were seen even after bending five times. Cracks were generated up to ten times. within the practical range. D: Cracks were generated before bending five times. Can't be practical.

[Table 4] Table 4 Example 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Polyimide resin (A) [parts by mass] P1 P2 P3 P4 P5 P6 P7 P8 P9 P10 P11 P12 P13 P14 P15 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Crosslinking agent (B) [parts by mass] (B)-1 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 (B)-2 (B)-3 (B)-4 (B)-5 (B)-6 (B)-7 (B)-8 UV absorber (C) [mass%] (C)-1 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Filler (D) [mass%] (D)-1 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 (D)-2 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 (D)-3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 (D)-4 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 (D)-5 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Indicates the temperature [°C] at which the storage modulus G' of the polyimide resin (A) is 1.0×10 ⁷ [Pa] 33 32 34 39 31 35 41 48 49 49 53 62 65 47 49 Tg of cured product of thermosetting composition [°C] 38 38 37 43 46 42 44 55 59 55 58 71 73 52 55 evaluate α: Lamination to LCP substrate A A A A A A A A A B B C C A A β: Resistance to plating solution B B B B B C A B A B A B A A A γ: Insulation reliability after thermal cycling B B B C B C A B A B A C B A A δ: laser processability A A A A A A A A A A A A A A A ω: bendability C C C C C C C C C C C C C C C

[table 5] table 5 Example 16 17 18 19 20 twenty one twenty two twenty three twenty four 25 26 27 28 29 30 Polyimide resin (A) [parts by mass] P16 P17 P18 P19 P20 P21 P22 P23 P24 P25 P18 P18 P18 P18 P18 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Crosslinking agent (B) [parts by mass] (B)-1 5 5 5 5 5 5 5 5 5 5 (B)-2 (B)-3 5 (B)-4 5 (B)-5 5 (B)-6 5 (B)-7 5 (B)-8 UV absorber (C) [mass%] (C)-1 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Filler (D) [mass%] (D)-1 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 (D)-2 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 (D)-3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 (D)-4 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 (D)-5 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Indicates the temperature [°C] at which the storage modulus G' of the polyimide resin (A) is 1.0×10 ⁷ [Pa] 38 41 40 46 45 42 81 20 13 3 40 40 40 40 40 Tg of cured product of thermosetting composition [°C] 44 48 51 49 41 43 85 twenty four 17 7 52 49 55 48 44 evaluate α: Lamination property to LCP substrate A A A A A A C A A A A A A A A β: Resistance to plating solution B A A A C B B B C C A A A A A γ: Insulation reliability after thermal cycling B A A A B C B B C C B C B B B δ: laser processability A A A A A A A A A A A A A A A ω: bendability C C C C C C C B A A C C C C C

[Table 6] Table 6 Example 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 Polyimide resin (A) [parts by mass] P18 P18 P18 P18 P1 P1 P1 P1 P1 P1 P18 P18 P18 P18 P18 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Crosslinking agent (B) [parts by mass] (B)-1 0.5 3 7 10 2.5 2.5 2.5 2.5 2.5 5 5 5 5 5 (B)-2 (B)-3 2.5 (B)-4 2.5 2.5 (B)-5 2.5 2.5 (B)-6 2.5 (B)-7 2.5 (B)-8 UV absorber (C) [mass%] (C)-1 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.4 5.4 5.5 5.4 5.3 Filler (D) [mass%] (D)-1 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 0.0 2.0 3.0 10.8 31.8 (D)-2 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 (D)-3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 (D)-4 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 (D)-5 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Indicates the temperature [°C] at which the storage modulus G' of the polyimide resin (A) is 1.0×10 ⁷ [Pa] 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 Tg of cured product of thermosetting composition [°C] 50 51 57 65 51 50 56 50 51 50 46 48 48 50 53 evaluate α: Lamination property to LCP substrate A A A B A A A A A A A A A A A β: Resistance to plating solution A A A A A A A A A A C C B A A γ: Insulation reliability after thermal cycling C A B C A B A B B B C C B A A δ: laser processability A A A A A A A A A A A A A A A ω: bendability C C C C C C C C C C C C C C C

[Table 7] Table 7 Example 46 47 48 49 50 51 52 53 54 55 56 57 58 59 Polyimide resin (A) [parts by mass] P18 P18 P18 P18 P18 P18 P18 P18 P18 P18 P18 P19 P20 P1 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Crosslinking agent (B) [parts by mass] (B)-1 5 5 5 5 5 5 5 5 5 5 5 5 5 (B)-2 5 (B)-3 (B)-4 (B)-5 (B)-6 (B)-7 (B)-8 UV absorber (C) [mass%] (C)-1 5.3 3.6 5.2 0.0 0.2 2.5 7.5 10.0 11.7 5.0 5.0 5.0 5.0 5.0 Filler (D) [mass%] (D)-1 42.0 60.0 63.7 20.0 20.0 20.0 20.0 20.0 20.0 0.0 0.0 0.0 0.0 20.0 (D)-2 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 20.0 0.0 0.0 0.0 0.0 (D)-3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 20.0 0.0 0.0 0.0 (D)-4 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 20.0 0.0 0.0 (D)-5 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 20.0 0.0 Indicates the temperature [°C] at which the storage modulus G' of the polyimide resin (A) is 1.0×10 ⁷ [Pa] 40 40 40 40 40 40 40 40 40 40 40 40 40 33 Tg of cured product of thermosetting composition [°C] 57 65 71 55 54 55 52 46 43 51 51 52 53 36 evaluate α: Lamination property to LCP substrate A B C A A A A A A A A A A A β: Resistance to plating solution A A A A A A A A A A A A A C γ: Insulation reliability after thermal cycling A A A A A A A A A A A A A C δ: laser processability A A A C B A A B C A A A A A ω: bendability C C C C C C C C C C C C C C

[Table 8] Table 8 comparative example 1 2 3 4 5 6 7 8 9 Polyimide resin (A) [parts by mass] P26 P27 P28 P29 P30 P18 P19 P18 P18 100 100 100 100 100 100 100 100 100 Crosslinking agent (B) [parts by mass] (B)-1 5 5 5 5 5 0.3 11 (B)-2 (B)-3 (B)-4 (B)-5 (B)-6 (B)-7 (B)-8 5 UV absorber (C) [mass%] (C)-1 5.0 5.0 5.0 5.0 5.0 5.2 5.0 5.0 5.0 Filler (D) [mass%] (D)-1 20.0 20.0 20.0 20.0 20.0 20.7 20.0 20.0 20.0 (D)-2 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 (D)-3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 (D)-4 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 (D)-5 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Indicates the temperature [°C] at which the storage modulus G' of the polyimide resin (A) is 1.0×10 ⁷ [Pa] 35 8 88 93 -8 40 40 40 40 Tg of cured product of thermosetting composition [°C] 37 9 83 85 -4 40 46 50 72 evaluate α: Lamination property to LCP substrate C C D. D. A C A A C β: Resistance to plating solution D. D. A A D. D. D. A A γ: Insulation reliability after thermal cycling C C C C D. D. D. D. D. δ: laser processability A A A A A C A A A ω: bendability C B D. D. A C C C C

As shown in Comparative Examples 1 and 2, the composition using a polyimide resin having no phenolic hydroxyl group was poor in plating solution resistance. In addition, in Comparative Example 3 using a polyimide resin having no residue X ² d derived from dimer diamine and/or dimer diisocyanate, the lamination property to the LCP substrate was poor. Furthermore, in Comparative Example 4 using a polyimide resin whose storage modulus G' becomes 1.0×10 ⁷ Pa at a temperature exceeding 90° C., the lamination property to the LCP substrate was also poor. In addition, for Comparative Examples 5 to 8 in which the amount of the crosslinking agent (B) was outside the range of 0.5 to 30 parts by mass relative to 100 parts by mass of the polyimide resin (A), after the thermal cycle test poor migration resistance. On the other hand, it was confirmed that Examples 1 to 59 of the present invention were excellent in lamination property on LCP base material even at low temperature and in a short time. In addition, it was confirmed that the cured product was excellent in alkali resistance and acid resistance, and that it was also excellent in insulation reliability after a thermal cycle test. [Industrial availability]

The thermosetting composition of the present invention is preferably used as an adhesive sheet. Moreover, this adhesive sheet is preferable as an adhesive sheet for bonding between various members represented by a printed wiring board. Furthermore, the cured product of the thermosetting composition of the present invention is preferably used as an adhesive layer between a heating element and a heat sink or as a heat sink. In addition, it is also preferably used as a heat dissipation layer covering one or more electronic components mounted on the substrate.

1: Polyimide film 2: Comb signal wiring for cathode electrodes 2': Cathode electrode connection point 3: Comb signal wiring for anode electrodes 3': Anode electrode connection point 4: Next film 4': hardened layer 5: Single-sided copper-clad laminate 5a: copper layer 5b: Insulation layer 10: Double-sided copper-clad laminate 11: copper foil 12: Polyimide film 20: Single-sided copper-clad laminate 21: copper foil 22: Polyimide film 30: blind hole 31: Side etching

FIG. 1 is a schematic plan view for explaining an evaluation substrate of this example. FIG. 2 is a schematic plan view for explaining the evaluation substrate of this example. FIG. 3 is a schematic plan view for explaining the evaluation substrate of this example. Fig. 4 is a cross-sectional view of a section IV-IV in Fig. 3 . FIG. 5 is a schematic explanatory diagram of the laser processing evaluation method of the present embodiment.

1: Polyimide film

2: Comb signal wiring for cathode electrodes

2': Cathode electrode connection point

3: Comb signal wiring for anode electrodes

3': Anode electrode connection point

Claims (9)

A thermosetting composition comprising a polyimide resin (A) and a crosslinking agent (B) having two or more functional groups. In the thermosetting composition, the polyimide resin (A) has A repeating unit of the structure represented by the general formula (1), and having a phenolic hydroxyl group,

X ¹ is independently a tetravalent tetracarboxylic acid residue in each repeating unit, and X ² is independently a divalent organic group in each repeating unit, and the X ¹ and the imide bond are bonded to each other to form two an imide ring, at least a part of X ² is the residue X ² d derived from dimer diamine and/or dimer diisocyanate, and the storage elastic coefficient G' in the polyimide resin (A) The temperature at which 1.0×10 7 Pa becomes 1.0×10 ⁷ Pa is any temperature between 0°C and 90°C, and the crosslinking agent (B) contains compounds selected from epoxy group-containing compounds (b1), cyanate ester compounds (b2), isocyanate-containing One or more of the group consisting of compound (b3), metal chelate compound (b4), carbodiimide-containing compound (b5) and maleimide-containing compound (b6), Epoxy group-containing compound (b1), cyanate ester compound (b2), isocyanate group-containing compound (b3), metal chelate compound (b4), The total content of the carbodiimide group-containing compound (b5) and the maleimide group-containing compound (b6) is 0.5 to 10 parts by mass. The thermosetting composition according to claim 1, wherein the glass transition temperature after thermosetting at 180°C for 60 minutes is 0°C to 70°C. The thermosetting composition according to claim 1 or 2, comprising, as the phenolic hydroxyl group, a phenolic hydroxyl group satisfying at least any one of the following (i) to (iv), (i) at the end of the molecular chain Has a phenolic hydroxyl group, and a nitrogen atom forming an imide ring derived from a monoamine is bonded to the meta-position or ortho-position of the aromatic ring having the phenolic hydroxyl group; (ii) has a phenolic hydroxyl group at the end of the molecular chain, Has an aliphatic group directly bonded to the aromatic ring having the phenolic hydroxyl group, and a nitrogen atom forming an imide ring derived from a monoamine is bonded to the aliphatic group; (iii) the ^X2 A part is a diamine residue X ² f having a phenolic hydroxyl group, and a nitrogen atom forming an imide ring derived from a diamine is bonded to the aromatic ring having the phenolic hydroxyl group; (iv) the X ² A part is a diamine residue X ² f having a phenolic hydroxyl group, has an aliphatic group directly bonded to an aromatic ring having the phenolic hydroxyl group, and has an acyl group derived from a diamine bonded to the aliphatic group. The nitrogen atom of the imine ring. The thermosetting composition according to claim 1 or 2, wherein at least a part of the X ¹ in the polyimide resin (A) is X ¹ a having an aliphatic group, and relative to the X ¹ 100 Mole %, having 60 mole % to 100 mole % of said X ¹ a. The thermosetting composition according to claim 1 or 2, which contains 0.1% by mass to 10% by mass of the ultraviolet absorber (C) relative to 100% by mass of non-volatile components. The thermosetting composition according to claim 1 or 2, which contains 3% by mass to 60% by mass of the filler (D) relative to 100% by mass of non-volatile components. An adhesive sheet comprising the thermosetting composition according to any one of claims 1 to 6. A printed wiring board formed using the bonding sheet as described in Claim 7. An electronic machine having the printed wiring board as described in Claim 8.

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