TW202217454A - Photosensitive resin composition - Google Patents

Abstract

To provide a photosensitive resin composition or the like which can give a cured product low in dielectric constant and dielectric loss tangent and is excellent in flexibility and developability. The photosensitive resin composition contains: (A) a resin containing an ethylenically unsaturated group and a carboxyl group; (B) an inorganic filler; (C) a photopolymerization initiator; (D) an epoxy resin; and (E) one or more resins selected from active ester resins, maleimide resins, and vinyl resins. The component (D) contains (D-1) an epoxy resin having a softening point lower than 30 DEG C and an epoxy equivalent of 150 g/eq. or less and (D-2) an epoxy resin having a softening point of 30 DEG C or higher and lower than 59 DEG C.

Description

Photosensitive resin composition

The present invention relates to a photosensitive resin composition. Furthermore, it relates to a photosensitive film, a printed wiring board, and a semiconductor device using the photosensitive resin composition.

On the printed wiring board, a solder resist is provided as a permanent protective film that suppresses solder adhesion of parts that do not require soldering and also prevents corrosion of the circuit board. As a soldering resist, it is common to use the photosensitive resin composition as described in patent document 1, for example. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2014-115672

[Problems solved by the invention]

The photosensitive resin composition is required in terms of developability and the like at the time of general development. In addition, in recent years, the photosensitive resin composition has been tried to be used as a material for an insulating layer or a sealing layer, and therefore, in addition to developability, excellent dielectric constant and dielectric loss tangent are also required. Furthermore, from the viewpoint of improving the workability of the photosensitive film containing the photosensitive resin composition, the flexibility of the photosensitive resin composition is also required to be improved.

The subject of the present invention is to provide a photosensitive resin composition which can obtain a cured product with low dielectric constant and dielectric loss tangent, which is excellent in flexibility and developability; a photosensitive film obtained by using the photosensitive resin composition, Printed wiring boards and semiconductor devices. [Means to solve the problem]

As a result of detailed examination by the present inventors, it was found that by using a combination of (A) a resin containing an ethylenically unsaturated group and a carboxyl group, (B) an inorganic filler, (C) a photopolymerization initiator, and (D) an epoxy resin, and (E) one or more resins selected from the group consisting of active ester resins, maleimide resins and vinyl resins, and when the (D) component contains a photosensitive resin composition of a specific epoxy resin in a predetermined amount, it may be The present invention was completed by obtaining a cured product having low dielectric constant and dielectric loss tangent, and improving flexibility and developability.

That is, the present invention includes the following contents. A photosensitive resin composition comprising: [1] (A) a resin containing an ethylenically unsaturated group and a carboxyl group, (B) Inorganic fillers, (C) photopolymerization initiator, (D) epoxy resin and (E) one or more resins selected from active ester resins, maleimide resins and vinyl resins, (D) Component contains (D-1) an epoxy resin having a softening point of less than 30°C and an epoxy equivalent of 150 g/eq. or less and (D-2) an epoxy resin having a softening point of 30°C or more and less than 59°C resin. [2] The content of the component (D-1) in the photosensitive resin composition when the non-volatile component is 100% by mass is referred to as D1, and the nonvolatile content of the (D-2) component in the photosensitive resin composition is defined as D1. The photosensitive resin composition as described in [1] in which D2/D1 is 0.5 or more and 2.5 or less, when the content in the case of 100 mass % of volatile components is set as D2. [3] The photosensitive resin composition as described in [1] or [2] in which content of (D-1) component is 90 mass % or less when the whole (D) component is taken as 100 mass %. [4] The photosensitive resin according to any one of [1] to [3] in which the content of the component (B) is 60 mass % or more, taking the nonvolatile matter in the photosensitive resin composition as 100 mass % composition. [5] (A) The photosensitive resin composition as described in any one of [1]-[4] which contains (A-1) a naphthalene skeleton-containing resin. [6] The photosensitive resin composition according to any one of [1] to [5], wherein the component (D-1) has a cyclic structure. [7] The photosensitive resin composition according to any one of [1] to [6], which contains an active ester resin and one or more resins selected from the group consisting of maleimide resins and vinyl resins. [8] The photosensitive resin composition according to any one of [1] to [7] where the breakpoint (Breakpoint) of the cured product of the photosensitive resin composition is 30 seconds or more and 150 seconds or less. [9] A photosensitive film comprising a support and a photosensitive resin composition layer containing the photosensitive resin composition according to any one of [1] to [8] provided on the support. [10] A printed wiring board including an insulating layer formed from a cured product of the photosensitive resin composition according to any one of [1] to [8]. [11] The printed wiring board according to [10] in which the insulating layer is a solder resist. [12] A semiconductor device including the printed wiring board according to [10] or [11]. [Effect of invention]

According to the present invention, there is provided a photosensitive resin composition excellent in flexibility and developability to obtain a cured product with low dielectric constant and dielectric loss tangent; photosensitive film and printed wiring obtained by using the photosensitive resin composition boards and semiconductor devices.

[Type of carrying out the invention]

Hereinafter, the photosensitive resin composition, photosensitive film, printed wiring board, and semiconductor device of the present invention will be described in detail.

[Photosensitive resin composition] The photosensitive resin composition of the present invention comprises (A) a resin containing an ethylenically unsaturated group and a carboxyl group, (B) an inorganic filler, (C) a photopolymerization initiator, (D) an epoxy resin, and (E) Photosensitive resin composition of one or more resins selected from active ester resins, maleimide resins and vinyl resins, (D) Component contains (D-1) a softening point of less than 30°C, and an epoxy equivalent of 150g The epoxy resin below /eq. and (D-2) the epoxy resin whose softening point is 30 degreeC or more and 59 degreeC or less.

The present invention can provide not only developability but also a cured product with low dielectric constant and dielectric loss tangent, and a photosensitive resin composition excellent in flexibility and developability. Moreover, a hardened|cured material with a high glass transition temperature is usually obtained.

The photosensitive resin composition may further contain optional components such as (F) a curing accelerator, (G) solvent, and (H) other additives as required. Hereinafter, each component contained in the photosensitive resin composition will be described in detail.

<(A) Resin containing ethylenically unsaturated group and carboxyl group> The photosensitive resin composition contains a resin containing an ethylenically unsaturated group and a carboxyl group as the component (A). Developability can be improved by containing (A) component in a photosensitive resin composition.

The ethylenically unsaturated group has a carbon-carbon double bond, for example, vinyl, allyl, propargyl, butenyl, ethynyl, phenylethynyl, maleimino, naphthyridinyl ( nadimide) and a (meth)acryloyl group, from the viewpoint of the reactivity of photoradical polymerization, a (meth)acryloyl group is preferable. The term "(meth)acryloyl" means that it includes a methacryloyl group, an acrylyl group, and a combination thereof. Since the component (A) contains an ethylenically unsaturated group, photoradical polymerization is possible. The number of ethylenically unsaturated groups per molecule in the component (A) may be one or two or more. Moreover, when two or more ethylenically unsaturated groups are contained per molecule of (A) component, these ethylenically unsaturated groups may be the same or different.

Moreover, since (A) component contains a carboxyl group, the photosensitive resin composition containing this (A) component shows solubility with respect to an alkaline solution (for example, the 1 mass % sodium carbonate aqueous solution which is an alkaline developing solution). The number of carboxyl groups per molecule in the component (A) may be one or two or more.

As (A) component, what is necessary is just resin containing an ethylenically unsaturated group and a carboxyl group. As the component (A), at least one of (A-1) a naphthalene skeleton-containing resin and (A-2) an acid-modified epoxy (meth)acrylate resin is preferable.

((A-1) Resin containing naphthalene skeleton) (A-1) Since the resin containing a naphthalene skeleton is the resin of the component (A), it is a resin containing an ethylenically unsaturated group and a carboxyl group. Therefore, the (A-1) component can be photoradically polymerized, and the photosensitive resin composition containing the (A-1) component all exhibits solubility in an alkaline solution.

Among the components (A-1), those having a plurality of ethylenically unsaturated groups in one molecule are preferred. Thereby, the mechanical strength and solubility resistance of the hardened|cured material of the photosensitive resin composition can be improved. Moreover, it is preferable that the component (A-1) has two or less ethylenically unsaturated groups per naphthalene skeleton. Thereby, since the crosslinking position (crosslinking point) can be adjusted, the mechanical strength and solubility resistance of the hardened|cured material of the photosensitive resin composition can be controlled. More preferably, the ethylenically unsaturated group is contained in the substituent which the naphthalene skeleton has. When the ethylenically unsaturated group is to be contained in the substituent of the naphthalene skeleton, as the first precursor, for example, the H atom in the OH group of naphthol is prepared from a substituent containing an epoxy group (such as an epoxy group, a glycidyl group, etc.). ) can be substituted with a compound having an ethylenically unsaturated bond (for example, an unsaturated carboxylic acid, preferably (meth)acrylic acid) to the first precursor. Thereby, an ethylenically unsaturated group can be introduce|transduced into the substituent which the naphthalene skeleton has.

The component (A-1) preferably has a plurality of carboxyl groups in one molecule. Thereby, the solubility of the photosensitive resin composition with respect to an alkaline solution (for example, an alkaline developing solution) can be improved. The component (A-1) preferably has two or less carboxyl groups per naphthalene skeleton. Thereby, solubility can be controlled. Preferably, the carboxyl group is contained in the naphthalene skeleton and has a substituent. Since the carboxyl group is contained in the substituent of the naphthalene skeleton, as the first precursor, for example, a compound in which the H atom of the OH group of naphthol is substituted with a substituent containing an epoxy group is prepared, which has vinyl properties for addition to the first precursor. A compound with an unsaturated bond (such as an unsaturated carboxylic acid, preferably (meth)acrylic acid), thereby obtaining a second precursor having a second-order hydroxyl group, and for the second precursor, adding a carboxylic anhydride (such as a tetra Hydrogen phthalic acid) is available. Thereby, both the ethylenically unsaturated group and the carboxyl group can be introduced into the substituent which the naphthalene skeleton has.

Moreover, (A-1) component is a resin containing a naphthalene skeleton. The naphthalene skeleton-containing resin refers to a compound containing one or more naphthalene skeletons in one molecule. Moreover, (A-1) component can be melt|dissolved in an alkaline solution (for example, an alkaline developing solution) at the dissolving rate of an appropriate range. In addition, when the photosensitive resin composition containing the component (A-1) is developed with an alkaline developing solution, it is possible to suppress the generation of undissolved parts and undissolved parts in the photosensitive resin composition against the purpose. local. The BP (Breakpoint) can be increased. Therefore, the developability of the photosensitive resin composition can be improved.

In addition, when a resin containing a naphthalene skeleton is used as the component (A-1), the rigidity of the molecules is usually increased, so that the action of the molecules in the photosensitive resin composition can be suppressed, and as a result, the photosensitive resin composition can be improved. The glass transition temperature of the hardened material. Moreover, by the action of the component (A-1), the resistance to internal stress due to thermal expansion or thermal shrinkage is generally improved, so that the flexibility of the photosensitive film can be improved.

The component (A-1) may contain one naphthalene skeleton or two or more naphthalene skeletons in one molecule.

The component (A-1) is, for example, a resin containing a structure represented by the following formula (1). The component (A-1) may have a plurality of structures represented by the following formula (1) (for example, 1 to 10, preferably 1 to 6), and when it has a plurality of structures represented by the following formula (1), ( A-1) Component can contain these plural structures represented by following formula (1) as a structural unit (repeating unit). In addition, in the following formula (1), the bonding site to which R ¹ is bonded may be bonded to any of the carbon atoms which can be bonded among the carbon atoms contained in the naphthalene skeleton. Thereby, the bonding site to which R ¹ is bonded is that the terminal bonding site is bonded to the carbon atom of the same benzene ring, and may be bonded to the carbon atom of a different benzene ring. The above-mentioned terminal bonding site refers to the bonding site bonded to the naphthalene ring, the bonding site bonded to R ¹ and the bonding site other than the bonding site bonded to OR', and specifically represents the left end of the formula (1). Depicted bond site. For example, the positional combination of the terminal bonding site in the naphthalene skeleton and the bonding site bonding with R ¹ can be the 1st, 2nd, 1st, 3rd, 1st, 4th, 1st, 5th, 1st 1,6, 1,7, 1,8, 2,3, 2,6, 2,7.

上述式(1)中，R ¹及R ²各獨立表示可具有取代基的伸烷基。R ¹的碳原子數通常為1～20，以1～10為佳，較佳為1～6。又，伸烷基可為直鏈狀，亦可為分支鏈狀。作為伸烷基，例如可舉出亞甲基、伸乙基、伸丙基、伸丁基等。

In the above formula (1), R ¹ and R ² each independently represent an optionally substituted alkylene group. The number of carbon atoms of R ¹ is usually 1-20, preferably 1-10, more preferably 1-6. In addition, the alkylene group may be linear or branched. As an alkylene group, a methylene group, an ethylidene group, a propylidene group, a butylene group, etc. are mentioned, for example.

The substituents that R ¹ and R ² have are independent of each other, and examples thereof include halogen atoms, alkyl groups, alkoxy groups, aryl groups, arylalkyl groups, silyl groups, aryl groups, aryloxy groups, carboxyl groups, and sulfonic acid groups. , cyano, nitro, hydroxyl, mercapto, oxo, etc.

In the above formula (1), X represents an optionally substituted aryl group. The number of carbon atoms of X is usually 6-30, preferably 6-20, more preferably 6-10. The arylidene group is, for example, a phenylene group, an anthracene group, a phenanthrene group, and a diphenylene group.

The substituent which X has, for example, is the same as the substituent which R ¹ and R ² have.

In the above formula (1), a represents 0 or 1. Among them, a is the number of base X.

In the above formula (1), s represents 0 or 1. Wherein, s and t are each the number of radicals R ¹ and R ² . Moreover, in said Formula (1), t represents 0 or 1. But s and t will not have s+t is 0. Among them, when a=1, it is better that both s and t are 1. When a=0, one of s and t is preferably 0.

In the above formula (1), OR' is a substituent on the naphthalene skeleton. In the above formula (1), R' each independently represents an organic group containing an ethylenically unsaturated group and a carboxyl group.

上述式(2)中，R ³表示3價基，較佳為表示可具有取代基的3價烴基(但，於碳-碳鍵(C-C鍵)之間可隔著雜原子)，其中亦以可具有取代基之3價脂肪族烴基為佳。該R ³亦可為可具有取代基的含有環氧基的取代基之3價殘基。R ³可具有取代基例如可舉出與R ¹及R ²可具有的取代基之相同例。 R' preferably represents a group represented by the following formula (2).

In the above formula (2), R ³ represents a trivalent group, preferably a trivalent hydrocarbon group which may have a substituent (however, a heteroatom may be interposed between carbon-carbon bonds (CC bonds)), wherein A trivalent aliphatic hydrocarbon group which may have a substituent is preferable. This R ³ may be a trivalent residue of an epoxy group-containing substituent which may have a substituent. R ³ may have a substituent, for example, the same examples as the substituent which R ¹ and R ² may have.

In the above formula (2), R ⁴ represents an ethylenically unsaturated group-containing organic group. As a preferable example of the organic group containing an ethylenically unsaturated group, (meth)acryloyloxy group is mentioned. The term "(meth)acryloyloxy" includes acryloxy, methacryloyloxy, and combinations thereof.

In the above formula (2), R ⁵ is a carboxyl group-containing organic group. An example of a carboxyl group-containing organic group is -OCO-R ⁶ -COOH. Here, R ⁶ represents a divalent group. As R ⁶ , a divalent hydrocarbon group which may have a substituent is preferred. The number of carbon atoms of R ⁶ is usually 1-30, preferably 1-20, more preferably 1-6. Examples of the divalent hydrocarbon group include linear or branched acyclic alkylene groups such as methylene, ethylidene, propylidene, and butylene; saturated or unsaturated bivalent alicyclic hydrocarbon groups ; Extension of phenyl, naphthylene and other extension of aryl and so on. Among them, a divalent alicyclic hydrocarbon group and an arylene group are also preferable, and a 4-cyclohexene group and a phenylene group are particularly preferable. Moreover, as a substituent which R ⁶ may have, for example, the same examples as the substituent which R ¹ and R ² may have are exemplified. -CO-R ⁶ -COOH in -OCO-R ⁶ -COOH is usually the residue of carboxylic acid anhydride. Examples of the carboxylic anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone Tetracarboxylic dianhydride.

In the above formula (1), c is usually 1 to 6, preferably 1 to 3, and more preferably an integer of 1 to 2. where c is the number of base OR'.

-(A-1) Component 1 (a=1)- A preferred example of the component (A-1) is a naphthol aralkyl type resin. The "naphthol aralkyl-type resin" refers to a resin containing a group having a structure in which the H atom of the OH group is removed from the naphthol aralkyl group.

Preferably, the naphthol aralkyl type resin is a resin having a structure in which a=1 in the above formula (1), for example, a resin having a structure represented by the following formula (3).

In the above formula (3), R ¹ , R ² , X, s, t, R′ and c are the same as described above. It is better if both s and t are 1.

A preferable resin of the naphthol aralkyl type resin is a resin containing a structure of c=1, s=1 and t=1 with respect to the above formula (3), for example, a resin containing a structure represented by the following formula (4) or (5) A bivalent naphthol aralkyl type resin showing the structure.

In the above formula (4) or (5), R ¹ , R ² , X, R′ and c are the same as described above. The naphthol aralkyl-type resin represented by the above formula (4) or (5) is a resin that can be synthesized using the naphthol aralkyl-type epoxy resin used in Synthesis Example 1 described later as a material. As a naphthol aralkyl type epoxy resin, for example, "ESN-475V" (epoxy equivalent 325 g/eq.) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. can be used.

上述式(6)中，R ¹、R及R’與前述相同。於上述式(6)所示含有萘骨架的樹脂為，將1,1’-雙(2,7-二縮水甘油基氧基萘)甲烷作為材料而可合成之樹脂。如此含有萘骨架的環氧樹脂，例如可使用大日本油墨化學工業公司製「EXA-4700」。 - The second example of the component (A-1) (a=0)- Among the components (A-1), preferable examples other than the naphthol aralkyl type resin (a=0) are those containing the above-mentioned formula (1) ), c=2, s=1, and t=0 structure resin, for example, a naphthalene skeleton-containing resin containing a divalent group of the structure represented by the following formula (6).

In the above formula (6), R ¹ , R and R' are the same as described above. The resin containing a naphthalene skeleton represented by the above formula (6) is a resin which can be synthesized using 1,1′-bis(2,7-diglycidyloxynaphthalene)methane as a material. As the epoxy resin containing a naphthalene skeleton in this manner, "EXA-4700" manufactured by Dainippon Ink Chemical Co., Ltd. can be used, for example.

The weight average molecular weight of the component (A-1) is preferably at least 500, more preferably at least 1,000, more preferably at least 1,500, and more preferably at least 2,000 from the viewpoint of film-forming properties. better. As the upper limit, from the viewpoint of developability, it is preferably 10,000 or less, more preferably 8,000 or less, and more preferably 7,500 or less. The weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

-(A-1) Manufacturing method of component- The component (A-1) may be a compound having a resin containing a naphthalene skeleton, an ethylenically unsaturated group, and a carboxyl group, and is not limited to the above-mentioned examples, and is not particularly limited. The naphthalene-type epoxy compound (epoxy compound containing a naphthalene skeleton) is an acid-modified unsaturated naphthalene skeleton-containing epoxy ester resin in which an unsaturated carboxylic acid is reacted, and then a carboxylic acid anhydride is reacted. The manufacturing method of the epoxy ester resin containing an acid-denatured unsaturated naphthalene skeleton is demonstrated. First, an unsaturated carboxylic acid is reacted with an epoxy compound containing a naphthalene skeleton to obtain an epoxy ester resin containing an unsaturated naphthalene skeleton, and then the epoxy ester resin containing an unsaturated naphthalene skeleton and a carboxylic acid anhydride are reacted. In this way, an epoxy ester resin containing an acid-modified unsaturated naphthalene skeleton can be obtained.

The epoxy compound containing a naphthalene skeleton may be used as long as it has one or more epoxy groups in the molecule, and examples thereof include monohydroxynaphthalene type epoxy resin, dihydrooxynaphthalene type epoxy resin, polyoxy Hydroxy binaphthalene-type epoxy resin, naphthalene-type epoxy resin obtained by condensation reaction of polyhydroxynaphthalene and aldehydes, and binaphthol-type epoxy resin are equal to naphthalene-type epoxy resin having a naphthalene skeleton in the molecule. These may be used individually by 1 type, and may use 2 or more types together.

As a monohydroxynaphthalene type epoxy resin, 1-glycidyloxynaphthalene and 2-glycidyloxynaphthalene are mentioned, for example. As dihydroxynaphthalene type epoxy resins, for example, 1,3-diglycidyloxynaphthalene, 1,4-diglycidyloxynaphthalene, 1,5-diglycidyloxynaphthalene, 1,5-diglycidyloxynaphthalene, , 6-diglycidyloxynaphthalene, 2,3-diglycidyloxynaphthalene, 2,6-diglycidyloxynaphthalene, 2,7-diglycidyloxynaphthalene, and the like.

Examples of polyhydroxybinaphthyl-type epoxy resins include 1,1'-bis-(2-glycidyloxy)naphthalene, 1-(2,7-diglycidyloxy)-1'- (2'-glycidyloxy)binaphthyl, 1,1'-bis-(2,7-diglycidyloxy)naphthalene, and the like.

Examples of naphthalene-type epoxy resins obtained by condensation reaction of polyhydroxynaphthalene and aldehydes include 1,1'-bis(2,7-diglycidyloxynaphthalene)methane, 1-(2, 7-Diglycidyloxynaphthalene)-1'-(2'-glycidyloxynaphthalene)methane, 1,1'-bis(2-glycidyloxynaphthalene)methane.

Among them, polyhydroxybinaphthalene-type epoxy resins having two or more naphthalene skeletons in one molecule, and naphthalene-type epoxy resins obtained by condensation reaction of polyhydroxynaphthalene and aldehydes are preferred, and particularly preferred are in one molecule 1,1'-bis(2,7-diglycidyloxynaphthalene)methane, 1-(2,7-diglycidyloxynaphthalene)-1'-( 2'-glycidyloxynaphthalene)methane, 1-(2,7-diglycidyloxy)-1'-(2'-glycidyloxy)binaphthyl, 1,1'-bis- (2,7-diglycidyloxy)naphthalene is preferable from the viewpoint of an average linear thermal expansion ratio and excellent heat resistance.

Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, cinnamic acid, and crotonic acid, and these may be used alone or in combination of two or more. Among them, acrylic acid and methacrylic acid are preferable from the viewpoint of improving the photocurability of the photosensitive resin composition. In addition, in this specification, the naphthalene-type epoxy compound ester resin of the reaction product of the above-mentioned naphthalene-type epoxy compound and (meth)acrylic acid may be described as "naphthalene-type epoxy compound (meth)acrylate", and the naphthalene-type epoxy compound (meth)acrylate The epoxy group of the type epoxy compound is usually substantially eliminated by the reaction with (meth)acrylic acid. "(Meth)acrylate" includes methacrylate, acrylate, and combinations thereof. Summarizing acrylic acid and methacrylic acid can be called "(meth)acrylic acid".

Examples of the carboxylic anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenone. Tetracarboxylic dianhydride and the like, but these can be used alone or in combination of two or more. Among them, succinic anhydride and tetrahydrophthalic anhydride are preferable from the viewpoint of improving the developability and insulation reliability of the cured product.

To obtain an epoxy ester resin containing an acid-denatured unsaturated naphthalene skeleton, the epoxy ester resin containing an unsaturated naphthalene skeleton can also be obtained by reacting an unsaturated carboxylic acid with an epoxy compound containing a naphthalene skeleton in the presence of a catalyst. , the epoxy ester resin containing unsaturated naphthalene skeleton is reacted with carboxylic acid anhydride.

The amount of the catalyst to be used at this time is preferably 2 mass % or less, preferably 0.0005 mass % to 1 mass % with respect to the total mass of the unsaturated carboxylic acid, the naphthalene skeleton-containing epoxy compound, and the carboxylic acid anhydride. The range of % is more preferably the range of 0.001 mass % to 0.5 mass %. As a catalyst, for example, N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7(DBU), 1,5-diazabicyclo[4.3 .0]nonene-5(DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, Octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3- (2-aminoethyl)aminopropylmethyldimethoxysilane, tetramethylammonium hydroxide and other amine compounds; trimethylphosphine, tributylphosphine, triphenylphosphine and other phosphines ; Tetramethylphosphonium salt, tetraethylphosphonium salt, tetrapropylphosphonium salt, tetrabutylphosphonium salt, trimethyl(2-hydroxypropyl)phosphonium salt, triphenylphosphonium salt, benzylphosphonium salt, etc. Phosphonium salts, as representative counter-anions, phosphonium salts having chloride, bromide, carboxylate, hydroxide, etc.; trimethylsulfonium salt, benzyltetramethylenesulfonium salt, Sulfonium salts such as phenylbenzylmethylsulfonium salt or phenyldimethylsulfonium salt, as representative negative ions, sulfonium salts such as carboxylate, hydroxide, etc.; , p-toluenesulfonic acid, acid compounds of sulfuric acid, etc. The reaction can be carried out in the range of 50°C to 150°C, preferably in the range of 80°C to 120°C.

In order to obtain an epoxy ester resin containing an acid-modified unsaturated naphthalene skeleton, an organic solvent can also be used, and the same solvent as the solvent (G) described later can be used as the organic solvent.

In order to obtain an epoxy ester resin containing an acid-denatured unsaturated naphthalene skeleton, a polymerization inhibitor such as hydroquinone can be used. The amount of the polymerization inhibitor to be used in this case is 2 mass % or less, preferably 0.0005 to 1 mass % with respect to the total mass of the unsaturated carboxylic acid, the naphthalene skeleton-containing epoxy compound, and the carboxylic acid anhydride. The range is more preferably the range of 0.001 mass % to 0.5 mass %.

As the epoxy ester resin containing an acid-modified unsaturated naphthalene skeleton, an epoxy (meth)acrylate containing an acid-modified naphthalene skeleton is preferable. Acid-modified naphthalene skeleton-containing epoxy (meth)acrylate refers to an acid-modified unsaturated naphthalene skeleton-containing ring obtained by using an epoxy compound containing a naphthalene skeleton and using (meth)acrylic acid as an unsaturated carboxylic acid. Oxyester resin.

As another aspect of (A-1) component, the (meth)acrylic resin which the structural unit obtained by polymerizing (meth)acrylic acid has, the epoxy compound containing an ethylenically unsaturated group and a naphthalene skeleton can be mentioned. The reaction is carried out to introduce an ethylenically unsaturated group-containing (meth)acrylic resin containing an unsaturated modified naphthalene skeleton. A hydroxyl group generated when an unsaturated group is further introduced may be reacted with a carboxylic acid anhydride. As a carboxylic acid anhydride, the same thing as the above-mentioned acid anhydride can be used, and the preferable range is also the same.

((A-2) Acid-modified epoxy (meth)acrylate resin) The acid-modified epoxy (meth)acrylate resin as the component (A-2) is a compound having a structure in which a carboxyl group is introduced into (meth)acrylate of an epoxy compound. However, the said (A-1) component is not contained in this (A-2) component.

As one aspect of the component (A-2), a cresol novolak type epoxy compound such as a cresol novolak A type epoxy compound and a cresol novolak F type epoxy compound is exemplified with (meth)acrylic acid. The acid-denatured cresol novolak-type epoxy (meth)acrylate etc. which react and further react the carboxylic anhydride. Specifically, cresol novolac epoxy (meth)acrylate is obtained by reacting a cresol novolak epoxy compound with (meth)acrylic acid, and a cresol novolak epoxy (meth)acrylic acid is The acid-modified cresol novolac epoxy (meth)acrylate can be obtained by reacting the ester with the carboxylic acid anhydride.

As another aspect of the component (A-2), an acid-modified epoxy compound obtained by reacting an epoxy compound other than the above-mentioned cresol novolak-type epoxy compound with (meth)acrylic acid and further reacting a carboxylic acid anhydride can be mentioned. (Meth)acrylate. Examples of such epoxy compounds include biphenyl-type epoxy compounds; bisphenol-type epoxy compounds such as bisphenol A-type epoxy compounds and bisphenol F-type epoxy compounds; phenol novolak-type epoxy resins; Novolak-type epoxy resins such as phenol A type novolak type epoxy resin, alkylphenol novolak type epoxy resin, etc.; fluorine-containing epoxy resin such as perfluoroalkyl type epoxy resin; bisxylenol type epoxy resin ; Dicyclopentadiene type epoxy resin; ginseng type epoxy resin, tert-butyl-catechol type epoxy resin, anthracene type epoxy resin and other epoxy resin containing condensed ring skeleton; glycidyl group Amine type epoxy resin; Glycidyl ester type epoxy resin; Linear aliphatic epoxy resin; Epoxy resin containing butadiene structure; Alicyclic epoxy resin; Heterocyclic epoxy resin; Spiro ring containing Epoxy resin; cyclohexanedimethanol type epoxy resin; trimethylol type epoxy resin; tetraphenylethane type epoxy resin; polyglycidyl (meth)acrylate, glycidyl methacrylic acid Acrylic resins containing glycidyl groups such as copolymers of esters and acrylates; fluorene epoxy resins; halogenated epoxy resins, etc.

Such acid-modified epoxy (meth)acrylate can be used as a commercially available product, and as a specific example, "CCR-1179" (Cresol Novolak F-type epoxy acrylate), "ZAR" manufactured by Nippon Kayaku Co., Ltd. -2000" (acid denatured bisphenol epoxy acrylate: bisphenol A epoxy resin, reactant of acrylic acid and succinic anhydride), "ZFR-1491H" (acid denatured bisphenol epoxy acrylate: bisphenol F type epoxy resin, acrylic acid and acid anhydride reactant), "ZFR-1533H" (acid modified bisphenol type epoxy acrylate: bisphenol F type epoxy resin, acrylic acid and tetrahydrophthalic anhydride reactant) , "ZCR-1569H" (acid-denatured biphenyl type epoxy acrylate: biphenyl type epoxy resin, acrylic acid and acid anhydride reactant), "PR-300CP" (cresol novolac type) manufactured by Showa Denko Corporation Epoxy resin, acrylic acid, and acid anhydride reactant), etc. These are used individually by 1 type, and may be used in combination of 2 or more types.

As another aspect of (A-2) component, with respect to (meth)acrylic resin which has a structural unit obtained by polymerizing (meth)acrylic acid, the (meth)acrylate of epoxy compound is reacted, An ethylenically unsaturated group-introduced unsaturated modified (meth)acrylic resin. Examples of (meth)acrylates of epoxy compounds include glycidyl methacrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and 3,4-epoxycyclohexylmethyl ( meth)acrylate, etc. In addition, the hydroxyl group generated when the unsaturated group is introduced may be reacted with the carboxylic acid anhydride. As a carboxylic acid anhydride, the same thing as the above-mentioned carboxylic acid anhydride can be used, and the preferable range is also the same.

Such unsaturated modified (meth)acrylic resins can be used as commercial products, and specific examples include "SPC-1000" and "SPC-3000" manufactured by Showa Denko Corporation, "Cyclomer P (ACA" manufactured by Daicel Ornex Corporation) )Z-250", "CyclomerP(ACA)Z-251", "CyclomerP(ACA)Z-254", "CyclomerP(ACA)Z-300", "CyclomerP(ACA)Z-320", etc.

The weight average molecular weight of the component (A-2) is preferably 1,000 or more, more preferably 1,500 or more, and more preferably 2,000 or more from the viewpoint of film-forming properties. As the upper limit, from the viewpoint of developability, it is preferably 20,000 or less, more preferably 15,000 or less, and more preferably 14,000 or less. The weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

(A) component may be (A-3) component other than the said (A-1) component and (A-2) component. This component does not contain (A-1) component and (A-2) component.

Although the weight average molecular weight and acid value of the component (A-3) are arbitrary, those within the same range as the weight average molecular weight and acid value of the component (A-2) described above are preferred. Thereby, the same advantage as demonstrated in the item of (A-2) component can be acquired.

The acid value of the component (A) is preferably 0.1 mgKOH/g or more, 0.5 mgKOH/g or more, or 1 mgKOH/g or more from the viewpoint of improving the solubility of the photosensitive resin composition in an alkaline solution. In addition, from the viewpoint of inhibiting the dissolution of the fine pattern of the hardened product in the alkaline solution, the acid value is preferably 150 mgKOH/g or less, more preferably 120 mgKOH/g or less, and more preferably 100 mgKOH/g or less. good. Here, the so-called acid value means the storage acid value of the carboxyl group present in the (A) component, and the acid value can be measured by the following method. First, after about 1 g of the resin solution for measurement was precisely weighed, 30 g of acetone was added to the resin solution to dissolve the resin solution uniformly. Next, an appropriate amount of phenolphthalein, an indicator drug, was added to the solution, and titration was performed using a 0.1N ethanolic KOH solution. Then, the acid value can be calculated by the following formula (1). Formula: A=Vf×5.611/(Wp×I)･･･(1)

Moreover, in the above formula (1), A represents the acid value [mgKOH/g], Vf represents the titration amount of the KOH solution [mL], Wp represents the measured resin solution mass [g], and I represents the measured non-volatile content of the resin solution. Proportion [mass %].

As the content of the component (A), from the viewpoint of adjusting the solubility of the photosensitive resin composition to an alkaline solution, when the nonvolatile content in the photosensitive resin composition is set to 100% by mass, it is 10% by mass or more. More preferably, it is 15 mass % or more, more preferably 20 mass % or more, more preferably 40 mass % or less, preferably 35 mass % or less, more preferably 30 mass % or less. In addition, in this invention, unless the content of each component in the photosensitive resin composition is specified, it is the value when the non-volatile matter in the photosensitive resin composition is taken as 100 mass %.

<(B) Inorganic filler> The (B) inorganic filler as (B) component may be contained in the photosensitive resin composition. When (B) component is contained in the photosensitive resin composition, the photosensitive resin composition which can obtain the hardened|cured material with low dielectric constant and dielectric loss tangent can be provided.

(B) The material of the inorganic filler is not particularly limited, but for example, silica, alumina, glass, cordierite, silicate, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, Hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, Magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate and zirconium tungstate phosphate, etc. Of these, silicon dioxide is also particularly preferred. In addition, spherical silica is preferable as silica. (B) The inorganic filler may be used alone or in combination of two or more.

(B) The average particle size of the inorganic filler is preferably 10 μm or less, more preferably 5 μm or less, more preferably 3 μm or less, and 2 μm or less, from the viewpoint of obtaining a cured product with low dielectric constant and dielectric loss tangent. , 1 μm or less or 0.7 μm or less. The lower limit of the average particle diameter is not particularly limited, but is preferably 0.01 μm or more, preferably 0.05 μm or more, more preferably 0.07 μm or more, 0.1 μm or more, or 0.2 μm or more.

The average particle diameter of the inorganic filler can be measured by a laser diffraction/scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler was prepared on a volume basis by a laser diffraction scattering particle size distribution analyzer, and the median diameter was measured as an average particle size. As a measurement sample, it is preferable to use the inorganic filler dispersed in water by ultrasonic waves. As a laser diffraction scattering particle size distribution analyzer, "LA-500" manufactured by Horiba Corporation, "SALD-2200" manufactured by Shimadzu Corporation, and the like can be used.

(B) The specific surface area of the inorganic filler is preferably 1 m 2 /g or more, more preferably 3 m ² /g or more, particularly preferably 1 m ² /g or more, from the viewpoint of obtaining a cured product with low dielectric constant and dielectric loss tangent. 5m ² /g or more. The upper limit is not particularly limited, but is preferably not more than 60 m ² /g, not more than 50 m ² /g, or not more than 40 m ² /g. The specific surface area was obtained by adsorbing nitrogen gas on the surface of the sample using a specific surface area measuring device (Macsorb HM-1210, manufactured by Mounttech) in accordance with the BET method, and calculating the specific surface area using the BET multipoint method.

(B) Inorganic fillers from the viewpoint of improving moisture resistance and dispersibility, include aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, and alkoxysilane-based coupling agents. Compounds, organosilazane compounds, and titanate-based coupling agents are preferably treated with one or more surface treatment agents. Examples of the surface treatment agent sold include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyl trimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. oxysilane), "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM- 4803" (long-chain epoxy silane coupling agent), etc.

(B) Inorganic filler can be used as a commercial item. Examples of commercially available products include "SC2050", "SC4050", and "AdmaFine" manufactured by Admatechs, "SFP Series" manufactured by Denki Chemical Industries, Ltd., "SP(H) Series" manufactured by Nippon Steel & Sumitomo Metal Materials, Sakai "Sciqas Series" manufactured by Chemical Industry Co., Ltd., "Seahoster Series" manufactured by Nippon Shokubai Co., Ltd., "AZ Series", "AX Series" manufactured by Nippon Steel & Sumitomo Metal Materials Corporation, "B Series" manufactured by Sakai Chemical Industry Co., Ltd., "BF Series" series" etc.

(B) The content of the inorganic filler, from the viewpoint of obtaining a cured product with low dielectric constant and dielectric loss tangent, is 50 mass % when the nonvolatile matter in the photosensitive resin composition is taken as 100 mass % % or more is preferable, preferably 55 mass % or more, more preferably 60 mass % or more. The upper limit is, for example, 75% by mass or less, 70% by mass or less, or 65% by mass or less, from the viewpoint of obtaining excellent developability that suppresses light reflection during exposure.

<(C) Photopolymerization Initiator> The photosensitive resin composition contains a photopolymerization initiator as the component (C). When the (C) photopolymerization initiator is contained in the photosensitive resin composition, the photosensitive resin composition can be efficiently photocured.

(C) As the photopolymerization initiator, any compound can be used, and examples thereof include bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide, 2,4,6-trimethylbenzyl Phosphine oxide-based photopolymerization initiators such as acyl-diphenyl-phosphine oxide; 1,2-octanedione, 1-4-(phenylthio)-2-(O-benzyl oxime ), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-, 1-(O-acetoxime) and other oxime esters Photopolymerization initiator; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-[ (4-Methylphenyl)methyl]-[4-(4-morpholinyl)phenyl]-1-butanone, 2-methyl-1-[4-(methylthio)phenyl] - α-aminoalkylbenzene-based photopolymerization initiators such as 2-morpholinopropan-1-one; benzophenone, methylbenzophenone, o-benzylbenzoic acid, benzyl Ethyl ether, 2,2-diethoxyacetophenone, 2,4-diethylthioxanthone, diphenyl-(2,4,6-trimethylbenzyl)phosphine oxide, ethyl-(2,4,6-trimethylbenzyl)phenylphosphonate, 4,4'-bis(diethylamino)benzophenone, 1-hydroxy-cyclic Hexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy -2-methyl-1-propan-1-one, etc., a sulfonium salt-based photopolymerization initiator may also be used. These may be used individually by 1 type, and may use 2 or more types together. Among these, from the viewpoint that the photosensitive resin composition can be photohardened more efficiently, either a phosphine oxide-based photopolymerization initiator or an oxime ester-based photopolymerization initiator is preferable , preferably phosphine oxide-based photopolymerization initiators. These may be used individually by 1 type, and may be used in combination of 2 or more types.

Specific examples of the (C) photopolymerization initiator include "Omnirad907", "Omnirad369", "Omnirad379", "Omnirad819", "OmniradTPO" manufactured by IGM Corporation, "IrgacureOXE-01" manufactured by BASF Corporation, "IrgacureOXE-02", "IrgacureTPO", "Irgacure819", "N-1919" manufactured by ADEKA, etc.

As the content of the photopolymerization initiator (C), from the viewpoint of sufficiently photohardening the photosensitive resin composition and improving insulation reliability, the non-volatile content of the photosensitive resin composition is set to 100 mass %, it is preferably 1 mass % or more, preferably 1.5 mass % or more, more preferably 2 mass % or more. On the other hand, from the viewpoint of suppressing a decrease in developability due to excessive sensitivity, the upper limit is preferably 5 mass % or less, preferably 4 mass % or less, and more preferably 3 mass % or less.

The photosensitive resin composition may be further combined with the component (C), and may contain N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isotope as a photopolymerization initiation assistant. Amyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine and other tertiary amines, and may also contain pyrazolines, anthracenes, coumarins, Photosensitizers such as xanthone and thioxanthone. Any one of these may be used alone, or two or more may be used in combination.

<(D) Epoxy resin> The photosensitive resin composition contains epoxy resin as (D)component. Insulation reliability can be improved by containing (D)component in the photosensitive resin composition. However, the epoxy resin which has an ethylenically unsaturated group and a carboxyl group is not contained in (D)component so-called here.

(D) epoxy resin containing epoxy resin with (D-1) softening point less than 30°C and epoxy equivalent of 150 g/eq. or less, and (D-2) softening point of 30°C or more and less than 30°C Epoxy resin at 59°C. From the viewpoint of obtaining a cured product having excellent dielectric constant and dielectric loss tangent, when the below-mentioned (E) component is contained in the photosensitive resin composition, since the (E) component is usually hydrophobic, it will cause photosensitive. The solubility of the resin composition decreases, and the developability tends to decrease. However, in this invention, when a softening point is low and an epoxy equivalent is used together with (D-1) component and (D-2) component, the fall of solubility can be suppressed. As a result, it is possible to realize a cured product which has the advantages of excellent developability and excellent permittivity and dielectric loss tangent inherent in (E) component.

The softening point of the component (D-1) is less than 30°C, preferably 25°C or lower, more preferably 20°C or lower, from the viewpoint that the effects of the present invention can be remarkably obtained. Although the lower limit is not particularly limited, it is preferably 0°C or higher, preferably 5°C or higher, and more preferably 10°C or higher. The softening point can be measured according to JISK7234.

The epoxy equivalent of the component (D-1) is not more than 150 g/eq., preferably not more than 148 g/eq., more preferably not more than 145 g/eq. 10 g/eq. or more is preferable, 50 g/eq. or more is preferable, and 100 g/eq. or more is more preferable. (D) The epoxy equivalent of a component is the mass of the epoxy resin containing 1 equivalent of epoxy groups. This epoxy equivalent can be measured based on JISK7236.

As the component (D-1), from the viewpoint that the effects of the present invention can be remarkably obtained, those having one or more epoxy groups in one molecule are preferred, and those having two or more epoxy groups in one molecule are preferred. Which is preferable, and one which has 3 or more epoxy groups in 1 molecule is more preferable. From the viewpoint of obtaining the desired effect of the present invention remarkably, the ratio of the epoxy resin having two or more epoxy groups in 1 molecule relative to 100% by mass of the nonvolatile content of the component (D-1) is 50. The content is preferably at least 60% by mass, more preferably at least 70% by mass, and more preferably at least 70% by mass.

The component (D-1) includes a liquid component at a temperature of 20°C and a solid component at a temperature of 20°C. As the component (D-1), from the viewpoint of improving flexibility, it is preferable to be in a liquid state.

As the component (D-1), an epoxy resin having an epoxy equivalent of 150 g/eq. or less can be used if the softening point is less than 59°C. As such an epoxy resin, from the viewpoint that the effects of the present invention can be remarkably obtained, those having a cyclic structure are preferred. As a cyclic structure, an aromatic ring structure, an alicyclic structure, etc. are mentioned. As an aromatic ring structure, a benzene ring, a naphthalene ring, an anthracene ring, etc. are mentioned. As an alicyclic structure, a cyclohexane ring, a cyclopentane ring, a cycloheptane ring, a cyclooctane ring, etc. are mentioned. Among them, the cyclic structure is also preferably an aromatic ring structure, preferably a naphthalene ring and a benzene ring, and more preferably a naphthalene ring.

Moreover, as (D-1) component, naphthalene type epoxy resin, glycidylamine type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, for example are mentioned Oxygen resin, glycidyl ester type epoxy resin, phenol novolac type epoxy resin, glycidyl cyclohexane type epoxy resin, isocyanuric cyclic epoxy resin, naphthylene ether type epoxy resin etc., naphthalene-type epoxy resins and glycidylamine-type epoxy resins are preferred, and naphthalene-type epoxy resins are preferred.

Specific examples of the component (D-1) include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "ELM-434L" (glycidol) manufactured by Sumitomo Chemical Corporation. amine type epoxy resin); "630" (glycidyl amine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1658GS" (liquid 1,4-glycidyl cyclohexyl) manufactured by Nippon Steel & Sumitomo Metal Chemical Corporation Alkyl epoxy resin); "EP-3980S" (2-functional glycidyl amine epoxy resin) manufactured by ADEKA; "EP-3950L" (3-functional glycidyl amine epoxy resin) from ADEKA; "TEPIC-VL" (isocyanuric cyclic epoxy resin) manufactured by Nissan Chemical Corporation; "ELM-100H" manufactured by Sumitomo Chemical Corporation (N-[2-methyl-4-(ethylene oxide) Methoxy)phenyl]-N-(oxiranylmethyl)oxiranemethaneamine); "EXA-7311-G4" (naphthylene ether type epoxy resin) manufactured by DIC Corporation. These may be used individually by 1 type, or may be used in combination of 2 or more types.

The weight average molecular weight (Mw) of the component (D-1) is preferably 100 or more, more preferably 200 or more, more preferably 250 or more, and preferably 5,000 or less, from the viewpoint that the desired effect of the present invention can be remarkably obtained. , preferably 3000 or less, more preferably 1500 or less. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by gel permeation chromatography (GPC).

The content of the component (D-1) is 90% when the whole component (D) is taken as 100% by mass, from the viewpoint of obtaining not only developability but also a cured product excellent in dielectric constant and dielectric loss tangent. It is preferably not more than 80% by mass, more preferably not more than 70% by mass, not more than 60% by mass, not more than 50% by mass, or not more than 40% by mass, preferably not less than 10% by mass, preferably not more than 20% by mass % or more, more preferably 30 mass % or more.

The content of the component (D-1) From the viewpoint of obtaining not only developability but also a cured product excellent in dielectric constant and dielectric loss tangent, the nonvolatile content in the photosensitive resin composition is taken as 100% by mass At this time, it is preferably 1 mass % or more, preferably 1.5 mass % or more, more preferably 2 mass % or more, preferably 10 mass % or less, preferably 8 mass % or less, more preferably 5 mass % or less.

The softening point of the component (D-2) is 30°C or higher, preferably 35°C or higher, more preferably 40°C or higher, from the viewpoint that the effects of the present invention can be remarkably obtained. The upper limit is less than 59°C, preferably 55°C or lower, more preferably 50°C or lower, from the viewpoint that the effects of the present invention can be remarkably obtained. The softening point can be measured by the same method as the component (D-1).

As the component (D-2), from the viewpoint that the effects of the present invention can be remarkably obtained, those having one or more epoxy groups in one molecule are preferred, and those having two or more epoxy groups in one molecule are preferred. More preferably, it is more preferable to have 3 or more epoxy groups in 1 molecule. From the viewpoint that the desired effect of the present invention can be remarkably obtained, the ratio of the epoxy resin having two or more epoxy groups in 1 molecule with respect to 100% by mass of the nonvolatile content of the component (D-2) is as follows: 50 mass % or more is preferable, 60 mass % or more is preferable, and 70 mass % or more is especially preferable.

The component (D-2) is preferably in a solid state at a temperature of 20°C.

As (D-2) component, the epoxy resin whose softening point is 30 degreeC or more and less than 59 degreeC can be used. As such an epoxy resin, from the viewpoint that the effects of the present invention can be remarkably obtained, those having a cyclic structure are preferred. As a cyclic structure, an aromatic ring structure, an alicyclic structure, etc. are mentioned. As an aromatic ring structure, a benzene ring, a naphthalene ring, an anthracene ring, a biphenyl group, etc. are mentioned. As an alicyclic structure, a cyclohexane ring, a cyclopentane ring, a cycloheptane ring, a cyclooctane ring, etc. are mentioned. Among them, the cyclic structure is also preferably an aromatic ring structure, preferably a benzene ring and a biphenyl ring, and more preferably a biphenyl ring.

Moreover, as (D-2) component, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, naphthylene ether type epoxy resin etc. are mentioned, for example, biphenyl type epoxy resin is better.

Specific examples of the component (D-2) include "NC3000L" (biphenyl-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "HP-7200L" (dicyclopentadiene-type epoxy resin) manufactured by DIC Corporation Oxygen resin), "HP-6000L" (naphthylene ether type epoxy resin); "NC3000" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. These may be used individually by 1 type, or may be used in combination of 2 or more types.

The epoxy equivalent of the component (D-2) is preferably 50g/eq.～5000g/eq., preferably 50g/eq.～3000g/eq., more preferably 80g/eq.～2000g/eq., More preferably, it is 110 g/eq. to 1000 g/eq. When it is this range, the crosslinking density of the hardened|cured material of the photosensitive resin composition layer can become sufficient, and an insulating layer with a small surface roughness can be obtained.

The weight-average molecular weight (Mw) of the component (D-2) is preferably 100 or more, more preferably 200 or more, more preferably 250 or more, and 5000 or less, from the viewpoint that the desired effect of the present invention can be remarkably obtained. Preferably, it is 3000 or less, more preferably 1500 or less.

The content of the component (D-2) From the viewpoint of obtaining a cured product with excellent developability and excellent dielectric constant and dielectric loss tangent, the content of the component (D) is 10% by mass or more when the whole of the component (D) is taken as 100% by mass. Preferably, it is preferably 20 mass% or more, more preferably 30 mass% or more, 40 mass% or more, 50 mass% or more, 60 mass% or more, preferably 90 mass% or less, preferably 80 mass% or less, More preferably, it is 70 mass % or less.

The content of the component (D-2) From the viewpoint of obtaining a cured product with excellent developability and excellent dielectric constant and dielectric loss tangent, when the nonvolatile content in the photosensitive resin composition is taken as 100% by mass, 1 mass % or more is preferable, 1.5 mass % or more is preferable, 2 mass % or more is more preferable, 15 mass % or less is preferable, 10 mass % or less is preferable, and 8 mass % or less is more preferable.

The content of the component (D-1) when the nonvolatile content in the photosensitive resin composition is taken as 100% by mass is taken as D1, and the nonvolatile content of the component (D-2) in the photosensitive resin composition is taken as D2/D1 is preferably 0.5 or more, more preferably 1 or more, more preferably 1.5 or more, more preferably 2.5 or less, preferably 2.3 or less, more preferably 2.2 or less, when the content at 100 mass % is D2. By setting the quantitative ratio of the (D-1) component to the (D-2) component within this range, the desired effect of the present invention can be obtained remarkably.

The photosensitive resin composition may contain epoxy resins other than (D-3) (D-1) component and (D-2) component. As (D-3) component, for example, (1) Epoxy resins with a softening point of 59°C or higher, and (2) An epoxy resin whose softening point is less than 30°C and whose epoxy equivalent exceeds 150 g/eq. The method for measuring the softening point of the component (D-3) is the same as that of the component (D-1).

As (D-3) component, bis-xylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, for example, are mentioned Oxygen resin, dicyclopentadiene type epoxy resin, ginseng type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin , naphthalene epoxy resin, naphthol epoxy resin, anthracene epoxy resin, glycidyl amine epoxy resin, glycidyl ester epoxy resin, cresol novolac epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing spiro ring, cyclohexane type ring Oxygen resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, etc. (D-3) An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types.

It is preferable that the photosensitive resin composition contains the epoxy resin which has two or more epoxy groups in 1 molecule as a (D-3) component. The ratio of the epoxy resin having two or more epoxy groups in 1 molecule with respect to 100 mass % of the nonvolatile content of the component (D-3) from the viewpoint of remarkably obtaining the desired effect of the present invention 50 mass % or more is preferable, 60 mass % or more is preferable, and 70 mass % or more is especially preferable.

The component (D-3) contains an epoxy resin that is liquid at a temperature of 20°C (hereinafter sometimes referred to as a "liquid epoxy resin"), and an epoxy resin that is a solid at a temperature of 20°C (hereinafter may be referred to as a "liquid epoxy resin"). called "solid epoxy resin"). As the component (D-3), only a liquid epoxy resin may be contained, only a solid epoxy resin may be contained, or a combination of a liquid epoxy resin and a solid epoxy resin may be contained. From the viewpoint of the desired effect of the present invention, it is preferable that only the solid epoxy resin is contained.

As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is preferable. better.

As the solid epoxy resin, bisxylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, Phenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type ring Oxygen resin and tetraphenylethane type epoxy resin are preferred, and naphthalene type epoxy resin is preferred.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin manufactured by DIC Corporation) resin); "N-690" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "HP- 7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene epoxy resin); "EXA-7311", "HP6000" (naphthylene ether epoxy resin) manufactured by DIC Corporation; "EPPN-502H" manufactured by Nippon Kayaku Co., Ltd. (Shenol type epoxy resin); "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H" manufactured by Nippon Kayaku Co., Ltd., "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.; "ESN485" (naphthol novolak type) manufactured by Nippon Steel & Sumigin epoxy resin); "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX4000HK" (bisxylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100", "CG-500" manufactured by Osaka Gas Chemical Corporation; "YL7760" (bisphenol AF type epoxy resin manufactured by Mitsubishi Chemical Corporation) ); "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (solid bisphenol A epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (four hydroxybenzene) manufactured by Mitsubishi Chemical Corporation Ethane type epoxy resin) etc. These may be used individually by 1 type, or may be used in combination of 2 or more types.

As a liquid epoxy resin, the liquid epoxy resin which has two or more epoxy groups in 1 molecule is preferable.

As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl Amine type epoxy resin, phenol novolak type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, glycidyl amine type epoxy resin Resins and epoxy resins with a butadiene structure are preferred, and bisphenol A type epoxy resins and bisphenol F type epoxy resins are preferred.

Specific examples of liquid epoxy resins include "828US", "jER828EL", "825", and "EPICOAT828EL" (bisphenol A epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER807" manufactured by Mitsubishi Chemical Corporation ", "1750" (bisphenol F type epoxy resin); "jER152" (phenol novolak type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630LSD" (glycidyl amine type epoxy resin manufactured by Mitsubishi Chemical Corporation) ); "ZX1059" (mixture of bisphenol A epoxy resin and bisphenol F epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.; "EX-721" manufactured by NagaseChemtex (glycidyl ester ring Oxygen resin); "CELLOXIDE2021P" (alicyclic epoxy resin with ester skeleton) manufactured by Daicel Chemical Industries, Ltd.; "PB-3600" (epoxy resin with butadiene structure) manufactured by Daicel Chemical Industries, Ltd. Resin); "ZX1658" (liquid 1,4-glycidyl cyclohexane type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., etc. These may be used individually by 1 type, or may be used in combination of 2 or more types.

As the component (D-3), when a combination of a liquid epoxy resin and a solid epoxy resin is used, the equivalent ratio (liquid epoxy resin: solid epoxy resin) is expressed as a mass ratio as 1: 1-1:20 is preferable, 1:1.5-1:15 is more preferable, and 1:2-1:10 is especially preferable. By setting the quantitative ratio of the liquid epoxy resin to the solid epoxy resin within these ranges, the desired effect of the present invention can be obtained remarkably.

The epoxy equivalent of the component (D-3) is preferably 50g/eq.～5000g/eq., preferably 50g/eq.～3000g/eq., more preferably 80g/eq.～2000g/eq., More preferably, it is 110 g/eq. to 1000 g/eq. By setting it in this range, the crosslinking density of the hardened|cured material of the photosensitive resin composition layer becomes sufficient, and an insulating layer with a small surface roughness can be obtained.

The weight average molecular weight (Mw) of the component (D-3) is preferably 100 to 5000, more preferably 250 to 3000, and more preferably 400 to 1500, from the viewpoint of remarkably obtaining the desired effect of the present invention.

The content of the component (D-3) is, from the viewpoint of improving the mechanical strength and solubility resistance of the cured product of the photosensitive resin composition, when the nonvolatile components in the photosensitive resin composition are taken as 100% by mass, 1 mass % or more is preferable, 1.5 mass % or more is preferable, and 2 mass % or more is more preferable. The upper limit of the content of the component (D-3) is preferably 10 mass % or less, preferably 5 mass % or less, and particularly preferably 3 mass % or less, from the viewpoint of remarkably obtaining the desired effect of the present invention.

The content of the component (D-3) is preferably 0% by mass or more, preferably 0.01% by mass or more, when the entire component (D) is taken as 100% by mass, from the viewpoint that the effects of the present invention can be remarkably obtained, 0.1 mass % or more is more preferable, 1 mass % or less is preferable, 0.5 mass % or less is preferable, and 0.3 mass % or less is more preferable.

<(E) One or more resins selected from active ester resins, maleimide resins and vinyl resins> The photosensitive resin composition contains at least one resin selected from the group consisting of an active ester resin, a maleimide resin, and a vinyl resin as the component (E). When the (E) component is contained in the photosensitive resin composition, the dielectric constant, the dielectric loss tangent, and the glass transition temperature can be increased.

Hereinafter, the active ester resin (hereinafter sometimes referred to as "(E1) component"), maleimide resin (hereinafter sometimes referred to as "(E2) component") and vinyl resin (hereinafter referred to as "(E2) component") of (E) component It is referred to as "(E3) ingredient") for explanation.

((E1) Active Ester Resin) The (E1) active ester resin which is the (E) component reacts with the epoxy group of the (D) component to obtain a cured product with low dielectric constant and dielectric loss tangent. One type of active ester resin may be used alone, or two or more types may be used in combination.

As the active ester resin (E1), generally, phenolic esters, thiophenolic esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc. having high reactivity and having two or more ester groups in one molecule can be used compound is preferred. The active ester resin is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester resin obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalazine, methylated bisphenol A, methylated bisphenol F, methylated Alkylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6- Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene diphenol Compounds, phenolic novolacs, etc. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol in one molecule of dicyclopentadiene.

(E1) Active ester resins include dicyclopentadiene-type active ester resins, naphthalene-type active ester resins containing a naphthalene structure, active ester resins containing acetylated phenol novolak, and phenol novolak-containing benzoyl The active ester resin of acylated compound is preferred, and at least one selected from the group consisting of dicyclopentadiene-type active ester resin and naphthalene-type active ester resin is preferred, and dicyclopentadiene-type active ester resin is preferred. for better. As the dicyclopentadiene-type active ester resin, an active ester resin containing a dicyclopentadiene-type diphenol structure is preferable. The "dicyclopentadiene-type diphenol structure" means a bivalent structural unit composed of phenylene-dicyclopentylene-phenylene.

(E1) Sales of active ester resins include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "EXB9451", "EXB9460", "EXB9460S", "HPC-8000H", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L", "EXB-8000L-65TM" (manufactured by DIC Corporation); as an active ester resin containing a naphthalene structure, "EXB-8151-62T", "HPC-8150-60T", "HPC-8150-62T", "EXB-8150-65T", "EXB-8100L-65T", "EXB-8150L-65T" , "EXB9416-70BK" (manufactured by DIC Corporation), "PC1300-02-65MA" (manufactured by Airwater Corporation); "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester resin containing novolac acetyl compound ); as the active ester resin containing the benzyl compound of novolak, "YLH1026" (manufactured by Mitsubishi Chemical Corporation); as the active ester resin of the acetyl compound of the novolac, "DC808" can be cited (manufactured by Mitsubishi Chemical Corporation); Examples of active ester resins of benzyl-based compounds of novolak include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation) chemical company) etc.

(E1) The active ester group equivalent of the active ester resin is preferably 50 g/eq. to 500 g/eq., more preferably 50 g/eq. from the viewpoint of obtaining a cured product with low dielectric constant and dielectric loss tangent. eq.～400g/eq., more preferably 100g/eq.～300g/eq.. The active ester group equivalent is the mass of the active ester resin containing 1 equivalent of active ester group.

The amount ratio of (D) epoxy resin to (E1) active ester resin is the ratio of [total number of epoxy groups of epoxy resin]:[total number of active groups of active ester resin], and is 1:0.01-1 The range of : 5 is preferable, 1:0.3-1:3 is more preferable, and 1:0.5-1:2 is more preferable. Here, "the epoxy group number of an epoxy resin" shows the total value of the value which divided all the mass of the nonvolatile matter of the epoxy resin which exists in the photosensitive resin composition by the epoxy equivalent. In addition, "the number of active groups of active ester resin" means the total value of all the values obtained by dividing the mass of the nonvolatile content of the active ester resin in the photosensitive resin composition by the equivalent of the active ester group. By setting the amount ratio of the (D) epoxy resin to the (E1) active ester resin within this range, the effects of the present invention can be clearly obtained."

As the content of the component (E1), from the viewpoint of obtaining a cured product with excellent dielectric constant and dielectric properties, the nonvolatile content in the photosensitive resin composition is 100 mass %, and the content is 1 mass % or more. More preferably, it is 1.5 mass % or more, more preferably 2 mass % or more, more preferably 15 mass % or less, preferably 10 mass % or less, and more preferably 8 mass % or less.

((E2) Maleimide resin) After the (E2) maleimide resin as the (E) component reacts with the ethylenically unsaturated group of the (A) component, a cured product with low dielectric constant and dielectric loss tangent can be obtained. However, (E2) maleimide resin does not contain those corresponding to the above-mentioned (A) components to (D) components and (E1) components. (E2) The maleimide resin may be used alone or in combination of two or more.

As the (E2) maleimide resin, a maleimide group-containing resin can be used. (E2) The number of maleimide groups per molecule of the maleimide resin may be one, or two or more, preferably two. The maleimide group is represented by the following formula (E).

(E2) The maleimide resin may be a resin containing a maleimide group. As (E2) maleimide resin, at least one selected from the following is preferable. (E2-1) a maleimide compound containing an aliphatic group having 5 or more carbon atoms directly bonded to the nitrogen atom of the maleimide group, (E2-2) a maleimide compound having an aromatic ring directly bonded to a nitrogen atom of a maleimide group, and (E2-3) A maleimide compound containing a trimethylindan skeleton.

Here, the term "direct" means that no other group exists between the nitrogen atom of the maleimide group and the aliphatic group having 5 or more carbon atoms for the component (E2-1). -2) Component means that no other group exists between the nitrogen atom of maleimide and the aromatic ring.

-(E2-1) Ingredient- The component (E2-1) is a maleimide compound containing an aliphatic group having 5 or more carbon atoms directly bonded to the nitrogen atom of maleimide. The component (E2-1) can be imidized by, for example, a component containing an aliphatic amine compound (diamine compound having a dimer acid skeleton, etc.), maleic anhydride, and optionally tetracarboxylic dianhydride response.

As a C5 or more aliphatic group, an alkyl group, an alkylene group, an alkenylene group, etc. are mentioned, for example.

The number of carbon atoms of the alkyl group having 5 or more carbon atoms is preferably 6 or more, preferably 8 or more, more preferably 50 or less, preferably 45 or less, more preferably 40 or less. The alkyl group may be linear, branched, or cyclic, and among them, linear is preferred. As such an alkyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, etc. are mentioned, for example. The alkyl group having 5 or more carbon atoms may have as a substituent of the alkylene group having 5 or more carbon atoms. The alkyl group having 5 or more carbon atoms may be a part of an alkenyl group or a part of an alkpolyalkenyl group (the number of double bonds is preferably 2).

The number of carbon atoms of the alkylene group having 5 or more carbon atoms is preferably 6 or more, preferably 8 or more, more preferably 50 or less, preferably 45 or less, more preferably 40 or less. The alkylene group may be any of linear, branched, and cyclic, and among them, linear is also preferred. Here, the term cyclic alkylene refers to a concept that also includes a case where only a cyclic alkylene is present, and both a linear alkylene and a cyclic alkylene are included. Condition. Examples of such alkylene groups include pentylene, hexyl, heptyl, octyl, nononyl, decyl, undecyl, dodecyl, and tridecyl. , Pentadecyl, trihexadecyl, bases with octyl-cyclohexyl structure, bases with octyl-cyclohexyl-octyl structures, propylidene-cyclohexyl groups -The base of the octyl structure, etc. The alkylene group having 5 or more carbon atoms may be a part of an alkenylene group or a part of an alkylene polyalkenyl group (the number of double bonds is preferably 2).

The number of carbon atoms of the alkenylene group having 5 or more carbon atoms is preferably 6 or more, preferably 8 or more, more preferably 50 or less, preferably 45 or less, more preferably 40 or less. The alkenylene group may be any of linear, branched, and cyclic, and among them, linear is preferred. Among them, the term "cyclic alkenylene group" also includes the concept of a case where the case is composed of only a cyclic alkenylene group and a case where both a linear alkenylene group and a cyclic alkenylene group are included. Condition. Examples of such alkenylene groups include pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, and dodecynyl groups. base, tridecynyl, pentadecynyl, trihexadecynyl, groups with octynyl-cyclohexylene structure, octynyl-cyclohexynyl-octynyl The base of the structure, the base with the structure of propyne-cyclohexyne-octynyl, etc.

一般式(E2-1-1)中，M表示可具有取代基之碳原子數5以上的2價脂肪族基，L表示單鍵或2價連結基。 As the component (E2-1), a compound represented by the following formula (E2-1-1) is preferable.

In general formula (E2-1-1), M represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent, and L represents a single bond or a divalent linking group.

M represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. The number of carbon atoms of the divalent aliphatic group having 5 or more carbon atoms is preferably 6 or more, preferably 8 or more, more preferably 50 or less, preferably 45 or less, more preferably 40 or less. The aliphatic group may be any of linear, branched, and cyclic, and among them, linear is preferable. Among them, the term "cyclic aliphatic group" refers to a concept including the case where it is composed of only a cyclic aliphatic group, and a case where both a linear aliphatic group and a cyclic aliphatic group are included. situation. As a divalent aliphatic group, an alkylene group, an alkenylene group, an alkylene polyalkenyl group (preferably the number of double bonds is 2), etc. are mentioned. The alkylene group and the alkenylene group are as described above.

Examples of the substituent of M include halogen atoms, -OH, -OC _1-10 alkyl, -N(C _1-10 alkyl) ₂ , C _1-10 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _6-10 aryl, -NH ₂ , -CN, -C(O)OC _1-10 alkyl, -COOH, -C(O)H, -NO ₂ and the like. Among them, the term "C _xy " (x and y are positive integers and satisfy x<y) means that the number of carbon atoms of the organic group described after the term means x to y. For example, the expression "C _1-10 alkyl group" means an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to form a ring, and the ring structure also contains a spiro ring or a condensed ring. The substituent is preferably an alkyl group having 5 or more carbon atoms.

L represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, an alkenylene group, an alkynylene group, an arylidene group, -C(=O)-, -C(=O)-O-, -NR ⁰ -(R ⁰ It is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms), an oxygen atom, a sulfur atom, C(=O)NR ⁰ -, a divalent group derived from phthalimide, a diimide derived from pyromellitic acid A divalent group of an amine, a group formed by a combination of two or more of these divalent groups, and the like. Alkylene group, alkenylene group, alkynylene group, arylidene group, divalent group derived from phthalimide, divalent group derived from pyromellitic acid diimide, and two or more divalent groups The group formed by the combination may have an alkyl group having 5 or more carbon atoms as a substituent. The divalent group derived from phthalimide refers to a divalent group derived from phthalimide, and is specifically a group represented by the general formula (E2-1-2). The divalent group derived from the pyromellitic acid diimide means a divalent group derived from the pyromellitic acid diimide, and it is specifically a group represented by the general formula (E2-1-3). In the formula, "*" represents the bonding site.

As the alkylene group of the divalent linking group in L, an alkylene group having 1 to 50 carbon atoms is preferable, an alkylene group having 1 to 45 carbon atoms is preferable, and an alkylene group having 1 to 40 carbon atoms is preferable. Alkylene groups are particularly preferred. The alkylene group may be linear, branched, or cyclic. Examples of such an alkylene group include methyl ethylidene, cyclohexylene, pentylene, hexylene, heptyl, octyl, nononyl, decyl, undecyl, and Dodecyl, tridecyl, pentadecyl, hexadecyl, base with octyl-cyclohexyl structure, base with octyl-cyclohexyl-octyl structure , A base with a propylidene-cyclohexyl-extendoctyl structure, etc.

As the alkenylene group of the divalent linking group in L, an alkenylene group having 2 to 50 carbon atoms is preferable, an alkenylene group having 2 to 45 carbon atoms is preferable, and an alkenylene group having 2 to 40 carbon atoms is preferable. Alkenyl groups are particularly preferred. The alkenylene group may be linear, branched, or cyclic. As such an alkenylene group, a methyl vinylene group, a cyclohexenylene group, a pentenylene group, a hexenylene group, a heptenene group, an octenylene group, etc. are mentioned, for example.

As the alkynylene group of the divalent linking group in L, an alkynylene group having 2 to 50 carbon atoms is preferred, an alkynylene group having 2 to 45 carbon atoms is preferred, and an alkynylene group having 2 to 40 carbon atoms is preferred. Alkynylene is particularly preferred. The alkynylene group may be linear, branched, or cyclic. Such an alkynylene group includes, for example, a methylethynylene group, a cyclohexylene group, a pentynyl group, a hexylene group, a heptynylene group, and an octylene group.

As the aryl extended group of the divalent linking group in L, an aryl extended group with 6 to 24 carbon atoms is preferable, an aryl extended group with 6 to 18 carbon atoms is preferable, and an aryl extended group with 6 to 14 carbon atoms is preferable. The aryl extended group is more preferable, and the aryl extended group having 6 to 10 carbon atoms is more preferable. As an arylene group, a phenylene group, a naphthylene group, an anthracene group, etc. are mentioned, for example.

The alkylene group, alkenylene group, alkynylene group, and arylidene group of the divalent linking group in L may have a substituent. The substituent is the same as that of M in the general formula (E2-1-1), and is preferably an alkyl group having 5 or more carbon atoms.

As a group formed by a combination of two or more divalent groups in L, for example, a divalent group formed by a combination of an alkylene group, a divalent group derived from phthalimide, and an oxygen atom; The divalent group formed by the combination of the divalent group of phthalimide, the oxygen atom, the arylidene group and the alkylene group; the combination of the alkylene group and the divalent group from pyromellitic acid diimide into the 2-valent basis and so on. A group consisting of a combination of two or more divalent groups can form a ring such as a condensed ring by the combination of each group. Moreover, the group which consists of a combination of 2 or more types of divalent groups may be a repeating unit whose number of repeating units is 1-10.

Wherein, as L in the general formula (E2-1-1), an oxygen atom, an aryl group with 6 to 24 carbon atoms which may have a substituent, and an alkylene group with 1 to 50 carbon atoms which may have a substituent group, an alkyl group having 5 or more carbon atoms, a divalent group derived from phthalimide, a divalent group derived from pyromellitic acid diimide, or a 2 group formed by a combination of two or more of these groups Price base is better. Among them, as L, also an alkylene group; a divalent group having a structure of alkylene group-divalent group derived from phthalimide-oxygen atom-divalent group derived from phthalimide ; with an alkylene group - a divalent group from phthalimide - an oxygen atom - an arylidene group - an alkylene group - an aryl group - an oxygen atom - one of the divalent groups from phthalimide The divalent group of the structure; the divalent group of the structure having an alkylene group-derived from the divalent group of diimide of pyromellitic acid; the divalent group of the structure having an alkynylene group-derived from the divalent group of phthalimide-oxygen atom - A divalent group derived from the structure of a divalent group of phthalimide; having an alkynylene group - a divalent group derived from phthalimide - oxygen atom - arylidene - alkynylene - extension Aryl-oxygen atom-a divalent group derived from the structure of a divalent group of phthalimide; preferably a divalent group having a structure of an alkynylene group-a divalent group derived from a diimide of pyromellitic acid .

一般式(E2-1-4)中，M ¹各獨立表示可具有取代基之碳原子數5以上的2價脂肪族基，Z各獨立表示可具有取代基的碳原子數5以上的2價脂肪族基，或具有可具有取代基之芳香環的2價基。t表示1～10的整數。 The maleimide resin represented by the general formula (E2-1-1) is preferably the maleimide resin represented by the general formula (E2-1-4).

In the general formula (E2-1-4), each M ¹ independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent, and each Z independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. Aliphatic group, or a divalent group having an aromatic ring which may have a substituent. t represents an integer of 1-10.

Each of M ¹ independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. M ¹ is the same as M in the general formula (E2-1-1).

Each Z independently represents an optionally substituted divalent aliphatic group having 5 or more carbon atoms, or a divalent group having an optionally substituted aromatic ring. As a divalent aliphatic group in Z, an alkylene group, an alkenylene group, an alkylene polyalkenyl group (preferably the number of double bonds is 2), etc. are mentioned, for example. The divalent aliphatic group may be any of chain, branched, and cyclic, and among them, a cyclic, that is, a cyclic divalent aliphatic group having 5 or more carbon atoms which may have a substituent is preferred.

The number of carbon atoms of the alkylene group is preferably 6 or more, preferably 8 or more, more preferably 50 or less, preferably 45 or less, more preferably 40 or less. As such an alkylene group, for example, a group having an octene-cyclohexylene structure, a group having a octylene-cyclohexene-octylene structure, a propylidene-cyclohexene-octylene group can be mentioned. The basis of the structure, etc.

The number of carbon atoms in the alkenylene group having 5 or more carbon atoms is preferably 6 or more, preferably 8 or more, more preferably 50 or less, preferably 45 or less, more preferably 40 or less. The alkenylene group may be any of linear, branched, and cyclic, and among them, linear is preferred. The term "cyclic alkenylene group" means the concept of including the case where it is composed of only a cyclic alkenylene group, and a case where both a linear alkenylene group and a cyclic alkenylene group are included. occasion. Examples of such alkenylene groups include pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, and dodecynyl groups. Alkyl, tridecynyl, pentadecynyl, hexadecynyl, base with octynyl-cyclohexylene structure, octynyl-cyclohexylene-cyclooctynyl structure The base, the base with the structure of propyne-cyclohexyne-octynyl, etc.

Examples of the aromatic ring in the divalent group having an aromatic ring represented by Z include a benzene ring, a naphthalene ring, an anthracene ring, a phthalimide ring, a pyromellitic acid diimide ring, and an aromatic ring. Heterocycles, etc., are preferably benzene ring, phthalimide ring and pyromellitic acid diimide ring. That is, as a divalent group having an aromatic ring, a divalent group having an optionally substituted benzene ring, a divalent group having an optionally substituted phthalimide ring, and an optionally substituted benzene ring The divalent group of the tetraacid diimide ring is preferred. Examples of the divalent group having an aromatic ring include a group formed by a combination of a divalent group derived from phthalimide and an oxygen atom; a divalent group derived from phthalimide, an oxygen atom , the group formed by the combination of arylidene and alkylene group; the group formed by the combination of alkylene group and diimide from pyromellitic acid; the divalent group from diimide of pyromellitic acid ; A base formed by a combination of a divalent group and an alkylene group derived from phthalimide. The above-mentioned aryl group is the same as the aryl group in the divalent linking group represented by L in the general formula (E2-1-1).

The divalent group having an alkylene group and an aromatic ring represented by Z may have a substituent. The substituents are the same as those that M in the general formula (E2-1-1) may have.

Specific examples of the group represented by Z include the following groups. In the formula, "*" represents the bonding site.

一般式(E2-1-5)中，M ²及M ³各獨立表示可具有取代基之碳原子數5以上的2價脂肪族基，R ⁴⁰各獨立表示氧原子、伸芳基、伸烷基或此等基之2個以上的組合所成的2價基。t1表示1～10的整數。 一般式(E2-1-6)中，M ⁴、M ⁶及M ⁷各獨立表示可具有取代基之碳原子數5以上的脂肪族基，M ⁵各獨立表示具有可具有取代基之芳香環的2價基，R ⁴¹及R ⁴²各獨立表示碳原子數5以上的烷基。t2表示0～10的整數，u1及u2各獨立表示0～4的整數。 The compound represented by the general formula (E2-1-1) is preferably either the compound represented by the general formula (E2-1-5) or the compound represented by the general formula (E2-1-6).

In the general formula (E2-1-5), M ² and M ³ each independently represent a divalent aliphatic group having 5 or more carbon atoms that may have a substituent, and R ⁴⁰ each independently represents an oxygen atom, an aryl group, an alkylene group A divalent group consisting of a group or a combination of two or more of these groups. t1 represents an integer of 1-10. In the general formula (E2-1-6), each of M ⁴ , M ⁶ and M ⁷ independently represents an aliphatic group having 5 or more carbon atoms which may have a substituent, and M ⁵ each independently represents an aromatic ring which may have a substituent In the divalent group of , R ⁴¹ and R ⁴² each independently represent an alkyl group having 5 or more carbon atoms. t2 represents an integer of 0 to 10, and u1 and u2 each independently represent an integer of 0 to 4.

Each of M ² and M ³ independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. M ² and M ³ are the same as the divalent aliphatic groups having 5 or more carbon atoms represented by M in the general formula (E2-1-1), and are preferably hexadecylene and hexadecylene.

R ⁴⁰ each independently represents an oxygen atom, an aryl group, an alkyl group, or a group formed by a combination of two or more divalent groups of these. The arylidene group and the alkylene group are the same as the arylidene group and the alkylene group in the divalent linking group represented by L in the general formula (E2-1-1). R ⁴⁰ is preferably a group formed by a combination of two or more divalent groups or an oxygen atom.

As a group formed by a combination of two or more divalent groups in R ⁴⁰ , an oxygen atom, a combination of an aryl group, and an alkyl group can be mentioned. As a specific example of the group which consists of a combination of 2 or more types of divalent groups, the following groups are mentioned. In the formula, "*" represents the bonding site.

M ⁴ , M ⁶ and M ⁷ each independently represent an optionally substituted aliphatic group having 5 or more carbon atoms. M ⁴ , M ⁶ and M ⁷ are the same as the aliphatic groups having 5 or more carbon atoms which may have a substituent represented by M in the general formula (E2-1-1), and are represented by hexyl, heptyl, and octyl groups. Radix, nonyl, and decyl are preferred, and octyl is preferred.

M ⁵ each independently represents a divalent group having an optionally substituted aromatic ring. M ⁵ is the same as the divalent group of an aromatic ring which may have a substituent represented by Z in the general formula (E2-1-4), and is the same as the divalent group of an alkylene group and a diimide derived from pyromellitic acid. The base formed by the combination; the base formed by the combination of the divalent group from phthalimide and the alkylene group is preferably the combination of the alkylene group and the divalent group from the diimide of pyromellitic acid base is better. The arylidene group and the alkylene group mentioned above are the same as the arylidene group and the alkylene group in the divalent linking group represented by L in the general formula (E2-1-1).

Specific examples of the group represented by M ⁵ include, for example, the following groups. In the formula, "*" represents the bonding site.

R ⁴¹ and R ⁴² each independently represent an alkyl group having 5 or more carbon atoms. R ⁴¹ and R ⁴² are the same as the above-mentioned alkyl groups having 5 or more carbon atoms, preferably hexyl, heptyl, octyl, nonyl, and decyl, and more preferably hexyl and octyl.

Each of u1 and u2 independently represents an integer of 1 to 15, preferably an integer of 1 to 10.

As a specific example of the (E2-1) component, the following compounds (Ei) to (E-iii) can be mentioned, but it is not limited to these specific examples. In the formula, v represents an integer of 1-10.

Specific examples of the component (E2-1) include "BMI1500" (compound of formula (E-i)), "BMI1700" (compound of formula (E-ii)), "BMI689" (compound of formula (E-ii)) manufactured by Digigner Moleculars (Compounds of E-iii)) and the like.

The weight average molecular weight (Mw) of the component (E2-1) is preferably 150 to 5000, more preferably 300 to 2500.

The maleimide group equivalent of the component (E2-1) is preferably 50 g/eq. to 2000 g/eq., more preferably 100 g/eq. to the viewpoint that the desired effect of the present invention can be remarkably obtained. 1000g/eq., more preferably 150g/eq.～500g/eq. The maleimide group equivalent is the mass of the component (E2-1) containing 1 equivalent of the maleimide group.

-(E2-2) Ingredient- The component (E2-2) is a maleimide compound having an aromatic ring directly bonded to the nitrogen atom of maleimide. The component (E2-2) can be obtained, for example, by subjecting a component containing an aromatic amine compound (aromatic diamine compound, etc.) and maleic anhydride to imidization reaction.

Aromatic rings can be carbocyclic or heterocyclic. Examples of the aromatic ring include a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, a pyrazole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an imidazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, Monocyclic aromatic rings such as pyrazine ring; naphthalene ring, anthracene ring, benzofuran ring, isobenzofuran ring, indole ring, isoindole ring, benzothiophene ring, benzimidazole ring, indazole Ring, benzoxazole ring, benzisoxazole ring, benzothiazole ring, quinoline ring, isoquinoline ring, quinoxaline ring, acridine ring, quinazoline ring, cinnoline ring, phthalazine ring Condensed rings in which two or more monocyclic aromatic rings are condensed; non-aromatic rings in which one or more monocyclic aromatic rings are condensed on one or more monocyclic aromatic rings such as indan ring, fluorene ring, tetrahydronaphthalene ring, etc. The condensed ring, etc. Among them, as the aromatic ring, a monocyclic aromatic ring is preferable, and a benzene ring is preferable.

As the component (E2-2), a compound represented by the following formula (E2-2-1) is preferable.

[In the formula, R ^c each independently represents a substituent; X ^c each independently represents a single bond, an alkylene group, an alkenylene group, -O-, -CO-, -S-, -SO-, -SO ₂ -, - CONH-, -NHCO-, -COO- or -OCO- (preferably a single bond or an alkylene group); Z ^c each independently represents a non-aromatic ring that may have a substituent or an aromatic ring that may have a substituent (preferably An aromatic ring which may have a substituent, particularly preferably a benzene ring which may have a substituent); s represents an integer of 1 or more (preferably an integer of 1-100, preferably an integer of 1-50, more preferably 1- 20); t each independently represents an integer of 0 or more; u each independently represents an integer from 0 to 2 (preferably 0)] maleimide compound represented by formula (E2-2- 2)～(E2-2-5):

式中，R ^c1、R ^c2及R ^c3各獨立表示烷基；X ^c1及X ^c2各獨立表示單鍵或伸烷基；s表示1以上的整數(以1～100的整數為佳，較佳為1～50的整數，更佳為1～20的整數)；t’表示1～5的整數；u1、u2及u3各獨立表示0～2的整數(較佳為0)。且s單位、t單位、t’單位、u單位、u1單位、u2單位及u3單位可在每單位中可相同亦可相異。

In the formula, R ^c1 , R ^c2 and R ^c3 each independently represent an alkyl group; X ^c1 and X ^c2 each independently represent a single bond or an alkylene group; s represents an integer of 1 or more (preferably an integer from 1 to 100, preferably is an integer of 1-50, more preferably an integer of 1-20); t' represents an integer of 1-5; u1, u2 and u3 each independently represent an integer of 0-2 (preferably 0). In addition, the s unit, the t unit, the t' unit, the u unit, the u1 unit, the u2 unit, and the u3 unit may be the same or different in each unit.

式中，R ³¹及R ³⁶表示馬來醯亞胺基，R ³²、R ³³、R ³⁴及R ³⁵各獨立表示氫原子、烷基或芳基，D各獨立表示2價芳香族基。m1及m2各獨立表示1～10的整數，a表示1～100的整數。 Moreover, as another embodiment, it is preferable that the component (E2-2) has a structure represented by the following formula (E2-2-6), for example.

In the formula, R ³¹ and R ³⁶ represent a maleimide group, R ³² , R ³³ , R ³⁴ and R ³⁵ each independently represent a hydrogen atom, an alkyl group or an aryl group, and D each independently represents a divalent aromatic group. m1 and m2 each independently represent an integer of 1 to 10, and a represents an integer of 1 to 100.

R ³² , R ³³ , R ³⁴ and R ³⁵ in formula (E2-2-6) each independently represent a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom.

The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. Alkyl groups can be straight chain, branched or cyclic. As such an alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, etc. are mentioned, for example.

The aryl group is preferably an aryl group having 6 to 20 carbon atoms, preferably an aryl group having 6 to 15 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. The aryl group may be a monocyclic ring or a condensed ring. As such an aryl group, a phenyl group, a naphthyl group, an anthracenyl group, etc. are mentioned, for example.

The alkyl group and the aryl group may have a substituent. The substituent is not particularly limited, and examples thereof include a halogen atom, -OH, -OC _1-6 alkyl, -N(C _1-10 alkyl) ₂ , C _1-10 alkyl, C _6-10 Aryl, -NH ₂ , -CN, -C(O)OC _1-10 alkyl, -COOH, -C(O)H, -NO ₂ and the like. Among them, "C _pq " (p and q are positive integers and satisfy p<q) is a term, and p to q after the term represent the number of carbon atoms of an organic group. For example, "C _1-10 alkyl group" means an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to form a ring, and the ring structure also contains a spiro ring or a condensed ring.

The above-mentioned substituent may further have a substituent (hereinafter sometimes referred to as a "secondary substituent"). As the secondary substituent, unless otherwise specified, the same ones as those described above can be used.

D in formula (E2-2-6) represents a divalent aromatic group. Examples of the divalent aromatic group include a phenylene group, a naphthylene group, an anthracene group, an aralkyl group, a diphenylene group, a biphenylene aralkyl group, and the like, and among them, a diphenylene group and a biphenyl group are also used. Aralkyl is preferred, and diphenylene is preferred. The divalent aromatic group may have a substituent. The substituent is the same as that of the alkyl group represented by R ³² in the formula (E2-2-6).

m1 and m2 each independently represent an integer of 1 to 10, preferably 1 to 6, more preferably 1 to 3, more preferably 1 to 2, and more preferably 1.

a represents an integer of 1-100, preferably 1-50, more preferably 1-20, more preferably 1-5.

式中，R ³⁷及R ³⁸表示馬來醯亞胺基。a1表示1～100的整數。 As the component (E2-2), the resin represented by the formula (E2-2-7) is preferable.

In the formula, R ³⁷ and R ³⁸ represent a maleimide group. a1 represents an integer of 1-100.

a1 is the same as a in formula (E2-2-6), and the preferred range is also the same.

Examples of products sold as the component (E2-2) include "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd.; "BMI-50P" manufactured by Keiai Kasei Corporation; and "BMI-1000" manufactured by Yamato Chemical Industry Co., Ltd. , "BMI-1000H", "BMI-1100", "BMI-1100H", "BMI-4000", "BMI-5100"; "BMI-4,4'-BPE", "BMI-70" manufactured by Keiai Kasei , "BMI-80" manufactured by Keiai Kasei Corporation, etc.

The weight average molecular weight (Mw) of the component (E2-2) is preferably 150 to 5000, more preferably 300 to 2500.

The functional group equivalent of the maleimide group of the component (E2-2) is preferably 50g/eq.～2000g/eq., preferably 100g/eq.～1000g/eq., more preferably 150g/eq. .～500g/eq., preferably 200g/eq.～300g/eq..

-(E2-3) Ingredient- The component (E2-3) is a maleimide compound containing a trimethylindan skeleton. The trimethylindan skeleton means a skeleton represented by the following formula (E2-3-1).

A substituent may be bonded to the benzene ring contained in the trimethylindane skeleton. As a substituent, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a cycloalkyl group, a halogen atom, a hydroxyl group, and a mercapto group are mentioned, for example. The number of carbon atoms of the alkyl group is preferably 1-10. As an alkyl group, a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, etc. are mentioned, for example. The number of carbon atoms of the alkyloxy group is preferably 1-10. As an alkyloxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc. are mentioned, for example. The number of carbon atoms of the alkylthio group is preferably 1-10. As an alkylthio group, a methylthio group, an ethylthio group, a propylthio group, a butylthio group etc. are mentioned, for example. The number of carbon atoms in the aryl group is preferably 6-10. As an aryl group, a phenyl group, a naphthyl group, etc. are mentioned, for example. The number of carbon atoms in the aryloxy group is preferably 6-10. As an aryloxy group, a phenyloxy group, a naphthoxy group, etc. are mentioned, for example. The number of carbon atoms in the arylthio group is preferably 6-10. As an arylthio group, a phenylthio group, a naphthylthio group, etc. are mentioned, for example. The number of carbon atoms in the cycloalkyl group is preferably 3 to 10. As a cycloalkyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, etc. are mentioned, for example. As a halogen atom, a fluorine atom, a chlorine atom, an iodine atom, etc. are mentioned, for example.

Among the aforementioned substituents, the hydrogen atom of the alkyl group, the alkyloxy group, the alkylthio group, the aryl group, the aryloxy group, the arylthio group and the cycloalkyl group may be substituted with a halogen atom.

The number of substituents bonded to one benzene ring contained in the trimethylindan skeleton may be 1, or may be 2 or more. The number of substituents bonded to the benzene ring contained in the trimethylindan skeleton is usually 0 or more and 3 or less. When the number of substituents is 2 or more, these 2 or more substituents may be the same or different. Among them, it is also preferable that a substituent is not bonded to the benzene ring contained in the trimethylindan skeleton.

The number of trimethylindan skeletons contained in 1 molecule of the component (E2-3) may be 1, or may be 2 or more. The upper limit is, for example, 10 or less, 8 or less, 7 or less, or 6 or less.

In addition to the above-mentioned trimethylindan skeleton, the component (E2-3) further contains an aromatic ring skeleton. The number of ring constituent carbons of the aromatic ring skeleton is preferably 6-10. As an aromatic ring skeleton, a benzene ring skeleton, a naphthalene ring skeleton, etc. are mentioned, for example. The number of the above-mentioned aromatic ring skeleton contained in one molecule of the component (E2-3) is preferably 1 or more, preferably 2 or more, preferably 6 or less, preferably 4 or less, particularly preferably 3 or less. When the component (E2-3) contains two or more aromatic ring skeletons in addition to the trimethylindan skeleton, these aromatic ring skeletons may be the same or different.

A substituent may be bonded to the aromatic ring contained in the above-mentioned aromatic ring skeleton. As a substituent, the said substituent and a nitro group which are a substituent which can be bonded to the benzene ring contained in a trimethylindan skeleton are mentioned, for example. The number of substituents bonded to one aromatic ring may be one or two or more. The number of substituents bonded to the aromatic ring is usually 0 or more and 4 or less. When the number of substituents is 2 or more, these 2 or more substituents may be the same or different.

In addition to the above-mentioned trimethylindan skeleton, the component (E2-3) may further contain a divalent aliphatic hydrocarbon group. In particular, when the component (E2-3) contains an aromatic ring skeleton other than the benzene ring contained in the trimethylindan skeleton, it is preferable that the component (E2-3) contains a divalent aliphatic hydrocarbon group. In this case, it is preferable that a divalent aliphatic hydrocarbon group connects between the benzene ring and the aromatic ring skeleton contained in the trimethylindan skeleton. Moreover, it is preferable that the bivalent aliphatic hydrocarbon group is connected to the aromatic ring skeleton than this.

The number of carbon atoms of the divalent aliphatic hydrocarbon group is preferably 1 or more, preferably 12 or less, more preferably 8 or less, particularly preferably 5 or less. The divalent aliphatic hydrocarbon group is preferably an alkylene group which is a saturated aliphatic hydrocarbon group. Examples of the divalent aliphatic hydrocarbon group include straight-chain alkylene groups such as methylene, ethylidene, trimethylene, tetramethylene, pentamethylene, and hexamethylene; ethylene (-CH( CH ₃ )-), propylene (-CH(CH ₂ CH ₃ )-), isopropylene (-C(CH ₃ ) ₂ -), ethylmethylmethylene (-C(CH ₃ ) (CH ₂ CH ₃ )-), diethylmethylene (-C(CH ₂ CH ₃ ) ₂ -) and other branched alkylenes, and the like. (E2-3) When the maleimide compound containing trimethylindan skeleton also contains 2 or more divalent aliphatic hydrocarbon groups in addition to the trimethylindan skeleton, these divalent aliphatic hydrocarbon groups may be the same can also be different.

The component (E2-3) preferably contains a structure represented by the following formula (E2-3-2). The whole of the component (E2-3) may have the structure represented by the formula (E2-3-2), and the part of the component (E2-3) may have the structure represented by the formula (E2-3-2).

(In the formula, Ar ^a1 represents a divalent aromatic hydrocarbon group which may have a substituent; R ^a1 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, and an alkyloxy group having 1 to 10 carbon atoms. 10 alkylthio groups, aryl groups with 6 to 10 carbon atoms, aryloxy groups with 6 to 10 carbon atoms, arylthio groups with 6 to 10 carbon atoms, cycloalkanes with 3 to 10 carbon atoms group, halogen atom, nitro group, hydroxyl group or mercapto group; R ^a2 independently represents an alkyl group with 1 to 10 carbon atoms, an alkyloxy group with 1 to 10 carbon atoms, and an alkylthio group with 1 to 10 carbon atoms , aryl group with 6-10 carbon atoms, aryloxy group with 6-10 carbon atoms, arylthio group with 6-10 carbon atoms, cycloalkyl group with 3-10 carbon atoms, halogen atom, hydroxyl group or mercapto group; R ^a3 each independently represents a divalent aliphatic hydrocarbon group; n _a1 represents a positive integer; _{n a2} each independently represents an integer of 0 to 4 ^; Hydrogen atoms of oxy, alkylthio, aryl, aryloxy, arylthio and cycloalkyl groups may also be substituted by halogen atoms. The alkyl group, alkyloxy group, alkylthio group of R ^a2 , The hydrogen atom of the aryl group, the aryloxy group, the arylthio group and the cycloalkyl group may also be substituted with a halogen atom. When n _a2 is 2 to 4, R ^a1 may be the same or different in the same ring. n _a3 When it is 2 to 3, R ^a2 can be the same or different in the same ring)

In formula (E2-3-2), Ar ^a1 represents a divalent aromatic hydrocarbon group which may have a substituent. The number of carbon atoms of the divalent aromatic hydrocarbon group is preferably 6 or more, preferably 20 or less, more preferably 16 or less. As a divalent aromatic hydrocarbon group, a phenylene group and a naphthylene group are mentioned, for example. Examples of the substituent which the divalent aromatic hydrocarbon group may have include an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, Aryl group having 6 to 10 carbon atoms, aryloxy group having 6 to 10 carbon atoms, arylthio group having 6 to 10 carbon atoms, cycloalkyl group having 3 to 10 carbon atoms, halogen atom, hydroxyl group and Sulfhydryl. The hydrogen atom of each substituent may be further substituted with a halogen atom. Moreover, as a specific example of such a substituent, the thing similar to the substituent which can be bonded to the benzene ring contained in a trimethylindan skeleton is mentioned, for example. When the divalent aromatic hydrocarbon group has a substituent, the number of the substituent is preferably 1 to 4. When the number of substituents which a divalent aromatic hydrocarbon group has is 2 or more, these 2 or more substituents may be the same or different. Among them, Ar ^a1 is also preferably a divalent aromatic hydrocarbon group having no substituent.

In formula (E2-3-2), R ^a1 independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a carbon Aryl group having 6 to 10 atoms, aryloxy group having 6 to 10 carbon atoms, arylthio group having 6 to 10 carbon atoms, cycloalkyl group having 3 to 10 carbon atoms, halogen atom, nitro group, hydroxyl or sulfhydryl. The hydrogen atom of the alkyl group, the alkyloxy group, the alkylthio group, the aryl group, the aryloxy group, the arylthio group and the cycloalkyl group may be substituted with a halogen atom. Specific examples of these groups include, for example, the same examples as those of the substituent which can be bonded to the benzene ring contained in the trimethylindan skeleton. Among them, R ^a1 is also preferably one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms. An alkyl group having 1 to 4 carbon atoms is particularly preferred.

In formula (E2-3-2), R ^a2 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a carbon Aryl group with 6 to 10 atoms, aryloxy group with 6 to 10 carbon atoms, arylthio group with 6 to 10 carbon atoms, cycloalkyl group with 3 to 10 carbon atoms, halogen atom, hydroxyl group or mercapto group . The hydrogen atom of the alkyl group, the alkyloxy group, the alkylthio group, the aryl group, the aryloxy group, the arylthio group and the cycloalkyl group may be substituted with a halogen atom. As a specific example without such a group, the same example as the substituent which can couple|bond with the benzene ring contained in a trimethylindan skeleton is mentioned, for example. Among them, R ^a2 is preferably one or more groups selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms, and aryl groups having 6 to 10 carbon atoms. .

In formula (E2-3-2), R ^a3 each independently represents a divalent aliphatic hydrocarbon group. The range of preferable divalent aliphatic hydrocarbon groups is as described above.

In formula (E2-3-2), n _a1 represents a positive integer. n _a1 is preferably 1 or more, preferably 10 or less, more preferably 8 or less.

In formula (E2-3-2), n _a2 each independently represents an integer of 0 to 4. n _a2 is preferably 2 or 3, more preferably 2. Although the plural n _a2 may be different, the same one is preferred. When n _a2 is 2 or more, the plural R ^a1 may be the same or different within the same ring.

In formula (E2-3-2), n _a3 each independently represents an integer of 0 to 3. Although the complex numbers n _a3 may be different, they are preferably the same. n _a3 is preferably 0.

(式中，R ^b1各獨立表示碳原子數1～10的烷基、碳原子數1～10的烷基氧基、碳原子數1～10的烷基硫基、碳原子數6～10的芳基、碳原子數6～10的芳基氧基、碳原子數6～10的芳基硫基、碳原子數3～10的環烷基、鹵素原子、硝基、羥基或巰基；R ^b2各獨立表示碳原子數1～10的烷基、碳原子數1～10的烷基氧基、碳原子數1～10的烷基硫基、碳原子數6～10的芳基、碳原子數6～10的芳基氧基、碳原子數6～10的芳基硫基、碳原子數3～10的環烷基、鹵素原子、羥基或巰基；n _b1表示正整數；n _b2各獨立表示0～4的整數；n _b3各獨立表示0～3的整數。R ^b1的烷基、烷基氧基、烷基硫基、芳基、芳基氧基、芳基硫基，及環烷基的氫原子亦可由鹵素原子進行取代。R ^b2的烷基、烷基氧基、烷基硫基、芳基、芳基氧基、芳基硫基，及環烷基的氫原子亦可由鹵素原子進行取代。n _b2若為2～4時，R ^b1在同一環內可相同亦可相異。n _b3若為2～3時，R ^b2在同一環內可相同亦可相異。) It is particularly preferable that the component (E2-3) contains a structure represented by the following formula (E2-3-3). The whole of the component (E2-3) may have the structure represented by the formula (E2-3-3), or the part having the component (E2-3) may have the structure represented by the formula (E2-3-3).

(in the formula, R ^b1 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, and an alkyl group having 6 to 10 carbon atoms. Aryl group, aryloxy group with 6-10 carbon atoms, arylthio group with 6-10 carbon atoms, cycloalkyl group with 3-10 carbon atoms, halogen atom, nitro group, hydroxyl group or mercapto group; R ^b2 Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms. Aryloxy group of 6-10, arylthio group of carbon number of 6-10, cycloalkyl group of carbon number of 3-10, halogen atom, hydroxyl or mercapto group; n _b1 represents a positive integer; n _b2 each independently represents An integer of 0 to 4; n _b3 each independently represents an integer of 0 to 3. R ^b1 represents an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, and a cycloalkyl group The hydrogen atom of R ^b2 can also be substituted by a halogen atom. The hydrogen atom of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group of R b2 can also be replaced by a halogen atom Substitution. When n _b2 is 2 to 4, R ^b1 may be the same or different within the same ring. When n _b3 is 2 to 3, R ^b2 may be the same or different within the same ring.)

For formula (E2-3-3), each of R ^b1 , R ^b2 , n _b1 , n _b2 and n _b3 is the same as R ^a1 , R ^a2 , n _a1 , n _a2 and n _a3 in formula (E2-3-2) same.

對於式(E2-3-4)，R ^c1、R ^c2、n _c2及n _c3各與式(E2-3-2)中之R ^a1、R ^a2、n _a2及n _a3相同。又，對於式(E2-3-4)，n _c1表示重複單位數的1～20的整數。且對於式(E2-3-4)，*表示鍵結部位。例如(E2-3)成分在式(E2-3-2)中，n _a2為3以下，且對於馬來醯亞胺基所鍵結的苯環之馬來醯亞胺基的鄰位及對位中，於2個以上未鍵結R ^a1時，可組合式(E2-3-2)所示結構而含有前述式(E2-3-4)所示結構。又，例如(E2-3)成分在式(E2-3-3)中，n _b2為3以下，且，對於馬來醯亞胺基所鍵結的苯環之馬來醯亞胺基的鄰位及對位中，於2個以上未鍵結R ^b1時，可組合式(E2-3-3)所示結構而含有前述式(E2-3-4)所示結構。 The component (E2-3) may further contain a structure represented by the following formula (E2-3-4).

For formula (E2-3-4), R ^c1 , R ^c2 , n _c2 and n _c3 are each the same as R ^a1 , R ^a2 , n _a2 and n _a3 in formula (E2-3-2). Moreover, in Formula (E2-3-4), n _c1 represents the integer of 1-20 of the repeating unit number. And in the formula (E2-3-4), * represents a bonding site. For example, in the formula (E2-3-2) of the component (E2-3), n _a2 is 3 or less, and the ortho and para positions of the maleimide group of the benzene ring to which the maleimide group is bonded are In the position, when two or more of R ^a1 are not bonded, the structure represented by the formula (E2-3-2) can be combined to include the structure represented by the aforementioned formula (E2-3-4). In addition, for example, in the formula (E2-3-3) of the component (E2-3), n _b2 is 3 or less, and the vicinal position of the maleimide group of the benzene ring to which the maleimide group is bonded is In the position and the para position, when two or more of R ^b1 are not bonded, the structure represented by the formula (E2-3-3) can be combined to include the structure represented by the aforementioned formula (E2-3-4).

(E2-3) A component may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

The maleimide group equivalent of the component (E2-3) is preferably 50 g/eq. or more, preferably 100 g/eq. or more, particularly preferably 200 g/eq. or more, and preferably 2000 g/eq. or less , preferably 1000 g/eq. or less, particularly preferably 800 g/eq. or less. The maleimide group equivalent means the mass of the maleimide compound per equivalent of the maleimide group. When the maleimide group equivalent of the component (E2-3) is within the aforementioned range, the effect of the present invention can be remarkably obtained.

(E2-3) The manufacturing method of a component is not specifically limited. The component (E2-3) can be produced, for example, by the method described in the Technical Publication No. 2020-500211 of the Institute of Invention. According to the production method described in the Published Technical Publication No. 2020-500211 of the Institute of Invention, a maleimide compound having a distribution of the number of repeating units of the trimethylindan skeleton was obtained. The maleimide compound obtained by this method has a structure represented by the following formula (E2-3-5). Therefore, (E2-3) component may contain the maleimide compound which has the structure represented by formula (E2-3-5).

(in the formula, R ¹ each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, and an alkylthio group having 1 to 10 carbon atoms. Aryl group, aryloxy group with 6-10 carbon atoms, arylthio group with 6-10 carbon atoms, cycloalkyl group with 3-10 carbon atoms, halogen atom, nitro group, hydroxyl group or mercapto group; R ² Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms. Aryloxy group of 6-10, arylthio group of carbon number of 6-10, cycloalkyl group of carbon number of 3-10, halogen atom, hydroxyl or mercapto group; n ₁ represents the average number of repeating units of 0.95-10.0 n ₂ each independently represents an integer from 0 to 4; n ₃ each independently represents an integer from 0 to 3. R ¹ represents an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, and an arylthio group The hydrogen atoms of R 2 and cycloalkyl groups can also be substituted by halogen atoms. R ² of alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl The hydrogen atom may also be substituted by a halogen atom. When n ₂ is 2 to 4, R ¹ may be the same or different in the same ring. When n ₃ is 2 to 3, R ² may be the same or different in the same ring )

In formula (E2-3-5), R ¹ , R ² , n ₂ and n ₃ are each the same as R ^a1 , R ^a2 , n _a2 and n _a3 in formula (E2-3-2).

In formula (E2-3-5), n ₁ represents the average number of repeating units, and the range is 0.95 to 10.0. A group of maleimide compounds containing the structure represented by the formula (E2-3-5) were obtained according to the production method described in the Technical Publication No. 2020-500211 of the Institute of Invention. From the fact that the average number of repeating units n ₁ in the formula (E2-3-5) can be made smaller than 1.00, it can be seen that in the maleimide containing the structure represented by the formula (E2-3-5) thus obtained Among the compounds, a maleimide compound in which the repeating unit number of the trimethylindan skeleton is 0 may be contained. Wherein, from the maleimide compound containing the structure represented by the formula (E2-3-5), after purification and removal of the maleimide compound whose repeating unit number of the trimethylindan skeleton is 0, (E2 -3) Component, only the obtained (E2-3) component may be contained in the photosensitive resin composition. However, even when the maleimide compound having a repeating unit number of 0 of the trimethylindan skeleton is contained in the photosensitive resin composition, the effect of the present invention can be obtained. In addition, when purification is omitted, cost can be suppressed. Among them, the maleimide compound having the structure represented by the formula (E2-3-5) is contained in the photosensitive Resin composition is preferred.

For formula (E2-3-5), the average number of repeating units n ₁ is preferably 0.95 or more, preferably 0.98 or more, more preferably 1.0 or more, particularly preferably 1.1 or more, preferably 10.0 or less, more preferably 8.0 Below, it is more preferable that it is 7.0 or less, and it is especially preferable that it is 6.0 or less. When the average repeating unit number n ₁ is within the aforementioned range, the effect of the present invention can be remarkably obtained. In particular, the glass transition temperature of the photosensitive resin composition can be effectively increased.

As an example of the structure represented by Formula (E2-3-5), the following are mentioned.

The maleimide compound containing the structure represented by the formula (E2-3-5) may further contain the structure represented by the aforementioned formula (E2-3-4). For example, in the maleimide compound containing the structure represented by the formula (E2-3-5), for the formula (E2-3-5), n ₂ is 3 or less, and for the benzene bonded to the maleimide group In the ortho and para positions of the maleimide group of the ring, when two or more R ¹ are not bonded, the formula (E2-3-4) combined with the structure represented by the formula (E2-3-5) may be included. ) shown in the structure.

The maleimide compound containing the structure represented by the formula (E2-3-5) is preferably one whose molecular weight distribution Mw/Mn calculated by gel permeation chromatography (GPC) is within a specific range. The molecular weight distribution is a value obtained by dividing the weight average molecular weight Mw by the number average molecular weight Mn, and is represented by "Mw/Mn". Specifically, the molecular weight distribution Mw/Mn of the maleimide compound containing the structure represented by the formula (E2-3-5) is preferably 1.0-4.0, preferably 1.1-3.8, more preferably 1.2-3.6, particularly preferably is 1.3 to 3.4. When the molecular weight distribution Mw/Mn of the maleimide compound having the structure represented by the formula (E2-3-5) is within the aforementioned range, the effect of the present invention can be remarkably obtained.

Among the maleimide compounds having the structure represented by the formula (E2-3-5), the amount of the maleimide compounds in which the average number of repeating units n ₁ is 0 is preferably within a specific range. When carrying out the aforementioned GPC measurement of the maleimide compound containing the structure represented by the formula (E2-3-5), the amount of the maleimide compound whose average repeating unit number _n is 0 can be determined according to the result of the GPC measurement It is expressed in area %. In detail, in the chromatogram obtained by the aforementioned GPC measurement, for the total area of the absorption peaks of the maleimide compound containing the structure represented by the formula (E2-3-5), the average repeating unit number n ₁ is 0. The absorption peak area ratio (area %) of the maleimide compound can represent the amount of the maleimide compound in which the average repeating unit number n ₁ is 0. Specifically, with respect to 100 area % of the total amount of the maleimide compound containing the structure represented by the formula (E2-3-5), the amount of the maleimide compound having an average repeating unit number n ₁ of 0 is 32 area % % or less is preferable, preferably 30 area % or less, more preferably 28 area % or less. When the amount of the maleimide compound in which the average number of repeating units n ₁ is 0 is within the aforementioned range, the effect of the present invention can be remarkably obtained.

The maleimide group equivalent of the maleimide compound containing the structure represented by the formula (E2-3-5) is preferably in the same range as the maleimide group equivalent of the above-mentioned (E2-3) component. . When the maleimide group equivalent of the maleimide compound having the structure represented by the formula (E2-3-5) is within the aforementioned range, the effect of the present invention can be remarkably obtained.

As the content of the component (E2), from the viewpoint of obtaining a cured product excellent in dielectric constant and dielectric properties, when the nonvolatile content in the photosensitive resin composition is set to 100% by mass, it is 0.5% by mass The above is preferable, preferably 1 mass % or more, more preferably 1.5 mass % or more, preferably 10 mass % or less, preferably 5 mass % or less, more preferably 3 mass % or less.

((E3) Vinyl Resin) After the (E3) vinyl resin as the (E) component reacts with the ethylenically unsaturated group of the (A) component, a cured product having a low dielectric constant and a low dielectric loss tangent can be obtained. However, (E3) vinyl resin does not contain the components corresponding to the components (A) to (D), (E1) and (E2) described above. (E3) Vinyl resin may be used individually by 1 type, and may be used in combination of 2 or more types.

As the (E3) vinyl resin, a vinyl group (-CH=CH ₂ )-containing resin can be used. The number of vinyl groups per molecule of vinyl resin may be one, or two or more, preferably two.

(E3) The vinyl resin should just have a vinyl group (-CH=CH ₂ ), for example, the concept of a resin that also contains a vinyl group, a vinyl phenyl group, an allyl group, and a maleic group.

The vinyl resin may be a resin containing a vinyl group. As (E3) vinyl resin, one or more selected from the following are preferable. (E3-1) Vinyl resin containing polyphenylene ether skeleton, (E3-2) vinyl resins containing a polyethylene backbone, and (E3-3) Resin containing an allyl group.

-Component (E3-1)- The component (E3-1) is a vinyl resin containing a polyphenylene ether skeleton. As (E3-1) component, the compound represented by following formula (E3-1-1) is mentioned.

For (formula (E3-1-1), L ¹ represents a divalent linking group; R ^B11 , R ^B12 , R ^B13 , R ^B21 , R ^B22 and R ^B23 each independently represent a hydrogen atom or an alkyl group; R ^B14 , R ^B15 , R ^B24 and R ^B25 each independently represent an alkyl group; R ^B16 and R ^B26 each independently represent an alkylene group; m _b11 and m _b21 each independently represent 0 or 1; m _b12 , m _b13 , m _b22 and m _b23 each independently represent An integer of 0 to 4; m _b14 and m _b24 each independently represent an integer of 0 to 300; m _b15 and m _b25 each independently represent 0 or 1).

In formula (E3-1-1), L ¹ represents a divalent linking group. Examples of the divalent linking group include alkylene, alkenylene, aryl, alkyl aryl, heteroaryl, -O-, -NH-, -NR ^x -, -CO-, - CS-, -SO-, -SO ₂ -, -C(=O)O-, -NHC(=O)-, -NC(=O)N-, -NHC(=O)O-, -C( =O)-, -S- and combining a plurality of these bases. R ^x represents a hydrocarbon group (Hydrocarbyl) having 1 to 12 carbon atoms. The number of carbon atoms of L ¹ is usually preferably 60 or less, preferably 48 or less, more preferably 36 or less, and particularly preferably 24 or less.

In formula (E3-1-1), R ^B11 , R ^B12 , R ^B13 , R ^B21 , R ^B22 and R ^B23 each independently represent a hydrogen atom or an alkyl group. R ^B11 , R ^B12 , R ^B13 , R ^B21 , R ^B22 and R ^B23 are the same as R ^A1 , R ^A2 and R ^A3 in the formula (E3-1-1). Among them, R ^B11 and R ^B21 are preferably hydrogen atoms or methyl groups, and R ^B12 , R ^B13 , R ^B22 and R ^B23 are preferably hydrogen atoms.

In formula (E3-1-1), R ^B14 , R ^B15 , R ^B24 and R ^B25 each independently represent an alkyl group. The number of carbon atoms of the alkyl group is preferably 1-12, preferably 1-6, more preferably 1-2. The alkyl group may be linear, branched, or cyclic. Examples of the alkyl group include methyl, ethyl, propyl, n-butyl, t-butyl and the like. Among them, R ^B14 , R ^B15 , R ^B24 and R ^B25 are also preferably methyl groups.

In formula (E3-1-1), R ^B16 and R ^B26 each independently represent an alkylene group. The number of carbon atoms of the alkylene group is preferably 1-10, preferably 1-6, more preferably 1-3. As the alkylene group, straight-chain alkylene groups are preferred, and methylene groups are preferred.

In formula (E3-1-1), m _b11 and m _b21 each independently represent 0 or 1.

In formula (E3-1-1), m _b12 , m _b13 , m _b22 and m _b23 each independently represent an integer of 0 to 4. Preferably, m _b12 , m _b13 , m _b22 and m _b23 are 1 to 4, preferably 2 to 3, and particularly preferably 2.

In formula (E3-1-1), m _b14 and m _b24 each independently represent an integer of 0 to 300. Specifically, m _b14 and m _b24 are usually 0 or more, preferably 1 or more, usually 300 or less, preferably 100 or less, preferably 50 or less, more preferably 20 or less, particularly preferably 10 or less.

In formula (E3-1-1), m _b15 and m _b25 each independently represent 0 or 1. When m _b11 is 0, m _b15 is preferably 1, and when m _b11 is 1, m _b15 is preferably 0. In addition, when m _b21 is 0, it is preferable that m _b25 is 1, and when m _b21 is 1, it is preferable that m _b25 is 0.

When a preferable example of the compound represented by the formula (E3-1-1) is given, the compound represented by the following formula (E3-1-2) can be given.

(對於式(E3-1-2)，L ²表示2價連結基；R ^C15及R ^C25各獨立表示烷基；R ^C16及R ^C26各獨立表示伸烷基；m _c14及m _c24各獨立表示0～300的整數)

(For formula (E3-1-2), L ² represents a divalent linking group; R ^C15 and R ^C25 each independently represent an alkyl group; R ^C16 and R ^C26 each independently represent an alkylene group; m _c14 and m _c24 each independently represent Integer from 0 to 300)

In formula (E3-1-2), L ² represents a divalent linking group. L ² may be the same as L ¹ in formula (E3-1-1). Among them, L ² is also preferably a divalent group represented by the following formula (E3-1-3).

(對於式(E3-1-3)，X ¹～X ⁸各獨立表示氫原子、碳原子數1～6的烷基或苯基。*表示鍵結部位)

(For formula (E3-1-3), X ¹ to X ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. * represents a bonding site.)

In formula (E3-1-2), R ^C15 and R ^C25 each independently represent an alkyl group. R ^C15 and R ^C25 may be the same as R ^B14 in formula (E3-1-1). Among them, R ^C15 and R ^C25 are also preferably methyl groups.

In formula (E3-1-2), R ^C16 and R ^C26 each independently represent an alkylene group. R ^C16 and R ^C26 may be the same as R ^B16 and R ^B26 in formula (E3-1-1). Among them, R ^C16 and R ^C26 are also preferably methylene groups.

In formula (E3-1-2), m _c14 and m _c24 each independently represent an integer of 0 to 300. m _c14 and m _c24 may be the same as m _b14 and m _b24 in formula (E3-1-1). In addition, in the formula (E3-1-2), a configuration in which one of m _c14 and m _c24 is excluded is preferably 0.

As a compound represented by formula (E3-1-2), a compound represented by the following formula (E3-1-4) is mentioned, for example. In the formula (E3-1-4), m _c14 and m _c24 represent the same numbers as in the formula (E3-1-2). As the compound represented by the formula (E3-1-4), "OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd. can be used.

若要舉出式(E3-1-1)所示化合物之其他較佳例子，可舉出下述式(E3-1-5)所示化合物。

Other preferable examples of the compound represented by the formula (E3-1-1) include the compound represented by the following formula (E3-1-5).

(對於式(E3-1-5)，L ³表示2價連結基；R ^D11及R ^D21各獨立表示氫原子或烷基；R ^D14、R ^D15、R ^D24及R ^D25各獨立表示烷基；m _d14及m _d24各獨立表示0～300的整數)

(For formula (E3-1-5), L ³ represents a divalent linking group; R ^D11 and R ^D21 each independently represent a hydrogen atom or an alkyl group; R ^D14 , R ^D15 , R ^D24 and R ^D25 each independently represent an alkyl group; m _d14 and m _d24 each independently represent an integer from 0 to 300)

In formula (E3-1-5), L ³ represents a divalent linking group. L ³ may be the same as L ¹ in formula (B2). Wherein, L ³ is also preferably any one selected from the group consisting of alkylene, alkenylene, -O-, -NR ^x -, -CO-, -CS-, -SO-, -SO ₂ - , alkylene is preferred, isopropylidene (-C(CH ₃ ) ₂ -) is particularly preferred.

In formula (E3-1-5), R ^D11 and R ^D21 each independently represent a hydrogen atom or an alkyl group. R ^D11 and R ^D21 may be the same as R ^B11 and R ^B21 in formula (E3-1-1). Among them, R ^D11 and R ^D21 are also preferably methyl groups.

In formula (E3-1-5), R ^D14 , R ^D15 , R ^D24 and R ^D25 each independently represent an alkyl group. R ^D14 , R ^D15 , R ^D24 and R ^D25 may be the same as R ^B14 in formula (E3-1-1). Among them, R ^D14 , R ^D15 , R ^D24 and R ^D25 are also preferably methyl groups.

In formula (E3-1-5), m _d14 and m _d24 each independently represent an integer of 0 to 300. m _d14 and m _d24 may be the same as m _b14 and m _b24 in formula (E3-1-1). In addition, the sum of m _b14 and m _b24 is preferably 2 or more.

As a compound represented by formula (E3-1-5), a compound represented by the following formula (E3-1-6) is mentioned, for example. For formula (E3-1-6), L ³ , m _d14 and m _d24 may be the same as formula (E3-1-5). As the compound represented by the formula (E3-1-4), "NORYL SA9000" manufactured by SABIC can be used.

-Component (E3-2)- The component (E3-2) is a vinyl resin containing a polyethylene skeleton. As (E3-2) component, the polymer of the structural unit represented by following formula (E3-2-1) is mentioned.

For (formula (E3-2-1), R ^E1 , R ^E2 and R ^E3 each independently represent a hydrogen atom or an alkyl group; R ^E4 each independently represents an alkyl group; R ^E5 , R ^E6 and R ^E7 each independently represent a hydrogen atom or an alkyl group An alkyl group having 1 to 6 carbon atoms; m _e1 represents 0 or 1; m _e2 represents an integer of 0 to 4; * represents a bonding site.)

In formula (E3-2-1), R ^E1 , R ^E2 and R ^E3 each independently represent a hydrogen atom or an alkyl group. The number of carbon atoms of the alkyl group is preferably 1-18, preferably 1-12, more preferably 1-6, particularly preferably 1-2. The alkyl group may be linear, branched, or cyclic. Examples of the alkyl group include methyl, ethyl, propyl, n-butyl, t-butyl and the like. Among them, R ^E1 , R ^E2 and R ^E3 are also preferably hydrogen atoms.

For formula (E3-2-1), R ^E4 each independently represents an alkyl group. R ^E4 may be the same as R ^B14 in formula (E3-1-1).

In formula (E3-2-1), R ^E5 , R ^E6 and R ^E7 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Among them, R ^E5 , R ^E6 and R ^E7 are also preferably hydrogen atoms.

In the formula (E3-2-1), m _e1 represents 0 or 1, preferably 0.

In formula (E3-2-1), m _e2 represents an integer of 0 to 4, preferably 0.

The molar content of the structural unit represented by the formula (E3-2-1) relative to the total 100 mol% of all the structural units contained in the polymer containing the structural unit represented by the formula (E3-2-1) It is better to set it within a specific range. Specifically, the molar content of the structural unit represented by the formula (E3-2-1) is preferably 2 mol % to 95 mol %, and more preferably 8 mol % to 81 mol %. In addition, the average number of the structural units represented by the formula (E3-2-1) contained in one molecule of the polymer is preferably 1 to 160, and more preferably 3 to 140.

對於(式(E3-2-2)，R ^E8、R ^E9及R ^E10各獨立表示氫原子或碳數1～6的烷基。Ar ^E1表示可具有取代基之芳基。作為Ar ^E1可具有的取代基，可舉出碳原子數1～6的烷基。*表示鍵結部位) The polymer containing the structural unit represented by the formula (E3-2-1) may further contain any structural unit combining the structural unit represented by the formula (E3-2-1). As an arbitrary structural unit, a structural unit represented by following formula (E3-2-2) is mentioned, for example.

In the formula (E3-2-2), R ^E8 , R ^E9 and R ^E10 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Ar ^E1 represents an optionally substituted aryl group. As Ar ^E1 , it may have The substituents of , include an alkyl group having 1 to 6 carbon atoms. * indicates a bonding site)

Examples of polymers containing a structural unit represented by the formula (E3-2-2) include those containing a structural unit represented by the following formula (E3-2-3) and those represented by the following formula (E3-2-4). A copolymer of a combination of a structural unit and a structural unit represented by the following formula (E3-2-5). In the formula (E3-2-3), the formula (E3-2-4), and the formula (E3-2-5), * represents a bonding site. For this copolymer, the molar contents of the structural unit represented by the formula (E3-2-3), the structural unit represented by the formula (E3-2-4), and the structural unit represented by the formula (E3-2-5) are respectively It is 8 mol% to 54 mol%, 0 mol% to 92 mol%, and 0 mol% to 89 mol%. In addition, the structural unit represented by the formula (E3-2-3), the structural unit represented by the formula (E3-2-4), and the structural unit represented by the formula (E3-2-5) contained in 1 molecule of the copolymer. The average numbers are 1 to 160, 0 to 350, and 0 to 270, respectively. As the copolymer, "ODV-XET(X03)", "ODV-XET(X04)" and "ODV-XET(X05)" manufactured by Nippon Steel Chemicals & Materials Co., Ltd. can be used.

(E3-2) A component may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

The vinyl equivalent of the component (E3-2) is preferably 250 g/eq. to 1200 g/eq., more preferably 300 g/eq. to 1100 g/eq. The radically polymerizable unsaturated group equivalent represents the mass of the radically polymerizable aromatic resin per 1 equivalent of vinyl groups. When the radically polymerizable unsaturated group equivalent of the component (E3-2) is in the aforementioned range, the effect of the present invention can be remarkably obtained.

The weight average molecular weight of the component (E3-2) is preferably 1,000 to 40,000, more preferably 1,500 to 35,000. The weight-average molecular weight of the resin was measured in terms of polystyrene by gel permeation chromatography (GPC).

-(E3-3) Ingredient- The so-called (E3-3) allyl-containing resin refers to a resin having at least one allyl group in the molecule. The component (E3-3) preferably has one or more allyl groups per molecule, and more preferably has two or more allyl groups. The lower limit is not particularly limited, but is preferably 10 or less, more preferably 5 or less.

In addition, the component (E3-3) also has a benzoxazine ring, a phenol ring, an isocyanuric acid ring, an epoxy group in addition to an allyl group from the viewpoint of remarkably obtaining the desired effect of the present invention. , and any one of carboxylic acid derivatives having a cyclic structure is preferred.

The component (E3-3) having a benzoxazine ring is preferably one bonded to either a nitrogen atom of the benzoxazine ring or a benzene ring, and preferably one bonded to a nitrogen atom.

As (E3-3) component which has a phenol ring, the allyl group containing cresol resin, the allyl group containing novolak-type phenol resin, the allyl group containing cresol novolak resin, etc. are mentioned, for example.

As the component (E3-3) having an isocyanuric acid structure, it is preferable that the nitrogen atom of the isocyanuric acid structure is directly bonded to an allyl group. As (E3-4) component which has an isocyanuric acid structure, an isocyanuric-acid allyl group, an isocyanuric-acid diallyl, an isocyanuric-acid triallyl, etc. are mentioned.

The component (E3-3) having an epoxy group is preferably one having two or more epoxy groups in one molecule. In addition, the (E3-3) component having an epoxy group is preferably one having an aromatic structure, and when two or more (E3-3) components are used in the epoxy group, at least one having an aromatic structure is preferred . The so-called aromatic structure generally refers to a chemical structure defined as aromatic, and also includes polycyclic aromatic and aromatic heterocycles. As (E3-3) component which has an epoxy group, what has a bisphenol structure is preferable, and as a bisphenol structure, a bisphenol A type, a bisphenol F type, a bisphenol AF type, etc. are mentioned, for example.

As the component (E3-3) containing a carboxylic acid derivative having a cyclic structure, an allyl carboxylate having a cyclic structure is preferable. The cyclic structure may be any of a cyclic group containing an alicyclic structure and a cyclic group containing an aromatic ring structure. In addition, the cyclic group may constitute a ring skeleton by a hetero atom other than a carbon atom. As a hetero atom, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned, for example, A nitrogen atom is preferable. The hetero atom may have one in the said ring, and may have two or more.

Examples of the carboxylic acid having a cyclic structure include isocyanuric acid, benzoic acid, phthalic acid, and cyclohexanedicarboxylic acid. Examples of the component (E3-3) containing a carboxylic acid derivative having a cyclic structure include allyl isocyanurate, diallyl isocyanurate, triallyl isocyanurate, and benzene. Diallyl formate, allyl benzoate, ortho-diallyl phthalate, meta-diallyl phthalate, p-diallyl phthalate, cyclohexyl Alkanedicarboxylate allyl, cyclohexanedicarboxylate diallyl, etc.

The component (E3-3) can be sold as a component. Examples of commercial products include "MEH-8000H" and "MEH-8005" (component (E3-3) with a phenolic ring) manufactured by Meiwa Chemical Co., Ltd.; "RE-810NM" manufactured by Nippon Kayaku Co., Ltd. Oxygen (E3-3) component); Shikoku Chemical Industry Co., Ltd. "ALP-d" ((E3-3) component with a benzoxazine ring); Shikoku Chemical Industry Co., Ltd. "L-DAIC" ( (E3-3) component with isocyanuric acid ring); "TAIC" manufactured by Nippon Chemicals Corporation ((E3-3) component with isocyanuric acid ring (triallyl isocyanurate)) ; Osaka Soda Co., Ltd. "MDAC" ((E3-3) component with cyclohexanedicarboxylic acid derivatives); Nikkei TechnoFineChemistry Co., Ltd. "DAD" (diallyl benzoate); Osaka Soda Co., Ltd. "DaisoDupMonomer" o-diallyl phthalate), etc.

The allyl equivalent of the component (E3-3) is preferably 20 g/eq. to 1000 g/eq., more preferably 50 g/eq. to 500 g/eq, from the viewpoint of remarkably obtaining the desired effect of the present invention. ., more preferably 100g/eq.～300g/eq.. The allyl equivalent is the mass of the component (E3-3) containing 1 equivalent of allyl.

As the content of the component (E3), from the viewpoint of obtaining a cured product with excellent dielectric constant and dielectric properties, the nonvolatile content in the photosensitive resin composition is 100 mass %, and the content is 1 mass % or more. More preferably, it is 1.5 mass % or more, more preferably 2 mass % or more, more preferably 15 mass % or less, preferably 10 mass % or less, and more preferably 8 mass % or less.

As the component (E), from the viewpoint of obtaining a cured product having excellent dielectric constant and dielectric loss tangent, one or more selected from active ester resins, maleimide resins, and vinyl resins More preferably, those containing an active ester resin are more preferable, and those containing an active ester resin and one or more resins selected from the group consisting of maleimide resins and vinyl resins are more preferable.

As the total content of the component (E), from the viewpoint of obtaining a cured product excellent in dielectric constant and dielectric properties, the nonvolatile content in the photosensitive resin composition is taken as 100% by mass, and the amount is 1% by mass. The above is preferable, preferably 1.5 mass % or more, more preferably 2 mass % or more, preferably 20 mass % or less, preferably 15 mass % or less, more preferably 10 mass % or less.

<(F) Hardening accelerator> In addition to the above-mentioned components, the photosensitive resin composition may further contain (F) a curing accelerator as an optional component. (F) component may be used individually by 1 type, and may be used in combination of 2 or more types.

As (F) component, a phosphorus type hardening accelerator, an amine type hardening accelerator, an imidazole type hardening accelerator, a guanidine type hardening accelerator, a metal type hardening accelerator, etc. are mentioned, for example.

Examples of phosphorus-based curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, and tetrabutylphosphonium decanoate , (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyl triphenylphosphonium thiocyanate, etc., with triphenylphosphine, tetrabutylphosphonium decane Alkanoates are preferred.

Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6,- ginseng (dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc., with 4-dimethylaminopyridine, 1,8-diaza Heterobicyclo(5,4,0)-undecene is preferred.

Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methylimidazole. Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Imidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2 -Ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl -2-Phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4- Diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4' -Methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s- Triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Hydroxymethylimidazole, 2,3-Dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2 - imidazole compounds such as methylimidazoline, 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins, with 2-ethyl-4-methylimidazole, 1-benzyl-2-phenylimidazole better.

As an imidazole type hardening accelerator, a commercial item can be used, for example, "P200-H50" by Mitsubishi Chemical Corporation etc. are mentioned.

Examples of guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dicyandiamide, and dicyandiamide. Methylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl -1,5,7-Triazabicyclo[4.4.0]dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecane yl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, etc., Dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene are preferred.

Examples of metal-based hardening accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organocobalt complexes such as cobalt(II) acetylacetone and cobalt(III) acetylacetone, organic copper complexes such as copper(II) acetylacetone, and zinc(II) Organic zinc complexes such as acetylacetone, organic iron complexes such as iron(III) acetylacetone, organic nickel complexes such as nickel(II) acetylacetone, organic manganese complexes such as manganese(II) acetylacetone, etc. As an organometallic salt, zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, etc. are mentioned, for example.

The content of the component (F) is preferably 0.001 mass % or more, preferably 0.001 mass % or more, when the non-volatile matter in the photosensitive resin composition is taken as 100 mass % from the viewpoint that the desired effect of the present invention can be remarkably obtained. 0.005 mass % or more, more preferably 0.01 mass % or more, preferably 0.15 mass % or less, preferably 0.1 mass % or less, more preferably 0.05 mass % or less.

<(G) Solvent> The (G) solvent as an optional component may be further contained in the photosensitive resin composition. Paint viscosity can be adjusted by containing (G) solvent. As (G) solvent, an organic solvent is mentioned.

Examples of the solvent (G) include ketones such as ethyl methyl ketone (MEK) and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; and diethylene glycol monoethyl ether ethyl ether. Ester (EDGAc), methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethyl ether Glycol ethers such as glycol monoethyl ether; ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, ethyl diethylene glycol acetate and other esters; octane, Aliphatic hydrocarbons such as decane; petroleum-based solvents such as petroleum ether, naphtha, hydrogenated naphtha, solvent naphtha, etc. These can be used individually by 1 type or in combination of 2 or more types. The content in the case of using the solvent can be appropriately adjusted from the viewpoint of the coatability of the photosensitive resin composition.

<(H) Other additives> The photosensitive resin composition may further contain (H) other additives to the extent that the object of the present invention is not inhibited. As (H) other additives, for example, reactive diluents, thermoplastic resins, organic fillers, melamine, fine particles such as organobentonite, phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide can be added. , carbon black, naphthalene black and other colorants, hydroquinone, phenothiazine, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol and other polymerization inhibitors, Benton, Mongolia Tackifiers such as destoner, silicone-based, fluorine-based, vinyl resin-based defoamer, brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphorus-based compounds, aromatic condensed phosphoric acid esters, containing Various additives such as flame retardants such as halogen condensed phosphoric acid esters, phenol-based curing agents, and thermosetting resins such as cyanate ester-based curing agents.

In the photosensitive resin composition, the above-mentioned components (A) to (E) can be mixed as essential components, and the above-mentioned components (F) to (H) can be appropriately mixed as optional components. It is produced by kneading or stirring by kneading means such as bead mills and sand mills, or by means of mixing means such as super mixers and planetary mixers.

<Physical properties and applications of photosensitive resin composition> The cured product obtained by photocuring the photosensitive resin composition exhibits the characteristics of excellent developability. Therefore, residue formation in the unexposed portion can be suppressed. The residue evaluation of the unexposed part can be evaluated according to the method described in the Example mentioned later.

The cured product obtained by photocuring the photosensitive resin composition exhibits the characteristics of excellent developability. Therefore, excellent properties of BP (Breakpoint) are exhibited. BP means the time until the unexposed part is dissolved by the developing solution until the dissolved resin disappears. BP is preferably 150 seconds or less, preferably 140 seconds or less, and more preferably 130 seconds or less. The lower limit is preferably 30 seconds or more, preferably 40 seconds or more, and more preferably 50 seconds or more. The measurement of BP can be carried out according to the method described in the following examples.

The cured product obtained by photocuring the photosensitive resin composition exhibits the characteristic of excellent developability. Therefore, residues, unstripped vias (Via), and unstripped or buried lines and spaces (L/S) can be formed. The minimum through-pipe diameter of the through-pipe is preferably 60 μm or less, preferably 55 μm or less, and more preferably 50 μm or less. The lower limit is not particularly limited, and may be 1 μm or more. The measurement of the minimum through-pipe diameter can be measured according to the method described in the Example mentioned later.

The cured product obtained by photocuring the photosensitive resin composition exhibits a characteristic of excellent dielectric constant. Therefore, an insulating layer and a solder resist having a low dielectric constant can be obtained. The dielectric constant is preferably 4.0 or less, preferably 3.5 or less, and more preferably 3.3 or less. The lower limit is not particularly limited, but may be 0.1 or more. The dielectric constant can be measured according to the method described in the examples described later.

The cured product obtained by photocuring the photosensitive resin composition exhibits the characteristic of excellent dielectric loss tangent. Therefore, an insulating layer and a solder resist having a low dielectric loss tangent can be obtained. The dielectric loss tangent is preferably less than 0.013, preferably 0.012 or less, and more preferably 0.011 or less. The lower limit is not particularly limited, but may be 0.0001 or more. The dielectric loss tangent can be measured according to the method described in the examples described later.

The photosensitive resin composition exhibits excellent flexibility. Therefore, the photosensitive resin composition can suppress the formation of cracks even when stress is input.

The cured product obtained by photocuring the photosensitive resin composition generally exhibits a high glass transition temperature. Therefore, an insulating layer and a solder resist having a high glass transition temperature and excellent heat resistance can be obtained. The glass transition temperature is preferably 140°C or higher, preferably 145°C or higher, and more preferably 150°C or higher. The upper limit is not particularly limited, but may be 300°C or lower. The measurement of glass transition temperature can be measured according to the method described in the Example mentioned later.

The application of the photosensitive resin composition of the present invention is not particularly limited, but can be used for photosensitive films, insulating resin sheets such as prepregs, circuit boards (for laminates, multilayer printed wiring boards, etc.), solder resists, Photosensitive resin compositions are required for a wide range of applications, such as underfill materials, mold bonding materials, semiconductor sealing materials, hole filling resins, and component mounting resins. Among them, photosensitive resin compositions for insulating layers of printed wiring boards (printed wiring boards with cured products of photosensitive resin compositions as insulating layers), photosensitive resin compositions for interlayer insulating layers (photosensitive resin compositions for insulating layers) The cured product of the composition is used as a printed wiring board for an interlayer insulating layer), a photosensitive resin composition for plating formation (a printed wiring board with plating formed on the cured product of the photosensitive resin composition), and a photosensitive resin for soldering resists A photosensitive resin composition (printed wiring board using the cured product of the photosensitive resin composition as a solder resist) is applied.

[Photosensitive film] The photosensitive film has a support, and a photosensitive resin composition layer containing the photosensitive resin composition of the present invention provided on the support.

Examples of the support include polyethylene terephthalate films, polyethylene naphthalate films, polypropylene films, polyethylene films, polyvinyl alcohol films, triacetate films, and the like. Preferred are polyethylene terephthalate films.

Examples of the sold support include "AlfoneMA-410" and "E-200C" manufactured by Oji Paper Co., Ltd., polypropylene films manufactured by Shin-Etsu Film Co., Ltd., and "PS-25" manufactured by Teijin Corporation. Polyethylene terephthalate films such as PS series, etc., etc., are not limited to these. Since these supports can be easily removed, it is preferable to apply a release agent such as a silicone coating agent to the surface. The thickness of the support is preferably in the range of 5 μm to 50 μm, and preferably in the range of 10 μm to 25 μm. When the thickness is set to 5 μm or more, breakage of the support when the support is peeled off before development can be suppressed, and when the thickness is set to 50 μm or less, the resolution during exposure from the support can be improved. Also, the support of the low silver point (Fisheye) is better. The silver dots indicate that foreign matter, undissolved matter, oxidatively degraded matter, etc. are doped in the thin film when the material is thermally melted, kneaded and pressed out, and the thin film is produced by biaxial stretching, casting, or the like. .

Moreover, in order to reduce light scattering at the time of exposure by active energy rays, such as an ultraviolet-ray, it is preferable that a support system is excellent in transparency. Specifically, it is preferable that the haze (haze standardized according to JISK6714) as a transparency index is 0.1 to 5 for the support. In addition, the photosensitive resin composition layer may be protected by a protective film.

By protecting the photosensitive resin composition layer side of the photosensitive film with a protective film, it is possible to prevent adhesion of dirt or the like to the surface of the photosensitive resin composition layer or to prevent scratches. As the protective film, a film made of the same material as the above-mentioned support can be used. The thickness of the protective film is not particularly limited, but is preferably in the range of 1 μm to 40 μm, preferably in the range of 5 μm to 30 μm, and more preferably in the range of 10 μm to 30 μm. When the thickness is set to 1 μm or more, the handleability of the protective film can be improved, and when the thickness is set to 40 μm or less, the low cost tends to be improved. In addition, the adhesive force of the protective film with respect to the photosensitive resin composition layer and the support is preferably the one with the smaller adhesive force between the photosensitive resin composition layer and the protective film.

The thickness of the photosensitive resin composition layer is preferably 10 μm or more, more preferably 15 μm or more, and more preferably 20 μm or more, from the viewpoint of improving handleability and suppressing the decrease in sensitivity and resolution inside the photosensitive resin composition layer. , preferably 30 μm or less, preferably 28 μm or less, more preferably 25 μm or less.

The photosensitive film is prepared from, for example, a resin varnish prepared by dissolving a photosensitive resin composition in an organic solvent, and the resin varnish is applied to a support using die coating or the like, and further dried to form a photosensitive resin composition. layers can be fabricated. As an organic solvent, the same thing as said (G) component can be used.

As a coating method of resin paint, for example, gravure coating method, microgravure coating method, reverse coating method, contact reverse coating method, die coating method, slot die method, tear coating method, Corner wheel coating method, blade coating method, roll coating method, blade coating method, curtain coating method, gravure coating method, slot method, spray coating method, dip coating method, etc.

Resin paint can be applied several times, or can be applied once, or combined with a plurality of different methods. Among them, a die coating method with excellent uniform coating properties is also preferred. In addition, in order to avoid the contamination of foreign matter, etc., it is preferable that the coating step can be carried out in an environment such as a clean room where the occurrence of foreign matter is small.

The drying temperature varies depending on the curability of the photosensitive resin composition and the amount of the (G) component in the resin coating, but it can be performed at 80°C to 120°C. However, the maximum drying temperature is preferably 105°C or higher, more preferably 110°C or higher, from the viewpoint of obtaining a cured product excellent in undercut resistance. The lower limit of the maximum temperature is not particularly limited, but is preferably 135°C or lower, more preferably 130°C or lower.

Although the drying time may vary depending on the curability of the photosensitive resin composition and the amount of the (G) component in the resin coating, it is preferably 6 minutes or more, preferably 30 minutes or less, more preferably 20 minutes or less. Here, the "drying time" means the time from when the drying temperature reaches 80°C.

The residual amount of the (G) component in the photosensitive resin composition layer is preferably 5 mass % or less, and more preferably 2 mass % or less with respect to the total amount of the photosensitive resin composition layer. The manufacturer can set the optimum drying conditions through simple experiments.

Since a photosensitive film contains the photosensitive resin composition layer which has the photosensitive resin composition of this invention, it shows the characteristic which is excellent in flexibility. For example, after the photosensitive film is rolled into a 3-inch core, the photosensitive film is cut with a hob. In this case, the generation of cracks on the photosensitive film can be suppressed.

[Printed Wiring Board] The printed wiring board of this invention contains the insulating layer formed with the hardened|cured material of the photosensitive resin composition of this invention. The insulating layer is preferably used as a solder resist or an interlayer insulating layer.

In detail, the printed wiring board of this invention can be manufactured using the said photosensitive film. An example in which the insulating layer is used as a solder resist will be described below.

<Coating and drying step> When the resin varnish containing the photosensitive resin composition is directly applied on the circuit board, the photosensitive resin composition layer is formed on the circuit board by drying and exerting the (G) component.

As a circuit board, a glass epoxy board, a metal board, a polyester board, a polyimide board, a BT resin board, a thermosetting polyphenylene ether board etc. are mentioned, for example. In addition, the term "circuit board" as used herein means a board in which a patterned conductor layer (circuit) is formed on one side or both sides of the above-mentioned support substrate. Also, for a multilayer printed wiring board in which conductor layers and insulating layers are alternately laminated, even a substrate on which patterned conductor layers (circuits) are formed on one or both sides of the outermost layer of the multilayer printed wiring board , is also included in the so-called circuit board. In addition, the surface of the conductor layer may be subjected to preliminary roughening treatment by blackening treatment, copper etching, or the like.

As a coating method, the full-surface printing by the screen printing method is generally used in many cases, but any method can be used as long as the coating method can be uniformly coated by other methods. For example, a spray coating method, a hot melt coating method, a bar coating method, an applicator method, a blade coating method, a blade coating method, an air blade coating method, a curtain flow coating method, a roll coating method, a gravure coating method, an offset printing method can be used Printing method, dip coating method, brush coating, all other general coating methods. After coating, it can be dried by a hot-air oven or a far-infrared oven as necessary. The drying conditions are preferably performed at 80°C to 120°C for 3 minutes to 13 minutes. In this way, the photosensitive composition layer can be formed on the circuit board.

<Lamination step> On the other hand, when a photosensitive film is used, the photosensitive resin composition layer side is laminated on one side or both sides of a circuit board using a vacuum laminate. In the lamination step, when the photosensitive film has a protective film, after removing the protective film, the photosensitive film and the circuit board are preheated as necessary, and the photosensitive resin composition layer is pressed against the circuit board while being pressurized and heated. superior. For the photosensitive film, the method of laminating it on a circuit board under reduced pressure by a vacuum lamination method is a preferable usage.

Although the conditions of the lamination step are not particularly limited, for example, the pressing temperature (lamination temperature) is preferably set at 70°C to 140°C, and the pressing pressure is preferably set at 1kgf/cm ² to 11kgf/cm ² (9.8 ×10 ⁴ N/m ² to 107.9 × 10 ⁴ N/m ² ), the pressing time is preferably set at 5 seconds to 300 seconds, and the air pressure is set at a reduced pressure of 20 mmHg (26.7 hPa) or less for lamination. whichever is better. Also, the lamination step may be batchwise or continuous using rolls. For vacuum lamination, commercially available vacuum laminates can be used. Examples of the commercially available vacuum laminates include vacuum applicators manufactured by Nikkomaterials, vacuum press laminates manufactured by Meiki Co., Ltd., roll drying coating manufactured by Hitachi Industries, Ltd., and vacuum laminates manufactured by HitachiAIC Corporation.

<Exposure step> After the photosensitive resin composition layer is provided on the circuit board by the coating and drying step or the lamination step, the photosensitive resin composition layer is then irradiated with actinic rays by patterning with a mask to irradiate a predetermined portion of the photosensitive resin composition layer. The exposure step of photohardening the photosensitive resin composition layer of the irradiation part. Examples of actinic rays include ultraviolet rays, visible rays, electron beams, X-rays, and the like, and ultraviolet rays are particularly preferred. The irradiation dose of ultraviolet rays is about 10mJ/cm ² to 1000mJ/cm ² . The exposure method includes a contact exposure method in which a mask pattern is adhered to a printed wiring board, and a non-contact exposure method in which the mask pattern is not adhered and exposed using parallel light, but any of them can be used. Moreover, when a support exists in the photosensitive resin composition layer, exposure may be performed from a support, and exposure may be performed after peeling a support.

The solder resist can have excellent developability by using the photosensitive resin composition of the present invention. Therefore, as an exposure pattern in a mask pattern, for example, a loop width (line; L) and a ratio (L/S) of the width (space; S) between loops of 100 μm/100 μm or less (that is, a wiring interval of 200 μm) can be used. Below), L/S=80μm/80μm or less (wiring interval 160μm or less), L/S=70μm/70μm or less (wiring interval 140μm or less), L/S=60μm/60μm or less (wiring interval 120μm or less) . In addition, it is not necessary to use the same interval in the whole circuit board.

The solder resist can have excellent developability by using the photosensitive resin composition of the present invention. Therefore, the through-pipe diameter is preferably 100 μm or less, preferably 90 μm or less, and more preferably 80 μm or less. The lower limit is not particularly limited, but may be 1 μm or more, 10 μm or more, and the like.

<Development procedure> After the exposure step, if there is a support on the photosensitive resin composition layer, after removing the support, wet development or dry development is used to remove the uncured part (unexposed part) and after development Patterns can be formed.

In the above wet development, as the developer, a safe and stable developer with good operability such as an alkaline aqueous solution, an aqueous developer, and an organic solvent can be used, and among them, the development step is preferably performed by an alkaline aqueous solution. Moreover, as a developing method, well-known methods, such as spraying, agitating dipping, brushing, and blade coating, can be suitably used.

Examples of the alkaline aqueous solution used as the developing solution include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, carbonates or bicarbonates such as sodium carbonate and sodium hydrogencarbonate, sodium phosphate, Aqueous solutions of alkali metal phosphates such as potassium phosphate, alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate, or aqueous solutions of organic bases that do not contain metal ions such as tetraalkylammonium hydroxide, which do not contain metal ions and are suitable for semiconductors An aqueous solution of tetramethylammonium hydroxide (TMAH) is preferred from the viewpoint of no effect on the wafer.

To improve the developing effect in these alkaline aqueous solutions, surfactants and antifoaming agents can be added to the developing solution. The pH of the above-mentioned alkaline aqueous solution is preferably in the range of 8 to 12, and preferably in the range of 9 to 11, for example. Moreover, it is preferable that the alkali concentration of the said alkaline aqueous solution is 0.1 mass % - 10 mass %. The temperature of the above-mentioned alkaline aqueous solution can be appropriately selected according to the developability of the photosensitive resin composition layer, and is preferably 20°C to 50°C.

The organic solvent used as the developer is, for example, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropanol, butyl alcohol, and diethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether.

The concentration of the organic solvent is preferably from 2 mass % to 90 mass % with respect to the total amount of the developing solution. In addition, the temperature of such an organic solvent can be adjusted according to the developability. And such an organic solvent can be used individually or in combination of 2 or more types. Examples of organic solvent-based developing solutions to be used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, γ-butyrolactone.

For pattern formation, if necessary, two or more of the above-mentioned developing methods may be used in combination. The imaging methods include dipping, paddle stirring, spraying, high-pressure spraying, brushing, slapping, etc. The high-pressure spraying method is preferable because it can improve the resolution. The spray pressure when the spray method is used is preferably 0.05 MPa to 0.3 MPa.

<Thermal hardening (post-baking) step> After the image development step is completed, a thermal hardening (post-baking) step is performed to form a solder resist. As a post-baking process, the ultraviolet irradiation process by a high pressure mercury lamp, the heating process using a clean oven, etc. are mentioned. When irradiating ultraviolet rays, the irradiation amount can be adjusted as necessary, for example, it can be irradiated with an irradiation amount of about 0.05 J/cm ² to 10 J/cm ² . In addition, the heating conditions may be appropriately selected according to the type and content of the resin components in the photosensitive resin composition. ℃ ~ 200℃ for 30 minutes ~ 120 minutes range for selection.

<Other steps> The printed wiring board may further include a hole opening step and a stain removal step after the solder resist is formed. These steps can be implemented in accordance with various methods known to those used in the manufacture of printed wiring boards.

After the solder resist is formed, as desired, the solder resist formed on the circuit board is subjected to a drilling step to form through holes and through holes. For example, the hole opening step can be performed by known methods such as drill, laser, plasma, etc., and these methods can also be combined as necessary. good.

The stain removal step is a step of performing stain removal treatment. Resin residues (smudges) generally adhere to the inside of the openings formed in the drilling step. This stain is a cause of poor electrical connection, so in this step, a stain removal process (smudge removal process) is performed.

The stain removal treatment can be performed by dry stain removal, wet stain removal, or a combination of these.

As a dry desmearing process, the desmutting process using a plasma etc. are mentioned, for example. The desmearing treatment using plasma can be performed using a commercially available plasma desmearing treatment apparatus. Among the commercially available plasma desmear treatment apparatuses, the microwave plasma apparatus manufactured by Nissin Co., Ltd. and the atmospheric pressure plasma etching apparatus manufactured by Sekisui Chemical Industry Co., Ltd. are mentioned as preferable examples for the manufacturing application of printed wiring boards. Wait.

As a wet stain removal process, the stain removal process using an oxidizing agent solution, etc. are mentioned, for example. When the stain removal treatment is performed using the oxidizing agent solution, it is preferable to perform the swelling treatment with the swelling liquid, the oxidation treatment with the oxidizing agent solution, and the neutralization treatment with the neutralizing liquid in this order. As swelling liquid, "Swelling Dip Security P", "Swelling Dip Securigant SBU" by Atotech Japan company, etc. are mentioned, for example. The swelling treatment is preferably performed by immersing the substrate on which the through holes and the like are formed in a swelling liquid heated at 60° C. to 80° C. for 5 minutes to 10 minutes. The oxidizing agent solution is preferably an alkaline permanganic acid aqueous solution, and examples thereof include a solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous sodium hydroxide solution. The oxidation treatment by the oxidizing agent solution is preferably performed by immersing the substrate after the swelling treatment in the oxidizing agent solution heated at 60° C. to 80° C. for 10 minutes to 30 minutes. As a sales item of the alkaline permanganic acid aqueous solution, "Concent rate compact CP", "Dosing Solution Security P" by Atotech Japan company, etc. are mentioned, for example. The neutralization treatment by the neutralization solution is preferably performed by immersing the substrate after the oxidation treatment in the neutralization solution at 30° C. to 50° C. for 3 minutes to 10 minutes. As a neutralization liquid, an acidic aqueous solution is preferable, and "Reduction Solution Security P" by Atotech Japan is mentioned as a commercial item, for example.

When the dry desmearing treatment and the wet desmearing treatment are combined, the dry desmearing treatment may be performed first, or the wet desmearing treatment may be performed first.

When the insulating layer is used as the interlayer insulating layer, the same as that of the solder resist can be performed, and the hole opening step, the stain removal step, and the plating step can also be performed after the thermal hardening step.

The plating step is a step of forming a conductor layer on the insulating layer. The conductor layer may be formed by combining electroless plating and electrolytic plating, or a plating resist having an opposite pattern to the conductor layer may be formed, and the conductor layer may be formed only by electroless plating. As a method of forming a pattern after that, for example, a subtractive method, a semi-additive method or the like known to those skilled in the art can be used.

[semiconductor device] The semiconductor device of the present invention includes a printed wiring board. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

Examples of semiconductor devices include various semiconductor devices provided in electrical appliances (eg, computers, cell phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trains, ships, aircraft, etc.).

The semiconductor device of the present invention can be manufactured by mounting parts (semiconductor chips) on the conductive portions of the printed wiring board. The so-called "conduction place" means "the place where the electrical signal is transmitted in the printed wiring board", and here it can be either the surface or the embedded place. In addition, the semiconductor wafer is not particularly limited as long as it is an electric circuit element using a semiconductor as a material.

The mounting method of the semiconductor chip in the manufacture of the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip can effectively function, and specific examples include a wire bonding mounting method, a flip chip mounting method, Mounting method of bump laminate layer (BBUL), mounting method by anisotropic conductive film (ACF), mounting method by non-conductive film (NCF), etc. Among them, the so-called "mounting method by the bumpless laminate layer (BBUL)" means "the mounting method of directly inserting the semiconductor chip into the concave portion of the printed wiring board, and connecting the semiconductor chip and the wiring on the printed wiring board". [Example]

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In addition, in the following description, unless otherwise specified, those representing "part" and "%" represent the meaning of "part by mass" and "% by mass", respectively. In addition, the epoxy equivalent of (D)component is measured based on JISK7236, and the softening point is measured based on JISK7234.

(Synthesis Example 1: Synthesis of Resin (A-1)) 325 parts of a naphthol aralkyl type epoxy resin represented by the following formula (1) (epoxy equivalent 325 g/eq., "ESN-475V" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.) was placed in a gas inlet pipe, To the flask of the stirring device, the cooling tube and the thermometer, 340 parts of carbitol acetate were added, and after heating and dissolving, 0.46 parts of hydroquinone and 1 part of triphenylphosphine were added. The mixture was heated at 95 to 105° C., 72 parts of acrylic acid was gradually added dropwise, and the reaction was carried out for 16 hours. This reaction product was cooled to 80-90 degreeC, 80 parts of tetrahydrophthalic anhydrides were added, it was made to react for 8 hours, and it was cooled. In this way, a resin solution having an acid value of 60 mgKOH/g of solid content (non-volatile content of 70%, hereinafter abbreviated as "resin solution (A-1)") can be obtained.

但，Z為縮水甘油基(G)或碳數1～8的烴基(R ⁶)，R ⁶/G的比率為0.05～2.0。又，n表示平均值的1至6的數。

However, Z is a glycidyl group (G) or a hydrocarbon group (R ⁶ ) having 1 to 8 carbon atoms, and the ratio of R ⁶ /G is 0.05 to 2.0. In addition, n represents the number of 1 to 6 of the average value.

It was confirmed that the resin solution (A-1) contained at least a resin having a structure represented by the following formula (2).

(Synthesis Example 2: Synthesis of Maleimide Compound (E-1)) 2,6-dimethylaniline was placed in a 300 mL flask equipped with a thermometer, a cooling tube, and a Dean Stark trap. 12.1 g (0.1 mol), 68.0 g (0.35 mol) of α,α'-dihydroxy-1,3-diisopropylbenzene, 100 g of xylene, and 20 g of activated clay were heated to 120° C. while stirring. Furthermore, the distilled water was removed with a Dean Stark tube, and the temperature was raised to 210° C., and the reaction was performed for 3 hours. Then, it cooled to 140 degreeC, 36.4 g (0.3 mol) of 2, 6- dimethylaniline were charged, and it heated up to 220 degreeC, and performed a reaction for 3 hours. After the reaction, the air was cooled to 100°C, diluted with 75 g of toluene, filtered to remove activated clay, and the solvent and unreacted materials were distilled off under reduced pressure to obtain an intermediate represented by the following formula (E-1). 91.0 g of amine compounds (n is an integer of 1 or more and 10 or less). The amine equivalent weight was 296, and the softening point was 70°C.

Next, 32.9 g (0.32 mol) of maleic anhydride and 200 g of toluene were placed in a 500 mL flask equipped with a thermometer, a cooling tube, a Dean Stark trap, and a stirrer, followed by stirring at room temperature. A mixed solution of 91 g of the intermediate amine compound represented by the formula (E-1) and 40 g of DMF was added dropwise over 1 hour. After the dropwise addition, the reaction was further performed at room temperature for 2 hours. 9.3 g of p-toluenesulfonic acid monohydrate was added, the reaction solution was heated and the azeotropic water and toluene were cooled and separated under reflux, and then only toluene was returned to the system to carry out a dehydration reaction for 8 hours. After air cooling to room temperature, the brown solution was dissolved in 150 g of ethyl acetate by concentration under reduced pressure, washed three times with 40 g of ion-exchanged water, washed three times with 40 g of 2% aqueous sodium bicarbonate solution, and added sodium sulfate. After drying, the reaction product obtained by concentration under reduced pressure was vacuum-dried at 80° C. for 4 hours to obtain 103.0 g of a product containing the maleimide compound (C-1). From the FD-MS spectrum of the maleimide compound (C-1), the absorption peaks of M+=560, 7, and 876 were confirmed, so the absorption peaks correspond to the cases where n is 0, 1, and 2. And the value of the repeating unit number n in the indane skeleton portion of the maleimide compound (C-1) (based on the number average molecular weight) was obtained by GPC, where n=1.47, molecular weight distribution (Mw/Mn)= 1.81. Moreover, in the said maleimide E-1 total amount 100 area %, the said maleimide whose average repeating unit number n is 0 is 26.5 area %.

<Examples 1 to 11, Comparative Examples 1 to 6> Each component was blended at the blending ratio shown in the following table, and a resin coating was prepared using a high-speed rotary mixer.

Next, a PET film (“Lumirer T6AM” manufactured by Toray Co., Ltd., thickness 38 μm, softening point 130° C.) was prepared as a support. The PET film is uniformly coated with resin paint by a mold, so that the thickness of the photosensitive resin composition layer after drying is 25 μm, and by drying at 80° C. to 110° C. for 6.5 minutes, the photosensitive resin on the PET film is obtained. The photosensitive film of the composition layer.

Furthermore, a PET film (“Lumirer T6AM” manufactured by Toray Co., Ltd.) subjected to mold release treatment with an alkyd resin-based mold release agent (“AL-5” manufactured by Lintec Co., Ltd., thickness 38 μm, softening point 130° C., “mold release PET film”) was prepared. ). The mold release PET film was uniformly coated with a resin paint so that the thickness of the dried photosensitive resin composition layer was 25 μm, and by drying at 80° C. to 110° C. for 6.5 minutes, the mold release PET film was obtained. The photosensitive film of the photosensitive resin composition layer.

＜Evaluation of flexibility＞ The photosensitive film having the photosensitive resin composition layer on the PET film was wound up with a 3-inch core, and it was confirmed whether the photosensitive film had cracks. Moreover, when the photosensitive film was cut with a hob (manufactured by DAHLE), it was confirmed whether or not the photosensitive film was cracked. If no cracks occurred in these operations, it was evaluated as "0", and if cracks were confirmed, it was evaluated as "x".

<Evaluation of developability> (Formation of laminate for evaluation) The copper layer of the glass epoxy substrate (copper-clad laminate) on which the circuit patterned as a copper layer with a thickness of 18 μm was formed was treated with a surface treatment agent (CZ8100, manufactured by MEC Company) containing an organic acid to give roughening . Next, the photosensitive resin composition layer of the photosensitive film with the photosensitive resin composition layer is placed on the PET film in contact with the surface of the copper circuit, and a vacuum laminate (VP160 manufactured by Nikkomaterials) is used for lamination. The laminate, the photosensitive resin composition layer, and the support are laminated in this order to form a laminate. Crimping conditions were an evacuation time of 30 seconds, a crimping temperature of 80° C., a crimping pressure of 0.7 MPa, and a pressurization time of 30 seconds. The laminate was left to stand at room temperature for more than 30 minutes, and the support of the laminate was exposed to ultraviolet rays using a pattern forming apparatus of a circular hole pattern. Use quartz glass mask to draw exposure pattern as opening: 50μm/60μm/70μm/80μm/90μm/100μm round hole, L/S (line/space): 50μm/50μm, 60μm/60μm, 70μm/70μm, 80μm/80μm, 90μm/90μm, 100μm/100μm line and space, 1cm×2cm square. After standing at room temperature for 30 minutes, the support was peeled off from the aforementioned laminate.

(residue of unexposed part) On the whole surface of the photosensitive resin composition layer on the laminate plate from which the support was peeled off, a 30°C 1 mass % sodium carbonate aqueous solution as a developer was spray-developed at a spray pressure of 0.2 MPa. The unexposed part of the 1 cm x 2 cm portion of the laminate after spray development was visually observed and evaluated based on the following criteria. ○: Resin does not remain in the unexposed part. ×: The resin can be visually confirmed or a film reduction occurs.

(Assessment of BP (Breakpoint)) While visually observing the unexposed portion of the 1 cm×2 cm portion of the laminate, a 30° C. 1 mass % sodium carbonate aqueous solution as a developer was spray-developed at a spray pressure of 0.2 MPa. The time (seconds) from the start of spraying to the point in time when the resin remaining on the substrate disappeared was recorded.

(Evaluation of resolution and minimum diameter) Next, the formed through-pipe and L/S were observed by SEM (magnification of 1000 times), and the minimum through-pipe diameter with no residue and peeling was measured, and the L/S shape at any three points was measured, and evaluated according to the following criteria. However, with regard to the minimum through-pipe diameter, if there is residue or peeling, it is evaluated as "X". If the minimum L/S exceeds 60μm/60μm, it is evaluated as "X". ○: Three-point L/S was observed, and there was no peeling and embedding between all L/S. ×: Three-point L/S was observed, and resin embedding or peeling was observed between any L/S.

<Measurement of dielectric constant, dielectric loss tangent, and glass transition temperature> (formation of hardened product for evaluation) On the photosensitive resin composition layer of the photosensitive film having the photosensitive resin composition layer on the mold release PET film 1 J/cm ² of ultraviolet light was irradiated, and further heat treatment was performed at 190° C. for 90 minutes to form a cured product. Then, the support body was peeled off, and the hardened|cured material A for evaluation was obtained.

(Determination of dielectric constant and dielectric loss tangent) The cured product A for evaluation was cut into a test piece having a width of 2 mm and a length of 80 mm to obtain a cured product B for evaluation. For each cured product B for evaluation, using "HP8362B" manufactured by Agilent Technologies, the value of the dielectric constant (Dk value) and The value of the dielectric loss tangent (Df value). Three test pieces (N=3) were measured, and the average was calculated.

(Measurement of glass transition temperature) The cured product A for evaluation was cut into a test piece having a width of about 5 mm and a length of about 15 mm, and thermomechanical analysis was performed by a tensile weighting method using a dynamic viscoelasticity measuring apparatus (EXSTAR6000, manufactured by SII Nanotech Co., Ltd.). After attaching the test piece to the aforementioned apparatus, the measurement was performed under the measurement conditions of a load of 200 mN and a temperature increase rate of 2°C/min. The absorption peak top of the obtained tanδ was calculated as a glass transition temperature (°C).

Abbreviations and the like in the table are as follows. (A) Component: ・CCR-1179: Cresol novolak F-type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 99 mgKOH/g, non-volatile content concentration 70%) ・A-1: synthesized in Synthesis Example 1 Resin solution (A-1) (B) component: ・SC2050: 100 parts by mass of fused silica (average particle size manufactured by Admatechs: 0.5 μm, specific surface area: 5.9 m ² /g) with aminosilane (Shin-Etsu Chemical Co., Ltd.) Company made, KBM573) 0.5 parts by mass surface-treated (C) Component: ・Irgacure TPO: bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide, manufactured by BASF Corporation) ・Irgacure OXE -01: 1,2-Octanedione-1-[4-(phenylthio)-2-(O-benzyl oxime)] (manufactured by BASF) (D) Component: ・HP4032: Naphthalene type Epoxy resin (manufactured by DIC Corporation, epoxy equivalent 144 g/eq., softening point less than 30°C) ・ELM-434VL: N,N,N',N'-4(oxiran-2-ylmethyl) )-4,4'-methylenediphenylamine (glycidylamine type epoxy resin, manufactured by Sumitomo Chemical Co., Ltd., epoxy equivalent 114g/eq., softening point less than 30℃) ・NC3000L: Biphenyl type ring Oxygen resin (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 271 g/eq., softening point 53°C) ・NC3000H: Biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 272 g/eq., softening point 70°C) ・1031S: 4-hydroxyphenylethane type epoxy resin (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 224g/eq., softening point 92°C) (E) Component: ・BMI-689: Malein Imine resin, dimer diamine type bismaleimide (manufactured by Digigner Moleculars) ・E-1: Maleimide compound (E-1) synthesized in Synthesis Example 2 ・BMI-5100: Maleimide resin, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimidediphenylmethanebismaleimide , Digigner Moleculars Co., Ltd. ・MIR3000: Maleimide resin, manufactured by Nippon Kayaku Co., Ltd. ・EXB-8151-62T: Active ester resin containing naphthalene structure, manufactured by DIC Corporation ・PC1300-02-65MA: Active ester containing naphthalene structure Resin, manufactured by Airwater Corporation ・DAD: Vinyl resin: Diallyl 2,2'-biphenyldicarboxylate (manufactured by Nikkei Techno Fine Chemistry Co., Ltd.) ・OPE-2St: Vinyl resin (vinylbenzene Methyl-modified polyphenylene ether, manufactured by Mitsubishi Gas Chemical Co., Ltd.) (F) Component ・1B2PZ: 2-phenyl-1-benzyl-1H-imidazole, manufactured by Shikoku Chemical Co., Ltd. (G) Ingredients: ・EDGAc: Diethylene glycol monoethyl ether acetate ・MEK: Methyl ethyl ketone (H) Ingredients: ・DOG-A: Dioxane glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. ・TD -2090-60M: Novolak-type phenolic resin, manufactured by DIC Corporation

In each Example, even in the case where the components (F) to (H) were not contained, the same results as those of the above-mentioned Examples were obtained, although the degree was inferior.

Claims (12)

A photosensitive resin composition comprising: (A) Resins containing ethylenically unsaturated groups and carboxyl groups, (B) Inorganic fillers, (C) photopolymerization initiator, (D) epoxy resin, and (E) At least one resin selected from the group consisting of active ester resins, maleimide resins, and vinyl resins, wherein the component (D) contains (D-1) a softening point of less than 30°C and an epoxy equivalent of 150 g/eq . The following epoxy resin and (D-2) the epoxy resin whose softening point is 30 degreeC or more and 59 degreeC or less. As in the photosensitive resin composition of claim 1, the content of the component (D-1) when the nonvolatile matter in the photosensitive resin composition is taken as 100% by mass is set as D1, and the content of the component (D-2) in the D2/D1 is 0.5 or more and 2.5 or less, when the content when the nonvolatile matter in the photosensitive resin composition is set as 100 mass % is set as D2. The photosensitive resin composition according to claim 1, wherein the content of the component (D-1) is 90% by mass or less when the entirety of the component (D) is taken as 100% by mass. The photosensitive resin composition of claim 1, wherein the content of the component (B) is 60 mass % or more when the nonvolatile matter in the photosensitive resin composition is taken as 100 mass %. The photosensitive resin composition according to claim 1, wherein the component (A) contains (A-1) a resin containing a naphthalene skeleton. The photosensitive resin composition according to claim 1, wherein the component (D-1) has a cyclic structure. The photosensitive resin composition according to claim 1, wherein the component (E) contains an active ester resin, and one or more resins selected from the group consisting of maleimide resins and vinyl resins. The photosensitive resin composition according to claim 1, wherein the breakpoint of the cured product of the photosensitive resin composition is 30 seconds or more and 150 seconds or less. A photosensitive film comprising a support, and a photosensitive resin composition layer containing the photosensitive resin composition according to any one of claims 1 to 8 provided on the support. A printed wiring board including an insulating layer formed of a cured product of the photosensitive resin composition according to any one of claims 1 to 8. The printed wiring board of claim 10, wherein the insulating layer is a solder resist. A semiconductor device comprising a printed wiring board as claimed in claim 10 or 11.