CN115542668A

CN115542668A - Photosensitive resin composition

Info

Publication number: CN115542668A
Application number: CN202210406833.2A
Authority: CN
Inventors: 海老泽和明
Original assignee: Tokyo Ohka Kogyo Co Ltd
Current assignee: Tokyo Ohka Kogyo Co Ltd
Priority date: 2021-06-14
Filing date: 2022-04-18
Publication date: 2022-12-30
Also published as: TW202307080A; JP2022190618A; KR20220167752A

Abstract

The invention provides a photosensitive resin composition capable of forming a patterned resin film with low dielectric loss tangent by applying a photolithography method, a photosensitive dry film having a photosensitive layer composed of the photosensitive resin composition, a method for manufacturing the photosensitive dry film, and a method for manufacturing the patterned resin film using the photosensitive resin composition. In the photosensitive resin composition containing a resin and a photosensitizer, at least 1 selected from the group consisting of polyimide resins, polyamic acids, polyamide resins, polybenzoxazole resins, and polybenzoxazole resin precursors, which contain structural units derived from diamine compounds having a specific structure of an aromatic group, is used as the resin.

Description

Photosensitive resin composition

Technical Field

The present invention relates to a photosensitive resin composition comprising at least 1 selected from the group consisting of a polyimide resin containing a structural unit derived from a diamine compound having a specific structure, a polyamic acid, a polyamide resin, a polybenzoxazole resin, and a polybenzoxazole resin precursor, and a photosensitizer, a photosensitive dry film having a photosensitive layer formed from the photosensitive resin composition, a method for producing the photosensitive dry film, and a method for producing a patterned resin film using the photosensitive resin composition.

Background

Polyimide resins, polyamide resins, and polybenzoxazole resins have excellent properties such as heat resistance, mechanical strength, insulation properties, and low dielectric constant, and thus have been widely used as insulating materials and protective materials for electric and electronic components such as electronic substrates of various devices, multilayer wiring boards, and the like.

In recent years, communication devices such as mobile phones have been increasing in frequency. Therefore, it is also required to make the insulating portion for insulating the metal wiring of the communication device high frequency.

Here, the higher the frequency, the more the transmission loss increases, and the higher the transmission loss, the more the electric signal attenuates. Therefore, resins such as polyimide resins, polyamide resins, and polybenzoxazole resins are required to have a further reduced dielectric loss tangent and a further reduced dielectric constant in a high frequency band in order to further reduce transmission loss in response to higher frequencies.

In addition, in manufacturing various elements or electronic substrates, it is often necessary to form an insulating material or a protective material only at desired positions. Therefore, a photosensitive resin composition which has a low dielectric loss tangent and a low dielectric constant and can form a patterned resin film has been demanded.

In view of the above-mentioned requirements, for example, as a photosensitive resin composition capable of forming a patterned polyimide resin film, there have been proposed a photosensitive resin composition comprising an aromatic polyamide resin having a specific structure derived from a structural unit of 4,4' -bis (4-aminophenoxy) biphenyl and a photopolymerization initiator (see patent document 1 and examples), a photosensitive resin composition comprising a polyimide precursor having an unsaturated double bond in a side chain and a photopolymerization initiator having an oxime structure showing a specific radical generation amount (see patent document 2).

Documents of the prior art

Patent document

Patent document 1: international publication No. 2019/044874

Patent document 2: international publication No. 2021/020463

Disclosure of Invention

Technical problem to be solved by the invention

When the photosensitive resin compositions described in patent documents 1 and 2 are used, a patterned polyimide resin film having a somewhat low dielectric loss tangent can be formed by applying a photolithography method. On the other hand, in the photosensitive resin composition described in patent document 1, it is desired to further reduce the dielectric loss tangent of the polyimide resin film to be formed.

The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a photosensitive resin composition capable of forming a patterned resin film having a low dielectric loss tangent by applying a photolithography method, a photosensitive dry film having a photosensitive layer formed of the photosensitive resin composition, a method for producing the photosensitive dry film, and a method for producing a patterned resin film using the photosensitive resin composition.

Solution for solving the above technical problem

The present inventors have found that the above-mentioned problems can be solved by using at least 1 selected from the group consisting of polyimide resins, polyamic acids, polyamide resins, polybenzoxazole resins, and polybenzoxazole resin precursors, which contain a structural unit derived from a diamine compound having a specific structure of an aromatic group, as a resin in a photosensitive resin composition containing the resin and a photosensitizer, and have completed the present invention. More specifically, the present invention provides the following aspects.

The invention of claim 1 is a photosensitive resin composition, comprising resin (A) and photosensitizer (C),

the resin (A) comprises

A polyimide resin (A-I) derived from a diamine compound and a tetracarboxylic acid dianhydride, and a polyamic acid (A-II),

Polyamide resin (A-III) derived from diamine compound and dicarboxylic acid compound or amide-forming derivative of dicarboxylic acid compound, and

at least 1 selected from the group consisting of polybenzoxazole resins (A-IV) and polybenzoxazole resin precursors (A-V) derived from a diamine compound which is an aromatic compound having 2 amino groups bonded to an aromatic ring and a hydroxyl group bonded to a carbon atom at a position adjacent to the carbon atom bonded to the amino group on the aromatic ring, a dicarboxylic acid compound or an amide-forming derivative of the dicarboxylic acid compound,

the resin (a) contains a structural unit derived from a compound represented by the following formula (A1).

[ solution 1]

(in the formula (A1), X is an organic group having 1 to 100 carbon atoms, and R ^a1 Is a hydroxyl, carboxyl or halogen atom, R ^a2 Is an aliphatic group having 1 to 20 carbon atoms, a hydroxyl group, a carboxyl group, a sulfonic acid group or a halogen atom, ar may be represented by R ^a2 Substituted phenyl, or may be substituted by R ^a2 A substituted naphthyl group, ma1 is an integer of 0 to 10 inclusive, ma2 is an integer of 0 to 7 inclusive, and ma3 is an integer of 1 to 10 inclusive. )

The invention of claim 2 is a photosensitive dry film, has a substrate film and formed on the surface of the substrate film of the photosensitive layer, the photosensitive layer is composed of the photosensitive resin composition of claim 1.

The invention of claim 3 is a photosensitive dry film manufacturing method, including the substrate film coated with the 1 st photosensitive resin composition to form a photosensitive layer.

The present invention in claim 4 is a method for producing a patterned resin film, comprising:

a laminating step of laminating a photosensitive layer comprising the photosensitive resin composition according to claim 1 on a substrate;

an exposure step of exposing the photosensitive layer by selectively irradiating the photosensitive layer with active light or radiation;

and a developing step of developing the exposed photosensitive layer to obtain a patterned resin film.

Effects of the invention

According to the present invention, it is possible to provide a photosensitive resin composition capable of forming a patterned resin film having a low dielectric loss tangent by applying a photolithography method, a photosensitive dry film having a photosensitive layer formed of the photosensitive resin composition, a method for producing the photosensitive dry film, and a method for producing a patterned resin film using the photosensitive resin composition.

Detailed Description

Photosensitive resin composition

The photosensitive resin composition comprises a resin (A) and a photosensitizer (C). The resin (a) includes at least 1 selected from the group consisting of a polyimide resin (a-I) and a polyamic acid (a-II) derived from a diamine compound and a tetracarboxylic dianhydride, a polyamide resin (a-III) derived from an amide-forming derivative of a diamine compound and a dicarboxylic acid compound or a dicarboxylic acid compound, and a polybenzoxazole resin (a-IV) and a polybenzoxazole resin precursor (a-V) derived from an aromatic compound having 2 amino groups bonded to an aromatic ring and having a hydroxyl group bonded to a carbon atom at a position adjacent to a carbon atom bonded to the amino group on the aromatic ring, a dicarboxylic acid compound, or an amide-forming derivative of a dicarboxylic acid compound.

[ solution 2]

(in the formula (A1), X is an organic group having 1 to 100 carbon atoms, and R ^a1 Is a hydroxyl group, a carboxyl group or a halogen atom, R ^a2 Is an aliphatic group having 1 to 20 carbon atoms, a hydroxyl group, a carboxyl group, a sulfonic acid group or a halogen atom, ar may be R ^a2 Substituted phenyl, or may be substituted by R ^a2 A substituted naphthyl group, ma1 is an integer of 0 to 10 inclusive, ma2 is an integer of 0 to 7 inclusive, and ma3 is an integer of 1 to 10 inclusive. )

By including the structural unit derived from the compound represented by the above formula (A1) in the resin (a), a resin film having a low dielectric loss tangent in a high frequency band can be formed.

The photosensitizer (C) is a component that imparts photosensitivity to the photosensitive resin composition. For example, in the case where the resin (a) has a polymerizable group or the photosensitive resin composition contains a compound having a polymerizable group, the photosensitizer (C) may be a so-called polymerization initiator which advances the polymerization reaction between the polymerizable groups. When the photosensitive resin composition contains a polymerizable group-containing resin (a), a compound other than the polymerizable group-containing resin (a), and a polymerization initiator as the photosensitizer (C) in combination, the photosensitive resin composition is insoluble in a developer by curing due to exposure. That is, a photosensitive resin composition containing a resin (a) having a polymerizable group, a compound other than the resin (a) having a polymerizable group, and a polymerization initiator as a photosensitizer (C) in combination belongs to a negative photosensitive resin composition.

From the viewpoint of good lithographic characteristics, the resin (a) preferably has a polymerizable group polymerizable by the action of the photosensitizer (C) on its molecular chain. The polymerizable group is typically preferably a radical polymerizable group or a cation polymerizable group, and more preferably a radical polymerizable group.

When the resin (a) has a polymerizable group, usually, the resin (a) has a radical polymerizable group on its molecular chain, and the photosensitizer (C) is a photo radical polymerization initiator (C1), or the resin (a) has a cation polymerizable group on its molecular chain, and the photosensitizer (C) is a photo cation polymerization initiator (C2).

The amount of the radical polymerizable group or the cation polymerizable group in the resin (a) is not particularly limited within a range not interfering with the object of the present invention. The amount of the radical polymerizable group or the cation polymerizable group in the resin (a) is, for example, preferably 0.0005 to 0.0500 mol/g, more preferably 0.001 to 0.0380 mol/g, and further preferably 0.0015 to 0.0028 mol/g, as the number of moles of the functional group relative to the weight of the resin (a). The amount of the radical polymerizable group or the cation polymerizable group in the resin (a) can be typically measured by NMR analysis.

The photosensitizer (C) may be a component which itself is soluble in the developer by the action of light. For example, a naphthoquinone diazide group-containing compound is solubilized with an alkaline developer by a carboxyl group generated by exposure. In the case where the photosensitive resin composition contains a photosensitizer (C) which makes itself soluble in a developer by the action of light, the photosensitive resin composition belongs to a positive photosensitive resin composition which is soluble in a developer by exposure to light.

The photosensitive resin composition containing the resin (A) and the photosensitizer (C) can provide a patterned resin film having a low dielectric loss tangent by applying a photolithography method, and can also provide a resin film having excellent mechanical properties such as tensile elongation by suppressing clouding of the resin film formed using the photosensitive resin composition.

Hereinafter, essential or optional components of the photosensitive resin composition will be described.

< resin (A) >

As described above, the resin (a) includes at least 1 selected from the group consisting of a polyimide resin (a-I) and a polyamic acid (a-II) derived from a diamine compound and a tetracarboxylic dianhydride, a polyamide resin (a-III) derived from an amide-forming derivative of a diamine compound and a dicarboxylic acid compound or a dicarboxylic acid compound, and a polybenzoxazole resin (a-IV) and a polybenzoxazole resin precursor (a-V) derived from an aromatic compound having 2 amino groups bonded to an aromatic ring and having a hydroxyl group bonded to a carbon atom at a position adjacent to a carbon atom bonded to the amino group on the aromatic ring, that is, a diamine compound, a dicarboxylic acid compound, or an amide-forming derivative of a dicarboxylic acid compound.

[ solution 3]

(in the formula (A1), X is an organic group having 1 to 100 carbon atoms, and R ^a1 Is a hydroxyl, carboxyl or halogen atom, R ^a2 Is an aliphatic group having 1 to 20 carbon atoms, a hydroxyl group, a carboxyl group, a sulfonic acid group or a halogen atom, ar may be represented by R ^a2 Substituted phenyl, orCan be replaced by R ^a2 A substituted naphthyl group, ma1 is an integer of 0 to 10 inclusive, ma2 is an integer of 0 to 7 inclusive, and ma3 is an integer of 1 to 10 inclusive. )

The polyimide resin (a-I), the polyamic acid (a-II), the polyamide resin (a-III), the polybenzoxazole resin (a-IV), and the polybenzoxazole resin precursor (a-V) will be described below.

[ polyimide resin (A-I) and Polyamic acid (A-II) ]

The polyimide resin (a-I) and the polyamic acid (a-II) are resins derived from a diamine compound and a tetracarboxylic dianhydride. The polyimide resin (a-I) and the polyamic acid (a-II) each contain a structural unit derived from a compound represented by the formula (A1).

The method for producing the polyimide resin (a-I) is not particularly limited. The polyimide resin (a-I) is generally obtained by ring closure and imidization of a polyamic acid (a-II) obtained by reacting a diamine compound containing a compound represented by the above formula (A1) with a tetracarboxylic dianhydride.

(diamine Compound)

The diamine compound includes a compound represented by the above formula (A1). The diamine compound may contain a diamine compound other than the compound represented by the formula (A1).

In the formula (A1), ar is optionally substituted by R ^a2 Substituted phenyl or optionally substituted by R ^a2 Substituted naphthyl. Preferably Ar is phenyl or naphthyl. That is, it is preferable that ma2 be 0 in the formula (A1).

In the formula (A1), R ^a2 An aliphatic group having 1 to 20 carbon atoms, a hydroxyl group, a carboxyl group, a sulfonic acid group, or a halogen atom. As R ^a2 The organic group (2) may contain a hetero atom such as O, N, S, P, B, si, or a halogen atom.

As R ^a2 The number of carbon atoms of the aliphatic group (2) is preferably 1 to 12, more preferably 1 to 6.

As R ^a2 The aliphatic group of (1) is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-hexylChain alkyl groups such as nonyl, n-decyl, n-undecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and n-eicosyl groups; chain alkenyl groups such as vinyl, 1-propenyl, 2-n-propenyl (allyl), 1-n-butenyl, 2-n-butenyl and 3-n-butenyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl; halogenated chain alkyl groups such as chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2-trifluoroethyl, pentafluoroethyl, heptafluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl, perfluorooctyl, perfluorononyl, and perfluorodecyl; halocycloalkyl groups such as 2-chlorocyclohexyl, 3-chlorocyclohexyl, 4-chlorocyclohexyl, 2, 4-dichlorocyclohexyl, 2-bromocyclohexyl, 3-bromocyclohexyl and 4-bromocyclohexyl; a hydroxy chain alkyl group such as a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxy-n-propyl group, or a 4-hydroxy-n-butyl group; hydroxycycloalkyl groups such as 2-hydroxycyclohexyl, 3-hydroxycyclohexyl and 4-hydroxycyclohexyl; chain alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, and n-eicosyloxy group; chain alkenyloxy groups such as vinyloxy, 1-propenyloxy, 2-n-propenyloxy (allyloxy), 1-n-butenyloxy, 2-n-butenyloxy and 3-n-butenyloxy; alkoxyalkyl groups such as methoxymethyl, ethoxymethyl, n-propoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-n-propoxyethyl, 3-methoxy-n-propyl, 3-ethoxy-n-propyl, 3-n-propoxy-n-propyl, 4-methoxy-n-butyl, 4-ethoxy-n-butyl and 4-n-propoxy-n-butyl; methoxymethoxy, ethoxymethoxy, n-propoxymethoxy, 2-methoxyethoxy, 2-ethoxyethoxy, 2-n-propoxyethoxyAlkoxyalkoxy groups such as methoxyethoxy, 3-methoxy-n-propoxy, 3-ethoxy-n-propoxy, 3-n-propoxy, 4-methoxy-n-butoxy, 4-ethoxy-n-butoxy and 4-n-propoxy-n-butoxy; aliphatic acyl groups such as formyl, acetyl, propionyl, butyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl and decanoyl; chain alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, n-butoxycarbonyl, n-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, n-nonyloxycarbonyl, and n-decyloxycarbonyl; aliphatic acyloxy groups such as formyloxy, acetoxy, propionyloxy, butyryloxy, valeryloxy, hexanoyloxy, heptanoyloxy, octanoyloxy, nonanoyloxy and decanoyloxy.

In the formula (A1), ma3 is an integer of 1 to 10 inclusive. The value of ma3 is not particularly limited as long as it is 1 to 10, and can be appropriately selected depending on the structure of X. The value of ma3 is preferably 1 to 4, more preferably 1 or 2.

In the formula (A1), X is an organic group having 1 to 100 carbon atoms. The organic group as X preferably has 2 to 80 carbon atoms, and more preferably 6 to 50 carbon atoms. The organic group as X may contain a hetero atom such as O, N, S, P, B, si, or a halogen atom. In the compound represented by the formula (A1), 2 amino groups are bonded to carbon atoms in the organic group as X.

The organic group as X may be an aliphatic group, an aromatic group, or a combination of an aliphatic group and an aromatic group. The organic group as X may be a group bonded via a bond including a heteroatom such as an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the bond containing a heteroatom such as an oxygen atom, a sulfur atom and a nitrogen atom in the organic group of X may include-CONH-, -NH-, -N = N-, -CH = N-, -COO-, -O-, -CO-, -SO ₂ -, -S-and-S-, etc., preferably-O-) -CO-and-S-.

When the organic group as X is an aliphatic group, the aliphatic group may be a saturated aliphatic group or an unsaturated aliphatic group. When the organic group as X is an aliphatic group, the aliphatic group is preferably an aliphatic hydrocarbon group. When the organic group as X is an aliphatic group, the aliphatic group may be a chain or ring-shaped group, or a combination of a chain aliphatic group and a ring-shaped aliphatic group. The chain aliphatic group may have a branch.

When the organic group as X is an aliphatic group, the aliphatic group is preferably a group obtained by removing (ma 1+ ma3+ 2) hydrogen atoms from an alkylene group having 1 to 20 carbon atoms, more preferably a group obtained by removing (ma 1+ ma3+ 2) hydrogen atoms from an alkylene group having 1 to 16 carbon atoms, and still more preferably a group obtained by removing (ma 1+ ma3+ 2) hydrogen atoms from an alkylene group having 1 to 12 carbon atoms.

When the organic group as X is a group containing an aromatic group, X, ar, R are represented by the formula (A1) ^a1 And R ^a2 Examples of the group to be constituted may include groups represented by the following formulae (11) to (15).

[ solution 4]

In the formulae (11) to (15), ar and R ^a1 、R ^a2 Ma1, ma2 and ma3, and Ar and R in formula (A1) ^a1 、R ^a2 Ma1, ma2, and ma3 are the same. In formula (13), ma4 and ma5 are each independently an integer of 0 to 4. ma6 and ma7 are each independently an integer of 0 to 4 inclusive, and the sum of ma6 and ma7 is 1 to 8 inclusive. In the formula (14), each of ma8, ma9, and ma10 is independently an integer of 0 to 4. The sum of ma8, ma9 and ma10 is 0 to 10, and each of ma11, ma12 and ma13 is independently an integer of 0 to 4. The sum of ma11, ma12 and ma13 is 1 to 10. In the formula (15), ma14 is an integer of 0 to 3. ma15 is an integer of 0 to 5 inclusive. The sum of ma14 and ma15 is 0 to 8. ma16 is an integer of 0 to 3. ma17 is an integer of 0 to 5 inclusive. The sum of ma16 and ma17 is 1Above 8 and below.

In the formula (11), ma1 is preferably 0, ma2 is preferably 0, and ma3 is preferably 1 or 2.

In the formula (12), ma1 is preferably 0, ma2 is preferably 0, and ma3 is preferably 1 or 2.

In the formula (13), ma2 is preferably 0, ma4 and ma5 are preferably 0, ma6 and ma7 are preferably 0, 1 or 2, and the sum of ma6 and ma7 is 1 or more, preferably 4 or less.

In the formula (14), ma2 is preferably 0, ma8, ma9, and ma10 are preferably 0, ma11, ma12, and ma13 are preferably 0, 1, or 2, the sum of ma11, ma12, and ma13 is 1 or more, and preferably 6 or less.

In the formula (15), ma2 is preferably 0, ma14 and ma15 are preferably 0, ma16 and ma17 are preferably 0, 1 or 2, and the sum of ma16 and ma17 is 1 or more, preferably 4 or less.

In the formulae (11) to (15), R ^a3 Is a single bond or a 2-valent linking group. Wherein the 2-valent linking group is not an aromatic group-containing group. As a 2-valent linking group, a cyclic alkyl group, examples thereof may include aliphatic hydrocarbon groups having 1 to 20 carbon atoms, -CONH-, -NH-, and-N = N-, -CH = N-, -COO-, -O-, -CO-, -SO ₂ A combination of 2 or more selected from the above-mentioned groups, and the like. The number of carbon atoms of the linking group is preferably 1 to 20, more preferably 1 to 12, and still more preferably 1 to 6. The aliphatic hydrocarbon group as the linking group may have 1 or more unsaturated bonds, may have a branched chain, or may have a ring structure. Specific examples of the aliphatic hydrocarbon group as the linking group may include methylene, ethane-1, 2-diyl (ethylene), ethane-1, 1-diyl, propane-1, 3-diyl, propane-1, 2-diyl, propane-1, 1-diyl, propane-2, 2-diyl, butane-1, 4-diyl, pentane-1, 5-diyl, hexane-1, 6-diyl, heptane-1, 7-diyl, octane-1, 8-diyl, nonane-1, 9-diyl, decane-1, 10-diyl, undecane-1, 11-diyl, dodecane-1, 12-diyl, tridecane-1, 13-diyl, tetradecane-1, 14-diyl, pentadecane-1, 15-diyl, hexadecane-1, 16-diyl, heptadecane-1, 17-diyl, octadecane-1, 18-diyl,Nonadecane-1, 19-diyl, eicosane-1, 20-diyl, ethylene-1, 2-diyl (vinylidene), propylene-1, 3-diyl, acetylene-1, 2-diyl, and propyne-1, 3-diyl, and the like.

Suitable examples of the linking group include an alkylene group having 1 to 6 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, an alkynylene group having 2 to 6 carbon atoms, an alkyleneoxy group having 1 to 6 carbon atoms, an alkenyloxy group having 2 to 6 carbon atoms, an alkynylene oxy group having 2 to 6 carbon atoms, an alkylenethio group having 1 to 6 carbon atoms, an alkenylthio group having 2 to 6 carbon atoms, an alkynylene thio group having 2 to 6 carbon atoms, an alkyleneamino group having 1 to 6 carbon atoms, an alkenylamino group having 2 to 6 carbon atoms, an alkynylene amino group having 2 to 6 carbon atoms, -CONH-, -NH-, -COO-, -O-, -CO-, -SO-, -a CONH-, -NH-, -a ₂ -, -S-, -OCONH-, and-OCOO-, etc.

The compound represented by the formula (A1) is preferably a compound represented by the following formula (A1-1) from the viewpoint that the formed resin film shows a low dielectric loss tangent and good mechanical properties.

[ solution 5]

(in the formula (A1-1), R ^a1 、R ^a2 Ar, ma1, ma2 and ma3 and R in the formula (A1) ^a1 、R ^a2 Ar, ma1, ma2 and ma3 are the same, Y ^a1 Is an organic group having 1 to 20 carbon atoms or a single bond, Y ^a2 An organic group having 1 to 20 carbon atoms, na1 is 0 or 1, and na2 is 0 or 1. When na1 is 1, Y ^a1 Not a single bond. )

In the formula (A1-1), as Y ^a1 The organic group (B) may contain hetero atoms such as O, N, S, P, B, si, halogen atoms, etc. As Y ^a1 The organic group of (2) is preferably a hydrocarbon group. As Y ^a1 The hydrocarbon group (C) may be an aliphatic hydrocarbon group or an aromatic hydrocarbon groupThe group hydrocarbon group may be a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. As Y ^a1 The hydrocarbon group of (2) is preferably an aromatic hydrocarbon group, and more preferably a phenylene group and a naphthalenediyl group. As Y ^a1 Suitable specific examples of the aromatic hydrocarbon group of (a) include p-phenylene, m-phenylene, o-phenylene, naphthalene-1, 4-diyl, naphthalene-1, 2-diyl, naphthalene-1, 3-diyl, naphthalene-1, 5-diyl, naphthalene-1, 6-diyl, naphthalene-1, 7-diyl, naphthalene-1, 8-diyl, naphthalene-2, 6-diyl, naphthalene-2, 7-diyl and naphthalene-2, 3-diyl. Among these aromatic hydrocarbon groups, p-phenylene and m-phenylene are preferable, and p-phenylene is more preferable.

In the formula (A1-1), na2 is preferably 1, and more preferably both na1 and na2 are 1, Y ^a1 Is an organic group. In this case, it is considered that since the steric degree of freedom of the ether bond is high, the structural unit represented by the formula (A1-1) is easily deposited well when the cured film is formed using the photosensitive resin composition, and the cured film having excellent mechanical properties, thermal properties, electrical properties, and the like is easily formed.

In the formula (A1-1), ma1 is preferably 0, ma2 is preferably 0, and ma3 is preferably 1 or 2.

Specific examples of the compound represented by the formula (A1) described above include the following compounds.

[ solution 6]

[ solution 7]

[ solution 8]

[ solution 9]

[ solution 10]

[ solution 11]

[ solution 12]

[ solution 13]

As described above, the diamine compound may contain another diamine compound other than the compound represented by the formula (A1).

When the resin (a) is the polyimide resin (a-I) and the polyamic acid (a-II), the ratio of the number of moles of the structural unit derived from the compound represented by the formula (A1) in the polyimide resin (a-I) and the polyamic acid (a-II) to the number of moles of the total structural units derived from the diamine compound is preferably 10 mol% or more and 100 mol% or less, more preferably 15 mol% or more and 100 mol% or less, and still more preferably 20 mol% or more and 100 mol% or less.

The other diamine compound is represented by the following formula (A2).

H ₂ N-A ¹ -NH ₂ …(A2)

(in the formula (A2), A ¹ Represents an organic group having a valence of 2. Wherein, as A ¹ The 2-valent organic group(s) of (A1) does not belong to the group consisting of X, ar and R ^a1 And R ^a2 A constituent group. )

A ¹ Is a 2-valent organic group. A. The ¹ In addition to 2 amino groups, 1 or more substituents may be present.

Preferable examples of the substituent include a fluorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, a fluoroalkoxy group having 1 to 6 carbon atoms, a carboxyl group, and a hydroxyl group.

In the case where the substituent is a fluoroalkyl group or a fluoroalkoxy group, a perfluoroalkyl group or a perfluoroalkoxy group is preferable.

As A ¹ The lower limit of the number of carbon atoms of the organic group (2) is preferably 2, more preferably 6, and the upper limit thereof is preferably 50, more preferably 30.

A ¹ May be an aliphatic group, and is preferably an organic group containing 1 or more aromatic rings.

In A ¹ In the case of an organic group containing 1 or more aromatic rings, the organic group may be 1 aromatic group per se, or 2 or more aromatic groups may be bonded via a bond of an aliphatic hydrocarbon group, a halogenated aliphatic hydrocarbon group, and a hetero atom such as an oxygen atom, a sulfur atom, and a nitrogen atom. As A ¹ <xnotran> , , -CONH-, -NH-, -N = N-, -CH = N-, -COO-, -O-, -CO-, -SO-, -SO </xnotran> ₂ <xnotran> -, -S- -S-S- , -COO-, -O-, -CO- -S-. </xnotran>

A ¹ The aromatic ring bonded to the amino group in (1) is preferably a benzene ring. At A ¹ In the case where the ring bonded to the amino group in (b) is a condensed ring including 2 or more rings, the ring bonded to the amino group in the condensed ring is preferably a benzene ring.

Furthermore, A ¹ The aromatic ring contained may be an aromatic heterocycle.

In A ¹ In the case of an organic group containing an aromatic ring, the organic group is preferably at least 1 of the groups represented by the following formulae (21) to (24) in view of improvement in the motor characteristics and mechanical characteristics of the resin film to be formed.

[ chemical 14]

In the formulae (21) to (24), R ¹¹¹ Represents 1 kind selected from the group consisting of a hydrogen atom, a fluorine atom, a carboxyl group, a sulfonic acid group, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, and a halogenated alkyl group having 1 to 4 carbon atoms. In the formula (24), Q ¹ Represents 9,9' -fluorenylidene or is represented by the formula-C ₆ H ₄ -、-C ₆ H ₄ -C ₆ H ₄ -、-O-C ₆ H ₄ -C ₆ H ₄ -O-、-O-C ₆ H ₄ -CO-C ₆ H ₄ -O-、-O-C ₆ H ₄ -C(CH ₃ ) ₂ -C ₆ H ₄ -O-、-OCO-C ₆ H ₄ -COO-、-OCO-C ₆ H ₄ -C ₆ H ₄ -COO-、-OCO-、-O-、-CO-、-C(CF ₃ ) ₂ -、-C(CH ₃ ) ₂ -、-CH ₂ -、-O-C ₆ H ₄ -SO ₂ -C ₆ H ₄ -O-、-C(CH ₃ ) ₂ -C ₆ H ₄ -C(CH ₃ ) ₂ -、-O-C ₁₀ H ₆ -O-、-O-C ₆ H ₄ -O-、-O-CH ₂ -O-、-O-(CH ₂ ) ₂ -O-、-O-(CH ₂ ) ₃ -O-、-O-(CH ₂ ) ₄ -O-、-O-(CH ₂ ) ₅ -O-and-O- (CH) ₂ ) ₆ 1 selected from the group consisting of groups represented by-O-.

Q ¹ In (b) is ₆ H ₄ Is phenylene, preferably m-phenylene and p-phenylene, more preferably p-phenylene. Furthermore, -C ₁₀ H ₆ Is a naphthalene diyl group, preferably a naphthalene-1, 2-diyl group, a naphthalene-1, 4-diyl group, a naphthalene-2, 3-diyl group, a naphthalene-2, 6-diyl group and a naphthalene-2, 7-diyl group, more preferably a naphthalene-1, 4-diyl group and a naphthalene-2, 6-diyl group.

In terms of improvement in electrical characteristics of the resin film formed, R in the formulae (21) to (24) is ¹¹¹ More preferred is a hydrogen atom, a fluorine atom, a methyl group, an ethyl group or a trifluoromethyl group, and particularly preferred is a hydrogen atom or a trifluoromethyl group.

In view of electrical and mechanical characteristics of the formed resin film, Q in the formula (24) ¹ Is preferably-C ₆ H ₄ -C ₆ H ₄ -、-O-C ₆ H ₄ -C ₆ H ₄ -O-、-O-C ₆ H ₄ -CO-C ₆ H ₄ -O-、-O-C ₆ H ₄ -C(CH ₃ ) ₂ -C ₆ H ₄ -O-、-OCO-C ₆ H ₄ -COO-、-OCO-C ₆ H ₄ -C ₆ H ₄ -COO-、-OCO-、-O-、-CO-、-C(CF ₃ ) ₂ -、-C(CH ₃ ) ₂ -、-CH ₂ -、-O-C ₆ H ₄ -SO ₂ -C ₆ H ₄ -O-、-C(CH ₃ ) ₂ -C ₆ H ₄ -C(CH ₃ ) ₂ -、-O-C ₁₀ H ₆ -O-、-O-C ₆ H ₄ -O-、-O-CH ₂ -O-、-O-(CH ₂ ) ₂ -O-、-O-(CH ₂ ) ₃ -O-、-O-(CH ₂ ) ₄ -O-、-O-(CH ₂ ) ₅ -O-and-O- (CH) ₂ ) ₆ -O-. Q in the formula (24) is Q in view of improvement of electrical and mechanical properties of the resin (A) in the photosensitive resin composition ¹ More preferably-O-C ₆ H ₄ -C ₆ H ₄ -O-、-O-C ₆ H ₄ -C(CH ₃ ) ₂ -C ₆ H ₄ -O-, particularly preferably-O-C ₆ H ₄ -C ₆ H ₄ -O-represents and-C ₆ H ₄ -groups which are all p-phenylene.

When an aromatic diamine compound is used as the other diamine compound represented by the formula (A2), for example, the aromatic diamine compounds shown below can be suitably used.

<xnotran> , , , ,2,4- ,4,4'- ,3,3' - ,3,4 '- ,1,5- ,2,6- ,9, 10- ,9, 10- (4- ) ,4,4' - -2,2'- ( ) ,4,4' - ,3,3'- ,3,4' - ,4,4'- ,3,3' - ,3,4 '- ,4,4' - ,3,3'- ,3, 4' - ,4,4'- ,3,3' - ,3,4 '- ,2,2- (4- ) , (3- -4- ) ,2,2- (3- -4- ) ,2,2- [4- (4- ) ] ,2,2- [4- (4- ) ] ,2,2' - [ N- (3- ) -3- -4- </xnotran> <xnotran> ] ,2,2 ' - [ N- (4- ) -3- -4- ] ,4,4' - ,3,4 ' - ,3,3' - ,3- -4,4' - ,3- -4,4' - ,4,4' - ,3,3' - ,1,4- (4- ) ,1,3- (4- ) ,1,4- (4- ) ,1,3- (4- ) ,1,3- (3- ) , (3- -4- ) , [4- (4- ) ] , [4- (3- ) ] ,4,4' - (4- ) ,3,4 ' - (4- ) ,3,3' - (4- ) , (3- -4- ) , (4- ) , (3- ) , </xnotran> <xnotran> [4- (4- ) ] , [4- (3- ) ] , [ N- (3- ) -3- -4- ] , [ N- (4- ) -3- -4- ] , [4- (4- ) ] ,2,2- [4- {4- -2- ( ) } ] ,9,9- (4- ) ,9,9- (4- -3- ) ,9,9- (3- -4- ) ,9,9- [ N- (3- ) -3- -4- ] ,9,9- [ N- (4- ) -3- -4- ] ,2,7- ,2- (4- ) -5- ,2- (3- ) -5- ,2- (4- ) -6- ,2- (3- ) -6- , </xnotran> 1, 4-bis (5-amino-2-benzoxazolyl) benzene, 1, 4-bis (6-amino-2-benzoxazolyl) benzene, 1, 3-bis (5-amino-2-benzoxazolyl) benzene, 1, 3-bis (6-amino-2-benzoxazolyl) benzene, 2, 6-bis (4-aminophenyl) benzobisoxazole, 2, 6-bis (3-aminophenyl) benzobisoxazole, bis [ (3-aminophenyl) -5-benzoxazolyl ], bis [ (4-aminophenyl) -5-benzoxazolyl ], bis [ (3-aminophenyl) -6-benzoxazolyl ], bis [ (4-aminophenyl) -6-benzoxazolyl ], N, N '-bis (3-aminobenzoyl) -2, 5-diamino-1, 4-dihydroxybenzene, N' -bis (4-aminobenzoyl) -4,4 '-diamino-3, 3-dihydroxybiphenyl, N' -bis (3-aminobenzoyl) -3,3 '-diamino-4, 4-dihydroxybiphenyl, N' -bis (4-aminobenzoyl) -3,3' -diamino-4, 4-dihydroxybiphenyl, 3,4' -diaminodiphenyl sulfide, 4' - [1, 4-phenylenebis (1-methylethyl-1, 1-diyl) diphenylamine, 3, 5-diaminobenzoic acid, 3, 4-diaminobenzoic acid, 4-aminophenyl 4-aminobenzoate, 1, 3-bis (4-anilino) tetramethyldisiloxane, 1, 4-bis (3-aminopropyldimethylsilyl) benzene, o-tolidine sulfone, and the like. Among these, 4' -bis (4-aminophenoxy) biphenyl, 3,4' -bis (4-aminophenoxy) biphenyl and 3,3' -bis (4-aminophenoxy) biphenyl are preferable from the viewpoint of improvement in electrical characteristics and mechanical characteristics.

Further, as A ¹ A silicon atom-containing group which may have a chain aliphatic group and/or an aromatic ring can be used. As such a silicon atom-containing group, typically, the following groups can be used.

[ solution 15]

Specific examples of the compound having amino groups at both ends and a group containing a silicon atom include amino group-modified methylphenylsilicones at both ends (for example, X-22-1660B-3 (about number average molecular weight 4,400) and X-22-9409 (about number average molecular weight 1,300) manufactured BY shin-Etsu chemical Co.), amino group-modified dimethylsilicones at both ends (for example, X-22-161A (about number average molecular weight 1,600), X-22-161B (about number average molecular weight 3,000) and KF8012 (about number average molecular weight 4,400) manufactured BY shin-Etsu chemical Co., ltd., BY16-835U (about number average molecular weight 900) manufactured BY Toho Corning, and Silaplane FM3311 (about number average molecular weight 1000) manufactured BY JNC Co., ltd.).

Further, as the other diamine compound represented by the formula (A2), a diamine having an oxyalkylene group can also be preferably used. Preferable examples of the oxyalkylene group include an ethyleneoxy group and a propyleneoxy group (-C (CH) ₃ )-CH ₂ -O-、-CH ₂ -C(CH ₃ ) -O-or-CH ₂ CH ₂ CH ₂ -O-)。

The diamine having an oxyalkylene group may also contain 2 or more oxyalkylene groups in combination. When the diamine having an oxyalkylene group contains 2 or more oxyalkylene groups, the 2 or more oxyalkylene groups may be contained in the diamine in a block form or may be contained in the diamine at random.

The diamine having an oxyalkylene group preferably does not contain a cyclic group, and more preferably does not contain an aromatic group.

Specific examples of the diamine having an oxyalkylene group include JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE (registered trademark) EDR-176, JEFFAMINE (registered trademark) D-200, JEFFAMINE (registered trademark) D-400, JEFFAMINE (registered trademark) D-2000 and JEFFAMINE (registered trademark) D-4000, and further, 1- (2- (2-aminopropoxy) ethoxy) propoxy) propan-2-amine and 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propan-2-amine, manufactured by HUNTSUMAN.

Further, a dimer diamine compound is also preferable as the diamine compound because a cured product having a low dielectric constant and dielectric tangent in a high frequency band can be easily formed using the photosensitive resin composition. The dimer diamine compound is a diamine compound in which both terminal carboxyl groups of the dimer acid are substituted with aminomethyl groups or amino groups. Dimer acids are known dibasic acids obtained by intermolecular polymerization of unsaturated fatty acids. The industrial manufacturing process for the manufacture of dimer acid is largely standardized. Typically, dimer acid is obtained by dimerizing unsaturated fatty acid having 11 to 22 carbon atoms in the presence of a clay catalyst or the like. The dimer acid industrially obtained is a dibasic acid having 36 carbon atoms obtained by dimerizing an unsaturated fatty acid having 18 carbon atoms such as oleic acid, linoleic acid, linolenic acid, or the like. The dimer acid obtained industrially may contain a monomer acid having 18 carbon atoms, a trimer acid having 54 carbon atoms, and other polymerized fatty acids having 20 to 54 carbon atoms, in arbitrary amounts, depending on the degree of purification.

As the dimer diamine compound, a diamine compound represented by the following formula (31) is preferable.

[ solution 16]

In the formula (31), e, f, g and h are each an integer of 0 or more. e + f is an integer of 6 to 17 inclusive, and g + h is 8 to 19 inclusive. In formula (31), the wavy portion represents a carbon-carbon single bond or a carbon-carbon double bond. Wherein, in 1 molecule of the compound represented by the formula (31), at least 1 has a carbon-carbon double bond.

Since a cured product having further excellent ductility can be formed, a compound represented by the following formula (32) is preferable as the diamine compound represented by formula (31).

[ chemical formula 17]

Commercially available diamine compounds represented by the formula (31) include Versamine551 (manufactured by BASF) and primamine 1074 (manufactured by Croda Japan) containing a compound represented by the following formula (33), versamine552 (manufactured by BASF) containing a compound represented by the above formula (32), primamine 1073 (manufactured by Croda Japan) and primamine 1075 (manufactured by Croda Japan). Such commercially available dimer diamine compounds are typically mixtures comprising a plurality of amine compounds.

[ solution 18]

Further, by reacting the diamine compound represented by the formula (31) with an acid halide derived from trimellitic anhydride, a tetracarboxylic dianhydride represented by the following formula (34) can be obtained. It is also preferable to use tetracarboxylic dianhydride represented by the following formula (34) as a raw material for producing the polyimide resin (a-I) and the polyamic acid (a-II).

In the formula (34), i, j, k and l are each an integer of 0 or more. i + j is an integer of 6 to 17, and k + l is 8 to 19. In the formula (34), the wavy portion represents a carbon-carbon single bond or a carbon-carbon double bond.

[ solution 19]

As described above, in terms of photosensitivity, the resin (a) blended in the photosensitive resin composition may have a polymerizable group polymerizable by the action of the photosensitizer (C) on its molecular chain. The polymerizable group is typically preferably a radical polymerizable group or a cation polymerizable group, and more preferably a radical polymerizable group.

The bonding position of the radical polymerizable group or the cation polymerizable group in the molecular chain of the polyimide resin (a-I) and the polyamic acid (a-II) is not particularly limited.

Examples of the radical polymerizable group typically include groups having an ethylenically unsaturated double bond. The ethylenically unsaturated double bond-containing group is preferably an alkenyl-containing group containing an alkenyl group such as a vinyl group and an allyl group, and more preferably a (meth) acryloyl group.

The cationically polymerizable group may typically be an epoxy group-containing group, an oxetanyl group, a vinyloxy group-containing group, or the like. Among them, preferred are epoxy group-containing groups and vinyloxy group-containing groups. The epoxy group-containing group is preferably an alicyclic epoxy group-containing group or a glycidyl group. The alicyclic epoxy group is an alicyclic group in which 2 carbon atoms adjacent to each other as a ring-constituting atom are bonded to each other through an oxygen atom. That is, the alicyclic epoxy group has an epoxy group containing a three-membered ring composed of 2 carbon atoms and 1 oxygen atom on an aliphatic ring.

The radical polymerizable group and the cation polymerizable group are preferably bonded to an aromatic ring in the molecular chain of the polyimide resin (a-I) and the polyamic acid (a-II).

Thus, the 2-valent organic radical A in the formula (A2) ¹ For example, the radical polymerizable group or the cation polymerizable group may be bonded to the aromatic ring of the aromatic group represented by the formulas (21) to (24).

Examples of suitable radical polymerizable groups to be bonded to the aromatic ring in the molecular chain of the polyimide resin (A-I) and the polyamic acid (A-II) include groups represented by the following formula (A-a) or the following formula (A-b) and not belonging to a vinyloxy group-containing group.

-(A ⁰¹ ) _na -R ⁰¹ …(A-a)

-(A ⁰¹ ) _na -R ⁰² -A ⁰² -R ⁰¹ …(A-b)

In the formulae (A-a) and (A-b), R ⁰¹ An alkenyl group having 2 to 10 carbon atoms. R ⁰² Is an alkylene group having 1 to 10 carbon atoms.

A ⁰¹ is-O-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-or-NH-.

A ⁰² is-O-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-or-NH-.

And na is 0 or 1.

Suitable examples of the radical polymerizable group bonded to the aromatic ring in the main chain include

-O-R ⁰³ 、

-O-CH ₂ CH ₂ -O-R ⁰³ 、

-O-CH ₂ CH ₂ CH ₂ -O-R ⁰³ 、

-O-CH ₂ CH ₂ CH ₂ CH ₂ -O-R ⁰³ 、

-CO-O-CH ₂ CH ₂ -O-R ⁰³ 、

-CO-O-CH ₂ CH ₂ CH ₂ -O-R ⁰³ 、

-CO-O-CH ₂ CH ₂ CH ₂ CH ₂ -O-R ⁰³ 、

-O-CH ₂ CH ₂ -NH-R ⁰³ 、

-O-CH ₂ CH ₂ CH ₂ -NH-R ⁰³ 、

-O-CH ₂ CH ₂ CH ₂ CH ₂ -NH-R ⁰³ 、

-CO-O-CH ₂ CH ₂ -NH-R ⁰³ 、

-CO-O-CH ₂ CH ₂ CH ₂ -NH-R ⁰³ 、

-CO-O-CH ₂ CH ₂ CH ₂ CH ₂ -R ⁰³ 、

-NH-R ⁰³ 、

-NH-CH ₂ CH ₂ -O-R ⁰³ 、

-NH-CH ₂ CH ₂ CH ₂ -O-R ⁰³ 、

-NH-CH ₂ CH ₂ CH ₂ CH ₂ -O-R ⁰³ 、

-CO-NH-CH ₂ CH ₂ -O-R ⁰³ 、

-CO-NH-CH ₂ CH ₂ CH ₂ -O-R ⁰³ 、

-CO-NH-CH ₂ CH ₂ CH ₂ CH ₂ -O-R ⁰³ 、

-NH-CH ₂ CH ₂ -NH-R ⁰³ 、

-NH-CH ₂ CH ₂ CH ₂ -NH-R ⁰³ 、

-NH-CH ₂ CH ₂ CH ₂ CH ₂ -NH-R ⁰³ 、

-CO-NH-CH ₂ CH ₂ -NH-R ⁰³ 、

-CO-NH-CH ₂ CH ₂ CH ₂ -NH-R ⁰³ And

-CO-NH-CH ₂ CH ₂ CH ₂ CH ₂ -NH-R ⁰³ the group shown. R in these radicals ⁰³ Is allyl or (meth) acryloyl.

It is preferable that the polyimide resin (A-I) and the polyamic acid (A-II) are bonded to an aromatic ring in the molecular chain. Suitable examples of the cationically polymerizable group bonded to the aromatic ring in the molecular chain of the polyimide resin (A-I) and the polyamic acid (A-II) include a vinyloxy group and groups represented by the following formulae (A-c) to (A-h).

-(A ⁰¹ ) _na -R ⁰⁴ …(A-c)

-(A ⁰¹ ) _na -R ⁰² -R ⁰⁵ …(A-d)

-(A ⁰¹ ) _na -R ⁰² -(CO) _nb -A ⁰³ -R ⁰⁴ …(A-e)

-(A ⁰¹ ) _na -R ⁰² -(CO) _nb -A ⁰³ -R ⁰⁷ -R ⁰⁵ …(A-f)

-(A ⁰¹ ) _na -R ⁰² -O-R ⁰⁶ …(A-g)

-(A ⁰¹ ) _na -R ⁰² -(CO) _nb -A ⁰³ -R ⁰⁷ -O-R ⁰⁶ …(A-j)

In the formulae (A-c) to (A-h), R ⁰² Is an alkylene group having 1 to 10 carbon atoms. R ⁰⁴ An epoxyalkyl group having 2 to 20 carbon atoms or an alicyclic epoxy group having 3 to 20 carbon atoms. R ⁰⁵ An alicyclic epoxy group having 3 to 20 carbon atoms. R ⁰⁶ Is a vinyl group. R ⁰⁷ Is an alkylene group having 1 to 10 carbon atoms.

A ⁰¹ is-O-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-or-NH-.

A ⁰³ is-O-or-NH-.

nb is 0 or 1.

Suitable specific examples of the cationically polymerizable group bonded to the aromatic ring in the main chain include

-R ⁰⁷ 、

-O-CH ₂ CH ₂ -R ⁰⁷ 、

-O-CH ₂ CH ₂ CH ₂ -R ⁰⁷ 、

-O-CH ₂ CH ₂ CH ₂ CH ₂ -R ⁰⁷ 、

-CO-O-CH ₂ CH ₂ -R ⁰⁷ 、

-CO-O-CH ₂ CH ₂ CH ₂ -R ⁰⁷ 、

-CO-O-CH ₂ CH ₂ CH ₂ CH ₂ -R ⁰⁷ 、

-NH-CH ₂ CH ₂ -R ⁰⁷ 、

-NH-CH ₂ CH ₂ CH ₂ -R ⁰⁷ 、

-NH-CH ₂ CH ₂ CH ₂ CH ₂ -R ⁰⁷ 、

-CO-NH-CH ₂ CH ₂ -R ⁰⁷ 、

-CO-NH-CH ₂ CH ₂ CH ₂ -R ⁰⁷ And

-CO-NH-CH ₂ CH ₂ CH ₂ CH ₂ -R ⁰⁷ the group represented. R in these radicals ⁰⁷ Is vinyloxy, glycidoxy, epoxycyclopentyl, epoxycyclohexyl or epoxycycloheptyl.

As A in the formula (A2) ¹ Specific examples of the aromatic group in the case of an aromatic group having a radical polymerizable group or a cation polymerizable group include the following groups.

[ solution 20]

[ solution 21]

[ solution 22]

(tetracarboxylic dianhydride)

As the tetracarboxylic dianhydride, those conventionally used in the production of polyamic acids and polyimide resins can be used without particular limitation.

The tetracarboxylic dianhydride may, for example, be a compound represented by the following formula (A3). The tetracarboxylic dianhydride may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

[ chemical No. 23]

(in the formula (A3), A ² Is a 4-valent organic group having 6 to 50 carbon atoms. )

In the formula (A3), A ² Is an organic group having a valence of 4 of from 6 to 50 carbon atoms, except that 2 acids represented by-CO-O-CO-in the formula (A3)The compound may have 1 or more substituents other than the anhydride group.

Preferable examples of the substituent include a fluorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, and a fluoroalkoxy group having 1 to 6 carbon atoms. The compound represented by the formula (a 1-1) may contain a carboxyl group or a carboxylate group in addition to the acid anhydride group.

The above substituents may be the same as 1 or more substituents which the aromatic group described later may have on the aromatic ring.

Constitution A ² The number of carbon atoms of (b) is more preferably 8 or more, and still more preferably 12 or more. Further, constitution A ² The number of carbon atoms of (b) is more preferably 40 or less, and still more preferably 30 or less. A. The ² The group may be an aliphatic group, an aromatic group, or a combination of these structures. A. The ² In addition to carbon atoms and hydrogen atoms, halogen atoms, oxygen atoms, nitrogen atoms, and sulfur atoms may be contained. In A ² <xnotran> , , , , -CONH-, -NH-, -N = N-, -CH = N-, -COO-, -O-, -CO-, -SO-, -SO </xnotran> ₂ -, -S-and-S-selected groups are contained in A ¹ In (1), more preferably as a mixture of-O-, -CO-, -S-selected radicals contained in A ¹ In (1).

The tetracarboxylic dianhydride represented by the formula (A3) may be an aliphatic tetracarboxylic dianhydride having 2 dicarboxylic anhydride groups bonded to an aliphatic group, or may be an aromatic tetracarboxylic dianhydride having at least 1 dicarboxylic anhydride group bonded to an aromatic group.

Further, the aromatic tetracarboxylic dianhydride preferably has 2 dicarboxylic anhydride groups bonded to the aromatic group.

The aliphatic tetracarboxylic dianhydride may also contain an alicyclic structure. The alicyclic structure may be polycyclic. Examples of the aliphatic tetracarboxylic dianhydride not having an alicyclic structure include 1,2,3,4-tetracarboxylic dianhydride (e.g., RIKACID BT-100, manufactured by Nippon chemical Co., ltd.).

Examples of the aliphatic tetracarboxylic dianhydride having an alicyclic structure include cyclobutanetetracarboxylic dianhydride, cyclopentane-1, 2,3, 4-tetracarboxylic dianhydride, cyclohexane-1, 2,4, 5-tetracarboxylic dianhydride, norbornane-2-spiro- α -cyclopentanone- α '-spiro-2 "-norbornane-5, 5",6 "-tetracarboxylic dianhydride (e.g., ENEHYDE (registered trademark) CpODA, manufactured by ENEOS), 2-bis (2, 3-dicarboxyphenoxy) hexafluoropropane dianhydride [5,5' - (1, 4-phenylene) bisnorbornane ] -2,2', 3' -tetracarboxylic dianhydride (e.g., ENEHYDE (registered trademark) BzDA, manufactured by ENEOS), 1,3, a,4,5, 9b-hexahydro-5 (tetrahydro-2, 5-dioxo-3-furanyl) naphtho [1,2-C ] furan-1, 3-dione (e.g., RIKAA-100, manufactured by NONY Co.).

<xnotran> (A3) 2 , ,1,4- (3,4- ) ,4,4'- ,3,3',4,4 '- ,2,3,3', 4'- ,3,3',4,4 '- ,2,2', 3,3'- ,3,3',4,4 '- ,3,3',4,4 '- , (3,4- ) ,1,2,5,6- ,2,3,6,7- ,2,3,5,6- ,3,4,9, 10- , (2,3- ) ,1,1- (2,3- ) ,2,2- [4- (3,4- ) ] ,4,4' - (3,4- ) ,2,6- (3,4- ) ,1,2- (3,4- ) ( RIKACID TMEG100, </xnotran> New japan physical and chemical company) and 1, 10-bis (3, 4-dicarboxyphenylcarbonyloxy) decane dianhydride (for example: 10BTA, manufactured by blackcurrant chemical corporation).

Among these aromatic tetracarboxylic dianhydrides, 2-bis [4- (3, 4-dicarboxyphenyloxy) phenyl ] propane dianhydride, 4 '-bis (3, 4-dicarboxyphenylcarbonyloxy) biphenyl dianhydride, 4' -bis (3, 4-dicarboxyphenyloxy) biphenyl dianhydride, 2, 6-bis (3, 4-dicarboxyphenylcarbonyloxy) naphthalene dianhydride, 1, 2-bis (3, 4-dicarboxyphenylcarbonyloxy) ethane dianhydride (for example, RIKACID TMEG100, manufactured by shin chemical company) and 1, 10-bis (3, 4-dicarboxyphenylcarbonyloxy) decane dianhydride (for example, 10BTA, manufactured by shin chemical company) are preferable from the viewpoint of easily forming a cured product excellent in electrical characteristics.

The aromatic tetracarboxylic dianhydride is also preferably a biphenyltetracarboxylic dianhydride in order to suppress warpage of the cured film of the photosensitive resin composition and to improve the lithographic characteristics of the photosensitive resin composition.

Examples of the biphenyltetracarboxylic dianhydride include 3,3',4' -biphenyltetracarboxylic dianhydride, 2,3,3',4' -biphenyltetracarboxylic dianhydride and 2,2', 3' -biphenyltetracarboxylic dianhydride, and 3,3',4' -biphenyltetracarboxylic dianhydride is preferred.

The aromatic tetracarboxylic dianhydride may be, for example, a compound represented by the following general formulae (a 3-2) to (a 3-4).

[ solution 24]

In the above formulae (a 3-2) and (a 3-3), R ^a01 、R ^a02 And R ^a03 Each represents a 2-valent group composed of an aliphatic group which may be substituted with a halogen, an oxygen atom, a sulfur atom, an aromatic group via 1 or more 2-valent elements, or a combination thereof. R is ^a02 And R ^a03 May be the same or different.

Namely, R ^a01 、R ^a02 And R ^a03 May also contain carbon-carbon single bonds, carbon-oxygen-carbon ether bonds or halogen elements (fluorine, chlorine, bromine, iodine). As toExamples of the compound represented by the formula (a 3-2) include 2, 2-bis (3, 4-dicarboxyphenoxy) propane dianhydride, bis (3, 4-dicarboxyphenoxy) methane dianhydride, 1-bis (3, 4-dicarboxyphenoxy) ethane dianhydride, 1, 3-bis (3, 4-dicarboxyphenoxy) benzene, 2-bis (3, 4-dicarboxyphenoxy) hexafluoropropane dianhydride and 1, 4-bis (3, 4-dicarboxyphenoxy) benzene dianhydride.

Furthermore, in the above formula (a 3-4), R ^a04 、R ^a05 Represents a substituent having a valence of 1, which is composed of an aliphatic group which may be substituted with a halogen, an aromatic group having 1 or more valences of 2, a halogen, or a combination thereof. R ^a04 And R ^a05 May be the same or different. As the compound represented by the formula (a 3-4), difluoropyromellitic dianhydride, dichloropyromellitic dianhydride, or the like can also be used.

As described above, the polyimide resin (a-I) and the polyamic acid (a-II) preferably have a radical polymerizable group or a cation polymerizable group in the molecular chain thereof.

Thus, the organic group A having a valence of 4 in the formula (A3) ² The group may be represented by the following formulae (a 3-5) to (a 3-7).

[ solution 25]

R in formulae (a 3-5) to (a 3-7) ^a01 、R ^a02 And R ^a03 And R in the formula (a 3-2), the formula (a 3-3) and the formula (a 3-4) ^a01 、Ra ⁰² And R ^a03 The same is true.

R in the formulae (a 3-5), (a 3-6) and (a 3-7) ^a06 Is a radical polymerizable group or a cation polymerizable group. Examples of the radical polymerizable group and the cation polymerizable group may include the above-mentioned groups.

The tetracarboxylic dianhydrides themselves are highly reactive. For example, epoxy groups readily react with carboxylic anhydride groups. Therefore, the corresponding results are from A ² Is a group represented by the formulae (a 3-5) to (a 3-7)When the constituent unit of the tetracarboxylic dianhydride (a) is introduced into the polyimide resin (a-I) or the polyamic acid (a-II), it is preferable to introduce a radical polymerizable group or a cation polymerizable group into the molecular chain of the polyimide resin (a-I) or the polyamic acid (a-II) after the synthesis of the polyimide resin (a-I) or the polyamic acid (a-II).

Examples of the reaction for introducing a radical polymerizable group or a cation polymerizable group include:

1) Etherification reaction of a halogen atom bonded to an aromatic ring in a molecular chain of the polyimide resin (a-I) or the polyamic acid (a-II) with an alcohol compound having a radical polymerizable group or a cation polymerizable group;

2) An esterification reaction of a hydroxyl group bonded to an aromatic ring in a molecular chain of the polyimide resin (a-I) or the polyamic acid (a-II) with a carboxylic acid halide having a radical polymerizable group or a cation polymerizable group;

3) Esterification reaction of a carboxyl group bonded to an aromatic ring in a molecular chain of the polyimide resin (a-I) or the polyamic acid (a-II) with an organic halide having a radical polymerizable group or a cation polymerizable group; and

4) And N-substitution reaction of an amino group bonded to an aromatic ring in a molecular chain of the polyimide resin (A-I) or the polyamic acid (A-II) with an organic halide having a radical polymerizable group or a cation polymerizable group. The reaction for introducing the radically polymerizable group or the cationically polymerizable group is not limited to these reactions.

Further, for example, a polyimide resin (a-I) or a polyamic acid (a-II) having a hydroxyl group, a carboxyl group, an amino group, or the like on an aromatic ring, which is protected with a protecting group such as an acetyl group, a carboxylate group such as a methoxycarbonyl group, an amino group protected with a protecting group such as a tert-butoxycarbonyl group, or the like is synthesized, and then deprotected by a known method, whereby a polyimide resin (a-I) or a polyamic acid (a-II) having a hydroxyl group, a carboxyl group, an amino group, or the like on an aromatic ring can be obtained.

(Process for producing polyimide resin (A-I) and Polyamic acid (A-II))

The method for producing the polyimide resin (A-I) and the polyamic acid (A-II) is not particularly limited. The polyimide resin (a-I) described above can be typically produced by reacting the diamine compound with a tetracarboxylic dianhydride to obtain a polyamic acid (a-II), and then imidizing the polyamic acid (a-II).

In the production of the polyamic acid (a-II), 1 kind of tetracarboxylic dianhydride and 1 kind of diamine may be used alone, or 2 or more kinds may be used in combination.

As described above, the polyimide resin (a-I) and the polyamic acid (a-II) may have a radical polymerizable group or a cation polymerizable group. The radical polymerizable group or the cation polymerizable group may be introduced into the molecular chain after the synthesis of the polyamic acid (a-II) or after the synthesis of the polyimide resin (a-I).

When the radical polymerizable group or the cation polymerizable group is introduced into the molecular chain of the polyamic acid (a-II) or the polyimide resin (a-I) after the synthesis of the polyamic acid (a-II) or the polyimide resin (a-I), the introduction method is not particularly limited.

Typical examples of the method for introducing a radically polymerizable group or a cationically polymerizable group into a molecular chain include a method in which a polyamic acid (a-II) or a polyimide resin (a-I) having a functional group such as a hydroxyl group, an amino group, or a carboxyl group is reacted with a carboxylic acid having a radically polymerizable group, a carboxylic acid halide having a radically polymerizable group, an alcohol having a radically polymerizable group, a phenol having a radically polymerizable group, an amine having a radically polymerizable group, a halogenated compound having a radically polymerizable group, a carboxylic acid having a cationically polymerizable group, a carboxylic acid halide having a cationically polymerizable group, an alcohol having a cationically polymerizable group, a phenol having a cationically polymerizable group, an amine having a cationically polymerizable group, or a halogenated compound having a cationically polymerizable group by a known method such as a condensation reaction or a williamson etherification reaction using a known condensing agent.

In view of easy reaction and easy availability of a compound having a radically polymerizable group or a cationically polymerizable group, it is preferable to condense a part or all of the carboxyl groups of the polyamic acid (a-II) with an alcohol having a radically polymerizable group or an alcohol having a cationically polymerizable group.

In addition, even if the carboxyl group of the polyamic acid (a-II) is modified with an alcohol having a radical polymerizable group or an alcohol having a cation polymerizable group, the modified polyamic acid (a-II) can be imidized by a method such as heating. In this case, imidization by ring closure is promoted while releasing the alcohol having a radical polymerizable group or the alcohol having a cation polymerizable group.

The method of the condensation reaction is not particularly limited. For example, the carboxyl group of the polyamic acid (a-II) and an alcohol having a radical polymerizable group or an alcohol having a cation polymerizable group can be condensed in the presence of a condensing agent such as a carbodiimide compound.

Further, after the carboxyl group of the polyamic acid (a-II) is reacted with a halogenating agent such as a sulfuryl chloride group to prepare a halocarbonyl group (carboxylic acid halide group), the halocarbonyl group may be reacted with an alcohol having a radical polymerizable group or an alcohol having a cation polymerizable group.

Examples of the alcohols having a radical polymerizable group include diol mono (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy-3-methoxypropyl (meth) acrylate, 2-hydroxy-3-butoxypropyl (meth) acrylate, 2-hydroxy-3-tert-butoxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-cyclohexyloxypropyl (meth) acrylate, 3-hydroxypropan-2-yl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 2- (2-hydroxyethoxy) ethyl (meth) acrylate, and 1- (2- (meth) acryloyloxyethyl) 2- (2-hydroxypropyl) phthalate; (meth) acrylates of polyhydric alcohols having hydroxyl groups such as glycerol-1, 3-di (meth) acrylate, glycerol-1, 2-di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate; hydroxyalkyl-substituted (meth) acrylamides such as N- (2-hydroxyethyl) (meth) acrylamide; hydroxyl group-containing ketones such as (hydroxymethyl) vinyl ketone and (2-hydroxyethyl) vinyl ketone; allyl alcohols such as allyl alcohol, 5-hexen-1-ol, 3-hexen-1-ol, 6-hepten-1-ol, 5-octen-1-ol, 3-nonen-1-ol, 6-nonen-1-ol, 9-decen-1-ol, 4-decen-1-ol, 10-undecen-1-ol, 11-dodecen-1-ol, heptadecalinolenol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, and erucyl alcohol.

In the specification of the present application, the term (meth) acrylate refers to both acrylate and methacrylate.

Examples of the alcohols having a cationically polymerizable group include monoglycidyl ethers of glycols such as ethylene glycol monoglycidyl ether, 1, 3-propylene glycol monoglycidyl ether, 1, 4-butylene glycol monoglycidyl ether, 1, 5-pentanediol monoglycidyl ether, 1, 6-hexanediol monoglycidyl ether, diethylene glycol monoglycidyl ether and dipropylene glycol monoglycidyl ether, and alkylene oxides obtained by substituting a hydroxyl group for a glycidyl alcohol or 3, 4-epoxy-1-butanol.

The amount of the tetracarboxylic dianhydride and the diamine compound used in the synthesis of the polyamic acid (a-II) is not particularly limited, but the diamine compound is preferably used in an amount of 0.8 to 1.2 moles, more preferably 0.9 to 1.1 moles, and particularly preferably 0.95 to 1.05 moles, based on 1 mole of the tetracarboxylic dianhydride.

The weight average molecular weight of the obtained polyamic acid (a-II) may be appropriately set according to the use thereof. The weight average molecular weight of the resin can be measured as a weight average molecular weight in terms of polystyrene based on GPC (gel permeation chromatography). For example, the weight average molecular weight of the polyamic acid (a-II) is 5000 or more, preferably 15000 or more, and more preferably 250000000 or more in terms of polystyrene, from the viewpoint of obtaining a cured film having good mechanical properties. On the other hand, the weight average molecular weight of the obtained polyamic acid (a-II) is, for example, 100000 or less, preferably 80000 or less, and more preferably 50000 or less in terms of polystyrene, from the viewpoint of improving the developability.

The weight average molecular weight may be adjusted to the above value by adjusting the reaction conditions such as the blending amount of the tetracarboxylic dianhydride and the diamine compound, the solvent, and the reaction temperature.

The reaction of the tetracarboxylic dianhydride with the diamine compound is generally carried out in an organic solvent. The organic solvent used in the reaction of the tetracarboxylic dianhydride and the diamine compound is not particularly limited as long as it is an organic solvent that can dissolve the tetracarboxylic dianhydride and the diamine compound and does not react with the tetracarboxylic dianhydride and the diamine compound. The organic solvent may be used alone or in combination of two or more.

Examples of the organic solvent used for the reaction of the tetracarboxylic dianhydride and the diamine compound include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinedione, N-dimethylacetamide, N-dimethylpropionamide, N-dimethylisobutylamide, N, N-diethylacetamide, N-dimethylformamide, N-diethylformamide, N-dimethylisobutyric acid amide, methoxy-N, N-dimethylpropionamide, butoxy-N, nitrogen-containing polar solvents such as N-dimethylpropionamide, N-methylcaprolactam, N '-dimethylpropyleneurea, N' -tetramethylurea, and pyridine; dimethyl sulfoxide; sulfolane; lactones such as γ -butyrolactone, γ -valerolactone, δ -valerolactone, γ -caprolactone, e-caprolactone and α -methyl- γ -caprolactone; esters such as methyl acetate, ethyl acetate, butyl acetate, and diethyl oxalate; carbonates such as ethylene carbonate and propylene carbonate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; acetonitrile; ethers such as ethylene glycol dimethyl ether, diethylene glycol diethyl ether, dioxane, and tetrahydrofuran; halogenated hydrocarbons such as methylene chloride, 1, 2-dichloroethane, 1, 4-dichlorobutane, chlorobenzene, and o-dichlorobenzene; hexane, heptane, benzene, toluene, xylene, and the like.

These organic solvents can be used alone in 1, can also be combined with more than 2.

Among these organic solvents, N-methyl-2-pyrrolidone, N-dimethylacetamide and N are preferable from the viewpoint of solubility of the resulting polyamic acid (A-II) and polyimide resin (A-I), nitrogen-containing polar solvents such as N-diethylacetamide, N-dimethylformamide, N-diethylformamide, N-methylcaprolactam, and N, N' -tetramethylurea.

The temperature at which the tetracarboxylic dianhydride and the diamine compound are reacted is not particularly limited as long as the reaction is favorably advanced. Typically, the reaction temperature of the tetracarboxylic dianhydride and the diamine compound is preferably from-5 ℃ to 120 ℃, more preferably from 0 ℃ to 80 ℃, and particularly preferably from 0 ℃ to 50 ℃. The time for reacting the tetracarboxylic dianhydride and the diamine compound varies depending on the reaction temperature, but is typically preferably 30 minutes to 20 hours, more preferably 1 hour to 8 hours, and particularly preferably 2 hours to 6 hours.

In addition, when the polyamic acid (a-II) is produced by the above method, a part of the polyamic acid may be ring-closed to partially progress imidization. For convenience, a resin having an imidization rate of 50% or less was used as the polyamic acid (a-II), and a resin having an imidization rate of more than 50% was used as the polyimide resin (a-I).

In addition, in the case where the tetracarboxylic dianhydride and/or the diamine compound has a radical polymerizable group-containing group containing an ethylenically unsaturated double bond, a polymerization inhibitor may be used in a small amount for the purpose of preventing crosslinking between ethylenically unsaturated double bonds during the reaction. Examples of the polymerization inhibitor include phenols and phenothiazine such as hydroquinone, 4-methoxyphenol, t-butylpyrocatechol and di-t-butylhydroxytoluene. The amount of the polymerization inhibitor used is preferably 0.01 mol% or more and 5 mol% or less based on the number of moles of the ethylenically unsaturated double bond, for example.

The solution containing polyamic acid (a-II) was obtained by the method described above.

The obtained polyamic acid (A-II) is ring-closed and imidized to produce a polyimide resin (A-I).

The method of imidization is not particularly limited. The imidization may be carried out by heating, or may be carried out using an imidizing agent.

When imidization is performed by heating, the heating may be performed on a solution or suspension of the polyamic acid (a-II), or may be performed on the solid polyamic acid (a-II).

When the solution of polyamic acid (a-II) is heated to effect imidization, it is preferable to perform heating while removing water produced as a by-product at the time of imidization.

The conditions of heating for imidization are not particularly limited as long as the polyamic acid (a-II) or the polyimide resin (a-I) does not decompose and imidization progresses well.

When the solution of polyamic acid (a-II) is heated, the heating temperature is typically preferably 80 ℃ to 220 ℃, more preferably 100 ℃ to 200 ℃, and particularly preferably 120 ℃ to 180 ℃. When solid polyamic acid (a-II) is heated, the heating temperature is typically preferably 180 ℃ to 400 ℃ inclusive, and more preferably 200 ℃ to 350 ℃ inclusive.

The heating time depends on the heating temperature, and is typically preferably 1 hour to 24 hours, and more preferably 2 hours to 12 hours.

When the polyamic acid (a-II) is imidized by an imidizing agent, the imidizing agent is usually added to a solution or suspension of the polyamic acid (a-II) to perform imidization. As the organic solvent that can be used in the case of performing imidization with an imidizing agent, for example, the same organic solvent as that which can be used in the preparation of the polyamic acid (a-II) can be used.

When imidization is performed by an imidizing agent, the concentration of the polyamic acid (a-II) in the solution or suspension of the polyamic acid (a-II) is not particularly limited. Typically, the concentration of the polyamic acid (a-II) in the solution or suspension of the polyamic acid (a-II) is preferably 5% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 30% by mass or less.

The amount of the imidizing agent to be used is not particularly limited. The amount of the imidizing agent to be used may be selected depending on the kind of the imidizing agent so that the polyamic acid (a-II) is imidized to a desired degree.

The reaction temperature in the case of imidizing with an imidizing agent is not particularly limited. The reaction temperature is, for example, preferably 0 ℃ to 100 ℃ and more preferably 5 ℃ to 50 ℃.

The time of the imidization reaction in the case of using an imidizing agent is not particularly limited. Depending on the type of imidizing agent, the imidization reaction is preferably carried out for, for example, about 30 minutes to 24 hours, more preferably 1 hour to 12 hours, and still more preferably 2 hours to 6 hours.

Examples of the imidizing agent include acetic anhydride, propionic anhydride, benzoic anhydride, trifluoroacetic anhydride, acetyl chloride, tosyl chloride, methylsulfonyl chloride, ethyl chloroformate, a dehydrating agent such as triphenylphosphine and dibenzoimidazolyl disulfide, dicyclohexylcarbodiimide, carbonyldiimidazole, 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline and oxalic acid N, N '-disuccinimidyl ester, and basic compounds such as pyridine, picoline, 2, 6-lutidine, collidine, triethylamine, N-methylmorpholine, 4-N, N' -dimethylaminopyridine, isoquinoline, triethylamine, 1, 4-diazabicyclo [ 2.2.2 ] octane and 1, 8-diazabicyclo [ 5.4.0 ] -7-undecene.

[ Polyamide resin (A-III) ]

The polyamide resin (a-III) is a resin derived from a diamine compound, a dicarboxylic acid compound, or an amide-forming derivative of a dicarboxylic acid compound.

(diamine Compound)

The diamine compound may be the same as the compound described for the polyimide resin (a-I) and the polyamic acid (a-II).

As described above, in view of photosensitivity, the resin (a) blended in the photosensitive resin composition may have a polymerizable group polymerizable by the action of the photosensitizer (C) on its molecular chain. The polymerizable group is typically preferably a radical polymerizable group or a cation polymerizable group, and more preferably a radical polymerizable group.

The bonding position of the radical polymerizable group or the cation polymerizable group in the molecular chain of the polyamide resin (A-III) is not particularly limited. The radical polymerizable group and the cation polymerizable group are as described for the polyimide resin (a-I) and the polyamic acid (a-II).

The amount of the radical polymerizable group or the cation polymerizable group in the polyamide resin (A-III) is the same as the amount of the radical polymerizable group or the cation polymerizable group in the polyimide resin (A-I) and the polyamic acid (A-II).

(dicarboxylic acid Compound and amide-Forming derivative of dicarboxylic acid Compound)

As the dicarboxylic acid compound, various dicarboxylic acid compounds conventionally used as raw materials for polyamide resins can be used without particular limitation.

The dicarboxylic acid compound is preferably an aliphatic dicarboxylic acid having 2 to 50 carbon atoms or an aromatic carboxylic acid having 8 to 50 carbon atoms, for example.

Examples of the amide-forming derivative of the dicarboxylic acid compound include a dicarboxylic acid halide of the dicarboxylic acid compound and an activated dicarboxylic acid compound. As the dicarboxylic acid halide, dicarboxylic acid chloride and dicarboxylic acid bromide are preferable, and dicarboxylic acid chloride is more preferable. Examples of the active group derived from the carboxyl group in the activated dicarboxylic acid compound include phenoxycarbonyl, (2-thio (thioxo) -2, 3-dihydrobenzoxazol-3-yl) carbonyl, 1H-1,2, 3-triazol-1-ylcarbonyl, 1H-benzotriazol-1-yloxycarbonyl, 1H-imidazol-1-ylcarbonyl, succinimidyloxycarbonyl and 3H-1,2, 3-triazolo [4,5-b ] pyridin-3-yloxycarbonyl.

When the active group derived from a carboxyl group contains an aromatic ring, the aromatic ring may be substituted with 1 or more substituents selected from the group consisting of methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, trifluoromethyl group, chlorine atom, bromine atom, iodine atom, phenoxy group, and nitro group.

Suitable examples of the dicarboxylic acid compound include adipic acid, sebacic acid, terephthalic acid, isophthalic acid, 2, 6-naphthalenedicarboxylic acid, 1, 6-naphthalenedicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, 1, 4-naphthalenedicarboxylic acid, 4' -dicarboxybiphenyl, and alkyl, alkoxy or halogen substituents thereof.

The alkyl group as a substituent is preferably an alkyl group having 1 to 4 carbon atoms. The alkoxy group as a substituent is preferably an alkoxy group having 1 to 4 carbon atoms.

When the dicarboxylic acid compound is substituted with an alkyl group, an alkoxy group or a halogen, the number of substitution is preferably 1 to 4, more preferably 1 or 2, and still more preferably 1.

Further, the following dicarboxylic acid compounds can also be suitably used as the dicarboxylic acid compound: a dicarboxylic acid compound having 2 carboxyl groups and 2 carboxylate groups or 2 carboxamide groups, which is obtained by reacting a monohydroxy compound or a monoamine compound with the acid anhydride groups of the carboxylic dianhydride described for the polyimide resin (a-I) and the polyamic acid (a-II).

<xnotran> ,1,4- (3,4- ) ,4,4'- ,3,3',4,4 '- ,2,3,3', 4'- ,3,3',4,4 '- ,2,2', 3,3'- ,3,3',4,4 '- ,3,3',4,4 '- , (3,4- ) ,1,2,5,6- ,2,3,6,7- ,2,3,5,6- ,3,4,9, 10- , [5,5' - (1,4- ) </xnotran>]2,2', 3' -tetracarboxylic dianhydrides (e.g. ENEHYDE (note)Trade mark) BzDA, manufactured by ENEOS Inc.), 1, 3a,4,5,9 b-hexahydro-5 (tetrahydro-2, 5-dioxo-3-furyl) naphtho [1,2-C ]]Furan-1, 3-dione (for example, RIKACID TDA-100, manufactured by Nippon Co., ltd.), 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl group]Propane dianhydride, 4' -bis (3, 4-dicarboxyphenylcarbonyloxy) biphenyl dianhydride, 2, 6-bis (3, 4-dicarboxyphenylcarbonyloxy) naphthalene dianhydride, 1, 2-bis (3, 4-dicarboxyphenylcarbonyloxy) ethane dianhydride (e.g., RIKACID TMEG100, manufactured by Nippon chemical Co., ltd.) and 1, 10-bis (3, 4-dicarboxyphenylcarbonyloxy) decane dianhydride (e.g., 10BTA, manufactured by Nippon chemical Co., ltd.) are preferably used in such a manner that R is equal to ^a21 An alcohol represented by-OH or R ^a21 -NH ₂ A dicarboxylic acid compound obtained by reacting the amine represented by the formula with an aromatic tetracarboxylic dianhydride.

R ^a21 Is a 1-valent organic group.

Such dicarboxylic acid compounds have 2 pairs of carboxyl groups and-CO-X groups located on adjacent carbon atoms in the dicarboxylic acid compound ^a -R ^a21 The pair of radicals indicated. X ^a is-O-or-NH.

As R ^a21 The number of carbon atoms of the 1-valent organic group(s) of (3) is preferably 1 to 20, more preferably 1 to 16, still more preferably 1 to 12, and particularly preferably 1 to 8.

As R ^a21 The 1-valent organic group (b) may, for example, be an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an alkoxyalkoxyalkyl group having 3 to 20 carbon atoms, a (meth) acryloyloxyalkyl group having 4 to 20 carbon atoms, a (meth) acryloyloxyalkyloxyalkyloxyalkyloxyalkyl group having 5 to 20 carbon atoms, a glycidyloxyalkyl group having 4 to 20 carbon atoms and a glycidyloxyalkyloxyalkyl group having 5 to 20 carbon atoms.

Having 2 pairs of carboxyl groups with-CO-X ^a -R ^a21 In the above dicarboxylic acid compound of the pair of the groups represented, there areAt the position of the carboxyl group with-CO-X ^a -R ^a21 The indicated groups are isomers with different positions. As the dicarboxylic acid compound, 1 kind of such isomer may be used alone, or 2 or more kinds may be used in combination.

For example, regarding the dicarboxylic acid compound corresponding to pyromellitic dianhydride, there are a compound represented by the following formula (a 4-a 1) and a compound represented by the following formula (a 4-a 2) as isomers. Further, as for the dicarboxylic acid compound corresponding to 1, 4-bis (3, 4-dicarboxyphenoxy) benzene dianhydride, there are a compound represented by the following formula (a 4-b 1), a compound represented by the following formula (a 4-b 2), and a compound represented by the following formula (a 4-b 3) as isomers.

In the following formulae (a 4-a 1), (a 4-a 2) and (a 4-b 1) to (a 4-b 3), X ^a And R ^a21 As described above respectively.

[ solution 26]

Examples of the dicarboxylic acid compound corresponding to the tetracarboxylic dianhydride represented by the above formulae (a 3-2) to (a 3-4) include compounds represented by the following formulae (a 4-2 a) to (a 4-2 c), formulae (a 4-3 a) to (a 4-3 c), and formulae (a 4-4 a) to (a 4-4 c). In the formulae (a 4-2 a) to (a 4-2 c), the formulae (a 4-3 a) to (a 4-3 c) and the formulae (a 4-4 a) to (a 4-4 c), R ^a01 ～R ^a05 The same applies to the formulae (a 3-2) to (a 3-4). In the formulae (a 4-2 a) to (a 4-2 c), the formulae (a 4-3 a) to (a 4-3 c) and the formulae (a 4-4 a) to (a 4-4 c), X ^a And R ^a21 As described above.

[ solution 27]

Examples of the dicarboxylic acid compound corresponding to the tetracarboxylic dianhydride represented by the above formulae (a 3-5) to (a 3-7) include the following formulae (a 4-5 a) to (a 4-5 c), formulae (a 4-6 a) to (a 4-6 c), and formulae(a 4-7 a) and a compound represented by the formula (a 4-7 b). In the formulae (a 4-5 a) to (a 4-5 c), the formulae (a 4-6 a) to (a 4-6 c), the formulae (a 4-7 a) and the formulae (a 4-7 b), R ^a01 ～R ^a03 、R ^a06 M1 and m2 are the same as those in the formulae (a 3-5) to (a 3-7). In the formulae (a 4-5 a) to (a 4-5 c), the formulae (a 4-6 a) to (a 4-6 c), the formulae (a 4-7 a) and the formulae (a 4-7 b), X ^a And R ^a21 As described above.

[ solution 28]

The monohydroxy compound which gives the dicarboxylic acid compound by the reaction with the tetracarboxylic dianhydride may, for example, be an alkanemonoalcohol such as methanol, ethanol, n-propanol, isopropanol, n-butanol, n-pentanol or n-hexanol; phenols or naphthols such as phenol, p-cresol, m-cresol, o-cresol, α -naphthol, and β -naphthol; glycol monoethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 1, 3-propylene glycol monomethyl ether, 1, 3-propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether; alcohols having the above radical polymerizable group; alcohols having the above-mentioned cationically polymerizable group.

The reaction of the tetracarboxylic dianhydride with the monohydroxy compound or the monoamine compound can be carried out in the same manner as the reaction of the tetracarboxylic dianhydride and the diamine compound described as the method for producing the polyamic acid (II). The reaction of the tetracarboxylic dianhydride with the monohydroxy compound or the monoamine compound may be carried out in the presence of an organic base such as pyridine, triethylamine, diisopropylethylamine, 4-dimethylaminopyridine, 1, 4-azabicyclo [2, 2] octane, or the like. These bases may be used alone or in combination of 2 or more.

The amount of the monohydroxy compound or the monoamine compound to be used is preferably 1.8 mol or more and 2.2 mol or less, and more preferably 2 mol or more and 2.1 mol or less, based on 1 mol of the tetracarboxylic dianhydride.

A dicarboxylic acid compound obtained by reacting a tetracarboxylic dianhydride with the monohydroxy compound or monoamine compound can be obtained. In the production of the dicarboxylic acid compound, depending on the production conditions, only one dicarboxylic anhydride group is reacted with a monohydroxy compound or a monoamine compound to produce a monocarboxylic acid compound having a dicarboxylic anhydride group, or a part of tetracarboxylic dianhydride is reacted with moisture in the reaction system to produce a tetracarboxylic acid compound or a tricarboxylic acid compound.

If a resin is obtained, a dicarboxylic acid compound containing at least 1 selected from the monocarboxylic acid compound, the tricarboxylic acid compound, and the tetracarboxylic acid compound can be used for the production of the polyamide resin (a-III).

When the dicarboxylic acid compound contains at least 1 selected from the monocarboxylic acid compound, the tricarboxylic acid compound, and the tetracarboxylic acid compound as an impurity, the content of the at least 1 selected from the monocarboxylic acid compound, the tricarboxylic acid compound, and the tetracarboxylic acid compound as an impurity in the dicarboxylic acid compound is preferably 30% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and particularly preferably 1% by mass or less, relative to the mass of the dicarboxylic acid compound containing the impurity.

(method for producing Polyamide resin (A-III))

The method for producing the polyamide resin (A-III) is not particularly limited.

A preferable production method of the polyamide resin (a-III) may, for example, be a method of condensing a diamine compound and a dicarboxylic acid compound with a condensing agent. Examples of the condensing agent include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1, 2-dihydroquinoline, 1-carbonyldioxy-di-1, 2, 3-benzotriazole and N, N' -disuccinimidyl carbonate.

Another preferable method is a method of condensing a dicarboxylic acid compound or an acid halide of a dicarboxylic acid compound with a diamine compound in the presence of a base. In this method, a condensing agent may be used together with a base as needed.

As the acid halide, acid chloride and acid bromide are preferable, and acid chloride is more preferable.

Examples of the base include pyridine, triethylamine, diisopropylethylamine, 4-dimethylaminopyridine and 1, 4-azabicyclo [2, 2] octane.

Examples of the condensing agent include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N ' -carbonyldiimidazole, dimethoxy-1, 3, 5-triazinylmethyl morpholine, O- (benzotriazol-1-yl) -N, N ' -tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N ' -tetramethyluronium hexafluorophosphate, diphenyl (2, 3-dihydro-2-thio (thioxo) -3-benzoxazolyl) phosphonate, and 4- (4, 6-dimethoxy-1, 3, 5-triazin-2-yl) 4-methoxymorpholino chloride hydrate.

Specifically, the dicarboxylic acid compound or the acid halide of the dicarboxylic acid compound or the diamine compound is reacted in an organic solvent in the presence of the base at, for example, -20 ℃ to 150 ℃ inclusive, preferably 0 ℃ to 50 ℃ inclusive, for 30 minutes to 24 hours inclusive, preferably 1 hour to 4 hours inclusive.

The amount of the base used is preferably 2 to 4 mol times based on the number of moles of the dicarboxylic acid compound or the acid halide of the dicarboxylic acid compound, from the viewpoint of easy removal and easy obtainment of a high molecular weight material.

Further, the following method is also preferable: after converting a carboxyl group of a dicarboxylic acid compound into an active group, a compound having an active group derived from a dicarboxylic acid compound is condensed with a diamine compound. Examples of the active group derived from the carboxyl group in the activated dicarboxylic acid compound include phenoxycarbonyl, (2-thio (thioxo) -2, 3-dihydrobenzoxazol-3-yl) carbonyl, 1H-1,2, 3-triazol-1-ylcarbonyl, 1H-benzotriazol-1-yloxycarbonyl, 1H-imidazol-1-ylcarbonyl, succinimidyloxycarbonyl and 3H-1,2, 3-triazolo [4,5-b ] pyridin-3-yloxycarbonyl.

[ polybenzoxazole resin (A-IV) and polybenzoxazole resin precursor (A-V) ]

The polybenzoxazole resin precursor (a-V) is a resin derived from an amide-forming derivative of a dicarboxylic acid compound or a dicarboxylic acid compound and a diamine compound which is an aromatic compound having 2 amino groups bonded to an aromatic ring and having a hydroxyl group bonded to a carbon atom at a position adjacent to the carbon atom bonded to the amino group on the aromatic ring.

Such polybenzoxazole resin precursors (a to V) have a hydroxyl group at a position adjacent to a carbon atom bonded to a carbonyl group in a carboxylic acid amide bond (-CO-NH-) on an aromatic ring.

The polybenzoxazole resin (A-IV) is produced by ring-closing a polybenzoxazole resin precursor (A-V).

Hereinafter, the diamine compound and the dicarboxylic acid compound will be described.

(diamine Compound)

As described above, the resin (a) contains a structural unit derived from a compound represented by the following formula (A1).

[ solution 29]

When the resin (a) is a polybenzoxazole resin (a-IV) or a polybenzoxazole resin precursor (a-V), the ratio of the number of moles of a structural unit derived from the compound represented by the formula (A1) in the polybenzoxazole resin (a-IV) or the polybenzoxazole resin precursor (a-V) to the number of moles of all structural units derived from the diamine compound is preferably 10 mol% or more and 100 mol% or less, more preferably 15 mol% or more and 100 mol% or less, and still more preferably 20 mol% or more and 100 mol% or less.

The other diamine compound is represented by the following formula (A2-1).

[ solution 30]

(in the formula (A2-1), A ³ Represents a 4-valent organic group containing 1 or more aromatic rings. Wherein, as A ³ The 2-valent organic group(s) of (A1) does not belong to the group consisting of X, ar and R ^a1 And R ^a2 A group of (a) a group of (b). In the compound represented by the formula (A2-1), 2 amino groups are bonded to the group A ³ The aromatic group in the organic group (2) is bonded. In the compound represented by the formula (A2-1), 2 hydroxyl groups are bonded to carbon atoms at positions adjacent to the carbon atom to which the amino group is bonded in the aromatic group, respectively. )

As the dicarboxylic acid compound and the amide-forming derivative of the dicarboxylic acid compound, the same compounds as those described for the polyamide resin (a-III) as the dicarboxylic acid compound and the amide-forming derivative of the dicarboxylic acid compound can be used.

(methods for producing polybenzoxazole resin (A-IV) and polybenzoxazole resin precursor (A-V))

The polybenzoxazole resin precursor (a-V) can be produced by reacting the diamine compound with a dicarboxylic acid compound in the same manner as the production method of the polyamide resin (a-III).

The polybenzoxazole resin precursors (a to V) thus obtained are subjected to ring closure by heating, thereby obtaining polybenzoxazole resins (a to IV). The heating temperature is, for example, preferably 120 ℃ to 350 ℃ inclusive, and more preferably 150 ℃ to 350 ℃ inclusive.

Further, the polybenzoxazole resin (a-IV) can also be obtained by chemically ring-closing by allowing a dehydrating agent to act on the polybenzoxazole resin precursors (a-V).

The main chain end of the resin (a) may be capped with a capping agent for the purpose of improving storage stability of the photosensitive resin composition, further improving mechanical properties of a film formed using the photosensitive resin composition, improving reproducibility of polymerization in producing the resin (a), and the like. Examples of the "end-capping agent" may include monoamines, acid anhydrides, monocarboxylic acids, monoacyl halides and mono-active ester compounds.

As the monoamine used for the end capping, a known compound can be used. Examples of the monoamine include aromatic monoamines such as aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 3-hydroxyaniline, 4-hydroxyaniline, 3-aminothiophenol and 4-aminothiophenol, aliphatic monoamines having a branched structure and having 3 to 20 carbon atoms such as hexylamine and octylamine, monoamines having an alicyclic structure such as cyclohexylamine, trimethoxyaminopropylsilane and triethoxyaminopropylsilane.

Among acid anhydrides, monoacyl halides, and mono-active ester compounds used as the end-capping agent, acid anhydrides are preferred. As the acid anhydride, a known acid anhydride or a derivative thereof can be used. Examples thereof include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, exo-3, 6-epoxy-1, 2,3, 6-tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, nadic anhydride and derivatives thereof.

The introduction rate of the end-capping agent into the resin (a) is preferably 40 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less based on the number of moles of all monomers, from the viewpoint of excellent mechanical properties of a film formed using the photosensitive resin composition and excellent developability of the photosensitive resin composition.

< monomer Compound (B) >

When the resin (a) has a radical polymerizable group, the photosensitive resin composition may contain a monomer compound having an ethylenically unsaturated double bond as the monomer compound (B) in addition to the polyimide resin (a). The monomer compound (B) may be a monofunctional monomer compound or a polyfunctional monomer compound, and is preferably a polyfunctional monomer compound.

Examples of the monofunctional monomer compound include: (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylylidene (meth) acrylamide, N-methylol (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, furfuryl mono (meth) acrylate, tetrahydroxy (meth) acrylate, dimethylamino (meth) acrylate, 2-trifluoroethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2,2,2,3,3-tetrafluoropropyl (meth) acrylate, a semi (meth) acrylate of a phthalic acid derivative, and the like. These monofunctional photopolymerizable monomers can be used alone or in combination of two or more.

Examples of the polyfunctional monomer compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, dimethylol decane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (3- (meth) acryloyloxypropyl) ether, glycerol di (meth) acrylate, tri (meth) acrylate of glycerol Ethylene Oxide (EO) adduct, tri (meth) acrylate of glycerol Propylene Oxide (PO) acrylate, tri (meth) acrylate of glycerol/PO co-adduct, and tri (meth) acrylate of ethylene oxide (meth) acrylate of trimethylolpropane Ethylene Oxide (EO) adduct, and tri (meth) acrylate of ethylene oxide (meth) acrylate, tri (meth) acrylate of trimethylolpropane PO adduct, tri (meth) acrylate of trimethylolpropane EO/PO co-adduct, tri (meth) acrylate of trimethylolethane EO adduct, tri (meth) acrylate of trimethylolethane PO adduct, tri (meth) acrylate of trimethylolethane EO/PO co-adduct, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, pentapentaerythritol undec (meth) acrylate, pentapentaerythritol dodeca (meth) acrylate, dimethylol-tricyclodecane di (meth) acrylate, 1, 3-adamantanediol di (meth) acrylate, 1,3, 5-adamantanetriol tri (meth) acrylate, 1, 4-cyclohexanedimethanol di (meth) acrylate, 2-acryloxy-2, 2- (4-acryloxy) propane di (meth) acrylate, examples of the monomer include a monomer such as 2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, 9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl ] fluorene, 9-bis [4- (2- (meth) acryloyloxypropyloxy) -3-methylphenyl ] fluorene, 9-bis [4- (2- (meth) acryloyloxyethoxy) -3, 5-dimethylphenyl ] fluorene, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (i.e., toluene diisocyanate), a reaction product of trimethylhexamethylene diisocyanate with hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, tris ((meth) acryloyloxyethyl) isocyanurate, methylenebis (meth) acrylamide, (meth) acrylamide methylene ether, a condensate of a polyhydric alcohol with N-methylol acrylamide, and other monomer such as a polyfunctional acetal compound. These polyfunctional monomer compounds can be used alone or in combination of 2 or more.

In addition, urethane (meth) acrylates described in Japanese patent application laid-open No. 48-41708, japanese patent application laid-open No. 50-6034, and Japanese patent application laid-open No. 51-37193; polyester (meth) acrylates described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490; epoxy (meth) acrylates as a reaction product of an epoxy resin and (meth) acrylic acid; compounds described in paragraphs [0254] to [0257] of japanese patent laid-open No. 2008-292970; a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having an epoxy group such as glycidol (meth) acrylate and an ethylenically unsaturated group; compounds or cardo resins having a fluorene ring and having 2 or more groups having an ethylenically unsaturated bond, described in japanese patent application laid-open nos. 2010-160418, 2010-129825, and 4364216; unsaturated compounds described in Japanese examined patent publication (Kokoku) Nos. 46-43946, 1-40337 and 1-40336; vinylphosphonic acid compounds described in Japanese patent laid-open No. 2-25493; a compound containing a perfluoroalkyl group described in Japanese patent application laid-open No. 61-22048; photopolymerizable monomers and oligomers described in journal of Japan Association, vol.20, no.7, pages 300 to 308 (1984).

Among these monomer compounds having an ethylenically unsaturated double bond, from the viewpoint of tending to improve the adhesion of the cured product to the substrate and the strength of the cured product, a polyfunctional monomer compound having 3 or more functions is preferred, a polyfunctional monomer compound having 4 or more functions is more preferred, and a polyfunctional monomer compound having 5 or more functions is even more preferred.

In the case where the resin (a) has a vinyloxy group-containing group as the cationically polymerizable group, the photosensitive resin composition may contain a vinyl ether compound as the monomer compound (B) together with the resin (a). The vinyl ether compound may be a monofunctional compound having 1 vinyloxy group, or may be a polyfunctional compound having 2 or more vinyloxy groups.

In the case where the resin (a) has an epoxy group-containing group as the cationically polymerizable group, the photosensitive resin composition may contain various epoxy compounds as the monomer compound (B).

The content of the monomer compound (B) in the photosensitive resin composition is not particularly limited within a range not to impair the object of the present invention. The content of the monomer compound (B) in the photosensitive resin composition is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 40 parts by mass, and particularly preferably 1 to 25 parts by mass, when the mass of the photosensitive resin composition excluding the mass of the solvent (S) described later is assumed to be 100 parts by mass.

< sensitizer (C) >

The photosensitive resin composition contains a photosensitizer (C) of a type determined by the type of the resin (A). In the case where the resin (a) has a radical polymerizable group on its molecular chain or the photosensitive resin composition contains the monomer compound (B) having a radical polymerizable group together with the resin (a), a photo radical polymerization initiator (C1) may be used as the photosensitizer (C). When the resin (a) has a cationically polymerizable group in its molecular chain, a photo cationic polymerization initiator (C2) may be used as the photosensitizer (C).

The photo radical polymerization initiator (C1) and the photo cation polymerization initiator (C2) are not particularly limited, and conventionally known photo polymerization initiators can be used.

Specific examples of the photo radical polymerization initiator (C1) include: 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] phenyl } -2-methyl-propan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-dimethoxy-1, 2-diphenylethan-1-one, bis (4-dimethylaminophenyl) one, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-carbonylphenyl-oxime, 1-phenyl-1, 2-propanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-2- (benzoyloximino) -1-propanone, 1-phenyl-1, 2-butanedione-2- (O-methoxycarbonyl) oxime, 1, 3-diphenylpropanetrione-2- (O-ethoxycarbonyl) oxime, ethanone, 1-phenyl-1, 2-propanedione-2- (O-benzoyl) oxime, 1-phenyl-3-ethoxypropanetrione-2- (O-benzoyl) oxime, O-acetyl-1- [6- (2-methylbenzoyl) -9-ethyl-9H-carbazol-3-yl ] ethanone oxime (Irgacure OXE02, manufactured by BASF BASPAN), 9-ethyl-6-nitro-9H-carbazol-3-yl) [4- (2-methoxy-1-methylethoxy) -2-methylphenyl ] O-acetyloxime, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (0-methoxy-1-methylethoxy) -2-methylphenyl ] acetyloxime, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (0- (1-octyloxy) -1- (1-benzoyloxy) -1- (1-phenyl) oxime, BASF JAPAN), NCI-831 (ADEKA), NCI-930 (ADEKA), OXE-03 (BASF JAPAN), OXE-04 (BASF JAPAN), 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) -2, 4-trimethylpentylphosphine oxide, 4-benzoyl-4' -methyldimethylsulphide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate 2-isoamyl 4-dimethylaminobenzoate, ethyl 4-diethylbenzoate, benzyl- β -methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime, methyl O-benzoylbenzoate, methyl benzoylformate, ethyl benzoylformate, 2, 4-diethylthioxanthone, 2-chlorothioxanthone, 2, 4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothiaxanthone, 2, 4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, anthraquinone, 2-ethylanthraquinone, ethyl 4-diethylthioxanthone, ethyl-ethoxycarbonyl-O-ethyl-oxoethyl-benzoylformate, 2, 4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, anthraquinone, 2-ethylanthraquinone, ethyl-ethylthioxanthone, ethyl-thioxanthone, methyl-thioxanthone, and their salts, <xnotran> 2- , ,2- , β - ,1,2- ,2,3- , , , , , , , ,2- ,2- ,2- ,2- ( ) -4,5- ( ) - , ,2- , p, p ' - ,4,4' - ,4,4' - ,3,3- -4- ,4- ,4- , , , , , , , , , ,2,2- , , ,2- -2- , , , ,2- , , , , α, α - -4- , ,2- ,2- ,2,4- ,2,4- , </xnotran> 2-chlorothioxanthone, 2, 4-dichlorothioxanthone, 2-hydroxy-3- (3, 4-dimethyl-9-oxo-9H-thioxanthen-2-yloxy) -N, N-trimethyl-1-propanaminium chloride, 4-azidobenzylideneacetophenone, 2, 6-bis (p-azidobenzylidene) cyclohexane, 2, 6-bis (p-azidobenzylidene) -4-methylcyclohexanone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-benzacridine, 1, 7-bis- (9-acridinyl) heptane, 1, 5-bis- (9-acridinyl) pentane, 1, 3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4, 6-tris (trichloromethyl) -s-triazine, 2-methyl-4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (3, 4-dimethoxyphenyl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2, 4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2, 4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2, 4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2, 4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine, 4-benzoyl-4 '-methyldiphenylketone, dibenzylketone, 4-benzoyl-4' -methyldiphenylsulfide, 3',4' -alkyldiphenylsulfide, 3',4' -tetrahydroxybutylbenzophenone, 3',4' -t-butyl-benzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl ] benzylammonium bromide, (4-benzoylbenzyl) trimethylammonium chloride, 2-hydroxy-3- (4-benzoylphenoxy) -N, N, N-trimethyl-1-propenylammonium chloride monohydrate, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, benzothiazyl disulfide, triphenylphosphine, carbon tetrabromide, tribromophenylsulfone, and the like. These photo radical polymerization initiators (C1) can be used alone or in combination of 2 or more.

From the viewpoint of good sensitivity, the photoradical polymerization initiator (C1) is preferably an oxime ester type photopolymerization initiator.

In view of sensitivity of the photosensitive resin composition, the photoradical polymerization initiator (C1) is preferably an oxime ester compound.

The oxime ester compound is preferably a compound having a partial structure represented by the following formula (c 1).

[ solution 31]

(in the formula (c 1),

n1 is 0 or 1, and n is a linear alkyl group,

R ^c2 is a 1-valent organic radical, and is,

R ^c3 an aliphatic hydrocarbon group which may have a substituent and has 1 to 20 carbon atoms or an aryl group which may have a substituent,

* Is a chemical bond. )

The photo-cationic polymerization initiator (C2) may typically be an onium salt. Examples of the photo cation polymerization initiator (C2) include oxonium salt, ammonium salt, phosphonium salt, sulfonium salt and iodonium salt, preferably sulfonium salt and iodonium salt, and more preferably sulfonium salt.

The content of the photo radical polymerization initiator (C1) or the photo cation polymerization initiator (C2) in the photosensitive resin composition is not particularly limited as long as the photosensitive resin composition has desired lithographic characteristics. The content of the photo radical polymerization initiator (C1) or the photo cation polymerization initiator (C2) in the photosensitive resin composition is typically preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and further preferably 1 to 10 parts by mass, relative to 100 parts by mass of the total of the mass of the resin (a) and the mass of the monomer compound (B).

The photosensitive resin composition may further contain a quinonediazido group-containing compound (C3) as the photosensitizer (C). The photosensitive resin composition containing the quinonediazido group-containing compound (C3) is a positive photosensitive resin composition soluble in an alkaline developer upon exposure to light.

The quinonediazide group-containing compound (C3) can be appropriately selected from compounds having quinonediazide groups that have been conventionally blended with various positive photosensitive resin compositions. The quinonediazide-containing compound (C3) may be used alone or in combination of 2 or more.

The quinonediazide-containing sulfonic acid used as the quinonediazide-containing compound (C3) is not particularly limited, and examples thereof include naphthoquinonediazide sulfonic acids such as naphthoquinonediazide-1, 2-diazide-5-sulfonic acid and naphthoquinonediazide-1, 2-diazide-4-sulfonic acid; ortho-anthraquinone diazide sulfonic acid and the like, and naphthoquinone diazide sulfonic acid is preferable. The above ester compound of a quinonediazido group-containing sulfonic acid, preferably naphthoquinonediazidosulfonic acid, is well dissolved in a solvent which is generally used when the photosensitive resin composition is used as a solution. When these compounds are blended as the quinonediazido group-containing compound (C3) with the quinonediazido group-containing compound (C3), a highly sensitive positive photosensitive resin composition can be easily obtained.

The method for producing the above ester compound of the quinonediazido group-containing compound (C3) is not particularly limited, and examples thereof include the following methods: a method in which a quinone diazide group-containing sulfonic acid is added as a sulfonyl chloride such as naphthoquinone-1, 2-diazide-sulfonyl chloride, and the resulting mixture is condensed in a solvent such as dioxane in the presence of a base such as triethanolamine, a base of carbonic acid, or a base of hydrogen carbonate to thereby completely or partially esterify the sulfonic acid.

From the viewpoint of sensitivity of the photosensitive resin composition, the content of the quinonediazido group-containing compound (C3) is preferably in the following range. The lower limit is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more, per 100 parts by mass of the resin (a). The upper limit is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and still more preferably 30 parts by mass or less, relative to 100 parts by mass of the resin (a).

< organic solvent (S) >

The photosensitive resin composition may contain an organic solvent (S) for the purpose of adjusting coatability, for example. The type of the organic solvent (S) is not particularly limited as long as the resin (a) and other components are satisfactorily dissolved.

Specific examples of the organic solvent (S) include, from the viewpoint of good solubility of the resin (a): nitrogen-containing polar solvents such as N, N-dimethylformamide, N-dimethylacetamide, N-diethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, hexamethylphosphoramide, 1, 3-dimethyl-2-imidazolidinone, N-dimethylisobutyramide, 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, N-dimethylisobutylamide, and N, N-dimethylacrylamide; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, diisobutyl ketone, cyclopentanone, cyclohexanone, and isophorone; gamma-butyrolactone, gamma-valerolactone, delta-valerolactone, gamma-caprolactone, epsilon-caprolactone, alpha-methyl-gamma-butyrolactone, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, isobutyl acetate, isoamyl acetate, n-pentyl formate, n-butyl propionate, isopropyl butyrate, ethyl butyrate, n-butyl butyrate, methyl methoxyacetate, ethyl methoxyacetate, n-butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, methyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl cellosolve, and the like; alcohols such as diacetone alcohol and 3-methyl-3-methoxybutanol; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether and the like; aromatic ethers such as anisole; cyclic ethers such as dioxane and tetrahydrofuran; cyclic esters such as ethylene carbonate and propylene carbonate; aromatic solvents such as anisole, toluene, and xylene; aliphatic hydrocarbons such as limonene; sulfoxides such as dimethyl sulfoxide.

The amount of the organic solvent (S) used is not particularly limited as long as a uniform liquid photosensitive resin composition can be prepared. The photosensitive resin composition may be a suspension or a solution, and is preferably a solution. Typically, the organic solvent (S) is used so that the solid content concentration of the photosensitive resin composition is preferably 15 mass% or more and 50 mass% or less, and more preferably 20 mass% or more and 45 mass% or less.

< other ingredients >

The photosensitive resin composition may contain various additives other than the above-described components as necessary. Examples of the additives include a colorant, a dispersant, a sensitizer, an adhesion promoter, a polymerization inhibitor, an antioxidant, an ultraviolet absorber, an anticoagulant, a defoaming agent, a surfactant, an imidization promoter, a nitrogen-containing heterocyclic compound as an adhesion promoter, and a silane coupling agent. The photosensitive resin composition may contain various fillers or reinforcing materials as necessary.

As the sensitizer, a known compound can be used. Examples of the sensitizer include bis (dimethylamino) benzophenone, bis (diethylamino) benzophenone, diethylthioxanthone, N-phenyldiethanolamine, N-phenylglycine, 7-diethylamino-3-benzoylcoumarin, 7-diethylamino-4-methylcoumarin, N-phenylmorpholine, and derivatives thereof.

As the polymerization inhibitor, a known compound can be used. Examples of the polymerization inhibitor include compounds having a phenolic hydroxyl group, nitroso compounds, N-oxide compounds, quinone compounds, N-oxyl compounds, phenothiazine compounds, and the like. More specifically, irganox1010, irganox1035, irganox1098, irganox1135, irganox245, irganox259, irganox3114 (both of BASF JAPAN Co., ltd.), 2, 6-di-t-butyl-p-cresol and 4-methoxyphenol are preferable as the polymerization inhibitor, and Irganox1010, 2, 6-di-t-butyl-p-cresol and 4-methoxyphenol are more preferable.

From the viewpoint of satisfying both excellent developability and good oxidation preventing effect of the photosensitive resin composition, the amount of the polymerization inhibitor used is preferably 0.005% by mass or more and 1% by mass or less, more preferably 0.01% by mass or more and 0.5% by mass or less, and still more preferably 0.03% by mass or more and 0.3% by mass or less, relative to the mass of the resin (a).

The nitrogen-containing heterocyclic compound is stabilized by coordination with the metal surface, thereby improving the adhesion of a film formed using the photosensitive resin composition to the metal surface. As the nitrogen-containing heterocyclic compound, a known compound can be used. Examples of the nitrogen-containing heterocyclic compound include imidazole, pyrazole, indazole, carbazole, triazole, pyrazoline, pyrazolidine, tetrazole, pyridine, piperidine, pyrimidine, pyrazine, triazine, cyanuric acid, isocyanuric acid, and derivatives thereof. Specific examples of the nitrogen-containing heterocyclic compound which is preferable from the viewpoint of coordination with a metal include triazoles such as 1H-benzotriazole, 4-methyl-1H-methylbenzotriazole, 5-methyl-1H-methylbenzotriazole, 4-carboxy-1H-methylbenzotriazole and 5-carboxy-1H-methylbenzotriazole, and tetrazoles such as 1H-tetrazole, 5-methyl-1H-tetrazole and 5-phenyl-1H-tetrazole.

The amount of the nitrogen-containing heterocyclic compound used is preferably 0.01 to 5 mass%, more preferably 0.05 to 3 mass%, based on the mass of the resin (a), from the viewpoint of satisfying both the excellent developability of the photosensitive resin composition and the improvement in adhesion of a film formed using the photosensitive resin composition to a substrate or the like.

By blending a silane coupling agent in the photosensitive resin composition, the adhesion of a film formed using the photosensitive resin composition to a substrate or the like can be improved. As the silane coupling agent, a known compound can be used. Examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (epoxycyclohexyl) ethyltrimethoxysilane, 2- (epoxycyclohexyl) triethoxysilane, tris (3-trimethoxysilylpropyl) isocyanurate, tris (3-triethoxysilylpropyl) isocyanurate, a reactant of 3-aminopropyltrimethoxysilane and an acid anhydride, and a reactant of 3-aminopropyltriethoxysilane and an acid anhydride.

Examples of the acid anhydride to be reacted with 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane include succinic anhydride, maleic anhydride, nadic anhydride, 3-hydroxyphthalic anhydride, pyromellitic dianhydride, 3',4' -biphenyltetracarboxylic dianhydride, 2', 3' -benzophenonetetracarboxylic dianhydride, and 4,4' -oxydiphthalic dianhydride.

The amount of the silane coupling agent used is preferably 0.01 mass% or more and 10 mass% or less with respect to the mass of the resin (a).

By blending a surfactant in the photosensitive resin composition, the coating property of the photosensitive resin composition is improved, and the wettability of the photosensitive resin composition and the substrate is improved. As the surfactant, a known compound can be used. Examples of the surfactant include fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants.

The amount of the surfactant used is preferably 0.001 mass% or more and 1 mass% or less with respect to the mass of the resin (a).

When the resin (a) is a resin that can be converted into a polyimide resin or a benzoxazole resin by heating, the photosensitive resin composition of the resin (a) may contain a cyclization accelerator. The cyclization accelerator promotes the production of a polyimide resin or a polybenzoxazole resin by cyclization of a polyamic acid (a-II), a polyamide resin (a-III) containing a structural unit derived from a dicarboxylic acid compound which can be synthesized by reaction of a tetracarboxylic dianhydride with a monohydroxy compound, and a polybenzoxazole resin precursor (a-V).

When the photosensitive resin composition contains a cyclization accelerator, the mechanical properties and weather resistance reliability of a film formed while a polyimide resin or a benzoxazole resin is formed by cyclization using the photosensitive resin composition are improved. As the cyclization accelerator, a known thermal alkali generator or thermal acid generator can be used.

The amount of each additive used is not particularly limited within a range not interfering with the object of the present invention. The amount of the additive not described above may be appropriately adjusted within a range of, for example, 0.001 to 60 mass% with respect to the mass of the solid content of the photosensitive resin composition, and is preferably 0.01 to 5 mass%.

< method for producing photosensitive resin composition >

The photosensitive resin composition can be prepared by uniformly mixing the essential components described above and optional components as needed in desired amounts. The mixing method is not particularly limited. For the purpose of removing foreign matter in the photosensitive resin composition, the photosensitive resin composition is preferably filtered by a filter.

Photosensitive dry film

The photosensitive dry film has a base film and a photosensitive layer formed on the surface of the base film, and the photosensitive layer is composed of the photosensitive resin composition.

The base film preferably has light transmittance. Specifically, a polyethylene terephthalate (PET) film, a polypropylene (PP) film, a Polyethylene (PE) film, and the like can be mentioned, and a polyethylene terephthalate (PET) film is preferable in terms of excellent balance between light transmittance and breaking strength.

The photosensitive resin composition is applied to a base film to form a photosensitive layer, thereby producing a photosensitive dry film.

When forming the photosensitive layer on the substrate film, the photosensitive resin composition is applied using a coater, a bar coater, a wire bar coater, a roll coater, a curtain coater, or the like and dried so that the film thickness after drying on the substrate film is preferably 0.5 μm or more and 300 μm or less, more preferably 1 μm or more and 300 μm or less, and particularly preferably 3 μm or more and 100 μm or less.

The photosensitive dry film may further have a protective film on the photosensitive layer. Examples of the protective film include a polyethylene terephthalate (PET) film, a polypropylene (PP) film, and a Polyethylene (PE) film.

Method for producing patterned resin film

Comprises a laminating step of laminating a photosensitive layer comprising the photosensitive resin composition on a substrate,

An exposure step of exposing the photosensitive layer by selectively irradiating the photosensitive layer with active light or radiation,

The method of the developing step of developing the exposed photosensitive layer to obtain a patterned resin film can produce a patterned resin film.

The substrate on which the photosensitive layer is laminated is not particularly limited, and conventionally known substrates can be used, and examples thereof include substrates for electronic components, substrates on which predetermined wiring patterns are formed, and the like. As the substrate, a silicon substrate, a glass substrate, or the like can also be used.

For example, a photosensitive layer is laminated on a substrate as follows. That is, a photosensitive layer having a desired film thickness is formed by applying a liquid photosensitive resin composition on a substrate and heating to remove the solvent. The thickness of the photosensitive layer is not particularly limited as long as a resist pattern as a mold can be formed with a desired film thickness. The thickness of the photosensitive layer is not particularly limited, but is preferably 0.5 μm or more, more preferably 0.5 μm or more and 300 μm or less, particularly preferably 1 μm or more and 150 μm or less, and most preferably 3 μm or more and 100 μm or less.

Further, the photosensitive dry film may be applied to a substrate, and a photosensitive layer may be laminated on the substrate.

As a method for applying the photosensitive resin composition to the substrate, a spin coating method, a slit coating method, a roll coating method, a screen printing method, an applicator method, or the like can be used. The photosensitive layer is preferably pre-baked. The prebaking conditions vary depending on the kind, blending ratio, coating film thickness and the like of each component in the photosensitive resin composition, but are usually from 70 ℃ to 200 ℃ and preferably from 80 ℃ to 150 ℃ for about 2 minutes to 120 minutes.

The photosensitive layer formed as described above is selectively irradiated (exposed) with active light or radiation, for example, ultraviolet light or visible light having a wavelength of 300nm to 500nm, through a mask having a predetermined pattern.

As a radiation source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, an argon laser, or the like can be used. The radiation includes microwave, infrared ray, visible ray, ultraviolet ray, X-ray, gamma ray, electron ray, proton ray, neutron ray, ion ray, and the like. The amount of radiation irradiation varies depending on the composition of the photosensitive resin composition, the film thickness of the photosensitive layer, and the like, and is, for example, 100mJ/cm in the case of using an ultra-high pressure mercury lamp ² Above 10000mJ/cm ² The following.

Then, the exposed photosensitive layer is developed by a conventionally known method, and unnecessary portions are dissolved and removed to form a resin film patterned into a predetermined shape. In this case, a developer corresponding to the components contained in the photosensitive resin composition is used. When the photosensitive resin composition contains a resin having an alkali-soluble group such as polyamic acid (a-II) as resin (a), or when the photosensitive resin composition contains a quinonediazido group-containing compound (C3), an alkaline aqueous solution can be used as the developer. When the photosensitive resin composition contains a resin having a radical polymerizable group or a cation polymerizable group as the resin (a) and contains no or only a small amount of a component soluble in an aqueous alkaline solution or a component soluble in an aqueous alkaline solution by exposure, the above-mentioned organic solvent (S) can be used as the developer.

Examples of the alkali developer include aqueous solutions of alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (tetramethylammonium hydroxide), tetraethylammonium hydroxide, pyrrole, piperidine, 1, 8-diazabicyclo [5,4,0] -7-undecene, and 1, 5-diazabicyclo [4,3,0] -5-nonane. In addition, an aqueous solution in which a suitable amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added to the alkali aqueous solution can be used as the developer.

The developing time varies depending on the composition of the photosensitive resin composition, the film thickness of the photosensitive layer, and the like, and is usually 1 minute to 30 minutes. The developing method may be any of a liquid method, a dipping method, a puddle method, a spray developing method, and the like.

After development, the patterned resin film is cleaned for a period of time of 30 seconds to 90 seconds as necessary, and dried using an air gun, an oven, or the like. In this way, the resin film patterned into a desired shape is formed on the surface of the substrate. The cleaning solvent is not particularly limited. For example, water, alcohols, or the like can be used as a cleaning solvent in the alkali development. In the case of performing development with an organic solvent, (S) an organic solvent may be used within a range that does not cause solvent impact.

In the case where the resin film contains polyamic acid (a-II), polyamide resin (a-III) containing structural units derived from a dicarboxylic acid compound that can be synthesized by the reaction of tetracarboxylic dianhydride and a monohydroxy compound, or polybenzoxazole resin precursor (a-V), the coating film after development may be subjected to baking as necessary after development, whereby polyamide resin (a-III) containing structural units derived from a dicarboxylic acid compound that can be synthesized by the reaction of tetracarboxylic dianhydride and a monohydroxy compound, polyamic acid (a-II) is converted into polyimide resin (a), or polybenzoxazole resin precursor (a-V) is converted into polybenzoxazole resin (a-IV).

The baking temperature is as described for resin (A). In addition, it is preferable to perform baking in an inert gas atmosphere such as nitrogen or argon, from the viewpoint of preventing oxidation of the cured film and obtaining a cured film having good mechanical properties.

The patterned resin film formed as described above is suitably used as, for example, an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, an insulating film or a protective film in a touch panel display, an organic electroluminescence display panel, or the like. Since the photosensitive resin composition has good resolution, the patterned resin film formed as described above can be particularly preferably used as an interlayer insulating film for a rewiring layer in a three-dimensional mounted device or the like.

The patterned resin film formed as described above can also be suitably used as a photoresist, a galvanic (electrolytic) resist, an etching resist, a solder resist, and the like for electronic devices.

The patterned resin film formed as described above can also be used for the production of printing plates such as offset printing plates and screen printing plates, the formation of etching masks in the etching of molded members, the production of protective varnishes and dielectric layers in electronic components, particularly microelectronic components, and the like.

[ examples ]

The present invention will be described in more detail with reference to examples below, but the scope of the present invention is not limited to these examples.

In examples 1 to 11, comparative example 1 and comparative example 2, the following DA1 to DA6 were used as diamine compounds.

[ solution 32]

[ example 1]

31.02g (0.10 mole) of 4,4' -oxydiphthalic dianhydride was dissolved in 69g of N-methyl-2-pyrrolidone (NMP). To the resulting solution were added 26.03g (0.20 mol) of 2-hydroxyethyl methacrylate (HEMA), 15.82g (0.20 mol) of pyridine and 24.43g (0.20 mol) of dimethylaminopyridine, and the solution was stirred at room temperature for 16 hours to obtain di-2-methacryloyloxyethyl ester of 4,4' -oxybisphthalic acid.

After a dicarboxylic acid solution of bis-2-methacryloyloxyethyl ester containing 0.1 mole of the obtained 4,4' -oxydiphthalic acid was cooled to 0 ℃, a solution composed of 42.30g (0.21 mole) dicyclohexylcarbodiimide and 42g of NMP, and a diamine solution composed of 36.84g (0.10 mole) of the above DA1 and 43g of NMP were dropwise added to the dicarboxylic acid solution. After the completion of the dropwise addition, the obtained reaction solution was stirred at room temperature for 4 hours to conduct a condensation reaction. After completion of the reaction, 19.7g of methanol was poured into the reaction solution, and then the precipitate was removed by filtration to obtain a reaction solution. The obtained reaction solution was added dropwise to an aqueous isopropanol solution to precipitate brown polyamide resin powder. The precipitated powder was collected by filtration and washed 3 times with isopropyl alcohol. The washed powder was dried under reduced pressure to obtain a polyamide resin which was a polycondensate of bis-2-methacryloyloxyethyl ester of 4,4' -oxybisphthalic acid and the DA 1. The obtained polyamide resin had a2- (methacryloyloxy) ethoxycarbonyl group as a radical polymerizable group.

The obtained polyamide resin was dissolved in γ -butyrolactone so that the concentration thereof became 30 mass%, and then an oxime ester initiator (Irgacure OXE02 (BASF JAPAN)) was added to the obtained solution in an amount of 5 mass% based on the mass of the polyamide resin, a polymerization inhibitor (Irganox 1010 (BASF JAPAN)) was added in an amount of 0.05 mass% based on the mass of the polyamide resin, a surfactant (POLYFLOW No.77 (synerger chemical corporation)) was added in an amount of 0.02 mass% based on the mass of the polyamide resin, and N- [3- (triethoxysilyl) propyl ] phthalic acid amide was added in an amount of 3 mass% based on the mass of the polyamide resin, thereby obtaining a photosensitive resin composition.

[ example 2]

A polyamide resin which was a polycondensate of bis-2-methacryloyloxyethyl ester of 4,4' -oxybisphthalic acid with DA1 and DA4 was obtained in the same manner as in example 1, except that the diamine compound was changed to 34.26g (0.093 mol) of DA1 and 2.58g (0.007 mol) of DA4, and a photosensitive resin composition comprising the polyamide resin was obtained.

[ example 3]

A polyamide resin which was a polycondensate of bis-2-methacryloyloxyethyl ester of 4,4' -oxydiphthalic acid with the DA1 and the DA4 was obtained in the same manner as in example 1, except that the diamine compound was changed to 31.32g (0.085 mol) of the DA1 and 5.53g (0.015 mol) of the DA4, and a photosensitive resin composition comprising the polyamide resin was obtained.

[ example 4]

A polyamide resin which was a polycondensate of bis-2-methacryloyloxyethyl ester of 4,4' -oxydiphthalic acid with DA1 and DA4 was obtained in the same manner as in example 1, except that the diamine compound was changed to 28.74g (0.078 mol) of DA1 and 8.11g (0.022 mol) of DA4, and a photosensitive resin composition comprising the polyamide resin was obtained.

[ example 5]

A polyamide resin which was a polycondensate of bis-2-methacryloyloxyethyl ester of 4,4' -oxybisphthalic acid with the DA1 and the DA4 was obtained in the same manner as in example 1, except that the diamine compound was changed to 11.79g (0.032 mol) of the DA1 and 21.37g (0.058 mol) of the DA4, and a photosensitive resin composition comprising the polyamide resin was obtained.

[ example 6]

A polyamide resin which was a polycondensate of bis-2-methacryloyloxyethyl ester of 4,4' -oxydiphthalic acid with DA1 and DA4 was obtained in the same manner as in example 1, except that the diamine compound was changed to 8.84g (0.024 mol) of DA1 and 28.00g (0.076 mol) of DA4, and a photosensitive resin composition containing the polyamide resin.

[ example 7]

A polyamide resin which was a polycondensate of bis-2-methacryloyloxyethyl ester of 4,4' -oxydiphthalic acid with DA1 and DA4 was obtained in the same manner as in example 1, except that the diamine compound was changed to 4.42g (0.012 mol) of DA1 and 30.21g (0.082 mol) of DA4, and a photosensitive resin composition containing the polyamide resin was obtained.

[ example 8]

A polyamide resin which was a polycondensate of di-2-methacryloyloxyethyl ester of 4,4' -oxybisphthalic acid with the DA1 and the DA4 was obtained in the same manner as in example 1, except that the diamine compound was changed to 2.95g (0.008 mol) of the DA1 and 33.90g (0.092 mol) of the DA4, and a photosensitive resin composition containing the polyamide resin was obtained.

[ example 9]

A polyamide resin which was a polycondensate of bis-2-methacryloyloxyethyl ester of 4,4' -oxybisphthalic acid and the DA2 was obtained in the same manner as in example 1 except that the diamine compound was changed to 39.25g (0.10 mol) of the DA2, and a photosensitive resin composition comprising the polyamide resin was obtained.

[ example 10]

A polyamide resin which was a polycondensate of bis-2-methacryloyloxyethyl ester of 4,4' -oxydiphthalic acid and DA7 was obtained in the same manner as in example 1, except that the diamine compound was changed to 30.04g (0.10 mol) of DA7, and a photosensitive resin composition comprising the same.

[ example 11]

A polyamide resin which was a polycondensate of bis-2-methacryloyloxyethyl ester of 4,4' -oxydiphthalic acid with DA3 and DA4 was obtained in the same manner as in example 1, except that the diamine compound was changed to 7.68g (0.035 mol) of DA3 and 23.95g (0.065 mol) of DA4, and a photosensitive resin composition comprising the polyamide resin was obtained.

[ example 12]

15.57g of DA1, 6.43g of DA6 and 250g of NMP were added as diamine components to a three-necked flask. Subsequently, the contents of the flask were stirred to dissolve DA1 and DA6 in NMP. Then, 40g of 2, 2-bis [4- (3, 4-dicarboxyphenyloxy) phenyl ] propane dianhydride (BPADA) was added to the solution in the flask, and the reaction solution in the flask was stirred at room temperature for 24 hours. Then, 0.88g of 5-norbornene-2, 3-dicarboxylic anhydride as a capping agent was added to the reaction solution, and the reaction solution was stirred at room temperature for 4 hours to obtain a polyamic acid.

The numerical value below and to the right of the parentheses in the following formula is the molar ratio (mol%) of each structural unit in the resin.

< formation of Polyamic acid >

[ chemical formula 33]

To the reaction liquid containing polyamic acid was added 33g of carbonyldiimidazole, and the reaction liquid was stirred at room temperature for 4 hours to convert polyamic acid into polyimide resin.

The stirred reaction solution was added dropwise to 5kg of water to form a precipitate. The resulting precipitate was recovered by filtration. The collected precipitate was washed with 2kg of water 3 times and then dried under reduced pressure at 50 ℃ to obtain a polyimide resin having a carboxyl group composed of a structural unit represented by the following formula.

< imidization >

[ chemical 34]

In a three-necked flask, the obtained polyimide resin having a carboxyl group, 8.25g of 2-hydroxyethyl methacrylate, 25.0g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WSC-HCl) and 5.15g of 4-Dimethylaminopyridine (DMAP) were added to 250g of NMP, and then the reaction mixture was stirred at room temperature for 6 hours.

The stirred reaction solution was added dropwise to 2kg of methanol to form a precipitate. The resulting precipitate was recovered by filtration. The collected precipitate was washed with 2kg of methanol 3 times and then dried under reduced pressure at 50 ℃ to obtain a polyimide resin having a methacryloyl group at the end of a side chain, which is composed of a structural unit represented by the following formula.

Subjecting the obtained polyimide resin to ¹ In the H-NMR measurement, imidization was confirmed by disappearance of a peak corresponding to an amide bond, and introduction of a theoretical amount of methacryloyl group into the polyimide resin was confirmed from an integral ratio of a wholly aromatic compound to an integral ratio of a double bond.

< introduction of methacryloyl group >

[ solution 35]

A photosensitive resin composition was obtained in the same manner as in example 1, except that the polyamide resin was changed to the polyimide resin obtained by the above-described method.

[ example 13]

A polyamide resin and a photosensitive resin composition were obtained in the same manner as in example 1, except that 31.02g (0.10 mol) of 4,4' -oxydiphthalic dianhydride was changed to 52.05g (0.10 mol) of 2, 2-bis [4- (3, 4-dicarboxyphenyloxy) phenyl ] propane dianhydride.

[ example 14]

A polyamide resin and a photosensitive resin composition were obtained in the same manner as in example 1, except that 31.02g (0.10 mol) of 4,4' -oxydiphthalic dianhydride was changed to 29.42g (0.10 mol) of 3,3',4' -biphenyltetracarboxylic dianhydride.

[ example 15]

A polyamide resin and a photosensitive resin composition were obtained in the same manner as in example 1 except that 31.02g (0.10 mol) of 4,4' -oxydiphthalic dianhydride was changed to 39.04g (0.075 mol) of 2, 2-bis [4- (3, 4-dicarboxyphenyloxy) phenyl ] propane dianhydride and 5.45g (0.025 mol) of pyromellitic dianhydride.

[ example 16]

A polyamide resin and a photosensitive resin composition were obtained in the same manner as in example 1, except that 31.02g (0.10 mol) of 4,4 '-oxydiphthalic dianhydride was changed to 53.44g (0.10 mol) of 4,4' -bis (3, 4-dicarboxyphenylcarbonyloxy) biphenyl dianhydride.

[ example 17]

A polyamide resin and a photosensitive resin composition were obtained in the same manner as in example 1 except that 31.02g (0.10 mol) of 4,4' -oxybisphthalic dianhydride was changed to 7.76g (0.025 mol) of 4,4' -oxybisphthalic dianhydride and 40.08g (0.075 mol) of 4,4' -bis (3, 4-dicarboxyphenylcarbonyloxy) biphenyl dianhydride.

[ example 18]

A polyamide resin and a photosensitive resin composition were obtained in the same manner as in example 1, except that 31.02g (0.10 mol) of 4,4' -oxybisphthalic dianhydride was changed to 15.51g (0.050 mol) of 4,4' -oxybisphthalic dianhydride and 26.72g (0.050 mol) of 4,4' -bis (3, 4-dicarboxyphenylcarbonyloxy) biphenyl dianhydride.

[ example 19]

A polyamide resin and a photosensitive resin composition were obtained in the same manner as in example 1 except that 31.02g (0.10 mol) of 4,4' -oxybisphthalic dianhydride was changed to 23.27g (0.075 mol) of 4,4' -oxybisphthalic dianhydride and 13.36g (0.025 mol) of 4,4' -bis (3, 4-dicarboxyphenylcarbonyloxy) biphenyl dianhydride.

[ example 20]

A polyamide resin and a photosensitive resin composition were obtained in the same manner as in example 1, except that 31.02g (0.10 mol) of 4,4' -oxydiphthalic dianhydride was changed to 50.84g (0.1 mol) of 2, 6-bis (3, 4-dicarboxyphenylcarbonyloxy) naphthalene dianhydride.

[ example 21]

A polyamide resin and a photosensitive resin composition were obtained in the same manner as in example 1 except that 31.02g (0.10 mol) of 4,4 '-oxydiphthalic dianhydride was changed to 15.51g (0.050 mol) of 4,4' -oxydiphthalic dianhydride and 25.42g (0.050 mol) of 2, 6-bis (3, 4-dicarboxyphenylcarbonyloxy) naphthalene dianhydride.

[ example 22]

A polyamide resin and a photosensitive resin composition were obtained in the same manner as in example 1 except that 31.02g (0.10 mol) of 4,4 '-oxybisphthalic dianhydride was changed to 23.27g (0.075 mol) of 4,4' -oxybisphthalic dianhydride and 12.71g (0.025 mol) of 2, 6-bis (3, 4-dicarboxyphenylcarbonyloxy) naphthalene dianhydride.

[ example 23]

A polyamide resin and a photosensitive resin composition were obtained in the same manner as in example 1 except that 23.27g (0.075 mol) of 4,4 '-oxybisphthalic dianhydride was changed to 23.27g (0.075 mol) of 4,4' -oxybisphthalic dianhydride and 11.11g (0.025 mol) of 2, 2-bis (3, 4-dicarboxyphenoxy) hexafluoropropane dianhydride.

[ comparative example 1]

A polyamide resin which was a polycondensate of bis-2-methacryloyloxyethyl ester of 4,4' -oxydiphthalic dianhydride and DA4 was obtained in the same manner as in example 1, except that the diamine compound was changed to 36.84g (0.1 mol) of DA4, and a photosensitive resin composition comprising the polyamide resin was obtained.

[ comparative example 2]

A polyamide resin which was a polycondensate of bis-2-methacryloyloxyethyl ester of 4,4' -oxydiphthalic dianhydride and DA5 was obtained in the same manner as in example 13 except that the diamine compound was changed to 20.02g (0.1 mol) of DA5, and a photosensitive resin composition comprising the polyamide resin was obtained.

Using the photosensitive resin compositions of examples 1 to 23, comparative example 1 and comparative example 2 obtained, the photosensitive evaluation, the evaluation of the dielectric loss tangent of the resin film, the evaluation of the appearance of the resin film and the tensile test of the resin film were performed in the following manner. The evaluation results are shown in table 1.

< evaluation of photosensitivity >

After the photosensitive resin composition was applied onto a copper substrate by a spin coater, the substrate was baked at 80 ℃ for 300 seconds to obtain a coating film having a thickness of 12 μm. The coating film was subjected to exposure to light at a focal length (Focus) of 0 μm at a depth of 100mJ/cm using a ghi line exposure machine (manufactured by ULTRATECH) through a negative mask capable of forming a through-hole having an opening diameter of 50 μm ² ～4000mJ/cm ² And (4) exposing. The exposed coating film was immersed in cyclopentanone for 60 seconds and developed. The developed patterned resin film was observed, and the photosensitivity was evaluated according to the following criteria.

Good: through-holes having an opening diameter of 50 μm were formed.

X: it was not possible to form a via having an opening diameter of 50 μm.

< evaluation of dielectric loss tangent >

After the photosensitive resin composition was applied to a silicon wafer by a spinner, a film of the photosensitive resin composition was baked at 90 ℃ for 240 seconds.Using a high-pressure mercury lamp to accumulate light quantity of 2000mJ/cm ² And exposing the baked coating film. The exposed film was heated to 230 ℃ in an inert oven in a nitrogen atmosphere at a heating rate of 5 ℃/min, and the coated film was heated at this temperature for 1 hour. When the temperature was lowered to 100 ℃, the wafer was taken out, immersed in a 2wt% hydrofluoric acid aqueous solution for 5 to 30 minutes, and the resin film was peeled from the wafer, thereby obtaining a resin film made of a polyimide resin in which the resin obtained in each example was imidized by ring closure. However, since the photosensitive resin composition obtained in example 12 contains a polyimide resin, the photosensitive resin composition of example 12 is baked at 180 ℃ for 30 minutes after exposure without baking under the above conditions for solvent removal. The film thickness of the resin film after peeling was 10 μm.

The dielectric loss tangent (tan δ) of the obtained film was measured by the method described in "study on evaluation of complex permittivity of millimeter wave by cylindrical cavity resonator method for photosensitive insulating film" in 3 months of 2019 (gaoou zhuiping (university of yudu), hai laozhen and ming (tokyo chemical industry co., ltd.), ancient convention (university of yudu) of information and communication society, vol.118, no.506, MW2018-158, pp.13-18, and 3 months of 2019. The measurement was carried out by a cavity resonator method using a network analyzer HP8510C (manufactured by Keysight Co., ltd.) under conditions of room temperature 25 ℃, humidity 50%, frequency 36GHz, and sample thickness 10 μm. Based on the measured value of the dielectric loss tangent, the dielectric loss tangent was evaluated according to the following criteria.

A: the dielectric loss tangent value is less than 0.008.

B: the dielectric loss tangent value is 0.008 or more and less than 0.011.

C: the dielectric loss tangent is 0.011 or more and less than 0.014.

D: the dielectric loss tangent is 0.014 or more.

< evaluation of appearance >

The appearance of the obtained film was visually observed in the same manner as in the evaluation of the dielectric loss tangent. The case where white turbidity was not observed was judged as "o", and the case where white turbidity was observed was judged as "x".

< tensile test >

A test piece was cut out in the form of a strip having a width of 1cm and a length of 5cm from the film obtained in the same manner as in the evaluation of dielectric loss tangent. The obtained test piece and a tensile tester (EZ-test, shimadzu corporation) were used to perform a tensile test under the conditions of a distance between chucks of 2cm and a tensile speed of 1 mm/min, and the tensile elongation was measured. The tensile elongation was determined according to the following equation.

Tensile elongation (%) = (distance between chucks at break (cm)/2 (cm) -1) × 100

Tensile elongation was judged as excellent at 40% or more, good at 30% or more but less than 40%, and poor at less than 30%.

[ Table 1]

	Evaluation of photosensitivity	Evaluation of dielectric loss tangent	Appearance evaluation	Tensile evaluation
					Example 1	○	A	○	◎
Example 2	○	A	○	◎
					Example 3	○	A	○	◎
Example 4	○	A	○	◎
					Example 5	○	A	○	◎
Example 6	○	A	○	◎
					Example 7	○	C	○	◎
Example 8	○	C	○	◎
					Example 9	○	A	○	○
Example 10	○	C	○	○
					Example 11	○	C	○	○
Example 12	○	A	○	◎
					Example 13	○	B	○	◎
Example 14	○	B	○	◎
					Example 15	○	B	○	◎
Example 16	○	A	○	◎
					Example 17	○	A	○	◎
Example 18	○	A	○	◎
					Example 19	○	A	○	◎
Example 20	○	A	○	◎
					Example 21	○	A	○	◎
Example 22	○	A	○	◎
					Example 23	○	B	○	◎
Comparative example 1	×	C	×	◎
					Comparative example 2	○	D	○	◎

From examples 1 to 23, it is understood that a photosensitive resin composition comprising a polyamide resin containing a structural unit having a specific structure represented by the formula (A1) and having a polymerizable group such as a methacryloyl group and an oxime ester compound as a sensitizer can provide a resin film which shows good photosensitivity, has a low dielectric loss tangent, has a good appearance without cloudiness, and is excellent in tensile strength.

On the other hand, as is clear from comparative examples 1 and 2, the photosensitive resin composition containing the polyamide resin or the polyimide resin not containing the structural unit having the specific structure represented by the above formula (A1) cannot form a resin film having a low dielectric loss tangent.

Claims

1. A photosensitive resin composition comprising a resin (A) and a sensitizer (C),

the resin (A) comprises

A polyimide resin (A-I) derived from a diamine compound and a tetracarboxylic dianhydride, a polyamic acid (A-II),

at least 1 selected from the group consisting of polybenzoxazole resins (A-IV) and polybenzoxazole resin precursors (A-V) derived from a diamine compound which is an aromatic compound having 2 amino groups bonded to an aromatic ring and a hydroxyl group bonded to a carbon atom at a position adjacent to the carbon atom bonded to the amino group on the aromatic ring, a dicarboxylic acid compound or an amide-forming derivative of a dicarboxylic acid compound,

the resin (A) contains a structural unit (A1) derived from a compound represented by the following formula (A1),

[ solution 1]

In the formula (A1), X is an organic group having 1 to 100 carbon atoms, and R is ^a1 Is a hydroxyl, carboxyl or halogen atom, R ^a2 Is an aliphatic group having 1 to 20 carbon atoms, a hydroxyl group, a carboxyl group, a sulfonic acid group or a halogen atom, ar may be represented by R ^a2 Substituted phenyl, or may be substituted by R ^a2 In the substituted naphthyl group, ma1 is an integer of 0 to 10 inclusive, ma2 is an integer of 0 to 7 inclusive, and ma3 is an integer of 1 to 10 inclusive.

2. The photosensitive resin composition according to claim 1, wherein the compound represented by the formula (A1) is a compound represented by the following formula (A1-1),

[ solution 2]

In the formula (A1-1), R ^a1 、R ^a2 Ar, ma1, ma2 and ma3 and R in the formula (A1) ^a1 、R ^a2 Ar, ma1, ma2 and ma3 are the same, Y ^a1 Is an organic group having 1 to 20 carbon atoms or a single bond, Y ^a2 Is an organic group having 1 to 20 carbon atoms, and when na1 is 0 or 1, na2 is 0 or 1, and na1 is 1, Y is ^a1 Is not a single bond, but is,

the resin (A) contains at least 1 selected from the group consisting of the polyimide resin (A-I), the polyamic acid (A-II), and the polyamide resin (A-III).

3. The photosensitive resin composition according to claim 1 or 2, wherein the resin (a) has a radical polymerizable group on its molecular chain, and the photosensitizer (C) is a photo radical polymerization initiator (C1), or the resin (a) has a cation polymerizable group on its molecular chain, and the photosensitizer (C) is a photo cation polymerization initiator (C2).

4. The photosensitive resin composition according to claim 3, wherein the resin (A) has a radical polymerizable group in a molecular chain thereof, and the photo-radical polymerization initiator (C1) is an oxime ester type photopolymerization initiator.

5. The photosensitive resin composition according to claim 1 or 2, wherein a ratio of the number of moles of the structural unit (a 1) in the resin (a) to the number of moles of all the structural units derived from the diamine compound is 10 mol% or more and 100 mol% or less.

6. A photosensitive dry film comprising a base film and a photosensitive layer formed on the surface of the base film, wherein the photosensitive layer is composed of the photosensitive resin composition according to any one of claims 1 to 5.

7. A method for producing a photosensitive dry film, comprising applying the photosensitive resin composition according to any one of claims 1 to 5 on a base film to form a photosensitive layer.

8. A method for manufacturing a patterned resin film, comprising:

a laminating step of laminating a photosensitive layer comprising the photosensitive resin composition according to any one of claims 1 to 5 on a substrate;

9. The method for producing a patterned resin film according to claim 8, wherein the resin (A) comprises the polyamic acid (A-II), the polyamide resin (A-III) comprising a structural unit derived from a dicarboxylic acid compound which can be synthesized by the reaction of a tetracarboxylic dianhydride with a monohydroxy compound, or the polybenzoxazole resin precursor (A-V),

the method for manufacturing a patterned resin film includes: after the patterned resin film is obtained, the resin film is baked, thereby converting the polyamic acid (a-II) or the polyamide resin (a-III) containing structural units derived from a dicarboxylic acid compound that can be synthesized by the reaction of a tetracarboxylic dianhydride with a monohydroxy compound into a polyimide resin (a-I), or converting the polybenzoxazole resin precursor (a-V) into a polybenzoxazole resin (a-IV).