JP2010185010A - Photobase-generating agent, light-sensitive resin composition and circuit board using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photobase-generating agent exhibiting improved heat resistance without causing a byproduct, to provide an alkali-developable photosensitive resin composition requiring no high-temperature curing, and to provide a circuit board using the composition. <P>SOLUTION: The photobase-generating agent contains a cyclic compound containing an acyloxyimino group represented by formula (1) (wherein, X<SP>1</SP>is a tetravalent organic group; n is an integer of 0-3; and R<SP>1</SP>is aromatic or ≥1C alkyl), and having a site cleavable by light in the cyclic structure. The light-sensitive resin composition contains the photobase-generating agent and a polyamic acid. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition using a photobase generator and a circuit board using the same.

  Polyimide resins are applied in various fields based on excellent properties such as high insulation, heat and cold resistance, and high strength. In recent years, polyimides have been used as base materials and coverlays in flexible printed wiring boards (hereinafter abbreviated as FPCs) that are remarkably elongated. FPCs are required to be finer in line with the recent advancement and density of IC mounting technology, and high workability is also required for coverlays using polyimide.

  In manufacturing the FPC, the polyimide base material is mechanically punched, and the alignment is performed for bonding. Therefore, there is a problem that the alignment accuracy cannot be increased. In order to solve this problem, a photosensitive film based on a solder resist film using an acrylate resin or an epoxy resin has been studied. However, in terms of physical properties such as flexibility, it was not as good as polyimide (for example, patents). Literatures 1-3).

  There is also a proposal of a photosensitive resin composition using a polyamic acid ester having a photosensitive group in the side chain. In this case, after development, the photosensitive group in the side chain is decomposed by high-temperature curing at about 300 ° C. to 450 ° C. It is necessary to imidize (for example, Patent Document 4). When these photosensitive polyamic acid esters are used as an FPC coverlay, there is a concern that curing at a high temperature may damage the circuit board.

  As photosensitive polyamic acid using a photobase generator, a positive photosensitive resin composition using nitrobenzyl carbamate as a photobase generator, or a negative type using a photobase generator having an acyloxyimino group. There is a proposal of a photosensitive resin composition (for example, Patent Documents 5 and 6).

  However, since conventionally known acyclic photobase generators exist after photocleavage, the radical species are divided into two molecules, so that the radical species diffuse to each other, reducing the probability of recoupling, The generation efficiency decreases. For this reason, it is necessary to add about 100 parts by mass of the photobase generator to 100 parts by mass of the resin, and there is a concern that the mechanical properties of the film are deteriorated. In addition, by-products of aldehyde compounds and ketone compounds are formed as completely separated molecules together with amines. In the negative photolithography process, the produced by-product is likely to be eluted into the developer and cause a reduction in film thickness. Further, when the by-product is highly volatile, there is a concern that it may cause odor and contaminate the optical system of photolithography. In view of this point, there is a proposal of a cyclic photobase generator (for example, Patent Document 7) in which a molecular design without a by-product is performed, but these do not necessarily satisfy heat-resistant stability. There is concern about the mechanical properties of the film when a film made of the photosensitive resin composition is used as a photosensitive coverlay.

JP-A-56-6498 JP-A 61-243869 JP-A-6-332171 Japanese Patent Laid-Open No. 2001-194783 Japanese Patent No. 3363580 JP-A-6-295063 JP 2008-003581 A

  The present invention has been made in view of such points, and a photobase generator with improved heat stability, a mechanical property of a film, which has been difficult with a photosensitive resin composition using a conventional photobase generator. It aims at providing the photosensitive resin composition which improved, and a circuit board using the same.

  The photobase generator of the present invention is a compound containing an acyloxyimino group represented by the formula (1).

（式中、Ｘ^１は４価の有機基であり、ｎは０〜３の整数を表す。Ｒ^１は芳香族基または炭素数が１以上のアルキル基である。）

(In the formula, X ¹ is a tetravalent organic group and n represents an integer of 0 to 3. R ¹ is an aromatic group or an alkyl group having 1 or more carbon atoms.)

  The photosensitive resin composition of the present invention is a photosensitive resin composition containing a photobase generator (A) and a polyamic acid (B), and the photobase generator is represented by the formula (1). And a compound containing an acyloxyimino group.

  In the photosensitive resin composition of the present invention, the photobase generator is a compound containing an acyloxyimino group represented by formula (1), and the compound is represented by formula (2) or formula (3). It is preferred that

（式中、ｎは０〜３の整数を表す。Ｒ^１は芳香族基または炭素数が１以上のアルキル基である。）

(In the formula, n represents an integer of 0 to 3. R ¹ is an aromatic group or an alkyl group having 1 or more carbon atoms.)

（式中、ｎは０〜３の整数を表す。Ｒ^１は芳香族基または炭素数が１以上のアルキル基である。）

(In the formula, n represents an integer of 0 to 3. R ¹ is an aromatic group or an alkyl group having 1 or more carbon atoms.)

  In the photosensitive resin composition of this invention, it is preferable that the said polyamic acid is a polyamic acid obtained using the diamine represented by Formula (4).

（式中Ｒ^ａは炭素数が１〜５０の２価の有機基である。ｋは１〜５０の数を表す。）

(In the formula, R ^a is ^a divalent organic group having 1 to 50 carbon atoms. K represents a number of 1 to 50.)

  In the photosensitive resin composition of the present invention, the polyamic acid is preferably a polyamic acid obtained using an acid dianhydride represented by the formula (5).

（式中ｌは１〜２０の数を表す。ｍは２〜５０の整数を表す。）

(In the formula, l represents a number of 1 to 20. m represents an integer of 2 to 50.)

  In the photosensitive resin composition of this invention, it is preferable that the said polyamic acid is a polyamic acid obtained using the diamine represented by Formula (6) further.

（式中、Ｚは２価の有機基であり、式（７）に示す有機基から選ばれる。）

(In the formula, Z is a divalent organic group and is selected from the organic groups shown in Formula (7).)

（式中ｐは３〜５の整数を表す。）

(In the formula, p represents an integer of 3 to 5.)

  In the photosensitive resin composition of the present invention, the polyamic acid is preferably a polyamic acid obtained by using oxydiphthalic dianhydride.

  In the photosensitive resin composition of this invention, it is preferable to contain a photosensitizer (C) further.

  In the photosensitive resin composition of this invention, it is preferable to contain a flame retardant (D) further.

  In the photosensitive resin composition of this invention, it is preferable to contain a plasticizer (E) further.

  The photosensitive film of this invention was comprised with the said photosensitive resin composition, It is characterized by the above-mentioned.

  The laminated film of the present invention comprises a carrier film and the photosensitive film provided on the carrier film.

  The laminated film of the present invention preferably includes a cover film formed on the photosensitive film.

  A circuit board according to the present invention includes a base material having wiring, and a cover lay configured using the photosensitive film or the laminated film.

  The method for producing a circuit board of the present invention includes a step of forming a resin composition layer on a substrate having at least wiring using the photosensitive resin composition, and a step of performing pattern exposure on the resin composition layer. And a step of developing the resin composition layer after pattern exposure using an alkaline aqueous solution and a step of curing the resin composition layer after the development processing.

  In the method for producing a circuit board of the present invention, at least a step of laminating at least one of the photosensitive film or the laminated film on a substrate having wiring to form a resin composition layer, and the resin composition A step of performing pattern exposure on the layer, a step of developing the resin composition layer after the pattern exposure using an alkaline aqueous solution, and a step of curing the resin composition layer after the development processing. It is preferable.

  Since the photobase generator of the present invention contains two acyloxyimino groups in the molecule, it can generate a bifunctional base and has a cleavage site by light in the cyclic structure. The resulting ketone is not liberated. Furthermore, since an arylene group is contained in the cyclic structure, the heat resistance stability is improved. The photosensitive resin composition of the present invention has the mechanical properties of a film, which was difficult with conventional photobase generators, due to the molecular design of these photobase generators and the design of alkali-soluble photosensitive polyamic acid resins. An improved photosensitive resin composition and a circuit board using the same can be provided.

Embodiments of the present invention will be described in detail.
The photobase generator (A) according to the present invention has a structure represented by the formula (1), can be decomposed satisfactorily with respect to light having a wavelength of 200 nm to 500 nm, and generate a base. At that time, since the photobase generator according to the present invention has two acyloxyimino groups, it can generate a bifunctional base. In addition, since the acyloxyimino group is included in the cyclic structure, radical species generated by the photocleavage reaction are covalently bonded to each other, and no by-product is generated. Furthermore, the photobase generator according to the present invention has radical recoupling efficiency higher than that of an acyclic photobase generator because radical species generated after cleavage by light are covalently bonded to each other. Thus, the base generation efficiency can be improved.

（式中、Ｘ¹は４価の有機基であり、ｎは０〜３の整数を表す。Ｒ^１は芳香族基または炭素数が１以上のアルキル基である。）

(In the formula, X ¹ is a tetravalent organic group, n represents an integer of 0 to 3. R ¹ is an aromatic group or an alkyl group having 1 or more carbon atoms.)

  The photobase generator according to the present invention is a compound containing an acyloxyimino group represented by the formula (1), which can use the photobase generator.

  Since the photobase generator in the present invention contains an arylene group in the cyclic structure, the thermal decomposability is improved. It is presumed that this is because thermal motion is suppressed by introducing an arylene group into the cyclic structure.

In formula (1), the tetravalent organic group represented by X ¹ is not particularly limited, but a cyclic structure is preferable from the viewpoint of heat resistance stability. The cyclic structure is, for example, a structure containing cycloalkane or a structure containing aromatics. Examples of the structure containing cycloalkane include cycloalkanes as shown in the formula (8). Examples of the structure containing aromatics include aromatics as shown in the formula (9). Among these tetravalent organic groups, an aromatic group-containing organic group represented by the formula (9) is preferable from the viewpoint of light absorption.

（式中、ｑは０〜４の整数でそれぞれ同じでも異なっていてもよい。）

(In the formula, q is an integer of 0 to 4, which may be the same or different.)

In the formula (1), n is preferably 0 to 3 from the viewpoint of radical coupling efficiency after cleavage of the photobase generator with light. In Formula (1), R ¹ is an aromatic group or an alkyl group having 1 or more carbon atoms.

The aromatic group for R ¹ is, for example, a phenyl group or a naphthyl group. These may have a substituent. Examples of the substituent that the aromatic group may have include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, an i-butyl group, an s-butyl group, a t-butyl group, and a phenoxy group. Methoxy group, ethoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group and the like. These substituents contribute to improving the solubility in the polymer varnish.

Examples of the alkyl group having 1 or more carbon atoms of R ¹ include, for example, methyl group, ethyl group, propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, phenoxy Group, methoxy group, ethoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group and the like. These alkyl groups having 1 or more carbon atoms are preferably alkyl groups having 1 to 50 carbon atoms from the viewpoint of suppressing heat scattering.

Among these substituents R ¹ , since the conjugation with the acyloxyimino group is extended, an aromatic group is particularly preferable from the viewpoint of contributing to improvement of photodegradability.

  Among the compounds containing an acyloxyimino group represented by the formula (1), a compound represented by the formula (2) or the formula (3) is preferable. These are preferable from the viewpoints of heat stability and photodegradability.

（式中、ｎは０〜３の整数を表す。Ｒ^１は芳香族基または炭素数が１以上のアルキル基である。）

(In the formula, n represents an integer of 0 to 3. R ¹ is an aromatic group or an alkyl group having 1 or more carbon atoms.)

（式中、ｎは０〜３の整数を表す。Ｒ^１は芳香族基または炭素数が１以上のアルキル基である。）

(In the formula, n represents an integer of 0 to 3. R ¹ is an aromatic group or an alkyl group having 1 or more carbon atoms.)

  These thermal decomposition improvements and thermal stability improvements due to improved thermal scattering properties do not cause deterioration of the physical properties of the film when the film is cured by heat treatment after development (hereinafter simply referred to as cure). preferable.

  In the photosensitive resin composition according to the present invention, the amount of the photobase generator represented by the formula (1) is based on 100 parts by mass of polyamic acid in consideration of photosensitivity and mechanical properties of the resin after curing. It is preferable to mix 1 part by mass to 50 parts by mass. More preferably, it is 2 mass parts-30 mass parts. Particularly preferred is 3 to 20 parts by mass.

  In the photosensitive resin composition of this invention, you may use together the photobase generator represented by Formula (1), and a well-known photobase generator. Known photobase generators include, for example, acyclic acyloxyimino compounds, acyclic carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamates. Compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, α-lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, and the like can be used. . Of these, acyloxyimino compounds having relatively high amine generation efficiency are preferred. The addition of a known photobase generator is preferably as small as possible.

  Next, the polyamic acid (B) will be described. There is no restriction | limiting in particular about the polyamic acid which concerns on this invention, A well-known polyamic acid can be used. For example, the polyamic acid can be obtained using diamine and tetracarboxylic dianhydride as raw materials.

  The polyamic acid according to the present invention is preferably synthesized using a diamine represented by the formula (4) as a diamine from the viewpoint of low warpage of the substrate.

（式中Ｒ^ａは炭素数が１〜５０の２価の有機基である。ｋは１〜５０の数を表す。）

(In the formula, R ^a is ^a divalent organic group having 1 to 50 carbon atoms. K represents a number of 1 to 50.)

The diamine represented by the general formula (4) is not particularly limited as long as it is a diamine having o-, m-, and p-aminobenzoic acid ester groups at both ends, but both ends are p-aminobenzoic acid esters. The group is more preferred. In formula (4), k is a number from 1 to 50, and more preferably, k is a number from 3 to 25. In formula (4), R ^a is a C 1-50 divalent organic group. Specifically, it is preferred that R ^a is a divalent organic group represented by the formula (10).

式（４）で表されるジアミンの具体例としては、例えばポリテトラメチレンオキシド−ジ−ｏ−アミノベンゾエート、ポリテトラメチレンオキシド−ジ−ｍ−アミノベンゾエート、ポリテトラメチレンオキシド−ジ−ｐ−アミノベンゾエート、ポリトリメチレンオキシド−ジ−ｏ−アミノベンゾエート、ポリトリメチレンオキシド−ジ−ｍ−アミノベンゾエート、ポリトリメチレンオキシド−ジ−ｐ−アミノベンゾエートなどが挙げられるが、これらに限定されない。ジアミンを２種以上、使用しても良い。好ましくは、ポリテトラメチレンオキシド−ジ−ｐ−アミノベンゾエートである。

Specific examples of the diamine represented by the formula (4) include, for example, polytetramethylene oxide-di-o-aminobenzoate, polytetramethylene oxide-di-m-aminobenzoate, polytetramethylene oxide-di-p-amino. Examples include, but are not limited to, benzoate, polytrimethylene oxide-di-o-aminobenzoate, polytrimethylene oxide-di-m-aminobenzoate, polytrimethylene oxide-di-p-aminobenzoate. Two or more diamines may be used. Polytetramethylene oxide-di-p-aminobenzoate is preferable.

  It is preferable that the polyamic acid which concerns on this invention contains 10 mol%-55 mol% of diamine represented by Formula (4) with respect to all the diamines. More preferably, it is 15 mol%-50 mol%. If content of diamine represented by Formula (4) is 15 mol% or more with respect to all the diamine, it will be excellent in low curvature and low resilience.

  In addition to the diamine represented by the formula (4), as another diamine that can be used in the present invention, for example, a diamine represented by the formula (6) is preferable from the viewpoint of alkali solubility and low warpage.

（式中、Ｚは２価の有機基であり、式（７）に示す有機基から選ばれる。）

(In the formula, Z is a divalent organic group and is selected from the organic groups shown in Formula (7).)

（式中ｐは３から５の整数を表す。）

(Wherein p represents an integer of 3 to 5)

  Specific examples of the diamine represented by the formula (6) include 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, and 1,3-bis (3-aminophenoxy). ) Benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 1,3 -Bis (4-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) heptane.

  It is preferable that the polyamic acid which concerns on this invention contains 10 mol%-90 mol% of diamine represented by Formula (6) with respect to all the diamines. More preferably, it is 20 mol%-85 mol%. When the content of the diamine represented by the formula (6) is 20 mol% or more with respect to the total diamine, the mechanical properties of the cured film are excellent.

  In addition to these diamines, examples of other diamines that can be used in the present invention include aromatic diamines, aliphatic diamines, diamines having a carboxyl group, diamines having a hydroxyl group, and diamines having a siloxane skeleton.

  As aromatic diamines, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,3′- Diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone 3,4′-diaminodiphenyl ketone, 4,4′-diaminodiphenyl ketone, 2,2-bis (3-aminophenyl) propane, 2,2- (3,4′-diaminodiphenyl) propane, 2,2 -Bis (4-aminophenyl) propane, 2, -Bis (3-aminophenyl) hexafluoropropane, 2,2- (3,4'-diaminodiphenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 3,3 '-[ 1,4-phenylenebis (1-methylethylidene)] bisaniline, 3,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisaniline, 4,4 ′-[1,4-phenylenebis (1 -Methylethylidene)] bisaniline, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4 -(3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane Bread, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4 -Aminophenoxy) phenyl] sulfone.

  Examples of the aliphatic diamine include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1, Examples include 8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, and 1,11-diaminoundecane.

  Examples of the diamine having a carboxyl group include 3,3'-dicarboxy-4,4'-diaminodiphenylmethane and 3,5-diaminobenzoic acid.

  Examples of the diamine having a hydroxyl group include 1,2-diamino-4-hydroxybenzene, 1,3-diamino-5-hydroxybenzene, 1,3-diamino-4-hydroxybenzene, 1,4-diamino-6-hydroxybenzene. 1,5-diamino-6-hydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, 1,2-diamino-3,5-dihydroxybenzene, 4- (3,5-diaminophenoxy) phenol, 3- (3,5-diaminophenoxy) phenol, 2- (3,5-diaminophenoxy) phenol, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 3,3′-diamino-4,4 ′ -Dihydroxybiphenyl, 2,2-bis (4-hydroxy-3-aminophenyl) propane, 2,2-bis (4-hydride) Xyl-3-aminophenyl) hexafluoropropane, bis (4-hydroxy-3-aminophenyl) ketone, 2,2-bis (4-hydroxy-3-aminophenyl) sulfide, 2,2-bis (4-hydroxy) -3-aminophenyl) ether, 2,2-bis (4-hydroxy-3-aminophenyl) sulfone, 2,2-bis (4-hydroxy-3-aminophenyl) methane, 4-[(2,4- Diamino-5-pyrimidinyl) methyl] phenol, p- (3,6-diamino-s-triazin-2-yl) phenol, 2,2-bis (4-hydroxy-3-aminophenyl) difluoromethane, 2,2 -Bis (4-amino-3-hydroxyphenyl) propane, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropa Bis (4-amino-3-hydroxyphenyl) ketone, 2,2-bis (4-amino-3-hydroxyphenyl) sulfide, 2,2-bis (4-amino-3-hydroxyphenyl) ether, 2, 2-bis (4-amino-3-hydroxyphenyl) sulfone, 2,2-bis (4-amino-3-hydroxyphenyl) methane, 2,2-bis (4-amino-3-hydroxyphenyl) difluoromethane Can be mentioned.

  These diamines having a carboxyl group or a hydroxyl group can be used from the viewpoint of improving alkali solubility.

  Examples of the diamine having a siloxane skeleton include α, ω-bis (2-aminoethyl) polydimethylsiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω-bis (4-aminobutyl) poly. Examples thereof include dimethylsiloxane, α, ω-bis (4-aminophenyl) polydimethylsiloxane, α, ω-bis (3-aminopropyl) polydiphenylsiloxane, and the like. These diamines can be used alone or in combination.

  In the polyamic acid according to the present invention, an acid dianhydride represented by the formula (5) is preferably used as the acid dianhydride from the viewpoint of low warpage of the substrate.

（式中ｌは１〜２０の数を表す。ｍは２〜５０の整数を表す。）

(In the formula, l represents a number of 1 to 20. m represents an integer of 2 to 50.)

  Specifically, ethylene glycol-bis-trimellitic anhydride ester, 1,3-propanediol-bis-trimellitic anhydride ester, butanediol-bis-trimellitic anhydride ester, pentanediol-bis-trimellitic anhydride Acid ester, heptanediol-bis-trimellitic anhydride ester, decanediol-bis-trimellitic anhydride ester. It is also preferable to use a mixture of two or more of these. Ethylene glycol-bis-trimellitic anhydride ester, pentanediol-bis-trimellitic anhydride ester, and decanediol-bis-trimellitic anhydride ester are preferable. More preferably, a combination of ethylene glycol-bis-trimellitic anhydride and pentanediol-bis-trimellitic anhydride, or ethylene glycol-bis-trimellitic anhydride and decandiol-bis-trimellitic anhydride It is a combination with an acid ester.

  As the acid dianhydride used in the present invention, other acid dianhydrides other than those of the formula (5) can be used, and among them, oxydiphthalic acid dianhydride is preferable from the viewpoint of improving developability.

  Other acid dianhydrides that can be used in the present invention besides these acid dianhydrides include, for example, aromatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, aliphatic tetracarboxylic dianhydrides Things.

  Examples of aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3′4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride. Anhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3- Dicarboxyphenyl) propane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2 , 3-Dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10- Perylene tetraca Boronic acid dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetra Carboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 1,2,5,6- Naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetra Carboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2, 3, 6, 7 Tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride Bis (3,4-dicarboxyphenyl) methylphenylsilane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) ) Benzene dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylenebis (trimellitic acid monoester anhydride) ), 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenyl) Enoxy) phenyl] hexafluoropropane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 4,4-bis (3,4-dicarboxyphenoxy) diphenyl And sulfide dianhydrides.

  Examples of the alicyclic tetracarboxylic dianhydride include 1,5-cyclooctadiene-1,2,5,6-tetracarboxylic dianhydride, 5-carboxymethylbicyclo [2.2.1] heptane- 2,3,6-tricarboxylic acid-2,3: 5,6-dianhydride, 1-carboxymethyl-2,3,5-cyclopentanetricarboxylic acid-2,6: 3,5-dianhydride, bicyclo [2.2.2] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3- Cyclohexene-1,2-dicarboxylic anhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3 4-tetrahydronaphthalene-1, Dicarboxylic anhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2 , 5,6-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, 1,2 , 3,4-cyclobutanetetracarboxylic dianhydride, bis (exo-bicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride) sulfone.

  Examples of the aliphatic tetracarboxylic dianhydride include ethylene tetracarboxylic dianhydride and 1,2,3,4-butanetetracarboxylic dianhydride. These tetracarboxylic dianhydride components can be used alone or in combination.

  The polyamic acid according to the present invention can be synthesized by mixing the diamine and the tetracarboxylic dianhydride in an arbitrary solvent to obtain a polyamic acid solution. As the method for producing a polyamic acid according to the present invention, all methods capable of producing a polyamic acid can be applied including known methods. Among these, it is preferable to perform the reaction in an organic solvent. As a solvent used in such a reaction, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, 1,2-dimethoxyethane, tetrahydrofuran, 1,3 -Dioxane, 1,4-dioxane, dimethyl sulfoxide, benzene, toluene, xylene, mesitylene, phenol, cresol and the like. These may be used alone or in combination of two or more.

  The density | concentration of the reaction raw material in this reaction is 2 mass%-50 mass% normally, Preferably it is 5 mass%-40 mass%.

  The reaction temperature is usually 80 ° C. or lower, preferably 70 ° C. or lower. The reaction pressure is not particularly limited, and can be sufficiently carried out at normal pressure. Moreover, although reaction time changes with the kind of reaction raw material, the kind of solvent, and reaction temperature, 0.5 to 24 hours are sufficient normally. By such a polycondensation reaction, the polyamic acid according to the present invention is produced.

  The molar ratio of the acid dianhydride to be reacted and the diamine is in the range of 0.8 to 1.2. Within this range, the molecular weight can be increased, and the elongation and the like are excellent. Preferably it is 0.9-1.1.

  The photosensitive resin composition according to the present invention may further contain a photosensitizer (C). When a photosensitizer is included, the decomposition of the photobase generator can be promoted, which is effective in reducing the exposure amount. There is no restriction | limiting in particular as a photosensitizer, A well-known photosensitizer can be used. For example, aromatic azides such as azidoanthraquinone and azidobenzalacetophenone; coumarin compounds such as coumarin, ketocoumarin, and 3,3′-carbonylbis (diethylaminocoumarin); benzanthrone, phenontolenquinone, benzyl, benzophenone, p, aromatic ketones such as p′-tetramethyldiaminobenzophenone; N-phenyldiethanolamine, N-phenylglycine, p-nitroaniline, 2,4-dinitroaniline, 2-chloro-4-nitroaniline, 2, Aromatic amines such as 6-dinitro-4-nitroaniline, Michler-ketone; thioxanthone compounds such as thioxanthone, diethylthioxanthone, isopropylthioxanthone; anthracene, naphthalene, diphenyl, p-nitrodipheny It is anthraquinone, naphthoquinone, quinones such as benzoquinone and the like; aromatic hydrocarbons such as.

  In addition, for example, a coumarin compound having a heterocyclic ring described in JP-A-3-239703 and JP-A-5-289335; 3-ketocoumarin compound described in JP-A 63-221110; Xanthene dyes described in JP-A Nos. 221958 and 4-219756; pyromethene dyes described in JP-A No. 6-19240; JP-A Nos. 47-2528 and 54-155292 (P-dialkylaminobenzylidene) ketone and styryl dye described in JP-A-56-166154 and JP-A-59-56403; having a julolidyl group described in JP-A-6-295061 Sensitizing dyes; and diaminobenzene compounds described in JP-A-11-326624. Kill.

  Of these, compounds having absorption in the vicinity of 300 nm to 450 nm are preferable, and specifically, benzophenones, coumarin compounds, thioxanthone compounds, aromatic ketones, and Michler ketones are preferable.

  The amount of the photosensitizer to be used is not particularly limited, but it is preferable to blend 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the polyamic acid in consideration of photosensitivity and mechanical properties of the resin after curing. . More preferably, it is 3 mass parts-30 mass parts.

  The photosensitive resin composition according to the present invention may further contain a flame retardant (D). The photosensitive resin composition according to the present invention can be further improved in flame retardancy by adding a flame retardant component. There is no restriction | limiting in particular as a flame retardant, A well-known flame retardant can be used.

  The flame retardant component is preferably a phosphorus-based flame retardant, and among them, a phosphate ester compound and / or a phosphazene compound are preferable from the viewpoint of flexibility and flexibility of the photosensitive resin composition. Among the phosphate ester compounds or phosphazene compounds, cyclic phosphazene compounds are more preferable from the viewpoint of heat stability.

  As the phosphoric acid ester compound, an aromatic phosphoric acid ester, an alkyl phosphoric acid ester or an alkoxyphosphoric acid ester is preferable.

  Examples of the aromatic phosphate ester include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, triisopropylphenyl phosphate, resorcinol bis (diphenyl phosphate) (hereinafter also referred to as “RDP”) and the like.

  Examples of the alkyl phosphate ester include triethyl phosphate, tripropyl phosphate, tributyl phosphate, triisobutyl phosphate (hereinafter also referred to as “TIBP”), and the like.

  Examples of the alkoxyphosphate include tris (butoxyethyl) phosphate, tris (butoxybutyl) phosphate (hereinafter also referred to as “TBXP”), tris (2-ethylhexyl) phosphate, and the like.

  As the phosphazene compound, a cyclic compound is preferable from the viewpoint of heat stability. For example, a compound selected from the compounds represented by formula (11) is preferable.

（式中、Ｘはそれぞれ３〜５の数を表す。）

(In the formula, each X represents a number of 3 to 5.)

  These flame retardant components can be used alone or in combination.

  The photosensitive resin composition according to the present invention may further contain a plasticizer (E). The photosensitive resin composition according to the present invention can be further improved in low warpage by adding a plasticizer component.

  Although there is no restriction | limiting in particular as a plasticizer, From the viewpoint of low curvature, the plasticizer containing an ethylene glycol chain and / or a propylene glycol chain is preferable. More preferred is a compound having an ethylene glycol chain and / or a propylene glycol chain and an isocyanuric acid ring from the viewpoint of flame retardancy. For example, the compound shown by Formula (12) etc. are mentioned.

（式中Ｒ^ｂはエチレングリコール鎖及び／又はプロピレングリコール鎖を含む有機基である。）

(In the formula, R ^b is an organic group containing an ethylene glycol chain and / or a propylene glycol chain.)

Specifically, for example, an organic group represented by the formula (13) is preferable as R ^b .

（式中、式中ｎ’は２〜８の数を表す。Ｌ’は２〜８の数を表す。）

(In the formula, n ′ represents a number of 2 to 8. L ′ represents a number of 2 to 8.)

  To the photosensitive resin composition according to the present invention, additives that are already known can be added as necessary within a quantitative and qualitative range that does not depart from the effects of the present invention. Specific additives include adhesion improvers, surfactants, antioxidants, UV inhibitors, light stabilizers, plasticizers, waxes, fillers, pigments, dyes, foaming agents, antifoaming agents, dehydration Agents, antistatic agents, antibacterial agents, antifungal agents, leveling agents, dispersants, ethylenically unsaturated compounds and the like.

  Examples of the adhesion improver include imidazole compounds, triazole compounds, tetrazole compounds, and sulfide compounds, preferably 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, and 2-ethyl-4-methylimidazole. 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1 Examples include silicon-containing imidazoles such as -cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, and imidazolesilane. As the imidazole silane, for example, IM-1000 manufactured by Nikko Metal Co., Ltd. is preferable.

  The photosensitive resin composition according to the present invention can be obtained by mixing a photobase generator, polyamic acid and, if necessary, a photosensitizer, a flame retardant and a plasticizer in an arbitrary solvent. The photosensitive resin composition according to the present invention may be in the form of a solution, but it is preferable to form a film. When forming a film, it can be obtained by mixing a photobase generator, polyamic acid and, if necessary, a photosensitizer, a flame retardant and a plasticizer in an arbitrary solvent and then drying by an arbitrary method. it can.

  The photosensitive resin composition according to the present invention can be suitably used for a photosensitive ink or a photosensitive film. When the photosensitive resin composition according to the present invention is used for a photosensitive ink or a photosensitive film, negative photolithography is possible.

  When using the photosensitive resin composition which concerns on this invention as a photosensitive ink, it can apply | coat by screen printing on arbitrary base materials, and can be dried, and a coverlay can be formed on arbitrary base materials. The screen printing method is a known printing method and is a method of printing by passing ink on a screen on which a pattern is formed using a squeegee or the like.

  When using the photosensitive resin composition which concerns on this invention for a photosensitive film, first, the photosensitive resin composition which concerns on this invention is coated on a base material, and a photosensitive film is created. The substrate is not limited as long as it is a substrate that is not damaged during the formation of the photosensitive film. Such a substrate is used as a carrier film.

  Examples of the carrier film include a heat resistant resin, a polyethylene terephthalate film, and a metal film. Among these, a heat-resistant resin and a polyethylene terephthalate film are preferable from the viewpoint of good handling, and a polyethylene terephthalate film is particularly preferable from the viewpoint of peelability after pressure bonding to the substrate.

  The photosensitive film comprised with the photosensitive resin composition which concerns on this invention can be processed into the laminated film which comprises a carrier film. The laminated film may include a cover film.

  The coating of the photosensitive resin composition on the carrier film is performed by, for example, bar coating, roller coating, die coating, blade coating, dip coating, doctor knife, spray coating, flow coating, spin coating, slit coating, brush coating, etc. It can be carried out. After coating, if necessary, heat treatment is performed with an oven, a hot plate, etc., and the solvent is dried to form a laminated film having a carrier film and a photosensitive film.

  Moreover, it is good also as a laminated | multilayer film by providing at least one layer of arbitrary antifouling or protective cover films on the photosensitive film according to the present invention. In the laminated film according to the present invention, as the cover film, for example, any antifouling film such as low-density polyethylene or a protective film can be used.

  By forming the photosensitive film according to the present invention as described above on a base material having wiring so as to cover the wiring, a circuit board having a cover lay can be formed on the base material. it can. In addition to the above photosensitive film, a circuit board can be similarly formed by using a laminated film provided with a carrier film and a photosensitive film or a laminated film further provided with a cover film on the laminated film. .

  The cover lay formed on an arbitrary substrate formed by using the photosensitive ink or the photosensitive film by the above method is subjected to a treatment such as curing through at least exposure and alkali development steps.

  A circuit board can be manufactured using the photosensitive resin composition according to the present invention. In this method of manufacturing a circuit board, a circuit board is manufactured, a photosensitive resin composition is applied onto a substrate having at least wiring, and then dried to form a resin composition layer, and pattern exposure is performed on the resin composition. The resin composition layer after pattern exposure is developed using an alkaline aqueous solution, and the resin composition layer after the development treatment is cured.

  In the method for producing a circuit board, at least either the photosensitive film or the laminated film is laminated on a substrate having wiring to form a resin composition layer, and a pattern is formed on the resin composition layer. Exposure is performed, the resin composition layer after the pattern exposure is developed using an aqueous alkaline solution, and the resin composition layer after the development treatment is cured.

  As a base material which has wiring, what has wiring on arbitrary base materials, such as hard base materials, such as a glass epoxy board | substrate and a glass maleimide board | substrate, or flexible substrates, such as a polyimide film, is mentioned. Among these, the base material which has wiring on a flexible board | substrate from a viewpoint which can be bent is preferable.

  As a method for forming the resin composition layer, the screen printing method described above is preferably used when a photosensitive ink is used.

  When using a photosensitive film, the method etc. which perform a hot press, a heat | fever lamination, a heat | fever vacuum press, a heat | fever vacuum lamination etc. in the state which contacted the wiring side and the photosensitive film of the base material which has the said wiring are mentioned. Among these, from the viewpoint of embedding the photosensitive film between the wirings, a heat vacuum press or a heat vacuum laminate is preferable. The heating temperature when laminating the photosensitive film on the substrate having the wiring is not limited as long as the photosensitive film can be in close contact with the substrate. 30 to 400 degreeC is preferable from a viewpoint of contact | adherence to a base material, a decomposition | disassembly of a photosensitive film, or a side reaction. More preferably, it is 50 degreeC-150 degreeC.

  The cover lay according to the present invention is subjected to a heat treatment (hereinafter referred to as PEB) as necessary after exposure and before development, and then the unexposed portion is dissolved by alkali development, whereby a negative photo Lithography is possible. In this case, examples of the light source used for exposure include a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a xenon lamp, a fluorescent lamp, a tungsten lamp, an argon laser, and a helium cadmium laser. Among these, a high pressure mercury lamp and an ultrahigh pressure mercury lamp are preferable.

  The temperature at which PEB is carried out is preferably 100 ° C. to 160 ° C. from the viewpoint of developability. Heating may be performed in either an air atmosphere or a nitrogen atmosphere. Moreover, there is no restriction | limiting in particular as a heating method, However, It can carry out using oven, a baking furnace, a hotplate, etc.

  The aqueous alkali solution used for development is not limited as long as it is a solution capable of dissolving the unexposed portion. Examples of such a solution include a sodium carbonate aqueous solution, a potassium carbonate aqueous solution, a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, and a tetramethylammonium hydroxide aqueous solution. From the viewpoint of developability, an aqueous sodium carbonate solution and an aqueous sodium hydroxide solution are preferred. Examples of the development method include spray development, immersion development, and paddle development.

  Next, the circuit board having the cover lay is formed by curing the circuit board on which the cover lay of the present invention is formed as necessary. The curing is preferably performed at a temperature of 30 ° C. to 400 ° C. from the viewpoint of removing the solvent, side reactions and decomposition, and not damaging the wiring on the substrate. More preferably, 100 to 200 ° C is preferable. More preferably, it is 120 degreeC-180 degreeC. Cure may be performed in either an air atmosphere or a nitrogen atmosphere. The curing method is not particularly limited, but can be performed using an oven, a baking furnace, a hot plate, or the like.

  The mechanism in which the difference in solubility and / or the difference in dissolution rate between the exposed portion and the unexposed portion of the photosensitive resin composition according to the present invention is estimated as follows. Since the base generated from the photobase generator upon exposure acts as an imidization catalyst when converting polyamic acid to polyimide, the imidization ratio of the exposed part is higher than that of the unexposed part, Solubility and / or dissolution rate in alkaline developer is reduced.

  At that time, imidation reaction can be promoted by applying PEB. By performing alkali development using the solubility and / or dissolution rate in the alkaline developer, negative photolithography in which the exposed portion remains undissolved in the developer can be achieved.

  The photosensitive resin composition according to the present invention is sufficiently suppressed in warping as a cover lay, has good developability, and exhibits chemical resistance when cured and cured, so that it is used in the electronics field. Forming protective layers for printed wiring boards and circuit boards used for operation panels of various electronic devices, forming insulating layers for laminated substrates, silicon wafers used for semiconductor devices, semiconductor chips, members around semiconductor devices, and semiconductor mounting It is used to form films on electronic components for use in protecting, insulating and bonding substrates, heat sinks, lead pins, semiconductors, etc.

  Next, the synthesis of the photobase generator according to the present invention will be described. The photobase generator according to the present invention can be synthesized, for example, using an appropriate acid dianhydride as a raw material, through three steps of introduction of a substituent, then oximation, and further condensation cyclization. First, the step of introducing a substituent will be described.

  Substituents can be introduced using an appropriate acid dianhydride as a raw material and an appropriate nucleophile. Suitable acid dianhydrides that can be used in the synthesis of the photobase generator according to the present invention include, for example, pyromellitic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride And anhydrides. Of these, naphthalene-1,4,5,8-tetracarboxylic dianhydride, which is a 6-membered acid dianhydride, is preferred from the viewpoint of the stability of the base obtained from the synthesized photobase generator.

  Suitable nucleophiles include, for example, Grignard reagent, organolithium reagent and the like. Among them, the Grignard reagent is preferable from the viewpoint of reactivity. Alkyl groups or aromatic groups can be introduced by Grignard reagents.

  Examples of the alkyl group that can be introduced by the Grignard reagent include a methyl group, an ethyl group, a propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl, a t-butyl group, and a vinyl group. .

  Examples of the aromatic group that can be introduced by the Grignard reagent include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2-methoxyphenyl group, a 3-methoxyphenyl group, and a 4-methoxyphenyl group. Group, 2-mesityl group, 1-naphthyl group, 2-naphthyl group, 2-methyl-1-naphthyl group, 4-methyl-1-naphthyl group, 3-biphenyl group, 9-phenanthryl group and the like.

  These substituents can be introduced by reacting Grignard reagents each having a corresponding substituent with the acid dianhydride described above. The solvent used at this time is not particularly limited, but an ether solvent can be used from the viewpoint of reactivity. Examples of the ether solvent include tetrahydrofuran, 1,2-dimethoxyethane, diethyl ether, isopropyl ether and the like. Of these, isopropyl ether is preferred because there is little risk of flammable explosion.

  Next, the oximation process will be described. The intermediate (hereinafter referred to as an intermediate) into which a substituent has been introduced by the above process can be oximed by an appropriate method.

The oximation reagent, e.g., _NH 2 OH aqueous _solution, such as NH 2 OH · HCl and the like. When an intermediate having a substituent having a large steric hindrance is oximeated, it is preferable to use NH ₂ OH · HCl in the presence of NaOH and perform the reaction while heating and refluxing the solvent.

  The solvent used at this time is not particularly limited, but polar solvents such as methanol, ethanol, ethylene glycol, water, and acetic acid can be used. These solvents may be used alone or in combination.

  The product of the oximation step is preferably purified by a conventionally known method such as silica gel chromatography or recrystallization in order to efficiently perform the next step of condensed cyclization.

Next, the process of condensed cyclization will be described. Cyclocondensation is, for example, a method using SOCl _2, a method using POCl _3, and a method using a condensing agent.

When using SOCl ₂ , for example, the product obtained in the above step (hereinafter referred to as oxime form) is added to an appropriate solvent, and SOCl ₂ previously diluted with the same solvent is gradually added. This can be done.

In the case of using POCl ₃ , for example, as in the case of using SOCl ₂ , the oxime body is added to an appropriate solvent, and POCl ₃ diluted in advance with the same solvent is gradually added. can do.

Is not particularly limited solvent used in the case of using the case and POCl ₃ using SOCl _2, it is possible to use a solvent of ether from the viewpoint of reactivity. Examples of the ether solvent include tetrahydrofuran, 1,2-dimethoxyethane, diethyl ether, isopropyl ether, and the like. In addition, because of the heat generated by the reaction heat, the reaction is preferably performed while cooling.

  When a condensing agent is used, examples of the condensing agent include dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, 2,4,6-trichlorobenzoyl chloride, 4-trifluoromethylbenzoic anhydride. 2-methyl-6 nitrobenzoic anhydride, etc. can be used. Among these, 2,4,6-trichlorobenzoyl chloride (hereinafter referred to as TCBC) is preferable from the viewpoint of high reaction yield.

  When a condensing agent is used, pyridine, dimethylaminopyridine, triethylamine, etc. can be added to the reaction solution as an auxiliary agent. The reaction solvent is not particularly limited, but ether-based, hydrocarbon-based and ester-based solvents can be used from the viewpoint of reactivity.

  Examples of the ether solvent include tetrahydrofuran, 1,2-dimethoxyethane, diethyl ether, isopropyl ether, and the like. Examples of the hydrocarbon solvent include hexane, cyclohexane, toluene, and methylene chloride. Examples of ester solvents include ethyl acetate and γ-butyrolactone. These may be used alone or in combination.

  After carrying out the condensed cyclization, it is preferable to purify the resulting crude product. For example, the removal of a highly polar compound can be carried out by dissolving the crude product in a suitable organic solvent and thoroughly washing with saturated saline. In addition, for example, in order to remove a compound having low crystallinity, it can be purified and carried out by a recrystallization method. There is a concern that the photobase generator obtained may be decomposed when washed with strong alkali in the purification step.

For example, the compound represented by the formula (2) uses pyromellitic dianhydride as a raw material, uses phenylmagnesium bromide as a Grignard reagent, introduces a phenyl group, then uses NH ₂ OH · HCl, undergoes oximation, and finally It is possible to synthesize using TCBC as a condensing agent. A schematic diagram is shown in Formula (14).

  Further, for example, the compound represented by the formula (3) can be synthesized in the same manner as the compound represented by the formula (2) using naphthalene-1,4,5,8-tetracarboxylic dianhydride as a raw material. It is. A schematic diagram is shown in Formula (15).

  The present invention can be applied to a patterning process using photolithography capable of alkali development.

Claims (16)

A photobase generator characterized by being a compound containing an acyloxyimino group represented by the formula (1).

(In the formula, X ¹ is a tetravalent organic group, n represents an integer of 0 to 3. R ¹ is an aromatic group or an alkyl group having 1 or more carbon atoms.)   A photosensitive resin composition containing a photobase generator (A) and a polyamic acid (B), wherein the photobase generator is a compound containing an acyloxyimino group represented by formula (1): A photosensitive resin composition characterized by being. The photobase generator is a compound containing an acyloxyimino group represented by the formula (1), and the compound is represented by the formula (2) or the formula (3). The photosensitive resin composition as described.

(In the formula, n represents an integer of 0 to 3. R ¹ is an aromatic group or an alkyl group having 1 or more carbon atoms.)

(In the formula, n represents an integer of 0 to 3. R ¹ is an aromatic group or an alkyl group having 1 or more carbon atoms.) The photosensitive resin composition according to claim 2, wherein the polyamic acid is a polyamic acid obtained using a diamine represented by the formula (4).

(In the formula, R ^a is ^a divalent organic group having 1 to 50 carbon atoms. K represents a number of 1 to 50.) The photosensitive resin composition according to claim 4, wherein the polyamic acid is a polyamic acid obtained by using an acid dianhydride represented by the formula (5).

(In the formula, l represents a number from 1 to 20. m represents an integer from 2 to 50.) The photosensitive resin composition according to claim 4 or 5, wherein the polyamic acid is a polyamic acid obtained by using a diamine represented by formula (6).

(In the formula, Z is a divalent organic group and is selected from the organic groups shown in Formula (7).)

(In the formula, p represents an integer of 3 to 5.)   The photosensitive resin composition according to claim 4, wherein the polyamic acid is a polyamic acid obtained using oxydiphthalic dianhydride.   Furthermore, a photosensitizer (C) is contained, The photosensitive resin composition in any one of the Claims 2-7 characterized by the above-mentioned.   Furthermore, a flame retardant (D) is contained, The photosensitive resin composition in any one of the Claims 2-8 characterized by the above-mentioned.   Furthermore, the plasticizer (E) is contained, The photosensitive resin composition in any one of the Claims 2-9 characterized by the above-mentioned.   A photosensitive film comprising the photosensitive resin composition according to claim 2.   A laminated film comprising: a carrier film; and the photosensitive film according to claim 11 provided on the carrier film.   The laminated film according to claim 12, further comprising a cover film formed on the photosensitive film.   A circuit board comprising: a base material having wiring; and a cover lay configured by using the photosensitive film according to claim 11 or the laminated film according to claim 12 or claim 13. .   A step of forming a resin composition layer on a substrate having at least wiring using the photosensitive resin composition according to claim 2, and pattern exposure is performed on the resin composition layer. A circuit comprising: a step; a step of developing the resin composition layer after the pattern exposure using an alkaline aqueous solution; and a step of curing the resin composition layer after the development treatment. A method for manufacturing a substrate.   Laminating at least the photosensitive film according to claim 11 or the laminated film according to claim 12 or 13 on a substrate having wiring, and forming a resin composition layer; A step of performing pattern exposure on the resin composition layer, a step of developing the resin composition layer after the pattern exposure using an alkaline aqueous solution, a step of curing the resin composition layer after the development treatment, A method for manufacturing a circuit board, comprising: