JP6138943B2 - Photosensitive resin composition, relief pattern film thereof, method for producing relief pattern film, electronic component or optical product including relief pattern film, and adhesive including photosensitive resin composition - Google Patents

Description

  The present invention relates to a polymer precursor having a polyamic acid or polyamic acid ester repeating unit at least partially, and a nonionic photoreactive latent that generates a strongly basic tertiary amine by irradiation with actinic rays. Photosensitive resin composition containing basic substance, relief pattern film (polymer film) using the same, method for producing relief pattern film, and electron having relief pattern film as surface protective film layer and / or interlayer insulating film The present invention relates to an adhesive including a component or an optical product and a photosensitive resin composition.

  Polyimide developed by DuPont in 1955 in the United States is widely applied in various fields based on excellent properties such as high insulation, heat resistance and high mechanical strength. In addition to the field of aerospace, which was first applied, it is being applied to coating films for semiconductor elements, flexible printed wiring boards, and heat-resistant insulating interlayers. Furthermore, in recent years, with the advancement of semiconductor mounting technology and higher density, further miniaturization of wiring patterns has been demanded, and high workability is also required for polyimide.

  However, polyimide has a side that it is difficult to process due to poor thermoplasticity and solubility in organic solvents. For this reason, polyimide is widely used by a method in which photosensitivity is imparted to a polyimide precursor, and a desired pattern is formed by irradiation with actinic rays, and then the ring is closed at a high temperature.

  In this way, so-called photosensitive polyimide, which has improved processability by imparting photosensitivity to the polyimide precursor, has the feature of shortening complicated processes, so from the viewpoint of productivity and process simplification. Higher utility than non-photosensitive polyimide.

  And the conventional photosensitive polyimide makes the polyimide precursor imidize by performing the heating process of 300 degreeC or more after image development (for example, refer patent document 1, 2).

  Moreover, the photosensitive resin composition which can imidize a polyimide precursor at low temperature and can form a polyimide film is disclosed (for example, refer patent document 3).

Japanese Patent No. 4830435 Japanese Patent No. 4756350 JP 2006-189591 A

  However, although the photosensitive polyimide described in Patent Document 1 can be imidized even at a low temperature, there is room for improvement in order to form a good pattern. This is because there is no change in the skeleton structure of the basic substance before and after exposure. Moreover, since the photobase generator used for imidation is ionic, the solubility with respect to an organic solvent is not enough.

  Furthermore, since a nonionic photobase generator (carbamate, acyloxime, etc.) is used for imidation of the polyimide precursor described in Patent Documents 2 and 3, the solubility in organic solvents is excellent. There is room for improvement in the tensile strength of the polymer film after curing by releasing a secondary or secondary amine.

  An object of the present invention is made in view of the above background, and is a photosensitive resin composition capable of easily forming a highly accurate pattern in a low-temperature process without having the disadvantages of the prior art. Relief pattern film (polymer film) used, method for producing relief pattern film, electronic component or optical product having relief pattern film as surface protective film layer and / or interlayer insulating film, and adhesion comprising photosensitive resin composition It is to provide an agent.

In order to achieve the above object, the present inventor has paid attention to a photosensitive polyimide composition using a photobase generator, and as a result of intensive research, generates a strongly basic tertiary amine by irradiation with actinic rays. It has been found that the object of the present invention can be achieved by a combination of a nonionic photoreactive latent basic substance and a specific polymer precursor.

  That is, the photosensitive resin composition according to the present invention comprises (A) a polymer precursor having a polyamic acid or polyamic acid ester repeating unit in at least a part thereof, and (B) a strongly basic compound by irradiation with actinic rays. And a nonionic photoreactive latent basic substance that generates a tertiary amine.

In the present invention, as the latent basic substance (B), a nonionic substance that generates a strong base by changing its chemical structure upon irradiation with actinic rays is used. Specifically, the latent basic substance (B) is excited by irradiation with actinic rays, and the chemical structure is changed to generate a strongly basic tertiary amine. And the strong basic tertiary amine which generate | occur | produced accelerates | stimulates low temperature imidation of a polymer precursor (A), Therefore An exposure part (imidized part) and an unexposed part (polymer precursor (A ), And a difference in solubility between the exposed part and the unexposed part occurs. That is, the latent basic substance (B) acts as a very effective photosensitive component on the polymer precursor (A), and facilitates development with a developer. Specifically, the imidization of the exposed part is promoted to make it have almost no solubility. On the other hand, since the unexposed portion remains soluble in the solution, development with a developer is facilitated.

The higher the polyamic acid component as the polymer precursor, the better the alkali solubility, and the more the polyamic acid ester component, the better the organic solvent solubility. By changing the ratio of amide acid to amide acid ester, solubility suitable for various developers can be obtained.

  In the present invention, the polymer precursor (A) is preferably a compound represented by the following general formula (1).

（式（１）中、
R₁は４価の有機基であり
R₂は２価の有機基であり、
Xは２価の有機基であり
R₃及びR₄は、相互に同一でも異なってもよく、水素原子又は１価の有機基またはケイ素を有する官能基であり、
mは１以上の整数であり、
nは０または１以上の整数である。）

(In the formula (1),
R ₁ is a tetravalent organic group
R ₂ is a divalent organic group,
X is a divalent organic group
R ₃ and R ₄ may be the same or different from each other, and are a hydrogen atom, a monovalent organic group or a functional group having silicon,
m is an integer greater than or equal to 1,
n is 0 or an integer of 1 or more. )

  In the present invention, the latent basic substance (B) is preferably a compound represented by the general formula (2).

（式（２）中、 R₅は、非置換であるか、または、１つ以上のアルキル、アルケニル、アルキニル、ハロアルキル、NR₁₂R₁₃、CN、OR₁₄、SR₁₅、COR₁₆、COOR₁₇、ハロゲンまたは式（３）

(In the formula (2), R ₅ is unsubstituted or one or more alkyl, alkenyl, alkynyl, haloalkyl, NR ₁₂ R ₁₃ , CN, OR ₁₄ , SR ₁₅ , COR ₁₆ , COOR ₁₇ , Halogen or formula (3)

によって置換された芳香族または複素芳香族基であり；あるいは
R₅は、式（４）

An aromatic or heteroaromatic group substituted by: or
R ₅ is the formula (4)

によって表わされる基であり；
R₆およびR₇は、互いに独立して、水素、アルキル、アルケニル、アルキニルであるか、非置換または１つ以上のアルキル、CN、OR₁₄、SR₁₅、ハロゲンまたはハロアルキルによって置換されたフェニルであり；
R₉は、アルキルまたはNR_14AR_15Aであり； R_14AおよびR_15Aは、ともに、非置換であるか、または１つ以上のアルキルによって置換されたアルキレンブリッジを形成し；
R₈、R₁₀、R₁₁、R₁₂およびR₁₃は、互いに独立して、水素またはアルキルであり；あるいは
R₈およびR₁₀は、ともに、非置換であるか、または１つ以上のアルキルによって置換されたアルキレンブリッジを形成し；あるいは
R₉およびR₁₁は、R₈およびR₁₀から独立して、ともに、非置換であるか、または１つ以上のアルキルによって置換されたアルキレンブリッジを形成し；
R₁₄、R₁₅およびR₁₇は、互いに独立して、水素またはアルキルであり；
R₁₆は水素又はアルキルであり；あるいは、非置換であるか、または１つ以上のアルキル、アルケニル、アルキニル、ハロアルキル、NR₁₂R₁₃、CN、OR₁₄、SR₁₅、COR₁₄、COOR₁₇、またはハロゲンによって置換された芳香族または複素芳香族基であり；
R₁₈は、非置換であるか、または１つ以上のアルキル、アルケニル、アルキニル、ハロアルキル、NR₁₂R₁₃、CN、OR₁₄、SR₁₅、COR₁₆、COOR₁₇、またはハロゲンによって置換された芳香族または複素芳香族基であり；
R₁₉は、水素またはアルキルであり；
R₂₀は、水素、アルキル、あるいは非置換であるか、または１つ以上のアルキル、ビニル、アルケニル、アルキニル、ハロアルキル、フェニル、NR₁₂R₁₃、CN、OR₁₄、SR₁₅、COR₁₆、COOR₁₇またはハロゲンによって置換されたフェニルである。）

A group represented by
R ₆ and R ₇ are, independently of one another, hydrogen, alkyl, alkenyl, alkynyl, or phenyl which is unsubstituted or substituted by one or more alkyl, CN, OR ₁₄ , SR ₁₅ , halogen or haloalkyl ;
R ₉ is alkyl or NR _14A R _15A ; R _14A and R _15A are both unsubstituted or form an alkylene bridge substituted with one or more alkyls;
R ₈ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are, independently of one another, hydrogen or alkyl; or
R ₈ and R ₁₀ together form an alkylene bridge that is unsubstituted or substituted by one or more alkyls; or
R ₉ and R ₁₁ , independently of R ₈ and R ₁₀ , together form an alkylene bridge that is unsubstituted or substituted by one or more alkyls;
R ₁₄ , R ₁₅ and R ₁₇ are independently of each other hydrogen or alkyl;
R ₁₆ is hydrogen or alkyl; or is unsubstituted or one or more alkyl, alkenyl, alkynyl, haloalkyl, NR ₁₂ R ₁₃ , CN, OR ₁₄ , SR ₁₅ , COR ₁₄ , COOR ₁₇ , or An aromatic or heteroaromatic group substituted by halogen;
R ₁₈ is unsubstituted or aromatic substituted by one or more alkyl, alkenyl, alkynyl, haloalkyl, NR ₁₂ R ₁₃ , CN, OR ₁₄ , SR ₁₅ , COR ₁₆ , COOR ₁₇ , or halogen Or a heteroaromatic group;
R ₁₉ is hydrogen or alkyl;
R ₂₀ is hydrogen, alkyl, or unsubstituted, or one or more alkyl, vinyl, alkenyl, alkynyl, haloalkyl, phenyl, NR ₁₂ R ₁₃ , CN, OR ₁₄ , SR ₁₅ , COR ₁₆ , COOR ₁₇ Or phenyl substituted by halogen. )

  Here, in this invention, it is preferable that the latent basic substance (B) represented by Formula (2) is a compound represented by Formula (5).

（式（５）中、
ｘは１〜５の整数であり；
ｙ及びｚは、互いに独立して、０〜６の整数であり；
R₂₁及びR₂₂は、互いに独立して、炭素数１〜４のアルキル基であり；
Ａは炭素又は窒素原子である。）

(In Formula (5),
x is an integer from 1 to 5;
y and z are independently an integer from 0 to 6;
R ₂₁ and R ₂₂ are each independently an alkyl group having 1 to 4 carbon atoms;
A is a carbon or nitrogen atom. )

  Furthermore, in the present invention, the latent basic substance (B) represented by the formula (2) is more preferably a compound represented by the formula (6-1) or the formula (6-2).

  Furthermore, in the present invention, the boiling point of the strongly basic tertiary amine generated from the latent basic substance (B) is preferably 100 ° C. or higher, and more preferably 150 ° C. or higher.

  In the present invention, the pKa of the conjugate acid of the strongly basic tertiary amine generated from the latent basic substance (B) is preferably 9 or more, and more preferably 12 or more.

  The wavelength of the high-pressure mercury lamp, which is a general exposure light source, is 436 nm, 405 nm, 365 nm, and the wavelength of the KrF laser is 248 nm. Therefore, the latent basic substance (B) is in the range of 240 nm to 450 nm. It is preferable to have absorption at any wavelength.

  The polymer precursor (A) of the present invention is not particularly limited in structure, but when developing with a developer, it is soluble in the developer, for example, when developing with an alkali developer. Is preferably a polyamic acid.

  Moreover, it is preferable that the photosensitive resin composition of this invention can form a pattern favorably at 200 degrees C or less.

  The relief pattern film of the present invention is a coating film formed by drying the above-mentioned photosensitive resin composition on a substrate, irradiating the coating film with actinic rays in a pattern, and irradiating the coating film with actinic rays. It is manufactured by heating at 200 ° C. or less and developing the heated coating film.

  The photosensitive resin composition of the present invention can be used as an adhesive component, and the relief pattern film obtained by imidizing the photosensitive resin composition is a surface protective film for electronic parts or optical products. It is suitably used as a layer and / or an interlayer insulating film.

  In the photosensitive resin composition according to the present invention, a strongly basic tertiary amine is generated by irradiating an actinic ray to the nonionic photoreactive latent basic substance (B). The imidization of the polymer precursor (A) was achieved at a low temperature (200 ° C. or less). The relief pattern film thus obtained is a material having both tensile strength and pattern formability.

  Since the photosensitive resin composition according to the present invention can be imidized even at 200 ° C. or lower, it can be applied to a wider range of applications in the technical field using polyimide, and the possibility of use as a material for various members is expanded. did.

  ADVANTAGE OF THE INVENTION According to this invention, the technical subject regarding the conventional polyimide precursor which was difficult to take the solubility contrast between an exposed part and an unexposed part can be overcome, and a favorable pattern shape can be obtained.

  Moreover, since the photosensitive resin composition according to the present invention can select a polymer precursor (A) having a wide range of structures, the polymer obtained thereby has functions such as heat resistance, dimensional stability, and insulation. Can be given.

  In particular, the photosensitive resin composition according to the present invention is mainly used as a pattern forming material, and the pattern formed thereby functions as a component that imparts heat resistance and insulation as a permanent film, such as a color filter. , Flexible substrate members, liquid crystal alignment films, semiconductor devices, electronic components, interlayer insulation films, wiring coating films such as solder resists and coverlays, solder dams, optical circuits, optical circuit components, antireflection films, other optical members, Or it is suitable for forming building materials.

It is the graph which showed the imidation ratio in each temperature of the photosensitive resin composition of this invention and the conventional photosensitive resin composition. It is the graph which showed the tension test result of the polymer film obtained from the photosensitive resin composition of this invention.

The present invention will be described in detail below.

  The photosensitive resin composition of the present invention comprises (A) a polymer precursor having at least a part of a polyamic acid or polyamic acid ester repeating unit, and (B) a strongly basic tertiary compound by irradiation with actinic rays. Contains a nonionic photoreactive latent basic substance that generates amines.

  The polymer precursor (A) used in the present invention is preferably represented by the following general formula (1).

式（１）中、R₁は４価の有機基であり、R₂は２価の有機基であり、Ｘが２価の有機基である。Ｘとしては、例えば、フェノール基、アルキルフェノール基、（メタ）アクリレート基、環状アルキル基、環状アルケニル基、ヒドロキシアミド酸基、芳香族又は脂肪族エステル基、アミド基、アミドイミド基、炭酸エステル基、シロキサン基、アルキレンオキサイド、ウレタン基、エポキシ基、オキセタニル基などを構成成分として含む基を挙げることができる。

In formula (1), R ₁ is a tetravalent organic group, R ₂ is a divalent organic group, and X is a divalent organic group. Examples of X include a phenol group, an alkylphenol group, a (meth) acrylate group, a cyclic alkyl group, a cyclic alkenyl group, a hydroxyamide acid group, an aromatic or aliphatic ester group, an amide group, an amidoimide group, a carbonate ester group, and a siloxane. And a group containing a group, an alkylene oxide, a urethane group, an epoxy group, an oxetanyl group or the like as a constituent component.

  m is an integer of 1 or more, and n is 0 or an integer of 1 or more. Here, the number average molecular weight of the polymer precursor (A) is preferably 1,000 or more and 1,000,000 or less, more preferably 5,000 to 500,000, and even more preferably 10,000 to 200,000.

In formula (1), R ₁ and R ₂ are aromatic groups, preferably aromatic groups having 6 to 32 carbon atoms, or aliphatic groups, preferably aliphatic groups having 4 to 20 carbon atoms, depending on the application. Selected from the group. R ₁ and R ₂ are preferably the following acid dianhydrides used in the production of the polymer precursor (A) and substituents R ₁ and R ₂ contained in the diamine.

Moreover, when patterning the photosensitive resin composition with short wavelength light, it is preferable to use an aliphatic group as R ₁ and R ₂ from the viewpoint of the absorption characteristics of the polymer. Further, for example, when a group containing fluorine is used as R ₁ and R ₂ , the wavelength of light absorption can be reduced or the dielectric characteristics can be improved.

  In the present invention, it is important that the structure of the polymer precursor (A) can be selected depending on the application.

In addition, although the tetravalence of R ₁ shows only the valence for bonding with an acid, R ₁ may have a substituent. Similarly, the divalent value of R ₂ indicates only the valence for bonding with the amine, but may have other substituents. R ₃ and R ₄ are a hydrogen atom, a monovalent organic group, or a functional group having silicon.

When R ₃ and R ₄ are monovalent organic groups, examples include alkyl groups, alkenyl groups, alkynyl groups, and aryl groups. When R ₃ and R ₄ are functional groups having monovalent silicon, for example, a siloxane group, a silane group, a silanol group, and the like can be given. Further, only a part of R ₃ and R ₄ can be hydrogen or a monovalent organic group, whereby the solubility can be controlled.

As the polymer precursor (A) according to the present invention, a polyamic acid in which R ₃ and R ₄ are hydrogen atoms is preferably used. Thereby, alkali developability becomes favorable and a favorable pattern is obtained.

(Polyamic acid)
The polyamic acid can be prepared by applying a conventionally known method. For example, it can be prepared simply by mixing acid dianhydride and diamine in a solution. It is preferably used because it can be synthesized by a one-step reaction, can be obtained easily and at low cost, and does not require further modification. Although the synthesis method of a polymer precursor (A) is not specifically limited, A well-known method is applicable.

  Examples of the tetracarboxylic dianhydride that can be used in the present embodiment include those represented by the following formula (8). However, the specific examples shown below are merely examples, and it goes without saying that known ones can be used as long as they do not contradict the gist of the present invention.

（式中のR₁は、上述したとおりである。）

(R ₁ in the formula is as described above.)

Incidentally, R ₁ group in the repeating unit of the polyamic acid according to the present embodiment is preferably derived from R ₁ of the tetracarboxylic dianhydride used as a raw material for polyamic acid production.

  Examples of the acid dianhydride applicable to the production of the polymer precursor (A) include ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetra. Aliphatic tetracarboxylic dianhydrides such as carboxylic dianhydride and cyclopentanetetracarboxylic dianhydride; pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2,3 ′, 3,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic acid Dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,3 ′, 3,4′-biphenyltetracarboxylic dianhydride, 2 2 ', 6,6'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane Dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane Anhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1, 1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride 1,3-bis (3,4-dicarboxy) benzoyl] benzene dianhydride, 1,4-bis [(3,4-dicarboxy) benzoyl] benzene dianhydride, 2,2-bis {4- [4- (1, 2-dicarboxy) phenoxy] phenyl} propane dianhydride, 2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} propane dianhydride, bis {4- [4- ( 1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, 4,4′-bis [4- ( 1,2-dicarboxy) phenoxy] biphenyl dianhydride, 4,4′-bis [3- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, bis {4- [4- (1,2- Dicarboxy) phenoxy] phenyl } Ketone dianhydride, bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} sulfone Dianhydride, bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} sulfone dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} sulfide dianhydride Bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} sulfide dianhydride, 2,2-bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl}- 1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} -1,1,1,3 , 3,3-Hexafluoropropane Anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis (2,3- or 3,4-di Carboxyphenyl) propane dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetra Carboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic Acid dianhydride, pyridinetetracarboxylic dianhydride, sulfonyldiphthalic anhydride, m-terphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, p-terphenyl-3,3 ', 4,4'-Tetracar Aromatics such emissions dianhydride tetracarboxylic dianhydride, and the like.

  These may be used alone or in combination of two or more. And as a particularly preferred tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetra Carboxylic dianhydride, 2,2 ′, 6,6′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3,4-di Carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride.

  When acid dianhydride into which fluorine is introduced or acid dianhydride having an alicyclic skeleton is used as the acid dianhydride to be used in combination, the physical properties such as solubility and thermal expansion coefficient are adjusted without significantly impairing transparency. It is possible. Also, rigid acid dianhydrides such as pyromellitic acid anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, etc. If used, the linear thermal expansion coefficient of the finally obtained polyimide becomes small, but it tends to inhibit the improvement of transparency, so it may be used in combination while paying attention to the copolymerization ratio.

  The plurality of carboxyl groups of the acid dianhydride may be present on a single aromatic ring or a plurality of aromatic rings.

で表される酸二無水物を使用することができる。透明性と機械特性の観点で、上記の酸二無水物の使用が好ましい。

An acid dianhydride represented by the formula can be used. From the viewpoint of transparency and mechanical properties, it is preferable to use the above acid dianhydride.

Examples of amines that can be used in the present invention include diamines represented by the following formula (10). However, the following are examples, and it goes without saying that known ones can be used as long as they do not contradict the gist of the present invention.

（式中R₂は、上述したとおりである。）

(Wherein R ₂ is as described above.)

Examples of diamines when the R ₂ group is a divalent aromatic group include paraphenylene diamine, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4 ′. -Diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 9,10-bis (4-aminophenyl) anthracene, 4,4 '-Diaminobenzophenone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfoxide, 1,3-bis (3-aminophenoxy) benzene, bis [4 -(4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4′-bis (4-aminophenoxy) bipheny 4,4′-bis (3-aminophenoxybiphenyl, bis [4- (4-aminophenoxy) phenyl] ether, 1,1,1,3,3,3-hexafluoro-2,2-bis ( 4-aminophenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,1,1,3,3 3-hexafluoro-2,2-bis (3-amino-4-methylphenyl) propane, metaphenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl ether 1,4-bis (4-aminophenoxy) benzene and 1,3-bis (4-aminophenoxy) benzene.

Examples of diamines when the R ₂ group is a divalent aliphatic group include 1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylene Diamine, Octamethylenediamine, Nonamethylenediamine, 4,4-Diaminoheptamethylenediamine, 1,4-Diaminocyclohexane, Isophoronediamine, Tetrahydrodicyclopentadienylenediamine, Hexahydro-4,7-methanoindanylenediethylenediamine , Tricyclo [6.2.1.02,7] -undecylenedimethyldiamine, 4,4′-methylenebis (cyclohexylamine), and isophoronediamine.

  Another example is diaminopolysiloxane represented by the following formula (11).

However, in the formula, R ₂₈ and R ₂₉ each independently represent a divalent hydrocarbon group, and R ₃₀ and R ₃₁ each independently represent a monovalent hydrocarbon group. p is 1 or more, preferably an integer of 1 to 10.

Specifically, as R ₂₈ and R ₂₉ in the above formula (11), an alkylene group having 1 to 7 carbon atoms such as a methylene group, an ethylene group and a propylene group, and an arylene group having 6 to 18 carbon atoms such as a phenylene group. Examples of R ₃₀ and R ₃₁ include an alkyl group having 1 to 7 carbon atoms such as a methyl group and an ethyl group, and an aryl group having 6 to 12 carbon atoms such as a phenyl group.

  The ester of polyamic acid can be obtained by a known method.

  For example, an acid anhydride such as 3,3′-benzophenone tetracarboxylic dianhydride is reacted with an alcohol such as ethanol to form a half ester. The half ester is converted to diester diacid chloride using thionyl chloride. An ester of polyamic acid can be obtained by reacting the diester diacid chloride with a diamine such as 3,5-diaminobenzoic acid.

In the photosensitive resin composition, at least a part of the polymer precursor (A) having a polyamic acid or polyamic acid ester repeating unit may be a single type of material or a mixture of a plurality of types. It may be used as Further, it may be a copolymer in which R ₁ and / or R ₂ each have a plurality of structures.

  The nonionic photoreactive latent basic substance (B) according to the present embodiment generates a strongly basic tertiary amine by irradiation with actinic rays. The latent basic substance (B) changes its chemical structure by light irradiation and generates a strongly basic tertiary amine. From the viewpoint of enhancing basicity and efficiently promoting partial imidization, the strongly basic tertiary amine generated is preferably, for example, amidine or guanidine.

Among the latent basic substances (B) of the present invention, for example, 8-benzyl-1,8-diazabicyclo [5.4.0] undecane (pKa = 7.46) is obtained by irradiation with actinic rays. To a tertiary amine having strong basicity (pKa = 13.28).

  Such a large change in basicity is a remarkable action not found in conventional ionic base generators, which promotes imidization of the polymer precursor (A) very well, and allows exposure. Since a part (polyimide-ized part) and an unexposed part (part which remains the polymer precursor (A)) are generated, patterning accuracy by development is improved.

  From the viewpoint of enhancing basicity, the tertiary amine generated by irradiation with actinic rays is more preferably a cyclic structure.

  In the present invention, visible light, ultraviolet rays, electron beams, X-rays and the like can be irradiated as active rays for the latent basic substance (B), and ultraviolet rays, particularly ultraviolet rays of 248 nm, 365 nm, 405 nm, and 436 nm. Is preferably used.

  The amount of the latent basic substance (B) to be used is appropriately selected according to the film thickness, the type of the latent basic substance (B), the type of the polymer precursor (A), and the like. For example, the addition amount of the latent basic substance (B) is 1 to 40 parts by mass with respect to 100 parts by mass of the polymer precursor (A). More preferably, it is 5-35 mass parts, More preferably, it is 10-30 mass parts. The polymer precursor (A) can be imidized satisfactorily by the added amount of the latent basic substance (B).

  Furthermore, since the latent basic substance (B) of the present invention is nonionic unlike conventional ionic photobase generators, it may be added to the photosensitive resin composition as a catalyst. In addition to excellent solubility in an organic solvent and easy handling, a composition and a polymer film obtained therefrom can be obtained uniformly.

  It is preferable that the latent basic substance (B) that generates a strongly basic tertiary amine by irradiation with the above-mentioned actinic ray is a compound represented by the general formula (2).

（式（２）中、R₅は、２００〜６５０ｎｍの波長範囲で光を吸収することが可能であり、非置換であるか、または１つ以上のアルキル、アルケニル、アルキニル、ハロアルキル、NR₁₂R₁₃、CN、OR₁₄、SR₁₅、COR₁₆、COOR₁₇、ハロゲンまたは

Wherein R ₅ is capable of absorbing light in the wavelength range of 200 to 650 nm and is unsubstituted or one or more alkyl, alkenyl, alkynyl, haloalkyl, NR ₁₂ R ₁₃ , CN, OR ₁₄ , SR ₁₅ , COR ₁₆ , COOR ₁₇ , halogen or

によって置換された芳香族または複素芳香族基であり；あるいはR₅は、

An aromatic or heteroaromatic group substituted by: or R ₅ is

であり；
R₆およびR₇は、互いに独立して、水素、アルキル、アルケニル、アルキニルであるか、非置換または１つ以上のアルキル、CN、OR₁₄、SR₁₅、ハロゲンまたはハロアルキルによって置換されたフェニルであり；
R₉は、アルキルまたはNR_14AR_15Aであり； R_14AおよびR_15Aは、ともに、非置換であるか、または１つ以上のアルキルによって置換されたアルキレンブリッジを形成し；
R₈、R₁₀、R₁₁、R₁₂およびR₁₃は、互いに独立して、水素またはアルキルであり；あるいは
R₈およびR₁₀は、ともに、非置換であるか、または１つ以上のアルキルによって置換されたアルキレンブリッジを形成し；あるいは
R₉およびR₁₁は、R₈およびR₁₀から独立して、ともに、非置換であるか、または１つ以上のアルキルによって置換されたアルキレンブリッジを形成し；
R₁₄、R₁₅およびR₁₇は、互いに独立して、水素またはアルキルであり；
R₁₆は水素又はアルキルであり；あるいは２００〜６５０nmの波長範囲で光を吸収することが可能であり、非置換であるか、または１つ以上のアルキル、アルケニル、アルキニル、ハロアルキル、NR₁₂R₁₃、CN、OR₁₄、SR₁₅、COR₁₄、COOR₁₇、またはハロゲンによって置換された芳香族または複素芳香族基であり；
R₁₈は、２００〜６５０ｎｍの波長範囲で光を吸収することが可能であり、非置換であるか、または１つ以上のアルキル、アルケニル、アルキニル、ハロアルキル、NR₁₂R₁₃、CN、OR₁₄、SR₁₅、COR₁₆、COOR₁₇、またはハロゲンによって置換された芳香族または複素芳香族基であり；
R₁₉は、水素またはアルキルであり；
R₂₀は、水素、アルキル、あるいは非置換であるか、または１つ以上のアルキル、ビニル、アルケニル、アルキニル、ハロアルキル、フェニル、NR₁₂R₁₃、CN、OR₁₄、SR₁₅、COR₁₆、COOR₁₇またはハロゲンによって置換されたフェニルである。）

Is;
R ₆ and R ₇ are, independently of one another, hydrogen, alkyl, alkenyl, alkynyl, or phenyl which is unsubstituted or substituted by one or more alkyl, CN, OR ₁₄ , SR ₁₅ , halogen or haloalkyl ;
R ₉ is alkyl or NR _14A R _15A ; R _14A and R _15A are both unsubstituted or form an alkylene bridge substituted with one or more alkyls;
R ₈ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are, independently of one another, hydrogen or alkyl; or
R ₈ and R ₁₀ together form an alkylene bridge that is unsubstituted or substituted by one or more alkyls; or
R ₉ and R ₁₁ , independently of R ₈ and R ₁₀ , together form an alkylene bridge that is unsubstituted or substituted by one or more alkyls;
R ₁₄ , R ₁₅ and R ₁₇ are independently of each other hydrogen or alkyl;
R ₁₆ is hydrogen or alkyl; or is capable of absorbing light in the wavelength range of 200-650 nm, is unsubstituted, or is one or more alkyl, alkenyl, alkynyl, haloalkyl, NR ₁₂ R ₁₃ , CN, OR ₁₄ , SR ₁₅ , COR ₁₄ , COOR ₁₇ , or an aromatic or heteroaromatic group substituted by halogen;
R ₁₈ can absorb light in the wavelength range of 200-650 nm and is unsubstituted or one or more alkyl, alkenyl, alkynyl, haloalkyl, NR ₁₂ R ₁₃ , CN, OR ₁₄ , SR ₁₅ , COR ₁₆ , COOR ₁₇ , or an aromatic or heteroaromatic group substituted by halogen;
R ₁₉ is hydrogen or alkyl;
R ₂₀ is hydrogen, alkyl, or unsubstituted, or one or more alkyl, vinyl, alkenyl, alkynyl, haloalkyl, phenyl, NR ₁₂ R ₁₃ , CN, OR ₁₄ , SR ₁₅ , COR ₁₆ , COOR ₁₇ Or phenyl substituted by halogen. )

  It is preferable that the latent basic substance (B) represented by Formula (2) is a compound represented by Formula (5).

（式（５）中、
ｘは１〜５の整数であり；
ｙ及びｚは、互いに独立して、０〜６の整数であり；
R₂₁及びR₂₂は、互いに独立して、炭素数１〜４のアルキル基であり；
Ａは炭素又は窒素原子であり；
R₅、R₆及びR₇は、以上に定義されている通りである）

(In Formula (5),
x is an integer from 1 to 5;
y and z are independently an integer from 0 to 6;
R ₂₁ and R ₂₂ are each independently an alkyl group having 1 to 4 carbon atoms;
A is a carbon or nitrogen atom;
R ₅ , R ₆ and R ₇ are as defined above)

Furthermore, it is preferable that the latent basic substance (B) represented by Formula (2) is represented by Formula (6-1) or Formula (6-2).

（式（６−１）、（６−２）中、R₅、R₆及びR₇は、以上に定義されている通りである。）

(In formulas (6-1) and (6-2), R ₅ , R ₆ and R ₇ are as defined above.)

  Specific examples of the compound include compounds represented by formula (7-a1), formula (7-a2), formula (7-b1), and formula (7-b2).

（式中、R₂₃〜R₂₇は、それぞれ独立に水素原子または一価の有機基であり、炭素以外に酸素または硫黄を含んでいてもよい。R₂₃〜R₂₇の２つ以上が同一であっても全てが異なってもよい。また、R₂₃〜R₂₇の２つ以上が結合して環状構造を形成していても良い。）

(In the formula, R _{23 to} R ₂₇ are each independently a hydrogen atom or a monovalent organic group, and may contain oxygen or sulfur in addition to carbon. Two or more of R _{23 to} R ₂₇ are the same. Or all of them may be different, or two or more of R _{23 to} R ₂₇ may be bonded to form a cyclic structure.)

  The boiling point of the strongly basic tertiary amine from which the latent basic substance (B) is generated is preferably 100 ° C. or higher, and more preferably 150 ° C. or higher.

  Further, the strongly basic tertiary amine from which the latent basic substance (B) is generated preferably has a conjugate acid having a pKa of 9 or more, more preferably 12 or more. Specifically, it is preferable in terms of both handling and imidization to use a strongly basic tertiary amine having a PKa in the range of 11 to 14, particularly 12.3 to 13.7 by irradiation with actinic rays.

  Further, by generating a strongly basic tertiary amine having a boiling point of 100 ° C. or higher, evaporation of the strongly basic tertiary amine during the imidation reaction can be suppressed, and the boiling point of the strongly basic tertiary amine is When it is 150 ° C. or higher, it is possible to suppress evaporation at post-cure after imidization.

  Furthermore, imidization can be easily performed when the pKa of the conjugate acid of the strongly basic tertiary amine is 9 or more. Furthermore, imidation can be performed more easily and rapidly by setting the pKa of the conjugate acid of a strongly basic tertiary amine to 12 or more.

  Considering that the wavelength of the high-pressure mercury lamp, which is a general exposure light source, is 436 nm, 405 nm, 365 nm, and the wavelength of the KrF laser is 248 nm, the latent basic substance (B) is in the range of 240 nm to 450 nm. In particular, it is preferable to have absorption in at least one wavelength among electromagnetic waves having wavelengths of 436 nm, 405 nm, 365 nm, and 248 nm.

The polymer precursor (A) and the latent basic substance so that decomposition of the latent basic substance (B) proceeds uniformly in the thickness direction when the coating film of the photosensitive resin composition is irradiated with actinic rays. The combination and addition amount of (B) are appropriately selected according to the coating film thickness and the like. It is preferable to use a polymer precursor (A) having a small absorption with respect to the wavelength of the actinic ray so as to achieve a low exposure amount and can cope with a thick film. Depending on the molecular design of the polymer precursor (A), the absorption characteristics can be appropriately changed. For example, in order to shift the absorption region to a short wavelength, the polymer precursor (A) having an aromatic group is used, the conjugated system such as R ₁ or / and R ₂ is shortened, or the charge transfer complex It is useful to prevent the formation of.

  Below, the other component which can be mix | blended with the photosensitive resin composition of this invention is demonstrated.

  The solvent (C) in the photosensitive resin composition is not particularly limited as long as it dissolves the polymer precursor (A), the latent basic substance (B), and other additives. Examples include N, N′-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N, N′-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ- Examples include butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, γ-butyrolactone, and diethylene glycol monomethyl ether. These may be used alone or in combination of two or more. The quantity of the solvent to be used can be used in 50-9000 mass parts with respect to 100 mass parts of polymer precursors (A) according to a coating film thickness and a viscosity.

  A sensitizer (D) can be added to the photosensitive resin composition according to this embodiment in order to further improve the photosensitivity. Examples of the sensitizer (D) include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzal) cyclopentane, and 2,6-bis (4′-diethylaminobenzene). Col) cyclohexanone, 2,6-bis (4′-dimethylaminobenzal) -4-methylcyclohexanone, 2,6-bis (4′-diethylaminobenzal) -4-methylcyclohexanone, 4,4′-bis ( Dimethylamino) chalcone, 4,4′-bis (diethylamino) chalcone, p-dimethylaminocinnamylideneindanone, p-dimethylaminobenzylideneindanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (P-dimethylaminophenylvinylene) benzothiazole, 2- (p-dimethyl) Ruaminophenylvinylene) isonaphthothiazole, 1,3-bis (4′-dimethylaminobenzal) acetone, 1,3-bis (4′-diethylaminobenzal) acetone, 3,3′-carbonyl-bis (7 -Diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3- Ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate Isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2- (p-dimethylaminostyryl) naphtho (1,2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene and the like, and 4- (1-methylethyl) -9H- It is preferable to use thioxanthones such as thioxanthen-9-one. These can be used alone or in combination of 2 to 5 kinds. It is preferable to use 0.1 to 10 parts by mass with respect to 100 parts by mass of the sensitizer (D) and the polymer precursor (A).

  In addition, an adhesion assistant may be added to the photosensitive resin composition according to Embodiment 1 for improving the adhesion to the substrate. Any known adhesion assistant can be used as long as it is not contrary to the gist of the present invention. For example, γ-aminopropyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, N- [3- ( And a reaction product of (triethoxysilyl) propyl] phthalamic acid, benzophenonetetracarboxylic dianhydride and (triethoxysilyl) propylamine. The addition amount of the adhesion assistant is preferably in the range of 0.5 to 10 parts by mass with respect to 100 parts by mass of the polymer precursor (A).

  Moreover, you may add a base growth agent to the photosensitive resin composition of this invention. When forming a thick film pattern, the decomposition rate of the latent basic substance (B) of the same degree is required from the surface to the bottom. In this case, in order to improve sensitivity, the addition of a base proliferating agent is preferable. For example, the base proliferating agent disclosed in JP2012-237776, JP2006-282657, and the like can be used.

  In addition, you may add to the photosensitive resin composition of this invention the other photosensitive component which generate | occur | produces an acid or a base with light in the range which does not impair the film | membrane characteristic after hardening significantly. When adding a compound having one or more ethylenically unsaturated bonds to the photosensitive resin composition of the present invention, a photo radical generator may be added.

  In order to impart processing characteristics and various functionalities to the resin composition according to the present invention, various organic or inorganic low-molecular or high-molecular compounds may be blended. For example, dyes, surfactants, leveling agents, plasticizers, fine particles and the like can be used. The fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, inorganic fine particles such as colloidal silica, carbon, and layered silicate, and these may have a porous or hollow structure. Specific materials for obtaining a porous shape or a hollow structure include various pigments, fillers, fibers, and the like.

  Next, the manufacturing method of the relief pattern using the said photosensitive resin composition is demonstrated.

  First, as Step 1, a photosensitive resin composition is applied onto a substrate and dried to obtain a coating film. As a method for coating the photosensitive resin composition on the substrate, methods conventionally used for coating the photosensitive resin composition, such as spin coater, bar coater, blade coater, curtain coater, screen printer, etc. The method of apply | coating, the method of spray-coating with a spray coater, Furthermore, the inkjet method etc. can be used. As a method for drying the coating film, methods such as air drying, heat drying with an oven or hot plate, and vacuum drying are used. Moreover, it is desirable that the coating film be dried under conditions such that imidization of the polymer precursor (A) in the photosensitive resin composition does not occur. Specifically, natural drying, blast drying, or heat drying can be performed at 20 ° C. to 140 ° C. for 1 minute to 1 hour. Preferably, drying is performed on a hot plate for 1 to 5 minutes. Moreover, vacuum drying is also possible, and in this case, it can be performed at room temperature for 1 minute to 1 hour.

  There is no restriction | limiting in particular in a base material, It can apply widely to a silicon wafer, a wiring board, various resin, a metal, the passivation protective film of a semiconductor device, etc.

  Further, since imidization at a low temperature is possible, it is characterized in that it can be widely applied to members and materials that are not suitable for high temperature processing such as a printed wiring board substrate.

  Next, as the step 2, the coating film is exposed through a photomask having a pattern or directly. The exposure light having a wavelength capable of activating the latent basic substance (B) to be changed into a strongly basic tertiary amine is used. As described above, the photosensitivity can be adjusted by appropriately using a sensitizer. As the exposure apparatus, a contact aligner, mirror projection, stepper, laser direct exposure apparatus, or the like can be used.

  Then, it heats so that the imidation of a coating film may be accelerated | stimulated by the base which generate | occur | produced in the coating film as step 3. Thereby, the base generated in the exposed portion in Step 2 serves as a catalyst, and the polymer precursor (A) is partially imidized. The heating time and the heating temperature are appropriately changed depending on the polymer precursor (A) to be used, the coating film thickness, and the type of the latent basic substance (B). Typically, in the case of a coating film thickness of about 10 μm, it is about 2 to 10 minutes at 110 to 200 ° C. If the heating temperature is too low, partial imidization cannot be achieved efficiently. On the other hand, if the heating temperature is too high, imidization of the unexposed area proceeds to reduce the difference in solubility between the exposed area and the unexposed area, which may cause a problem in pattern formation.

  Next, in step 4, the coating film is treated with a developer. Thereby, the unexposed part in a coating film is removed and the pattern which consists of a polymer precursor (A) and a partially imidized polyimide can be formed on a base material.

  As a method used for the development, an arbitrary method can be selected from conventionally known photoresist development methods such as a rotary spray method, a paddle method, and an immersion method involving ultrasonic treatment. Developers include inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide. An aqueous solution of quaternary ammonium salts such as Further, if necessary, a water-soluble organic solvent such as methanol, ethanol, isopropyl alcohol, or a surfactant can be used in an appropriate amount as an aqueous solution. Thereafter, the coating film is washed with a rinse solution as necessary to obtain a pattern coating film. As the rinsing liquid, distilled water, methanol, ethanol, isopropanol or the like can be used alone or in combination. Moreover, you may use the said solvent (C) as a developing solution.

  Then, the coating film patterned as step 5 is heated. The heating temperature is appropriately set so that the polyimide pattern can be cured. For example, heating is performed at 150 to 300 ° C. for about 5 to 120 minutes in an inert gas. A more preferable range of the heating temperature is 150 to 250 ° C, and a more preferable range is 180 to 220 ° C. The heating is performed by using, for example, a hot plate, an oven, or a temperature rising oven in which a temperature program can be set. At this time, the atmosphere (gas) may be air, or an inert gas such as nitrogen or argon.

  The photosensitive resin composition according to the present invention is a known resin material such as printing ink, adhesive, filler, electronic material, optical circuit component, molding material, resist material, building material, three-dimensional modeling, and optical member. A wide range of fields and products in which the properties such as heat resistance, dimensional stability and insulation of polyimide films are effective, such as paints or printing inks, color filters, and films for flexible displays The photosensitive resin according to the present invention is suitably used as a material for forming semiconductor devices, electronic components, interlayer insulating films, wiring coating films, optical circuits, optical circuit components, antireflection films, holograms, optical members or building materials. Printed matter, color filter, film for flexible display, semiconductor device, electronic component, interlayer insulating film, wiring containing at least part of composition or its polymer film Kutsugaemaku, optical circuit, an optical circuit component, the anti-reflection film, hologram, such as an optical member or building material is provided.

In particular, the photosensitive resin composition containing the polymer precursor (A) is mainly used as a pattern forming material (resist), and the pattern formed thereby has a heat resistance and insulating property as a permanent film made of polyimide. For example, color filters, flexible display films, electronic components, semiconductor devices, interlayer insulation films, wiring coating films such as solder resists and coverlay films, solder dams, optical circuits, optical circuit components, It is suitable for forming an antireflection film, other optical members or electronic members.
[Synthesis Example 1]

Preparation of nonionic photoreactive latent basic material 1: 8-benzyl-1,8-diazabicyclo [5.4.0] undecane 1,8-diazabicyclo [5. 4.0] Undecane was produced.

（ｉ）１,８-ジアザビシクロ[５.４.０]ウンデカンの調製
２.５Lのフラスコに、tert−ブチルメチルエーテル１４７０mLと１,８-ジアザビシクロ[５.４.0]ウンデカ−7−エン１５２ g（１mol）を装填した。その後、水素化リチウムアルミニウム１８.９７g（０.５ mol）を数回に分けてフラスコの中に導入し、生じたエマルジョンを室温で１時間攪拌した。続いて反応混合物を2時間にわたり５５〜５７℃に加温し、その後室温にて一晩攪拌した。薄層クロマトグラフィーにより、反応完了を確認した。反応混合物を０℃に冷却し、注意して水１９mLおよび次に濃度１０％の水酸化ナトリウム溶液１９mLを添加した。さらに水５７mLを添加した。得られた混合物を1時間攪拌した後、ろ過し、吸引フィルタ上の生成物をtert−ブチルメチルエーテル２００mL、および塩化メチレン２００mL×２回によって洗浄した。洗浄液を硫酸ナトリウム上で乾燥させ、回転蒸発器で溶媒を留去した。１,８-ジアザビシクロ[５.４.０]ウンデカンが黄色を帯びた油状物として得られた

(I) Preparation of 1,8-diazabicyclo [5.4.0] undecane In a 2.5 L flask, 1470 mL of tert-butyl methyl ether and 1,8-diazabicyclo [5.4.0] undec-7-ene 152 g (1 mol) was charged. Thereafter, 18.97 g (0.5 mol) of lithium aluminum hydride was introduced into the flask in several portions, and the resulting emulsion was stirred at room temperature for 1 hour. The reaction mixture was subsequently warmed to 55-57 ° C. over 2 hours and then stirred overnight at room temperature. The completion of the reaction was confirmed by thin layer chromatography. The reaction mixture was cooled to 0 ° C. and carefully added 19 mL of water and then 19 mL of 10% strength sodium hydroxide solution. An additional 57 mL of water was added. The resulting mixture was stirred for 1 hour, then filtered, and the product on the suction filter was washed with 200 mL of tert-butyl methyl ether and 200 mL of methylene chloride twice. The washing liquid was dried over sodium sulfate and the solvent was distilled off with a rotary evaporator. 1,8-diazabicyclo [5.4.0] undecane was obtained as a yellowish oil.

For further purification, the crude product was distilled at 47-53 mbar using a Vigreux column. The 82-85 ° C. fraction contained pure product. The structure was confirmed using ¹ H-NMR.

(Ii) Preparation of 8-benzyl-1,8-diazabicyclo [5.4.0] undecane In a 750 mL flask, 21.0 g (0.525 mol) sodium hydroxide and 5.81 g (0.035 g) potassium iodide. mol) was suspended in 350 mL of dichloromethane. Then 44.31 g (0.35 mol) of benzyl chloride and 54.00 g (0.35 mol) of 1,8-diazabicyclo [5.4.0] undecane obtained above are added and the suspension is stirred at room temperature. For 24 hours. The peak of benzylic proton in benzyl chloride could no longer be confirmed in the ¹ H-NMR spectrum.

  The reaction mixture was poured into 200 mL of water and the organic phase solvent separated on a separatory funnel was removed on a rotary evaporator. To the remaining yellowish liquid, 500 mL of hexane was added. The precipitated salt was removed by filtration and the solvent was distilled off on a rotary evaporator. After standing, the solution slowly solidified and 8-benzyl-1,8-diazabicyclo [5.4.0] undecane was obtained as a pale yellowish oil.

For further purification, the crude product was distilled under reduced pressure (p = 10 ⁻¹ mbar) on a Vigreux column and the fractions at 129-136 ° C. containing the desired product were combined. Colorless 8-benzyl-1,8-diazabicyclo [5.4.0] undecane (pKa = 7.46) crystallized out upon cooling. The structure was confirmed using ¹ H-NMR. The pKa value of 8-benzyl-1,8-diazabicyclo [5.4.0] undecane is based on the method described in K. Dietliker et al., Progress in Organic Coatings (2007), 146-157.

Further, 8-benzyl-1,8-diazabicyclo [5.4.0] undecane becomes DBU (pKa = 13.28) of a strongly basic tertiary amine when irradiated with actinic rays (see the above document).
[Synthesis Example 2]

Nonionic photoreactive latent basic substance 2: Preparation of 5-benzyl-1,5-diazabicyclo [4.3.0] nonane 1,8-diazabicyclo [5.4.0] undec-7-ene Instead, 5-benzyl-1,5-diazabicyclo [4.3 is represented by the following formula by the same procedure as Synthesis Example 1 except that 1,5-diazabicyclo [4.3.0] non-5-ene was used. 0.0] nonane (pKa = 7.46) was prepared. The product was obtained as a pale yellowish oil. The structure was confirmed using ¹ H-NMR. The pKa value of 5-benzyl-1,5-diazabicyclo [4.3.0] nonane is based on the method described in the above document.

Further, 5-benzyl-1,5-diazabicyclo [4.3.0] nonane is obtained by irradiating actinic rays with DBN (1,5-diazabicyclo [4.3.0] nona--a strongly basic tertiary amine. 5-ene) (pKa = 13.42) (see the above document).
[Synthesis Example 3]

Nonionic photoreactive latent basic substance 3: Preparation of 5-methylstyrene-1,5-diazabicyclo [4.3.0] nonane 5-Methylstyrene-1, represented by the following formula: 5-Diazabicyclo [4.3.0] nonane was prepared.

２.５ Lフラスコの中で５００mLトルエンに１,５−ジアザビシクロ[４.３.０]ノナン７７．１４g（（０．５ mol）を溶解させ、撹拌しながらα-ブロモアセトフェノン９９.５２g(０.５mol)と５００mLトルエン中の溶液を加えて、さらに一晩室温で撹拌した。反応混合物をろ過し、脱イオン水で洗浄して、硫酸マグネシウム上で乾燥した。続いて、さらに真空中で乾燥して、α−アミノケトンを約８５％の収率で得た。

In a 2.5 L flask, 77.14 g ((0.5 mol) of 1,5-diazabicyclo [4.3.0] nonane was dissolved in 500 mL toluene and 99.52 g (0. 0.5 mol) and 500 mL toluene in solution and stirred overnight at room temperature The reaction mixture was filtered, washed with deionized water and dried over magnesium sulfate, followed by further drying in vacuo. Thus, α-aminoketone was obtained in a yield of about 85%.

The dichloromethane solution of the α-aminoketone thus obtained was added to a solution obtained by stirring methyltriphenylphosphonium bromide and sodium amide in dichloromethane for 15 minutes, and the resulting mixture was stirred at room temperature for 18 minutes. Stir for hours. The resulting solution was filtered and the filtrate was concentrated in vacuo. 5-methylstyrene-1,5-diazabicyclo “4.3.0] nonane (pKa = 7.49) was obtained. The structure was confirmed using ¹ H-NMR. 5-methylstyrene-1,5 The pKa value of -diazabicyclo [4.3.0] nonane is based on the method described in the above document.

Further, 5-methylstyrene-1,5-diazabicyclo [4.3.0] nonane is obtained by irradiating actinic rays with DBN (1,5-diazabicyclo [4.3.0] of a strongly basic tertiary amine. ] Nona-5-ene) (pKa = 13.42) (see the above document).
[Synthesis Example 4]

Polymer precursor In a 500 mL three-necked flask, 12.01 g (60 mmol) of 4,4′-diaminodiphenyl ether was added to 141.3 g of dehydrated N-methyl-2-pyrrolidone (NMP). Stir at room temperature to dissolve. To this solution, pyromellitic dianhydride (13.09 g, 60 mmol) was gradually added. After the addition was completed, the solution was stirred at room temperature for 12 hours under a nitrogen stream to obtain a polyamic acid solution as a polymer precursor. .

  71.6 mg of the nonionic photoreactive latent basic substance 1 was dissolved in 3 g of the polymer precursor solution to obtain a photosensitive resin composition (photosensitive resin composition 1) of the present invention.

  71.6 mg of the nonionic photoreactive latent basic substance 2 was dissolved in 3 g of the polymer precursor solution to obtain a photosensitive resin composition (photosensitive resin composition 2) of the present invention.

71.6 mg of the nonionic photoreactive latent basic substance 3 was dissolved in 3 g of the polymer precursor solution to obtain a photosensitive resin composition (photosensitive resin composition 3) of the present invention.
[Comparative Example 1]

  71.6 mg of the photosensitive material 4 of the following formula was dissolved in 3 g of the polymer precursor solution to obtain a photosensitive resin composition (photosensitive resin composition 4) of a comparative example.

[比較例２]

[Comparative Example 2]

  71.6 mg of the photosensitive material 5 of the following formula was dissolved in 3 g of the polymer precursor solution to obtain a photosensitive resin composition (photosensitive resin composition 5) of a comparative example.

[比較例３]

[Comparative Example 3]

  7 g of the following photosensitive material 6 was dissolved in 3 g of the polymer precursor solution to obtain a photosensitive resin composition (photosensitive resin composition 6) of a comparative example.

[比較例４]

[Comparative Example 4]

  The photosensitive resin composition (photosensitive resin composition 7) of the comparative example which consists only of the said polymer precursor solution 3g was obtained.

<Test>
(1) Ultraviolet irradiation / low temperature heating test (1-1) Preparation of cured samples according to Examples 1 and 2 and Comparative Example 4 (ultraviolet irradiation and low temperature heating)
Photosensitive resin compositions 1 and 2 (Examples 1 and 2) and photosensitive resin composition 7 (Comparative Example 4) were applied on a copper plate to a final film thickness of 1 μm. These were dried on a hot plate at 100 ° C. for 15 minutes, and then irradiated with 10 J ultraviolet rays in terms of h-line in an exposure apparatus (manufactured by Oak Manufacturing Co., Ltd.) equipped with a metal halide lamp.
(1-2) Preparation of standard cured sample (high temperature heating)
The photosensitive resin composition 7 (Comparative Example 4) was applied on the wafer so as to have a final film thickness of 1 μm, and this was applied on a hot plate at 100 ° C. for 30 minutes, 200 ° C. for 30 minutes, 250 ° C. for 30 minutes, 300 ° C. Heated for 1 hour. Thus, imidization was performed to obtain a standard imide film.
(1-3) Preparation of dry sample The photosensitive resin composition 7 (Comparative Example 4) was applied on the wafer so as to have a final film thickness of 1 μm, and this was heated at 100 ° C. for 15 minutes to dry the sample. It was.

  For the cured samples according to Examples 1 and 2 and Comparative Example 4 prepared as described above, and the standard cured sample, Nicolet 4700 FT-IR manufactured by Thermo Scientific, an observation table equipped with a heating device and a reflecting mirror, and Shimaden Infrared spectroscopic spectra were measured while increasing the temperature from 100 ° C. to 200 ° C. using a DSM Temperature Control Unit manufactured by DSM.

The spectrum derived from the precursor disappeared with heating, and a peak derived from polyimide generated by heating appeared. To check the progress of imidization, the resulting ratio of the height to the 1234Cm ^-1 peaks from ether COC peak polyimide CN derived 1368cm ^-1 and (CN / COC) was calculated (the imidization ratio Calculation).

  Formula 1 shows the formula for calculating the imidization ratio of each sample.

（式１）
但し、式1中、各符号は以下の意味を有する：
a: (C-N)_{1374 cm-1}の吸光度
b: (C-O-C)_{1237 cm-1}の吸光度
(a/b)_PI: 標準硬化サンプルのC-N由来のピークのC-O-C由来のピークに対する高さの比
(a/b)_PAA,init : 乾燥サンプルのC-N由来のピークのC-O-C由来のピークに対する高さの比
(a/b)_sample : 実施例１、２、及び比較例４による硬化サンプルのC-N由来のピークのC-O-C由来のピークの高さの比

(Formula 1)
However, in formula 1, each symbol has the following meaning:
a: (CN) Absorbance at _{1374 cm-1}
b: (COC) Absorbance at _{1237 cm-1}
(a / b) _PI : Ratio of height of CN-derived peak to peak of COC derived from standard cured sample
(a / b) _{PAA, init} : Ratio of the height of the CN-derived peak to the COC-derived peak in the dried sample
(a / b) _sample : ratio of peak height derived from COC to peak derived from CN of cured samples according to Examples 1 and 2 and Comparative Example 4

  According to Formula 1, the imidation ratio of the photosensitive resin composition was calculated at each temperature. The result is as shown in FIG. In the photosensitive resin compositions 1 and 2 (Examples 1 and 2), imidization occurred at a lower temperature than the photosensitive resin composition 7 (Comparative Example 4), and the photosensitive resin compositions 1 and 7 (implemented). It was found that the difference in imidization ratio between Example 1 and Comparative Example 4) was maximized at around 170 ° C. Furthermore, the imidation ratio of the photosensitive resin composition 1 reaches 100% around 180 ° C. On the other hand, the imidation ratio of the photosensitive resin composition 7 was 75% up to 200 ° C.

(2) Physical properties of polymer film Photosensitive resin compositions 1, 2, and 4, 5 (Examples 1 and 2 and Comparative Examples 1 and 2) were placed on electrolytic copper foil (Furukawa Electric, GTS-treated product). The film was applied to a final film thickness of 50 μm and dried with a hot air circulating dryer at 80 ° C. for 30 minutes. Thereto, 10J UV irradiation was performed in terms of h-line conversion with an exposure apparatus (manufactured by Oak Manufacturing Co., Ltd.) equipped with a metal halide lamp, and then each sample was heated at 180 ° C. for 1 hour for imidization.
(2-1) Self-supporting film formation A flat and uniform self-supporting cured film was obtained from the photosensitive resin compositions 1 and 2 (Examples 1 and 2). On the other hand, the photosensitive resin compositions 4 and 5 were brittle and could not be self-supporting. The reason why the properties of the cured film differed is that the secondary base generated by irradiation with actinic rays has a weak imidization promoting effect, and the active hydrogen of the secondary amine has caused some reaction with the polyamic acid.
(2-2) Tensile test results The cured films of the photosensitive resin composition 1 (Example 1) and the photosensitive resin compositions 4 and 5 (Comparative Examples 1 and 2) were 10 × 40 × 0.05 (mm). As a test piece, a SHIMADZU AG-X (tensile tester) was used, and a tensile test was performed at a tensile speed of 1 mm / min. The results are shown in FIG. The photosensitive resin composition 1 (Example 1) had a tensile elastic modulus of 2.2 GPa and a tensile elongation of 26%, and exhibited good physical properties. On the other hand, the photosensitive resin compositions 4 and 5 (Comparative Examples 1 and 2) were not easily tested because cracks were easily generated.

(3) Pattern formation The photosensitive resin compositions 1-3 and 6 (Examples 1-3, Comparative Example 3) were spin-coated on a wafer so that the final film thickness might be 1 micrometer, and on a hot plate of 80 degreeC. Dry for 30 minutes. On the other hand, in the exposure apparatus (Oak Manufacturing Co., Ltd.) equipped with a metal halide lamp, it was irradiated with 10 J ultraviolet rays in terms of h-line, and then heated on a hot plate at 170 ° C. for 5 minutes. It was immersed in a .38% solution. As a result, the photosensitive resin compositions 1 to 3 (Examples 1 to 3) were able to obtain a good pattern because the exposed portion was not dissolved in the developer. On the other hand, it was found that the photosensitive resin composition 6 (Comparative Example 3) was difficult to dissolve in the unexposed part and the dissolution rate contrast was insufficient. Furthermore, the pattern obtained from the photosensitive resin compositions 1-3 was heated at 180 degreeC for 1 hour, and imidation was performed.

  As a result, it was revealed that the photosensitive resin composition of the present invention can form a good pattern.

  The present invention is not limited to the configurations and examples of the above-described embodiment, and various modifications are possible within the scope of the gist of the invention.

Claims (13)

(A) a polymer precursor having a repeating unit of polyamic acid or polyamic acid ester at least in part,
(B) General formula (2)

(In the formula (2),
R ₅ is unsubstituted or one or more alkyl, alkenyl, alkynyl, haloalkyl, NR ₁₂ R ₁₃ , CN, OR ₁₄ , SR ₁₅ , COR ₁₆ , COOR ₁₇ , halogen or formula (3)

An aromatic or heteroaromatic group substituted by: or
R ₅ is the formula (4)

A group represented by
R ₆ and R ₇ are, independently of one another, hydrogen, alkyl, alkenyl, alkynyl, or phenyl which is unsubstituted or substituted by one or more alkyl, CN, OR ₁₄ , SR ₁₅ , halogen or haloalkyl ;
R ₉ is alkyl or NR _14A R _15A ; R _14A and R _15A are both unsubstituted or form an alkylene bridge substituted with one or more alkyls;
R ₈ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are, independently of one another, hydrogen or alkyl; or
R ₈ and R ₁₀ together form an alkylene bridge that is unsubstituted or substituted by one or more alkyls; or
R ₉ and R ₁₁ , independently of R ₈ and R ₁₀ , together form an alkylene bridge that is unsubstituted or substituted by one or more alkyls;
R ₁₄ , R ₁₅ and R ₁₇ are independently of each other hydrogen or alkyl;
R ₁₆ is hydrogen or alkyl; or is unsubstituted or one or more alkyl, alkenyl, alkynyl, haloalkyl, NR ₁₂ R ₁₃ , CN, OR ₁₄ , SR ₁₅ , COR ₁₄ , COOR ₁₇ , or An aromatic or heteroaromatic group substituted by halogen;
R ₁₈ is unsubstituted or aromatic substituted by one or more alkyl, alkenyl, alkynyl, haloalkyl, NR ₁₂ R ₁₃ , CN, OR ₁₄ , SR ₁₅ , COR ₁₆ , COOR ₁₇ , or halogen Or a heteroaromatic group;
R ₁₉ is hydrogen or alkyl;
R ₂₀ is hydrogen, alkyl, or unsubstituted, or one or more alkyl, vinyl, alkenyl, alkynyl, haloalkyl, phenyl, NR ₁₂ R ₁₃ , CN, OR ₁₄ , SR ₁₅ , COR ₁₆ , COOR ₁₇ Or phenyl substituted by halogen. )
A nonionic photoreactive latent basic substance that generates a strongly basic tertiary amine by irradiation with actinic rays,
A photosensitive resin composition comprising: (A) a polymer precursor having a repeating unit of polyamic acid or polyamic acid ester at least in part,
(B) a nonionic photoreactive latent basic substance that generates a strongly basic tertiary amine having a pKa of a conjugate acid of 9 or more by irradiation with actinic rays;
A photosensitive resin composition comprising: The photosensitive resin composition according to claim 1, wherein the polymer precursor (A) is a compound represented by the general formula (1).

(In the formula (1),
R ₁ is a tetravalent organic group
R ₂ is a divalent organic group,
X is a divalent organic group
R ₃ and R ₄ may be the same or different from each other, and are a hydrogen atom, a monovalent organic group or a functional group having silicon,
m is an integer greater than or equal to 1,
n is 0 or an integer of 1 or more. ) The photosensitive resin composition according to claim 1 or 3 , wherein the latent basic substance (B) represented by the formula (2) is a compound represented by the general formula (5).

(In Formula (5),
x is an integer from 1 to 5;
y and z are independently an integer from 0 to 6;
R ₂₁ and R ₂₂ are each independently an alkyl group having 1 to 4 carbon atoms;
A is a carbon or nitrogen atom. ) The photosensitive resin according to claim 1 or 3 , wherein the latent basic substance (B) represented by the formula (2) is a compound represented by the formula (6-1) or the formula (6-2). Composition.

The photosensitive resin composition according to claim 1, wherein the latent basic substance (B) has absorption at any wavelength in the range of 240 nm to 450 nm. The photosensitive polymer composition according to claim 1, wherein the polymer precursor (A) is soluble in an alkaline solution. The polymer precursor (A) The photosensitive resin composition according to claim 1 which is a polyamic acid. It is possible to form a pattern at 200 degrees C or less, The photosensitive resin composition of any one of Claims 1-8 . The relief pattern film | membrane obtained from the photosensitive resin composition of any one of Claims 1-9 . A coating film formed by drying the photosensitive resin composition according to any one of claims 1 to 9 is formed on a substrate,
Irradiating the coating film with actinic rays in a pattern,
The coating film irradiated with the active light is heated at 200 ° C. or lower,
A method for producing a relief pattern film, wherein the heated coating film is developed. An electronic component or an optical product having the relief pattern film according to claim 10 as a surface protective film layer and / or an interlayer insulating film. The adhesive agent containing the photosensitive resin composition of any one of Claims 1-9 .

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