KR20160027189A - 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

Abstract

An object of the present invention is to obtain a photosensitive resin composition capable of forming a polyimide pattern with high precision in a low-temperature process without any problems in the prior art.
(A) a polymer precursor having at least a part of a repeating unit of a polyamic acid or a polyamide acid ester, (B) a nonionic photoreactive latent basic substance which generates a strong basic tertiary amine by irradiation of an actinic ray By weight based on the total weight of the photosensitive resin composition.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, a relief pattern film thereof, a method of producing a relief pattern film, an electronic component or an optical product including the relief pattern film, and an adhesive containing the photosensitive resin composition. , ELECTRONIC COMPONENT OR OPTICAL PRODUCT INCLUDING RELIEF PATTERN FILM, AND ADHESIVE INCLUDING PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a polymeric precursor having at least a part of a polyamic acid or a polyamide acid ester repeating unit and a nonionic photoreactive latent basic substance which generates a strong basic tertiary amine upon irradiation with an actinic ray, A relief pattern film (polymer film) using the same, a method of producing a relief pattern film, and an adhesive containing an electronic component or optical product having a relief pattern film as a surface protective film layer and / or an interlayer insulating film, and a photosensitive resin composition .

Polyimide, developed by DuPont, USA in 1955, is widely applied to various fields based on excellent properties such as high insulation, heat resistance and high mechanical strength. Application to a coating film of a semiconductor element, a flexible printed wiring board, and a heat-resisting insulating interlayer material has been progressed without staying in the aerospace field first applied. In addition, in recent years, along with the advancement and higher density of semiconductor mounting technology, there has been a demand for further miniaturization of wiring patterns, and a high degree of processability is demanded also for polyimide.

However, the polyimide has a thermoplasticity and insufficient solubility in an organic solvent, and has the aspect that processing is difficult. For this reason, polyimide is widely used by a method of imparting photosensitivity to a polyimide precursor, forming a desired pattern by irradiation of an actinic ray, and then cyclizing the polyimide precursor at a high temperature.

As described above, the so-called photosensitive polyimide, which is improved in processability by imparting photosensitivity to the polyimide precursor, has a feature of shortening a troublesome process, and therefore has a higher usability than a non-photosensitive polyimide at the time of productivity and simplification of the process .

In the conventional photosensitive polyimide, after the development, the polyimide precursor is imidized by heating at 300 DEG C or higher (see, for example, Patent Documents 1 and 2).

Also disclosed is a photosensitive resin composition capable of forming a polyimide film by imidizing a polyimide precursor at a low temperature (see, for example, Patent Document 3).

Japanese Patent No. 4830435 Japanese Patent No. 4756350 Japanese Patent Application Laid-Open No. 2006-189591

However, the photosensitive polyimide described in Patent Document 1 can be imidized even at a low temperature, but there is room for improvement in order to form a good pattern. This is because there is no change in the skeletal structure of the basic substance before and after the exposure. In addition, since the photobase generator used in the imidization is ionic, the solubility in an organic solvent is not sufficient.

In addition, since a non-ionic photo-base generator (carbamate, acyloxime, etc.) is used for imidization of the polyimide precursor described in Patent Documents 2 and 3, the solubility in an organic solvent is excellent, There is a room for improvement in the tensile strength of the polymer film after curing by releasing secondary amine.

SUMMARY OF THE INVENTION An object of the present invention is to provide a photosensitive resin composition capable of forming a pattern easily and precisely in a low temperature process without the problems of the prior art, which is made in view of the background, and a relief pattern film (high molecular film) A method for producing a relief pattern film, and an adhesive comprising an electronic component or an optical product having a relief pattern film as a surface protective film layer and / or an interlayer insulating film, and a photosensitive resin composition.

In order to achieve the above object, the inventors of the present invention have focused on a photosensitive polyimide composition using a photo-base generator. As a result of intensive researches, the inventors have found that a non-ionic photo- It has been found that the object of the present invention can be achieved by the combination of the reactive 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 repeating unit of a polyamic acid or a polyamide acid ester at least in part, (B) a strongly basic tertiary amine generated by irradiation of an actinic ray Which is characterized by containing a nonionic photoreactive latent basic substance.

In the present invention, as the latent basic substance (B), a nonionic substance which changes its chemical structure upon irradiation with an actinic ray to generate a strong base is used. Specifically, the latent basic substance (B) is excited by irradiation of an actinic ray to change the chemical structure to generate a strongly basic tertiary amine. Then, the strongly basic tertiary amine generated promotes the low-temperature imidization of the polymer precursor (A), whereby an exposed portion (imaged portion) and an unexposed portion (a portion corresponding to the polymer precursor (A) The difference in solubility between the exposed portion and the unexposed portion occurs. That is, the latent basic substance (B) acts as a highly effective photosensitive component for the polymer precursor (A), and facilitates development by the developer. More specifically, the imidization of the exposed portion is promoted so that most of the solubility is not obtained. On the other hand, in order to keep the unexposed portion soluble in a solution, development with a developer is facilitated.

As the polyamic acid component increases as the polymer precursor, the alkali solubility is excellent, and as the polyamide acid ester component increases, the solubility of the organic solvent is excellent. By changing the ratio of the amide acid to the amide acid ester, the solubility suitable for various developers can be obtained.

In the present invention, it is preferable that the polymer precursor (A) is a compound represented by the following 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 and are each a hydrogen atom or a monovalent organic group or a functional group having silicon,

m is an integer of 1 or more,

n is 0 or an integer of 1 or more)

Further, in the present invention, it is preferable that the latent basic substance (B) is a compound represented by the general formula (2).

(Wherein R ₅ is unsubstituted or substituted with one or more of alkyl, alkenyl, alkynyl, haloalkyl, NR ₁₂ R ₁₃ , CN, OR ₁₄ , SR ₁₅ , COR ₁₆ , COOR ₁₇ , (3)

Lt; / RTI > is an aromatic or heteroaromatic group substituted by one or more heteroatoms; or

R ₅ is represented by the formula (4)

≪ / RTI >

R ₆ and R ₇ are independently of each other hydrogen, alkyl, alkenyl, alkynyl or phenyl 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 by one or more alkyl;

R ₈ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are independently of each other hydrogen or alkyl; or

R ₈ and R ₁₀ are both unsubstituted or form an alkylene bridge substituted by one or more alkyl; or

R ₉ and R ₁₁ , independently of R ₈ and R ₁₀ , are both unsubstituted or form an alkylene bridge substituted by one or more alkyl;

R ₁₄ , R ₁₅ and R ₁₇ independently from each other are hydrogen or alkyl;

R ₁₆ is hydrogen or alkyl; Or unsubstituted or at least one alkyl, alkenyl, alkynyl, haloalkyl, NR ₁₂ R _13, CN, OR _14, SR _15, COR _14, COOR _17, or a halogen of the aromatic or heterocyclic aromatic group substituted by a ;

R ₁₈ is an unsubstituted or substituted aromatic or heteroaromatic group substituted by one or more alkyl, alkenyl, alkynyl, haloalkyl, NR ₁₂ R ₁₃ , CN, OR ₁₄ , SR ₁₅ , COR ₁₆ , COOR ₁₇ , ego;

R < ₁₉ > is hydrogen or alkyl;

R ₂₀ is hydrogen, alkyl, or unsubstituted or substituted with one or more of alkyl, vinyl, alkenyl, alkynyl, haloalkyl, phenyl, NR ₁₂ R ₁₃ , CN, OR ₁₄ , SR ₁₅ , COR ₁₆ , COOR ₁₇ , Lt; / RTI >

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

(In the formula (5)

x is an integer from 1 to 5;

y and z are, independently of each other, an integer from 0 to 6;

R ₂₁ and R ₂₂ are, independently of each other, an alkyl group having 1 to 4 carbon atoms;

A is a carbon or nitrogen atom)

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

Further, in the present invention, the strongly basic tertiary amine generated from the latent basic substance (B) preferably has a boiling point of 100 캜 or higher, more preferably 150 캜 or higher.

Further, 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, more preferably 12 or more.

Since the wavelength of the high-pressure mercury lamp, which is a general exposure light source, is 436 nm, 405 nm, and 365 nm, and the wavelength of the KrF laser is 248 nm, the latent basic material (B) has absorption at any one of wavelengths from 240 nm to 450 nm desirable.

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

It is also preferable that the photosensitive resin composition of the present invention is capable of satisfactorily forming a pattern at 200 占 폚 or lower.

The relief pattern film of the present invention can be obtained by forming a coating film obtained by drying the photosensitive resin composition described above on a substrate, irradiating the coating film with an actinic ray in a pattern, heating the coating film irradiated with actinic rays at 200 DEG C or lower, And then developing the coating film.

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

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

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

According to the present invention, it is possible to overcome the technical problems of conventional polyimide precursors which have difficulty in obtaining a contrast of solubility between the exposed portion and the unexposed portion, and obtain a good pattern shape.

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

Particularly, the photosensitive resin composition according to the present invention can be used mainly as a pattern forming material, and the pattern formed thereby serves as a component for imparting heat resistance and insulation as a permanent film. For example, a color filter, , A liquid crystal alignment film, a semiconductor device, an electronic component, an interlayer insulating film, a wiring coating film such as a solder resist or a coverlay, a solder dam, an optical circuit, an optical circuit component, an antireflection film, .

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the imidization rate of the photosensitive resin composition of the present invention and the conventional photosensitive resin composition at each temperature. Fig.
2 is a graph showing a tensile test result of a polymer film obtained from the photosensitive resin composition of the present invention.

Hereinafter, the present invention will be described in detail.

The photosensitive resin composition of the present invention comprises (A) a polymer precursor having at least a part of a polyamic acid or a repeating unit of a polyamide acid ester, and (B) a polymer precursor which generates a strong basic tertiary amine Contains non-ionic photoreactive latent basic material.

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

In the 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 hydroxyamidic acid group, an aromatic or aliphatic ester group, an amide group, an amideimide group, An alkoxy group, an acid group, an alkylene oxide group, a urethane group, an epoxy group, an oxetanyl group and the like.

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 from 1,000 to 1,000,000, more preferably from 5,000 to 500,000, even more preferably from 10,000 to 200,000.

In formula (1), R ₁ and R ₂ may be selected from an aromatic group, preferably an aromatic group having 6 to 32 carbon atoms, or an aliphatic group, preferably an aliphatic group having 4 to 20 carbon atoms do. R ₁ and R _2, it is preferred if the substituents R ₁ and R ₂ contained in the acid dianhydride and diamine which will be described later to be used in the manufacture of a polymer precursor (A).

When the photosensitive resin composition is patterned by 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 fluorine-containing groups are used as R ₁ and R ₂ , the lowering of light absorption or the dielectric property can be improved.

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

In addition, although the 4-valent of R ₁ represents only a valence for bonding with an acid, R ₁ may have a substituent. Likewise, although the valence of R ₂ represents only a valence for bonding with a two-valent amine, it may also have an additional substituent. R ₃ and R ₄ are each a hydrogen atom, or a monovalent organic group or a functional group having silicon.

When R ₃ and R ₄ are monovalent organic groups, examples thereof include an alkyl group, an alkenyl group, an alkynyl group and an aryl group. When R ₃ and R ₄ are functional groups having monovalent silicon, examples thereof include a siloxane group, a silane group and a silanol group. It is also possible that only a part of R ₃ and R ₄ is hydrogen or a monovalent organic group, whereby the solubility can be controlled.

As the polymer precursor (A) according to the present invention, a polyamidic acid such as those wherein R ₃ and R ₄ are hydrogen atoms is suitably used. As a result, the alkali developability is improved, and a good pattern is obtained.

(Polyamide acid)

The polyamic acid can be produced by applying conventionally known methods. For example, it can be prepared by simply mixing an acid dianhydride and a diamine in a solution. It can be synthesized by a one-step reaction, and is easily and inexpensively obtained, and further modification is unnecessary, and therefore it is preferably used. A method of synthesizing the polymer precursor (A) is not particularly limited, but known methods can be applied.

Examples of the tetracarboxylic dianhydride that can be used in the present embodiment include those represented by the following formula (8). It should be noted that the following specific examples are merely examples, and it is needless to say that known ones can be used as long as they do not contradict the object of the present invention.

(Wherein R < _{1 >} is as described above)

The R ₁ group in the repeating unit in the polyamic acid according to the present embodiment is preferably derived from R ₁ of a tetracarboxylic acid dianhydride which can be used as a raw material for producing polyamic acid.

The acid dianhydride applicable to the production of the polymer precursor (A) includes, for example, ethylene tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetracarboxylate Aliphatic tetracarboxylic acid dianhydrides such as acid dianhydride and cyclopentanetetracarboxylic acid dianhydride; Pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic acid dianhydride, 2,3 ', 3 , 4'-benzophenonetetracarboxylic acid dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic acid dianhydride , 2,3 ', 3,4'-biphenyltetracarboxylic dianhydride, 2,2', 6,6'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-di Bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis Bis (2,3-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis , 2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2,3- 1,1,3,3,3-hexapple Benzoyl benzene dianhydride, 1,4-bis [(3,4-dicarboxy) benzoyl] benzene dianhydride, 2,2-bis Phenyl} propane dianhydride, 2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} propane dianhydride , Bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, 4 {4- [4- (1,2-dicarboxy) phenoxy] , Bis [4- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, 4,4'-bis [3- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, bis (4 - [[3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, bis {4 Phenyl} sulfone dianhydride, bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} sulfone dianhydride, bis {4- [ 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 dianhydride, Naphthalene tetracarboxylic acid dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis (2,3- or 3,4-dicarboxyphenyl) propane dianhydride, 1 , 4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, 3,4 , 9,10-perylene tetracarboxylic acid dianhydride, 2,3,6,7-anthracene tetracarboxylic acid dianhydride, 1,2,7,8-phenanthrene tetracarboxylic acid dianhydride, pyridine tetracarboxylic acid dianhydride, M-terphenyl-3,3 ', 4,4'-tetracarboxylic acid dianhydride, p-terphenyl-3,3', 4,4'-tetracarboxylic dianhydride An aromatic tetracarboxylic acid such as an acid dianhydride And the like can be sumul.

These may be used alone or in combination of two or more. Particularly preferred tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-bis Bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3,4-dihydroxyphenyl) ether dianhydride, 2,2'-biphenyltetracarboxylic dianhydride, -Dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride.

Use of an acid dianhydride to which fluorine is introduced as an acid dianhydride or an acid dianhydride having a backbone skeleton to be used in combination enables adjustment of physical properties such as solubility and thermal expansion ratio without impairing transparency as much. Further, it is also possible to use an imitative acid dianhydride such as pyromellitic anhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 1,4,5,8-naphthalenetetracarboxylic dianhydride , The linear heat expansion coefficient of the finally obtained polyimide tends to be small, but the improvement in transparency tends to be inhibited.

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

Lt; RTI ID = 0.0 > dianhydride < / RTI > From the viewpoints of transparency and mechanical properties, the use of the above-mentioned acid dianhydride is preferable.

Examples of the amine usable in the present invention include diamines represented by the following formula (10). However, the following is merely an example, and it is needless to say that any known one can be used as long as it does not contradict the object of the present invention.

(Wherein R < _{2 >} is as defined above)

Examples of the diamine when the R ₂ group is a divalent aromatic group include paraphenylenediamine, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl Diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 9,10-bis (4-aminophenyl) anthracene, 4,3'-dimethoxy- , 4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfoxide, 1,3-bis 4-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- Bis [4- (4-aminophenoxy) phenyl] ether, 1,1,1,3,3,3-hexafluoro-biphenyl, 4,4'- Bis (4-aminophenoxy) phenyl] propane, 1,1,1,3,3,3-hexafluoro-2,2- 1,1,3,3,3-hexafluoro-2,2-bis (3-amino-4-methylphenyl) propane, metaphenylenediamine, 4,4'- Diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-amino Phenoxy) benzene.

When the R ₂ group is a divalent aliphatic group, examples of the diamine include 1,1-meta-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, Diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindanediyldimethylenediamine, triethanolamine, triethanolamine, Cyclo [6.2.1.02,7] undecylenedimethyldiamine, 4,4'-methylenebis (cyclohexylamine), and isophoronediamine.

Other examples include diaminopolysiloxanes represented by the following formula (11).

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 an integer of 1 or more, preferably 1 to 10.

Specific examples of R ₂₈ and R ₂₉ in the formula (11) include an alkylene group having 1 to 7 carbon atoms such as a methylene group, an ethylene group and a propylene group, 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'-benzophenonetetracarboxylic dianhydride is reacted with an alcohol such as ethanol to obtain a half ester. The half ester is converted to diester diacid chloride using thionyl chloride. The polyamide acid ester can be obtained by reacting the diester diacid chloride with a diamine such as 3,5-diaminobenzoic acid.

As the polymer precursor (A) having a repeating unit of a polyamic acid or a polyamic acid ester in at least a part of the photosensitive resin composition, a single kind of material may be used, or a plurality of kinds thereof may be used as a mixture. Alternatively, R ₁ or / and R ₂ may each be a copolymer having a plurality of structures.

The nonionic photoreactive latent basic substance (B) according to the present embodiment is to generate a strongly basic tertiary amine by irradiation with an actinic ray. The latent basic substance (B) changes its chemical structure by light irradiation and generates strongly basic tertiary amines. From the viewpoint of increasing the basicity and promoting the partial imidization efficiently, it is preferable that the strongly basic tertiary amine generated is, 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) It changes to a strong basic (pKa = 13.28) tertiary amine.

This large change in basicity is a remarkable action not seen in conventional ionic base generators, whereby the imidization of the polymer precursor (A) is promoted very well and the exposed portion (polyimide portion) and the unexposed portion (Part of the polymer precursor (A)) is generated, so that the accuracy of patterning due to development is improved.

Further, from the viewpoint of enhancing the basicity, the tertiary amine generated by irradiation with an actinic ray is more preferably a cyclic structure.

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

The amount of the latent basic substance (B) to be used is appropriately selected in accordance with the film thickness, the kind of the latent basic substance (B), the kind of the polymer precursor (A), and the like. For example, the amount of the latent basic substance (B) to be added to 100 parts by mass of the polymer precursor (A) is 1 to 40 parts by mass. More preferably from 5 to 35 parts by mass, and still more preferably from 10 to 30 parts by mass. With the added amount of the latent basic substance (B), it becomes possible to imidize the polymer precursor (A) well.

In addition, the latent basic substance (B) of the present invention is different from the conventional ionic photo-nucleating agent and is nonionic, so that even when it is added to the photosensitive resin composition as a catalyst, solubility in an organic solvent The composition and the polymer membrane obtained therefrom can be uniformly obtained.

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

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

Lt; / RTI > is an aromatic or heteroaromatic group substituted by one or more heteroatoms; Or R < _{5 &}

ego

R ₆ and R ₇ are independently of each other hydrogen, alkyl, alkenyl, alkynyl or phenyl 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 by one or more alkyl;

R ₈ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are independently of each other hydrogen or alkyl; or

R ₈ and R ₁₀ are both unsubstituted or form an alkylene bridge substituted by one or more alkyl; or

R ₉ and R ₁₁ , independently of R ₈ and R ₁₀ , are both unsubstituted or form an alkylene bridge substituted by one or more alkyl;

R ₁₄ , R ₁₅ and R ₁₇ independently from each other are hydrogen or alkyl;

R ₁₆ is hydrogen or alkyl; NR ₁₂ R ₁₃ , CN, OR ₁₄ , SR ₁₅ , COR ₁₄ , NR ₁₅ R ₁₃ , CN, COOR < ₁₇ > or an aromatic or heteroaromatic group substituted by halogen;

R ₁₈ is capable of absorbing light in the wavelength range of 200 to 650 nm and is either unsubstituted or substituted with one or more of 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 substituted with one or more of alkyl, vinyl, alkenyl, alkynyl, haloalkyl, phenyl, NR ₁₂ R ₁₃ , CN, OR ₁₄ , SR ₁₅ , COR ₁₆ , COOR ₁₇ , Lt; / RTI >

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

(In the formula (5)

x is an integer from 1 to 5;

y and z are, independently of each other, an integer from 0 to 6;

R ₂₁ and R ₂₂ are, independently of each other, 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.

It is also preferable that the latent basic substance (B) represented by the formula (2) is represented by the formula (6-1) or (6-2).

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

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

(Wherein 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, and two or more of R ₂₃ to R ₂₇ are the same or different from each other Or two or more of R ₂₃ to R ₂₇ may combine to form a cyclic structure)

The strongly basic tertiary amine generating the latent basic substance (B) preferably has a boiling point of 100 캜 or higher, more preferably 150 캜 or higher.

In the strong basic tertiary amine in which the latent basic substance (B) is generated, the pKa of the conjugated acid is preferably 9 or more, more preferably 12 or more. Specifically, when a strongly basic tertiary amine having a pKa of 11 to 14, particularly 12.3 to 13.7, is used by irradiation with an actinic ray, it is preferable in both handling and imidization.

By generating a strongly basic tertiary amine having a boiling point of 100 DEG C or more, it becomes possible to inhibit the evaporation of strongly basic tertiary amine at the time of the imidization reaction, and when the boiling point of the strongly basic tertiary amine is 150 DEG C or more , It becomes possible to suppress the evaporation in post-curing after imidization.

Further, imidization can be easily carried out because the pKa of the conjugate acid of the strongly basic tertiary amine is 9 or more. Further, by setting the pKa of the conjugate acid of the strongly basic tertiary amine to 12 or more, the imidization can be performed more easily and quickly.

Considering that the wavelength of the high-pressure mercury lamp as a general exposure light source is 436 nm, 405 nm and 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, particularly 436 nm, 405 nm, It is preferable to have absorption in at least one of the electromagnetic waves having a wavelength of 248 nm.

It is preferable that the combination of the polymer precursor (A) and the latent basic substance (B) or the amount of the addition of the polymeric precursor (B), such as the progress of the decomposition of the latent basic substance (B) uniformly in the thickness direction when the coating film of the photosensitive resin composition is irradiated with actinic light, Is appropriately selected in accordance with the thickness of the coating film or the like. It is preferable to use a polymer precursor (A) having a small absorption with respect to the wavelength of the active ray so as to attain a low exposure amount and to cope with thickening. 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, it is preferable to use a polymer precursor (A) having an aromatic group to shorten a conjugate system such as R ₁ or / and R ₂ , or to prevent the formation of a charge transfer complex .

Hereinafter, other components that can be incorporated into the photosensitive resin composition of the present invention will be described.

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, Butyrolactone,? -Acetyl-? -Butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolidone, N-cyclohexyl-2-pyrrolidone, dimethylsulfoxide, hexamethylphosphor Amide, pyridine,? -Butyrolactone, and diethylene glycol monomethyl ether. These may be used alone or in combination of two or more. The amount of the solvent to be used may be in the range of 50 to 9000 parts by mass based on 100 parts by mass of the polymer precursor (A), depending on the coating film thickness and viscosity.

In the photosensitive resin composition according to the present embodiment, a sensitizer (D) may be further added to improve the light sensitivity. Examples of the sensitizer (D) include: Michler's ketone, 4,4'-bis (diethylamino) benzophenone, 2,5-bis (4'-diethylaminobenzal) cyclopentane, 2,6- (4'-diethylaminobenzal) cyclohexanone, 2,6-bis (4'-dimethylaminobenzal) -4-methylcyclohexanone, 2,6- -Methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone, p-dimethylaminocinnamylideneindanone, p- Benzothiazole, 2- (p-dimethylaminophenylvinyl) benzothiazole, 2- (p-dimethylaminophenylvinylene) benzothiazole, 2- (4'-dimethylaminobenzal) acetone, 1,3-bis (4'-diethylaminobenzal) acetone, 3,3'-carbonyl- Dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylamino N-phenylethanolamine, N-phenyldiethanolamine, Np-diethylaminocoumarin, N-phenylethanolamine, N- N-phenylethanolamine, 4-morpholinobenzophenone, dimethylaminobenzoic acid isoamyl, diethylaminobenzoic acid isoamyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercapto (P-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzothiazole, 2- (1,2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene and the like. In terms of sensitivity, 4- (1-methylethyl) -9H-thioxanthen- It is preferable to use thioacids. These may be used alone or in combination of 2 to 5 kinds. The amount of the sensitizer (D) is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the polymer precursor (A).

Further, in the photosensitive resin composition according to Embodiment 1, an adhesion assisting agent may be added for the purpose of improving adhesion with a substrate. As the adhesion assisting agent, known adhesives can be used so long as they do not contradict the object of the present invention. For example, there may be mentioned γ-aminopropyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane , N- [3- (triethoxysilyl) propyl] phthalamidic acid, reaction product of benzophenonetetracarboxylic dianhydride and (triethoxysilyl) propylamine. The amount of the adhesion promoter to be added is preferably in the range of 0.5 to 10 parts by mass based on 100 parts by mass of the polymer precursor (A).

Further, a base proliferator may be added to the photosensitive resin composition of the present invention. When forming a thick film pattern, the decomposition rate of the latent basic material (B) to the same extent from the surface to the bottom is obtained. In this case, in order to improve the sensitivity, addition of a base proliferator is preferable. For example, it is possible to use a base proliferator disclosed in Japanese Patent Application Laid-Open Nos. 2012-237776 and 2006-282657.

In the photosensitive resin composition of the present invention, other photosensitive components which generate an acid or a base by light may be added within a range that does not significantly impair the cured film properties. When a compound having one or more ethylenic unsaturated bonds in the photosensitive resin composition of the present invention is added, 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 weight or high molecular compounds of various colors 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, and inorganic fine particles such as colloidal silica, carbon, layered silicate and the like, and they may be porous or hollow. Specific materials for obtaining a porous shape or a hollow structure include various pigments, fillers and fibers.

Next, a method for producing a relief pattern using the photosensitive resin composition will be described.

First, as a step 1, a photosensitive resin composition is coated on a base material and dried to obtain a coated film. Examples of the method of applying the photosensitive resin composition on a substrate include a method which has been conventionally used for coating a photosensitive resin composition, such as a method of coating with a spin coater, a bar coater, a blade coater, a curtain coater or a screen printing machine, A spray coating method, an ink jet method, or the like can be used. As the drying method of the coating film, a method of drying by heating with a air dryer, an oven or a hot plate, or vacuum drying may be used. The drying of the coating film is preferably carried out under such conditions that imidization of the polymer precursor (A) in the photosensitive resin composition does not occur. Concretely, natural drying, air drying, or heat drying can be carried out at a temperature of 20 ° C to 140 ° C for 1 minute to 1 hour. Preferably, drying is performed on the hot plate for 1 to 5 minutes. Vacuum drying is also possible, and in this case, it can be carried out at room temperature for 1 minute to 1 hour.

The substrate is not particularly limited and can be widely applied to a silicon wafer, a wiring substrate, various resin, metal, and a passivation protective film of a semiconductor device.

In addition, since imidization can be performed at a low temperature, it is widely applicable to members and materials which are not suitable for high-temperature processing such as substrates for printed wiring boards.

Subsequently, as the step 2, the coating film is directly exposed through a photomask having a pattern. The exposure light beam has a wavelength capable of activating the latent basic substance (B) and converting it into a strong basic tertiary amine. As described above, if the sensitizer is suitably used, the light sensitivity can be adjusted. As the exposure apparatus, a contact aligner, a mirror projection, a stepper, a laser direct exposure apparatus, or the like can be used.

Subsequently, as step 3, heating is carried out to promote imidization of the coating film by the base generated in the coating film. Thus, in step 2, the base generated in the exposed portion serves as a catalyst, and the polymer precursor A partially imidizes. The heating time and heating temperature are appropriately changed depending on the kind of the polymer precursor (A), the coating film thickness and the latent basic substance (B) to be used. Typically, in the case of a coating film thickness of about 10 탆, it is about 2 to 10 minutes at 110 to 200 캜. If the heating temperature is too low, partial imidization can not be efficiently achieved. On the other hand, if the heating temperature is too high, the imidization of the unexposed portion progresses and the difference in solubility between the exposed portion and the unexposed portion becomes small, which may cause trouble in pattern formation.

Subsequently, in Step 4, the coating film is treated with a developing solution. Thereby, the unexposed portions in the coating film can be removed, and a pattern including the polymer precursor (A) and partially imidized polyimide can be formed on the substrate.

As a method for use in development, any of a conventionally known developing method of a photoresist, for example, a rotary spray method, a paddle method, a method of immersing with ultrasonic treatment, and the like can be selected. Examples of the developer include inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate and aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine and triethanolamine, and organic amines such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide Quaternary ammonium salts and the like. If necessary, a water-soluble organic solvent such as methanol, ethanol, isopropyl alcohol or the like or a surfactant can be used as an aqueous solution to which an appropriate amount is added. Thereafter, if necessary, the coating film is rinsed with a rinsing liquid to obtain a pattern coating film. As the rinsing liquid, distilled water, methanol, ethanol, isopropanol, etc. may be used alone or in combination. The solvent (C) may also be used as a developing solution.

Thereafter, the patterned coating film is heated in Step 5. The heating temperature is appropriately set so that the pattern of the polyimide can be cured. For example, heating is carried out at 150 to 300 DEG 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, and a heating oven capable of setting a temperature program. As the atmosphere (gas) at this time, air may be used, or an inert gas such as nitrogen or argon may be used.

The photosensitive resin composition according to the present invention can be applied to various known fields in which resin materials such as printing ink, adhesive, filler, electronic material, optical circuit component, molding material, resist material, building material, For example, paints or printing inks, or color filters, films for flexible displays, semiconductor devices, electronic components, interlayer insulating films, and the like, in which the characteristics of products, especially polyimide films, A color filter, a color filter, a color filter, and the like, which are suitably used as a material for forming a wiring coating film, an optical circuit, an optical circuit component, an antireflection film, a hologram, an optical member or a building material, Film for flexible display, semiconductor device, electronic component, interlayer insulating film, wiring coating film, optical circuit, light circuit This part, the anti-reflection film, a hologram, and an optical member or the 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 serves as a permanent film containing polyimide as a component for imparting heat resistance and insulation, For example, a wiring film such as a color filter, a film for a flexible display, an electronic part, a semiconductor device, an interlayer insulating film, a solder resist or a coverlay film, a solder dam, an optical circuit, an optical circuit component, It is also suitable for forming electronic components.

[Synthesis Example 1]

Nonionic photoreactive latent basic substance 1: Preparation of 8-benzyl-1,8-diazabicyclo [5.4.0] undecane

1,8-diazabicyclo [5.4.0] undecane represented by the following formula was prepared by the following procedure.

(i) Preparation of 1,8-diazabicyclo [5.4.0] undecane

In a 2.5 L flask, 1470 mL of tert-butyl methyl ether and 152 g (1 mol) of 1,8-diazabicyclo [5.4.0] undeca-7-ene were 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. Subsequently, the reaction mixture was warmed to 55-57 占 폚 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 < 0 > C and 19 ml of water were carefully added and then 19 ml of a 10% strength sodium hydroxide solution were added. An additional 57 mL of water was added. The resulting mixture was stirred for 1 hour, 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 washings were dried over sodium sulfate and the solvent was distilled off in a rotary evaporator. 1,8-diazabicyclo [5.4.0] undecane was obtained as a yellow oily product.

In further purification, the crude product was distilled at 47-53 mbar using a Vigreux column. Pollen from 82 to 85 占 폚 contained pure product. The structure was confirmed by 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) of sodium hydroxide and 5.81 g (0.035 mol) of potassium iodide were suspended in 350 mL of dichloromethane. Next, 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 as described above were added, and the suspension was stirred at room temperature for 24 hours. ^{In the 1} H-NMR spectrum, the peak of benzylic proton in benzyl chloride could not be confirmed any longer.

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

For further purification, the crude product under reduced pressure (p = 10 ^{- 1} mbar) in Alesund lux column by distillation at, teamed pollen from 129 to 136 ℃ containing the desired product. Benzyl-1,8-diazabicyclo [5.4.0] undecane (pKa = 7.46) was colorless and crystallized by cooling. The structure was confirmed by 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 .

In addition, 8-benzyl-1,8-diazabicyclo [5.4.0] undecane becomes a strongly basic tertiary amine DBU (pKa = 13.28) upon irradiation with an actinic ray (cf.

[Synthesis Example 2]

Nonionic photoreactive latent basic substance 2: Preparation of 5-benzyl-1,5-diazabicyclo [4.3.0] nonane

Diazabicyclo [4.3.0] non-5-ene was used in place of 1,8-diazabicyclo [5.4.0] undeca-7- Benzyl-1,5-diazabicyclo [4.3.0] nonane (pKa = 7.46) represented by the following formula was prepared. The product was obtained as a pale yellow oily matter. The structure was confirmed by 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.

In addition, 5-benzyl-1,5-diazabicyclo [4.3.0] nonane can be obtained by reacting DBN (1,5-diazabicyclo [4.3.0] - yen) (pKa = 13.42) (see above).

[Synthesis Example 3]

Nonionic photoreactive latent basic substance 3: Preparation of 5-methylstyrene-1,5-diazabicyclo [4.3.0] nonane

Methylstyrene-1,5-diazabicyclo [4.3.0] nonane represented by the following formula was prepared by the following procedure.

77.14 g (0.5 mol) of 1,5-diazabicyclo [4.3.0] nonane was dissolved in 500 mL toluene in a 2.5 L flask, and 99.52 g (0.5 mol) of? -Bromoacetophenone and a solution in 500 mL toluene And further stirred overnight at room temperature. The reaction mixture was filtered, washed with deionized water and dried over magnesium sulfate. Subsequently, the product was further dried in vacuo to obtain? -Amino ketone in a yield of about 85%.

The dichloromethane solution of the? -Amino ketone 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 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 by ¹ H-NMR. The pKa value of 5-methylstyrene-1,5-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 can be obtained by reacting DBN (1,5-diazabicyclo [4.3.0] nona- 5-ene) (pKa = 13.42) (see above).

[Synthesis Example 4]

Polymer precursor

(60 mmol) of 4,4'-diaminodiphenyl ether was added to 141.3 g of dehydrated N-methyl-2-pyrrolidone (NMP) in a 500 mL three-necked flask, and the mixture was stirred at room temperature Lt; / RTI > To this solution, 13.09 g (60 mmol) of pyromellitic dianhydride was gradually added. After completion of the addition, the mixture was stirred at room temperature for 12 hours under a nitrogen stream to obtain a polyamic acid solution as a polymer precursor.

Example 1

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

Example 2

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.

Example 3

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.

[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 the comparative example.

[Comparative Example 3]

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

[Comparative Example 4]

A photosensitive resin composition (photosensitive resin composition 7) of Comparative Example containing only 3 g of the polymer precursor solution 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 respectively coated on a copper plate to a final film thickness of 1 m. These were dried at 100 ° C on a hot plate for 15 minutes, and then irradiated with 10 J ultraviolet rays on h-line conversion with an exposure apparatus (Oak Seisakusho Co., Ltd.) equipped with a metal halide lamp.

(1-2) Production of standard hardened samples (high-temperature heating)

The photosensitive resin composition 7 (Comparative Example 4) was coated on the wafer to a final film thickness of 1 m and heated on a hot plate at 100 占 폚 for 30 minutes, 200 占 폚 for 30 minutes, 250 占 폚 for 30 minutes, and 300 占 폚 for 1 hour. As a result, a standard imide film was obtained by imidization.

(1-3) Production of dry sample

The photosensitive resin composition 7 (Comparative Example 4) was coated on the wafer to a final film thickness of 1 m and heated at 100 占 폚 for 15 minutes to obtain a dried sample.

The cured samples and the standard cured samples according to Examples 1 and 2 and Comparative Example 4 prepared as described above were measured with a Thermo Scientific Nikolet 4700 FT-IR, an observation table equipped with a heating device and a reflector, The infrared spectroscopic spectrum was measured while raising the temperature from 100 占 폚 to 5 占 폚 / min to 200 占 폚 using a DENZHE DSM temperature control unit.

The spectrum derived from the precursor was lost by heating, and a peak derived from polyimide produced by heating appeared. In order to confirm the progress of the imidation, the ratio (CN / COC) of the height from the produced polyimide CN to the 1,234 cm ^-1 peak derived from ether COC of 1368 cm ^-1 peak (CN / COC) was calculated .

The imidation rate of each sample is expressed by Equation (1).

In Equation 1, the symbols have the following meanings:

absorbance of a: (CN) _{1374 cm} &lt; _{-1 &gt;}

b: absorbance at (COC) _{1237 cm &lt;&quot; 1 &}

(a / b) _PI : ratio of the height of the CN-derived peak of the standard hardened sample to the peak of the COC-derived peak

(a / b) _{PAA, init} : the ratio of the height from the CO-derived peak of the CN-derived peak of the dried sample

(a / b) _sample : the height ratio of the peak derived from the COC of the CN-derived peak of the cured sample according to Examples 1 and 2 and Comparative Example 4

The imidization ratio of the photosensitive resin composition at each temperature was calculated according to the formula (1). The results are shown in Fig. The photosensitive resin compositions 1 and 2 (Examples 1 and 2) had imidization at a lower temperature than the photosensitive resin composition 7 (Comparative Example 4), and photosensitive resin compositions 1 and 7 (Example 1 and Comparative Example 4) It was found that the difference in the duty ratio was maximum at around 170 占 폚. Further, the imidization rate of the photosensitive resin composition 1 reached 100% at around 180 캜. On the other hand, the imidization rate of the photosensitive resin composition 7 was 75% even at 200 占 폚.

(2) Properties of Polymer Membranes

The photosensitive resin compositions 1, 2, 4 and 5 (Examples 1 and 2 and Comparative Examples 1 and 2) were coated on an electrolytic copper foil (FURUKAWA DENKI KOGYO Co., GTS treated product) Lt; 0 &gt; C for 30 minutes. Thereafter, h-line conversion and 10J ultraviolet irradiation were carried out in an exposure apparatus (Oak Seisakusho Co., Ltd.) equipped with a metal halide lamp, and then each sample was heated at 180 DEG C for 1 hour to imidize .

(2-1) Self-supporting film formation

From the photosensitive resin compositions 1 and 2 (Examples 1 and 2), a flat and uniform self-standing cured film was obtained. On the other hand, in the photosensitive resin compositions 4 and 5, no free-standing self-supporting film was formed. The reason why the properties of the cured film was different was thought to be that the secondary base generated by the irradiation of the actinic ray was weak in the imidization promoting effect and the active hydrogen of the secondary amine generated some reaction with the polyamic acid.

(2-2) Tensile test result

A cured film of the photosensitive resin composition 1 (Example 1) and the photosensitive resin compositions 4 and 5 (Comparative Examples 1 and 2) was used as a test piece having a size of 10 x 40 x 0.05 (mm), SHIMADZU AG-X ) Was used, and a tensile test was conducted at a tensile rate of 1 mm / min. This result is shown in Fig. The photosensitive resin composition 1 (Example 1) exhibited good physical properties with a tensile modulus of 2.2 GPa and a tensile elongation of 26%. On the other hand, in the photosensitive resin compositions 4 and 5 (Comparative Examples 1 and 2), the test could not be performed because cracks easily occurred.

(3) Pattern formation

The photosensitive resin compositions 1 to 3 and 6 (Examples 1 to 3 and Comparative Example 3) were spin-coated on the wafer to a final film thickness of 1 m and dried on a hot plate at 80 占 폚 for 30 minutes. On the other hand, h-line conversion and 10J ultraviolet irradiation were performed in an exposure apparatus equipped with a metal halide lamp (Oak Seisakusho Co., Ltd.), then heated on a hot plate at 170 DEG C for 5 minutes and tetramethylammonium And immersed in a 2.38% solution of hydroxide. As a result, in the photosensitive resin compositions 1 to 3 (Examples 1 to 3), the exposed portions did not dissolve in the developer, and good patterns were obtained. On the other hand, it was found that the photosensitive resin composition 6 (Comparative Example 3) hardly melts the unexposed portion and the contrast of the dissolution rate is insufficient. Further, the patterns obtained from the photosensitive resin compositions 1 to 3 were imidized by heating at 180 DEG C for 1 hour.

As a result, it has become clear that the photosensitive resin composition of the present invention can form a good pattern.

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

Claims (14)

(A) a polymer precursor having a repeating unit of a polyamic acid or a polyamide acid ester at least in part,
(B) Nonionic photoreactive latent basic materials which generate strongly basic tertiary amines upon irradiation with actinic light
Wherein the photosensitive resin composition is a photosensitive resin composition. 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 and are each a hydrogen atom or a monovalent organic group or a functional group having silicon,
m is an integer of 1 or more,
n is 0 or an integer of 1 or more) The photosensitive resin composition according to claim 1 or 2, wherein the latent basic substance (B) is a compound represented by the general formula (2).

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

Lt; / RTI &gt; is an aromatic or heteroaromatic group substituted by one or more heteroatoms; or
R ₅ is represented by the formula (4)

&Lt; / RTI &gt;
R ₆ and R ₇ are independently of each other hydrogen, alkyl, alkenyl, alkynyl or phenyl 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 by one or more alkyl;
R ₈ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are independently of each other hydrogen or alkyl; or
R ₈ and R ₁₀ are both unsubstituted or form an alkylene bridge substituted by one or more alkyl; or
R ₉ and R ₁₁ , independently of R ₈ and R ₁₀ , are both unsubstituted or form an alkylene bridge substituted by one or more alkyl;
R ₁₄ , R ₁₅ and R ₁₇ independently from each other are hydrogen or alkyl;
R ₁₆ is hydrogen or alkyl; Or an unsubstituted or substituted aromatic or heteroaromatic group substituted by one or more alkyl, alkenyl, alkynyl, haloalkyl, NR ₁₂ R ₁₃ , CN, OR ₁₄ , SR ₁₅ , COR ₁₄ , COOR ₁₇ or halogen;
R ₁₈ is an unsubstituted or substituted aromatic or heteroaromatic group substituted by one or more alkyl, alkenyl, alkynyl, haloalkyl, NR ₁₂ R ₁₃ , CN, OR ₁₄ , SR ₁₅ , COR ₁₆ , COOR ₁₇ , ego;
R &lt; ₁₉ &gt; is hydrogen or alkyl;
R ₂₀ is hydrogen, alkyl, or unsubstituted or substituted with one or more of alkyl, vinyl, alkenyl, alkynyl, haloalkyl, phenyl, NR ₁₂ R ₁₃ , CN, OR ₁₄ , SR ₁₅ , COR ₁₆ , COOR ₁₇ , Lt; / RTI &gt; The photosensitive resin composition according to claim 3, wherein the latent basic substance (B) represented by the formula (2) is a compound represented by the general formula (5).

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

The photosensitive resin composition according to claim 1 or 2, wherein the pKa of the conjugate acid of the strongly basic tertiary amine in which the latent basic substance (B) is generated is 9 or more. 3. The photosensitive resin composition according to claim 1 or 2, wherein the latent basic substance (B) has absorption at any one of wavelengths in the range of 240 nm to 450 nm. The photosensitive resin composition according to claim 1 or 2, wherein the polymer precursor (A) is soluble in an alkali solution. The photosensitive resin composition according to claim 1 or 2, wherein the polymer precursor (A) is polyamide acid. 3. The photosensitive resin composition according to claim 1 or 2, wherein the pattern can be formed at 200 DEG C or lower. A relief pattern film obtained from the photosensitive resin composition according to claim 1 or 2. A coating film formed by drying the photosensitive resin composition according to claim 1 or 2 is formed on a substrate,
The coating film is irradiated with an actinic ray in a pattern shape,
The coating film irradiated with the active ray is heated at 200 DEG C or lower,
And the heated coating film is developed. An electronic component or optical product having the relief pattern film according to claim 11 as a surface protective film layer and / or an interlayer insulating film. An adhesive comprising the photosensitive resin composition according to claim 1 or 2.

Images