KR101599571B1 - Photosensitive resin composition, article using same, and method for forming negative pattern - Google Patents

Photosensitive resin composition, article using same, and method for forming negative pattern Download PDF

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KR101599571B1
KR101599571B1 KR1020117007618A KR20117007618A KR101599571B1 KR 101599571 B1 KR101599571 B1 KR 101599571B1 KR 1020117007618 A KR1020117007618 A KR 1020117007618A KR 20117007618 A KR20117007618 A KR 20117007618A KR 101599571 B1 KR101599571 B1 KR 101599571B1
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resin composition
photosensitive resin
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슌지 후꾸다
？지 후꾸다
가쯔야 사까요리
마미 가따야마
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다이니폰 인사츠 가부시키가이샤
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/20—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/24—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0387—Polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition

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  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Provided is a photosensitive resin composition capable of obtaining a pattern having a good sensitivity, high resolution, regardless of the kind of the polyimide precursor, and having a good dissolution contrast and consequently maintaining a sufficient process margin. A photosensitive resin composition comprising a photo-base generator represented by the formula (I) and a polyimide precursor (each symbol is as defined in the specification).

Figure 112011023960095-pct00022

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, an article using the same, and a method for forming a negative pattern,

The present invention relates to a photosensitive resin composition excellent in resolution, low cost, and wide range of choices applicable to the structure of a polyimide precursor. More particularly, the present invention relates to a photosensitive resin composition which is formed by a patterning process using electromagnetic waves , An electronic part, an optical product, a molding material of an optical component, a layer forming material or an adhesive), an article produced using the resin composition, and a negative type pattern using the resin composition Forming method.

Background Art [0002] Conventionally, polyimide resins having excellent heat resistance, electrical characteristics, and mechanical properties have been used as insulating materials for surface protective films, interlayer insulating films, and electronic parts of semiconductor devices (Non-Patent Document 1).

Formation of a circuit pattern on a semiconductor integrated circuit or a printed circuit board is carried out through various processes such as forming a resist film on the surface of a workpiece, removing unnecessary portions by exposure to a predetermined portion, etching or the like, There is a demand for a heat-resistant photosensitive material that can be used as an insulating material to leave a portion of the resist which is necessary even after pattern formation by exposure and development in order to simplify the manufacturing process of the circuit pattern. A heat-resistant photosensitive material having polyimide as a base polymer has been proposed as these materials.

As such a photosensitive polyimide, for example, in Patent Document 1, a system comprising a polyimide precursor and a dichromate salt has been proposed for the first time. However, this material has advantages such as practical light sensitivity and high film-forming ability, however, it has insufficient storage stability and chromium ion remains in polyimide, which is insufficient for practical use. Patent Document 2 discloses that a compound in which a photosensitive group is introduced into polyamic acid as a polyimide precursor by an ester bond and Patent Document 3 discloses a method in which an amine compound having a methacryloyl group in a polyimide precursor is added to a polyamic acid, Ion-bonded compounds have been introduced. However, cobalt-type photosensitive polyimides represented by ester bonds have problems in that the synthesis process is troublesome and the cost is increased. In addition, the ion-binding photosensitive polyimide has a problem in that the bonding strength between the polyimide skeleton and the photosensitive group is small and the exposed portion is also dissolved, whereby the residual film ratio is lowered and it is difficult to form a thick film (Non-Patent Document 2). Most of these compounds are organic solvent-developable, and in view of the cost and environment, a compound that can be developed with an aqueous alkali solution is preferable.

Such polyimide precursors use aromatic monomers in the basic skeleton to provide excellent heat resistance and mechanical properties. Generally, a polyimide precursor having an aromatic ring in a basic skeleton has a broad absorption band in an ultraviolet-visible region with a wavelength of 400 nm or less, particularly a wavelength region below an i-line (wavelength: 365 nm) The light transmittance is low. For this reason, the photosensitive polyimide has a problem that the photochemical reaction does not sufficiently proceed in the exposed portion, the sensitivity is lowered, or the shape of the pattern deteriorates. As the application range of the heat-resistant photosensitive material becomes wider, the demand for the materials has been diversified and a thick film-forming ability has been demanded in the photosensitive polyimide. When the formation pattern is a thick film, the problem of low light transmittance becomes more serious. Therefore, in order to realize an excellent heat-resistant photosensitive resin in terms of both physical properties and sensitivity, a photoreaction (photoluminescence) is required in the g-line (wavelength: 436 nm), the h-line (wavelength: 405 nm) It is desirable to construct a photosensitive system having photoreaction activity in the g-line (wavelength: 436 nm) and the h-line (wavelength: 405 nm) region.

In recent years, photobase generators have attracted attention as one of the new pattern forming materials. For example, Non-Patent Document 3 discloses 2-nitrobenzyloxycarbonylcyclohexylamine as a photobase generator. However, since this compound has no sensitivity to h-line, it is difficult to generate a base by h-line.

Patent Document 4 discloses a latent curable epoxy resin composition comprising an epoxy resin and a compound having two or more groups represented by the following formula in the molecule. However, in Patent Document 4, it is disclosed that the epoxy resin composition is irradiated with light using an ultra-high pressure mercury lamp, and subsequently cured by heating.

Figure 112011023960095-pct00001

(In the above formula, R is hydrogen, an alkyl group or an aryl group.)

Further, Patent Document 5 discloses a resist-forming material using 2-nitro-4, 5-dimethoxybenzyloxycarbonylcyclohexylamine and styrene-acrylic acid copolymer as a base generating compound. However, the compound generating base disclosed in Patent Document 5 has sensitivity to i-line, but there is no description that it has sensitivity to h-line.

Patent Document 6 discloses a photosensitive resin composition comprising a photo-base generator and a polyimide precursor.

Patent Document 1: Japanese Patent Publication No. 49-17374 Patent Document 2: Japanese Patent Publication No. 55-30207 Patent Document 3: JP-A-54-145794 Patent Document 4: Japanese Patent Publication No. 51-46159 Patent Document 5: JP-A-6-345711 Patent Document 6: Japanese Patent Application Laid-Open No. 2006-189591

Non-Patent Document 1: " Latest polyimide to base and application ", NTS Corporation, 2002, pages 327 to 338 Non-Patent Document 2: "Recent Trends of Polymer Materials for Electronic Components III", Sumibe Techno Research, 2004, pages 36 to 39 Non-Patent Document 3: J. Am Chem. Soc., 1991, 113, p. 4303-4313

There has been a problem in terms of the absorption wavelength in order to apply the conventional photo-nucleating agent to the system of the polyimide precursor. That is, the conventional photobase generators often have absorption wavelengths of 400 nm or less, and when they are added to the polyimide precursor as an imidization promoter by photoreaction, the absorption wavelengths of the polyimide precursor and the photobase generator overlap There is a problem in sensitivity. In addition, as shown in the comparative example described later, even when the conventional photobase generator had an absorption wavelength of 400 nm or more, the photoreaction activity in a wavelength region of 400 nm or more was not observed. For this reason, in order to realize a heat-resistant photosensitive resin having excellent heat resistance, mechanical properties and sensitivity, it is preferable to use a light-emitting element in a wavelength region of 400 nm or more, for example, a g-line (wavelength: 436 nm) A base generator having a reaction activity is required.

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-described circumstances. It is a first object of the present invention to provide a photosensitive polyimide film which can obtain a pattern having a good shape while maintaining a sufficient process margin and a solubility contrast regardless of the kind of polyimide precursor, And to provide a resin composition.

A second object of the present invention is to provide a photosensitive resin composition having a photoreactive activity in a wavelength region of 400 nm or more, for example, a g-line (wavelength: 436 nm) and h-line (wavelength: 405 nm) .

The photosensitive resin composition according to the present invention contains a photopolymerization initiator and a polyimide precursor represented by the general formula (I).

(I)

Figure 112011023960095-pct00002

(In the general formula (Ⅰ), R 1 and R 2 each independently represents a have also containing from 1 to 12 carbon atoms may have an alkyl group or a substituent having 6 to 12 carbon atoms, aryl group of which that substituent, the R 1 and R 2 An alkylene group having 1 to 24 carbon atoms which may have a substituent and an arylene group having 6 to 24 carbon atoms which may have a substituent,

R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent or an aryl group having 6 to 12 carbon atoms which may have a substituent, and at least one of R 3 and R 4 is not a hydrogen atom , R 3 and R 4 may be connected to form a cyclic structure which may contain a hetero atom,

R 5 to R 9 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyano group, , An acyloxy group having 1 to 12 carbon atoms, a nitro group, or an acyl group having 1 to 12 carbon atoms.

The present inventors have found that the N (α-aromatic substituted-2-nitro-4, 5-dialkoxybenzyloxycarbonyl) amine compound represented by the above formula (I) And can achieve a photosensitive polyimide with high sensitivity by combining it with a polyimide precursor, and have reached the present invention.

The photobase generator represented by the formula (I) used in the present invention has a longer wavelength due to the introduction of an alkoxy group into the nitrobenzyl group by OR 1 and OR 2 . Further, the sensitivity to the h line is increased by introducing an aromatic group at the? -Position of the nitrobenzyl group.

The photo-base generator represented by the formula (I) used in the present invention is a compound which, upon irradiation with an electromagnetic wave, generates hydrogen at a benzylic position and then radically cleaves the bond to generate an amine which is a basic substance. As a highly effective photosensitive component for a polyimide precursor which promotes the reaction to the final product.

Since the photo-base generator has the specific structure, it can have a photo-reaction activity in a wavelength region of 400 nm or more, and thus has an aromatic ring having a wide absorption band in the i-line (wavelength: 365 nm) The absorption wavelength does not overlap with the polyimide precursor and functions as a photobase generator with high sensitivity. Therefore, according to the present invention, it is possible to increase the difference in solubility between the electromagnetic wave irradiated portion and the non-irradiated portion on the coated film or molded article of the photosensitive resin composition, and as a result, a pattern having a good shape can be obtained while maintaining a sufficient process margin have.

In the photosensitive resin composition of the present invention, in the photobase generator, R 3 and R 4 are preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms which may have a substituent, and R 3 and R 4 are substituents Which may have an alkyl group having 1 to 12 carbon atoms, is preferable in view of the large catalytic effect of the basic substance.

Further, in the photosensitive resin composition of the present invention, in the photobase generator, R 3 and R 4 are connected to form a cyclic structure which may contain a hetero atom, and the catalytic effect of the basic substance generated is large .

In the photobase generator represented by the above formula (I), it is preferable that R 1 and R 2 are methyl groups in view of the amount of base generation per unit weight and ease of preparation.

As the polyimide precursor used in the photosensitive resin composition of the present invention, a compound which itself promotes the reaction to the final product by the action of a basic substance, in which the reaction to the final product by the action of a basic substance itself It is preferable to use a polyimide precursor such as polyamic acid as a compound that is accelerated and changes its solubility by heating. When such a polyimide precursor is used, a photosensitive polyimide resin composition excellent in heat resistance and mechanical properties can be obtained.

According to the present invention, a good pattern shape can be obtained without applying a dissolution inhibitor or a dissolution inhibitor to a polyimide precursor which has difficulty in obtaining a contrast of dissolution between the exposed portion and the unexposed portion.

In one embodiment of the present invention, a sensitizer may be added to the photosensitive resin composition to improve the irradiation sensitivity.

In the photosensitive resin composition of the present invention, it is preferable that the 5% weight reduction temperature of the photobase generator is 170 DEG C or higher. When the photobase generator is decomposed at the imidization temperature of the coating film of the photosensitive resin composition before exposure after development Which is preferable in view of difficulty.

Further, since the photosensitive resin composition of the present invention can select a polyimide precursor having a wide range of structures, the cured product obtained therefrom is capable of imparting a characteristic characteristic of polyimide such as heat resistance, dimensional stability, , All known member films, coating films or three-dimensional structures to which polyimide is applied.

Particularly, the photosensitive composition according to the present invention is mainly used as a pattern forming material (resist), and the pattern formed thereby functions as a component for imparting heat resistance and insulating property as a permanent film. For example, a color filter, It is suitable for forming devices, electronic parts, interlayer insulating films, wiring coating films, light circuits, light guide parts, antireflection films, other optical members, or building materials.

In addition, the present invention relates to a photosensitive resin composition according to the present invention or a printed matter on which at least a part is formed by the cured product, a color filter, a film for a flexible display, a semiconductor device, an electronic component, an interlayer insulating film, , An optical circuit component, an antireflection film, a hologram, an optical member, or a building material.

The present invention also provides a negative pattern forming method using the photosensitive resin composition. In the negative pattern forming method according to the present invention, electromagnetic wave is irradiated onto the surface of a coating film or a molded body made of the photosensitive resin composition in a predetermined pattern, and if necessary, post-treatment (usually heat treatment) And then developing the solution after selectively lowering the solubility of the site irradiated with the electromagnetic wave.

In the negative type pattern forming method, the surface of a coating film or a molded article made of a photosensitive resin composition is coated with a developing solution (developer) by using a combination of a polyimide precursor and a photo base generating agent represented by the formula (I) It is possible to form a negative pattern in which development is carried out without using a resist film for protecting the photoresist pattern.

INDUSTRIAL APPLICABILITY As described above, according to the present invention, a novel photobase generator having a photoreaction activity in the g-line (wavelength: 436 nm) and h-line (wavelength: 405 nm) The photosensitive polyimide resin composition can be prepared and used in a simple manner. The photo-base generator represented by the above formula (I) has an activity to act as a catalyst since hydrogen is extracted from the benzyl position when irradiated with an electromagnetic wave, and the radical is cleaved to generate an amine as a basic substance And can be applied to polyimide precursors having various structures.

Therefore, the photosensitive resin composition according to the present invention can be used as a photosensitive polyimide resin composition which can select the final polyimide structure from a wide range without being limited by the pattern formation process, and has excellent heat resistance and mechanical properties.

According to the present invention, a favorable pattern shape can be obtained without applying a dissolution inhibitor or a dissolution inhibitor to a polyimide precursor which has difficulty in obtaining a contrast of dissolution between the conventional exposed portion and the unexposed portion.

1 is a view showing a transmittance curve of the filter 1 and the filter 2.
2 is a graph showing the relationship between the imidization rate and the heat curing treatment temperature in the case of unexposed light and after exposure in the photosensitive resin composition.

The present invention includes a photosensitive resin composition using a photo-base generator, an article using the photosensitive resin composition, and a negative pattern forming method. Hereinafter, the photosensitive resin composition will be described in order.

In addition, in the present invention, as long as it is capable of causing an electron wave and a hydrogen releasing reaction to cleave the bond of the photo-base generator as represented by the formula (I), it is possible to use not only electromagnetic waves having wavelengths in visible and non- And a radiation or ionizing radiation collectively referred to as an electromagnetic wave and a particle beam.

The photosensitive resin composition of the present invention contains a photobase generator represented by the formula (I) and a polyimide precursor.

(I)

Figure 112011023960095-pct00003

(In the general formula (Ⅰ), R 1 and R 2 each independently represents a have also containing from 1 to 12 carbon atoms may have an alkyl group or a substituent having 6 to 12 carbon atoms, aryl group of which that substituent, the R 1 and R 2 An alkylene group having 1 to 24 carbon atoms which may have a substituent and an arylene group having 6 to 24 carbon atoms which may have a substituent,

R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent or an aryl group having 6 to 12 carbon atoms which may have a substituent, and at least one of R 3 and R 4 is not a hydrogen atom , R 3 and R 4 may be connected to form a cyclic structure which may contain a hetero atom,

R 5 to R 9 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyano group, , An acyloxy group having 1 to 12 carbon atoms, a nitro group, or an acyl group having 1 to 12 carbon atoms.

The photo-base generator represented by the formula (I) used in the present invention generates hydrogen in the benzylic position and then radically cleaves bonds to generate an amine as a basic substance when an electromagnetic wave is irradiated. On the other hand, the polyimide precursor can lower the temperature at which the imidization reaction is initiated, for example, by the catalytic action of a basic substance. That is, when the polyimide precursor is allowed to coexist with the photo-base generator and a base is generated by irradiation of electromagnetic waves, the site irradiated with the electromagnetic wave promotes the reaction of the polyimide precursor to the final product and imidization proceeds at a lower temperature . In order to obtain a pattern using the photosensitive resin composition of the present invention, for example, after irradiating electromagnetic waves at a place where a pattern is desired to be left, imidization proceeds at a place where a basic substance exists and at a place where a basic substance is not present Heating is performed at a temperature at which the imidization does not proceed. As a result, only a place where a basic substance exists, that is, a place irradiated with an electromagnetic wave, is imidized and the solubility is lowered, so that a pattern can be obtained by developing with a predetermined developer (organic solvent or an aqueous alkali solution). Thereafter, the polyimide pattern can be formed by further heating according to the purpose.

In the photobase generator represented by the formula (I) used in the present invention, since the alkoxy group is introduced into the nitrobenzyl group by OR 1 and OR 2 in particular, the wavelength of the light absorbed by the compound is long. Further, the sensitivity to the h line is increased by introducing an aromatic group at the? -Position of the nitrobenzyl group. Thus, the photobase generator used in the present invention has a photoreaction activity in a wavelength region of 400 nm or more. Therefore, it is preferable to use a polyimide having an aromatic ring having a broad absorption band in the i-line (wavelength: 365 nm) It is possible to increase the difference in solubility between the electromagnetic wave irradiation site on the coated film or the molded article of the photosensitive resin composition and the non-irradiated site, and as a result, a sufficient process margin can be obtained It is possible to obtain a pattern having a good shape while keeping it.

First, the photobase generator represented by the above formula (I) will be described. A photobase generator means a chemical substance decomposed by light irradiation to generate a basic substance.

≪ About R 1 and R 2 >

In the general formula (Ⅰ), R 1 and R 2 each independently represents a have also containing from 1 to 12 carbon atoms may have an alkyl group or a substituent having 6 to 12 carbon atoms, aryl groups of which of which the substituents, R 1 and R 2 is connected An alkylene group having 1 to 24 carbon atoms which may have a substituent, or an arylene group having 6 to 24 carbon atoms which may have a substituent, to form a cyclic structure. OR 1 and OR 2 constitute an alkoxy group, and such an alkoxy group is introduced into the nitrobenzyl group, whereby the compound represented by the formula (I) can lengthen the wavelength of absorbed light. As a result, the compound represented by the formula (I) used in the present invention can generate a base by absorbing h rays.

Among the alkyl groups having 1 to 12 carbon atoms which may have substituents, alkyl groups having 1 to 6 carbon atoms, which may have a substituent, are preferable in terms of the amount of base generation per unit weight and ease of preparation. Alkyl groups having 1 to 3 carbon atoms Is more preferable. Examples of the substituent include a methoxy group, a phenyl group, and a 2-thioxanthyl group.

Examples of the alkyl group having 1 to 12 carbon atoms which may have a substituent include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group and i-butyl group. Of these, a methyl group and an ethyl group are preferable in view of the amount of base generation per unit weight, and a methyl group is particularly preferable. In the present invention, the "number of carbon atoms of the alkyl group having 1 to 12 carbon atoms (1 to 6, 1 to 3) which may have a substituent" is the number of carbon atoms in the alkyl group portion and does not include the number of carbon atoms in the substituent.

Among the aryl groups having 6 to 12 carbon atoms which may have a substituent, an aryl group having 6 carbon atoms which may have a substituent is preferable in terms of the amount of base generation per unit weight and the ease of preparation. Examples of the substituent include the same as those exemplified in the description of the alkyl group having 1 to 12 carbon atoms which may have a substituent.

Examples of the aryl group having 6 to 12 carbon atoms which may have a substituent include a phenyl group, a naphthyl group and a toluyl group. In the present invention, the "number of carbon atoms of the aryl group having 6 to 12 (6) carbon atoms which may have a substituent" is the number of carbon atoms in the aryl group portion and does not include the number of carbon atoms in the substituent.

Also, R 1 and R 2 may be connected to form an alkylene group or an arylene group to form a cyclic structure, which may have a substituent attached thereto. Examples of the substituent include a methyl group, an ethyl group, a methoxy group, and a phenyl group. The R 1 and R 2 are connected to the examples of the groups R 1 and R 2 in the case of forming a cyclic structure configuration may be mentioned methylene, ethylene, 1,3-propylene group, a 1,2-phenylene group, etc. . In the present invention, the carbon number of the "alkylene group having 1 to 24 carbon atoms which may have a substituent" and the "arylene group having 6 to 24 carbon atoms which may have a substituent" are the carbon numbers of the alkylene group and the arylene group, And the number of carbon atoms in the substituent is not included.

≪ R 3 and R 4 >

R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent or an aryl group having 6 to 12 carbon atoms which may have a substituent, and R 3 and R 4 is not a hydrogen atom, and R 3 and R 4 may be connected to form a cyclic structure which may contain a hetero atom. At least one of R 3 and R 4 is not a hydrogen atom, because if both are hydrogen atoms, the stability of the compound is poor and the resulting amine also becomes ammonia, so that it is not useful as a base generator.

It is possible to change the physical properties such as basicity, thermal properties and solubility of the amine by changing the number of hydrogen atoms introduced into the positions of R 3 and R 4 and the kind of substituent. The amine having a higher basicity has a strong catalytic action with respect to the dehydration condensation reaction and the like in the imidization of a polyimide precursor which will be described later, for example. Thus, the catalytic effect in the dehydration condensation reaction at a lower temperature Can be expressed. As a result, even when the sensitivity to the electromagnetic wave of the compound represented by the formula (I) is low, the sensitivity of the appearance as the photosensitive resin composition is improved because the catalytic effect of the generated basic substance is great.

The basic substance generated by the dissociation reaction accompanying the absorption of electromagnetic waves of the compound represented by the formula (I) is preferably an aliphatic amine in view of the effect given by the basic substance such as the catalytic effect as described above . Of these, secondary aliphatic amines are preferred from the viewpoint of basicity. However, even when an aliphatic primary amine is used, a sufficient catalytic effect can be obtained as compared with the case where an aromatic amine is used. Therefore, among the aliphatic amines, it is also desirable to properly select amines from the viewpoints of other properties such as a 5% weight reduction temperature, a 50% weight reduction temperature, thermal properties such as thermal decomposition temperature and solubility, desirable.

R 3 and R 4 are each a hydrogen atom or an alkyl group having 1 to 12 carbon atoms which may have a substituent, provided that such an aliphatic amine is generated to achieve high sensitivity and further to increase the solubility contrast of the exposed portion. R < 3 > and R < 4 > are hydrogen atoms). R 3 and R 4 are preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent.

Examples of the alkyl group having 1 to 12 carbon atoms which may have such a substituent include a straight chain alkyl group, a branched alkyl group and a cyclic alkyl group, or an alkyl group composed of a combination of these. The alkyl group may have a substituent such as an aromatic group or may contain a bond other than a hydrocarbon such as a heteroatom in the hydrocarbon chain. For example, a linear or branched saturated or unsaturated alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 12 carbon atoms, a phenoxyalkyl group having 7 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, a hydroxy group having 1 to 12 carbon atoms Alkyl groups and the like.

Specific examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, ethynyl, propyl, isopropyl, n-butyl, t-butyl, A thiol group, a benzyl group, and the like, but are not limited thereto.

R 3 and R 4 may be connected to form a cyclic structure, or may be connected to form a cyclic structure to form a heterocyclic structure including a nitrogen atom bonded to R 3 and R 4 . Even in such a case, the catalytic effect of the basic material generated is preferable in view of the large catalytic effect.

Examples of the heterocyclic structure in which two of R 3 and R 4 are connected to form a cyclic structure to form a heterocyclic structure containing a nitrogen atom bonded to R 3 and R 4 include aziridine (3 Azetidine (4-membered ring), pyrrolidine (5-membered ring), piperidine (6-membered ring), azepane (7-membered ring), azokane (8-membered ring) and the like. The cyclic structure may contain a hetero atom in addition to the nitrogen atom to which R 3 and R 4 are bonded. Examples of such a heterocyclic structure include morpholine, thiomorpholine, oxazolidine, thiazolidine, etc. have. These heterocyclic structures may have a substituent such as a straight chain or branched alkyl group. Examples of the alkyl substituent include monoalkyl aziridines such as methyl aziridine, dialkyl aziridines such as dimethyl aziridine, and mono Dialkyl azetidine such as alkyl azetidine and dimethyl azetidine, trialkyl azetidine such as trimethyl azetidine, monoalkyl pyrrolidine such as methyl pyrrolidine, dialkyl pyrrolidine such as dimethyl pyrrolidine, Trialkylpyrrolidines such as tetramethylpyrrolidine and the like, monoalkylpiperidines such as methylpiperidine, dialkylpiperidines such as dimethylpiperidine, trimethylpiperidine such as trimethylpiperidine, Tetraalkylpiperidine such as tetramethylpiperidine, pentaalkylpiperidine such as pentamethylpiperidine, and the like can be given.

Among the alkyl groups having 1 to 12 carbon atoms which may have substituents, alkyl groups having 1 to 8 carbon atoms which may have a substituent are preferable in terms of the amount of base generation per unit weight and the ease of preparation, and alkyl groups having 1 to 6 carbon atoms Is more preferable. Examples of the above substituents include those exemplified in the description of the alkyl group having 1 to 12 carbon atoms which may have a substituent group of R 1 and R 2 .

The heterocyclic structure which may have a substituent preferably has 1 to 12 carbon atoms, more preferably 1 to 8, from the viewpoints of the amount of base generation per unit weight and ease of preparation. The substituent in this case is preferably a straight chain or branched alkyl group.

Examples of the aryl group having 6 to 12 carbon atoms which may have a substituent include the same ones as exemplified in the explanation of the alkyl group having 1 to 12 carbon atoms which may have a substituent of R 1 and R 2 .

≪ R 5 to R 9 >

In the formula (I), each of R 5 to R 9 independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, , An alkylamino group having 1 to 12 carbon atoms, an acyloxy group having 1 to 12 carbon atoms, a nitro group, or an acyl group having 1 to 12 carbon atoms.

In the present invention, the sensitivity to the h line is increased by introducing an aromatic group at the? -Position of the nitrobenzyl group. Therefore, R 5 to R 9 may all be hydrogen atoms.

With respect to the aromatic substituents R 5 to R 9 , it is possible to selectively introduce the kinds of substituents relatively freely in view of improving the sensitivity or adjusting the absorption wavelength. This makes it possible to improve the sensitivity of the photosensitive resin composition while taking into consideration the absorption wavelength of the polyimide precursor to be combined. For example, the absorption wavelength can be shifted to the longer wavelength side by binding of an aromatic substituent. The degree of shift (shift value) differs depending on the kind of the substituent. This shift value is referred to the table described in "Identification by Spectroscopy of Organic Chemistry (5) (RM Silverstein, 281, published by Tokyo Chemical Industry Association, 1993)".

Among the alkyl groups having 1 to 12 carbon atoms, alkyl groups having 1 to 6 carbon atoms are preferable, and alkyl groups having 1 to 3 carbon atoms are more preferable in terms of the amount of base generation per unit weight and ease of preparation. Examples of the alkyl group having 1 to 12 carbon atoms include those exemplified in the description of R 3 and R 4 .

Of the aryl groups having 6 to 12 carbon atoms, an aryl group having 6 carbon atoms is preferable in view of the amount of base generation per unit weight and ease of preparation. Examples of the aryl group having 6 to 12 carbon atoms which may have a substituent include the same groups as those exemplified above for R 1 and R 2 .

Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group and an ethoxy group.

Examples of the halogen atom include a chlorine atom and a bromine atom.

Examples of the alkyl of the alkylamino group having 1 to 12 carbon atoms include a methyl group, an ethyl group and a propyl group.

Examples of the acyloxy group having 1 to 12 carbon atoms include an acetoxyl group and a propionyloxy group.

Examples of the acyl group having 1 to 12 carbon atoms include a formyl group, an allyl group including an aromatic group such as a benzoyl group in addition to an acetyl group.

Examples of the photobase generator represented by the formula (I) include, but are not limited to, those represented by the following formulas.

Figure 112011023960095-pct00004

The compound of the present invention can be produced by a method using a carbon nucleophilic agent such as Grignard reaction. Specifically, it is possible to react an aldehyde compound represented by the following formula (II) with an aromatic compound represented by the following formula (III), and then reacting the compound represented by the following formula (IV) can do.

Figure 112011023960095-pct00005

In the general formula (Ⅱ), R 1 and R 2 are the same as those of R 1 and R 2 in the above formula (Ⅰ) respectively.

In the general formula (Ⅲ), R 5 to R 9 are each is the same as R 5 to R 9 in the above formula (Ⅰ), M is a substituent containing a metal, the metal is Mg, Zn, Li, Sn or Cu. As M, for example, a halogen atom or an alkoxy group may be added to the metal. Specific examples of M include Li, MgCl, MgBr and ZnCl.

In the general formula (Ⅳ), R 3 and R 4 is the same as R 3 and R 4 in the above formula (Ⅰ), respectively, X is a halogen atom selected from fluorine, chlorine, bromine and iodine.

As a specific example of this reaction, 2-nitro-4, 5-dimethoxybenzaldehyde is reacted with phenylmagnesium bromide and then reacted with morpholine carbonyl chloride either isolated or not, -Dimethoxybenzyloxycarbonylmorpholine. ≪ / RTI >

Figure 112011023960095-pct00006

Further, as another method, a carbinol compound represented by the following formula (VI) can be produced by reacting with a compound represented by the following formula (IV) or an isocyanate compound represented by the following formula (V).

Figure 112011023960095-pct00007

In the general formula (Ⅵ), R 1 and R 2 is the same as R 1 and R 2 in the above formula (Ⅰ), respectively, R 5 to R 9 is R 5 to in the above formula (Ⅰ) respectively R 9 . The compound represented by the formula (VI) is obtained by reacting the aldehyde compound represented by the formula (II) described above with the aromatic compound represented by the formula (III), but the compound can be synthesized by a known method. For example, it can be synthesized by the method described in the literature [Tetrahedron, 63, (2007), 474] and [Molecules, 1999, 4, M113].

In the general formula (Ⅳ), R 3 and R 4 are the same as R 3 and R 4 in the above formula (Ⅰ) respectively.

In the general formula (V), R 4 is the same as R 4 in the above formula (Ⅰ).

As a separate method, the compound of the present invention may be produced by reacting a carbinol compound represented by the following formula (VI) with a carbonyl compound represented by the following formula (VII) to synthesize an ester compound represented by the following formula (VIII) , And reacting the ester compound with an amine compound represented by the following formula (IX). In this case, the ester compound may be reacted with the amine compound represented by the formula (IX) after isolating the resulting ester compound by reacting the carbinol compound and the carbonyl compound represented by the following formula (VII) .

Figure 112011023960095-pct00008

In the general formula (Ⅵ) and formula (Ⅷ), R 1 and R 2 is the same as R 1 and R 2 in the above formula (Ⅰ), respectively, R 5 to R 9 has the formula (Ⅰ) respectively in the Are the same as R 5 to R 9 in the formula (1).

In the above formula (VII), Z is a chlorine atom, a bromine atom, an iodine atom, a trichloromethoxy group or a 1-imidazolyl group.

In the formulas (VII) and (VIII), R 10 is a chlorine atom, a trichloromethoxy group, a 1-imidazolyl group, a phenoxy group, a 4-nitrophenoxy group or a 4-cyanophenoxy group.

Examples of the compound represented by the above general formula (VII) include phosgene, trichloromethyl chloroformate, triphosgene, trifluoromethanesulfonyl chloride, and the like, in view of the fact that R 10 functions as a leaving group when reacted with the above formula (IX) Carbonyldiimidazole, p-nitrophenyl chloroformate, and p-cyanophenyl chloroformate are preferable.

In the above formula (Ⅸ) R 3 and R 4 are the same as R 3 and R 4 in the above formula (Ⅰ) respectively.

According to this method, even when it is difficult to obtain the compound represented by the above formula (IV) for introducing an amine, the desired secondary amine type compound of the present invention can be synthesized.

Examples of the basic substance generated upon decomposition of the photo-base generator represented by the formula (I) include primary amines such as n-butylamine, amylamine, hexylamine, cyclohexylamine, octylamine, amantadine and benzylamine, Linear secondary amines such as ethylamine, dipropylamine, diisopropylamine and dibutylamine, cyclic secondary amines such as aziridine, azetidine, pyrrolidine, piperidine, azepane, And secondary amines such as alkyl substituents. Examples of the basic substance having a heterocyclic structure including a hetero atom in addition to a nitrogen atom include morpholine, thiomorpholine, oxazolidine, thiazolidine, and the like.

The photoacid generators represented by the formula (I) and the photoacid generators represented by the formula (I) according to the present invention can be produced by a photoacid generator comprising the photoacid generator of the present invention It is preferable that the coating film of the photosensitive resin composition is not decomposed at the temperature of heating (partial imidization temperature for pattern formation) performed before development after exposure and before development. Concretely, the temperature (5% weight reduction temperature) when the weight of the basic substance generated by the photo-base generator or photodegradation reaction represented by the formula (I) is reduced by 5% from the initial weight is 170 ° C More preferably 200 DEG C or higher.

Further, when the photosensitive resin composition containing the photo-base generator of the present invention is used as a product, it is preferable that no basic substance remains in the photosensitive resin composition. Therefore, the process of heating (post-imidization process) It is preferable that it is a basic substance which is decomposed or volatilized. Specifically, it is preferable that the temperature (50% weight reduction temperature) when the weight of the basic substance generated by the photodegradation reaction is reduced by 50% from the initial weight is 400 캜 or lower.

Typical emission wavelengths of high-pressure mercury lamps, which are general exposure light sources, are 436 nm, 405 nm and 365 nm, but polyimide precursors having aromatic rings in their basic skeleton often have a wide absorption band at 365 nm. It is preferable that the photo-base generator represented by the formula (I) has absorption of an electromagnetic wave having a wavelength of 400 nm or more.

When the photo-base generator has absorption of an electromagnetic wave having a wavelength of 400 nm or more, the absorption wavelength of the photo-base generator does not overlap with the polyimide precursor, and the sensitivity can be improved. In view of using a typical emission wavelength of a high-pressure mercury lamp as a general exposure light source, it is preferable that the photobase generator absorbs at least one of the electromagnetic waves having wavelengths of 436 nm and 405 nm.

The photobase generator represented by the formula (I) of the present invention preferably has photodegradability to an electromagnetic wave having a wavelength of 400 nm or more and 400 nm to 500 nm.

In particular, it is preferable that the photobase generator has not only absorption in at least one wavelength of electromagnetic waves having wavelengths of 436 nm and 405 nm, but also has photodegradability with respect to electromagnetic waves of at least one of 436 nm and 405 nm. There is a possibility that even if it absorbs at least one wavelength of an electromagnetic wave having a wavelength of 436 nm and 405 nm, it does not have photodegradability with respect to an electromagnetic wave having such a wavelength.

The presence or absence of photodegradation of an electromagnetic wave having a wavelength of 405 nm or more can be determined by irradiating the photocatalyst with a high-pressure mercury lamp through a filter which does not allow a wavelength of, for example, i-line (wavelength: 365 nm) It can be judged by observing whether or not the photobase generator is decomposed or whether a basic substance is generated. Similarly, the presence or absence of photodegradation with respect to an electromagnetic wave having a wavelength of 436 nm or more can be determined by using a high-pressure mercury lamp, for example, through a filter that does not allow passage of a wavelength of h line (wavelength: 405 nm) It can be judged by observing whether or not the photoacid generator is decomposed or whether a basic substance is generated.

Next, the polyimide precursor will be described.

The polyimide precursor used in the present invention is preferably soluble in any solvent (organic solvent or aqueous solution). If the polyimide precursor is soluble in a solvent (organic solvent or aqueous solution), the solubility of the polyimide precursor in the solvent may be changed so that the development of the organic solvent, basic aqueous solution, acidic aqueous solution or neutral aqueous solution .

Here, the solubility in any solvent refers specifically to the dissolution rate of the coating film formed on the substrate at 25 DEG C with respect to the solvent of 100 angstroms / sec or more. The dissolution rate is more preferably 1000 angstroms / sec or more.

For example, to be soluble in a basic aqueous solution, specifically, the dissolution rate of a coating film formed on a substrate to an aqueous solution of 0.1 wt% tetramethylammonium hydroxide (TMAH) at 25 캜 is 100 Å / sec or more. The dissolution rate is more preferably 1000 angstroms / sec or more. Further, it is preferable that the dissolution rate to a 2.38% by weight aqueous solution of tetramethylammonium hydroxide, which is a more commonly used developing solution, is 100 Å / sec or more, more preferably 1000 Å / sec or more. When the dissolution rate according to the above definition is less than 100 Å / sec, the development time is slowed, and workability and productivity are deteriorated, and the dissolution contrast between the exposed portion and the unexposed portion becomes difficult to obtain.

Therefore, the dissolution rate of the photosensitive resin composition of the present invention to any solvent is preferably 100 Å / sec or more, more preferably 1000 Å / sec or more at 25 ° C.

As a specific procedure for measuring the dissolution rate, a coating film of a polyimide precursor formed on a substrate such as alkali-free glass is immersed in a developing solution (0.1 wt% TMAH aqueous solution or 2.38 wt% aqueous TMAH solution such as a basic aqueous solution , Organic solvent or the like), rinsing with distilled water, and drying, the difference between the film thickness measured after drying and the initial film thickness is taken as the film reduction amount, and the film reduction amount divided by the time immersed in the developer is 25 ° C Is the dissolution rate per unit time in the reaction.

In order to obtain sufficient solubility contrast between the exposed portion and the unexposed portion, when the photosensitive resin composition is actually used in a predetermined photosensitive pattern forming process, pattern exposure and a post-process (usually a heating process) (The dissolution rate per unit time to the developing solution at the unexposed area / dissolution rate per unit time to the developing solution at the exposed area) of the unexposed area and the exposed area to the developing solution before the developing step is preferably 10 or more .

The dissolution rate per unit time is obtained in the same manner as described above. The patterning of the photosensitive resin composition is subjected to pattern exposure, and after the exposure, the dissolution rates of the exposed portion and the unexposed portion are obtained.

In the present invention, a polyimide precursor which promotes the reaction to the final product by the action of a basic substance is used. Here, in the embodiment in which the reaction of the polyimide precursor to the final product is promoted by the action of the basic substance, not only the polyimide precursor changes to the final product only by the action of the basic substance, but also the polyimide precursor The temperature of the reaction to the final product of the reaction mixture is lowered as compared with the case where there is no action of the basic substance.

When a reaction temperature difference occurs depending on the presence or absence of such a basic substance, only the polyimide precursor coexisting with the basic substance is heated at a suitable temperature at which the basic precursor reacts with the final product, using the reaction temperature difference to produce a polyimide coexisting with a basic substance Only the precursor changes its solubility in a solvent that reacts with the final product. Therefore, it is possible to change the solubility of the polyimide precursor in any solvent depending on the presence or absence of the basic substance, and furthermore, the solvent can be used as a developer to enable patterning by development. Therefore, as the polyimide precursor to be used in the present invention, a polyimide precursor in which the reaction to the final product is promoted by the action of a basic substance and the solubility is lowered by heating as compared with that before heating is suitably used.

Here, as the polyimide precursor, polyamic acid as represented by the following formula (X) is preferably used.

(X)

Figure 112011023960095-pct00009

(In the formula (X), R 11 is a tetravalent organic group and R 12 is a divalent organic group.)

The four valences of R < 11 > represent only a valence to be bonded to an acid, but may have an additional substituent. Likewise, although the valence of R 12 represents only a valence to bond with the amine, it may have an additional substituent.

Since polyamic acid is obtained only by mixing acid dianhydride and diamine in a solution, it can be synthesized by a one-step reaction, which is preferable because it is easy to synthesize and can be obtained at low cost.

In the case of using a polyimide precursor whose thermal curing temperature is lowered by catalytic action of a base such as polyamic acid, a pattern on a coated film or a molded article of the photosensitive resin composition obtained by combining such a polyamic acid with the photo- And irradiates electromagnetic waves to the desired portion. Then, a basic substance is generated in the irradiation portion, and the imidation temperature of the portion is selectively lowered. Subsequently, the irradiating portion is heated at a treatment temperature at which the imidization reaction does not occur, while the non-irradiated portion is partially imidized to such an extent that only the irradiated portion is not dissolved in at least the developer. Then, a non-irradiated portion is dissolved with a predetermined developer (such as an organic solvent or a basic aqueous solution) to form a pattern made of thermosetting resin. This pattern is further heated as necessary to complete the imidation. By the above process, a desired two-dimensional resin pattern (general plane pattern) or a three-dimensional resin pattern (three-dimensionally molded shape) is obtained.

In the present invention, the compound represented by the formula (I) functions as a high-sensitivity photobase generator, and the difference in solubility between the electromagnetic wave irradiated portion and the non-irradiated portion on the coated film or molded article of the photosensitive resin composition is made large Therefore, even when an organic solvent is used instead of a basic aqueous solution, excellent developability is obtained.

As a secondary effect, when the polyimide precursor to be used is a polyamic acid, it is sufficient that the temperature required for the imidization is low due to the catalytic effect of the basic substance, so that the final cure temperature is lower than 300 ° C, more preferably 250 ° C Or less. In order to imidize the conventional polyamic acid, it was necessary to set the final cure temperature to 300 DEG C or higher, so that the application was limited. However, since it is possible to lower the final cure temperature, it can be applied to a wider range of applications.

With respect to the polyimide precursor, in the application where the heat resistance and dimensional stability of the finally obtained polyimide are strictly required, the portion derived from the acid dianhydride has an aromatic structure, and the portion derived from the diamine also has a wholly aromatic It is preferably a polyimide precursor. Therefore, the structure derived from a diamine component is also preferably a structure derived from an aromatic diamine.

Here, the wholly aromatic polyimide precursor is a polyimide precursor and derivatives thereof obtained by copolymerization of an aromatic acid component and an aromatic amine component or by polymerization of an aromatic acid / amino component. The aromatic acid component means a compound in which all of the four acid groups forming the polyimide skeleton are substituted on the aromatic ring and the aromatic amine component means that both of the two amino groups forming the polyimide skeleton are substituted on the aromatic ring And the aromatic acid / amino component is a compound in which both an acid group and an amino group forming a polyimide skeleton are substituted on an aromatic ring. However, it is not necessary that all the acid groups or amino groups are present on the same aromatic ring, as is clear from the specific examples of the raw materials described later.

As a method for producing the polyimide precursor of the present invention, conventionally known methods can be applied. For example, (1) a method of synthesizing a polyamic acid which is a precursor from an acid dianhydride and a diamine. (2) Synthesis of a polyimide precursor by reacting a diamino compound or a derivative thereof with a carboxylic acid of an ester acid or an amide acid monomer synthesized by reacting an acid dianhydride with a monohydric alcohol, an amino compound, an epoxy compound or the like And the like, but the present invention is not limited thereto.

Examples of the acid dianhydride applicable to the polyimide precursor of the present invention include diethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetracarboxylic acid dianhydride Aliphatic tetracarboxylic acid dianhydrides such as water 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, (3, 4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis Di (2, 3-dicarboxyphenyl) methane dianhydride, bis (3, 4-dicarboxyphenyl) methane dianhydride, 2 , 2-bis (3,4-dicarboxyphenyl) -1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis Benzoyl benzene dianhydride, 1,4-bis [(3,4-dicarboxy) benzoyl] benzene dianhydride, 1,1,1,3,3,3,3,3-hexafluoropropane dianhydride, Benzene dianhydride, 2,2-bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} propane dianhydride,

2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} propane dianhydride, bis {4- [4- Water, bis [4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, 4,4'-bis [4- (1,2-dicarboxy) phenoxy] biphenyl dianhydride , Bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, 4- { Bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} sulfone dianhydride, bis {4- [3- Phenyl} sulfone dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} sulfide dianhydride, 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} -1,1,3,3 , 3-hexa Fluoropropane dianhydride, 1,2,3,6,7-naphthalenetetracarboxylic 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-perylenetetracarboxylic acid dianhydride, 2,3,6-anthracenetetracarboxylic acid dianhydride, 1,2,7,8- Terphenyl-3,3 ', 4'-tetracarboxylic dianhydride, p-terphenyl-3,3', 4'-tetracarboxylic dianhydride, , 3 ', 4,4'-tetracarboxylic acid dianhydride and the like, and the like. These may be used alone or in combination of two or more. Particularly preferred tetracarboxylic acid dianhydrides include pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-bis Bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3,4,6-biphenyltetracarboxylic acid dianhydride, - dicarboxyphenyl) -1,1,3,3,3,3-hexafluoropropane dianhydride.

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

On the other hand, the amine component may also be used as a single diamine or as a mixture of two or more diamines. The diamine component to be used is not limited, and examples thereof include aromatic diamines such as p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3,3'-diaminodiphenyl ether, Diaminodiphenylsulfide, 3, 3'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 3,3'- Diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, Diaminodiphenylmethane, 3, 4'-diaminodiphenylmethane, 2,2-di (3,3'-diaminodiphenylmethane, (3-aminophenyl) propane, 2, 2-di (3-aminophenyl) propane, 2- 1, 1, 3, 3, 3-hexafluoropropane, 2- (3-methylphenyl) -Aminophenyl) -2- (4-aminophenyl) -1, 1, 1, 3, (3-aminophenyl) -1-phenylethane, 1,1-di (4-aminophenyl) Benzene, 1,3-bis (4-aminophenoxy) benzene, 1,1-bis (4-aminophenoxy) Benzene, 1, 3-bis (4-aminobenzoyl) benzene, 1, Benzene, 1,4-bis (4-aminobenzoyl) benzene, 1,3-bis (3-amino-a, (4-amino-a, -dimethylbenzyl) benzene, 1,4-bis (3-amino-?,? - dimethylbenzyl) benzene, 1, 3-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4- Bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis Bis (3-aminophenoxy) benzene, benzene, 2,6-bis (3-aminophenoxy) benzonitrile, 2,6- Bis (4-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl]

Bis (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) 2-bis [4- (4-aminophenoxy) phenyl] propane, 2, Bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2- Benzoylbenzene, 1,3-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,2,3,4- Benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, Bis [4- (4-aminophenoxy) -?,? - dimethylbenzyl] benzene, 1,4-bis [ (4-aminophenoxy) -?,? - dimethylbenzyl] benzene, 4,4'-bis [4- (4-aminophenoxy ) Benzoyl] diphenyl ether, 4,4'-bis [4- (4-amino- alpha, alpha -dimethylbenzyl) phenoxy] benzophenone, (4-aminophenoxy) phenoxy] diphenyl sulfone, 3,3'-diamino-4,4'-diphenoxy Diamino-4-phenoxybenzophenone, 3,3'-diamino-4-biphenoxy, 3,3'-diamino-4-phenoxybenzophenone, (3-aminophenoxy) -3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane, 6,6'-bis Phenoxy) -3,3,3 ', 3 ' -tetramethyl-l, l '-spirobiindane;

Bis (3-aminopropyl) polydimethylsiloxane,?,? - bis (3-aminopropyl) tetramethyldisiloxane, Bis (3-aminopropyl) ether, bis (2-aminomethoxy) ethyl] ether, bis (aminomethyl) Bis (2-aminoethoxy) ethyl] ether, bis [2- (3-aminopropoxy) ethyl] (2-aminoethoxy) ethoxy] ethane, ethylene glycol bis (3-amino (methoxymethoxy) ethoxy] ethane, Diethyleneglycol bis (3-aminopropyl) ether, triethyleneglycol bis (3-aminopropyl) ether, ethylenediamine, 1, 3- diaminopropane, 1,4-diaminobutane, 1,5 -Diaminopentane, 1,6-diaminohexane, 1,7-diamine Aliphatic amines, such as heptane, 1, 8-diamino-octane, 1, 9-dia mi Nonomuria i, 1, 10-diamino-decane, 1, 11-diamino undecane, 1, Fig. 12-diamino-decane;

(2-aminoethyl) cyclohexane, 1, 2-diaminocyclohexane, 1, 3-diaminocyclohexane, 1,4-diaminocyclohexane, (Aminomethyl) bicyclo [2.2.1] heptane, 2, 5-dihydroxybenzoic acid, -Bis (aminomethyl) bicyclo [2.2.1] heptane, and the like. Examples of the guanamine include acetoguanamine and benzoguanamine, and a part or all of the hydrogen atoms in the aromatic ring of the diamine may be substituted with a fluorine group, a methyl group, a methoxy group, a trifluoromethyl group, or a trifluoromethoxy group May also be used.

Also, one or two or more kinds of an ethynyl group, a benzocyclobutene-4'-yl group, a vinyl group, an allyl group, a cyano group, an isocyanate group and an isopropenyl group, May be introduced into a part or all of the hydrogen atoms as a substituent.

The diamine can be selected according to the physical properties of the object, and when a rigid diamine such as p-phenylenediamine is used, the finally obtained polyimide has a low expansion rate. Examples of the rigid diamines include diamines having two amino groups bonded to the same aromatic ring. Examples of the diamines include p-phenylenediamine, m-phenylenediamine, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, Diaminonaphthalene, 2, 7-diaminonaphthalene, and 1,4-diaminoanthracene.

Further, diamines in which two or more aromatic rings are bonded by a single bond and two or more amino groups are respectively bonded to separate aromatic rings directly or as a part of a substituent, and examples thereof include a diamine represented by the following formula (XI) . Specific examples include benzidine and the like.

(XI)

Figure 112011023960095-pct00010

(a is a natural number of 1 or more, and the amino group is bonded to the meta position or the para position with respect to the bond between the benzene rings.)

In the formula (XI), a diamine having a substituent at a position at which the amino group on the benzene ring does not substitute for other benzene rings is not used. These substituents are monovalent organic groups, which may be bonded to each other.

Specific examples include 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 3,3'-dichloro- Diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, and 3,3'-dimethyl-4,4'-diaminobiphenyl.

When the finally obtained polyimide is used as an optical waveguide or an optical circuit part, the introduction of fluorine as a substituent of an aromatic ring can improve the transmittance to electromagnetic waves having a wavelength of 1 μm or less.

On the other hand, when a diamine having a siloxane skeleton such as 1,3-bis (3-aminopropyl) tetramethyldisiloxane is used as the diamine, the elastic modulus of the finally obtained polyimide lowers and the glass transition temperature can be lowered.

Here, the selected diamine is preferably an aromatic diamine in view of heat resistance, but may be an aromatic diamine such as an aliphatic diamine or a siloxane diamine in an amount not exceeding 60 mol%, preferably 40 mol% Other diamines may be used.

On the other hand, in order to synthesize a polyimide precursor, for example, a solution obtained by dissolving 4,4'-diaminodiphenyl ether in an organic polar solvent such as N-methylpyrrolidone as an amine component is cooled, Of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride is slowly added to the solution to obtain a polyimide precursor solution.

When the polyimide precursor thus synthesized is required to have heat resistance and dimensional stability to the finally obtained polyimide, it is preferable that the copolymerization ratio of the aromatic acid component and / or the aromatic amine component is as large as possible. Specifically, the proportion of the aromatic acid component in the acid component constituting the repeating unit of the imide structure is preferably 50 mol% or more, particularly preferably 70 mol% or more, and the proportion of the aromatic component in the amine component constituting the repeating unit of the imide structure The proportion of the amine component is preferably not less than 40 mol%, particularly preferably not less than 60 mol%, particularly preferably a wholly aromatic polyimide.

It is preferable that the polyimide precursor exhibits a transmittance of at least 5% or more with respect to the exposure wavelength at a film thickness of 5 占 퐉 and a transmittance of 15% or more with respect to the exposure wavelength in order to obtain a pattern shape that accurately reproduces the mask pattern by raising the sensitivity when the photosensitive resin composition is used. Or more of the transmittance.

The fact that the transmittance of the polyimide precursor to the exposure wavelength is high means that the loss of light is small so that a highly sensitive photosensitive resin composition can be obtained.

When exposure is performed using a high-pressure mercury lamp, which is a general exposure light source, when the transmittance of electromagnetic waves having a wavelength of at least 436 nm, 405 nm, and 365 nm to electromagnetic waves having a wavelength of 5 μm is formed , Preferably at least 5%, more preferably at least 15%, and even more preferably at least 50%.

In particular, when the film is formed into a film having a thickness of 5 탆, the transmittance for electromagnetic waves having a wavelength of 405 nm is preferably 5% or more, more preferably 15% or more, in view of combining with the photobase generator according to the present invention. , And even more preferably 50% or more.

The weight average molecular weight of the polyimide precursor varies depending on the use, but is preferably in the range of 3,000 to 1,000,000, more preferably in the range of 5,000 to 500,000, and still more preferably in the range of 10,000 to 500,000. When the weight average molecular weight is less than 3,000, sufficient strength is hardly obtained in the case of a coating film or a film. Further, when the polymer is made of a polyimide or the like by heat treatment or the like, the strength of the film is also lowered. On the other hand, when the weight-average molecular weight exceeds 1,000,000, the viscosity increases and the solubility decreases, so that it is difficult to obtain a coating film or film having smooth surface and uniform film thickness.

The molecular weight used herein refers to the value in terms of polystyrene calculated by gel permeation chromatography (GPC), and may be the molecular weight of the polyimide precursor itself, or may be obtained by chemical imidization treatment with acetic anhydride or the like.

The polyimide precursor is preferably a polar solvent. Examples of the solvent include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N, N-dimethylacetamide, N, N-dimethylmethoxyacetamide, dimethylsulfoxide, hexamethylphosphoramide, pyridine, dimethylsulfone, tetra Methylene sulfone, dimethyltetramethylene sulfone, diethylene glycol dimethyl ether, cyclopentanone,? -Butyrolactone,? -Acetyl-? -Butyrolactone, etc. These solvents may be used alone or in combination of two or more do. Non-polar solvents such as benzene, benzonitrile, 1,4-dioxane, tetrahydrofuran, butyrolactone, xylene, toluene, and cyclohexanone, which are used in combination as solvents, A dispersant, a reaction modifier or a volatile regulator of a solvent from a product, a film smoothing agent, and the like.

The photosensitive resin composition according to the present invention may be a simple mixture of the photo-base generator, the polyimide precursor and a solvent alone, but may be a sensitizer, a light or thermosetting component, a non-polymerizable binder resin other than the polyimide precursor, May be further blended to prepare a photosensitive resin composition.

As the solvent for dissolving, dispersing or diluting the photosensitive resin composition, various general-purpose solvents can be used. When a polyamic acid is used as the polyimide precursor, the solution obtained by the reaction for the synthesis of polyamic acid may be used as it is, and other components may be mixed therewith as needed.

When the absorption wavelength of the photobase generator overlaps with the absorption wavelength of the polyimide precursor and sufficient sensitivity can not be obtained, the addition of the sensitizer may be effective as a means for improving the sensitivity. Further, even when the photobase generator has an absorption wavelength at a wavelength band of an electromagnetic wave transmitted through the polyimide precursor, a sensitizer may be added as a means for improving the sensitivity. However, it is necessary to consider the deterioration of film properties, particularly the film strength and heat resistance, of the obtained pattern accompanied by the decrease of the content of the polyimide precursor by the addition of the sensitizer.

Specific examples of the compound referred to as a sensitizer include compounds such as thioxanthone and its derivatives such as diethylthioxanthone, cyanine and its derivatives, melocyanine and its derivatives, coumarin and its derivatives, ketocoumarin and its derivatives, And derivatives thereof, cyclopentanone and derivatives thereof, cyclohexanone and derivatives thereof, thiopyrylium salts and derivatives thereof, quinoline derivatives and derivatives thereof, styrylquinoline derivatives and derivatives thereof, thioxanthene derivatives and xanthene derivatives and derivatives thereof , Oxolone-based compounds and derivatives thereof, rhodamine-based compounds and derivatives thereof, pyrylium salts and derivatives thereof, and the like.

Specific examples of cyanine, melocyanine and derivatives thereof include 3,3'-dicarboxyethyl-2, 2 'thiocin bromide, 1-carboxymethyl-1'-carboxyethyl-2,2'-quinoxybromide, (3-ethyl-2 (3H) -benzothiazolylidene) ethylidene] -2-thioxo-2, 2'-quinotriacene iodide, -4-oxazolidine, and the like.

Specific examples of coumarin, ketocoumarin and derivatives thereof include 3- (2'-benzoimidazole) -7-diethylaminocoumarin, 3,3'-carbonylbis (7-diethylaminocoumarin) -Carbonylbiscumarin, 3,3'-carbonylbis (5,7-dimethoxycoumarin), and 3,3'-carbonylbis (7-acetoxycoumarin).

Specific examples of thioxanthone and its derivatives include diethylthioxanthone, isopropylthioxanthone and the like.

Other examples include benzophenone, acetophenone, anthrone, p, p'-tetramethyldiaminobenzophenone (Michler's ketone), phenanthrene, 2-nitrosfluorene, 5-nitroasenaphthene, benzoquinone, N- nitroaniline, 2-ethyl anthraquinone, 2-tert-butyl anthraquinone, N-acetyl-4-nitro-1-naphthylamine, Methyl-1,3-diaza-1,9-benzanthrone, p, p'-tetraethyldiaminobenzophenone, 2-chloro-4-nitroaniline, dibenzalacetone, 1,2- (4'-diethylaminobenzal) -cyclohexanone, 2,6-bis- (4'-diethylaminobenzal) -cyclopentane, 2,6- 4-methyl-cyclohexanone, 2,6-bis- (4'-diethylaminobenzal) -4-methyl-cyclohexanone, 4,4'-bis- (dimethylamino) Chalcone, 4,4'-bis- (diethylamino) -chalcone, p-dimethylaminobenzylideneindanone, 1,3-bis- (4'-dimethylamino Benzene) -acetone, 1, 3-bis- (4'-diethylaminobenzal) -acetone, N-phenyl-diethanolamine and N-p-tolyl-diethylamine.

In the present invention, one or more of these sensitizers may be used.

Examples of the solvent used in the composition include ethers such as diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether and propylene glycol diethyl ether; Glycol monoethers (so-called cellosolves) such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; Ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; Propyl acetate, n-butyl acetate, i-butyl acetate, acetic acid esters of the glycol monoethers (for example, methyl cellosolve acetate, ethyl cellosolve acetate ), Esters such as methoxypropyl acetate, ethoxypropyl acetate, dimethyl oxalate, methyl lactate, and ethyl lactate; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, and glycerin; Halogenated compounds such as methylene chloride, 1,1-dichloroethane, 1,2-dichloroethylene, 1-chloropropane, 1-chlorobutane, 1- chloropentane, chlorobenzene, bromobenzene, o-dichlorobenzene and m- Hydrocarbons; Amides such as N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide and N, N-diethylacetamide; Pyrrolidones such as N-methylpyrrolidone; lactones such as? -butyrolactone; Sulfoxides such as dimethyl sulfoxide and other organic polar solvents, and further aromatic hydrocarbons such as benzene, toluene and xylene, and other organic non-polar solvents. These solvents may be used alone or in combination.

Among these, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, Dimethyl sulfoxide, dimethylsulfoxide, hexamethylphosphoramide, N-acetyl-2-pyrrolidone, pyridine, dimethyl sulfone, tetramethylene sulfone, dimethyltetramethylene sulfone, diethylene glycol dimethyl ether, cyclopentanone, ? -butyrolactone,? -acetyl-? -butyrolactone, and the like.

As the photo-curable component, a compound having one or more ethylenic unsaturated bonds can be used, and examples thereof include amide-based monomers, (meth) acrylate monomers, urethane (meth) acrylate oligomers, polyester (Meth) acrylate, and aromatic vinyl compounds such as hydroxyl group-containing (meth) acrylate and styrene. When the polyimide precursor has a carboxylic acid component such as a polyamic acid in its structure, an ethylenically unsaturated bond-containing compound having a tertiary amino group is used to form an ionic bond with the carboxylic acid of the polyimide precursor, The contrast of the dissolution rate of the exposed portion and the unexposed portion when the composition is formed becomes large.

When such a photocurable compound having an ethylenically unsaturated bond is used, a photo-radical generator may be further added. Examples of photo radical generating agents include benzoin and alkyl ethers thereof such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; Acetophenone, 1,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxyacetophenone, 1-hydroxycyclohexyl Acetophenones such as phenyl ketone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one; Anthraquinone such as 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-tert-butyl anthraquinone, 1-chloro anthraquinone and 2-amylanthraquinone; Thioxanthones such as 2, 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisoprothioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Monoacylphosphine oxide or bisacylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Benzophenones such as benzophenone; And xanthones.

In order to impart processing characteristics and various functions to the resin composition of the present invention, various organic or inorganic low molecular weight or high molecular weight 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, and inorganic fine particles such as colloidal silica, carbon and layered silicate, and they may be porous or hollow. The functions or forms thereof include pigments, fillers, and fibers.

In the photosensitive resin composition according to the present invention, the polyimide precursor (solid content) is preferably not less than 30% by weight, not less than 50% by weight, and more preferably not less than 50% by weight based on the total solid content of the photosensitive resin composition, . The photobase generator represented by the above formula (I) is usually used in an amount of 0.01 to 50 parts by weight, preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the solid content of the polyimide precursor contained in the photosensitive resin composition . If the amount is less than 0.01 part by weight, the effect of accelerating the cyclization reaction tends to be insufficient. If the amount is more than 50 parts by weight, it is difficult to satisfy the physical properties required for the finally obtained resin cured product.

The blending amount of the sensitizer is preferably less than 50 parts by weight, more preferably less than 30 parts by weight based on 100 parts by weight of the solid content of the polyimide precursor. In order to prevent deterioration of the physical properties required for the resin cured product finally obtained, the total amount of the photo-base generating agent and the sensitizer represented by the formula (I) of the present invention is preferably 100 parts by weight or more relative to 100 parts by weight of the polyimide precursor 50 parts by weight or less.

The blending ratio of other arbitrary components is preferably in the range of 0.1 wt% to 20 wt% with respect to the total solid content of the photosensitive resin composition. If the amount is less than 0.1% by weight, the effect of adding the additive is difficult to be exerted, and if it exceeds 20% by weight, the properties of the finally obtained resin cured product are hardly reflected in the final product. Further, the solid content of the photosensitive resin composition is all the components other than the solvent, and the liquid monomer component is also included in the solid content.

The photosensitive resin composition according to the present invention can be used in various coating processes or molding processes to produce a film or a molded article having a three-dimensional shape.

The polyimide obtained from the photosensitive resin composition of the present invention does not impair intrinsic properties such as heat resistance, dimensional stability, and insulation, and is good.

For example, the 5% weight reduction temperature measured in nitrogen of the polyimide obtained from the photosensitive resin composition of the present invention is preferably 250 DEG C or higher, more preferably 300 DEG C or higher. Particularly, in the case of using for an electronic part or the like which allows the solder reflow process to pass, when the 5% weight reduction temperature is 300 ° C or less, problems such as bubbles are caused by the decomposition gas generated in the solder reflow process There is a concern.

Here, the 5% weight reduction temperature refers to the temperature at which the weight of the sample decreases 5% from the initial weight when the weight loss is measured using a thermogravimetric analyzer (that is, the point at which the sample weight becomes 95% of the initial weight). Likewise, the 10% weight reduction temperature is the temperature at which the sample weight is reduced by 10% from the initial weight.

The glass transition temperature of the polyimide obtained from the photosensitive resin composition of the present invention is preferably as high as possible from the viewpoint of heat resistance but is preferably in the range of from 120 to 450 ° C in applications where a thermoforming process is considered, And more preferably a glass transition temperature of about 200 ° C to 400 ° C. When the polyimide obtained from the photosensitive resin composition can be made into a film, the glass transition temperature in the present invention can be measured by dynamic viscoelasticity measurement to determine tan δ (tan δ = loss elastic modulus (E ") / storage elastic modulus (E ')) The dynamic viscoelasticity measurement can be performed, for example, by a viscoelasticity measuring device, Solid Analyzer RSA II (manufactured by Rheometric Scientific) at a frequency of 3 Hz and a temperature raising rate of 5 ° C / min. When the polyimide can not be formed into a film, it is determined as the temperature of the inflection point of the baseline of the differential thermal analysis apparatus (DSC).

From the viewpoint of dimensional stability of the polyimide obtained from the photosensitive resin composition of the present invention, the coefficient of linear thermal expansion is preferably 60 ppm or less, more preferably 40 ppm or less. When a film is formed on a silicon wafer in a manufacturing process of a semiconductor device or the like, it is more preferably 20 ppm or less from the viewpoints of adhesion and warping of the substrate. Herein, the coefficient of linear thermal expansion in the present invention can be obtained by a thermomechanical analyzer (TMA) of a film of polyimide obtained from the photosensitive resin composition obtained in the present invention. The heating rate is set at 10 ° C / min by a thermomechanical analyzer (for example, Thermo Plus TMA8310 (manufactured by Rigaku)), and the tensile weight is set to 1 g / 25000 μm 2 so that the weight per unit area of the evaluation sample becomes the same.

As described above, in the photosensitive polyimide resin composition according to the present invention, the compound represented by the formula (I) functions as a photoreactive base generator with high sensitivity, so that a wide variety of polyimide precursors can be applied and the finally obtained polyimide Can be selected from a wide range.

Further, according to the present invention, the photosensitive polyimide resin composition can be obtained by a simple method of mixing the photo-base generator represented by the formula (I) of the present invention with the polyimide precursor, and the cost performance is also excellent .

Furthermore, since the catalytic effect of the amine generated by the irradiation of electromagnetic waves can reduce the processing temperature required for the reaction with the final product such as imidization, it is possible to reduce the damage caused by heat to the process or to the product It is possible to do.

The photosensitive resin composition according to the present invention can be applied to all known fields and products using resin materials such as printing ink, adhesive, filler, electronic material, optical circuit component, molding material, resist material, .

The photosensitive resin composition according to the present invention can be applied to a wide range of fields and products in which properties such as heat resistance, dimensional stability, and insulation are effective, such as paints or printing inks or color filters, films for flexible displays, semiconductor devices, , A wiring coating film, an optical circuit, an optical circuit component, an antireflection film, a hologram, an optical member, or a building material. Specifically, for example, a buffer coat film for a semiconductor device, an interlayer insulating film of a multilayer wiring board, and the like can be given.

Particularly, since the photosensitive resin composition of the present invention is mainly used as a pattern forming material (resist), and the pattern formed thereby serves as a permanent film made of polyimide as a component for imparting heat resistance and insulating property, It is suitable for forming a display film, an electronic part, a semiconductor device, an interlayer insulating film, a wiring coating film, an optical circuit, an optical circuit component, an antireflection film, and other optical members or electronic members.

In the present invention, the photosensitive resin composition according to the present invention or a printed matter in which at least a part thereof is formed by the thermosetting resin, a color filter, a film for a flexible display, a semiconductor device, an electronic component, an interlayer insulating film, , An optical circuit component, an antireflection film, a hologram, an optical member, or a building material.

Next, a negative pattern forming method according to the present invention will be described.

The negative pattern forming method according to the present invention is a negative pattern forming method according to the present invention, in which a surface of a coating or a molded article made of the photosensitive resin composition according to the present invention is irradiated with electromagnetic waves in a predetermined pattern, Characterized in that the solubility of the electromagnetic wave irradiated portion of the molded article is selectively lowered and then developed.

When the photosensitive resin composition according to the present invention is coated on a support and electromagnetic waves are irradiated in a predetermined pattern shape, the photo-basic substance is decomposed only in the exposed portion to generate a basic substance. The basic substance functions as a catalyst for promoting the reaction of the polyimide precursor in the exposed portion to the final product.

In the case where the polyimide precursor in the exposed portion directly reacts with the final product by the basic substance and the solubility of the polyimide precursor in the exposed portion is selectively lowered, it is preferable that the solubility of the exposed portion in the solvent Can be used as a developing solution to dissolve only the unexposed portion which has not been degraded in solubility.

The photosensitive resin composition of the present invention may contain at least one selected from the group consisting of N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, , N, N-dimethylmethoxyacetamide, dimethylsulfoxide, hexamethylphosphoramide, N-acetyl-2-pyrrolidone, pyridine, dimethylsulfone, tetramethylene sulfone, dimethyltetramethylene sulfone, diethylene glycol dimethyl ether , A silicon wafer, a metal substrate, a ceramic substrate, and the like by a dipping method, a spraying method, a screen printing method, or a spin coating method after dissolving in a polar solvent such as cyclopentanone,? -Butyrolactone,? -Acetyl- A coating film having no tackiness can be imparted to the surface of the substrate by applying the coating solution to the surface of the substrate such as a substrate and removing most of the solvent by heating. The thickness of the coating film is not particularly limited, but is preferably 0.5 to 50 탆, and more preferably 1.0 to 20 탆 in terms of sensitivity and developing speed. The drying condition of the coated film is, for example, 80 to 100 ° C for 1 minute to 20 minutes.

A desired patterned film can be obtained by irradiating the coating film with electromagnetic waves through a mask having a predetermined pattern to perform exposure in a pattern form, heating and then developing the unexposed portion of the film with an appropriate developing solution.

The exposure method and the exposure apparatus used in the exposure process are not particularly limited and may be indirect exposure or indirect exposure or may be a contact / proximity exposure apparatus using a g line stepper, an i-line stepper, an ultra high pressure mercury lamp, a mirror projection exposure apparatus, , A visible light, an X-ray, an electron beam, or the like can be used.

In the negative pattern forming method according to the present invention, post-treatment such as heat treatment may be performed between the exposure step and the developing step as necessary. Here, the post-treatment is a treatment for selectively lowering the solubility of the coating film or the molded article in a solvent of the electromagnetic wave irradiation site.

The post-treatment such as heat treatment is a treatment for causing the polyimide precursor in the exposed portion coexisting with the basic substance to react with the final product. Therefore, in the case of performing the heat treatment, it is preferable that the heat treatment is carried out at a temperature at which the rate of conversion of the polyimide precursor in the exposed portion in which the basic substance exists and in the unexposed portion in which the basic substance is not present is different.

For example, when polyamic acid is imidized, the preferable temperature range of the heat treatment at this stage is usually about 60 to 200 占 폚. If the heat treatment temperature is lower than 60 占 폚, the imidization efficiency becomes poor, and it becomes difficult to create a difference in the imidization ratio between the exposed and unexposed portions under realistic process conditions. On the other hand, when the heat treatment temperature is 200 ° C or higher, a neutral compound which generates a basic substance due to an intracellular decomposition reaction accompanying the absorption of electromagnetic waves is thermally decomposed or imidization proceeds even in an unexposed portion where amines are not present, It is difficult to obtain a difference in solubility between the minerals and the minerals.

Concretely, for example, heating is carried out at 120 to 200 ° C for 1 minute to 20 minutes.

The heat treatment may be any known method, and examples thereof include a circulating oven under air or a nitrogen atmosphere, heating with a hot plate, and the like, but there is no particular limitation.

The developing solution used in the developing step is not particularly limited and may be suitably selected in accordance with the polyimide precursor to be used, such as a basic aqueous solution or an organic solvent.

The basic aqueous solution is not particularly limited. For example, it is possible to use aqueous solution of tetramethylammonium hydroxide (TMAH) at a concentration of 0.01 wt% to 10 wt%, preferably 0.05 wt% to 5 wt% But are not limited to, ethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogen carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, , Cyclohexylamine, ethylenediamine, hexamethylenediamine, tetramethylammonium and the like.

The solute may be one kind or two kinds or more, and 50% or more, more preferably 70% or more of the total weight, and an organic solvent if water is contained.

Examples of the organic solvent include, but are not limited to, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, Polar solvents such as methanol, ethanol and isopropanol; esters such as ethyl acetate and propylene glycol monomethyl ether acetate; ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone; Or two or more kinds thereof may be added in combination. After development, cleaning is carried out with water. In this case, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water.

After development, rinse with water or a poor solvent as needed, and dry at 80 to 100 캜 to make the pattern stable. In order to make the relief pattern heat-resistant, by heating at a temperature of 180 to 500 ° C, preferably 200 to 350 ° C for several tens of minutes to several hours, the imidization proceeds completely to form a patterned high heat-resistant resin layer.

<Examples>

[Synthesis Example 1]

10.9 g of 2-nitro-4, 5-dimethoxybenzaldehyde (Tokyo Chemical Reagent) was dissolved in 150 ml of anhydrous tetrahydrofuran, cooled to 0 캜 with stirring in a nitrogen stream, and 50 ml of a tetrahydrofuran solution of phenylmagnesium bromide 1 mol / L, manufactured by Aldrich) was added dropwise over 15 minutes.

After completion of the dropwise addition, 7.51 g of cyclohexyl isocyanate (Tokyo Chemical Industry Co., Ltd.) was added to the reaction solution at room temperature, and the mixture was left stirring overnight for 5 hours.

On the next day, an aqueous solution (100 ml of water) in which 3.2 g of ammonium chloride was dissolved was added and stirred for 10 minutes. The mixture was extracted with ethyl acetate. The organic phase was washed with a saturated aqueous solution of sodium hydrogencarbonate and washed with water. A solid was obtained. The obtained solid was purified by column chromatography using a mixed solvent of hexane and ethyl acetate, and the fraction was concentrated to obtain N- (? -Phenyl-2-nitro-4,5-dimethoxybenzyloxycarbonyl) cyclohexylamine (1.2 g of light yellow crystals of the photobase generator 1).

It was confirmed by 1 H-NMR that this crystal was N- (α-phenyl-2-nitro-4,5-dimethoxybenzyloxycarbonyl) cyclohexylamine represented by the following formula (1.0-2.0 ppm m 10H-CH2-, 3.5 ppm m 1H-CH-N, 3.9 ppm s 6H OCH3, 4.7 ppm d 1H NH, 7.1 ppm s 1HCH-O, 7.2-7.7 ppm 7H aromatic CH)

Figure 112011023960095-pct00011

[Synthesis Example 2]

(Α-phenyl-2-nitro-4,5-dimethoxybenzyloxycarbonyl) morpholine (prepared in Example 1) was obtained in the same manner as in Example 1 except that 7.5 g of morpholine carbonyl chloride was used instead of cyclohexyl isocyanate 9.6 g of light yellow crystals of the photo-base generator 2) were obtained.

This crystal was confirmed to be N- (? -Phenyl-2-nitro-4, 5-dimethoxybenzyloxycarbonyl) morpholine represented by the following formula by 1 H-NMR. (3.4-3.7 ppm 8H OCH 2 CH 2 N , 3.9 ppm 6H OCH3, 6.9 ppm s 1HCH-O, 7.2-7.7 ppm 7H aromatic CH)

Figure 112011023960095-pct00012

[Synthesis Example 3]

To a 100 ml two-necked flask were added 1.25 g of N- (? -Phenyl-2-nitro-4,5-dimethoxybenzyloxycarbonyl) cyclohexylamine synthesized in Synthesis Example 1, 1.9 g of tetrahydrofuran Amide (2.0 ml) was added and dissolved. 0.144 g of sodium hydride was added while cooling with ice. Then, methyl iodide (0.56 ml) was added thereto, stirred at 0 ° C for 10 minutes, and refluxed with heating for 7 hours. When solidified, 10 ml of dimethylformamide was added and dissolved, and the reaction solution was added to a 10 wt% hydrochloric acid aqueous solution (22 ml). Ethyl acetate (22 ml) was added to extract and the organic layer was dehydrated with anhydrous magnesium sulfate. The resulting solid was purified using silica gel chromatography to obtain N- (α-phenyl-2-nitro-4,5-dimethoxy Benzyloxycarbonyl) cyclohexylmethylamine (photo-base generator 3) as a light yellow solid. The obtained solid was identified by 1 H-NMR to be N- (α-phenyl-2-nitro-4,5-dimethoxybenzyloxycarbonyl) cyclohexylmethylamine represented by the following formula (1.0-2.0 ppm m 10 H -CH 2 -, 2.8 ppm s 3 H NCH 3, 3.9 ppm m 1H -CH-N, 3.9 ppm s 6 H OCH 3, 7.1 ppm s 1H CH-O, 7.2-7.7 ppm 7H aromatic CH)

Figure 112011023960095-pct00013

[Synthesis Example 4]

5.8 g of? -Phenyl-2-nitro-4, 5-dimethoxybenzyl alcohol, 4.4 g of nitrophenyl chloroformate and 0.1 g of N, N-dimethyl-4-aminopyridine (DMAP) were placed in a 200- Under nitrogen flow, a mixture of dehydrated N, N-dimethylacetamide (80 ml) and triethylamine (4.1 g) was added dropwise while cooling with ice, and the mixture was stirred for 3 hours. Thereafter, the mixture was stirred at room temperature for 2 hours, and 1.4 g of nitrophenyl chloroformate was drawn and stirred overnight. The next day, the reaction solution was poured into 1.5 L of ice water, stirred until the ice melted, and then subjected to suction filtration, and the obtained solid was washed with water. Extraction was carried out using ethyl acetate, and the organic layer was dehydrated with sodium sulfate and then concentrated in an evaporator to obtain 11.2 g of a yellow solid. Phenyl-2-nitro-4, 5-dimethoxybenzyl-4-nitrophenyl carbonate as a yellow green solid was obtained by HPLC with a purity of 97.7 area% , And an isolation yield of 50%.

phenyl-2-nitro-4,5-dimethoxybenzyl-4-nitrophenyl carbonate, 0.4 g of 1-hydroxy-7-azabenzotriazole (HOAt) 6.7 g of piperidine and 50 ml of dehydrated N, N-dimethylacetamide were placed in a 300 ml flask, and stirred at 60 DEG C for 3 hours under a nitrogen stream, followed by stirring at 70 DEG C for 1 hour. The reaction solution was poured into 1.4 L of 1 wt% sodium hydrogencarbonate, and the precipitated solid was subjected to suction filtration. The solid of the filtrate was washed with 1% by weight of sodium hydrogencarbonate until the filtrate became colorless transparent, and then washed with water. The resulting solid was transferred to an Erlenmeyer flask, and 200 ml of ethyl acetate was added, followed by dehydration with sodium sulfate and concentration in an evaporator. The obtained solid was purified by means of medium pressure preparative chromatography (YFLC-Eprep, Yamazen K.K.) using a mixed solvent of hexane and ethyl acetate, and the fraction was concentrated to obtain 3.6 g of a solid having an HPLC purity of 97.2 area%. This was recrystallized again using a mixed solvent of ethanol and hexane (volume ratio 1: 8) to obtain N- (α-phenyl-2-nitro-4,5-dimethoxybenzyloxycarbonyl) 2, 6-dimethylpiperidine (photobase generator 4). The HPLC purity was 98.5 area%, and the isolation yield to? -Phenyl-2-nitro-4, 5-dimethoxybenzyl alcohol was 36%. This compound was identified by 1 H-NMR (1.0 ppm d 3 H -CH 3 , 1.3 ppm d 3 H -CH 3 , 1.4-1.9 ppm m 6 H -CH 2 -, 3.9 ppm s 6 H 2 OCH 3 , 3.9 ppm s 6 H OCH 3 , 4.4 ppm m 2H -CH-N, 7.1 ppm s 1H CH-O, 7.2-7.7 ppm 7H aromatic CH).

Figure 112011023960095-pct00014

[Synthesis Example 5]

except that? - (4-nitrophenyl) -2-nitro-4,5-dimethoxybenzyl alcohol was used in place of? -phenyl-2-nitro-4,5-dimethoxybenzyl alcohol. By the same procedure, a solution of N- (α- (4-nitrophenyl) -2-nitro-4,5-dimethoxybenzyloxycarbonyl) -2,6-dimethylpiperidine 5) was synthesized (isolation yield: 33%). This compound was identified by 1 H-NMR (1.1 ppm d 3 H -CH 3 , 1.3 ppm d 3 H -CH 3 , 1.4-1.9 ppm m 6 H -CH 2 -, 3.9 ppm s 3 H OCH 3 , 3.9 ppm s 3 H OCH 3, 4.4ppm m 2H -CH- N, 7.1ppm s 1H CH-O, 7.5-8.2ppm 6H aromatic CH).

Figure 112011023960095-pct00015

[Synthesis Example 6]

(2-nitro-4,5-dimethoxyphenyl) -2-nitro-4, 5-dimethoxybenzyl alcohol instead of using? -phenyl- (Α- (2-nitro-4,5-dimethoxyphenyl) -2-nitro-4,5-dimethoxybenzyloxycarbital represented by the following formula by the same procedure as in Synthesis Example 4, (2,6-dichlorophenyl) boryl) -2, 6-dimethylpiperidine (photobase generator 6) was synthesized (isolation yield: 16%). This compound was identified by 1 H-NMR (1.3ppm d 6H -CH 3, 1.4-1.9ppm m 6H -CH 2 -, 3.7ppm s 6H OCH 3, 4.0ppm s 6H OCH 3, 4.3ppm m 2H - CH-N, 6.7 ppm s 2H aromatic C, 7.7 ppm s 2H aromatic C, 7.9 ppm s 1H CH-O).

Figure 112011023960095-pct00016

[Synthesis Example 7]

N- (α-phenyl-2-nitro-4-naphthoquinolin-4-yl) -4,5-dicarboxylic acid represented by the following formula was obtained by the same procedure as in Synthesis Example 4 except that piperidine was used instead of cis- 5-dimethoxybenzyloxycarbonyl) piperidine (photobase generator 7) was synthesized (isolation yield: 16%). This compound was identified by 1 H-NMR (1.4-1.8 ppm m 6 H -CH 2 -, 3.5 ppm br 4 H -CH 2 -N, 3.9 ppm s 3 H OCH 3 , 3.9 ppm s 3 H OCH 3 , 7.0 ppm s 1H CH-O, 7.2-7.7 ppm 7H aromatic CH).

Figure 112011023960095-pct00017

[Comparative Synthesis Example 1]

Referring to Japanese Patent Application Laid-Open No. 6-345711, from 6.24 g of 2-nitro-4, 5-dimethoxybenzyl alcohol and 5.13 g of cyclohexyl isocyanate, 9.53 g of 2-nitro-4, 5-dimethoxybenzyloxycar (Comparative photoacid generator 1) was obtained.

[Comparative Synthesis Example 2]

Under a nitrogen atmosphere, 8.2 g of 4, 5-dimethoxy-2-nitrobenzaldehyde in 100 ml of dehydrated 2-propanol in a 200 ml three-necked flask equipped with a Dean-Stark apparatus was added, and 2.0 g of aluminum isopropoxide was added thereto Lt; 0 &gt; C for 7 hours. 40 mL of 2-propanol was added 4 times while evaporation of the solvent was reduced. The reaction was terminated with 150 mL of 0.2N hydrochloric acid, followed by extraction with chloroform. The solvent was distilled off under reduced pressure to obtain 7.2 g of 6-nitroberatryl alcohol.

Under a nitrogen atmosphere, 5.3 g of 6-nitroveratryl alcohol in a 200 mL three-necked flask was dissolved in 100 mL of dehydrated dimethylacetamide, and 7.0 mL of triethylamine was added. P-Nitrophenyl chloroformate (5.5 g) was added in an ice bath, and the mixture was stirred at room temperature for 16 hours. The reaction solution was poured into 2 L of water and the resulting precipitate was filtered and purified by silica gel column chromatography to obtain 6.4 g of 4, 5-dimethoxy-2-nitrobenzyl-p-nitrophenyl carbonate.

In a 100 mL three-necked flask, 3.6 g of 4, 5-dimethoxy-2-nitrobenzyl-p-nitrophenyl carbonate was dissolved in 50 mL of dehydrated dimethylacetamide under a nitrogen atmosphere, 5 mL of 2, 6- dimethylpiperidine, 0.36 g of 1-hydroxybenzotriazole was added and the mixture was heated and stirred at 90 캜 for 18 hours. The reaction solution was poured into 1 L of a 1% aqueous solution of sodium hydrogencarbonate and the resulting precipitate was filtered and washed with water to give N - {[(4, 5-dimethoxy- Nitrobenzyl) oxy] carbonyl} -2, 6-dimethylpiperidine (comparative photo-base generating agent 2) was obtained.

[Synthesis Example 3: Synthesis of polyimide precursor]

20.0 g (100 mmol) of 4,4'-diaminodiphenyl ether and 200 mL of dehydrated N-methylpyrrolidone were placed in a nitrogen-substituted 500 mL four-neck separable flask, and the mixture was stirred and dissolved in an ice bath. 29.4 g (100 mmol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride was added to this solution, and the mixture was stirred for 2 hours in an ice bath. The reaction solution was reprecipitated with acetone, filtered and the resulting precipitate was dried under reduced pressure at room temperature for 8 hours to obtain polyamic acid (polyimide precursor 1) as a white solid quantitatively.

<Test>

(1) Measurement of molar extinction coefficient

Photocatalytic groups 1 to 7 and comparative photocatalytic groups 1 and 2 were each weighed using an electronic balance and an acetonitrile solution with a concentration of 10 -4 mol / L was prepared by using a mass flask. This solution was placed in a quartz cell (optical path length 1 cm), and the ultraviolet-visible absorption spectrum in a wavelength range of 190 to 800 nm was measured by a spectrophotometer (UV-2550, manufactured by Shimadzu Corporation). The molar extinction coefficient? (365, 405, 436 nm) was measured from the absorbance obtained in the spectrum according to the following formula. The results are shown in Table 1. It was found that the photobase generators 1 to 6 used in the present invention absorb light having wavelengths of 405 and 436 nm. It was found that the photo-base generator 7 absorbs light having a wavelength of 405 nm. It was found that the comparative photocatalysts 1 and 2 do not absorb the light at a wavelength of 436 nm but are weaker than the photocatalytic photoconductors 1 to 7 at 405 nm.

Figure 112011023960095-pct00018

(2) Measurement of optical resolution

For the photobase generators 1 to 7 and the comparative photobase generators 1 to 2, 1.0 mg of a quartz NMR tube was weighed using an electronic balance and 0.5 mL of acetonitrile was added and dissolved. The entire wavelength of the high-pressure mercury lamp (SPOT CURE SP-III 250 UA, lamp type number: USH-255BY, manufactured by Ushiodeni Co., Ltd.) was passed through the filter 1 which does not transmit wavelengths of 350 nm or less through this sample to 100 J / (UIT-150 made by Ushio Denki Co., UVD-S365), 18.2 J / cm 2 (i line converted: UV light meter: , And the NMR spectra before and after irradiation were compared to evaluate the photodegradability in the wavelength range of i (365 nm) or more.

Similarly, the total wavelength of the high-pressure mercury lamp was changed to 100 J / cm 2 (i line conversion: ultraviolet light illuminance meter: UIT-150 manufactured by Usuio Denki Co., Ltd., receiver: UVD-S365) via a filter 2 which does not transmit wavelengths of 380 nm or less, (UIT-101 manufactured by Ushio Denki Co., Ltd., UVD-405PD), after passing through the filter, 0 J / cm 2 (i line conversion: UV light meter: UIT- Light 405 (UVD-S365) and 160J / cm2 (h line conversion: UV illuminometer: UIT-101 manufactured by Ushio Denki Co., Ltd., UVD-405PD) Nm) or more.

Fig. 1 shows the transmittance curves of the filter 1 and the filter 2. Table 2 shows the evaluation results of photodegradability.

Figure 112011023960095-pct00019

It has been clarified that the photobase generators 1 to 7 are photodegradable in the wavelength region of i-line and h-line. It was clear that Comparative Photobase Generators 1 and 2 had no photodegradability in the h line and that the sensitivity of the i line was lower than that in Photobase generators 1 to 7. [

(3) Measurement of thermal stability

TG-DTA measurement was performed on the photo-base generators 1 to 7 and the comparative photo-base generators 1 and 2 using a DTG-60 (Shimadzu Corporation) at a rate of 10 ° C / min from 30 ° C to 600 ° C . A 5% weight reduction temperature was calculated, and heat resistance was evaluated. The evaluation results of the heat resistance are shown in Table 3.

Figure 112011023960095-pct00020

Photobase generators 1 to 7 and comparative photobase generators 1 and 2 were found to have a 5% weight reduction temperature of 200 ° C or more.

(Example 1)

0.2 g of the photo-base generator 1, 1 g of the polyimide precursor 1 and 9 g of N-methylpyrrolidone were dissolved to obtain a photosensitive resin composition (photosensitive resin composition 1) of the present invention.

(Example 2)

0.18 g of the photobase generator 1, 1.2 g of the polyimide precursor 1 and 8.8 g of N-methylpyrrolidone were dissolved to obtain the photosensitive resin composition (photosensitive resin composition 2) of the present invention.

(Example 3)

0.18 g of the photo-base generator 3, 1.2 g of the polyimide precursor 1 and 8.8 g of N-methylpyrrolidone were dissolved to obtain a photosensitive resin composition (photosensitive resin composition 3) of the present invention.

(Comparative Example 1)

0.18 g of the comparative photo-acid generator 1, 1.2 g of the polyimide precursor 1 and 8.8 g of N-methyl pyrrolidone were dissolved to obtain a photosensitive resin composition (comparative photosensitive resin composition 1).

(Comparative Example 2)

0.18 g of the comparative photo-base generator 2, 1.2 g of the polyimide precursor 1 and 8.8 g of N-methyl pyrrolidone were dissolved to obtain a photosensitive resin composition (comparative photosensitive resin composition 2).

[evaluation]

(1) Heat curing temperature

The photosensitive resin composition 1 was used to compare a coating film in which an amine was generated from a photobase generator and a coating film in which an amine was not generated from a photobase generator without exposure to obtain a polyimide precursor The difference in the imidization rate was observed.

The photosensitive resin composition 1 was spin-coated on a chromium-plated glass plate to a final film thickness of 1 탆 and dried on a hot plate at 100 캜 for 5 minutes. Then, 2J / cm 2 ultraviolet-visible light irradiation was performed in an i-line conversion with a manual exposure device (Dainippon Chemical Co., MA-1100). The coating film and the unexposed coating film were measured by infrared spectroscopy using FTS7000 manufactured by Varian Co., and HOTPLATE EC-1200 manufactured by Asuzen Co., Ltd., heating from room temperature to 5 ° C / min up to 300 ° C.

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 imidation, a peak height of 1770 cm &lt; -1 &gt; derived from the produced polyimide after measurement was plotted.

The results are shown in Fig. The coating film in which the amine is generated from the photobase generator by exposure is lower in temperature than the coating film which does not generate amine from the photobase generator of unexposed light at a lower temperature and the difference in the imidization ratio due to the presence or absence of the amine And reached a maximum at around 170 ° C. It was found that the PEB temperature is preferably 140 to 200 DEG C from the difference in the imidization ratio between the exposed portion and the unexposed portion.

(2) Pattern formation

The photosensitive resin composition 2 was dried on a glass plate, spin-coated to a film thickness of 10 mu m, and dried on a hot plate at 100 DEG C for 15 minutes. Irradiated with ultraviolet visible light of 3000 mJ / cm 2 in terms of i-line with a manual exposure apparatus (Dainippon Kagaku, MA-1100), and then heated on a hot plate at 145 ° C for 10 minutes. Then, tetramethylammonium hydroxide To the seed 2.38% solution was immersed in a solution containing 10% by weight of isopropanol. As a result, a pattern in which the exposed portion remained without dissolving in the developer was obtained. Further, these samples were heated at 300 DEG C for 1 hour to perform imidization.

From these results, it became clear that the photosensitive resin composition of the present invention can form a good pattern.

Similarly, the pattern formation was carried out using the photosensitive resin composition 3, and a pattern in which the exposed portions remained without dissolving in the developing solution at the time of 3000 mJ / cm 2 exposure could be obtained.

Further, the pattern was formed using the comparative photosensitive resin composition 1 in the same manner, but the residual film ratio in the exposed portion was lowered even at 6000 mJ / cm 2 exposure, and a good pattern film could not be obtained.

In addition, the pattern was formed using the comparative photosensitive resin composition 2 in the same manner. However, even when the exposure was performed at 6000 mJ / cm 2, the residual film ratio in the exposed portion decreased and a good pattern film could not be obtained.

none

Claims (15)

A photosensitive resin composition comprising a photobase generator represented by the formula (I) and a polyimide precursor.
<Formula I>
Figure 112011023960095-pct00021

(In the general formula (Ⅰ), R 1 and R 2 each independently represents a have also containing from 1 to 12 carbon atoms may have an alkyl group or a substituent having 6 to 12 carbon atoms, aryl group of which that substituent, the R 1 and R 2 An alkylene group having 1 to 24 carbon atoms which may have a substituent and an arylene group having 6 to 24 carbon atoms which may have a substituent,
R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent or an aryl group having 6 to 12 carbon atoms which may have a substituent, and at least one of R 3 and R 4 is not a hydrogen atom , R 3 and R 4 may be connected to form a cyclic structure which may contain a hetero atom,
R 5 to R 9 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyano group, , An acyloxy group having 1 to 12 carbon atoms, a nitro group, or an acyl group having 1 to 12 carbon atoms. The photosensitive resin composition according to claim 1, wherein R 3 and R 4 in the photo-base generator are a hydrogen atom or an alkyl group having 1 to 12 carbon atoms which may have a substituent. The photosensitive resin composition according to claim 2, wherein R 3 and R 4 in the photobase generator are alkyl groups having 1 to 12 carbon atoms which may have a substituent. The photosensitive resin composition according to claim 1, wherein R 3 and R 4 are connected to form a cyclic structure which may contain a hetero atom in the photobase generator. The photosensitive resin composition according to any one of claims 1 to 4, wherein R 1 and R 2 are methyl groups in the photobase generator represented by the formula (I). The photosensitive resin composition according to any one of claims 1 to 4, wherein the polyimide precursor itself promotes the reaction to the final product by the action of a basic substance. The photosensitive resin composition according to any one of claims 1 to 4, wherein the polyimide precursor is a photosensitive resin which is itself itself capable of promoting the reaction to the final product by the action of a basic substance and changing its solubility by heating Composition. The photosensitive resin composition according to any one of claims 1 to 4, further comprising a sensitizer. The photosensitive resin composition according to any one of claims 1 to 4, wherein the polyimide precursor is polyamic acid. The photosensitive resin composition according to any one of claims 1 to 4, wherein the photobase generator has photodegradability to an electromagnetic wave having a wavelength of 400 nm or more. The photosensitive resin composition according to any one of claims 1 to 4, wherein the 5% weight reduction temperature of the photobase generator is 170 占 폚 or higher. delete A cured product of the photosensitive resin composition according to any one of claims 1 to 4. A method for producing a photosensitive resin composition comprising the steps of irradiating electromagnetic waves in a predetermined pattern on the surface of a coating film or a molded article comprising the photosensitive resin composition according to any one of claims 1 to 4 to selectively lower the solubility of the electromagnetic- Is formed. 15. The negative pattern forming method according to claim 14, wherein a heat treatment is performed after irradiation of an electromagnetic wave to selectively lower the solubility of the electromagnetic radiation site of the coated film or the molded article.
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Family Cites Families (16)

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