TWI662368B - Photosensitive resin composition, its dry film and cured product, electronic parts or optical products containing cured product, and adhesive containing photosensitive resin composition - Google Patents

Abstract

Provides a large contrast ratio (solubility contrast) in the development speed between exposed and unexposed areas caused by active light irradiation, and can easily form a photosensitive resin composition with high accuracy.

A photosensitive resin composition characterized by containing (A) at least one repeating unit having polyamic acid and polyamino acid obtained from an acid anhydride component having an aliphatic skeleton and an aromatic skeleton and an amine component And (B) a photoreactive latent basic substance that generates a base by irradiation with active light.

Description

Photosensitive resin composition, its dry film and cured product, electronic parts or optical products containing cured product, and adhesive containing photosensitive resin composition

The present invention relates to the photosensitivity of a polymer precursor containing at least one repeating unit of a polyamic acid and a polyamic acid ester, and a photoreactive latent alkaline substance that generates a base upon irradiation with active light. A resin composition, a dry film having the composition, a hardened product of the composition (generally a relief pattern film (polymer film)), and an electronic part or an optical product having the hardened product, And an adhesive containing a photosensitive resin composition.

The polyimide developed by DuPont in the United States in 1955 is widely used in various fields based on its excellent properties such as high insulation, heat resistance, and high mechanical strength. Not only the aerospace field originally used, but also the application of coating films for semiconductor devices, flexible printed wiring boards, and heat-resistant insulating interlayer materials. Furthermore, in recent years, with the advancement of semiconductor packaging technology or higher density, wiring patterns have been required to be more refined, and polyimide has also been required to have high processability.

However, polyimide lacks thermoplasticity and solubility in organic solvents, so it has a difficult processing side. Therefore, polyimide systems are widely used to combine polyimide precursors and photoreactive initiators to impart photosensitivity, and irradiate with active light to form a desired pattern, and then close the ring at high temperature.

As described above, the so-called photosensitive polyimide that imparts photosensitivity to a resin composition containing a polyimide precursor to improve processability has a feature of shortening a complicated process, and therefore has a viewpoint of productivity or simplified steps. , Higher utilization than non-photosensitive polyfluorene imine.

The photosensitive polyimide is composed of a polyimide precursor containing polyamic acid and the like, and a latent basic substance (photobase generator) that generates a strong basic amine by activating light. Thing.

For example, Cited Document 1 proposes a photosensitive resin composition containing an oxime ester derivative containing a specific structure and a polyimide precursor. In the example of the cited document 1, a polyimide precursor is obtained by reacting 4,4'-diaminodiphenyl ether with pyromellitic dianhydride.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2007-249013

However, a photosensitive resin as described in Reference 1 is used. In the case of a composition, it is difficult to form a pattern with sufficient contrast and accuracy.

Therefore, an object of the present invention is to provide a photosensitive resin composition having a high contrast (solubility contrast) in development speed between exposed and unexposed areas caused by active light irradiation, and capable of easily forming a highly accurate pattern.

Another object of the present invention is to provide a photosensitive resin composition that can be cured at low temperatures.

Furthermore, it is an object of the present invention to provide a dry film using the photosensitive resin composition, a cured product obtained from the photosensitive resin composition or the dry film, and the cured product (undulating pattern film (polymer film)) ) Electronic parts or optical products, and adhesives containing a photosensitive resin composition.

In order to achieve the above-mentioned object, the present inventors have repeatedly studied the photosensitive resin composition using a photobase generator, and found that the use of a specific polymer precursor can achieve the purpose of the present invention.

That is, the present invention is a photosensitive resin composition characterized by containing (A) a polyamic acid and a polyamine obtained from an acid anhydride component containing a cyclic aliphatic skeleton and an aromatic skeleton, and an amine component. A polymer precursor of at least one repeating unit of an acid ester, and (B) a photoreactive latent basic substance that generates an alkali upon irradiation with active light.

In the present invention, (B) a latent alkaline substance is excited by irradiation with active light, and a chemical structure changes to produce a tertiary amine, etc. The alkali produced by the base promotes the low-temperature ammonium imidization of the polymer precursor (A), which will generate an exposed part (the part that has been imidized) and an unexposed part (maintaining the (A) polymer). Precursor part), there is a difference in solubility between the exposed part and the unexposed part. The specific (A) polymer precursor of the present invention easily promotes its imidization reaction with a latent alkaline substance, and development with a developing solution becomes easy. That is, the imidization of the exposed portion is promoted to a state where it has almost no solubility. On the other hand, the unexposed portion remains in a state of being soluble in the solution. Therefore, development with a developing solution is facilitated.

Generally speaking, as the polymer precursor, the more the polyamidic acid component increases, the better the alkali solubility, the more the polyamidate component increases, and the better the organic solvent solubility. By changing the ratio of amidine to amidate, solubility suitable for various developing solutions can be obtained.

Suitable aspects of the photosensitive resin composition of the present invention are listed below.

(1) The polymer precursor of (A), which is represented by the following general formula (I):

(In formula (1), R ₁ is a tetravalent organic group including a condensed ring of an aromatic ring and an aliphatic hydrocarbon ring, or a tetravalent organic group including an aromatic group and an alicyclic hydrocarbon group, and R ₂ is a divalent organic group. X is a divalent organic group, R ₃ , R ₄ and R ₅ are monovalent organic groups or functional groups having silicon which may be the same or different from each other, and m1, m2 and m3 are each 0 or 1 A compound represented by the above integer, and any one of m1 and m2 is an integer of 1 or more, and n is an integer of 0 or 1 or more).

(2) The polymer precursor of (A), which is represented by the following general formula (II):

Represented compounds.

(3) The polymer precursor (A) is soluble in an alkaline solution.

(4) The photosensitive resin composition can be patterned at 200 ° C or lower.

(5) The photosensitive resin composition can be patterned at 150 ° C or lower.

The present invention is also a dry film having a resin layer obtained by drying the photosensitive resin composition on a film.

The present invention also includes the photosensitive resin composition described above, Or the hardened material obtained by the above dry film.

Further, the present invention is also an electronic part or an optical product having the above-mentioned hardened material.

Furthermore, this invention is an adhesive containing the said photosensitive resin composition.

In the dry film, cured product, electronic part or optical product and adhesive of the present invention described above, the present invention can also be applied to a suitable aspect of the photosensitive resin composition.

Since the photosensitive resin composition of the present invention contains (B) a latent alkaline substance and the (A) polymer precursor having the above-mentioned specific structure, the photosensitive resin composition contains a derivative derived from an acid anhydride component having only an aromatic skeleton. In the case of polymer precursors, the solubility contrast is larger, and it is easier to form a pattern with high accuracy, that is, the resolution is excellent.

By irradiating the photosensitive resin composition of the present invention with active light, an alkali is generated from a latent alkaline substance (B), and its catalytic action is easily performed at a low temperature (for example, 200 ° C or lower) to achieve the above specific ( A) Imidation of polymer precursors. Thereby, a pattern with excellent resolvability can be formed. Here, the pattern also refers to a hardened object in the shape of a pattern.

The photosensitive resin composition of the present invention can be imidized at 200 ° C or lower, so it can be applied to a wider range of applications in the technical field where polyimide is used, and the possibility of use as a material for various members is also expanded. .

In addition, in the present invention, a large solubility contrast can be exhibited even when a general-purpose photobase generator is used.

The present invention is explained in detail below.

The photosensitive resin composition of the present invention contains (A) at least one repeating unit having polyamino acid and polyamino acid obtained from an acid anhydride component having an aliphatic skeleton and an aromatic skeleton, and an amine component. Polymer precursors, and (B) photoreactive latent alkaline substances.

Furthermore, in the present invention, the polyamic acid and the polyamic acid ester contained in the polymer precursor (A) of the uncured photosensitive resin composition are not substantially imidized.

Here, "not substantially ammonium imidization" means, for example, that the ratio of the amidine group represented by the above formula (I) and formula (II) to a carboxyl group or an ester group to form a amidine ring is a polymer. Less than 5% of the total amount of precursors. Here, the fluorene imidization rate can be measured by a well-known method using IR.

The reason why the photosensitive resin composition of the present invention exhibits better resolution than a photosensitive resin composition containing a polymer precursor derived from an acid anhydride component having only an aromatic skeleton is not clear, but the present invention As a result of discussing the structure of various polymer precursors, it is believed that by having a cyclic aliphatic skeleton and an aromatic skeleton, the exposure wavelength can be exhibited more effectively than in the past, thereby making the contrast larger.

Moreover, in the present invention, the polyamine and polyamidate contained in the polymer precursor (A) correspond to a portion of R ¹ described later, and are particularly composed of a saturated cyclic aliphatic skeleton and an aromatic group. In the case of a skeleton structure, excellent resolvability can be exhibited without having a polymerizable group such as an ethylenic double bond or a triple bond.

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

(In formula (I), R ₁ is a tetravalent organic group containing a condensed ring of an aromatic ring and an aliphatic hydrocarbon ring, or a tetravalent organic group containing an aromatic group and an alicyclic hydrocarbon group, and R ₂ is a divalent organic group. X is a divalent organic group, R ₃ , R ₄ and R ₅ are monovalent organic groups or functional groups having silicon which may be the same or different from each other, and m1, m2 and m3 are each 0 or 1 The above integer, and any of m1 and m2 is an integer of 1 or more, and n is an integer of 0 or 1 or more).

Furthermore, in the compound of the formula (I), the order of the polyamic acid, the polyamic acid partial ester, and the polyamic acid ester moiety on the main chain is not limited to the order represented by the formula (I), and for example, it may be Place polymer at both ends of the polyamic acid The phosphoric acid partial ester and polyamic acid ester may further be in the form of a block polymer that repeats each portion of the polyamic acid, the polyamic acid partial ester, and the polyamic acid moiety, or It is constituted as a random polymer having each of the above-mentioned portions randomly.

As the tetravalent organic group of R ₁ containing a condensed ring of an aromatic ring and an aliphatic hydrocarbon ring, it is preferably

Any one of them is displayed.

Formula (1-1): Z ₁ is 4 to 12 carbon atoms which form an aromatic ring (preferably a benzene ring, a naphthalene ring, and especially a benzene ring) together with the ethyl group shared with Z ₂ Unsaturated hydrocarbon group, the aromatic ring may have at least one alkyl group (1 to 4 carbon atoms), alkoxy group (1 to 4 carbon atoms), aryl group (6 to 10 carbon atoms) , A hydroxyl group, a halogen atom as a substituent.

Z ₂ is 3 to 10 (preferably 4 to 6, especially 4) carbon atoms which form an aliphatic hydrocarbon ring (alicyclic hydrocarbon) together with the ethyl group shared with Z ₁ Aliphatic hydrocarbon group, aliphatic hydrocarbon ring may also have at least one alkyl group (1 to 4 carbon atoms), alkoxy group (1 to 4 carbon atoms), aryl group (6 to 10 carbon atoms) ), A hydroxyl group, and a halogen atom as substituents. Two "-" monovalent bond sites (ie, the two bond sites to the right of Z ₂ (the resulting bond is assumed to be the bond x, y)) are each bound to the fat Carbons adjacent to each other in the group hydrocarbon ring (Z ₂ ), but constituting the remaining bonding site of the divalent radical represented by "= CR ^6- " (the monovalent bonding site on the right side of R ⁶ ), preferably the bonding site The carbon atom adjacent to each carbon atom having the two bonds x and y or the adjacent carbon atom. Especially the latter is better. For example, when the aliphatic hydrocarbon ring (Z ₂ ) is a cyclohexane ring, it is preferable that two bonding sites are bonded to the 3 and 4 positions (bonding x, y), and "= CR ^6- " is bonded to 2 or 1 digit (preferably 1 digit). R _{6 is} generally a hydrogen atom, an alkyl group (1 to 4 carbon atoms), an alkoxy group (1 to 4 carbon atoms), a hydroxyl group, and a halogen atom, and preferably a hydrogen atom.

Formula (1-2): Z ₃ is 4-12 carbon atoms that form an aromatic ring (preferably a benzene ring, a naphthalene ring, and especially a benzene ring) together with the ethyl group shared with Z ₄ Unsaturated hydrocarbon group, the aromatic ring may also have at least one alkyl group (1 to 4 carbon atoms), alkoxy group (1 to 4 carbon atoms), aryl group (6 to 10 carbon atoms) ), A hydroxyl group, and a halogen atom as substituents.

Z ₄ is 3 to 10 (preferably 4 to 6, especially 4) carbon atoms that form an aliphatic hydrocarbon ring (alicyclic hydrocarbon) together with the ethyl group shared with Z ₃ Aliphatic hydrocarbon group, aliphatic hydrocarbon ring may also have at least one alkyl group (1 to 4 carbon atoms), alkoxy group (1 to 4 carbon atoms), aryl group (6 to 10 carbon atoms) ), A hydroxyl group, and a halogen atom as substituents. A set of two 1-valent bond sites (a set of bond sites on the right side of Z ₄ or a set of bond sites on the left side) are respectively bonded to adjacent carbons, but a set of bonds The knots may be arranged adjacent to each other. If the ring is large, they may be arranged with at least one carbon atom spaced apart from each other.

Formula (1-3): Z ₅ is 4-12 carbon atoms that form an aromatic ring (preferably a benzene ring, a naphthalene ring, and especially a benzene ring) together with the ethyl group shared with Z ₆ Unsaturated hydrocarbon group, the aromatic ring may also have at least one alkyl group (1 to 4 carbon atoms), alkoxy group (1 to 4 carbon atoms), aryl group (6 to 10 carbon atoms) ), A hydroxyl group, and a halogen atom as substituents. Two 1-valent bond sites (the resulting bonds are assumed to be bonds x, y) are adjacent carbons that are respectively bonded to the aromatic ring, but two of the adjacent monovalent bonds are indicated by "-" The combination of the bonding sites may be arranged adjacent to each other. If the ring is large, they may be arranged with at least one carbon atom spaced from each other. Two monovalent bonding sites indicated by "-" are bonded to adjacent carbons, but constitute the remaining bonding sites of the bivalent base indicated by "= CR _7- " (bonding to the right of R ₇ The site) is preferably bonded to an adjacent carbon atom adjacent to each carbon atom adjacent to the carbon atom having the two bonds x and y described above. R _{7 is} generally a hydrogen atom, an alkyl group (1 to 4 carbon atoms), an alkoxy group (1 to 4 carbon atoms), a hydroxyl group, and a halogen atom, preferably a hydrogen atom.

Z ₆ is an aliphatic hydrocarbon ring (alicyclic hydrocarbon ring) having 3 to 10 carbon atoms (preferably 4 to 6, especially 4) together with the ethyl group shared with Z ₅ ) Aliphatic hydrocarbon group, saturated hydrocarbon ring may also have at least one alkyl group (1 to 4 carbon atoms), alkoxy group (1 to 4 carbon atoms), aryl group (6 to 10 carbon atoms) Each), a hydroxyl group, and a halogen atom as substituents.

Formula (1-4): Z ₇ is 4 to 12 carbon atoms which form an aromatic ring (preferably a benzene ring, a naphthalene ring, and especially a benzene ring) together with the ethyl group shared with Z ₈ Unsaturated hydrocarbon group, the aromatic ring may have at least one alkyl group (1 to 4 carbon atoms), alkoxy group (1 to 4 carbon atoms), aryl group (6 to 10 carbon atoms) ), A hydroxyl group, and a halogen atom as substituents. In bonded portion 2 1 price of a bond portion of a group (Z group bonding sites on the right side ₇ of, or Z group bonding sites left side of _7), lines were bonded to adjacent to the carbon, However, a group of bonding sites may be arranged adjacent to each other. If the ring is large, they may be arranged with at least one carbon atom spaced from each other. For example, it is preferable that two bonding sites constituting a group of bonding sites are bonded to adjacent carbon atoms of the aromatic ring (for example, the 1 and 2 positions of a 6-membered ring) and 2 of the other group of bonding sites are formed. Each bonding site is not bonded to the 6th or 3rd position of the 6-member ring, but to the 4th and 5th positions.

Z ₈ is an aliphatic hydrocarbon ring (alicyclic hydrocarbon ring) having 3 to 10 carbon atoms (preferably 4 to 6, especially 4) together with the ethyl group shared with Z ₇ ) Saturated hydrocarbon group, saturated hydrocarbon ring may also have at least one alkyl (1 to 4 carbon atoms), alkoxy (1 to 4 carbon atoms), aryl (6 to 10 carbon atoms) ), A hydroxyl group, and a halogen atom as substituents.

Among the formulae (1-1) to (1-4), the organic groups represented by the formulae (1-1) and (1-2) are preferred, and the organic groups represented by the formula (1-1) are particularly preferred.

R ₁ is a tetravalent organic group containing an aromatic group and an alicyclic hydrocarbon group, preferably [Chem 8] = B ¹ -R ₈ -A ¹ -R ₉ -B ² = indicator.

A ¹ is a divalent aromatic ring (preferably a benzene ring, a naphthalene ring, and especially a benzene ring) or AR-R ₁₀ -AR [However, AR is an alkyl group which may have a substituent {preferably at least one (1 to 4 carbon atoms), aryl (6 to 10 carbon atoms), alkoxy (1 to 4 carbon atoms), hydroxyl, halogen atoms) divalent benzene ring (preferably (Unsubstituted), R ₁₀ is an alkylene group (preferably 1 to 4 carbon atoms), -SO _2- , -COO-, -CONH, preferably -SO _2- ].

R ₈ and R ₉ are each independently a single bond, an alkylene (1 to 4 carbon atoms), -SO _2- , -COO-, -CONH-, preferably a single bond, -CONH-.

B ¹ and B ² are each independently an alicyclic hydrocarbon group (cyclic aliphatic hydrocarbon group) having 5 to 12 carbon atoms (preferably 6 to 8, especially 6), and the saturated hydrocarbon ring may have At least one alkyl group (1 to 4 carbon atoms), an alkoxy group (1 to 4 carbon atoms), an aryl group (6 to 10 carbon atoms), a hydroxyl group, and a halogen atom are used as substituents.

In the formula (I), X is a divalent organic group as described above, and examples thereof include repeating units including hydroxyphenylene, alkylhydroxyphenylene, (meth) acrylate, and cyclic alkylene. , Cyclic alkenyl, hydroxyamidate, aromatic or aliphatic ester, amidate, amidate, imino, carbonate, siloxane, alkylene oxide, urethane A group containing an epoxy group, an epoxy group-containing group, an oxetanyl group-containing group, or the like as a component.

m1, m2, and m3 are integers of 0 or 1 as described above, and any of m1 and m2 are integers of 1 or more. (A) The preferred number average molecular weight of the polymer precursor is from 1,000 to 1,000,000, more preferably from 5,000 to 500,000, and even more preferably from 10,000 to 200,000. Set m1, m2, and m3.

R ₃ , R _4, and R ₅ are the same as or different from each other, as described above, and are monovalent organic groups or functional groups having silicon. Examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, Aryl, etc. Examples of the monovalent functional group having silicon include a siloxy group, a silyl group, and a silanol group.

In addition, solubility can be controlled by changing the ratio of m1, m2, and m3. By increasing the proportion of m1, alkali developability becomes good, and a good pattern can be obtained.

The polymer precursor (A) is particularly preferably the following general formula (II):

Represented compounds. m is an integer of 1 or more, and R ₂ , X, and n are as described in formula (I).

When the photosensitive resin composition is patterned with short-wavelength light, R ₁ and R ₂ may each contain an aliphatic group from the viewpoint of the absorption characteristics of the polymer. For example, when R ₁ and R ₂ include a fluorine-containing group, the wavelength of light absorption can be reduced or the dielectric characteristics can be improved.

Thereby, alkali developability becomes favorable, and a favorable pattern can be obtained.

(A) The acid value of the polymer precursor is preferably 100 mgKOH / g or more, more preferably 150 mgKOH / g or more, and still more preferably 200 mgKOH / g or more. The upper limit of the acid value is preferably 300 mgKOH / g.

(A) The acid value of the polymer precursor is based on JIS K- 5601-2-1 measured. In addition, the diluted solvent of the sample is a acetone / water (9/1 volume ratio) mixed solvent which can also measure the acid value of the acid anhydride and has an acid value of 0.

(Polyamine / Polyamidate)

Polyamic acid and / or polyamic acid ester can be prepared by a conventionally known method. For example, it can be formulated only by mixing a specific acid dianhydride of the present invention and a diamine in a solution. It can be synthesized in a single-stage reaction, is easy and can be obtained at low cost, and requires no further modification, so it is preferably used. (A) The method for synthesizing the polymer precursor is not particularly limited, and a known method can be applied.

Examples of the specific acid dianhydride that can be used in the present invention include a tetracarboxylic dianhydride represented by the following formula (8).

(Wherein R ₁ is as described in formula (I)).

That is, the present invention polyamide acid / polyamide acid ester of the repeating unit R ₁ group, the R line from the tetracarboxylic acid dianhydride used as a raw material for producing the polyamide acid _1.

The acid anhydride component preferably has an acid anhydride group having a succinic anhydride structure. Examples of the acid anhydride group having a succinic anhydride structure include the following acids Anhydride group.

Among the tetracarboxylic dianhydrides of the present invention, the following compounds are preferred.

The cyclic aliphatic skeleton of the acid anhydride component is preferably a cyclohexane skeleton.

The molecular weight of the acid anhydride component is preferably 600 or less, more preferably 500 or less, and still more preferably 400 or less. The lower limit of the molecular weight is preferably 250.

The known tetracarboxylic dianhydride other than the specific tetracarboxylic dianhydride of the present invention may be used in combination as long as the purpose of the present invention is not violated.

Examples of such acid dianhydride include ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, methylcyclobutane tetracarboxylic dianhydride, and cyclopentane tetracarboxylic acid. Aliphatic tetracarboxylic dianhydride, such as dianhydride; pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3'-di Benzophenone tetracarboxylic dianhydride, 2,3 ', 3,4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,3 ', 3,4'-biphenyltetracarboxylic dianhydride, 2,2', 6,6'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl ) Propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) Perylene dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) Methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2,3-dicarboxyl Phenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 1,3-bis [(3,4-dicarboxy) benzylfluorenyl] phthalic anhydride, 1,4-bis [ (3,4-dicarboxy) benzylfluorenyl] phthalic anhydride, 2,2-bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} propane dianhydride, 2,2- Bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} propane dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} one di Anhydride, bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, 4,4'-bis [4- (1,2-dicarboxy) phenoxy] bi Phenyl dianhydride, 4,4'-bis [3- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy ] Phenyl} ketone dianhydride, bis { 4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} fluorene dianhydride, Bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} fluorenic dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} sulfide Dianhydride, bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} sulfide dianhydride, 2,2-bis {4- [4- (1,2-dicarboxy) benzene Oxy] phenyl} -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl } -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,1,1,3,3,3-hexafluoro- 2,2-bis (2,3- or 3,4-dicarboxyphenyl) propanedi Anhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4 , 9,10-fluorene tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,7,8-phenanthrene tetracarboxylic dianhydride, pyridine tetracarboxylic dianhydride, Fluorenyl diphthalic anhydride, m-bitriphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, p-bitriphenyl-3,3', 4,4'-tetracarboxylic acid Aromatic tetracarboxylic dianhydride and the like. Among the above, it is preferred to use an aromatic tetracarboxylic dianhydride in combination with a cyclic aliphatic tetracarboxylic dianhydride.

Examples of the amine usable in the present invention include a diamine represented by the following formula (10). However, the following is an example, and a publicly known person can be used as long as it does not violate the purpose of the present invention.

[Chemical Formula 13] H ₂ NR ₂ . NH ₂ (10)

(Wherein R ₂ is as described in formula (I)).

Examples of the diamine when the R ₂ group is a divalent aromatic group include p-phenylenediamine, 3,3'-dimethyl-4,4'-diaminobiphenyl, and 2,2'-dimethyl -4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diamine Biphenyl, 9,10-bis (4-aminophenyl) anthracene, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylphosphonium, 3,3'-di Aminodiphenylphosphonium, 4,4'-diaminodiphenylsulfinium, 1,3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) Phenyl] fluorene, bis [4- (3-aminophenoxy) phenyl] fluorene, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-bis (3- Aminophenoxybiphenyl, bis [4- (4-aminophenoxy) phenyl] ether, 1,1,1,3,3,3-hexafluoro-2,2-bis (4-amine Phenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,1,1,3 , 3,3-hexafluoro-2,2-bis (3-amino-4-methylphenyl) propane, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4 ' -Diaminodiphenyl sulfide, 3,4'-diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminobenzene (Oxy) benzene. Among the above, aromatics having an ether group are preferred. Diamine, particularly preferably diamine diphenyl ether.

Examples of the diamine when the R ₂ group is a divalent aliphatic group include 1,1-m-xylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, and hexamethylene Methylene diamine, heptaethylene diamine, octa methylene diamine, nona methylene diamine, 4,4-diamino heptamethylene diamine, 1,4-diamino cyclohexane, isophorone Diamine, tetrahydrodicyclopentadienylene diamine, hexahydro-4,7-methanoindanylene dimethylenediamine, tricyclic [6.2.1.02,7] -Undecyl dimethyldiamine, 4,4'-methylenebis (cyclohexylamine), isophoronediamine.

In addition, as another example, a diamine polysiloxane represented by the following formula (11) can be mentioned.

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

Specifically, R ₂₈ and R ₂₉ in the formula (11) include a carbon number of 6 to 7 such as methylene, ethylidene, and propyl, and a carbon number of 6 to phenyl, and the like. Examples of the aryl group such as 18 to R ₃₀ and R ₃₁ include alkyl groups having 1 to 7 carbon atoms such as methyl and ethyl, and aryl groups having 6 to 12 carbon such as phenyl and the like.

Polyamic acid esters can be obtained by a known method. For example, an acid anhydride such as 3,3'-benzophenone tetracarboxylic dianhydride is reacted with an alcohol such as ethanol to form a half ester. This half-ester was used as a chlorinated diester diacid using thionyl chloride. By reacting this chlorinated diester diacid with a diamine such as 3,5-diamino benzoic acid, a polyamic acid ester can be obtained.

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

In the present invention, as long as the latent alkaline substance (B) generates a base by irradiation with active light, an ionic or non-ionic photobase generator can be used.

(B) Alkali produced by a potentially alkaline substance can be a primary amine, a secondary amine, or a tertiary amine, and preferably a nonionic tertiary amine that produces a strongly basic tertiary amine by irradiation with active light . From the viewpoint of increasing alkalinity and efficiently promoting partial imidization, the strongly basic tertiary amine produced, Preferred are, for example, hydrazones or guanidines.

Furthermore, as the (B) potential alkaline substance, a substance having an oxime ester structure, a substance having an amine acetophenone structure, a substance having a urethane structure, and a substance having a sulfonamide cinnamate structure can also be used. Substances, substances with Grade 4 ammonium salt structure, etc.

Among the (B) potential alkaline substances of the present invention, for example, 8-benzyl-1,8-diazabicyclo [5.4.0] undecane (pKa = 7.46) is irradiated by active light, A tertiary amine with strong basicity (pKa = 13.28) was changed as shown below.

With such a large alkaline change, the ammonization of the (A) polymer precursor can be very well promoted, and exposed portions (polyimidized portions) and unexposed portions (maintained) (A) part of the polymer precursor), thereby improving the accuracy of patterning in development.

From the viewpoint of enhancing alkalinity, the tertiary amine generated by irradiation with active light is more preferably a cyclic structure.

In the present invention, as the active light rays to the (B) latent alkaline substance, visible light, ultraviolet rays, electron beams, X-rays, etc. can be irradiated, and it is preferable to use ultraviolet rays, especially ultraviolet rays of 248 nm, 365 nm, 405 nm, and 436 nm.

The amount of the (B) latent alkaline substance used is appropriately selected depending on the film thickness, (B) the type of the latent alkaline substance, (A) the type of the polymer precursor, and the like. For example, the amount of the (B) latent alkaline substance added is 1 to 40 parts by mass relative to 100 parts by mass of the polymer precursor (A). It is more preferably 5 to 35 parts by mass, and even more preferably 10 to 30 parts by mass. With the (B) latent alkaline substance in the above-mentioned added amount, the (A) polymer precursor can be well-imidized.

Furthermore, when the (B) latent alkaline substance is nonionic, when it is added as a catalyst in the photosensitive resin composition, it has excellent solubility in an organic solvent, easy handling, and easy to obtain a uniform composition. Material and the polymer film obtained therefrom.

The (B) latent basic substance that generates a strongly basic tertiary amine by the above-mentioned active light irradiation is preferably a compound represented by the general formula (2).

(In formula (2), R ₅ is capable of absorbing light in a wavelength range of 200 to 650 nm, and is unsubstituted or may pass through more than one alkyl, alkenyl, alkynyl, haloalkyl, NR ₁₂ R ₁₃ , CN, OR ₁₄ , SR ₁₅ , COR ₁₆ , COOR ₁₇ , halogen or

Substituted aromatic or heteroaromatic groups; or R ₅ is ; R ₆ and R ₇ are independently of each other hydrogen, alkyl, alkenyl, alkynyl, or unsubstituted or substituted with more than one alkyl, CN, OR ₁₄ , SR ₁₅ , halogen or haloalkyl Phenyl; R ₉ is alkyl or NR _14A R _15A ; R ₈ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are each independently hydrogen or alkyl; or R ₈ and R ₁₀ are together to form an unsubstituted, Or an alkylene bridge substituted with more than one alkyl group; or R ₉ and R ₁₁ are independently from R ₈ and R ₁₀ together to form an unsubstituted or alkylated bridge substituted with more than one alkyl group Or when R ₉ is NR _14A R _15A , R _14A and R _15A together form an unsubstituted or substituted alkylene bridge with one or more alkyl groups; R ₁₄ , R ₁₅ and R ₁₇ are independently of each other as Hydrogen or alkyl; R ₁₆ is hydrogen or alkyl; or is capable of absorbing light in a wavelength range of 200 to 650 nm, and is unsubstituted, or has more than one alkyl, alkenyl, alkynyl, haloalkyl, NR ₁₂ R ₁₃ , CN, OR ₁₄ , SR ₁₅ , COR ₁₄ , COOR ₁₇ , or halogen-substituted aromatic or heteroaromatic groups; R ₁₈ is a non-substituted, which can absorb light in the wavelength range of 200 ~ 650nm, Or through more than one alkyl, olefin Group, alkynyl, haloalkyl, NR ₁₂ R ₁₃ , CN, OR ₁₄ , SR ₁₅ , COR ₁₆ , COOR ₁₇ , or halogen-substituted aromatic or heteroaromatic group; R ₁₉ is hydrogen or alkyl; R ₂₀ It is hydrogen, alkyl, or unsubstituted, or may pass through more than one alkyl, vinyl, alkenyl, alkynyl, haloalkyl, phenyl, NR ₁₂ R ₁₃ , CN, OR ₁₄ , SR ₁₅ , COR ₁₆ , COOR ₁₇ or halogen substituted phenyl).

The (B) latent basic substance represented by the formula (2) is preferably a compound represented by the formula (5).

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

Further, (B) of the formula (2) is potentially alkaline. The substance is preferably represented by formula (6-1) or formula (6-2).

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

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

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

Considering that the wavelength of a high-pressure mercury lamp for general exposure light sources is 436nm, 405nm, 365nm, and the wavelength of KrF laser is 248nm, the aforementioned (B) potential alkaline substance is preferably in the range of 240nm ~ 450nm, especially At least one of the electromagnetic waves having a wavelength of 436 nm, 405 nm, 365 nm, or 248 nm has absorption.

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

The solvent (C) in the photosensitive resin composition is not particularly limited as long as it dissolves the polymer precursor (A), the latent alkaline substance (B), and other additives. Examples include N, N'-dimethylformamidine, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N, N'-dimethylacetamidine, diethylene glycol Dimethyl ether, cyclopentanone, γ -butyrolactone, α-ethylamyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazoline, N-cyclohexyl- 2-pyrrolidone, dimethyl sulfene, hexamethylphosphoramidine, pyridine, γ -butyrolactone, diethylene glycol monomethyl ether. These can be used alone or in combination of two or more. The amount of the solvent to be used may be within a range of 50 to 9000 parts by mass relative to 100 parts by mass of the polymer precursor (A), depending on the thickness or viscosity of the coating film.

In the photosensitive resin composition of the present invention, (D) a sensitizer may be added in order to further improve the light sensitivity. (D) Sensitizers include, for example, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, and 2,5-bis (4'-diethylamine). Benzylidene) cyclopentane, 2,6-bis (4'-diethylaminobenzylidene) cyclohexanone, 2,6-bis (4'-dimethylaminobenzylidene)- 4-methylcyclohexanone, 2,6-bis (4'-diethylaminobenzylidene) -4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone Ketone, 4,4'-bis (diethylamino) chalcone, p-dimethylamino cinnamyl dihydroindenone, p-dimethylamino benzylidene indanone, 2 -(p-dimethylaminophenylphenylphenyl) -benzothiazole, 2- (p-dimethylaminophenylphenylvinyl) benzothiazole, 2- (p-dimethylaminophenylbenzene Vinylidene) isonaphthothiazole, 1,3-bis (4'-dimethylaminobenzylidene) acetone, 1,3-bis (4'-diethylaminobenzylidene) acetone, 3 , 3'-carbonyl-bis (7-diethylaminocoumarin), 3-ethylamino-7-dimethylaminocoumarin, 3-ethoxy Carbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinylbenzophenone, dimethylaminoisobenzoate isoamyl, diethylaminoisobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzothiazole, 2- (p-di From the viewpoint of sensitivity, methylaminostyryl) naphtho (1,2-d) thiazole, 2- (p-dimethylaminobenzylfluorenyl) styrene, etc. are preferably used. -Methylethyl) -9H-thioxanthen-9-one and other thioxanthones. These can be used alone or in combination of 2 to 5 types. (D) The sensitizer is preferably used in an amount of 0.1 to 10 parts by mass based on 100 parts by mass of the polymer precursor (A).

Moreover, in the photosensitive resin composition of this invention, you may add an adhesion adjuvant in order to improve adhesiveness with a base material. As the adhesion promoter, a known one can be used as long as it does not violate the purpose of the present invention. Examples include γ -aminopropyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, and γ -glycidoxypropylmethyl Dimethoxysilane, γ -mercaptopropylmethyldimethoxysilane, N- [3- (triethoxysilyl) propyl] phthalic acid, benzophenone tetracarboxylate Reaction products of acid dianhydride and (triethoxysilyl) propylamine. The amount of the additive to be added is preferably in the range of 0.5 to 10 parts by mass relative to 100 parts by mass of the polymer precursor (A).

The photosensitive resin composition of the present invention may be added with Add alkali multiplier. When forming a thick film pattern, it is required that the decomposition rate of (B) a latent alkaline substance is the same degree from the surface to the bottom. In this case, in order to increase sensitivity, it is preferable to add an alkali multiplying agent. For example, an alkali multiplying agent disclosed in Japanese Patent Laid-Open No. 2012-237776 and Japanese Patent Laid-Open No. 2006-282657 can be used.

Furthermore, in the photosensitive resin composition of the present invention, other photosensitive components that generate an acid or an alkali by light may be added within a range that does not significantly impair the film properties after curing. When a compound having one or more ethylenically unsaturated bonds is added to the photosensitive resin composition of the present invention, a photo radical generator may be added.

In order to impart processing characteristics or various functions to the resin composition of the present invention, various other organic or inorganic low-molecular or high-molecular compounds may be blended. For example, dyes, surfactants, leveling agents, plasticizers, microparticles, and the like can be used. The microparticles include organic fine particles such as polystyrene and polytetrafluoroethylene; colloidal silicon dioxide, carbon, and inorganic fine particles such as layered silicate. These may also have a porous or hollow structure. Specific materials used to obtain porous shapes or hollow structures include various pigments, fillers, and fibers.

〔Dry film〕

The dry film of the present invention has a resin layer formed by applying and drying the photosensitive resin composition of the present invention. The dry film of the present invention is used by laminating a curable resin layer in contact with a substrate.

The dry film of the present invention can be obtained by using a doctor blade on the carrier film. A suitable method such as a coater, a lip coater, a comma coater, a thin film coater, etc., uniformly coats the photosensitive resin composition and dries to form the aforementioned resin layer. A cover film is laminated thereon to produce it. The cover film and the carrier film may use the same film material, or may use different films.

In the dry film of the present invention, the film material of the carrier film and the cover film can be used as long as it is known as a dry film.

As the carrier film, a thermoplastic film such as a polyester film such as polyethylene terephthalate having a thickness of 2 to 150 μm can be used.

As the cover film, a polyethylene film, a polypropylene film, or the like can be used, but it is more preferable that the adhesion force to the photosensitive resin layer is smaller than that of the carrier film.

The film thickness of the photosensitive resin layer on the dry film of the present invention is preferably 100 μm or less, and more preferably 5 to 50 μm.

Using the photosensitive resin composition of the present invention, the relief pattern of the cured product is produced, for example, in the following manner.

First, as step 1, a photosensitive resin composition is coated on a substrate and dried, or a resin layer is transferred onto the substrate from a dry film to obtain a coating film. As a method for coating the photosensitive resin composition on a substrate, a conventional method for coating a photosensitive resin composition can be used, such as a spin coater, a bar coater, and a blade coater. , Coating method such as curtain coater, screen printing machine, spray coating method with spray coater, and inkjet method. The drying method of the coating film may be air drying, heating drying in an oven or a hot plate, and vacuum drying. In addition, it is desirable to dry the coating film before it causes the (A) polymer in the photosensitive resin composition. The sulfonium is imidized under flooding conditions. Specifically, natural drying, air-drying, or heat-drying can be performed under conditions of 20 ° C to 140 ° C for 1 minute to 1 hour. Preferably, it is dried on a hot plate for 1 to 5 minutes. In addition, vacuum drying may be performed, and in this case, it may be performed under the conditions of room temperature and 1 minute to 1 hour.

The substrate is not particularly limited, and can be widely used in passivation protection films of silicon wafers, wiring substrates, various resins, metals, and semiconductor devices.

In addition, because it can be imidized at a low temperature, it is characterized in that it can be widely applied to members and materials that are not suitable for high-temperature processing of substrates such as printed wiring boards.

Next, as step 2, the coating film is transmitted through a mask having a pattern, or directly exposed. The exposure light is a wavelength that uses (B) a potentially alkaline substance that is activated to change to a strong alkaline substance such as a tertiary amine. As described above, when a sensitizer is appropriately used, the light sensitivity can be adjusted. The exposure device can be a contact aligner, a mirror projection, a stepper, a laser direct exposure device, or the like.

Next, as Step 3, heating is performed so that the imidization of the coating film is promoted by the alkali generated in the coating film. Thereby, the alkali system generated in the exposure part in the said step 2 becomes a catalyst, and (A) a polymer precursor is partially imidized. The heating time and heating temperature are appropriately changed depending on the type of the polymer precursor (A) used, the thickness of the coating film, and (B) the underlying alkaline substance. Typically, in the case of a coating film thickness of about 10 μm, it is about 110 to 200 ° C. and about 2 to 10 minutes. By setting the heating temperature to When it is 110 ° C or higher, partial imidization can be efficiently achieved. On the other hand, by setting the heating temperature to 200 ° C. or lower, the imidization of the unexposed portion can be suppressed, the solubility between the exposed portion and the unexposed portion is increased, and the pattern is easily formed.

Next, as step 4, the coating film is treated with a developing solution. Thereby, the unexposed portion in the coating film can be removed, and a pattern formed by the (A) polymer precursor and the partially fluorinated polyfluorene imine can be formed on the substrate.

The method used for development can be selected from conventionally known development methods of photoresist, such as a rotary spray method, a paddle method, and an immersion method with ultrasonic treatment. Examples of the developing solution include inorganic bases such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia; organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine; tetramethylammonium hydroxide , Quaternary ammonium salts such as tetrabutylammonium hydroxide, etc. In addition, it can be used in the form of an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, isopropyl alcohol, or a surfactant, as needed. After that, the coating film is washed with a rinse solution as needed to obtain a pattern coating film. The rinse solution can be used alone or in combination with distilled water, methanol, ethanol, isopropanol, and the like. The developer (C) may also be used as the developer.

Then, in step 5, the patterned coating film is heated to obtain a cured coating film (cured material). The heating temperature is appropriately set so that the pattern of the polyfluorene imine is hardened. For example, in an inert gas, heating is performed at 150 to 300 ° C. for about 5 to 120 minutes. A more preferable range of the heating temperature is 150 to 250 ° C, and a more preferable range is 180 to 220 ° C. Heating is by This is performed using, for example, a hot plate, an oven, and a temperature-adjustable oven with a programmable temperature pattern. The ambient atmosphere (gas) at this time may be air, or an inert gas such as nitrogen or argon.

The photosensitive resin composition of the present invention is suitably used for printing inks, adhesives, fillers, electronic materials, optical circuit parts, molding materials, resist materials, construction materials, three-dimensional shapes, and optical members. A wide range of fields / products in which the properties of heat resistance, dimensional stability, and insulation of polyimide films are particularly effective, such as coatings or printing inks, or color filters, and flexible displays Film, semiconductor device, electronic component, interlayer insulation film, wiring coating film, optical circuit, optical circuit component, anti-reflection film, hologram, optical component or building material. The present invention also provides at least a part of a printed matter containing the photosensitive resin composition of the present invention or a cured product thereof, a color filter, a film for a flexible display, a semiconductor device, an electronic component, an interlayer insulating film, a wiring coating film, Optical circuits, optical circuit parts, anti-reflection films, holograms, optical components or building materials, etc.

In particular, a photosensitive resin composition containing (A) a polymer precursor is mainly used as a pattern-forming material (resistance agent), and the pattern formed by this is used as a permanent pattern formed by polyimide It is suitable for forming wiring coating films such as color filters, films for flexible displays, electronic parts, semiconductor devices, interlayer insulating films, solder resists, or coating films, and functions that impart heat resistance or insulation properties to films. , Solder dam (solder dam), optical circuits, optical circuit parts, anti-reflection films, other optical components or electronic components.

[Example]

The following examples and comparative examples of the present invention are enumerated to specifically describe the present invention, but the present invention is not limited to the following examples.

[Synthesis Examples 1 to 5 (Synthesis of Polymer Precursors 1 to 5)]

Into a separable flask having a capacity of 300 mL, 30 mmol of the diamine described in Table 1 below was added, and the diamine was dissolved in dehydrated NMP (N-methylpyrrolidone) while flowing nitrogen gas. After all the diamine was dissolved, 30 mmol of the acid anhydride described in Table 1 was slowly added. After the acid anhydride attached to the flask wall was poured into the reaction solution with a small amount of NMP, the reaction was stirred at room temperature for 24 hours to obtain a 15% by mass polyamic acid (PAA) solution. The input amount of dehydrated NMP was 75% by mass of the solution amount of PAA.

The molecular weight of TDA used in the synthesis of polymer precursor 1 is 300.26, and the molecular weight of PPHT used in the synthesis of polymer precursor 3 is 468.46.

The acid value of the polymer precursor 1 was 223 mgKOH / g, and the acid value of the polymer precursor 3 was 167 mgKOH / g.

[Examples 1 to 3 (Preparation of photosensitive resin composition 1 to 3)]

In the above polymer precursor solutions 1 to 3, the photoreactive latent alkaline substance is dissolved so that the solid content of the polymer precursor becomes 10% by mass, respectively, to obtain the photosensitive resin composition 1 to the present invention. 3. For example, in Example 1, 60 mg of a photoreactive latent alkaline substance was dissolved.

[Comparative Examples 1, 2 (Preparation of Photosensitive Resin Compositions 4, 5)]

In the above-mentioned polymer precursor solutions 4, 5 for comparison, the photoreactive latent alkaline substance was dissolved so that the solid content of the polymer precursor became 10% by mass, respectively, and a photosensitive resin composition for comparison was obtained.物 4,5.

〔Photoreactive latent alkaline substance〕

[Evaluation of photosensitive resin composition]

The photosensitive resin compositions 1 to 5 (Examples 1 to 3, Comparative Examples 1 and 2) were spin-coated on a wafer so that the film thickness after drying became 5 μm, and dried on a hot plate at 80 ° C for 10 minutes. minute.

Only a half mask (transmittance 0%) was placed on the obtained dried film, and 1J wide exposure was performed with a desktop exposure device (Sanyung Electric).

This wafer was heated on a hot plate at 150 ° C. for 6 minutes, and then immersed in a 1% by mass sodium hydroxide aqueous solution.

(Compared)

The above comparison is obtained by the following formula.

Contrast = Development speed of unexposed area (film thickness μm / development time min) / Development speed of exposed section (film thickness μm / development time min)

Film thickness (μm): The value of the film thickness before development minus the film thickness after development

Development time (min): the time of immersion in the developer

The evaluation was performed in accordance with the comparison value as follows.

◎: 15 or more

○: 5 or more to less than 15

×: less than 5

The above evaluation results are shown in Table 2 below.

From this result, it is clear that the photosensitive resin composition of the present invention has a high contrast and can form a good pattern.

The present invention is not limited to the configuration and examples of the embodiments described above, and various changes can be made within the scope of the gist of the invention.

Claims (10)

A photosensitive resin composition containing (A) at least one repeating unit having polyamic acid and polyamino acid obtained from an anhydride component containing a cyclic aliphatic skeleton and an aromatic skeleton, and an amine component And (B) a photoreactive latent basic substance that generates a base by irradiation with active light. The photosensitive resin composition according to claim 1, wherein the polymer precursor (A) is a compound represented by the following general formula (I):

(In formula (I), R ₁ is a tetravalent organic group containing a condensed ring of an aromatic ring and an aliphatic hydrocarbon ring, or a tetravalent organic group containing an aromatic group and an alicyclic hydrocarbon group, and R ₂ is a divalent organic group. X is a divalent organic group, R ₃ , R ₄ and R ₅ are monovalent organic groups or functional groups having silicon which may be the same or different from each other, and m1, m2 and m3 are each 0 or 1 The above integer, and any of m1 and m2 is an integer of 1 or more, and n is an integer of 0 or 1 or more). The photosensitive resin composition according to claim 1, wherein the polymer precursor (A) is a compound represented by the following general formula (II):

(However, R ₂ is a divalent organic group, X is a divalent organic group, m is an integer of 1 or more, and n is an integer of 0 or 1 or more). The photosensitive resin composition according to claim 1, wherein the polymer precursor (A) is soluble in an alkaline solution. For example, the photosensitive resin composition of claim 1 can be patterned at 200 ° C or lower. The photosensitive resin composition according to any one of claims 1 to 4, which can form a pattern at 150 ° C or lower. A dry film comprising a resin layer obtained by drying the photosensitive resin composition according to any one of claims 1 to 6 on the film. A cured product obtained from the photosensitive resin composition according to any one of claims 1 to 6 or the resin layer of the dry film according to claim 7. An electronic part or optical article having a hardened body as claimed in claim 8. An adhesive containing the photosensitive resin composition according to any one of claims 1 to 6.