TW201704876A - Positive-tone photosensitive resin composition, dry film, cured product, and printed wiring board - Google Patents

Abstract

Provided are a positive-tone photosensitive resin composition of exceptional resolution, a dry film having a resin layer obtained from the composition, a cured product of the composition or of the resin layer of the dry film, and a printed circuit board having the cured product. This positive-tone photosensitive resin composition is characterized by containing (A) an acid anhydride having a cyclic aliphatic backbone and an aromatic backbone, and a polyamic acid obtained from a diamine, and (B) a photo-acid generating agent. The polyamic acid (A) is preferably a compound having a structure represented by general formula (I) (where R1 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, R2 is a divalent organic group, X is a divalent organic group, m is an integer of 1 or greater, and n is 0 or an integer of 1 or greater).

Description

Positive photosensitive resin composition, dry film, cured product, and printed wiring board

The present invention relates to a positive photosensitive resin composition, a dry film, a cured product, and a printed wiring board.

Polyimine is widely used in various fields based on excellent properties such as high insulation properties, heat resistance, and high mechanical strength. For example, it does not stagnate in the aerospace field that was originally applied, and is now also applied to a coating film of a semiconductor element, a flexible printed wiring board, or a heat-resistant insulating interlayer.

Polyimine is thermoplastic and has poor solubility in organic solvents, so it is difficult to process. Therefore, polyimine is widely used by irradiating active light rays to a photosensitive resin composition obtained by mixing a poly-proline and a photoreactive compound, and then developing the image by irradiation. A desired pattern film is formed, and then a high temperature is applied to cause ring closure to be imidized.

For example, Patent Document 1 describes a positive photosensitive resin composition containing a polyamic acid condensate and a quinonediazide compound, wherein The polyamic acid condensate is a polyamine condensate of an aromatic dianhydride and an aromatic diamine. Further, Patent Document 2 describes a positive photosensitive resin composition containing a poly(amine-imine) resin having a specific structure and a photoacid generator.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 52-13315

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-196041

In recent years, with the increase in the size and density of semiconductor mounting technology, it has been required to make the pattern film finer. However, as described above, the photosensitive resin composition is difficult to obtain high resolution.

Therefore, an object of the present invention is to provide a positive photosensitive resin composition excellent in resolution, a dry film having a resin layer obtained from the composition, a cured product having the composition or the resin layer of the dry film, and A printed wiring board having the cured product.

As a result of reviewing the above problems, the present inventors have found that the use of polyamic acid obtained from an acid anhydride having a cyclic aliphatic skeleton and an aromatic skeleton and a diamine to replace an acid having an aromatic skeleton is used. The polyamic acid obtained from the anhydride and the diamine unexpectedly obtains a cured product excellent in resolution.

Further, the inventors of the present invention have found that a poly(decylamine-imide) resin which is imidized by using a part of polyamic acid is substantially a polyfluorene which is imidized. Amino acid is obtained as a cured product excellent in resolution.

Therefore, the present invention is composed of a positive photosensitive resin containing (A) a polyamic acid obtained from an acid anhydride having a cyclic aliphatic skeleton and an aromatic skeleton and a diamine, and (B) a photoacid generator. Things.

In the positive photosensitive resin composition of the present invention, the (A) polyaminic acid is preferably a compound having a structure represented by the following general formula (I).

(wherein 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 an R ₂ -based divalent organic group; And X is a divalent organic group, m is an integer of 1 or more, n is 0 or an integer of 1 or more).

In the positive photosensitive resin composition of the present invention, the (A) polyaminic acid is preferably a compound having a structure represented by the following general formula (II).

(wherein R ₂ is a divalent organic group, an X-based divalent organic group, m is an integer of 1 or more, n is 0 or an integer of 1 or more).

In the positive photosensitive resin composition of the present invention, the (A) polyamine acid is preferably a compound having a structure represented by the following general formula (III).

(wherein 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, R ₂ , R ₄ and R ₆ is a divalent organic group, R ₃ and R ₅ are a tetravalent organic group, m is an integer of 1 or more, n and s are each independently, and are 0 or 1 or more, and at least one of n and s is 1 or more. The integer).

In the positive photosensitive resin composition of the present invention, the (A) polyaminic acid is preferably a compound having a structure represented by the following general formula (V).

(wherein R ₂ , R ₄ and R ₆ are a divalent organic group, R ₃ and R ₅ are a tetravalent organic group, m is an integer of 1 or more, n and s are each independently, and are an integer of 0 or 1 or more, And at least one of n and s is an integer of 1 or more).

In the positive photosensitive resin composition of the present invention, the amount of the (B) photoacid generator to be blended is preferably from 1 to 50 parts by mass based on 100 parts by mass of the (A) polyglycine.

The positive photosensitive resin composition of the present invention is preferably used in a method of forming a pattern film comprising the following steps: an exposure step of exposing a coating film of a positive photosensitive resin composition, after the aforementioned exposure step A heating step of heating the coating film and a developing step of developing the image after the heating step.

The dry film of the present invention is characterized in that it has a resin layer obtained by applying the positive photosensitive resin composition to a film and drying the film.

The cured product of the present invention is characterized in that the positive photosensitive resin composition or the resin layer of the dry film is cured.

The printed wiring board of the present invention is characterized in that it has the above-mentioned cured product.

According to the present invention, it is possible to provide a positive photosensitive resin composition excellent in resolution, a dry film having a resin layer obtained from the composition, a cured product having the composition or the resin layer of the dry film, and A printed wiring board of the cured product.

[Fig. 1] A positive pattern film of (A) L/S = 3/3 μm, (B) 7/7 μm, and (C) 9/9 μm obtained by using a positive photosensitive resin composition of Example 8 under a microscope. Image.

The positive photosensitive resin composition of the present invention contains (A) a polyamic acid obtained from an acid anhydride having a cyclic aliphatic skeleton and an aromatic skeleton and a diamine, and (B) a photoacid generator.

In the present invention, in the case of using an acid anhydride having a cyclic aliphatic skeleton and an aromatic skeleton, a cured product having excellent resolution is obtained. For example, a pattern film having an L/S of 10/10 μm or less can be obtained.

Moreover, the positive photosensitive resin composition of the present invention exhibits particularly excellent resolution when heated after light irradiation and before development. In other words, when the coating film of the positive photosensitive resin composition of the present invention is irradiated with active light rays, the solubility of the irradiated portion increases, and a difference in solubility between the irradiated portion and the non-irradiated portion occurs. Then, it is heated, and a part of the polylysine of the unexposed part is imidized, and then formed by development. Positive pattern film with excellent resolution. After the development, the heating is carried out at a high temperature, and if the imidization is completely carried out.

Hereinafter, the components contained in the positive photosensitive resin composition of the present invention will be described in detail.

[(A) Polyglycine obtained from an acid anhydride having a cyclic aliphatic skeleton and an aromatic skeleton and a diamine]

(A) Poly (amic acid) obtained from an acid anhydride having a cyclic aliphatic skeleton and an aromatic skeleton and a diamine (hereinafter also referred to as "(A) poly-proline)" is substantially not used in the present invention.醯imination. (A) Polylysine is preferably a structure having the following general formula (I).

(wherein 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 an R ₂ -based divalent organic group; And X is a divalent organic group, m is an integer of 1 or more, n is 0 or an integer of 1 or more).

(A) Polyproline is obtained from an acid anhydride having a cyclic aliphatic skeleton and an aromatic skeleton, and a diamine. In other words, in the general formula (I), even if n is 0.

The tetravalent organic group containing a condensed ring of an aromatic ring and an aliphatic hydrocarbon ring of R ₁ is preferably at least one of the following

Formula (1-1):

Z ₁ is an unsaturated hydrocarbon group having a carbon number of 4 to 12 which is an aromatic ring (preferably a benzene ring, a naphthalene ring, particularly a benzene ring) which is common to Z ₂ and which forms an aromatic ring. It has at least one alkyl group (having 1 to 4 carbon atoms), an alkoxy group (having 1 to 4 carbon atoms), an aryl group (having 6 to 10 carbon atoms), a hydroxyl group, and a halogen atom as a substituent.

An aliphatic group having 3 to 10 (preferably 4 to 6, especially 4) carbon atoms of the aliphatic hydrocarbon ring (alicyclic hydrocarbon) which is formed by the Z ₂ system and Z ₁ in combination with the extended ethyl group. The hydrocarbon group and the aliphatic hydrocarbon ring system may have at least one alkyl group (having 1 to 4 carbon atoms), an alkoxy group (having 1 to 4 carbon atoms), and an aryl group (having 6 to 10 carbon atoms). A hydroxyl group or a halogen atom is used as a substituent. The two-valent bond keys shown in the two "-" (that is, the bond key of one set and the bond key on the right side of Z ₂ ) are mutually bonded to the adjacent carbon, but "=CR ₆ - The two-valent bond bond shown is preferably bonded to a carbon atom adjacent to a carbon atom adjacent to a carbon bond of two "-" bond bonds or a carbon atom adjacent thereto. Especially the latter is better. For example, when the aliphatic hydrocarbon ring is a cyclohexane ring, there are two "-" bond bonds at the 3,4 position, and "=CR" at the 2 or 1 position (preferably 1 position). ₆ - "The key is good. R _{6 is} generally a hydrogen atom, an alkyl group (having 1 to 4 carbon atoms), an alkoxy group (having 1 to 4 carbon atoms), a hydroxyl group or a halogen atom, and a hydrogen atom is preferred.

Equation (1-2):

Z ₃ is an unsaturated hydrocarbon group having a carbon number of 4 to 12 which is an aromatic ring (preferably a benzene ring, a naphthalene ring, particularly a benzene ring) which is common to Z ₄ and which forms an aromatic ring. It has at least one alkyl group (having 1 to 4 carbon atoms), an alkoxy group (having 1 to 4 carbon atoms), an aryl group (having 6 to 10 carbon atoms), a hydroxyl group, and a halogen atom as a substituent.

An aliphatic group having 3 to 10 (preferably 4 to 6, especially 4) carbon atoms of the aliphatic hydrocarbon ring (alicyclic hydrocarbon) which is formed by the Z ₄ system and Z ₃ in combination with the extended ethyl group. The hydrocarbon group and the aliphatic hydrocarbon ring system may have at least one alkyl group (having 1 to 4 carbon atoms), an alkoxy group (having 1 to 4 carbon atoms), and an aryl group (having 6 to 10 carbon atoms). A hydroxyl group or a halogen atom is used as a substituent. Two "-" bond keys (a set of bond keys, a set of bond bonds on the right side of Z ₄ or a set of bond bonds on the left side) shown by "-" are each bonded to adjacent carbon. A set of bonding bonds may be disposed adjacent to each other, and the larger the ring, the more the carbon atoms may be spaced apart from each other.

Formula (1-3):

The Z ₅ system and the Z ₆ are bonded together with the ethyl group to form an aromatic ring (preferably a benzene ring, a naphthalene ring, particularly a benzene ring), and an unsaturated hydrocarbon group having 4 to 12 carbon atoms, and the aromatic ring system may be used. It has at least one alkyl group (having 1 to 4 carbon atoms), an alkoxy group (having 1 to 4 carbon atoms), an aryl group (having 6 to 10 carbon atoms), a hydroxyl group, and a halogen atom as a substituent. The two-valent bond bonds shown by the two "-" are adjacent to the carbon bond, and the adjacent one-valent bond bonds represented by two "-" are arranged adjacent to each other, and the ring is more Large, or at least one carbon atom apart from each other. The two-valent bond key shown by the two "-" is bonded to the adjacent carbon bond, and the two-valent bond key shown by "=CR ₇ -" is bonded by the bond key of the interval "-". It is preferred that at least one carbon atom of the carbon is bonded to the carbon atom adjacent to it. R _{7 is} generally a hydrogen atom, an alkyl group (having 1 to 4 carbon atoms), an alkoxy group (having 1 to 4 carbon atoms), a hydroxyl group or a halogen atom, and a hydrogen atom is preferred.

The Z ₆ system and the Z _{5 are in} common with the ethyl group to form an aliphatic hydrocarbon ring (alicyclic hydrocarbon ring) having 3 to 10 (preferably 4 to 6, especially 4) carbon atoms. The hydrocarbon group and the saturated hydrocarbon ring system may have at least one alkyl group (having 1 to 4 carbon atoms), an alkoxy group (having 1 to 4 carbon atoms), and an aryl group (having 6 to 10 carbon atoms). A hydroxyl group or a halogen atom is used as a substituent.

Formula (1-4):

Z ₇ is a common hydrocarbon group having a carbon number of 4 to 12 which is an aromatic ring (preferably a benzene ring, a naphthalene ring, particularly a benzene ring) which is common to Z ₈ and which forms an aromatic ring. It has at least one alkyl group (having 1 to 4 carbon atoms), an alkoxy group (having 1 to 4 carbon atoms), an aryl group (having 6 to 10 carbon atoms), a hydroxyl group, and a halogen atom as a substituent. 2 "-" of FIG. 1 a monovalent bond bonding (Z ₇ on the right side of the bonding bond, or, Z ₇ of the left key bonding) system are each bonded to adjacent carbon atoms, a group bonded The bonds may be arranged adjacent to each other, and if the rings are larger, they may be arranged with at least one carbon atom apart from each other.

The Z ₈ series and Z _{7 are in} common with the ethyl group to form an aliphatic hydrocarbon ring (alicyclic hydrocarbon ring), and the number of carbon atoms is 3 to 10 (preferably 4 to 6, especially 4). The hydrocarbon group and the saturated hydrocarbon ring system may have at least one alkyl group (having 1 to 4 carbon atoms), an alkoxy group (having 1 to 4 carbon atoms), an aryl group (having 6 to 10 carbon atoms), and a hydroxyl group. A halogen atom is used as a substituent.

Among the formulae (1-1) to (1-4), the organic group represented by the formulae (1-1) and (1-2) is preferred, and the organic group represented by the formula (1-1) is particularly good.

The aromatic group of R ₁ and the tetravalent organic group of the alicyclic hydrocarbon group,

The one shown is good.

A ¹ is a divalent aromatic ring (preferably a benzene ring, a naphthalene ring, particularly a benzene ring) or an AR-R ₁₀ -AR [only, AR is an alkyl group which may have a substituent { preferably at least 1) a benzene ring having two valences (having 1 to 4 carbon atoms), an aryl group (6 to 10 carbon atoms), an alkoxy group (1 to 4 carbon atoms), a hydroxyl group or a halogen atom (preferably Unsubstituted), R ₁₀ is an alkylene group (preferably having 1 to 4 carbon atoms), -SO ₂ -, -COO-, -CONH, preferably -SO ₂ -.

R ₈ and R ₉ are each independently a single bond, an alkyl group (having 1 to 4 carbon atoms), -SO ₂ -, -COO-, or -CONH-, and a single bond or -CONH- is preferred.

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, particularly 6), and the saturated hydrocarbon ring system may have at least One alkyl group (having 1 to 4 carbon atoms), an alkoxy group (having 1 to 4 carbon atoms), an aryl group (having 6 to 10 carbon atoms), a hydroxyl group, and a halogen atom are used as a substituent.

In the formula (I), the X system is a divalent organic group as described above, and examples thereof include a proline group, a hydroxyproline group, an aromatic or aliphatic ester group, a guanamine group, and an amidoxime group. A decyloxy group, an epoxy group, an oxetanyl group or the like is at least partially constituted.

The m system is an integer of 1 or more as described above. Since the preferred number average molecular weight of (A) polyglycine is from 1,000 to 1,000,000, more preferably from 5,000 to 500,000, more preferably from 10,000 to 200,000, it is preferred to set m to satisfy this condition.

A compound having the structure represented by the general formula (I) is represented by the following general formula (II):

The compounds shown are particularly preferred. R ₂ , X, m, and n are as described in the formula (I).

Further, a compound having a structure represented by the general formula (I) can also be applied to a compound having a structure represented by the following general formula (III). In the general formula (I), n is 1 or more, and by using a polyamic acid having a copolymerization structure represented by the general formula (III), the glass transition temperature (Tg) of the cured product can be improved. In other words, it is possible to obtain a cured product which is excellent in resolution and excellent in heat resistance, etc., based on a positive photosensitive resin composition containing a polyamic acid having a copolymerization structure.

(wherein 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, R ₂ , R ₄ and R ₆ is a divalent organic group, R ₃ and R ₅ are a tetravalent organic group, m is an integer of 1 or more, n and s are each independently, and are 0 or 1 or more integers, and at least one of n and s is 1 or more. The integer).

R ₁ and R ₂ in the general formula (III) are as described in the formula (I).

R ₃ and R ₅ in the general formula (III) are a tetravalent organic group as described above, and may, for example, be a group having a substituted or unsubstituted aromatic skeleton or a substituted or unsubstituted cyclic aliphatic skeleton. The group is preferably a group having a substituted or unsubstituted aromatic skeleton, more preferably a group having a benzene skeleton, a group having a biphenyl skeleton or a group having a bisbenzene skeleton.

Here, as the bisbenzene skeleton, for example, -O-, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -SO ₂ - a double benzene skeleton linked to -SO-, -S- or -CO-.

R ₄ and R ₆ in the general formula (III) are a divalent organic group as described above, and are the same as R ₂ in the above general formula (I).

The sum of n and s, with respect to m, is, for example, m:(n+s)=1:0~10, preferably m:(n+s)=1:0.1~5, more preferably m:(n +s) = 1:0.3~3.

Further, in the general formula (III), the compound wherein s is 0 can be represented by the following general formula (IV).

R ₁ to R ₄ , m and n are as described in the formula (III).

a compound having the structure represented by the general formula (III), each It is preferable to have a structure represented by the following general formula (V).

R ₂ to R ₆ , m, n, and s are as described in the formula (III).

Further, in the general formula (V), the compound in which s is 0 can be represented by the following general formula (VI).

R ₂ to R ₄ , m and n are as described in the formula (III).

Further, when a pattern film is formed by short-wavelength light, R ₁ to R ₆ each may contain an aliphatic group from the viewpoint of absorption characteristics of the polymer. Further, for example, when R ₁ to R ₆ contain a fluorine-containing group, the low-wavelength or dielectric properties of light absorption can be improved.

Thereby, the alkali developability is improved, and a favorable pattern film can be obtained.

The acid value of the (A) polyproline 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 or less.

(A) The acid value of polylysine is determined according to JIS K-5601-2-1 of. Further, in the case of the dilution solvent of the sample, a mixed solvent of acetone/water (9/1 by volume) was used, and the acid value was 0 so that the acid value of the anhydrous acid can also be measured.

The method for synthesizing the above (A) polyproline is not particularly limited, and can be prepared by a conventionally known method. For example, an acid dianhydride having a cyclic aliphatic skeleton and an aromatic skeleton is mixed with a diamine in a solution to synthesize it. Such a synthesis method can be synthesized in a one-stage reaction, and can be obtained easily and at low cost, and is preferable because no further modification is required. In addition, since at least two of the acid anhydride and the diamine are used, the compound having the structure represented by the general formula (III) can be copolymerized and easily produced.

In order to obtain the acid anhydride having a cyclic aliphatic skeleton and an aromatic skeleton used in the above (A) polyproline, it is preferably a carboxylic acid dianhydride or a tetracarboxylic dianhydride. The following general formula (8) is taken as an example.

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

(A) The raw material for the synthesis of polylysine can be easily introduced into the polyamic acid of the above general formula (I) by using the acid anhydride of the general formula (8), and the R in the repeating unit ₁ base.

The cyclic aliphatic skeleton of the above acid anhydride is preferably a cyclohexane skeleton. The above-mentioned acid anhydride is preferably one which does not have an alkyl group (for example, t-butyl group) in the aromatic skeleton.

The foregoing acid anhydride is preferably one containing an acid anhydride group having an anhydrous succinic acid structure. The acid anhydride group having an anhydrous succinic acid structure may, for example, be an acid anhydride group as described below.

Among the above acid anhydrides, the following compounds are more preferred.

The molecular weight of the acid anhydride 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 or more.

In the synthesis of (A) polyaminic acid, other known acid dianhydrides may be used in combination without departing from the gist of the present invention.

Examples of such other acid dianhydrides include ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, methylcyclobutane tetracarboxylic dianhydride, and cyclopentane. An aliphatic tetracarboxylic dianhydride such as tetracarboxylic dianhydride; pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3 '-benzophenone tetracarboxylic dianhydride, 2,3',3,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,3',3,4'-biphenyltetracarboxylic dianhydride, 2,2',6,6'-biphenyltetracarboxylate Acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, bis(3,4-dicarboxyl) Phenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)ruthenium anhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyl) Phenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3- Hexafluoropropane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 1,3-double [(3,4) -dicarboxy)benzimidylbenzene phthalic anhydride, 1,4-bis[(3,4-dicarboxyl) Benzyl hydrazinyl phthalic anhydride, 2,2-bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}propane dianhydride, 2,2-double {4-[3 -(1,2-dicarboxy)phenoxy]phenyl}propane dianhydride, bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}one dianhydride, double {4- [3-(1,2-Dicarboxy)phenoxy]phenyl}one dianhydride, 4,4'-bis[4-(1,2-dicarboxy)phenoxy]biphenyl dianhydride, 4, 4'-double [3- (1,2-dicarboxy)phenoxy]biphenyl dianhydride, bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}one dianhydride, double {4-[3- (1,2-dicarboxy)phenoxy]phenyl}one dianhydride, bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}ruthenic anhydride, double {4-[ 3-(1,2-dicarboxy)phenoxy]phenyl}ruthenic anhydride, bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}thioether dianhydride, double { 4-[3-(1,2-dicarboxy)phenoxy]phenyl}thioether dianhydride, 2,2-bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl }-1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}-1,1 , 1,3,3,3-hexafluoropropane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-double (2,3- or 3,4-dicarboxyphenyl)propane dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1 , 2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-decanetetracarboxylic dianhydride, 2,3,6,7-nonanedicarboxylic dianhydride, 1,2,7, 8-phenanthrenecarboxylic acid dianhydride, pyridine tetracarboxylic dianhydride, sulfonyl phthalic anhydride, m-ter-phenyl-3,3',4,4'-tetracarboxylic dianhydride, p- Aromatic tetracarboxylic dianhydride such as ter-phenyl-3,3',4,4'-tetracarboxylic dianhydride Wait.

In order to obtain the diamine used in the above (A) polyproline, the diamine represented by the following general formula (10) can be mentioned. However, the following is an example, and a person skilled in the art can be used without departing from the gist of the present invention.

H ₂ NR ₂ . NH ₂ (10)

(wherein R ₂ is as described in the formula (I)).

The above diamine is preferably one having an aromatic ring and more preferably having a plurality of aromatic rings. When there are a plurality of aromatic rings, the aromatic ring This is preferred by direct bonding or by trans (thio)ether groups.

Examples of the diamine in which R ₂ is a divalent aromatic group include p-phenylenediamine, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'- Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-di Aminobiphenyl, 9,10-bis(4-aminophenyl)anthracene, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylanthracene, 3,3' -diaminodiphenylphosphonium, 4,4'-diaminodiphenylarylene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy) Phenyl]anthracene, bis[4-(3-aminophenoxy)phenyl]anthracene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-double ( 3-aminophenoxybiphenyl, bis[4-(4-aminophenoxy)phenyl]ether, 1,1,1,3,3,3-hexafluoro-2,2-dual (4 -aminophenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,1,1 , 3,3,3-hexafluoro-2,2-bis(3-amino-4-methylphenyl)propane, m-phenylenediamine, 3,4'-diaminodiphenyl ether, 4, 4'-Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxyl) Base) benzene, 1,3-bis(4-aminophenoxy)benzene.

Examples of the diamine in which R ₂ is a divalent aliphatic group include 1,1-m-dimethylphenylene diamine, 1,3-propanediamine, tetramethylenediamine, and quinone. Methyldiamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, ninethylenediamine, 4,4-diaminoheptamethylenediamine, 1,4 - diaminocyclohexane, isophorone diamine, tetrahydrobicyclopentylene diamine, hexahydro-4,7-methylene quinone dimethylene diamine, tricyclo [6.2. 1.02,7]-undecene dimethyldiamine, 4,4'-methylenebis(cyclohexylamine), isophoronediamine.

In addition, as another example, a diamine-based polyoxane represented by the following formula (11) and the like can be given.

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, examples of R ₂₈ and R ₂₉ in the above formula (11) include carbons having a carbon number of 1 to 7 such as a methylene group, an ethyl group and a stretching group, and a phenyl group. In the case of R ₃₀ and R ₃₁ , an alkyl group having 1 to 7 carbon atoms such as a methyl group or an ethyl group, an aryl group having a carbon number of 6 to 12 such as a phenyl group, or the like can be given.

The diamine is particularly preferably a diaminodiphenyl ether such as 3,4'-diaminodiphenyl ether or 4,4'-diaminodiphenyl ether.

In the photosensitive resin composition, a single type of material may be used as the (A) polyglycolic acid, and a plurality of types may be used as a mixture. Further, it may be a copolymer composed of a plurality of structures of R ₁ and R ₂ .

The amount of (A) polyglycine blended is preferably from 20 to 80% by mass based on the solid content of the composition.

[(B) Photoacid generator]

(B) The photoacid generator may, for example, be a naphthoquinonediazide compound, Diarylsulfonium salt, triarylsulfonium salt, dialkyl benzamidine methyl phosphonium salt, diarylsulfonium salt, aryl diazonium salt, aromatic tetracarboxylic acid ester, aromatic sulfonate, nitrobenzyl A base ester, an aromatic N-oxy sulfenedimine sulfonate, an aromatic sulfonamide, a benzofluorene diazo sulfonate or the like. (B) The photoacid generator is preferably a solvent retarder. Among them, naphthoquinone diazide compounds are preferred.

As the naphthoquinonediazide compound, specifically, for example, a naphthoquinonediazide adduct of 1,4-(hydroxyphenyl)-1-ethyl-4-isopropylbenzene (for example, three treasures) can be used. TS533, TS567, TS583, TS593, manufactured by Chemical Research Institute, or naphthoquinonediazide adduct of tetrahydroxybenzophenone (for example, BS550, BS570, BS599, manufactured by Sambo Chemical Research Co., Ltd.) .

The (B) photoacid generator may be used singly or in combination of two or more kinds as appropriate. (B) The amount of the photoacid generator to be blended is preferably from 1 to 50 parts by mass based on 100 parts by mass of the above (A) polyglycine. By making it in this range, the balance between the dissolution inhibiting effect and the dissolution promoting effect is improved. More preferably, it is 10 to 40 parts by mass, more preferably 10 to 35 parts by mass, particularly preferably 10 to 25 parts by mass.

Hereinafter, other components which are incorporated in the photosensitive resin composition of the present invention will be described.

In the positive photosensitive resin composition of the present invention, the solvent (C) can be blended. (C) The solvent is not particularly limited as long as it can dissolve (A) polyphthalic acid, (B) photoacid generator, and other additives. For example, N,N'-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N,N'-dimethylacetamide, diethylene glycol Dimethyl ether, cyclopentane Ketone, γ-butyrolactone, α-ethinyl-γ-butyrolactone, tetramethyl urea, 1,3-dimethyl-2-imidazolidinone, N-cyclohexyl-2-pyrrolidone, Dimethyl sulfonium, hexamethylphosphoniumamine, pyridine, γ-butyrolactone, diethylene glycol monomethyl ether. These may be used singly or in combination of two or more. The amount of the solvent to be used may be in the range of 50 to 9000 parts by mass based on 100 parts by mass of the (A) polyphthalic acid, depending on the coating film thickness or viscosity.

In the positive photosensitive resin composition of the present invention, a known sensitizer is blended in order to further improve the light sensitivity.

Further, in the positive photosensitive resin composition of the present invention, a known adhesion aid may be added in order to improve the adhesion to the substrate.

The positive photosensitive resin composition of the present invention is preferably one which does not contain a compound having a phenolic hydroxyl group.

In order to impart processing characteristics or various functional properties to the resin composition of the present invention, various other organic or inorganic low molecular or high molecular compounds may be blended. For example, a coloring agent, a surfactant, a leveling agent, a plasticizer, fine particles, or the like can be used. The fine particles may contain organic fine particles such as polystyrene or polytetrafluoroethylene, colloidal cerium oxide, carbon material, or layered niobate. Further, various coloring agents, fibers, and the like may be blended in the resin composition of the present invention.

[Dry film]

The dry film of the present invention is a resin layer formed by applying and drying a positive photosensitive resin composition of the present invention. The dry film of the present invention can be used by laminating a resin layer to a substrate.

The dry film of the present invention can uniformly coat the positive film of the present invention on a carrier film by a suitable method such as a knife coater, a lip coater, a notch coater, a film coater or the like. The photosensitive resin composition is dried to form the resin layer, and it is preferably produced by laminating a film thereon. The coated film and the carrier film may be the same film material, and different films may also be used.

In the dry film of the present invention, any of known films can be used as the dry film for the carrier film and the film material of the film to be coated.

As the carrier film, for example, 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 coating film, a polyethylene film, a polypropylene film, or the like can be used, but the adhesion 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 positive photosensitive resin composition of the present invention, a patterned film as a cured product thereof is produced as follows.

First, in the first step, a positive-type photosensitive resin composition is applied onto a substrate and dried, or a resin film is transferred from a dry film to a substrate to obtain a coating film. In the method of applying the positive photosensitive resin composition to the substrate, a method for coating a photosensitive resin composition in the past, for example, a spin coater or a bar coating can be used. A method of coating by a machine, a knife coater, a curtain coater, a screen printing machine, or the like, a spray coating method by a spray coater, and an inkjet method or the like can be used. As the drying method of the coating film, a method of heating drying, vacuum drying, or the like by air drying, an oven or a hot plate can be used. Further, the drying of the coating film is preferably carried out under the conditions of imidization of the (A) polyglycolic acid in the photosensitive resin composition. Specifically, it is carried out under natural drying, air drying or heating and drying at 70 to 120 ° C for 20 minutes to 1 hour. It is preferably dried on a hot plate for 20 to 40 minutes. Further, it may be dried in a vacuum, and it is carried out at room temperature for 20 minutes to 1 hour.

The substrate is not particularly limited, and can be widely applied to tantalum wafers, wiring boards, various resins, metals, passivation protective films for semiconductor devices, and the like.

Next, in the second step, the coating film is passed through a mask having a pattern or directly exposed. The exposure light is a wavelength at which the (B) photoacid generator can be activated and the acid can be generated. Specifically, the exposure light is preferably in a range in which the maximum wavelength is in the range of 350 to 410 nm. As described above, when an appropriate sensitizer is used, the light sensitivity can be adjusted. For the exposure device, a contact aligner, a mirror projection, a stepper, a laser direct exposure device, or the like can be used.

Next, in the third step, heat is applied to partially iridize one of the (A) polylysines in the unexposed portion. Here, the oxime imidization ratio is about 30%. The heating time and the heating temperature can be appropriately changed depending on the type of (A) polyphthalic acid, the coating film thickness, and (B) the photoacid generator. Typically, a coating film thickness of about 10 μm is 30 seconds to 3 minutes at 110 to 200 ° C. degree. By setting the heating temperature to 110 ° C or higher, partial sulfiliation can be efficiently achieved. In addition, when the heating temperature is 200° C. or lower, the imidization of the exposed portion can be suppressed, and the difference in solubility between the exposed portion and the unexposed portion can be increased, and the pattern film can be easily formed.

Next, in the case of step 4, the coating film is treated with a developing solution. Thereby, the exposed portion in the coating film is removed, and a pattern film formed of a partially fluorinated (A) polyphthalic acid is formed on the substrate.

As the method used in the development, a conventional development method of a photoresist such as a rotary spray method, a paddle stirrer method, or a dipping method accompanying ultrasonic treatment can be selected. Examples of the developing solution include inorganic bases such as sodium hydroxide, sodium carbonate, sodium citrate, and aqueous ammonia, and organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine, and hydrogen peroxide. An aqueous solution of a quaternary ammonium salt such as tetramethylammonium or tetrabutylammonium hydroxide. Further, an appropriate amount of a water-soluble organic solvent such as methanol, ethanol or isopropyl alcohol or a surfactant may be added thereto as needed. Then, if necessary, the coating film can be washed with a rinsing liquid to obtain a pattern film. As the rinse liquid, distilled water, methanol, ethanol, isopropyl alcohol or the like may be used alone or in combination. Further, as the developing liquid, the above (C) solvent can also be used.

Then, in the case of step 5, the pattern film is heated to obtain a hardened coating film (cured material). At this time, (A) poly-proline is completely imidized, and if it is obtained by polyimine. The heating temperature may be appropriately set so that the pattern film of the polyimide may be hardened. For example, it is heated at 150 to 300 ° C for 5 to 120 minutes in an inert gas. The heating temperature is preferably in the range of 150 to 250 ° C, and more preferably in the range of 180 to 220 ° C. Heating system This is done by using, for example, a heating plate, an oven, or a temperature-increasing oven that can be set with a thermometer. In the atmosphere (gas) at this time, air may be used, and an inert gas such as nitrogen or argon may be used.

The positive photosensitive resin composition of the present invention can be used as a printing ink, an adhesive, a filler, an electronic material, an optical circuit component, a molding material, a resist material, a building material, a three-dimensional shape, an optical member, or the like, and a resin material. A wide range of fields and products, such as paints or printing inks, or color filters, which are widely used in various fields and products, particularly in the properties of heat resistance, dimensional stability, and insulation properties of polyimide films. A material for forming a film for a flexible display, a semiconductor device, an electronic component, an interlayer insulating film, a wiring coating film, an optical circuit, an optical circuit component, an antireflection film, a stereoscopic image, an optical member, and a building material.

In particular, the positive photosensitive resin composition of the present invention is mainly used as a pattern forming material (resist), and the patterned film formed thereby is formed on a permanent film formed of polyimine. It has a function of imparting heat-resistant or insulating components, and is suitable for forming wiring such as a color filter, a film for a flexible display, an electronic component, a semiconductor device, an interlayer insulating film, a solder resist, or a clad film. Coating film, solder dum, optical circuit, optical circuit component, anti-reflection film, other optical components or electronic components. Further, the positive photosensitive resin composition of the present invention is excellent in resolution, and is suitable for use in a package substrate, in particular, a pattern film forming material of a wafer-level package substrate.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention should not be construed as limited. In addition, the following "parts" and "%" are all based on quality unless otherwise specified.

[Synthesis Example 1: Synthesis of Polyaminic Acid A-1]

After placing 30 mmol of the diamine of the following Table 1 in a separation flask having a capacity of 300 mL, the diamine was dissolved by dehydrating NMP (N-methylpyrrolidone) while introducing nitrogen gas. After all the diamine was dissolved, 30 mmol of the anhydride of Table 1 below was slowly added. After the acid anhydride adhering to the wall of the flask was poured into the reaction solution with a small amount of NMP, the mixture was stirred at room temperature for 24 hours to obtain a 15% by mass paint of polyacrylic acid (PAA) A-1. The input amount of the dehydrated NMP was 75% by mass of the paint amount of the PAA. Further, the acid anhydride "TDA" in the table is 4-(2,5-di-oxytetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride (new Japan Science Corporation RIKACID TDA-100). As the diamine "4,4'-ODA", 4,4'-diaminodiphenyl ether (manufactured by Wakayama Seika Co., Ltd.) was used.

[Synthesis Example 2, 3: Synthesis of Polyaminic Acid A-2, A-3]

Except that the diamine and the acid anhydride were each changed to the compound shown in the following Table 2, the same procedure as in Synthesis Example 1 was carried out to obtain a paint of polyamine acid A-2 and A-3. Further, in the table, N,N'-bis(1,2-cyclohexanedicarboxylic anhydride-4-yl)carbonyl-1,4-phenylenediamine (manufactured by Nippon Seika Co., Ltd.) was used as the acid anhydride "PPHT". In the case of the diamine "3,4'-ODA", 3,4'-diaminodiphenyl ether (manufactured by Nippon Pure Chemical Co., Ltd.) was used.

[Synthesis Example 4: Synthesis of polyaminic acid A-4]

After introducing 30 mmol of the diamine of the following Table 3 into a separable flask having a capacity of 300 mL, the diamine was dissolved by dehydrating NMP (N-methylpyrrolidone) while introducing nitrogen gas. After all the diamine was dissolved, 22.5 mmol of the anhydride TDA and 7.5 mmol of PMDA were added slowly in the following table. After the acid anhydride adhering to the wall of the flask was poured into the reaction solution with a small amount of NMP, the mixture was stirred at room temperature for 24 hours to obtain a 15% by mass of a coating of polyacrylic acid (PAA) A-4. The amount of dehydrated NMP is the amount of paint applied by PAA. 75 mass%. Further, in the case of the acid anhydride "PMDA" in the table, pyromellitic anhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was used.

[Synthesis Example 5: Synthesis of polyaminic acid A-5]

The coating of polyaminic acid A-5 was obtained in the same manner as in Synthesis Example 4 except that the amount of the acid anhydride was changed to 15 mg of TDA and 15 mmol of PMDA.

[Synthesis Example 6: Synthesis of polyaminic acid A-6]

The same procedure as in Synthesis Example 4 was carried out except that the amount of the acid anhydride was changed to 7.5 mmol of TDA and 22.5 mmol of PMDA, and a coating of polyamine acid A-6 was obtained.

[Comparative Synthesis Examples 1, 2: Synthesis of Polylysine R-1, R-2]

In addition to changing the diamine and the anhydride to each of the compounds shown in Table 4 below The rest of the composition was carried out in the same manner as in Synthesis Example 1, and the paints of polyamine acids R-1 and R-2 were synthesized. Further, in the case of the acid anhydride "CBDA" in the table, 1,2,3,4-cyclobutanetetracarboxylic dianhydride (manufactured by Nippon Pharmaceutical Co., Ltd.) was used.

(Examples 1 to 16 and Comparative Examples 1 to 3)

In the combination of Table 5, the photoacid generator was blended and dissolved with respect to the coating of polyamic acid to obtain photosensitive resin compositions of the examples and the comparative examples. Further, the blending amount of the photoacid generator in the table is the blending amount per 100 parts by mass of the solid content of the paint of the polyproline.

[Formation method of positive pattern film]

Each of the photosensitive resin compositions of the examples and the comparative examples was uniformly coated with a stirring and defoaming device, and then applied to a decylene plate using a spin coater, and dried at 100 ° C for 30 minutes on a hot plate. A dried coating film of a photosensitive resin composition having a film thickness of about 5 μm was obtained. On the dry coating film, only one half of the mask (transmission rate: 0%) was placed, and the 1J wide-area exposure was performed by a desktop exposure apparatus (manufactured by Sanyo Electric Co., Ltd.) equipped with a high-pressure mercury lamp. Next, post-exposure heating (PEB) was carried out under the conditions of Table 5 using a hot plate. This was developed with a 1% aqueous NaOH solution or a 1% aqueous Na ₂ CO ₃ solution, and washed with water and dried at room temperature to obtain a positive-type film. Table 5 shows the results of the evaluation of the addition amount of the photoacid generator and the PEB conditions.

[comparative evaluation]

The above comparison was obtained by the following formula.

Contrast = exposure portion development speed (film thickness μm / development time min) / unexposed portion development speed (film thickness μm / development time min)

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

Imaging time (min): the time it is immersed in the imaging solution

Based on the value of the comparison, the evaluation is as follows.

◎: 10 or more

○: 2 or more ~ less than 10

△: 1 or more ~ not up to 2

×: none (undesolved)

[Formation of fine positive pattern film]

The photosensitive resin composition of Example 8 was uniformly coated with a stirring and defoaming device, and then applied to a decylene plate using a spin coater, and dried at 100 ° C for 30 minutes to obtain a film thickness. A dried coating film of a photosensitive resin composition of about 5 μm. A thin-line pattern mask of L/S=3/3 μm, 7/7 μm, and 9/9 μm was mounted on the dried film, and a wide-area light exposure of 300 mJ was performed using a mask adhesion exposure stage (Litho Tech Japan). . Thereafter, the PEB was heated at 160 ° C for 1 minute. This was developed with a 1% Na ₂ CO ₃ aqueous solution, washed with water, and dried at room temperature to obtain a positive pattern film. A microscope image of the obtained positive pattern film is shown in Fig. 1. Further, the step (the difference between the surface of the line and the surface of the pitch portion) is shown in Table 6.

(Examples 17 to 20)

[Evaluation of glass transition temperature]

3 g of paint was applied to 15% by mass of polyaminic acid A-1, A-4, A-5, and A-6, and photoacid generator B-1 was added (TS583, DNQ (two manufactured by Sambo Chemical Research Co., Ltd.) 0.075 g of azonaphthylquinone)), and the photosensitive resin compositions of Examples 17-20 were obtained. The obtained photosensitive resin composition was applied onto a crucible wafer by an applicator, and heated at 100 ° C for 10 minutes, and then heated. The film was heat-treated at 200 ° C for 30 minutes to prepare a cured film. The cured film was peeled off from the tantalum wafer, and the glass transition temperature (Tg) was measured. The Tg was measured under the conditions of 50 ° C to 350 ° C, a temperature increase rate of 10 ° C/min, and a frequency of 1 Hz using a dynamic viscoelasticity measuring apparatus RSA-G2 manufactured by TA Instrument.

As is apparent from the results shown in Tables 5 and 6, and the photosensitive resin composition of the present invention, a positive pattern film having excellent contrast and high resolution can be obtained. In particular, even in the case of L/S=3/3 μm, the step difference is large, and a dissolution promoting effect and a blocking effect are obtained, and the resolution is excellent. Further, with respect to the specific polyamine acid of the present invention, the photosensitive resin composition of the comparative example in which other polyglycine was blended was not able to be compared, and a positive pattern film could not be formed.

Further, as shown in Tables 5 and 7, the polyamino acid (A) can be obtained by using TDA as an acid anhydride having a cyclic aliphatic skeleton and an aromatic skeleton and optionally copolymerizing it. A material that is excellent in resolution and imparts heat resistance.

Claims (12)

A positive photosensitive resin composition containing the following (A) and (B), (A) a polyamic acid obtained from an acid anhydride having a cyclic aliphatic skeleton and an aromatic skeleton and a diamine, (B) ) Photoacid generator. The positive photosensitive resin composition of claim 1, wherein the (A) polyphthalic acid has a compound having the structure represented by the following general formula (I): (wherein 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 an R ₂ -based divalent organic group; And X is a divalent organic group, m is an integer of 1 or more, n is 0 or an integer of 1 or more). The positive photosensitive resin composition of claim 2, wherein the (A) polyamic acid has a compound having the structure represented by the following general formula (II): (wherein R ₂ is a divalent organic group, an X-based divalent organic group, m is an integer of 1 or more, n is 0 or an integer of 1 or more). The positive photosensitive resin composition of claim 2, wherein the (A) polyamic acid has a compound having the structure represented by the following general formula (III): (wherein 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, R ₂ , R ₄ and R ₆ is a divalent organic group, R ₃ and R ₅ are a tetravalent organic group, m is an integer of 1 or more, n and s are each independently, and are 0 or 1 or more, and at least one of n and s is 1 or more. The integer). The positive photosensitive resin composition of claim 4, wherein the (A) polyphthalic acid has a compound having the structure represented by the following general formula (V): (wherein R ₂ , R ₄ and R ₆ are a divalent organic group, R ₃ and R ₅ are a tetravalent organic group, m is an integer of 1 or more, n and s are each independently, and are an integer of 0 or 1 or more, And at least one of n and s is an integer of 1 or more). The positive photosensitive resin composition of claim 1, wherein the amount of the (B) photoacid generator blended is 1 to 50 parts by mass based on 100 parts by mass of the (A) polyamine. The positive photosensitive resin composition of claim 1, which is used in a method of forming a pattern film comprising the step of exposing a coating film of a positive photosensitive resin composition to an exposure step Then, the heating step of heating the coating film and the developing step of developing after the heating step are performed. A dry film comprising a positive-type photosensitive resin composition according to any one of claims 1 to 7 which is applied onto a film and dried to obtain a resin layer. A cured product obtained by hardening a positive photosensitive resin composition according to any one of claims 1 to 7. A cured product characterized by hardening a resin layer of the dry film of claim 8. A printed wiring board characterized by having a cured product as claimed in claim 9. A printed wiring board characterized by having a cured product as claimed in claim 10.