TWI696893B - Positive photosensitive resin composition, dry film, hardened material and printed wiring board - Google Patents

Abstract

The present invention provides a positive photosensitive resin composition excellent in resolution, a dry film having a resin layer obtained from the composition, a cured product of a resin layer having the composition or the dry film, and having the cured Printed wiring board.

(式中，R₁係含由芳香族環與脂肪族烴環所成縮合環之4價有機基、或含芳香族基與脂環式烴基之4價有機基、R₂係2價有機基、X係2價有機基、m係1以上之整數、n係0或1以上之整數)。 The present invention contains (A) an acid anhydride having a cyclic aliphatic skeleton and an aromatic skeleton, a polyamic acid obtained from a diamine, and (B) a positive photosensitive resin composition characterized by a photoacid generator, etc. . The aforementioned (A) polyamide is preferably a compound having a structure represented by the following general formula (I),

(In the formula, R ₁ is a tetravalent organic group containing a condensed ring formed by 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, m is an integer of 1 or more, and n is an integer of 0 or more).

Description

Positive photosensitive resin composition, dry film, hardened material 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.

Polyimide is widely used in various fields based on its excellent properties such as high insulation, heat resistance, and high mechanical strength. For example, it does not stagnate in the aerospace field that was initially applied, and now also relates to the application of coated films of semiconductor elements, flexible printed wiring boards, and heat-resistant insulating interlayer materials.

Polyimide is thermoplastic and has poor solubility in organic solvents, making it difficult to process. Therefore, polyimide is widely used by the following method: after irradiating active light to a photosensitive resin composition obtained by blending a compound of polyamic acid and a photoreactive compound, by imaging The desired patterned film is formed, and then a high temperature is applied to close the ring, and the compound is 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 polyamic acid condensate of aromatic dianhydride and aromatic diamine. In addition, Patent Document 2 describes a positive photosensitive resin composition containing a poly(amide-amide) resin having a specific structure and a photoacid generator.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Unexamined Patent Publication No. 52-13315

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

In recent years, with the advancement of semiconductor mounting technology and higher density, it is required to make the patterned film finer. However, as with the photosensitive resin composition described above, it is difficult to obtain a 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 of a resin layer having the composition or the dry film, and A printed wiring board having the hardened material.

The inventors of the present invention have taken into consideration the above-mentioned problems and found that if the polyamic acid obtained from the anhydride and the diamine having a cyclic aliphatic skeleton and an aromatic skeleton is used to replace the acid having an aromatic skeleton The polyamic acid obtained from the anhydride and the diamine unexpectedly obtains a hardened product with excellent resolution.

Moreover, the present inventors have found that, compared to poly(amide-amide) resins which are partially imidized by using polyamic acid, poly(amide-imide) resins which are not imidized are used in essence. The amine acid can obtain a hardened product with excellent resolution.

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

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

(In the formula, R ₁ is a tetravalent organic group containing a condensed ring formed by 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, m is an integer of 1 or more, and n is an integer of 0 or more).

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

(In the formula, 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 more).

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

(In the formula, R ₁ is a tetravalent organic group containing a condensed ring formed by 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 independent, an integer of 0 or more, and at least one of n and s is 1 or more Integer).

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

(In the formula, R ₂ , R ₄ and R ₆ are divalent organic groups, R ₃ and R ₅ are tetravalent organic groups, m is an integer of 1 or more, n and s are each independent, and are integers of 0 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 blending amount of the (B) photoacid generator is preferably 1 to 50 parts by mass for 100 parts by mass of the (A) polyamic acid.

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

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

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 by having the aforementioned 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 of the resin layer having the composition or the dry film, and having The printed wiring board of the hardened material.

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

The positive photosensitive resin composition of the present invention is characterized by 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.

In the present invention, the acid anhydride of the raw material of polyamic acid is obtained by using a cyclic aliphatic skeleton and an aromatic skeleton, thereby obtaining a hardened product excellent in resolution. For example, a patterned film with L/S of 10/10 μm or less can be obtained.

In addition, the positive photosensitive resin composition of the present invention exhibits particularly excellent resolution when heated after light irradiation and before development. That is, by irradiating active light to the coating film of the positive photosensitive resin composition of the present invention, the solubility of the irradiated portion increases, and a difference in solubility occurs between the irradiated portion and the non-irradiated portion. Then, it is heated, and a part of the polyamic acid in the unexposed part is imidized and then formed by development. Positive type film with excellent resolution. After the development, it is heated at a high temperature, as long as it can be completely imidized.

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

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

The (A) polyamic acid obtained from the acid anhydride and diamine having a cyclic aliphatic skeleton and aromatic skeleton used in the present invention (hereinafter also referred to as "(A) polyamic acid") is not substantially Amidation. (A) Polyamic acid, preferably having a structure represented by the following general formula (I).

(In the formula, R ₁ is a tetravalent organic group containing a condensed ring formed by 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, m is an integer of 1 or more, and n is an integer of 0 or more).

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

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

Formula (1-1):

Z ₁ is common with Z ₂ to form an aromatic ring (preferably a benzene ring, a naphthalene ring, especially a benzene ring) together with an ethylidene group, and an unsaturated hydrocarbon group having 4 to 12 carbon atoms. The aromatic ring system may be It has at least one alkyl group (1 to 4 carbon atoms), alkoxy group (1 to 4 carbon atoms), aryl group (6 to 10 carbon atoms), hydroxyl group, and halogen atom as substituents.

Z ₂ is an aliphatic group having 3 to 10 (preferably 4 to 6, especially, 4) carbon atoms which form an aliphatic hydrocarbon ring (alicyclic hydrocarbon) together with Z _{1 in} common with Z ₁ Hydrocarbon group, aliphatic hydrocarbon ring system may have at least one alkyl group (carbon number 1-4), alkoxy group (carbon number 1-4), aryl group (carbon number 6-10), Hydroxyl groups and halogen atoms are used as substituents. Two 1-valent bonding bonds (that is, a group of bonding bonds, a bonding bond to the right of Z ₂ ) shown by two "-" are bonded to adjacent carbons, but "=CR _6- "The bivalent bond shown in "is preferably bonded to the carbon atom adjacent to the carbon atom or the carbon atom adjacent to it by the two "-" bonding bonds. Especially the latter is better. For example, when the aliphatic hydrocarbon ring is a cyclohexane ring, it is bonded with 2 "-" bonds at the 3,4 position, and "=CR at the 2 or 1 position (preferably 1 position)" ₆ -" The bond is better. 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, and a halogen atom, among which a hydrogen atom is preferred.

Formula (1-2):

Z ₃ is common with Z ₄ to form an aromatic ring (preferably a benzene ring, a naphthalene ring, especially a benzene ring) with 4 to 12 carbon atoms unsaturated hydrocarbon groups together with ethylidene. The aromatic ring system can be It has at least one alkyl group (1 to 4 carbon atoms), alkoxy group (1 to 4 carbon atoms), aryl group (6 to 10 carbon atoms), hydroxyl group, and halogen atom as substituents.

Z ₄ is an aliphatic group having 3 to 10 carbon atoms that form an aliphatic hydrocarbon ring (alicyclic hydrocarbon) with ethyl groups in common with Z ₃ (preferably 4 to 6 carbon atoms, especially 4 carbon atoms) Hydrocarbon group, aliphatic hydrocarbon ring system may have at least one alkyl group (carbon number 1-4), alkoxy group (carbon number 1-4), aryl group (carbon number 6-10), Hydroxyl groups and halogen atoms are used as substituents. Two 1-valent bonding bonds (a group of bonding bonds, a group of bonding bonds on the right side of Z ₄ or a group of bonding bonds on the left side) shown by "-" are each bonded to the adjacent carbon, A group of bonding bonds can also be arranged adjacent to each other. If the ring is larger, it can also be arranged with at least one carbon atom apart from each other.

Formula (1-3):

Z ₅ is an unsaturated hydrocarbon group with 4 to 12 carbon atoms, which is common to Z ₆ and forms an aromatic ring (preferably a benzene ring, a naphthalene ring, especially a benzene ring) together with ethylidene. The aromatic ring system can be It has at least one alkyl group (1 to 4 carbon atoms), alkoxy group (1 to 4 carbon atoms), aryl group (6 to 10 carbon atoms), hydroxyl group, and halogen atom as substituents. Two "-" monovalent bonding bonds are shown to be bonded to adjacent carbon, and two "-" adjacent monovalent bonding bonds can be placed adjacent to each other in combination. It can be arranged at least one carbon atom apart from each other. Two 1-valent bond bonds shown by "-" are bonded to the adjacent carbon, and a 2-valent bond bond shown by "=CR ₇ -" is bonded by a bond bond separated by "-" At least one carbon atom of the carbon is preferably bonded to the carbon atom next to it. R _{7 is} generally a hydrogen atom, an alkyl group (with 1 to 4 carbon atoms), an alkoxy group (with 1 to 4 carbon atoms), a hydroxyl group, and a halogen atom, preferably a hydrogen atom.

Z ₆ is a fat having 3 to 10 (preferably 4 to 6, especially 4) carbon atoms that form an aliphatic hydrocarbon ring (alicyclic hydrocarbon ring) together with Z _{5 in} common with Z ₅ Group hydrocarbon group, saturated hydrocarbon ring system may have at least one alkyl group (carbon number 1-4), alkoxy group (carbon number 1-4), aryl group (carbon number 6-10), Hydroxyl groups and halogen atoms are used as substituents.

Formula (1-4):

Z ₇ is common with Z ₈ to form an aromatic ring (preferably benzene ring, naphthalene ring, especially benzene ring) with 4 to 12 carbon atoms unsaturated hydrocarbon group together with ethylidene ring. The aromatic ring system can be It has at least one alkyl group (1 to 4 carbon atoms), alkoxy group (1 to 4 carbon atoms), aryl group (6 to 10 carbon atoms), hydroxyl group, and halogen atom as substituents. 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 as the ring is larger, it may be arranged with at least one carbon atom apart from each other.

Z ₈ is common to Z ₇ and is saturated with ethylidene groups to form an aliphatic hydrocarbon ring (alicyclic hydrocarbon ring) with 3 to 10 carbon atoms (preferably 4 to 6, especially, 4). Hydrocarbon group, saturated hydrocarbon ring system may have at least one alkyl group (carbon number 1-4), alkoxy group (carbon number 1-4), aryl group (carbon number 6-10), hydroxyl group , Halogen atom as a substituent.

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

With respect to the tetravalent organic group containing the aromatic group and the alicyclic hydrocarbon group of R ₁ ,

The ones shown are better.

A ¹ is a divalent aromatic ring (preferably a benzene ring, a naphthalene ring, especially a benzene ring) or AR-R ₁₀ -AR [however, AR is an alkyl group which may have a substituent {preferably at least one alkyl group (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 having 1 to 4 carbon atoms), -SO ₂ -, -COO-, and -CONH, preferably -SO ₂ -].

R ₈ and R ₉ are each independently a single bond, an alkylene group (with 1 to 4 carbon atoms), -SO ₂ -, -COO-, and -CONH-, and preferably a single bond and -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 system may have at least One alkyl group (with 1 to 4 carbon atoms), alkoxy group (with 1 to 4 carbon atoms), aryl group (with 6 to 10 carbon atoms), hydroxyl group, and halogen atom as substituents.

In formula (I), X is a divalent organic group as described above, and examples thereof include an amide acid group, a hydroxy amide acid group, an aromatic or aliphatic ester group, an amide group, an amide amide imine group , Siloxane groups, epoxy groups, oxetanyl groups, etc. are at least partially constituted groups.

m is an integer of 1 or more as described above. Since (A) the polyamide preferably has a number average molecular weight of 10 to 1 million, more preferably 5,000 to 500,000, and more preferably 10,000 to 200,000, it is better to set m to satisfy this condition.

The 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 formula (I).

In addition, the compound having the structure represented by the general formula (I) can also be applied to the compound having the structure represented by the following general formula (III). In general formula (I), n is 1 or more. By using a polyamide having a copolymerization structure shown in general formula (III), for example, the glass transition temperature (Tg) of the cured product can be increased. That is, according to the positive photosensitive resin composition containing polyamic acid having a copolymer structure, it is possible to obtain a cured product that is excellent in terms of resolution and excellent in heat resistance.

(In the formula, R ₁ is a tetravalent organic group containing a condensed ring formed by 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 independent, an integer of 0 or more, and at least one of n and s is 1 or more Integer).

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

R ₃ and R ₅ in general formula (III) are as described above and are tetravalent organic groups, and examples thereof include 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, and more preferably a group having a benzene skeleton, a group having a biphenyl skeleton or a group having a biphenyl skeleton.

Here, the bisbenzene skeleton includes, for example, -O-, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -SO _2- , -SO-, -S- or -CO- linked bisbenzene skeleton.

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

The sum of n and s, relative 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.

In addition, in the general formula (III), the compound in which s is 0 can be represented by the following general formula (IV).

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

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

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

In addition, 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 formula (III).

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

With this, the alkali developability is improved, and a good patterned film can be obtained.

The acid value of the aforementioned (A) polyamic acid is preferably 100 mgKOH/g or more, more preferably 150 mgKOH/g or more, and even 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 polyamide is determined according to JIS K-5601-2-1 of. In addition, for the dilution solvent of the sample, a mixed solvent of acetone/water (9/1 volume ratio) and an acid value of 0 were used so that the acid value of the anhydrous acid can also be measured.

The synthesis method of (A) polyamic acid is not particularly limited, and can be prepared by a conventionally known method. For example, acid dianhydride and diamine having cyclic aliphatic skeleton and aromatic skeleton can be synthesized by mixing in solution. Such a synthesis method can be synthesized in a one-stage reaction and can be obtained easily and at low cost, and is preferred because it does not require further modification. In addition, since at least one of acid anhydride and diamine is used in two or more types, the compound having the structure represented by the general formula (III) described above is copolymerized to be easily produced.

In order to obtain the acid anhydride having a cyclic aliphatic skeleton and an aromatic skeleton used in the aforementioned (A) polyamic acid, a carboxylic dianhydride is preferable, and a tetracarboxylic dianhydride is more preferable. An example can be given as shown in the following general formula (8).

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

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

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

The aforementioned acid anhydride preferably includes an acid anhydride group having an anhydrous succinic acid structure. Examples of the acid anhydride group having an anhydrous succinic acid structure include the following acid anhydride groups.

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

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

(A) In the synthesis of polyamic 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. Aliphatic tetracarboxylic dianhydride such as tetracarboxylic dianhydride; pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3 '-Benzophenone tetracarboxylic dianhydride, 2,3',3,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,3',3,4'-biphenyltetracarboxylic dianhydride, 2,2',6,6'-biphenyltetracarboxylic dianhydride Acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl) propane dianhydride, bis(3,4-dicarboxy Phenyl) ether dianhydride, bis(3,4-dicarboxyphenyl) lanthanide dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxy 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-bis ((3,4 -Dicarboxy)benzoyl]phthalic anhydride, 1,4-bis[(3,4-dicarboxy)benzoyl]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}ketone dianhydride, bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}ketone dianhydride, 4, 4'-bis[4-(1,2-dicarboxy)phenoxy]biphenyl dianhydride, 4,4'-bis[3- (1,2-dicarboxy)phenoxy]biphenyl dianhydride, bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}ketone dianhydride, bis{4-[3- (1,2-dicarboxy)phenoxy]phenyl} ketone dianhydride, bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl} benzene dianhydride, bis{4-[ 3-(1,2-dicarboxy)phenoxy]phenyl} benzene dianhydride, bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl} sulfide dianhydride, bis{ 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-bis (2,3- or 3,4-dicarboxyphenyl) propane dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1 ,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7, 8-phenanthrene tetracarboxylic dianhydride, pyridine tetracarboxylic dianhydride, sulfonyl phthalic anhydride, m-ter-phenyl-3,3',4,4'-tetracarboxylic dianhydride, p- Ter-phenyl-3,3',4,4'-tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, etc.

In order to obtain the diamine used for the said (A) polyamic acid, the diamine represented by the following general formula (10) is mentioned. However, the following is an example, and a known one can be used without departing from the gist of the present invention.

H ₂ NR ₂ . NH ₂ (10)

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

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

Examples of the diamine when R ₂ 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'-di Aminobiphenyl, 9,10-bis(4-aminophenyl)anthracene, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylbenzene, 3,3' -Diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfoxide, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy Radical) phenyl] lanthanum, bis [4- (3-aminophenoxy) phenyl] lanolin, 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 -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-aminophenoxy Group) benzene, 1,3-bis(4-aminophenoxy)benzene.

Examples of the diamine when R ₂ is a divalent aliphatic group include 1,1-m-dimethylenediphenyldiamine, 1,3-propanediamine, tetramethylenediamine, and pentamethylene Methyldiamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1,4 -Diamine cyclohexane, isophorone diamine, tetrahydrodicyclopentadienyl diamine, hexahydro-4,7-methylene indane dimethylene diamine, tricyclic [6.2. 1.02,7]-undecene dimethyl diamine, 4,4'-methylene bis (cyclohexyl amine), isophorone diamine.

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

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

Specifically, the aspects of R ₂₈ and R ₂₉ in the above formula (11) include carbon atoms such as methylene, ethylidene, and propylidene, which have a carbon number of 1 to 7, and phenylidene. Examples of R 6 and 18 are aryl aryl groups, and 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 atoms such as phenyl.

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

In the photosensitive resin composition, (A) for the polyamic acid, a single kind of material may be used, or plural kinds may be used as a mixture. In addition, it may be a copolymer composed of a plurality of structures of each of R ₁ and R ₂ .

(A) The blending amount of the polyamic acid is preferably 20 to 80% by mass based on the solid content of the composition.

[(B) Photoacid generator]

(B) The photoacid generator includes naphthoquinonediazide compounds, Diarylammonium salt, triarylammonium salt, dialkylbenzylmethylammonium salt, diarylphosphonium salt, aryldiazonium salt, aromatic tetracarboxylic acid ester, aromatic sulfonate, nitrobenzyl Esters, aromatic N-oxyamide imine sulfonate, aromatic sulfonamide, benzoquinone diazosulfonate, etc. (B) The photoacid generator is preferably a solvent-resisting agent. Among them, naphthoquinonediazide compounds are preferred.

For naphthoquinonediazide compounds, specifically, naphthoquinonediazide adducts of ginseng (4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene (for example, Sambo TS533, TS567, TS583, TS593 manufactured by the Institute of Chemistry), or naphthoquinone diazide adducts of tetrahydroxybenzophenone (e.g., BS550, BS570, BS599 manufactured by Sambo Chemical Institute), etc. .

Such (B) photoacid generators may be used alone or in combination of two or more. (B) The blending amount of the photoacid generator is preferably 1 to 50 parts by mass relative to 100 parts by mass of the aforementioned (A) polyamic acid. By making it within this range, the balance between the dissolution inhibiting effect and the dissolution promoting effect becomes better. It is more preferably 10 to 40 parts by mass, more preferably 10 to 35 parts by mass, and particularly preferably 10 to 25 parts by mass.

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

In the positive photosensitive resin composition of the present invention, the (C) solvent may be blended. (C) The solvent is not particularly limited as long as it can dissolve (A) polyamic 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-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolidinone, N-cyclohexyl-2-pyrrolidone, Dimethyl sulfoxide, hexamethylphosphoramide, pyridine, γ-butyrolactone, diethylene glycol monomethyl ether. These can be used alone or in combination of two or more. The amount of solvent used depends on the coating film thickness or viscosity, and it can be used in the range of 50 to 9000 parts by mass relative to (A) 100 parts by mass of polyamide.

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

In addition, in the positive photosensitive resin composition of the present invention, in order to improve the adhesion with the base material, a known adhesion aid may be added.

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

In order to impart processing properties 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, coloring agents, surfactants, leveling agents, plasticizers, fine particles, and the like can be used. The fine particles may contain organic fine particles such as polystyrene and polytetrafluoroethylene, inorganic fine particles such as colloidal silica, carbon materials, and layered silicate. Furthermore, the resin composition of the present invention may be blended with various coloring agents and fibers.

[Dry film]

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

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

In the dry film of the present invention, as the film material of the carrier film and the coating film, any of the known ones can be used as the dry film.

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

For the coating film, polyethylene film, polypropylene film, etc. can be used, but the adhesion to the photosensitive resin layer is better than the carrier film.

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

Using the positive photosensitive resin composition of the present invention, a patterned film as its cured product is manufactured as follows.

First, in step 1, the coating film is obtained by applying a positive photosensitive resin composition on a substrate and drying it, or transferring the resin layer onto the substrate from a dry film. As for the method of applying the positive photosensitive resin composition on the substrate, the method used for coating the photosensitive resin composition in the past can be used, for example, a spin coater or a bar coater The method of coating by a machine, a blade coater, a screen coater, a screen printing machine, etc., the method of spray coating by a spray coater, and the inkjet method etc. can also be used. As for the drying method of the coating film, methods such as heat drying, vacuum drying, etc. using air drying, an oven or a hot plate can be used. In addition, the drying of the coating film is preferably performed under conditions that do not cause the imidate of (A) polyamic acid in the photosensitive resin composition. Specifically, it is performed under conditions of natural drying, air drying or heat drying at 70 to 120°C for 20 minutes to 1 hour. Preferably, it is dried on a hot plate for 20 to 40 minutes. In addition, it can also be vacuum-dried. In this case, it is performed at room temperature under the conditions of 20 minutes to 1 hour.

There is no particular limitation on the substrate, and it can be widely applied to silicon wafers, wiring boards, various resins, metals, and passivation protective films of semiconductor devices.

Next, in step 2, the coating film is exposed through a photomask with a pattern or directly exposed. The exposure light is a wavelength that can activate (B) the photoacid generator and can generate the acid. Specifically, the exposure light is preferably in the range of 350-410 nm with the maximum wavelength. As described above, if an appropriate sensitizer is used, the light sensitivity can be adjusted. For the exposure device, a contact aligner, mirror projection, stepper, laser direct exposure device, etc. can be used.

Next, in step 3, heating is performed to partially imidize a part of the (A) polyamic acid in the unexposed portion. Here, the imidate ratio is about 30%. The heating time and heating temperature can be appropriately changed according to (A) polyamide, coating film thickness, and (B) type of photoacid generator. Typically, the coating thickness of about 10μm is 30 seconds to 3 minutes at 110~200℃ degree. By setting the heating temperature to 110°C or higher, partial imidization can be efficiently achieved. In addition, if the heating temperature is 200° C. or lower, the imidization of the exposed portion can be suppressed, the difference in solubility between the exposed portion and the unexposed portion can be increased, and the patterned film can be easily formed.

Next, in step 4, the coating film is treated with a developing solution. In this way, the exposed portion of the coating film is removed, and a patterned film made of partially imidate (A) polyamic acid is formed on the substrate.

As a method used in the development, any conventionally known method for developing a photoresist, for example, a rotary spray method, a paddle stirrer method, an immersion method with ultrasonic treatment, etc., can be selected. The developer includes inorganic bases such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia, organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine. Aqueous solutions of quaternary ammonium salts such as tetramethylammonium and tetrabutylammonium hydroxide. In addition, if necessary, an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, isopropyl alcohol, or a surfactant may be added to these. Then, if necessary, the coating film can be washed with a lotion to obtain a patterned film. For the lotion, it can be used alone or in combination with distilled water, methanol, ethanol, isopropanol, etc. As for the developing solution, the above-mentioned (C) solvent can also be used.

Then, in step 5, the patterned film is heated to obtain a cured coating film (cured product). At this time, (A) polyamic acid is completely imidized, and it is sufficient if polyimide is obtained. The heating temperature may be appropriately set in such a manner that the patterned film of polyimide can be cured. For example, it is heated in an inert gas at 150 to 300°C for about 5 to 120 minutes. The better heating temperature range is 150~250℃, and the better range is 180~220℃. Heating system This is performed by using, for example, a heating plate, an oven, and a temperature-increasing oven that can set a thermometer. At this time, the atmosphere (gas) may be air, or an inert gas such as nitrogen or argon may be used.

The positive photosensitive resin composition of the present invention can be used as printing inks, adhesives, fillers, electronic materials, optical circuit parts, molding materials, resist materials, construction materials, three-dimensional molding, optical components, etc., resin materials Various well-known fields and products used, especially a wide range of fields and products that are effective in the properties of polyimide film such as heat resistance, dimensional stability, and insulation, such as paint or printing ink, or color filter Forming materials for devices, films for flexible displays, semiconductor devices, electronic parts, interlayer insulating films, wiring coating films, optical circuits, optical circuit parts, anti-reflection films, stereo photography, optical components, and building materials.

In particular, the positive photosensitive resin composition of the present invention is mainly used as a patterned film forming material (resist), and the patterned film formed by this is on a permanent film made of polyimide , With the function of imparting heat resistance or insulation, suitable for forming wiring such as color filters, films for flexible displays, electronic parts, semiconductor devices, interlayer insulating films, solder resists, or coating films Coating film, solder dum, optical line, optical line parts, anti-reflection film, other optical components or electronic components. In addition, the positive photosensitive resin composition of the present invention is excellent in resolution, and thus can be applied to a patterned film forming material of a package substrate, particularly a wafer-level package substrate.

[Example]

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to the following examples. In addition, the so-called "parts" and "%" below are all quality standards unless otherwise specified.

[Synthesis Example 1: Synthesis of Polyamide A-1]

After putting 30 mmol of the diamine of the following Table 1 into a separation flask with a capacity of 300 mL, the diamine was dissolved with dehydrated NMP (N-methylpyrrolidone) while introducing nitrogen gas. After all the diamines were dissolved, the acid anhydride 30 mmol in Table 1 below was slowly added. After the acid anhydride adhering to the flask wall was poured into the reaction solution with a small amount of NMP, the mixture was stirred at room temperature for 24 hours to react to obtain 15% by mass of polyamic acid (PAA) A-1 paint. The input amount of dehydrated NMP is 75% by mass of the paint amount of PAA. In addition, the acid anhydride "TDA" in the table uses 4-(2,5-bi- pendant tetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride (new RIKACID TDA-100 manufactured by Japan Science Corporation). The diamine "4,4’-ODA" uses 4,4’-diaminodiphenyl ether (manufactured by Wakayama Seiki Chemical Co., Ltd.).

[Synthesis Examples 2, 3: Synthesis of Polyamide A-2, A-3]

Except that the diamine and the acid anhydride were changed to the compounds shown in Table 2 below, the rest was carried out in the same manner as in Synthesis Example 1 to obtain coatings of polyamide A-2 and A-3. In the table, N,N’-bis(1,2-cyclohexanedicarboxylic anhydride-4-yl)carbonyl-1,4-phenylenediamine (manufactured by Nippon Seika Chemical Co., Ltd.) is used as the acid anhydride "PPHT". For the diamine "3,4'-ODA", 3,4'-diaminodiphenyl ether (manufactured by Nippon Pure Chemical Co., Ltd.) is used.

[Synthesis Example 4: Synthesis of Polyamide A-4]

After putting 30 mmol of the diamine in the following Table 3 into a separation flask with a capacity of 300 mL, the diamine was dissolved with dehydrated NMP (N-methylpyrrolidone) while introducing nitrogen gas. After completely dissolving the diamine, slowly add the following anhydrides TDA 22.5 mmol and PMDA 7.5 mmol. 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 react to obtain 15% by mass of polyamic acid (PAA) A-4 paint. The input amount of dehydrated NMP is the amount of PAA paint 75% by mass. In addition, for the anhydride "PMDA" in the table, pyromellitic anhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd.) is used.

[Synthesis Example 5: Synthesis of Polyamide A-5]

Except that the amount of acid anhydride was changed to 15 mmol of TDA and 15 mmol of PMDA, the rest was carried out in the same manner as in Synthesis Example 4 to obtain a coating of polyamide A-5.

[Synthesis Example 6: Synthesis of Polyamide A-6]

Except that the amount of acid anhydride was changed to TDA 7.5 mmol and PMDA 22.5 mmol, the rest was carried out in the same manner as in Synthesis Example 4 to obtain a coating of polyamide A-6.

[Comparative Synthesis Examples 1 and 2: Synthesis of Polyamide R-1 and R-2]

In addition to changing the diamine and acid anhydride to the compounds shown in Table 4 below Except for this, the rest was carried out in the same manner as in Synthesis Example 1 to synthesize the paints of polyamides R-1 and R-2. In addition, for the acid anhydride "CBDA" in the table, 1,2,3,4-cyclobutanetetracarboxylic dianhydride (manufactured by Nippon Pharmaceutical Co., Ltd.) is used.

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

In the combination of Table 5, the photoacid generator was blended and dissolved with respect to the polyamic acid paint to obtain the photosensitive resin compositions of Examples and Comparative Examples. In addition, 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 polyamic acid paint.

[Method of forming positive pattern film]

After the photosensitive resin compositions of the examples and comparative examples were uniformized with a stirring and defoaming device, the coating concentration was applied to the silane plate using a spin coater, and dried on a heating plate at 100°C for 30 minutes. A dry coating film of a photosensitive resin composition having a film thickness of about 5 μm was obtained. On this dry coating film, only half of the mask (transmittance 0%) was placed, and a 1J wide-area exposure was performed with a desktop exposure device (manufactured by Sanyong Electric Co., Ltd.) equipped with a high-pressure mercury lamp. Next, post-exposure heating (PEB) was performed on the conditions of Table 5 using a hot plate. This was developed with a 1% NaOH aqueous solution or a 1% Na ₂ CO ₃ aqueous solution, rinsed with water, and then dried at room temperature to obtain a positive pattern film. Table 5 shows the comparison evaluation results of the addition amount of the photoacid generator and the PEB conditions.

[Comparative evaluation]

The above comparison is obtained by the following formula.

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

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

Development time (min): Time to immerse it in the developing solution

Based on the comparison value, the following evaluation is made.

◎: 10 or more

○: 2 or more ~ less than 10

△: Above 1~Under 2

×: None (not dissolved)

[Formation of Fine Positive Pattern Film]

After the photosensitive resin composition of Example 8 was uniformly applied with a stirring and defoaming device, the coating concentration was applied to a silane plate using a spin coater, and dried at a heating plate of 100°C for 30 minutes to obtain a film thickness. A dry coating film of a photosensitive resin composition of about 5 μm. A thin-line pattern mask of L/S=3/3μm, 7/7μm, and 9/9μm was mounted on this dry film, and a wide-area light exposure of 300mJ was carried out using a mask close exposure table (Litho Tech Japan) . After that, PEB was carried out on a hot plate at 160°C for 1 minute. This was developed with a 1% Na ₂ CO ₃ aqueous solution, rinsed with water, and then dried at room temperature to obtain a positive pattern film. The microscope image of the obtained positive-type film is shown in FIG. 1. In addition, the step difference (the difference between the surface of the line and the surface of the pitch portion) is shown in Table 6.

(Examples 17-20)

[Evaluation of glass transition temperature]

3g of 15% by mass paint of polyamide A-1, A-4, A-5, A-6 was added with photoacid generator B-1 (TS583, DNQ (two (Azonaphthoquinone)) 0.0675g, the photosensitive resin composition of Examples 17-20 was obtained. After applying the obtained photosensitive resin composition on a silicon wafer with an applicator and heating it on a hot plate at 100°C for 10 minutes, then Heat treatment at 200°C for 30 minutes to produce a cured film. This hardened film was peeled off from the silicon wafer, and the glass transition temperature (Tg) was measured. Tg is measured under the conditions of 50°C to 350°C, a heating rate of 10°C/min, and a frequency of 1 Hz under the atmosphere, using a dynamic viscoelasticity measuring device RSA-G2 manufactured by TA Instrument.

It can be seen from the results shown in Tables 5 and 6 and FIG. 1 that the photosensitive resin composition of the present invention can provide a positive pattern film with excellent contrast and high resolution. In particular, even in the case of L/S=3/3 μm, the step is still large, the dissolution promoting effect and the dissolution preventing effect are obtained, and the resolution is excellent. In addition, with respect to the specific polyamide in the present invention, the photosensitive resin composition of the comparative example in which other polyamides were blended could not be compared, and a positive pattern film could not be formed.

In addition, as shown in Tables 5 and 7, regarding (A) polyamic acid, by using TDA as an acid anhydride having a cyclic aliphatic skeleton and an aromatic skeleton and selecting another acid anhydride for copolymerization, it can become A material with excellent resolution and heat resistance.

Claims (9)

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 ) A photoacid generator, the aforementioned (A) polyamic acid is a compound having a structure represented by the following general formula (II):

(In the formula, R ₂ is a divalent organic group having a plurality of aromatic rings and the aromatic groups are directly bonded to each other or through a (thio) ether group, X is a divalent organic group, m is an integer of 1 or more , N is an integer of 0 or more). The positive photosensitive resin composition according to claim 1, wherein the aforementioned (A) polyamide is a compound having a structure represented by the following general formula (V):

(In the formula, R ₂ is a divalent organic group having a plurality of aromatic rings and the aromatic groups are directly bonded to each other or through a (thio)ether group, R ₄ and R ₆ are divalent organic groups, R ₃ And R ₅ is a tetravalent organic group having a substituted or unsubstituted aromatic skeleton, m is an integer of 1 or more, n and s are each independently, an integer of 0 or more, and at least one of n and s is 1 Integer above). The positive photosensitive resin composition according to claim 1, wherein the blending amount of the (B) photoacid generator is 1 to 50 parts by mass for 100 parts by mass of the (A) polyamic acid. The positive photosensitive resin composition according to claim 1, which is a method for forming a patterned film comprising the following steps: an exposure step of exposing the coating film of the positive photosensitive resin composition, in the aforementioned exposure step Then, the heating step of heating the aforementioned coating film and the developing step of developing after the aforementioned heating step. A dry film characterized by having a resin layer obtained by applying a positive photosensitive resin composition as described in any one of claims 1 to 4 to a film and drying it. A hardened product characterized by hardening the positive photosensitive resin composition according to any one of claims 1 to 4. A hardened product characterized by hardening the resin layer of the dry film according to claim 5. A printed wiring board characterized by having a cured product as in claim 6. A printed wiring board characterized by having a cured product as in claim 7.

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