KR20170128440A - A positive photosensitive resin composition, a dry film, a cured product and a printed wiring board - Google Patents

Abstract

(식 중, R₁은, 방향족환과 지방족 탄화수소환의 축합환을 포함하는 4가의 유기기, 또는 방향족기와 지환식 탄화수소기를 포함하는 4가의 유기기이며, R₂는 2가의 유기기이며, X는 2가의 유기기이며, m은 1 이상의 정수이며, n은 0 또는 1 이상의 정수이다.)
로 표시되는 구조를 갖는 화합물인 것이 바람직하다.A dry film having a resin layer obtained from the composition, a cured product of the composition or the resin layer of the dry film, and a printed wiring board having the cured product. (A) a positive photosensitive resin composition comprising an acid anhydride having a cyclic aliphatic skeleton and an aromatic skeleton, a polyamic acid obtained from a diamine, and (B) a photoacid generator. Wherein the polyamic acid (A) is 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, R ₂ is a divalent organic group, and X is 2 M is an integer of 1 or more, and n is 0 or an integer of 1 or more.
Is preferably a compound having a structure represented by the following formula

Description

A positive photosensitive resin composition, a dry film, a cured product and a 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 has been widely applied to various fields based on excellent properties such as high insulation, heat resistance and high mechanical strength. For example, application to a coating film of a semiconductor device, a flexible printed wiring board, and a heat-resisting insulating interlayer material is not limited to the aerospace field applied for the first time.

Polyimide has a problem in that it is insufficient in thermoplasticity and solubility in an organic solvent and is difficult to process. For this reason, polyimide is widely used by a method in which a desired pattern film is formed by irradiating actinic light with a photosensitive resin composition obtained by blending a polyamic acid and a photoreactive compound, followed by cyclization by applying a high temperature to the imide .

For example, Patent Document 1 discloses a positive photosensitive resin composition comprising an aromatic dianhydride, a polyamic acid condensate of an aromatic diamine, and a quinone diazide compound. Further, Patent Document 2 describes a positive photosensitive resin composition comprising a poly (amide-imide) resin having a specific structure and a photo acid generator.

Japanese Patent Application Laid-Open No. 52-13315 Japanese Patent Application Laid-Open No. 2010-196041

In recent years, along with the advancement and higher density of the semiconductor mounting technology, further miniaturization of the pattern film is required. However, in such a photosensitive resin composition, it has been difficult to obtain high resolution.

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

The present inventors have intensively studied in view of the above. As a result, it has been found that, when an acid anhydride having a cyclic aliphatic skeleton and an aromatic skeleton and a polyamic acid obtained from a diamine are used instead of the polyamic acid obtained from an acid anhydride having an aromatic skeleton and a diamine, It is possible to obtain a cured product having excellent properties.

Further, the present inventors have found that a cured product excellent in resolution can be obtained by using a polyamic acid which is substantially imidized, rather than a poly (amide-imide) resin in which a part of the polyamic acid is imidized.

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

The positive photosensitive resin composition of the present invention is characterized in that the above (A) polyamic acid is 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,

R ₂ is a divalent organic group,

X is a divalent organic group,

m is an integer of 1 or more, and n is 0 or an integer of 1 or more.

Is preferably a compound having a structure represented by the following formula

The positive photosensitive resin composition of the present invention is characterized in that the (A) the polyamic acid is represented by the following general formula (II):

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

Is preferably a compound having a structure represented by the following formula

The positive photosensitive resin composition of the present invention is characterized in that the above-mentioned (A) polyamic acid is 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 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 independently 0 or an integer of 1 or more, and at least one of n and s is an integer of 1 or more.

Is preferably a compound having a structure represented by the following formula

The positive photosensitive resin composition of the present invention is characterized in that the above-mentioned (A) polyamic acid is represented by the following general formula (V):

(Wherein 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 independently 0 or an integer of 1 or more, and at least one of n and s is an integer of 1 or more.

Is preferably a compound having a structure represented by the following formula

In the positive photosensitive resin composition of the present invention, it is preferable that the blending amount of the photo acid generator (B) is 1 to 50 parts by mass relative to 100 parts by mass of the polyamic acid (A).

The positive photosensitive resin composition of the present invention is characterized by comprising an exposure step of exposing a coating film of the positive photosensitive resin composition to light, a heating step of heating the coating film after the exposure step, and a developing step of developing after the heating step It is preferable to use it for the film formation method.

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

The cured product of the present invention is obtained by curing the positive photosensitive resin composition or the resin layer of the dry film.

The printed wiring board of the present invention is characterized by having the 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 resin layer of the composition or the dry film and a printed wiring board having the cured product have.

Brief Description of the Drawings Fig. 1 is a graph showing the relationship between (A) a positive patterned film of L / S = 3/3 占 퐉, (B) 7/7 占 퐉 and (C) 9/9 占 퐉 obtained by using the positive photosensitive resin composition of Example 8, As shown in FIG.

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

In the present invention, an acid anhydride as a raw material of polyamic acid, which has a cyclic aliphatic skeleton and an aromatic skeleton, is used, whereby a cured product having excellent resolution can be obtained. For example, a pattern film having L / S of 10/10 m or less can be obtained.

In addition, the positive photosensitive resin composition of the present invention exhibits particularly good resolution when heated before and after the light irradiation. That is, by irradiating the coating film of the positive photosensitive resin composition of the present invention with an actinic ray, the solubility of the irradiated portion increases, and a difference in solubility arises between the irradiated portion and the non-irradiated portion. Thereafter, a portion of the polyamic acid in the unexposed portion is heated to be imidized and then developed, whereby a positive patterned film having excellent resolution can be formed. After the development, the imidization may be performed by heating at a higher temperature.

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

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

(A) an acid anhydride having a cyclic aliphatic skeleton and an aromatic skeleton used in the present invention and a polyamic acid (hereinafter also referred to as "(A) polyamic acid") obtained from a diamine are substantially imidized. The polyamic acid (A) preferably has 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,

R ₂ is a divalent organic group,

X is a divalent organic group,

m is an integer of 1 or more, and n is 0 or an integer of 1 or more.

The polyamic acid (A) is obtained from an acid anhydride having a cyclic aliphatic skeleton and an aromatic skeleton and only diamines, that is, n in the general formula (I) may be zero.

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

It is preferable to display them as any one of them.

Equation (1-1):

Z ₁ is an unsaturated hydrocarbon group having 4 to 12 carbon atoms which forms an aromatic ring (preferably a benzene ring, a naphthalene ring, particularly a benzene ring) together with an ethylene group common to Z _2, and the aromatic ring has at least one substituent An 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.

Z ₂ is an aliphatic hydrocarbon group having 3 to 10 (preferably 4 to 6, especially 4) carbon atoms forming an aliphatic hydrocarbon ring (alicyclic hydrocarbon) together with an ethylene group common to Z ₁ , The hydrocarbon ring may have at least one alkyl group (1 to 4 carbon atoms), an alkoxy group (1 to 4 carbon atoms), an aryl group (6 to 10 carbon atoms), a hydroxy group and a halogen atom as substituents . (I.e., a _pair of binding hands and a binding hand of the right side of Z ₂ ) are bonded to adjacent carbon atoms, but a divalent group represented by " = CR ₆ - " It is preferable that the bonding hands are bonded to adjacent carbon atoms or adjacent carbon atoms of adjacent carbon atoms to which two "-" bonding hands are bonded. The latter is particularly desirable. For example, when the aliphatic hydrocarbon ring is a cyclohexane ring, two "-" bonding hands are bonded at the 3 and 4 positions, and "= CR ₆ -" bonding at the 2 or 1 position (preferably at the 1 position) . 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, a halogen atom, and is preferably a hydrogen atom.

Equation (1-2):

Z ₃ is an unsaturated hydrocarbon group having 4 to 12 carbon atoms which forms an aromatic ring (preferably a benzene ring, a naphthalene ring, particularly a benzene ring) together with an ethylene group common to Z _4, and the aromatic ring contains at least one An 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.

Z ₄ is an aliphatic hydrocarbon group having 3 to 10 (preferably 4 to 6, particularly preferably 4) carbon atoms forming an aliphatic hydrocarbon ring (alicyclic hydrocarbon) together with an ethylene group common to Z ₃ , The hydrocarbon ring may have at least one alkyl group (1 to 4 carbon atoms), an alkoxy group (1 to 4 carbon atoms), an aryl group (6 to 10 carbon atoms), a hydroxy group and a halogen atom as substituents . The unidirectional binding hands (one pair of binding hands, one pair of binding hands on the right side of Z ₄ or one pair of binding hands on the left) represented by two "-" are each bonded to adjacent carbon, May be disposed adjacent to each other, or at least one carbon atom may be disposed therebetween if the ring is large.

Equation (1-3):

Z ₅ is an unsaturated hydrocarbon group having 4 to 12 carbon atoms which forms an aromatic ring (preferably a benzene ring, a naphthalene ring, especially a benzene ring) together with an ethylene group common to Z _6, and the aromatic ring has at least one substituent An 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. The monovalent bonding hands represented by two " - " are bonded to adjacent carbon, but adjacent monovalent bonding hands represented by two " - " may be disposed adjacent to each other. Carbon atoms. A monovalent bonding hand represented by two "-" is bonded to adjacent carbon, but a bivalent bonding hand represented by "= CR ₇ -" is a bond in which at least 1 Lt; RTI ID = 0.0 > carbon atoms. ≪ / RTI > 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, a halogen atom, and is preferably a hydrogen atom.

Z ₆ represents an aliphatic hydrocarbon group having 3 to 10 carbon atoms (preferably 4 to 6, particularly 4) carbon atoms forming an aliphatic hydrocarbon ring (ring of an alicyclic hydrocarbon) together with an ethylene group common to Z ₅ , The saturated hydrocarbon ring has at least one alkyl group (1 to 4 carbon atoms), an alkoxy group (1 to 4 carbon atoms), an aryl group (6 to 10 carbon atoms), a hydroxy group and a halogen atom .

Equation (1-4):

Z ₇ is an unsaturated hydrocarbon group having 4 to 12 carbon atoms which forms an aromatic ring (preferably a benzene ring, a naphthalene ring, particularly a benzene ring) together with an ethylene group common to Z _8, and the aromatic ring has at least one substituent An 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. 2 '-' monovalent binding hand (combined hand, or a combination of the left side of the Z ₇ hand on the right side of Z ₇₎ represented by is, but is bound to a carbon adjacent to, respectively, may be disposed adjacent kkirido pair of coupling hands And when the ring is large, they may be arranged with at least one carbon atom interposed therebetween.

Z ₈ is a saturated hydrocarbon group having 3 to 10 (preferably 4 to 6, especially 4) carbon atoms forming an aliphatic hydrocarbon ring (ring of an alicyclic hydrocarbon) together with an ethylene group common to Z ₇ , The saturated hydrocarbon ring has at least one alkyl group (1 to 4 carbon atoms), an alkoxy group (1 to 4 carbon atoms), an aryl group (6 to 10 carbon atoms), a hydroxy group and a halogen atom .

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

As a tetravalent organic group containing an aromatic group and an alicyclic hydrocarbon group represented by R ₁ ,

.

AR ¹ represents a divalent aromatic ring (preferably a benzene ring, a naphthalene ring, especially a benzene ring), or AR-R ₁₀ -AR [wherein AR represents a substituent (preferably at least one alkyl group (Preferably an unsubstituted) benzene ring which may have an aryl group (having 6 to 10 carbon atoms), an alkoxy group (having 1 to 4 carbon atoms), a hydroxyl group, a halogen atom} R ₁₀ is an alkylene group (preferably having 1 to 4 carbon atoms), -SO ₂ -, -COO-, -CONH, and -SO ₂ - is preferred.

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

B ₁ and B ₂ each independently represent an alicyclic hydrocarbon group (cyclic aliphatic hydrocarbon group) having 5 to 12 (preferably 6 to 8, particularly preferably 6) carbon atoms, and the saturated hydrocarbon ring is at least (1 to 4 carbon atoms), an alkoxy group (1 to 4 carbon atoms), an aryl group (6 to 10 carbon atoms), a hydroxyl group, and a halogen atom.

In the formula (I), X is a divalent organic group and is, for example, a divalent organic group such as an amide group, a hydroxyamide group, an aromatic or aliphatic ester group, an amide group, an amide imide group, a siloxane group, And a group containing at least a partial structure of a silyl group and a silyl group.

m is an integer of 1 or more, as described above. The number average molecular weight of the polyamic acid (A) is preferably from 1,000 to 1,000,000, more preferably from 5,000 to 500,000, and still more preferably from 10,000 to 200,000, so that m is preferably set so as to satisfy this.

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

Is particularly preferable. R ₂ , X, m and n are the same as described in formula (I).

The compound having the structure represented by the general formula (I) may also preferably be a compound having a structure represented by the following general formula (III). By using a polyamic acid having a copolymerization structure represented by the general formula (I) wherein n is 1 or more, for example, the general formula (III), it is possible to improve the glass transition temperature (Tg) of the cured product. That is, according to the positive photosensitive resin composition comprising a polyamic acid having a copolymerized structure, a cured product excellent in heat resistance and the like can be obtained in addition to the resolution.

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 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 independently 0 or an integer of 1 or more, and at least one of n and s is an integer of 1 or more.

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

As described above, R ₃ and R ₅ in the general formula (III) are tetravalent organic groups, for example, a group having a substituted or unsubstituted aromatic skeleton or a group having a substituted or unsubstituted cyclic aliphatic skeleton , 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 biphenyl skeleton.

Examples of the biphenyl skeleton include -O-, -CH ₂ -, -C ₂ H ₄ -, -C (CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -, -SO ₂ -, - SO-, -S-, or -CO-.

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

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

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 defined in formula (III).

Each of the compounds having the structure represented by the general formula (III) preferably has a structure represented by the following formula (V).

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

In the general formula (V), the compound wherein 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).

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 contain an aliphatic group. Further, for example, when R ₁ to R ₆ include a fluorine-containing group, the lowering of the light absorption or the dielectric property can be improved.

As a result, the alkali developability is improved, and a good pattern film is obtained.

The acid value of the polyamic acid (A) 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.

The acid value of the polyamic acid (A) was measured according to JIS K-5601-2-1. As a diluting solvent for the sample, a mixed solvent of acetone / water (volume ratio 9/1) having an acid value of 0 is used so that an acid value of anhydrous acid can be measured.

The method of synthesizing the polyamic acid (A) is not particularly limited, and can be produced by conventionally known methods. For example, it can be synthesized only by mixing an acid dianhydride having a cyclic aliphatic skeleton and an aromatic skeleton and a diamine in a solution. Such a synthesis method is preferable because it can be synthesized by a one-step reaction, easily obtained at a low cost, and requires no additional formula. Also, by using at least two kinds of at least one of acid anhydride and diamine, a compound having the structure represented by general formula (III) can be easily produced as a copolymer.

The acid anhydride having a cyclic aliphatic skeleton and an aromatic skeleton used for obtaining the polyamic acid (A) is preferably a carboxylic acid dianhydride, more preferably a tetracarboxylic acid dianhydride. Examples thereof include those represented by the following general formula (8).

(Wherein R < ₁ > is as defined in formula (I)).

The R ₁ group in the repeating unit in the polyamic acid of the formula (I) can be easily introduced by using the acid anhydride of the formula (8) as the starting material for the synthesis of the polyamic acid (A).

The cyclic aliphatic skeleton of the acid anhydride is preferably a cyclohexane skeleton. It is preferable that the acid anhydride does not have an alkyl group (e.g., t-butyl group) on the aromatic skeleton.

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

Among the acid anhydrides, the following compounds are preferred.

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

In the synthesis of the polyamic acid (A), other known dianhydrides may be used in combination as long as they do not contradict the object of the present invention.

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

Examples of the diamine used for obtaining the polyamic acid (A) include diamines represented by the following general formula (10). However, the following is only an example, and any known one may be used as long as it is not contrary to the object of the present invention.

(Wherein R < ₂ > is as defined in formula (I)).

The diamine preferably has an aromatic ring, and more preferably has a plurality of aromatic rings. In the case of having a plurality of aromatic rings, it is preferable that the aromatic rings are bonded to each other through a direct bond or a (thio) ether group.

When R ₂ is a divalent aromatic group, examples of the diamine include paraphenylenediamine, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'- Phenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 9,10- 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 1,3-bis (3,3'-diaminodiphenylsulfone, 4-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- ) Biphenyl, 4,4'-bis (3-aminophenoxybiphenyl, bis [4- (4-aminophenoxy) phenyl] ether, 1,1,1,3,3,3-hexafluoro- (4-aminophenoxy) phenyl] propane, 1,1,1,3,3,3-hexafluoro-2,2-bis [4- , 1,3,3,3-hexafluoro-2,2-bis (3-amino-4-methylphenyl) propane, metaphenylenediamine, 3,4'- Diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) Benzene, and 1,3-bis (4-aminophenoxy) benzene.

Examples of the diamine when R ₂ is a bivalent aliphatic group include 1,1-meta-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, Diaminocyclohexane, 1,4-diaminoheptamethylene diamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindenyldimethylenediamine, Tricyclo [6.2.1.02,7] -undecylenediimethyldiamine, 4,4'-methylenebis (cyclohexylamine), and isophoronediamine.

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

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

Specific examples of R ₂₈ and R ₂₉ in the formula (11) include an alkylene group having 1 to 7 carbon atoms such as a methylene group, an ethylene group and a propylene group, an arylene group having 6 to 18 carbon atoms such as a phenylene group, Examples of R ₃₀ and R ₃₁ include an alkyl group having 1 to 7 carbon atoms such as a methyl group and an ethyl group and an aryl group having 6 to 12 carbon atoms such as a phenyl group.

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

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

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

[(B) photoacid generator]

Examples of the photoacid generator (B) include naphthoquinone diazide compounds, diarylsulfonium salts, triarylsulfonium salts, dialkylphenylacylsulfonium salts, diaryliodonium salts, aryldiazonium salts, aromatic tetracarboxylic acid esters , Aromatic sulfonic acid esters, nitrobenzyl esters, aromatic N-oxyimidosulfonates, aromatic sulfamides, benzoquinonediazosulfonic acid esters and the like. The photoacid generator (B) is preferably a dissolution inhibitor. Among them, naphthoquinone diazide compounds are preferred.

Specific examples of the naphthoquinone diazide compound include a naphthoquinone diazide adduct of tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene (for example, (E.g., TS533, TS567, TS583, and TS593, manufactured by Gengen Co., Ltd.), and naphthoquinone diazide adducts of tetrahydroxybenzophenone (for example, BS550, BS570, and BS599 available from Sanpou Chemical Industries, Ltd.) have.

These photoacid generators (B) may be used singly or in combination of two or more. The blending amount of the photo acid generator (B) is preferably 1 to 50 parts by mass relative to 100 parts by mass of the polyamic acid (A). By setting this range, the balance between the dissolution inhibiting effect and the dissolution promoting effect is improved. More preferably 10 to 40 parts by mass, still 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.

(C) a solvent may be added to the positive photosensitive resin composition of the present invention. The solvent (C) is not particularly limited as long as it dissolves the polyamic acid (A), the photoacid generator (B) and other additives. Examples include N, N'-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N, N'-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, Butyrolactone,? -Acetyl-? -Butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolidone, N-cyclohexyl-2-pyrrolidone, dimethylsulfoxide, hexamethylphosphor Amide, pyridine,? -Butyrolactone, and diethylene glycol monomethyl ether. These may be used alone or in combination of two or more. The amount of the solvent to be used may be in the range of 50 to 9000 parts by mass based on 100 parts by mass of the polyamic acid (A), depending on the coating film thickness and viscosity.

A known sensitizer may be added to the positive photosensitive resin composition of the present invention in order to further improve the light sensitivity.

A known adhesion auxiliary agent may be added to the positive photosensitive resin composition of the present invention for the purpose of improving adhesion with a substrate.

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

In order to impart processing characteristics and various functionalities to the resin composition of the present invention, various other organic or inorganic low molecular weight or high molecular compounds may be added. For example, a coloring agent, a surfactant, a leveling agent, a plasticizer, a fine particle, and the like can be used. The fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, and inorganic fine particles such as colloidal silica, carbon, and layered silicate. In addition, various coloring agents, fibers and the like may be added to the resin composition of the present invention.

[Dry Film]

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

In the dry film of the present invention, the positive photosensitive resin composition of the present invention is uniformly applied to a carrier film by a suitable method such as a blade coater, a lip coater, a comma coater, a film coater, and the like, followed by drying to form the resin layer , Preferably by laminating a cover film thereon. The cover film and the carrier film may be the same film material or different films.

In the dry film of the present invention, the film material of the carrier film and the cover film may be any of those known for use in a dry film.

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 mu m is used.

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

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

Using the positive photosensitive resin composition of the present invention, the patterned film as the cured product is produced, for example, as follows.

First, as a step 1, a coating film is obtained by coating a positive photosensitive resin composition on a base material and drying it, or by transferring a resin layer from a dry film onto a base material. Examples of the method of applying the positive photosensitive resin composition on a substrate include a method which has been conventionally used for coating a photosensitive resin composition such as a spin coating method, a bar coater method, a blade coater method, a curtain coater method, a screen printing method, A spray coating method using a coater, and further an ink jet method. As the drying method of the coating film, a method of drying by heating with a air dryer, an oven or a hot plate, or vacuum drying may be used. The drying of the coating film is preferably performed under the condition that the imidization of the polyamic acid (A) in the photosensitive resin composition does not occur. Concretely, natural drying, air blow drying, or heat drying can be carried out at 70 to 120 ° C for 20 minutes to 1 hour. Preferably, drying is performed on a hot plate for 20 to 40 minutes. Vacuum drying can also be carried out. In this case, the reaction can be carried out at room temperature for 20 minutes to 1 hour.

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

Subsequently, as the step 2, the coating film is directly exposed through a photomask having a pattern. The exposure light beam (B) is activated by activating the photo acid generator to generate an acid. Specifically, it is preferable that the exposure light has a maximum wavelength in the range of 350 to 410 nm. As described above, when a sensitizer is appropriately used, light sensitivity can be produced. As the exposure apparatus, a contact aligner, a mirror projection, a stepper, a laser direct exposure apparatus, or the like can be used.

Subsequently, as step 3, a portion of the polyamic acid (A) in the unexposed portion is imidized by heating. Here, the imidization rate is about 30%. The heating time and heating temperature are appropriately changed depending on (A) the polyamic acid, the coating film thickness, and (B) the type of the photo acid generator. Typically, it is about 30 seconds to 3 minutes at 110 to 200 DEG C in the case of a coating film thickness of about 10 mu m. By setting the heating temperature to 110 deg. C or more, partial imidization can be efficiently achieved. On the other hand, by setting the heating temperature to 200 占 폚 or less, 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, thereby facilitating the formation of the patterned film.

Subsequently, as a step 4, the coating film is treated with a developing solution. Thereby, the exposed portion in the coated film can be removed to form a patterned film containing the polyamic acid (A) partially imaged on the substrate.

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

Thereafter, as the step 5, the pattern film is heated to obtain a cured coating film (cured product). At this time, the polyamic acid may be completely imidized (A) to obtain polyimide. The heating temperature is appropriately set so that the polyimide pattern film can be cured. For example, heating is carried out at 150 to 300 DEG C for about 5 to 120 minutes in an inert gas. A more preferable range of the heating temperature is 150 to 250 占 폚, and a more preferable range is 180 to 220 占 폚. The heating is performed by using, for example, a hot plate, an oven, and a heating oven capable of setting a temperature program. As the atmosphere (gas) in this case, air may be used, or an inert gas such as nitrogen or argon may be used.

INDUSTRIAL APPLICABILITY The positive photosensitive resin composition of the present invention can be applied to various known fields in which resin materials such as printing ink, adhesive, filler, electronic material, optical circuit component, molding material, resist material, building material, · A wide range of products and products, such as paints or printing inks, or color filters, films for flexible displays, semiconductor devices, electronic components, interlayer insulating films, A wiring circuit film, an optical circuit, an optical circuit component, an antireflection film, a hologram, an optical member, and a building material.

Particularly, the positive photosensitive resin composition of the present invention is used mainly as a pattern film forming material (resist), and the pattern film formed thereby serves as a permanent film containing polyimide as a component for imparting heat resistance and insulating properties, A wiring film such as a color filter, a film for a flexible display, an electronic part, a semiconductor device, an interlayer insulating film, a solder resist or a coverlay film, a solder dam, an optical circuit, an optical circuit component, an antireflection film, Lt; / RTI > Further, since the positive photosensitive resin composition of the present invention is excellent in resolution, it can be suitably used for 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 with reference to Examples, but the present invention is not limited to the following Examples. In the following, " part " and "% " are on a mass basis unless otherwise specified.

[Synthesis Example 1: Synthesis of polyamic acid A-1]

To a separable flask having a capacity of 300 mL, 30 mmol of the diamine shown in the following Table 1 was charged, and while flowing nitrogen, the diamine was dissolved with dehydrated NMP (N-methylpyrrolidone). After all the diamines were dissolved, 30 mmol of the acid anhydride described in the following Table 1 was gradually added. An acid anhydride adhered to the wall of the flask was poured into the reaction solution with a small amount of NMP and reacted by stirring at room temperature for 24 hours to obtain a 15% by mass polyamic acid (PAA) A-1 varnish. The amount of dehydrated NMP added was 75% by mass of the varnish amount of PAA. As the acid anhydride " TDA " in the table, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride (Ricaside TDA-100 from Shin-Nippon Rikagaku) was used. 4,4'-diaminodiphenyl ether (manufactured by Wakayama Seika) was used as the diamine 4,4'-ODA.

[Synthesis Examples 2 and 3: Synthesis of polyamic acid A-2, A-3]

Diamine and acid anhydride were changed to the compounds shown in Table 2 below, respectively, to obtain varnishes of polyamic acid A-2 and A-3. Further, N, N'-bis (1,2-cyclohexanedicarboxylic anhydride-4-yl) carbonyl-1,4-phenylenediamine (manufactured by Nippon Seika Co., Ltd.) as the acid anhydride "PPHT" Respectively. As the diamine " 3,4'-ODA ", 3,4'-diaminodiphenyl ether (manufactured by Nichimen Corporation) was used.

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

In a separable flask having a capacity of 300 mL, 30 mmol of the diamine shown in the following Table 3 was charged, and while the nitrogen was flowing, the diamine was dissolved with dehydrated NMP (N-methylpyrrolidone). After dissolving all of the diamines, 22.5 mmol of the acid anhydride TDA and 7.5 mmol of PMDA described in the following table were slowly added. An acid anhydride adhered to the wall of the flask was poured into the reaction solution with a small amount of NMP and reacted by stirring at room temperature for 24 hours to obtain a 15% by mass polyamic acid (PAA) A-4 varnish. The amount of dehydrated NMP added was 75% by mass of the varnish amount of PAA. Further, pyromellitic anhydride (manufactured by Mitsubishi Gas Chemical Company) was used as the acid anhydride "PMDA" in the table.

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

A varnish of polyamic 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 mmol of TDA and 15 mmol of PMDA.

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

The varnish of polyamic acid A-6 was obtained in the same manner as in Synthesis Example 4 except that the amount of the acid anhydride was changed to 7.5 mmol of TDA and 22.5 mmol of PMDA.

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

Diamines and acid anhydrides were respectively changed to the compounds shown in Table 4 below, the varnishes of polyamic acid R-1 and R-2 were synthesized in the same manner as in Synthesis Example 1. Further, 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride (manufactured by Shin Nippon Yakuhin Co., Ltd.) was used as the acid anhydride "CBDA" in the table.

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

The photo acid generator was blended and dissolved in the varnish of polyamic acid in the combinations described in Table 5 to obtain photosensitive resin compositions of Examples and Comparative Examples. Incidentally, the blending amount of photoacid generator in the table is the blending amount per 100 parts by mass of the varnish solid content of polyamic acid.

[Formation method of positive pattern film]

Each of the photosensitive resin compositions of Examples and Comparative Examples was applied on a silicon substrate using a spin coater after uniformizing the varnish concentration using a stirring and defoaming device and dried on a hot plate at 100 DEG C for 30 minutes to form a film thickness A dried coating film of a photosensitive resin composition of about 5 탆 was obtained. A mask (transmittance of 0%) was placed on this dry coating film by half, and 1J broad exposure was performed with a tabletop type exposure apparatus (manufactured by SAN-EI DENKI CO., LTD.) Equipped with a high-pressure mercury lamp. Subsequently, post-exposure baking (PEB) was performed on the hot plate under the conditions shown in Table 5. This was developed with 1% NaOH aqueous solution or 1% Na ₂ CO ₃ aqueous solution, rinsed with water, and then dried at room temperature to obtain a positive patterned film. Table 5 shows the addition amount of photoacid generator, PEB conditions, and contrast evaluation results.

[Evaluation of contrast]

The contrast was obtained by the following formula.

(Film thickness 占 퐉 / developing time min) / unexposed area developing speed (film thickness 占 퐉 / developing time min)

Film thickness (占 퐉): value obtained by subtracting film thickness after development from film thickness before development

Development time (min): time for immersion in developer

The contrast values were evaluated as follows.

◎: 10 or more

?: 2 or more to less than 10

?: Not less than 1 and not more than 2

X: none (not dissolved)

* 1: TS583, DNQ (diazonaphthoquinone) manufactured by Sanpo Yakugen Kagaku Co.,

* 2: WPAG-149 manufactured by Wako Pure Chemical Industries, Ltd., (2-methyl-2 - [(4-methylphenyl) sulfonyl] -1 - [(4-methylthio) phenyl]

[Formation of fine positive pattern film]

The photosensitive resin composition of Example 8 was applied on a silicon substrate using a spin coater after uniformizing the varnish concentration using a stirring and defoaming device and then dried on a hot plate at 100 DEG C for 30 minutes to form a film thickness of 5 mu m To obtain a dried coating film of the photosensitive resin composition. A thin line pattern photomask of L / S = 3/3, 7/7, and 9/9 mu m was placed on the dried film and exposed to light of 300 mJ using a mask close-contact exposure stage (Risotech Japan) . Thereafter, PEB was performed on a hot plate at 160 DEG 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 patterned film. FIG. 1 is a microphotograph of the obtained positive pattern film. Table 6 shows the step difference (the difference between the surface of the line and the surface of the space part).

(Examples 17 to 20)

[Evaluation of glass transition temperature]

(Photo acid generator B-1 (TS583, DNQ (diazonaphthoquinone) manufactured by Sanpo Pure Chemical Industries, Ltd.) was added to 3 g of 15 mass% varnish of polyamic acid A-1, A-4, A- Was added to obtain the photosensitive resin compositions of Examples 17 to 20. The obtained photosensitive resin composition was coated on a silicon wafer with an applicator, heated at 100 DEG C for 10 minutes on a hot plate, and further heat-treated at 200 DEG C for 30 minutes to prepare a cured film. The cured film was peeled off from the silicon wafer, and the glass transition temperature (Tg) was measured. Tg was measured under the conditions of 50 ° C to 350 ° C, a temperature raising rate of 10 ° C / min, and a frequency of 1Hz under the atmosphere using a dynamic viscoelasticity measuring device RSA-G2 manufactured by TA Instrument.

From the results shown in Tables 5 and 6 and Fig. 1, it can be seen that the photosensitive resin composition of the present invention has a high contrast and a high resolution positive pattern film can be obtained. In particular, even when L / S = 3/3 占 퐉, the step is large, and the dissolution promoting effect and dissolution inhibiting effect are obtained, and the resolution is excellent. On the other hand, in the photosensitive resin composition of the comparative example in which other polyamic acid was incorporated instead of the specific polyamic acid in the present invention, no contrast was obtained and a positive pattern film could not be formed.

Further, as shown in Tables 5 and 7, TDA was used as the acid anhydride having a cyclic aliphatic skeleton and an aromatic skeleton for the polyamic acid (A), and other acid anhydrides to be copolymerized were selected, It can be a material imparted with heat resistance.

Claims (12)

(A) an acid anhydride having a cyclic aliphatic skeleton and an aromatic skeleton, a polyamic acid obtained from a diamine,
(B) a photoacid generator. The polyamic acid composition according to claim 1, wherein the polyamic acid (A)

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 is a divalent organic group,
X is a divalent organic group,
m is an integer of 1 or more, and n is 0 or an integer of 1 or more.
Wherein the positive photosensitive resin composition is a compound having a structure represented by the following formula. The polyamic acid composition according to claim 2, wherein the polyamic acid (A)

(Wherein R ₂ is a divalent organic group, X is a divalent organic group, m is an integer of 1 or more, and n is 0 or an integer of 1 or more).
Wherein the positive photosensitive resin composition is a compound having a structure represented by the following formula. The polyamic acid composition according to claim 2, wherein the polyamic acid (A)

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 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 independently 0 or an integer of 1 or more, and at least one of n and s is an integer of 1 or more.
Wherein the positive photosensitive resin composition is a compound having a structure represented by the following formula (1). 5. The polyamic acid composition according to claim 4, wherein the polyamic acid (A)

(Wherein 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 independently 0 or an integer of 1 or more, and at least one of n and s is an integer of 1 or more.
Wherein the positive photosensitive resin composition is a compound having a structure represented by the following formula. The positive photosensitive resin composition according to claim 1, wherein the blending amount of the photo acid generator (B) is 1 to 50 parts by mass relative to 100 parts by mass of the polyamic acid (A). The positive photosensitive resin composition according to claim 1, which further comprises: an exposure step of exposing the coating film of the positive photosensitive resin composition to light;
A heating step of heating the coating film after the exposure step,
Wherein the positive photosensitive resin composition is used in a method of forming a pattern film including a developing step of developing after the heating step. A dry film comprising a resin layer obtained by applying the positive-working photosensitive resin composition according to any one of claims 1 to 7 to a film and drying the positive-working photosensitive resin composition. A cured product obtained by curing the positive photosensitive resin composition according to any one of claims 1 to 7. A cured product obtained by curing a resin layer of the dry film according to claim 8. A printed wiring board having the cured product according to claim 9. A printed wiring board having the cured product according to claim 10.

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