KR102597875B1 - Positive photosensitive resin composition, dry film, cured product, and 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 positive photosensitive resin composition with excellent resolution, 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 are provided. A positive photosensitive resin composition characterized by containing (A) an acid anhydride having a cyclic aliphatic skeleton and an aromatic skeleton, a polyamic acid obtained from diamine, and (B) a photoacid generator. The (A) polyamic acid has the following general formula (I):

(In the formula, 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 It is a valent organic group, m is an integer of 1 or more, and n is 0 or an integer of 1 or more.)
It is preferable that it is a compound having a structure represented by .

Description

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

The present invention relates to positive photosensitive resin compositions, dry films, cured products, and printed wiring boards.

Polyimide is widely applied in various fields based on its excellent properties such as high insulation, heat resistance, and high mechanical strength. For example, beyond the aerospace field where it was first applied, application is progressing to coating films for semiconductor devices, flexible printed wiring boards, and heat-resistant insulating interlayer materials.

Polyimide is poor in thermoplasticity and solubility in organic solvents, and has the aspect of being difficult to process. For this reason, polyimide is widely used by a method in which a photosensitive resin composition obtained by mixing a polyamic acid and a photoreactive compound is irradiated with actinic light and developed to form a desired patterned film, and then subjected to high temperature to ring-close and imidize. .

For example, Patent Document 1 describes a positive photosensitive resin composition containing a polyamic acid condensate of an aromatic dianhydride and an aromatic diamine, and a quinonediazide compound. Additionally, Patent Document 2 describes a positive photosensitive resin composition containing a poly(amide-imide) resin of a specific structure and a photoacid generator.

Japanese Patent Publication No. 52-13315 Japanese Patent Publication No. 2010-196041

In recent years, with the advancement and density of semiconductor packaging technology, there has been a demand for further refinement of pattern films. However, it was difficult to obtain a high level of resolution with the above photosensitive resin composition.

Here, the object of the present invention is to provide a positive photosensitive resin composition with excellent 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. It is to provide.

In view of the above, the present inventors have carefully studied the results and found that if a polyamic acid obtained from an acid anhydride having a cyclic aliphatic skeleton and an aromatic skeleton and a diamine is used instead of a polyamic acid obtained from an acid anhydride having an aromatic skeleton and a diamine, the resolution is unexpectedly high. It was found that a cured product with excellent properties could be obtained.

Additionally, the present inventors found that a cured product with excellent resolution could be obtained by using a polyamic acid that was not substantially imidized, rather than a poly(amide-imide) resin in which a portion of the polyamic acid was imidized.

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

In the positive photosensitive resin composition of the present invention, the polyamic acid (A) has the following general formula (I):

(In the formula, 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 greater than 1, and n is an integer greater than 0 or 1.)

It is preferable that it is a compound having a structure represented by .

In the positive photosensitive resin composition of the present invention, the polyamic acid (A) has 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 0 or an integer of 1 or more.)

It is preferable that it is a compound having a structure represented by .

In the positive photosensitive resin composition of the present invention, the polyamic acid (A) has the following general formula (III):

(In the formula, 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 an integer of 0 or 1 or more, and at least one of n and s is an integer of 1 or more.)

It is preferable that it is a compound having a structure represented by .

In the positive photosensitive resin composition of the present invention, the polyamic acid (A) has 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 independently an integer of 0 or 1 or more, and at least one of n and s is an integer of 1 or more.)

It is preferable that it is a compound having a structure represented by .

In the positive type photosensitive resin composition of the present invention, the compounding amount of the photo acid generator (B) is preferably 1 to 50 parts by mass based on 100 parts by mass of the polyamic acid (A).

The positive photosensitive resin composition of the present invention is a pattern comprising an exposure process of exposing a coating film of the positive photosensitive resin composition to light, a heating process of heating the coating film after the exposure process, and a development process of developing after the heating process. It is preferable to use it in a film formation method.

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

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

According to the present invention, it is possible to provide a positive photosensitive resin composition with excellent resolution, 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. there is.

Figure 1 is a microscopic view of a positive pattern film of (A) L/S = 3/3 ㎛, (B) 7/7 ㎛, and (C) 9/9 ㎛ obtained using the positive photosensitive resin composition of Example 8. This is a photo observed as well.

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 diamine, and (B) a photoacid generator.

In the present invention, since an acid anhydride having a cyclic aliphatic skeleton and an aromatic skeleton is used as the raw material for polyamic acid, a cured product with excellent resolution can be obtained. For example, a patterned film with L/S of 10/10㎛ 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 actinic 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. Afterwards, a portion of the polyamic acid in the unexposed area is imidized by heating and then developed, thereby forming a positive pattern film with excellent resolution. After development, it is sufficient to heat at a higher temperature to completely imidize.

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

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

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

(In the formula, 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 greater than 1, and n is an integer greater than 0 or 1.)

(A) The polyamic acid is obtained only from an acid anhydride having a cyclic aliphatic skeleton and an aromatic skeleton and a diamine, that is, in the general formula (I), n may be 0.

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 any one type.

Equation (1-1):

Z ₁ is an unsaturated hydrocarbon group having 4 to 12 carbon atoms that forms an aromatic ring (preferably a benzene ring, a naphthalene ring, especially a benzene ring) together with the ethylene group common to Z ₂ , and the aromatic ring has at least one substituent. It may have an 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, or a halogen atom.

Z ₂ is an aliphatic hydrocarbon group having 3 to 10 carbon atoms (preferably 4 to 6, especially 4) that forms an aliphatic hydrocarbon ring (alicyclic hydrocarbon) together with the 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, or a halogen atom as a substituent. . The two monovalent bonding hands indicated by “-” (i.e., the first pair of bonding hands, the bonding hand to the right of Z ₂ ) are bonded to adjacent carbons, but the divalent bonding hands indicated by “=CR ₆ -” The bond is preferably bonded to the adjacent carbon atom of the adjacent carbon atom to which two "-" bond hands are bonded or to the adjacent carbon atom. The latter is especially preferable. For example, when the aliphatic hydrocarbon ring is a cyclohexane ring, two "-" bonds are bonded at the 3 and 4 positions, and "=CR ₆ -" is bonded at the 2 or 1 position (preferably the 1 position). It is desirable to have R ₆ is generally a hydrogen atom, an alkyl group (1 to 4 carbon atoms), an alkoxy group (1 to 4 carbon atoms), a hydroxy group, or a halogen atom, and a hydrogen atom is preferred.

Equation (1-2):

Z ₃ is an unsaturated hydrocarbon group having 4 to 12 carbon atoms that forms an aromatic ring (preferably a benzene ring, a naphthalene ring, especially a benzene ring) together with the ethylene group common to Z ₄ , and the aromatic ring has at least one substituent. It may have an 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, or a halogen atom.

Z ₄ is an aliphatic hydrocarbon group having 3 to 10 carbon atoms (preferably 4 to 6, especially 4) that forms an aliphatic hydrocarbon ring (alicyclic hydrocarbon) together with the 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, or a halogen atom as a substituent. . The monovalent bond represented by two "-" (one set of bond, one set of bond on the right side of Z ₄ or one set of bond on the left side) are each bonded to adjacent carbons, but one set of bond hands They may be arranged adjacent to each other, and if the ring is large, they may be arranged with at least one carbon atom attached to each other.

Equation (1-3):

Z ₅ is an unsaturated hydrocarbon group having 4 to 12 carbon atoms that forms an aromatic ring (preferably a benzene ring, a naphthalene ring, especially a benzene ring) together with the ethylene group common to Z ₆ , and the aromatic ring has at least one substituent. It may have an 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, or a halogen atom. Two monovalent bonding hands indicated by "-" are bonded to adjacent carbons, but combinations of two adjacent monovalent bonding hands indicated by "-" may also be arranged adjacent to each other, and if the ring is large, they are at least 1 to each other. It may be arranged with two carbon atoms. The two monovalent bonds represented by “-” are bonded to adjacent carbons, but the divalent bonds represented by “=CR ₇ -” are bonded to at least one carbon to which the “-” bonds are bonded. It is preferable that the carbon atoms are bonded to adjacent carbon atoms. R ₇ is generally a hydrogen atom, an alkyl group (1 to 4 carbon atoms), an alkoxy group (1 to 4 carbon atoms), a hydroxy group, or a halogen atom, and a hydrogen atom is preferred.

Z ₆ is an aliphatic hydrocarbon group having 3 to 10 carbon atoms (preferably 4 to 6, especially 4) that forms an aliphatic hydrocarbon ring (alicyclic hydrocarbon ring) together with the 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 as substituents. You can stay.

Equation (1-4):

Z ₇ is an unsaturated hydrocarbon group with 4 to 12 carbon atoms that forms an aromatic ring (preferably a benzene ring, a naphthalene ring, especially a benzene ring) together with the ethylene group common to Z ₈ , and the aromatic ring has at least one substituent. It may have an 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, or a halogen atom. The two monovalent bonding hands indicated by “-” (the bonding hand on the right side of Z ₇ or the bonding hand on the left side of Z ₇ ) are each bonded to adjacent carbons, but even if a set of bonding hands are placed adjacent to each other, Alternatively, if the ring is large, it may be arranged with at least one carbon atom attached to each other.

Z ₈ is a saturated hydrocarbon group with 3 to 10 carbon atoms (preferably 4 to 6, especially 4) that forms an aliphatic hydrocarbon ring (alicyclic hydrocarbon ring) together with the 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 as substituents. You can stay.

Among formulas (1-1) to (1-4), the organic group represented by formula (1-1) and (1-2) is preferable, and the organic group represented by formula (1-1) is especially preferable.

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

It is preferable to display as .

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 a substituent {preferably at least one alkyl group (with 1 to 1 carbon atoms) 4), an aryl group (6 to 10 carbon atoms), an alkoxy group (1 to 4 carbon atoms), a hydroxy group, a halogen atom}, and is a divalent benzene ring (preferably unsubstituted), R ₁₀ is an alkylene group (preferably having 1 to 4 carbon atoms), -SO ₂ -, -COO-, or -CONH, and -SO ₂ - is preferred.

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

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 carbon atoms, especially 6 carbon atoms), and the saturated hydrocarbon ring has at least one substituent. It may have 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, or a halogen atom.

In formula (I), Examples include groups containing at least a part of a cetanyl group or the like.

As described above, m is an integer of 1 or more. (A) The preferred number average molecular weight of the polyamic acid is 1,000 to 1,000,000, more preferably 5,000 to 500,000, and even more preferably 10,000 to 200,000, so it is desirable to set m to satisfy this.

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

It is particularly preferable that it is a compound represented by . 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 preferably used as the compound having the structure represented by the following general formula (III). In General Formula (I), n is 1 or more, for example, by using a polyamic acid having a copolymer structure as represented by General Formula (III), it becomes possible to improve the glass transition temperature (Tg) of the cured product. That is, according to a positive photosensitive resin composition containing a polyamic acid having a copolymerization structure, a cured product that is excellent in heat resistance in addition to resolution can be obtained.

(In the formula, 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 an integer of 0 or 1 or more, and at least one of n and s is an integer of 1 or more.)

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

As described above, R ₃ and R ₅ in 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. , and 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 bisphenyl skeleton.

Here, examples of the bisphenyl skeleton include -O-, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -SO ₂ -, - A bisphenyl skeleton linked to SO-, -S-, or -CO- may be mentioned.

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

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

In addition, in general formula (III), a 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).

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

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

In addition, in general formula (V), a 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).

Additionally, when forming a patterned film using short-wavelength light, from the viewpoint of the absorption characteristics of the polymer, R ₁ to R ₆ may each contain an aliphatic group. In addition, for example, when a group containing fluorine is included as R ₁ to R ₆ , the wavelength of light absorption can be reduced or the dielectric properties can be improved.

Thereby, alkali developability becomes good and a good patterned 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 still more preferably 200 mgKOH/g or more. The upper limit of the acid value is preferably 300 mgKOH/g or less.

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

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

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

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

(A) By using an acid anhydride of the general formula (8) as a raw material for the synthesis of the polyamic acid, the R ₁ group in the repeating unit in the polyamic acid of the general formula (I) can be easily introduced.

As the cyclic aliphatic skeleton of the acid anhydride, a cyclohexane skeleton is preferable. The acid anhydride preferably does not have an alkyl group (for example, 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 above acid anhydrides, the following compounds are preferable.

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

(A) In the synthesis of polyamic acid, other known acid dianhydrides can be used in combination, as long as they do not conflict with the spirit of the present invention.

Other such acid dianhydrides include, for example, ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, methylcyclobutane tetracarboxylic dianhydride, and cyclopentane tetracarboxylic acid. Aliphatic tetracarboxylic dianhydride such as boxylic dianhydride; Pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,3',3 ,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride , 2,3',3,4'-biphenyltetracarboxylic dianhydride, 2,2',6,6'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-di Carboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)sulfone Dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 2 ,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)-1, 1,1,3,3,3-hexafluoropropane dianhydride, 1,3-bis[(3,4-dicarboxy)benzoyl]benzene dianhydride, 1,4-bis[(3,4-dicarboxy) )benzoyl]benzene dianhydride, 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-di) Carboxy)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}sulfone dianhydride, bis{4-[3-(1,2-dicarboxy)phenoxy ]phenyl}sulfone dianhydride, bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}sulfide dianhydride, bis{4-[3-(1,2-dicarboxy)phenoxy] Phenyl} sulfide dianhydride, 2,2-bis{4-[4-(1,2-dicarboxy)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-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3, 4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, pyridine tetra Carboxylic dianhydride, sulfonyldiphthalic anhydride, m-terphenyl-3,3',4,4'-tetracarboxylic dianhydride, p-terphenyl-3,3',4,4'-tetracarboxylic acid. Aromatic tetracarboxylic dianhydride, such as boxylic acid dianhydride, etc. are mentioned.

Examples of the diamine used to obtain the polyamic acid (A) include diamine represented by the following general formula (10). However, the following are examples, and known ones can be used as long as they do not conflict with the spirit of the present invention.

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

It is preferable that the said diamine has an aromatic ring, and it is more preferable that it has multiple aromatic rings. When having multiple aromatic rings, it is preferable that the aromatic rings are directly bonded to each other or bonded to each other through a (thio)ether group.

Examples of diamines in which R ₂ is a divalent aromatic group include paraphenylenediamine, 3,3'-dimethyl-4,4'-diaminobiphenyl, and 2,2'-dimethyl-4,4'-diaminobi. Phenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 9,10-bis(4-aminophenyl)anthracene, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl sulfoxide, 1,3-bis( 3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 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, metaphenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'- Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4) -Aminophenoxy) benzene can be mentioned.

Examples of diamines when R ₂ is a divalent aliphatic group include 1,1-methoxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, Nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1,4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindanylenedimethylenediamine, Examples include tricyclo[6.2.1.02,7]-undecylenedimethyldiamine, 4,4'-methylenebis(cyclohexylamine), and isophorone diamine.

Moreover, as another example, diaminopolysiloxane represented by the following formula (11), etc. can 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 to 10.

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

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

Among the photosensitive resin compositions, as (A) polyamic acid, a single type of material may be used, or multiple types may be used as a mixture. Additionally, R ₁ and R ₂ may each be a copolymer containing a plurality of structures.

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

[(B) Mineral acid generator]

(B) As photoacid generators, naphthoquinonediazide compounds, diarylsulfonium salts, trialrylsulfonium salts, dialkylpheneacylsulfonium salts, diaryliodonium salts, aryldiazonium salts, and aromatic tetracarboxylic acid esters. , aromatic sulfonic acid ester, nitrobenzyl ester, aromatic N-oxiimidosulfonate, aromatic sulfamide, benzoquinone diazosulfonic acid ester, etc. (B) The photo acid generator is preferably a dissolution inhibitor. Among these, a naphthoquinonediazide compound is preferable.

As a naphthoquinonediazide compound, specifically, for example, a naphthoquinonediazide adduct of tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene (e.g., Sanpo Chemical) TS533, TS567, TS583, TS593 manufactured by Kenkensho Co., Ltd.) or naphthoquinonediazide adducts of tetrahydroxybenzophenone (for example, BS550, BS570, BS599 manufactured by Sanpo Chemical Co., Ltd.) can be used. there is.

These (B) photoacid generators may be used individually, or two or more types may be used in appropriate combination. The compounding amount of the photo acid generator (B) is preferably 1 to 50 parts by mass based on 100 parts by mass of the polyamic acid (A). By setting it within this range, the balance between the dissolution suppressing effect and the dissolution promoting effect becomes good. More preferably, it is 10 to 40 parts by mass, still more preferably 10 to 35 parts by mass, and particularly preferably 10 to 25 parts by mass.

Below, other components that can be blended with the photosensitive resin composition of the present invention are explained.

A solvent (C) can be blended with the positive photosensitive resin composition of the present invention. (C) The solvent is not particularly limited as long as it dissolves (A) the polyamic acid, (B) the photo acid generator, and other additives. As examples, N,N'-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N,N'-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ- Butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphor Amide, pyridine, γ-butyrolactone, and diethylene glycol monomethyl ether can be mentioned. These may be used individually or in combination of two or more types. The amount of solvent used can be in the range of 50 to 9000 parts by mass based on 100 parts by mass of 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 to further improve light sensitivity.

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

It is preferable that the positive photosensitive resin composition of the present invention 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-weight compounds may be added. For example, colorants, surfactants, leveling agents, plasticizers, fine particles, etc. can be used. Fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, and inorganic fine particles such as colloidal silica, carbon, and layered silicate. Additionally, various colorants, fibers, etc. 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 then drying the positive photosensitive resin composition of the present invention. The dry film of the present invention is used by laminating a resin layer so that it is in contact with a substrate.

The dry film of the present invention is made by uniformly applying the positive photosensitive resin composition of the present invention to a carrier film by an appropriate method such as a blade coater, lip coater, comma coater, or film coater, and drying to form the above-mentioned 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 may be used.

In the dry film of the present invention, all film materials known as those used in dry films can be used as the film materials for the carrier film and cover film.

As the carrier film, for example, a thermoplastic film such as a polyester film such as polyethylene terephthalate with a thickness of 2 to 150 μm is used.

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

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

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

First, in Step 1, a coating film is obtained by applying and drying the positive photosensitive resin composition on a substrate or transferring a resin layer from a dry film onto the substrate. Methods for applying the positive photosensitive resin composition onto a substrate include methods that have been conventionally used to apply photosensitive resin compositions, such as applying with a spin coater, bar coater, blade coater, curtain coater, screen printer, etc., spraying. A spray application method using a coater or an inkjet method can be used. As a drying method for the coating film, methods such as air drying, heating drying using an oven or hot plate, and vacuum drying are used. In addition, drying of the coating film is preferably performed under conditions in which imidization of the polyamic acid (A) in the photosensitive resin composition does not occur. Specifically, natural drying, blow drying, or heat drying can be performed 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 is also possible, and in this case, it can be performed at room temperature for 20 minutes to 1 hour.

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

Next, as Step 2, the coating film is exposed through a photomask having a pattern or directly. The exposure light has a wavelength that can activate the photo acid generator (B) and generate acid. Specifically, the exposure light preferably has a maximum wavelength in the range of 350 to 410 nm. As described above, photosensitivity can be achieved by appropriately using a sensitizer. As an exposure device, a contact aligner, mirror projection, stepper, laser direct exposure device, etc. can be used.

Subsequently, as Step 3, a portion of the polyamic acid in the unexposed portion (A) is imidized by heating. Here, the imidization rate is about 30%. The heating time and heating temperature are appropriately changed depending on the type of (A) polyamic acid, coating film thickness, and (B) photoacid generator. Typically, in the case of a coating film thickness of about 10 μm, the time is about 30 seconds to 3 minutes at 110 to 200°C. By setting the heating temperature to 110°C or higher, partial imidization can be efficiently achieved. On the other hand, by setting the heating temperature to 200°C or lower, imidization of the exposed area can be suppressed, the difference in solubility between the exposed area and the unexposed area can be increased, and formation of a pattern film becomes easy.

Subsequently, as step 4, the coating film is treated with a developer. Thereby, the exposed portion in the coating film can be removed, and a pattern film containing the partially imidized (A) polyamic acid can be formed on the substrate.

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

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

The positive photosensitive resin composition of the present invention is used in various known fields in which resin materials are used, such as printing ink, adhesive, filler, electronic material, optical circuit component, molding material, resist material, building material, three-dimensional modeling, and optical members. · A wide range of fields and products in which the properties of heat resistance, dimensional stability, and insulation of products, especially polyimide films, are effective, such as paints or printing inks, color filters, films for flexible displays, semiconductor devices, electronic components, interlayer insulating films, It is suitably used as a forming material for wiring coating films, optical circuits, optical circuit components, anti-reflection films, holograms, optical members, and building materials.

In particular, the positive photosensitive resin composition of the present invention is mainly used as a pattern film forming material (resist), and the pattern film formed thereby functions as a permanent film containing polyimide and a component that imparts heat resistance and insulation, for example For example, color filters, films for flexible displays, electronic components, semiconductor devices, interlayer insulating films, wiring coating films such as solder resist and cover layer films, solder dams, optical circuits, optical circuit components, anti-reflective films, and other optical or electronic members. It is suitable for forming. In addition, since the positive photosensitive resin composition of the present invention has excellent resolution, it can be suitably used as a pattern film forming material for package substrates, especially wafer level package substrates.

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, in the following, “part” and “%” are all based on mass unless otherwise specified.

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

After adding 30 mmol of the diamines listed in Table 1 below to a separable flask with a capacity of 300 mL, the diamine was dissolved with dehydrated NMP (N-methylpyrrolidone) while flowing nitrogen. After dissolving all of the diamine, 30 mmol of the acid anhydride listed in Table 1 below was slowly added. After pouring the acid anhydride adhering to the wall of the flask with a small amount of NMP into the reaction solution, it was stirred at room temperature for 24 hours to react, and a varnish of 15% by mass of polyamic acid (PAA) A-1 was obtained. The input amount of dehydrated NMP was 75% by mass of the amount of PAA varnish. In addition, as the acid anhydride "TDA" in the table, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride (Likasid TDA-100 manufactured by New Nippon Rika Co., Ltd.) was used. As diamine "4,4'-ODA", 4,4'-diaminodiphenyl ether (manufactured by Wakayama Seika Co., Ltd.) was used.

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

Varnishes of polyamic acids A-2 and A-3 were obtained in the same manner as in Synthesis Example 1 except that the diamine and acid anhydride were changed to the compounds shown in Table 2 below. In addition, as the acid anhydride "PPHT" in the table, N,N'-bis(1,2-cyclohexanedicarboxylic acid anhydride-4-yl)carbonyl-1,4-phenylenediamine (manufactured by Nippon Seika Co., Ltd.) used. As diamine "3,4'-ODA", 3,4'-diaminodiphenyl ether (manufactured by Nichijun Chemical Co., Ltd.) was used.

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

After adding 30 mmol of the diamines listed in Table 3 below to a separable flask with a capacity of 300 mL, the diamine was dissolved with dehydrated NMP (N-methylpyrrolidone) while flowing nitrogen. After dissolving all of the diamine, 22.5 mmol of acid anhydride TDA and 7.5 mmol of PMDA listed in the table below were slowly added. After pouring the acid anhydride adhering to the wall of the flask with a small amount of NMP into the reaction solution, it was stirred at room temperature for 24 hours to react, and a varnish of 15 mass% polyamic acid (PAA) A-4 was obtained. The input amount of dehydrated NMP was 75% by mass of the amount of PAA varnish. In addition, pyromellitic anhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd.) 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 acid anhydride was changed to 15 mmol of TDA and 15 mmol of PMDA.

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

A varnish of polyamic acid A-6 was obtained in the same manner as in Synthesis Example 4, except that the amount of 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 acids R-1 and R-2]

Varnishes of polyamic acids R-1 and R-2 were synthesized in the same manner as in Synthesis Example 1, except that the diamine and acid anhydride were changed to the compounds shown in Table 4 below. In addition, as the acid anhydride "CBDA" in the table, 1,2,3,4-cyclobutane tetracarboxylic dianhydride (manufactured by Nippon Yakuza Co., Ltd.) was used.

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

A photoacid generator was mixed and dissolved in the polyamic acid varnish in the combination shown in Table 5 to obtain the photosensitive resin compositions of Examples and Comparative Examples. In addition, the mixing amount of the photoacid generator in the table is the mixing amount per 100 parts by mass of the varnish solid content of polyamic acid.

[Method for forming positive pattern film]

Each photosensitive resin composition of Examples and Comparative Examples was coated on a silicon substrate using a spin coater after making the varnish concentration uniform using a stirring and degassing device, and dried on a hot plate at 100°C for 30 minutes to determine the film thickness. A dry film of the photosensitive resin composition of about 5㎛ was obtained. A half mask (transmittance: 0%) was placed on this dried coating film, and 1J broad exposure was performed using a tabletop exposure apparatus (manufactured by Sanei Denki Co., Ltd.) equipped with a high-pressure mercury lamp. Subsequently, post-exposure heating (PEB) was performed on a hot plate under the conditions shown in Table 5. This was developed with a 1% NaOH aqueous solution or a 1% Na ₂ CO ₃ aqueous solution, rinsed with water, and dried at room temperature to obtain a positive pattern film. Table 5 shows the amount of photoacid generator added, PEB conditions, and contrast evaluation results.

[Evaluation of contrast]

The contrast was obtained by the following equation.

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

Film thickness (㎛): Value obtained by subtracting the film thickness after development from the film thickness before development.

Development time (min): Time immersed in developer

The contrast values were evaluated as follows.

◎: 10 or more

○: 2 or more to less than 10

△: 1 or more to less than 2

×: None (not dissolved)

*1: TS583, DNQ (Diazonaphthoquinone) manufactured by Sanpo Chemical Co., Ltd.

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

[Formation of fine positive pattern film]

The photosensitive resin composition of Example 8 was applied to a silicon substrate using a spin coater after uniforming the varnish concentration using a stirring/defoaming device, and dried on a hot plate at 100°C for 30 minutes to obtain a film thickness of 5 μm. A dry film of the photosensitive resin composition was obtained. On this dry film, a thin line pattern photomask of L/S = 3/3㎛, 7/7㎛, and 9/9㎛ was placed, respectively, and a 300mJ broad light was applied using a mask adhesion exposure stage (Lisotek Japan). was exposed to light. Afterwards, PEB was performed at 160°C for 1 minute on a hot plate. This was developed with a 1% Na ₂ CO ₃ aqueous solution, rinsed with water, and dried at room temperature to obtain a positive pattern film. A micrograph of the obtained positive pattern film is shown in Figure 1. Additionally, the level difference (difference between the surface of the line and the surface of the space portion) is shown in Table 6.

(Examples 17 to 20))

[Evaluation of glass transition temperature]

Photoacid generator B-1 (TS583, DNQ (diazonaphthoquinone) manufactured by Sanpo Chemical Company) for 3 g of 15 mass% varnish of polyamic acid A-1, A-4, A-5, and A-6. By adding 0.0675 g, the photosensitive resin compositions of Examples 17 to 20 were obtained. The obtained photosensitive resin composition was applied on a silicon wafer with an applicator, heated on a hot plate at 100°C for 10 minutes, and then further heat treated at 200°C for 30 minutes to produce a cured film. This cured film was peeled off from the silicon wafer, and the glass transition temperature (Tg) was measured. Tg was measured using a dynamic viscoelasticity measuring device RSA-G2 manufactured by TA Instrument under the conditions of 50°C to 350°C in air, a temperature increase rate of 10°C/min, and a frequency of 1Hz.

From the results shown in Tables 5, 6, and Figure 1, it can be seen that the photosensitive resin composition of the present invention has excellent contrast, and a positive pattern film with high resolution can be obtained. In particular, it can be seen that even when L/S = 3/3㎛, the step difference is large, dissolution promoting and dissolution inhibiting effects are obtained, and resolution is excellent. On the other hand, the photosensitive resin composition of the comparative example in which another polyamic acid was blended instead of the specific polyamic acid in the present invention did not provide contrast and could not form a positive pattern film.

In addition, as shown in Tables 5 and 7, for the polyamic acid (A), by using TDA as an acid anhydride having a cyclic aliphatic skeleton and an aromatic skeleton and selecting another acid anhydride to be copolymerized, excellent resolution and It can be made with a material that provides heat resistance.

Claims (12)

(A) an acid anhydride having a cyclic aliphatic skeleton and an aromatic skeleton, and a polyamic acid obtained from diamine,
(B) A positive type photosensitive resin composition containing a photoacid generator,
The (A) polyamic acid has the following general formula (II):

(In the formula, R ₂ is a divalent organic group having a plurality of aromatic rings and the aromatic rings are bonded directly or through a (thio) ether group, , n is an integer greater than or equal to 0 or 1.)
A positive photosensitive resin composition, characterized in that it is a compound having a structure represented by . The method of claim 1, wherein the polyamic acid (A) has the following general formula (V):

(In the formula, R ₂ is a divalent organic group that has a plurality of aromatic rings and the aromatic rings are directly bonded to each other or bonded to each other through a (thio)ether group,
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 an integer of 0 or 1 or more, and at least one of n and s is an integer of 1 or more.)
A positive photosensitive resin composition, characterized in that it is a compound having a structure represented by . The positive photosensitive resin composition according to claim 1, wherein the amount of the photo acid generator (B) is 1 to 50 parts by mass based on 100 parts by mass of the polyamic acid (A). The method of claim 1, comprising: an exposure step of exposing a coating film of a positive photosensitive resin composition to light;
a heating process of heating the coating film after the exposure process;
A positive photosensitive resin composition, characterized in that it 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 photosensitive resin composition according to any one of claims 1 to 4 onto a film and drying it. A cured product obtained by curing the positive photosensitive resin composition according to any one of claims 1 to 4. A cured product obtained by curing the resin layer of the dry film according to claim 5. A printed wiring board comprising the cured product according to claim 6. A printed wiring board comprising the cured product according to claim 7. delete delete delete