CN111936930A - Photosensitive resin composition, cured film, laminate, manufacturing method of cured film, and semiconductor device - Google Patents

Abstract

The invention provides a photosensitive resin composition, a cured film, a laminated body, a manufacturing method of the cured film and a semiconductor device, wherein the photosensitive resin composition contains a precursor containing a heterocyclic polymer, a thermokalite generating agent and a free radical polymerization compound, the precursor containing the heterocyclic polymer has a free radical polymerization group, the free radical polymerization compound comprises at least 1 free radical polymerization compound selected from the group consisting of a compound with more than 4 polymerization functional groups and a compound with 3 polymerization functional groups and molecular weight of less than 400.

Description

Photosensitive resin composition, cured film, laminate, method for producing cured film, and semiconductor device

technical field

The present invention relates to a photosensitive resin composition, a cured film, a laminate, a method for producing the cured film, and a semiconductor device.

Background technique

Heterocycle-containing polymers such as polyimide and polybenzoxazole are excellent in heat resistance and insulating properties, and are therefore used for insulating films of semiconductor devices and the like. Furthermore, in order to perform film formation or molding, the precursors before the cyclization reaction with high solvent solubility, such as polyimide precursors and polybenzoxazole precursors, are often dissolved in a solvent. used in the state. After applying this resin composition to a substrate or the like, it is possible to form a cured film by heating to cyclize the aforementioned precursor.

As a resin composition of such a heterocyclic polymer precursor, for example, Patent Document 1 discloses a thermosetting resin composition containing a specific thermal base generator and a heterocyclic polymer precursor. In this way, it is described that a thermosetting resin composition which can be cyclized at a low temperature and is excellent in stability is provided.

Previous technical literature

Patent Literature

Patent Document 1: Japanese Patent Laid-Open No. 2015/199219

SUMMARY OF THE INVENTION

The technical problem to be solved by the invention

Through the development of compositions containing heterocycle-containing polymer precursors as described above, attempts have been made in many applications to improve properties corresponding to their needs and to improve their suitability for manufacture. However, many parts of this resin and the precursor are unknown, and various properties are required, and research and development are yet to be carried out. For example, when it is used as an insulating film of a semiconductor device, metal etching and the like are performed, and various chemical treatments are performed in order to form the device structure. Therefore, resistance to chemical treatment is required. In addition, considering the durability and impact resistance of the device, it is also required to have a sufficient elongation at break. Generally, when chemical resistance is improved, the elongation at break tends to decrease, and it is difficult to achieve both.

Therefore, an object of the present invention is to provide a photosensitive resin composition which can achieve both chemical resistance of cured resin and excellent elongation at break. And the objective is to provide the manufacturing method of the cured film using the said photosensitive resin composition, a laminated body, a cured film, and a semiconductor device.

Means for solving technical problems

Based on the above-mentioned problems, the present inventors have conducted intensive studies and found that a specific compound is selected as a radically polymerizable compound, and a precursor of a radically polymerizable group-introduced heterocyclic-containing polymer and a thermal base are used in combination A generating agent can solve the above-mentioned problems. Specifically, the above-mentioned problems are solved by the following method <1>, preferably by <2> to <27>.

<1> A photosensitive resin composition comprising a heterocycle-containing polymer precursor, a thermal base generator, and a radically polymerizable compound,

The precursor of the above-mentioned heterocycle-containing polymer has a radically polymerizable group,

The above-mentioned radically polymerizable compound includes at least one radically polymerizable compound selected from the group consisting of compounds having 4 or more polymerizable functional groups and compounds having 3 polymerizable functional groups and having a molecular weight of 400 or less.

<2> The photosensitive resin composition according to <1>, wherein the polymerizable functional groups are each independently a group selected from a vinylphenyl group, a vinyl group, and a (meth)acryloyl group.

<3> The photosensitive resin composition according to <1> or <2>, wherein the thermal alkali generator has a cation represented by the formula (101) or the formula (102),

[Chemical formula 1]

In formula (101) and formula (102), R ¹ to R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, and R ⁹ represents a hydrocarbon group.

<4> The photosensitive resin composition according to any one of <1> to <3>, wherein the precursor of the heterocycle-containing polymer includes a polyimide precursor or a polybenzoxazole precursor.

<5> The photosensitive resin composition according to any one of <1> to <3>, wherein the precursor of the heterocyclic ring-containing polymer includes a polyimide precursor.

<6> The photosensitive resin composition according to any one of <1> to <5>, wherein the precursor of the heterocyclic ring-containing polymer contains a structural unit represented by the following formula (1),

[Chemical formula 2]

In formula (1), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or Monovalent organic group.

<7> The photosensitive resin composition according to the item <6>, wherein at least one of the above R ¹¹³ and the above R ¹¹⁴ contains a radically polymerizable group.

<8> The photosensitive resin composition according to the item <6> or <7>, wherein said R ¹¹⁵ contains an aromatic ring.

<9> The photosensitive resin composition according to any one of <6> to <8>, wherein the above R ¹¹¹ is represented by -Ar ⁰ -L ⁰ -Ar ⁰ -, and each Ar ⁰ independently contains an aromatic Ring divalent group, L ⁰ is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms that may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ -, -NHCO - and groups formed by combining two or more of these groups.

<10> The photosensitive resin composition according to any one of <6> to <9>, wherein R ¹¹¹ is a group represented by the following formula (51) or (61),

[Chemical formula 3]

In formula (51), R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group, a fluoromethyl group, or a difluoro group methyl or trifluoromethyl,

[Chemical formula 4]

In formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group.

<11> The photosensitive resin composition according to any one of <1> to <10>, which contains a photopolymerization initiator.

<12> The photosensitive resin composition according to any one of <1> to <11>, wherein the mass ratio of the thermal base generator to the radically polymerizable compound is 1.0 to 80.

<13> The photosensitive resin composition according to any one of <1> to <12>, wherein the amount of 2.5 parts by mass or more and 62.5 parts by mass or less is used with respect to 100 parts by mass of the precursor of the heterocyclic polymer. The above-mentioned radically polymerizable compound.

<14> The photosensitive resin composition according to any one of <1> to <13>, which further contains a solvent.

<15> The photosensitive resin composition according to any one of <1> to <14>, which is used for development by a developer containing an organic solvent in an amount of 90% by mass or more.

<16> The photosensitive resin composition according to any one of <1> to <15>, which is used for formation of an interlayer insulating film for rewiring layers.

<17> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <16>.

<18> A laminate having two or more layers of the cured film described in <17>.

<19> The laminate according to <18>, which has a metal layer between the cured films.

<20> The laminate according to <18> or <19>, which has 3 to 7 layers of the cured film.

<21> A method for producing a cured film comprising applying the photosensitive resin composition according to any one of <1> to <16> to a substrate to form a photosensitive resin composition layer an object layer forming step; and an exposure step of exposing the above-mentioned photosensitive resin composition layer.

<22> The manufacturing method of the cured film as described in <21> which further includes the developing process of developing the said photosensitive resin composition layer after the said exposure process.

<23> The method for producing a cured film according to <22>, wherein the image development step is developed using a developer containing an organic solvent in an amount of 90% by mass or more.

<24> The method for producing a cured film according to <22> or <23>, which includes a post-development heating step of heating the photosensitive resin composition layer at a temperature of 50 to 450° C. after the image development step .

<25> The manufacturing method of the cured film of <24> whose said heating temperature is 50-250 degreeC.

<26> The method for producing a cured film according to any one of <21> to <25>, wherein the cured film has a film thickness of 1 to 30 μm.

<27> A semiconductor device having the cured film according to <17> or the laminate according to any one of <18> to <20>.

Invention effect

According to the present invention, it is possible to provide a photosensitive resin composition that can achieve both chemical resistance and high elongation at break of cured resin. Moreover, the cured film using the said photosensitive resin composition, a laminated body, the manufacturing method of a cured film, and a semiconductor device can be provided.

Description of drawings

FIG. 1 is a schematic diagram showing the configuration of an embodiment of a semiconductor device.

Detailed ways

The description of the constituent elements in the present invention described below may be based on a representative embodiment of the present invention, but the present invention is not limited to this embodiment.

Regarding the labeling of groups (atomic groups) in this specification, labels that are not substituted and unsubstituted include both unsubstituted and substituted ones. For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups).

In this specification, "actinic radiation" means, for example, the bright line spectrum of a mercury lamp, extreme ultraviolet rays typified by excimer laser light, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. In addition, in the present invention, "light" refers to actinic rays or radiation. Unless otherwise specified, the term “exposure” in this specification includes not only exposure by mercury lamps, extreme ultraviolet rays represented by excimer lasers, X-rays, EUV light, etc., but also exposure by particle beams such as electron beams and ion beams. portrayed.

In this specification, the numerical range represented by "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", and "(meth)acrylic acid" means "acrylic acid" and "methacrylic acid" Both or either, "(meth)acryloyl" means both or either of "acryloyl" and "methacryloyl".

In this specification, the term "step" is not only an independent step, but also included in this term if the intended effect of the step can be achieved even if it cannot be clearly distinguished from other steps.

In this specification, the solid content concentration means the mass percentage of the mass of the components other than the solvent with respect to the total mass of the composition. In addition, unless otherwise stated, the solid content concentration refers to the concentration at 25°C.

In this specification, unless otherwise stated, the weight average molecular weight (Mw)/number average molecular weight (Mn) is defined as a styrene-equivalent value by gel permeation chromatography (GPC measurement). In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be, for example, HLC-8220GPC (manufactured by TOSOH CORPORATION), and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, One or more of TSKgel Super HZ3000 and TSKgel SuperHZ2000 (manufactured by TOSOH CORPORATION) were obtained. Unless otherwise specified, the eluent is measured with THF (tetrahydrofuran). In addition, unless otherwise stated, a UV-ray (ultraviolet) wavelength 254nm detector was used for detection.

The photosensitive resin composition of the present invention contains a precursor of a heterocycle-containing polymer, a thermal base generator, and a radically polymerizable compound, wherein the precursor of the heterocycle-containing polymer has a radically polymerizable group. , the above-mentioned radically polymerizable compound includes at least one radically polymerizable compound selected from the group consisting of a compound having 4 or more polymerizable functional groups and a compound having 3 polymerizable functional groups and a molecular weight of 400 or less .

The photosensitive resin composition containing the precursor of the heterocycle-containing polymer and the thermal base generator can improve chemical resistance by using a polyfunctional radically polymerizable compound. However, only by the above method, there is a tendency for the elongation at break to decrease. Therefore, if it is assumed that, in addition to the polymerizable compound, the polymer and the thermal base generator are involved in the crosslinking in the present invention, it is desirable that the crosslinking is appropriately cut along with the cyclization. For this reason, it can be understood that the site contributing to the cyclization reaction preferably has a form of a radically polymerizable group, and the above-mentioned structure is realized. In addition, the description of the mechanism includes the content of estimation, and the present invention is not to be interpreted in a limited way.

<Specific radically polymerizable compound>

The radically polymerizable compound used in the present invention (in this specification, it may be referred to as a "specific radically polymerizable compound") is at least one radically polymerizable compound selected from the group consisting of four Compounds of the above polymerizable functional groups and compounds having three polymerizable functional groups and a molecular weight of 400 or less. The polymerizable functional group is preferably a group selected from vinylphenyl, vinyl, and (meth)acryloyl groups (in this specification, such a polymerizable functional group is referred to as "polymerizable functional group Ps").

When the number of polymerizable functional groups is 4 or more, the number of functional groups of the specific radically polymerizable compound is preferably 10 or less, more preferably 8 or less, and still more preferably 6 or less. Furthermore, the molecular weight of the radically polymerizable compound having four or more polymerizable functional groups is preferably 1,000 or less, more preferably 800 or less, and further preferably 600 or less. The lower limit value is actually 400 or more. By setting it as the said range, the crosslinking density of a film becomes optimal, and elongation at break and chemical resistance improve.

The specific radically polymerizable compound preferably separates the radically polymerizable groups from each other by a linking group having a linear structure of 2 or more atoms.

When the polymerizable functional group is 3, the molecular weight of the specific radically polymerizable compound is more preferably 370 or less, more preferably 340 or less, and still more preferably 300 or less. The lower limit value is actually 150 or more. By setting it as the said range, the crosslinking density of a film becomes optimal, and elongation at break and chemical resistance improve.

The trifunctional radically polymerizable compound is preferably a compound represented by the following formula (P-1).

[Chemical formula 5]

In formula (P-1), Ps is each independently a group selected from vinylphenyl, vinyl and (meth)acryloyl, R ^B1 is a hydrogen atom or a substituent (except for a polymerizable functional group), L ^P is each independently a single bond or a linking group. L ^Q is the linking group.

In the formula, Ps is preferably a (meth)acryloyl group.

R ^B1 is preferably an optionally substituted alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6, further preferably 1 to 3), -NH-Ps or -CH ₂ -OL ^P -Ps. As an arbitrary substituent, a hydroxyl group, a carboxyl group, or a group combining these with the linking group ^LP can be mentioned.

When L ^P is a linking group, examples of the linking group include an oxygen atom, a sulfur atom, an amino group (NH), a carbonyl group, an (oligo)alkyleneoxy group, an alkylene group, an (oligo)alkyleneamino group, and combinations thereof. the linking base.

The (oligo)alkyleneoxy group preferably includes (oligo)methyleneoxy, (oligo)ethyleneoxy, and (oligo)propyleneoxy. The linking group may be substituted with a substituent such as hydroxy. In addition, the (oligo)alkyleneoxy group may represent a single alkyleneoxy group or an oligomeric alkyleneoxy group in which a plurality of these may be repeated. The number of repetitions of the (oligo)alkyleneoxy group is preferably 1-8, more preferably 1-4, still more preferably 1-2.

1-12 are preferable, as for the carbon number of an alkylene group, 1-6 are more preferable, and 1-3 are still more preferable. The alkylene group may be substituted with a substituent such as hydroxy.

The (oligo)alkyleneamino groups are preferably (oligo)methyleneamino groups, (oligo)ethyleneamino groups, and (oligo)propyleneamino groups. The (oligo)alkyleneamino group may be substituted with a substituent such as hydroxy. The number of repetitions of the (oligo)alkyleneamino group is preferably 1-12, more preferably 1-6, still more preferably 1-3.

Regarding the divalent ^linking group formed by LP, the number of atoms excluding the participation of hydrogen atoms in the bonding is preferably 1 to 30, more preferably 2 to 20, and further preferably 3 to 16.

L ^Q is a linking group, and specific examples thereof include the linking groups exemplified in ^LP . Among them, an alkylene group is preferable, and 1-12 are preferable, 1-6 are more preferable, and 1-3 are still more preferable. In particular, a methylene group or an ethylene group is preferable, and a methylene group is more preferable.

The tetrafunctional or more radically polymerizable compound is preferably a compound represented by the following formula (P-2).

[Chemical formula 6]

In formula (P-2), Ps is each independently a group selected from vinylphenyl, vinyl and (meth)acryloyl, R ^B2 is a hydrogen atom or a substituent (excluding polymerizable functional groups), L ^P is each independently a single bond or a linking group, pm is an integer of 1 to 6, and pn is 1 or 2.

The definitions of Ps, R ^B2 , L ^P and L ^Q are respectively the same as those of Ps, R ^B1 , L ^P and L ^Q in formula (P-1), and the preferred ranges are also the same.

When pn is 1, R ^B2 is a hydrogen atom or a substituent (except for a polymerizable functional group). As a substituent, an alkyl group is preferable (1-12 carbon atoms are preferable, 1-6 are more preferable, and 1-3 are still more preferable).

When pn is 2, R ^B2 is a divalent linking group. Examples of the divalent linking group include an alkylene group (preferably 1 to 12 carbon atoms, more preferably 1 to 6, and still more preferably 1 to 3), an oxygen atom, a carbonyl group, an amino group (NH), or those related to their combination. group.

The compound represented by the following formula (P-3) is also preferable as the radically polymerizable compound having tetrafunctional or more.

[Chemical formula 7]

In formula (P-3), Ps is each independently a group selected from vinylphenyl, vinyl and (meth)acryloyl, L ^q is a linking group of rm+1 valence, and rm is 0-12 Integer.

In the formula, Ps is preferably a (meth)acryloyl group.

L ^q is an alkylene group (preferably the number of carbon atoms is 1 to 60, more preferably 3 to 40, further preferably 4 to 24), an amino group (NH), a carbonyl group, an oxygen atom, an (oligo)alkyleneoxy group (for example, ( The preferred number of oligo)methyleneoxy, (oligo)ethyleneoxy, (oligo)propyleneoxy, and repeating numbers is preferably 1 to 24, more preferably 3 to 18, and still more preferably 4 to 14), (oligo) alkylene amino (NH) group (for example, (oligo) methylene amino, (oligo) ethylene amino, (oligo) propylene amino, the preferred number of repeating numbers is preferably 1～ 24, more preferably 3 to 18, further preferably 4 to 14) or preferably a combination thereof.

Ps can be substituted not only at the end of ^Lq , but also at the middle. L ^q is preferably a relatively long chain group, and the number of atoms not including hydrogen atoms in the bond is preferably 5 or more and 100 or less, more preferably 6 or more and 50 or less, and further preferably 7 or more and 40 or less.

rm is an integer of 0-12, Preferably it is 1-8, More preferably, it is 1-6.

The radically polymerizable compound represented by any one of formulae (P-1) to (P-3) preferably has a linking group represented by L ^P +L ^Q or L ^q present in the compound with a corresponding length. When the length is expressed as the ratio of the mass in one molecule, the ratio represented by the formula amount of L ^P + L ^Q or L ^q /the molecular weight of the radical polymerizable compound×100 is preferably 5 mass % or more and 80 mass % or less , more preferably 10 mass % or more and 70 mass % or less, further preferably 15 mass % or more and 50 mass % or less.

Examples of specific radically polymerizable compounds are given below, but the present invention is not limited to these.

[Chemical formula 8]

[Chemical formula 9]

[Chemical formula 10]

[Chemical formula 11]

[Chemical formula 12]

[Chemical formula 13]

[Chemical formula 14]

l to o are each independently a natural number of 1 to 3.

[Chemical formula 15]

B-8 is a single compound of the above-mentioned tetrafunctional compound or trifunctional compound or a mixture of the above-mentioned compounds.

[Chemical formula 16]

[Chemical formula 17]

l to q are each independently a natural number of 1 to 3.

[Chemical formula 18]

[Chemical formula 19]

[Chemical formula 20]

[Chemical formula 21]

2 mass % or more is preferable in the solid content of a photosensitive resin composition, as for content of a specific radically polymerizable compound, 5 mass % or more is more preferable, and 10 mass % or more is still more preferable. As an upper limit, 50 mass % or less is preferable, 30 mass % or less is more preferable, and 20 mass % or less is further more preferable.

The ratio of the precursor of the heterocycle-containing polymer to the specific radically polymerizable compound is preferably 2.5 parts by mass or more, more preferably 6.2 parts by mass or more, and still more preferably 12.5 parts by mass relative to 100 parts by mass of the precursor of the heterocycle-containing polymer parts by mass or more. The upper limit is preferably 62.5 parts by mass or less, more preferably 37.5 parts by mass or less, and further preferably 25 parts by mass or less.

One kind of specific radically polymerizable compound may be used, and a plurality of kinds may be used. When a plurality of kinds are used, the total amount thereof is in the above-mentioned range.

Furthermore, in the present invention, a polymerizable compound other than the specific radically polymerizable compound (hereinafter, also referred to as another polymerizable compound) and a precursor of the heterocyclic ring-containing polymer described later may be contained or not contained.

One Embodiment of this invention is an aspect which contains other polymerizable compound exceeding 10 mass % of content of a specific radically polymerizable compound. In the present embodiment, the content of the other polymerizable compound is preferably more than 10% by mass and 30% by mass or less of the content of the specific radically polymerizable compound. As other polymerizable compounds, compounds having a polymerizable functional group Ps can be used. As for the number of the polymerizable group which other polymerizable compound has, for example, 1 or 2 are mentioned. The molecular weight of the other polymerizable compound is preferably 2,000 or less, more preferably 1,500 or less, and still more preferably 900 or less. The lower limit of the molecular weight of the polymerizable compound is preferably 100 or more. In addition, as another polymerizable compound, a compound having a methylol group, an alkoxymethyl group, or an acyloxymethyl group; an epoxy compound; an oxetane compound; and a benzoxazine compound can be mentioned. Specific examples of other polymerizable compounds include compounds described in paragraphs 0102 to 0126 of International Publication No. 2017/104672 that do not correspond to specific radically polymerizable compounds, and the contents are incorporated in the present specification.

One Embodiment of this invention is an aspect which does not contain another radically polymerizable compound substantially. Substantially not containing means that the content of other polymerizable compounds other than the specific radically polymerizable compound is 10% by mass or less, preferably 5% by mass or less, and more preferably 3% by mass or less of the content of the specific radically polymerizable compound , more preferably 1 mass % or less.

<Heterocycle-containing polymer precursor>

The precursor of the heterocycle-containing polymer used in the present invention has a radically polymerizable group. The radically polymerizable group may be bonded to the side chain of the precursor of the heterocyclic polymer, or may be bonded to the main chain. Bonding to a side chain is preferred.

As the precursor of the heterocycle-containing polymer, a polyimide precursor or a polybenzoxazole precursor is preferably contained. As the polymer precursor, a polyimide precursor is more preferable, and a polyimide precursor containing a structural unit represented by the following formula (1) is still more preferable.

＜＜Polyimide precursor＞＞

The polyimide precursor used in the present invention has a radically polymerizable group. It is preferable to have a radically polymerizable group in a side chain.

As a polyimide precursor, it is more preferable to contain the structural unit represented by following formula (1). By setting it as such a structure, the composition which is more excellent in film strength can be obtained.

[Chemical formula 22]

In formula (1), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or Monovalent organic group.

A ¹ and A ² are each independently an oxygen atom or NH, preferably an oxygen atom.

R ¹¹¹ represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, an aromatic heterocyclic group, or a group composed of a combination thereof, and the number of carbon atoms is 2 to 20 linear aliphatic groups, branched aliphatic groups with 3 to 20 carbon atoms, cyclic aliphatic groups with 3 to 20 carbon atoms, aromatic groups with preferably 6 to 20 carbon atoms, or The group constituted by a combination of these is more preferably an aromatic group having 6 to 20 carbon atoms.

R ¹¹¹ is preferably derived from a diamine. As a diamine used for manufacture of a polyimide precursor, a linear or branched aliphatic, cyclic aliphatic, or aromatic diamine etc. are mentioned. Only one type of diamine may be used, or two or more types may be used.

Specifically, the diamine preferably contains a linear aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or contains A group of these combinations is more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. As an example of an aromatic group, the following aromatic group is mentioned.

[Chemical formula 23]

In the formula, A is preferably a single bond or selected from aliphatic hydrocarbon groups having 1 to 10 carbon atoms that may be substituted with fluorine atoms, -O-, -C(=O)-, -S-, -S(=O) ₂ Groups in -, -NHCO- and their combinations are more preferably single bonds or alkylene groups having 1 to 3 carbon atoms which may be substituted with fluorine atoms, -O-, -C(=O)-, -S The groups in - and -SO ₂ - are more preferably selected from -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ - and -C(CH ₃ ) ₂ - A divalent group in the group consisting of.

Specific examples of the diamine include those selected from the group consisting of 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminopropane. Aminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane or 1,4-diamino Cyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, or 1,4-bis(aminomethyl)cyclohexane, bis-(4 -aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; m-phenylenediamine and p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl and 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether , 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone and 3,3'-diaminodiphenylsulfone, 4 ,4'-diaminodiphenyl sulfide and 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone and 3,3'-diaminobenzophenone, 3,3 '-Dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl (4,4'-diamine-2,2'-dimethyl biphenyl), 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl) ) Hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3 -Amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino) -3-Hydroxyphenyl)sulfone, 4,4'-diamino-terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)benzene yl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy) ) Benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy) ) benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenyl methane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy base)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3, 3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3 -Dihydroxy-4 ,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3', 5,5'-Tetramethyl-4,4'-diaminodiphenylmethane, 2-(3',5-diaminobenzoyloxy)ethyl methacrylate, 2,4-diamino Cumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4, 6-Trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4 -Aminophenyl)ethane, diaminobenzoanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoro Propane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecane Fluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3, 5-Bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoro) Methylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethyl) Phenoxy)diphenylsulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 2,2-bis[4-(4-amino-3- Trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2 At least one diamine selected from '-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorobitoluidine and 4,4'-diaminotetrabiphenyl .

In addition, the diamines (DA-1) to (DA-18) shown below are also preferable.

[Chemical formula 24]

Moreover, as a preferable example, the diamine which has at least 2 or more of alkylene glycol units in a main chain is mentioned. It is preferable to combine the diamine which contains any one or both of ethylene glycol chain and propylene glycol chain at least 2 or more in 1 molecule, and the diamine which does not contain an aromatic ring is more preferable. Specific examples include JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148 , JEFFAMINE (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (the above are the product names, manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy) yl)ethoxy)propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, etc., but not It is not limited to these.

The following shows JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE (registered trademark) registered trademark) structure of EDR-176.

[Chemical formula 25]

In the above, x, y, and z are average values.

In formula (1), R ¹¹¹ is represented by -Ar ⁰ -L ⁰ -Ar ⁰ -, each Ar ⁰ is each independently a divalent group containing an aromatic ring, and L ⁰ is preferably a single bond, which may be substituted by a fluorine atom. Aliphatic hydrocarbon groups having 1 to 10 carbon atoms, -O-, -CO-, -S-, -SO ₂ -, -NHCO-, and groups formed by combining two or more of these groups.

The number of carbon atoms of Ar ⁰ is preferably 6 to 22, more preferably 6 to 18, further preferably 6 to 10, and particularly preferably a phenylene group. The definition of the preferable range of L ⁰ is the same as the definition of A in the above-mentioned AR-8.

From the viewpoint of i-ray transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoints of i-ray transmittance and availability, the divalent organic group represented by the formula (61) is more preferable.

[Chemical formula 26]

In formula (51), R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group, a fluoromethyl group, or a difluoro group methyl or trifluoromethyl;

Examples of the monovalent organic group of R ⁵⁰ to R ⁵⁷ include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably carbon number 1 to 6), an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably carbon number 1 ~6) fluorinated alkyl groups, etc.

[Chemical formula 27]

In formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group.

As the diamine compound giving the structure of formula (51) or (61), dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4' can be mentioned -Diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. One of them may be used, or two or more of them may be used in combination.

R ¹¹⁵ in formula (1) represents a tetravalent organic group. As the tetravalent organic group, a group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable.

[Chemical formula 28]

The definition of R ¹¹² is the same as that of A, and the preferred range is also the same.

Specific examples of the tetravalent organic group represented by R ¹¹⁵ in the formula (1) include the tetracarboxylic acid residue remaining after removing the acid dianhydride group from the tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).

[Chemical formula 29]

R ¹¹⁵ represents a tetravalent organic group. The definition of R ¹¹⁵ is the same as that of R ¹¹⁵ of formula (1).

Specific examples of the tetracarboxylic dianhydride include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3 ',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane Ketonetetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3 ,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxodiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2 ,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane- 3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3, 4,9,10-Perylenetetracarboxylic dianhydride, 1,2,4,5-Naphthalenetetracarboxylic dianhydride, 1,4,5,8-Naphthalenetetracarboxylic dianhydride, 1,8,9,10 -Phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethanedianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethanedianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethanedianhydride At least one of 2,3,4-benzenetetracarboxylic dianhydrides and their alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

In addition, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below can also be mentioned as preferable examples.

[Chemical formula 30]

R ¹¹³ and R ¹¹⁴ in formula (1) each independently represent a hydrogen atom or a monovalent organic group. It is preferable that at least one of R ¹¹³ and R ¹¹⁴ contains a radically polymerizable group, and it is more preferable that both of them contain a radically polymerizable group. A radical polymerizable group is a group which can carry out a crosslinking reaction by the action of a radical, and the group which has an ethylenically unsaturated bond is mentioned as a preferable example.

As a group which has an ethylenically unsaturated bond, a vinyl group, an allyl group, a (meth)acryloyl group, the group represented by following formula (III), etc. are mentioned.

[Chemical formula 31]

In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, more preferably a methyl group.

In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH(OH)CH ₂ - or a (poly)oxyalkylene group having 4 to 30 carbon atoms (as an alkylene group). , the number of carbon atoms is preferably 1-12, more preferably 1-6, especially preferably 1-3; the number of repetitions is preferably 1-12, more preferably 1-6, especially preferably 1-3). In addition, the (poly)oxyalkylene group represents an oxyalkylene group or a polyoxyalkylene group.

Examples of preferable R ²⁰¹ include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, and hexamethylene. group, octamethylene, dodecylene, -CH ₂ CH(OH)CH ₂ -, more preferably ethylene, propylene, trimethylene, -CH ₂ CH(OH)CH ₂ -.

It is especially preferred that R ²⁰⁰ is methyl and R ²⁰¹ is ethylene.

The polymerizable group equivalent (value obtained by dividing the weight average molecular weight by the number of polymerizable groups) of the radically polymerizable group is preferably 0.0001 or more, more preferably 0.0005 or more, and further preferably 0.001 or more. As an upper limit, 0.05 or less is preferable, 0.001 or less is more preferable, and 0.005 or less is still more preferable. In addition, the number of polymerizable groups can be estimated based on the blending amount of the raw materials at the time of synthesis.

Examples of the embodiment of the polyimide precursor in the present invention include aliphatic groups, aromatic groups, and aralkyl groups having 1, 2, or 3 acid groups as the monovalent organic group of R ¹¹³ or R ¹¹⁴ Wait. Specifically, an aromatic group having 6 to 20 carbon atoms having an acid group, and an aralkyl group having 7 to 25 carbon atoms having an acid group can be mentioned. More specifically, the phenyl group which has an acid group and the benzyl group which has an acid group are mentioned. The acid group may be a hydroxyl group. That is, R ¹¹³ or R ¹¹⁴ may be a group having a hydroxyl group.

As the monovalent organic group represented by R ¹¹³ or R ¹¹⁴ , a substituent which improves the solubility of the developer can be used.

R ¹¹³ or R ¹¹⁴ may be a hydrogen atom, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group, or a 4-hydroxybenzyl group from the viewpoint of solubility in an aqueous developer.

From the viewpoint of solubility in an organic solvent, R ¹¹³ or R ¹¹⁴ may be a monovalent organic group. The monovalent organic group may include a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or an alkyl group substituted with an aromatic group.

The number of carbon atoms of the alkyl group may be 1 to 30 (3 or more in the case of cyclic). The alkyl group may be any of straight chain, branched chain and cyclic. Examples of straight-chain or branched-chain alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and tetradecyl. , octadecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, 1-ethylpentyl and 2-ethylhexyl. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. As a monocyclic cyclic alkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group are mentioned, for example. Examples of the polycyclic cyclic alkyl group include adamantyl, norbornyl, bornyl, camphenyl, decalinyl, tricyclodecyl, tetracyclodecyl, camphenyl Acyl, dicyclohexyl and pinenyl. Among them, a cyclohexyl group is exemplified from the viewpoint of achieving high sensitivity. In addition, as the alkyl group substituted with an aromatic group, a straight-chain alkyl group substituted with an aromatic group described later may be used.

As an aromatic group, an aromatic hydrocarbon group or an aromatic heterocyclic group is mentioned.

(chrysene)环、联三伸苯环、芴环、联苯环等具有芳香族烃环的基团。Specific examples of the aromatic hydrocarbon group include substituted or unsubstituted benzene rings, naphthalene rings, pentalene rings, indene rings, azulene rings, heptalene rings, indene rings, perylene rings ring, fused pentabenzene ring, acenaphthene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring,

A group having an aromatic hydrocarbon ring, such as a (chrysene) ring, a bitriphenylene ring, a fluorene ring, and a biphenyl ring.

Examples of the aromatic heterocyclic group include substituted or unsubstituted pyrrole rings, furan rings, thiophene rings, pyrazole rings, imidazole rings, oxazole rings, thiazole rings, pyridine rings, pyrazine rings, pyrimidine rings, and pyridazine rings. , triazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolizine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxa Line, quinoxazoline (quinoxazoline) ring, isoquinoline ring, carbazole ring, phenanthroline ring, acridine ring, phenanthroline (phenanthroline) ring, thien ring, chromene (chromene) ring, xanthene ( A group having an aromatic heterocycle such as a xanthene ring, a phenoxathiine ring, a phenothiazine ring, or a phenazine ring.

In addition, the polyimide precursor preferably also has a fluorine atom in the structural unit. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less. The upper limit is not particularly limited, but is actually 50% by mass or less.

Furthermore, in order to improve the adhesiveness with a board|substrate, the aliphatic group which has a siloxane structure and the structural unit represented by Formula (1) can be copolymerized. Specifically, as a diamine component, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. are mentioned.

The structural unit represented by the formula (1) is preferably the structural unit represented by the formula (1-A).

[Chemical formula 32]

The definitions of A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ are the same as those of A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (1), respectively, and the preferred ranges are also the same. Definition of R ¹¹² R ¹¹² in formula (5) has the same definition, and the preferred range is also the same.

In the polyimide precursor, the structural unit represented by the formula (1) may be one type or two or more types. In addition, structural isomers of the structural unit represented by the formula (1) may also be included. Furthermore, the polyimide precursor may contain other kinds of structural units in addition to the structural unit of the above-mentioned formula (1).

As one embodiment of the polyimide precursor in the present invention, it is exemplified that 50 mol % or more of the entire structural unit, further 70 mol % or more, especially 90 mol % or more are the structural unit represented by the formula (1), And at least one (preferably two) of R ¹¹³ and R ¹¹⁴ is a polyimide precursor of a radically polymerizable group. The upper limit is practically 100 mol% or less.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and further preferably 10,000 to 50,000. In addition, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.

The degree of dispersion (weight average molecular weight/number average molecular weight) of the molecular weight of the polyimide precursor is preferably 1.5 to 3.5, and more preferably 2 to 3.

The polyimide precursor can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. It is preferably obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative using a halogenating agent and then reacting with a diamine.

In the manufacturing method of a polyimide precursor, it is preferable to use an organic solvent during a reaction. One kind of organic solvent may be sufficient as it, and two or more kinds may be sufficient as it.

The organic solvent can be appropriately set according to the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone.

When producing a polyimide precursor, it is preferable to include a step of precipitating a solid. Specifically, solid precipitation can be performed by precipitating the polyimide precursor in the reaction liquid in water and dissolving it in a solvent such as tetrahydrofuran that can dissolve the polyimide precursor.

＜＜Polybenzoxazole precursor＞＞

The polybenzoxazole precursor used in the present invention has a radically polymerizable group. It is preferable to have a radically polymerizable group in a side chain.

The polybenzoxazole precursor more preferably contains a structural unit represented by the following formula (2).

[Chemical formula 33]

R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group.

R ¹²¹ represents a divalent organic group. The divalent organic group preferably includes an aliphatic group (preferably 1 to 24 carbon atoms, more preferably 1 to 12, and particularly preferably 1 to 6) and an aromatic group (preferably 6 to 22 carbon atoms, more preferably 6 to 6 carbon atoms). 14, at least one group of 6 to 12) is particularly preferred. Examples of the aromatic group constituting R ¹²¹ include R ¹¹¹ in the above formula (1). As said aliphatic group, a linear aliphatic group is preferable. R ¹²¹ is preferably derived from 4,4'-oxodibenzoyl chloride.

In formula (2), R ¹²² represents a tetravalent organic group. As a tetravalent organic group, the definition is the same as that of R ¹¹⁵ in the above formula (1), and the preferred range is also the same. R ¹²² is preferably derived from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane.

R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group, and the definitions are the same as those of R ¹¹³ and R ¹¹⁴ in the above formula (1), and the preferred ranges are also the same.

In addition to the structural unit of the above-mentioned formula (2), the polybenzoxazole precursor may contain other kinds of structural units.

The precursor preferably contains a diamine residue represented by the following formula (SL) as another kind of structural unit from the viewpoint of being able to suppress the warpage of the cured film accompanying ring closure.

[Chemical formula 34]

Z has a structure and b structure, R ^1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (preferably carbon number 1 to 6, more preferably carbon number 1 to 3), R ^2s is carbon number 1 to 10 (preferably carbon number 1-6, more preferably carbon number 1-3), at least one of R ^3s , R ^4s , R ^5s , R ^6s is an aromatic group (preferably carbon number 6-22, More preferably carbon number 6-18, particularly preferably carbon number 6-10), the rest is hydrogen atom or carbon number 1-30 (preferably carbon number 1-18, more preferably carbon number 1-12, especially preferred The organic groups having 1 to 6 carbon atoms) may be the same or different. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. In the Z part, it is preferable that the a structure is 5 to 95 mol%, the b structure is 95 to 5 mol%, and the a+b is 100 mol%.

In formula (SL), as preferable Z, R ^5s and R ^6s in the structure b are phenyl groups. Also, the molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. The molecular weight can be determined by a commonly used gel permeation chromatography. By making the said molecular weight into the said range, the effect of reducing the elastic modulus after dehydration ring closure of a polybenzoxazole precursor, and suppressing warpage, and the effect of improving solubility can be combined.

When the precursor contains the diamine residue represented by the formula (SL) as another kind of structural unit, it is preferable to further contain the tetracarboxylic acid remaining after removing the acid dianhydride from the tetracarboxylic dianhydride from the viewpoint of improving the alkali solubility residues as building blocks. As an example of such a tetracarboxylic-acid residue, the example of ^R115 in Formula (1) is mentioned.

The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and further preferably 10,000 to 50,000. In addition, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.

The degree of dispersion of the polybenzoxazole precursor is preferably 1.5 to 3.5, and more preferably 2 to 3.

The content of the polymer precursor in the photosensitive resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and still more preferably 50% by mass with respect to the total solid content of the composition As mentioned above, 60 mass % or more is still more preferable, and 70 mass % or more is still more preferable. Furthermore, the content of the polymer precursor in the photosensitive resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, still more preferably 98% by mass or less, and still more preferably 95% by mass with respect to the total solid content of the composition. mass % or less, more preferably 95 mass % or less.

The photosensitive resin composition of this invention may contain 1 type of polymer precursor, and may contain 2 or more types. When two or more types are contained, it is preferable that the total amount is in the above-mentioned range.

＜Heat alkali generator＞

The photosensitive resin composition of this invention contains a thermal alkali generator. By using a thermal base generator, when the heating step of the ring-closure reaction of the precursor of the heterocyclic-containing polymer is performed, the base species that promote the ring-closure reaction can be generated, so the ring-closure rate is further improved. On the other hand, when the cyclization is promoted by the thermal base generator, the number of crosslinking points of the polymer precursor decreases. On the other hand, in the present invention, after cyclization, a part of the crosslinking is cut off, and the crosslinking agent is supplemented with multiple points, thereby contributing to the improvement of the effect of the present invention.

As the thermal base generator used in the present invention, a tertiary amine compound can be mentioned. For example, it is a compound represented by the following formula (A1).

(R ^A1 )N(R ^A2 ) ₂ (A1)

In the formula, R ^A1 is an alkyl group (preferably 1-12 carbon atoms, more preferably 1-6, further preferably 1-3), alkenyl (preferably 2-12 carbon atoms, more preferably 2-6, further preferably 2 ～3), aryl group (preferably 6-22 carbon atoms, more preferably 6-18, further preferably 6-10), aralkyl (preferably 7-23 carbon atoms, more preferably 7-19, further preferably 7- 11), preferably aryl. R ^A2 is an alkyl group (preferably 1-12 carbon atoms, more preferably 1-6, further preferably 1-3) which may have an acidic group (especially preferably a carboxyl group).

As the thermal base generator used in the present invention, ammonium salts (including pyridinium bases) are preferred. Specifically, it is preferable to contain a cation represented by the following formula (101) or formula (102), and a base formed with an anion is more preferable. The anion may be bonded to any part of the ammonium cation through a covalent bond (specifically, betaine), and may exist outside the molecule of the ammonium cation, but preferably exists outside the molecule of the ammonium cation. In addition, the presence of an anion outside the molecule of the ammonium cation means that the ammonium cation and the anion are not bound by covalent bonds. Hereinafter, anions other than the molecules of the cationic portion are also referred to as counter anions.

[Chemical formula 35]

In formula (101) and formula (102), R ¹ to R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, and R ⁹ represents a hydrocarbon group.

Here, the hydrocarbon group means that it may have a hydroxyl group, a halogen atom, an oxo group (=O), or the like within a range in which the effect of the present invention is exhibited.

R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁵ and R ⁹ , and R ⁶ and R ⁹ may be bonded to each other to form a ring.

The hydrocarbon group of R ¹ to R ⁶ is preferably an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6, further preferably 1 to 3), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6, and furthermore Preferably 2-3), aryl group (preferably 6-22 carbon atoms, more preferably 6-18, further preferably 6-10) or aralkyl (preferably 7-23 carbon atoms, more preferably 7-19, still more preferably 7 to 11).

The hydrocarbon group of R ⁹ is preferably a methylene group or an alkylene group (the number of carbon atoms is preferably 2-12, more preferably 2-6, further preferably 2-3). Methylene group and alkylene group may be substituted with amino group (NH ₂ ). The amino group may constitute a linking group (NH) when forming a ring. The ring formed by R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁵ and R ⁹ , and R ⁶ and R ⁹ includes a 4- to 8-membered nitrogen-containing heterocyclic ring. As a compound in formula (102) in which R ⁵ and R ⁶ , and R ⁵ and R ⁹ are bonded to form a ring, diazbicycloundecene, diazbicyclononene, and the like are exemplified.

The ammonium cation is preferably represented by any one of the following formulae (Y1-1) to (Y1-5).

[Chemical formula 36]

In formulae (Y1-1) to (Y1-5), R ¹⁰¹ represents an n-valent organic group, and R ¹ and R ⁷ have the same definitions as R ¹ in formula (101) or formula (102).

Among them, R ¹⁰¹ is preferably a group with an alkane structure (preferably 1-12 carbon atoms, more preferably 1-6, further preferably 1-3), or a group with an olefin structure (preferably 2-12 carbon atoms, more preferably 2-6, more preferably 2-3), aryl-structured groups (preferably 6-22 carbon atoms, more preferably 6-18, further preferably 6-10), more preferably aryl-structured groups (especially benzene) ring-structured groups).

In the formulae (Y1-1) to (Y1-4), Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group (the number of carbon atoms is preferably 6 to 22, more preferably 6 to 18, further preferably 6 to 10), and n represents 1 In the above integers, m represents an integer of 0-5.

In formula (Y1-3), a bicyclic ring may be formed by bonding two R ^1s . As an example of a bi compound, a diazabicycloundecene, a diazbicyclononene, etc. are mentioned.

In this embodiment, the ammonium salt has an anion and an ammonium cation having a pKa1 of preferably 0 to 4. The upper limit of the pKa1 of the anion is more preferably 3.5 or less, and still more preferably 3.2 or less. The lower limit is preferably 0.5 or more, and more preferably 1.0 or more. As long as the pKa1 of the anion is within the above range, the heterocyclic ring-containing polymer precursor and the like can be cyclized at a lower temperature, and further, the stability of the photosensitive resin composition can be improved. As long as pKa1 is 4 or less, the stability of the thermal alkali generator is favorable, the generation of alkali is suppressed without heating, and the stability of the photosensitive resin composition is favorable. As long as pKa1 is 0 or more, the generated base is not easily neutralized, and the cyclization efficiency of the heterocyclic-ring-containing polymer precursor or the like is good.

The type of anion is preferably one selected from the group consisting of carboxylate anion, phenol anion, phosphate anion, and sulfate anion, and a carboxylate anion is more preferable because the stability of the salt and thermal decomposability can be achieved. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion.

The carboxylate anion is preferably an anion of a divalent or more carboxylic acid having two or more carboxyl groups, and more preferably an anion of a divalent carboxylic acid. According to this aspect, it can be used as a thermal alkali generator which can further improve the stability, curability, and developability of the photosensitive resin composition. In particular, by using an anion of a divalent carboxylic acid, the stability, curability, and developability of the photosensitive resin composition can be further improved.

In the present embodiment, the carboxylic acid anion is preferably an anion of a carboxylic acid having a pKa1 of 4 or less. pKa1 is more preferably 3.5 or less, still more preferably 3.2 or less. According to this aspect, the stability of the photosensitive resin composition can be further improved.

Here, pKa1 is a value calculated by the structural formula using the software of ACD/pKa (manufactured by ACD/LA Systems Inc.).

The carboxylate anion is preferably represented by the following formula (X1).

[Chemical formula 37]

In formula (X1), EWG represents an electron withdrawing group.

In the present embodiment, the electron withdrawing group means that the Hammett substituent constant σm is expressed as a positive value. Among them, σm is described in detail in Yusho Tono, Journal of Synthetic Organic Chemistry, Japan Vol. 23 No. 8 (1965) pp. 631-642. In addition, the electron withdrawing group in the present embodiment is not limited to the substituents described in the above-mentioned documents.

Examples of the substituent in which σm represents a positive value include a CF ₃ group (σm=0.43), a CF ₃ CO group (σm=0.63), a HC≡C group (σm=0.21), and a CH ₂ =CH group (σm= 0.06), Ac group (σm=0.38), MeOCO group (σm=0.37), MeCOCH=CH group (σm=0.21), PhCO group (σm=0.34), H ₂ NCOCH ₂ group (σm=0.06) and the like. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (it is the same below).

EWG is preferably a group represented by the following formulae (EWG-1) to (EWG-6).

[Chemical formula 38]

In formulae (EWG-1) to (EWG-6), R ^x1 to R ^x3 each independently represent a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6, and further preferably 1 to 3), Alkenyl (preferably 2-12 carbon atoms, more preferably 2-6, further preferably 2-3), aryl (preferably 6-22 carbon atoms, more preferably 6-18, further preferably 6-10), hydroxyl or Carboxyl group, Ar is an aromatic group, preferably an aromatic hydrocarbon group (preferably 6-22 carbon atoms, more preferably 6-18, further preferably 6-10) or an aromatic heterocyclic group (preferably 1-12 carbon atoms, more preferably 1 to 6, more preferably 1 to 3. Examples of hetero atoms include nitrogen atoms, sulfur atoms, and oxygen atoms). Ar may have a substituent, for example, may have 1 to 5 groups of R ^x1 .

Np is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2.

In the present embodiment, the carboxylate anion is preferably represented by the following formula (XA).

Formula (XA)

[Chemical formula 39]

In the formula (XA), L ¹⁰ represents a single bond or an alkylene group (preferably 1-12 carbon atoms, more preferably 1-6, further preferably 1-3), alkenylene (preferably 2-12 carbon atoms, more preferably 1-3). Preferably 2 to 6, more preferably 2 to 3), aromatic group (aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, further preferably 6 to 10) or aromatic heterocyclic group (number of carbon atoms) 1 to 12 are preferred, 1 to 6 are more preferred, and 1 to 3 are further preferred. Examples of hetero atoms include nitrogen atoms, sulfur atoms, and oxygen atoms)), -NR ^X -, and a divalent linking group selected from their combination, R ^X represents a hydrogen atom, an alkyl group (preferably 1-12 carbon atoms, more preferably 1-6, further preferably 1-3), an alkenyl group (preferably 2-12 carbon atoms, more preferably 2-6, still more preferably 2- 3) or an aryl group (the number of carbon atoms is preferably 6-22, more preferably 6-18, further preferably 6-10).

Specific examples of the carboxylate anion include maleic acid anion, phthalic acid anion, N-phenyliminodiacetic acid anion, and oxalic acid anion.

Specific examples of the thermal alkali generator include the following compounds.

[Chemical formula 40]

[Chemical formula 41]

[Chemical formula 42]

[Chemical formula 43]

It is preferable that content of the thermal alkali generator in the photosensitive resin composition of this invention is 0.1-50 mass % with respect to the total solid content of the photosensitive resin composition. The lower limit is more preferably 0.5% by mass or more, still more preferably 0.85% by mass or more, and still more preferably 1% by mass or more. The upper limit is more preferably 30 mass % or less, still more preferably 20 mass % or less, still more preferably 10 mass % or less, and may be 5 mass % or less, or 4 mass % or less.

The mass ratio of the thermal alkali generator to the specific radically polymerizable compound (specific radically polymerizable compound/thermal alkali generator) is preferably 1.0 to 80. As a lower limit, 1.5 or more are preferable, 2 or more are more preferable, and 3 or more are still more preferable. As an upper limit, 50 or less are preferable, 20 or less are more preferable, and 10 or less are still more preferable. By setting this ratio to the above-mentioned range, the values of elongation at break and chemical resistance become optimal.

One type or two or more types of thermal alkali generators can be used. When two or more kinds are used, the total amount is preferably the above range.

<Other components of the photosensitive resin composition>

The photosensitive resin composition of this invention may contain components other than the above. Specifically, a photopolymerization initiator, a solvent, a polymerization inhibitor, and the like are exemplified. In addition, impurities derived from raw materials used in the synthesis of the heterocyclic-ring-containing polymer precursor may be contained.

＜＜Photopolymerization initiator＞＞

It is preferable that the photosensitive resin composition of this invention contains a photoinitiator.

There is no restriction|limiting in particular as a photoinitiator which can be used for this invention, It can select suitably from a well-known photoinitiator. For example, a photopolymerization initiator having photosensitivity to light from an ultraviolet region to a visible region is preferable. In addition, it can be an activator that interacts with a photo-excited sensitizer and generates active free radicals.

The photopolymerization initiator preferably contains at least one compound having an absorption coefficient of at least about 50 molar in the range of about 300 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of the compound can be measured by a known method. For example, the measurement is performed at a concentration of 0.01 g/L by an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian), preferably using an ethyl acetate solvent.

The photosensitive resin composition of the present invention contains a photopolymerization initiator, and after the photosensitive resin composition of the present invention is applied to a substrate such as a semiconductor wafer to form a photosensitive resin composition layer, the photosensitive resin composition is irradiated with light to cause the generation of The curing by radicals can reduce the solubility in the light-irradiated part. Therefore, there is an advantage that, for example, regions with different solubility can be easily produced according to the electrode pattern by exposing the photosensitive resin composition through a photomask having a pattern that shields only the electrode portion.

As the photopolymerization initiator, any known compound can be used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, hexaarylbisimidazoles, oximes, etc. can be mentioned. Oxime compounds such as derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, Organic boron compounds, iron aromatic complexes, etc. For details of them, the descriptions in paragraphs 0165 to 0182 of JP 2016-027357 A can be referred to, and the contents are incorporated into the present specification.

As the ketone compound, for example, the compound described in paragraph 0087 of JP-A No. 2015-087611 is exemplified, and the content is incorporated in the present specification. Among the commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in Japanese Patent Laid-Open No. 10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used.

As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCURE 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (product names: all manufactured by BASF Corporation) can be used.

As the aminoacetophenone-based initiator, commercially available IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF Corporation) can be used.

As the aminoacetophenone-based initiator, the compounds described in Japanese Patent Laid-Open No. 2009-191179 can also be used whose maximum absorption wavelength is matched to a light source with a wavelength of 365 nm or 405 nm.

2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide etc. are mentioned as an acylphosphine type initiator. In addition, commercially available IRGACURE-819 or IRGACURE-TPO (trade name: both manufactured by BASF Corporation) can be used.

As a metallocene compound, IRGACURE-784 (made by BASF) etc. are illustrated.

As a photopolymerization initiator, an oxime compound is mentioned more preferably. By using the oxime compound, the exposure range can be further effectively increased. The oxime compound preferably has a wide exposure range (exposure margin).

As specific examples of the oxime compound, compounds described in JP 2001-233842 A, compounds described in JP 2000-080068 A, and compounds described in JP 2006-342166 A can be used .

Examples of preferable oxime compounds include compounds having the following structures, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, and 3-propionyloxy yliminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyidene Amino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1 - Ketones etc.

[Chemical formula 44]

Among the commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE03, IRGACURE OXE 04 (the above are manufactured by BASF Corporation), ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, Japanese Patent Laid-Open No. 2012-014052) can also be preferably used. Photopolymerization initiator 2) described in . In addition, TR-PBG-304 (manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.), ADEKAARKLS NCI-831, and ADEKAARKLS NCI-930 (manufactured by ADEKACORPORATION) can be used. In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can also be used.

Furthermore, an oxime compound having a fluorine atom can also be used. Specific examples of such oxime compounds include compounds described in JP 2010-262028 A, compounds 24, 36 to 40 described in paragraphs 0345 to 0348 of JP 2014-500852 A, and Japanese Compound (C-3) and the like described in paragraph 0101 of JP-A No. 2013-164471.

As the most preferable oxime compound, the oxime compound having a specific substituent shown in JP 2007-269779 A, and the oxime compound having a thioaryl group shown in JP 2009-191061 A can be mentioned. Wait.

From the viewpoint of exposure sensitivity, the photopolymerization initiator is selected from the group consisting of trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, and phosphine oxide compounds , metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl-benzene-iron complex Compounds in the group consisting of compounds and their salts, halomethyl oxadiazole compounds, and 3-aryl-substituted coumarin compounds.

More preferred photopolymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, diphenylene A ketone compound, an acetophenone compound, more preferably at least one selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound Compounds, metallocene compounds or oxime compounds are more preferably used, and oxime compounds are particularly preferred.

In addition, as the photopolymerization initiator, N,N'-tetraalkyl-4 such as benzophenone and N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone) can also be used. ,4'-Diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-methyl-1-[4- Aromatic ketones such as (methylthio)phenyl]-2-morpholinyl-acetone-1, quinones obtained by condensing aromatic rings such as alkylanthraquinones, benzoin ether compounds such as benzoin alkyl ethers, benzoin , benzoin compounds such as alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, etc. In addition, a compound represented by the following formula (I) can also be used.

[Chemical formula 45]

In formula (I), R ⁵⁰ is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, Phenyl, cyclopentyl, cyclohexyl, alkenyl having 2 to 12 carbon atoms, alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and 1 to 4 carbon atoms at least one substituted ^phenyl group or ^{biphenyl group} in the ^alkyl group of An alkyl group having 1 to 12 atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen.

[Chemical formula 46]

In the formula, R ⁵⁵ to R ⁵⁷ are the same as R ⁵² to R ⁵⁴ in the above formula (I).

In addition, the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469 can also be used as the photopolymerization initiator.

The content of the photopolymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 1 to 5% by mass, and still more preferably 1 to 4% by mass relative to the total solid content of the photosensitive resin composition of the present invention. %. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more types of photopolymerization initiators are contained, the total of the above-mentioned ranges is preferable.

＜＜Solvent＞＞

It is preferable that the photosensitive resin composition of this invention contains a solvent.

As the solvent, any known solvent can be used. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.

Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, and ethyl butyrate. , butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, Ethoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc. )), alkyl 3-alkoxypropanoates (for example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropanoate, etc. (for example, methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxypropionic acid alkyl esters (for example, 2-alkane Methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, Propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methyl propionate and 2-alkane Ethyl oxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate , ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc.

As ethers, for example, preferable ones include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve ethyl acid ester, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc.

As ketones, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, etc. are mentioned, for example as a preferable thing.

As aromatic hydrocarbons, toluene, xylene, anisole, limonene, etc. are mentioned as a preferable thing, for example.

As the sulfoxides, for example, dimethyl sulfoxide is mentioned as a preferable substance.

Preferable examples of the amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, and the like.

Regarding the solvent, it is also preferable to mix two or more types from the viewpoint of improving the coating surface shape and the like. Among them, it is preferably selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate , 3-methoxypropionate methyl ester, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol A mixed solution of two or more structures of acetate, propylene glycol methyl ether and propylene glycol methyl ether acetate. The simultaneous use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

Regarding the content of the solvent, from the viewpoint of coatability, the total solid content concentration of the photosensitive resin composition of the present invention is preferably 5 to 80% by mass, more preferably 5 to 70% by mass, and particularly preferably 10 to 80% by mass. 60% by mass.

The solvent may contain only one type or two or more types. When two or more kinds of solvents are contained, the total of the above-mentioned ranges is preferable.

＜＜Migration inhibitor＞＞

The photosensitive resin composition preferably further contains a migration inhibitor. By including the migration inhibitor, the transfer of metal ions derived from the metal layer (metal wiring) into the photosensitive resin composition layer can be effectively suppressed.

The migration inhibitor is not particularly limited, and examples include those having a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring) ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring) compounds, with thiourea and mercapto compounds, hindered phenolic compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazoles (for example, 1,2,4-triazole), triazole-based compounds such as benzotriazole, and tetrazole-based compounds such as tetrazole and benzotetrazole can be preferably used.

In addition, an ion scavenger that captures anions such as halogen ions can also be used.

As other migration inhibitors, the rust inhibitor described in paragraph 0094 of JP 2013-015701 A, the compounds described in paragraphs 0073 to 0076 of JP 2009-283711 A, and JP 2011 A can be used. - Compounds described in paragraph 0052 of Japanese Patent Application Publication No. 059656, compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Laid-Open Publication No. 2012-194520, and the like.

Specific examples of the migration inhibitor include 1H-1,2,3-triazole and 1H-tetrazole.

When the photosensitive resin composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass %, more preferably 0.05 to 2.0 mass %, and further preferably 0.1 to 1.0 mass % with respect to the total solid content of the photosensitive resin composition.

Only one type of migration inhibitor may be used, or two or more types may be used. When there are two or more kinds of migration inhibitors, the total of them is preferably the above range.

<<Inhibitor>>

It is preferable that the photosensitive resin composition of this invention contains a polymerization inhibitor.

As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol (1,4-methoxyphenol), di-tert-butyl-p-cresol, pyrogallol, p-tert-butyl-ortho-, can be preferably used Hydroquinone, p-benzoquinone (1,4-benzoquinone), diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2' - Methylenebis(4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenyl Naphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-diamine Nitro-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropane) amine) phenol, N-nitroso-N-(1-naphthyl) hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl) phenylmethane, etc. In addition, the polymerization inhibitor described in paragraph 0060 of JP 2015-127817 A and the compounds described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used.

In addition, the following compounds (Me is a methyl group) can also be used.

[Chemical formula 47]

When the photosensitive resin composition of this invention has a polymerization inhibitor, it is preferable that content of a polymerization inhibitor is 0.01-5 mass % with respect to the total solid content of the photosensitive resin composition of this invention.

Only one kind of polymerization inhibitor may be sufficient as it, and two or more kinds may be sufficient as it. When there are two or more kinds of polymerization inhibitors, the total of the polymerization inhibitors is preferably the above-mentioned range.

<<Metal Adhesion Improver>>

It is preferable that the photosensitive resin composition of this invention contains the metal adhesiveness improver for improving the adhesiveness with the metal material used for electrodes, wiring, etc.. As a metal adhesion improving agent, a silane coupling agent etc. are mentioned.

Examples of the silane coupling agent include compounds described in paragraphs 0062 to 0073 of JP 2014-191002 A, compounds described in paragraphs 0063 to 0071 of WO 2011/080992, and JP 2011/080992 A. Compounds described in paragraphs 0060 to 0061 of JP 2014-191252 A, compounds described in paragraphs 0045 to 0052 of JP 2014-041264 A, and compounds described in paragraph 0055 of International Publication No. 2014/097594 . In addition, as described in paragraphs 0050 to 0058 of JP 2011-128358 A, it is also preferable to use two or more different silane coupling agents. In addition, the following compounds are also preferably used as the silane coupling agent. In the following formula, Et represents an ethyl group.

[Chemical formula 48]

In addition, the compounds described in paragraphs 0046 to 0049 of JP 2014-186186 A and the sulfides described in paragraphs 0032 to 0043 of JP 2013-072935 A can be used as the metal adhesion improving agent.

The content of the metal adhesion improver is preferably in the range of 0.1 to 30 parts by mass, and more preferably 0.5 to 15 parts by mass, with respect to 100 parts by mass of the heterocycle-containing polymer precursor. By setting it as 0.1 mass part or more, the adhesiveness of the cured film after a hardening process and a metal layer becomes favorable, and by setting it as 30 mass parts or less, the heat resistance and mechanical properties of the cured film after a curing process become favorable. Only one type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, the total of the above-mentioned ranges is preferable.

<<Other additives>>

Various additives such as thermal acid generators, sensitizing dyes, chain transfer agents, surfactants, higher fatty acid derivatives can be added to the photosensitive resin composition of the present invention as needed within the range that does not impair the effects of the present invention. Compounds, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, UV absorbers, aggregation inhibitors, etc. are blended. When such additives are blended, the total blending amount is preferably 3 mass % or less of the solid content of the photosensitive resin composition.

＜＜＜Thermal acid generator＞＞＞

The photosensitive resin composition of this invention may contain a thermal acid generator. The thermal acid generator generates an acid by heating, and promotes the cyclization of the precursor of the heterocyclic polymer to further improve the mechanical properties of the cured film. As the thermal acid generator, compounds described in paragraph 0059 of JP-A No. 2013-167742, and the like can be mentioned.

The content of the thermal acid generator is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, based on 100 parts by mass of the precursor of the heterocyclic polymer. By containing a thermal acid generator in an amount of 0.01 parts by mass or more, the crosslinking reaction and the cyclization of the heterocyclic-ring-containing polymer precursor are accelerated, and the mechanical properties and chemical resistance of the cured film can be further improved. Furthermore, from the viewpoint of the electrical insulating properties of the cured film, the content of the thermal acid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and particularly preferably 10 parts by mass or less.

Only one type of thermal acid generator may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above-mentioned range.

＜＜＜Sensitizing Pigment＞＞＞

The photosensitive resin composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs specific active radiation and becomes an electronically excited state. The sensitizing dye in the electronically excited state contacts with a thermal alkali generator, a thermal radical polymerization initiator, a radical polymerization initiator, etc., to generate electron transfer, energy transfer, and heat generation. Thereby, the thermal base generator, the thermal radical polymerization initiator, and the radical polymerization initiator undergo chemical changes and decompose, and generate radicals, acids, or bases. For details of the sensitizing dye, the descriptions in paragraphs 0161 to 0163 of JP 2016-027357 A can be referred to, and the contents are incorporated in the present specification.

When the photosensitive resin composition of the present invention contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.01 to 20% by mass relative to the total solid content of the photosensitive resin composition of the present invention. 0.5 to 10 mass %. One of the sensitizing dyes may be used alone, or two or more of them may be used simultaneously.

＜＜＜Chain transfer agent＞＞＞

The photosensitive resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the 3rd edition of the Dictionary of Polymers (edited by The Society of Polymer Science, Japan, 2005), pages 683-684. As the chain transfer agent, for example, a compound group having SH, PH, SiH, and GeH in the molecule is used. Such a radical is generated by supplying hydrogen to a low-activity radical, or after oxidation, a radical can be generated by deprotonation. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles) can be preferably used Wait).

When the photosensitive resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition of the present invention parts, particularly preferably 1 to 5 parts by mass. Only one type of chain transfer agent may be used, or two or more types may be used. When two or more kinds of chain transfer agents are used, the total range thereof is preferably the above-mentioned range.

＜＜＜Surfactant＞＞＞

From the viewpoint of improving coatability, various surfactants can be added to the photosensitive resin composition of the present invention. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicon-based surfactant can be used. In addition, the following surfactants are also preferable.

[Chemical formula 49]

When the photosensitive resin composition of the present invention has a surfactant, the content of the surfactant is preferably 0.001 to 2.0 mass % with respect to the total solid content of the photosensitive resin composition of the present invention, and more preferably 0.005 to 1.0 mass %. Only one type of surfactant may be used, or two or more types may be used. When two or more types of surfactants are used, the total range thereof is preferably the above-mentioned range.

＜＜＜Higher fatty acid derivatives＞＞＞

In order to prevent polymerization inhibition by oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to the photosensitive resin composition of the present invention, and it may be locally present in the drying process after coating. The surface of the photosensitive resin composition.

When the photosensitive resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the photosensitive resin composition of the present invention. Only one type of higher fatty acid derivatives may be used, or two or more types may be used. When there are two or more kinds of higher fatty acid derivatives, the total range thereof is preferably the above-mentioned range.

<<Restrictions on other contained substances>>

The water content of the photosensitive resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and particularly preferably less than 0.6% by mass, from the viewpoint of the coated surface.

From the viewpoint of insulating properties, the metal content of the photosensitive resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and particularly preferably less than 0.5 mass ppm. As a metal, sodium, potassium, magnesium, calcium, iron, chromium, nickel, etc. are mentioned. When a plurality of metals are contained, the total of such metals is preferably in the above-mentioned range.

In addition, as a method of reducing the metal impurities contained in the photosensitive resin composition of the present invention unintentionally, as a raw material constituting the photosensitive resin composition of the present invention, a raw material with a small metal content is selected. The raw material of the photosensitive resin composition is filtered through a filter, and the inside of the apparatus is lined with polytetrafluoroethylene or the like, and methods such as distillation are performed under conditions that suppress contamination as much as possible.

From the viewpoint of wiring corrosion, the photosensitive resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and particularly preferably less than 200 mass ppm. Among them, the substances present in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and particularly preferably less than 0.5 mass ppm. As a halogen atom, a chlorine atom and a bromine atom are mentioned. The total of chlorine atoms and bromine atoms or chlorine ions and bromide ions is preferably the above ranges, respectively.

<Preparation of photosensitive resin composition>

The photosensitive resin composition of this invention can be prepared by mixing each said component. The mixing method is not particularly limited, and can be performed by a conventionally known method.

Furthermore, for the purpose of removing foreign matter such as garbage and fine particles in the photosensitive resin composition, it is preferable to perform filtration using a filter. The filter pore diameter is preferably 1 μm or less, more preferably 0.5 μm or less, and further preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. Filters can be pre-cleaned with organic solvents. In the filtering step of the filter, a plurality of types of filters can be used in parallel or in series. When using multiple filters, filters with different pore sizes or materials can be used in combination. Also, various materials can be filtered multiple times. When filtering multiple times, it can be a loop filter. Also, filtration may be performed after pressurization. When filtration is performed after pressurization, the pressure for pressurization is preferably 0.05 MPa or more and 0.3 MPa or less.

In addition to filtration using a filter, impurity removal treatment using an adsorbent can also be performed. It is also possible to combine filter filtration and impurity removal treatment using adsorbent materials. As the adsorbent, a known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be mentioned.

<A cured film, a laminate, a semiconductor device, and their manufacturing method>

Next, a cured film, a laminated body, a semiconductor device, and their manufacturing methods will be described.

The cured film of the present invention is formed by curing the photosensitive resin composition of the present invention. The film thickness of the cured film of the present invention can be, for example, 0.5 μm or more, and can be 1 μm or more. Moreover, as an upper limit, it can be 100 micrometers or less, and can also be 30 micrometers or less.

Two or more layers of the cured film of the present invention may be laminated to form a laminate, and further 3 to 7 layers may be laminated to form a laminate. It is preferable that the laminated body in the cured film of this invention which has two or more layers has the aspect which has a metal layer between cured films. Such a metal layer can be preferably used as a metal wiring such as a rewiring layer.

The manufacturing method of the cured film of this invention includes the case where the photosensitive resin composition of this invention is used. Specifically, it includes a photosensitive resin composition layer forming step of applying the photosensitive resin composition of the present invention to a substrate to form a photosensitive resin composition layer, and an exposure step of exposing the photosensitive resin composition layer. It is preferable that the manufacturing method of a cured film further includes the developing process of developing the said photosensitive resin composition layer after the said exposure process. After this development, the exposed resin layer can be further cured by including a heating step of heating (preferably at 50 to 450°C (more preferably 50 to 250°C)). In addition, as described above, when the photosensitive resin composition is used, it can be further cured by heating by curing the composition by exposure in advance, and then performing necessary processing (for example, lamination described below) as necessary.

The manufacturing method of the laminated body of this invention includes the manufacturing method of the cured film of this invention. In the method for producing the laminate of the present invention, according to the above-mentioned method for producing a cured film, it is preferable to perform the film forming step (layer forming step) and the heating step of the photosensitive resin composition again after forming the cured film, or when imparting photosensitivity, according to In the above-mentioned steps, a film formation step (layer formation step), an exposure step, and a development step (further, a heating step as necessary) are performed. It is particularly preferable that each of the above steps is sequentially performed a plurality of times, for example, 2 to 5 times (that is, 3 to 6 times in total). By laminating the cured films in this way, a laminated body can be obtained. In the present invention, it is particularly preferable to provide a metal layer on the upper surface of the portion where the cured film is provided, between the cured films, or between the two.

These will be described in detail below.

<<Film forming process (layer forming process)>>

The manufacturing method of the preferable embodiment of this invention includes the film formation process (layer formation process) of applying a photosensitive resin composition to a board|substrate and making it a film (layer form).

The type of the plate can be appropriately determined according to the application, and is not particularly limited to semiconductor production substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, etc. Reflective films, metal substrates such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, electrode plates of plasma display devices (PDP), etc. In the present invention, a semiconductor production substrate is particularly preferable, and a silicon substrate is more preferable.

And when a photosensitive resin composition layer is formed on the surface of a resin layer or the surface of a metal layer, a resin layer or a metal layer becomes a board|substrate.

As a method of applying the photosensitive resin composition to a substrate, coating is preferable.

Specifically, dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, and spin coating are exemplified as methods to be used. , slit coating method and inkjet method, etc. From the viewpoint of the uniformity of the thickness of the photosensitive resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an ink jet method are more preferable. By adjusting appropriate solid content concentration and coating conditions according to the method, a resin layer having a desired thickness can be obtained. In addition, the coating method can be appropriately selected according to the shape of the substrate. As long as it is a circular substrate such as a wafer, a spin coating method, a spray coating method, an ink jet method, or the like is preferable. For a rectangular substrate, a slit coating method or a spray coating method is preferable. , inkjet method, etc. In the case of the spin coating method, for example, it can be performed at a rotation speed of 500 to 2000 rpm for about 10 seconds to 1 minute.

＜＜Drying process＞

The production method of the present invention may include a step of drying to remove the solvent after the film forming step (layer forming step) after forming the photosensitive resin composition layer. The preferable drying temperature is 50 to 150°C, more preferably 70°C to 130°C, further preferably 90°C to 110°C. As a drying time, 30 second - 20 minutes are illustrated, Preferably it is 1 minute - 10 minutes, More preferably, it is 3 minutes - 7 minutes.

＜＜Exposure process＞＞

The manufacturing method of this invention may include the exposure process of exposing the said photosensitive resin composition layer. The exposure amount is not particularly limited as long as the photosensitive resin composition can be cured. For example, in terms of exposure energy at a wavelength of 365 nm, irradiation is preferably 100 to 10000 mJ/cm ² , and more preferably 200 to 8000 mJ/cm ² .

The exposure wavelength can be appropriately determined in the range of 190 to 1000 nm, and is preferably 240 to 550 nm.

In terms of the relationship with the light source, examples of exposure wavelengths include (1) semiconductor lasers (wavelengths of 830 nm, 532 nm, 488 nm, 405 nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays (wavelengths of 830 nm, 532 nm, 488 nm, 405 nm, etc.) 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), broad (three wavelengths of g, h, i-ray), (4) excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer laser Molecular laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beam, etc. About the photosensitive resin composition of this invention, exposure by a high-pressure mercury-vapor lamp is especially preferable, and especially, the exposure by i-ray is preferable. Thereby, a particularly high exposure sensitivity can be obtained.

<<Development process>>

The production method of the present invention may include a development treatment step of subjecting the exposed photosensitive resin composition layer to development treatment. By performing development, unexposed parts (non-exposed parts) can be removed. The development method is not particularly limited as long as a desired pattern can be formed, and for example, development methods such as spin-on immersion, spray, immersion, and ultrasonic waves can be employed.

A developing solution is used for development. The developing solution can be used without particular limitation as long as it can remove unexposed parts (non-exposed parts). The developer preferably contains an organic solvent. In the present invention, the developer preferably contains an organic solvent having a ClogP value of -1 to 5, more preferably an organic solvent having a ClogP value of 0 to 3. The ClogP value can be calculated based on the input structural formula in ChemBioDraw.

As the organic solvent, as esters, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, isoamyl acetate, butyl propionate, isopropyl butyrate, Ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetic acid (eg: alkoxyacetic acid methyl ester, ethyl alkoxyacetate, butyl alkoxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxyacetate ethyl acetate, etc.)), 3-alkoxypropionic acid alkyl esters (for example: methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, 3-methoxypropionate) acid methyl ester, 3-methoxy ethyl propionate, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, etc.)), 2-alkoxy propionate alkyl esters (such as : Methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, 2-methoxypropionate acid ethyl ester, 2-methoxy propionate propyl ester, 2-ethoxy propionate methyl ester, 2-ethoxy propionate ethyl ester)), 2-alkoxy-2-methyl propionate methyl ester And 2-alkoxy-2-methyl propionate ethyl ester (for example, 2-methoxy-2-methyl propionate methyl ester, 2-ethoxy-2-methyl propionate ethyl ester, etc.), Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc.; and, as ethers, For example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, and diethylene glycol monomethyl ether are preferably used. ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc.; and, as ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc.; and, as aromatic hydrocarbons, such as Preferable examples include toluene, xylene, anisole, limonene, and the like; as the sulfoxides, dimethyl sulfoxide is preferably used.

In the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred.

The developer is preferably 50% by mass or more of an organic solvent, more preferably 70% by mass or more of an organic solvent, and still more preferably 90% by mass or more of an organic solvent. In addition, the developer may be an organic solvent of 100% by mass.

The development time is preferably 10 seconds to 5 minutes. The temperature of the developing solution at the time of development is not particularly limited, but it can usually be performed at 20 to 40°C.

After treatment with a developer, further rinsing may be performed. It is preferable to perform rinsing with a solvent different from that of the developer. For example, rinsing can be performed using the solvent contained in the photosensitive resin composition. The flushing time is preferably 5 seconds to 1 minute.

＜＜Heating process＞

The production method of the present invention preferably includes a film forming step (layer forming step), a drying step, or a step of heating in a developing step. In the heating step, a cyclization reaction of the polymer precursor proceeds. Furthermore, the composition of the present invention may contain a radically polymerizable compound other than the polymer precursor, but curing of the radically polymerizable compound other than the unreacted polymer precursor and the like can also be performed in this step. The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50°C or higher, more preferably 80°C or higher, still more preferably 140°C or higher, still more preferably 160°C or higher, and still more preferably 170°C or higher. The upper limit is preferably 500°C or lower, more preferably 450°C or lower, still more preferably 350°C or lower, still more preferably 250°C or lower, and still more preferably 220°C or lower.

The heating is preferably performed at a temperature increase rate of 1 to 12°C/min, more preferably 2 to 10°C/min, still more preferably 3 to 10°C/min from the temperature at the start of heating to the maximum heating temperature. By setting the temperature increase rate to 1°C/min or more, it is possible to prevent excessive volatilization of the amine while ensuring productivity, and to reduce the residual stress of the cured film by setting the temperature increase rate to 12°C/min or less.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, further preferably 25°C to 120°C. The temperature at the start of heating is referred to as the temperature at the time of starting the process of heating up to the maximum heating temperature. For example, when the photosensitive resin composition is applied to a substrate and then dried, the temperature of the film (layer) after drying is preferably 30 to 200° C. lower than the boiling point of the solvent contained in the photosensitive resin composition, for example. The temperature gradually increased.

The heating time (heating time at the highest heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and further preferably 30 to 240 minutes.

In particular, when forming a multilayer laminate, the heating temperature is preferably 180°C to 320°C, and more preferably 180°C to 260°C, from the viewpoint of the adhesiveness between the layers of the cured film. The reason for this is not clear, but it is considered that by setting this temperature, the acetylene groups of the polymer precursors between the layers undergo a crosslinking reaction.

Heating can be performed in stages. As an example, for example, the following pretreatment steps may be performed: the temperature is increased from 25°C to 180°C at 3°C/min, the temperature is maintained at 180°C for 60 minutes, the temperature is increased from 180°C to 200°C at 2°C/min, and the temperature is maintained at 200°C 120 minutes. As a heating temperature in a pretreatment process, 100-200 degreeC is preferable, 110-190 degreeC is more preferable, 120-185 degreeC is still more preferable. Also in this pretreatment step, as described in US Pat. No. 9,159,547, it is preferable to perform treatment while irradiating with ultraviolet rays. Through such a pretreatment step, the characteristics of the film can be improved. The pretreatment step can be performed in a short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment can be performed in two or more steps. For example, the pretreatment step 1 is performed in the range of 100 to 150°C, and then the pretreatment step 2 is performed in the range of 150 to 200°C.

Furthermore, cooling may be performed after heating, and the cooling rate at this time is preferably 1 to 5°C/min.

From the viewpoint of preventing decomposition of the polymer precursor, it is preferable to perform the heating step in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, and argon. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

<<Metal layer forming process>>

The production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the photosensitive resin composition layer after the development treatment.

The metal layer is not particularly limited, and existing metals can be used, and examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten, copper and aluminum are more preferred, and copper is further preferred.

The formation method of the metal layer is not particularly limited, and an existing method can be used. For example, the methods described in JP 2007-157879 A, JP 2001-521288 A, JP 2004-214501 A, and JP 2004-101850 A can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, methods of combining them, and the like are contemplated. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electrolytic plating are exemplified.

The thickness of the metal layer is preferably 0.1 to 50 μm, and more preferably 1 to 10 μm, based on the thickest part.

＜＜Lamination process＞＞

The production method of the present invention preferably further includes a lamination step.

The lamination step means that the above-mentioned film forming step (layer forming step) and the heating step are performed again on the surface of the cured film (resin layer) or the metal layer, or the above-mentioned film forming step (layer forming step), the above-mentioned film forming step (layer forming step) are sequentially performed on the photosensitive resin composition. A series of steps of the exposure step and the above-mentioned development treatment step. Of course, the above-mentioned drying step, heating step, and the like may also be included in the lamination step.

When the lamination process is further performed after the lamination process, the surface activation treatment process may be performed after the above-mentioned heating process, after the above-mentioned exposure process, or after the above-mentioned metal layer formation process. As the surface activation treatment, plasma treatment is exemplified.

The above lamination step is preferably performed 2 to 5 times, more preferably 3 to 5 times.

For example, as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, the resin layer preferably has a structure of 3 to 7 layers, more preferably 3 to 5 layers.

That is, in the present invention, it is particularly preferable to perform the film forming step (layer forming step) and the heating step of the above-mentioned photosensitive resin composition in order to cover the above-mentioned metal layer after the metal layer is provided, or to sequentially carry out the above-mentioned photosensitive resin composition. The said film formation process (layer formation process), the said exposure process, and the said development process process (the heating process is further performed as needed). The photosensitive resin composition layer (resin layer) and the metal layer can be alternately laminated by alternately performing the lamination step of laminating the photosensitive resin composition layer (resin) and the metal layer forming step.

The present invention also discloses a semiconductor device having the cured film or laminate of the present invention. As a specific example of a semiconductor device in which the photosensitive resin composition of the present invention is used to form an interlayer insulating film for a rewiring layer, reference can be made to the descriptions in paragraphs 0213 to 0218 of JP 2016-027357 A and the description in FIG. 1 . described, and the contents are incorporated into this manual.

Next, one Embodiment of the semiconductor device which used the said photosensitive resin composition for the interlayer insulating film for rewiring layers is demonstrated.

The semiconductor element 100 shown in FIG. 1 is a so-called three-dimensional mounting apparatus, and a laminate 101 in which a plurality of semiconductor elements (semiconductor wafers) 101 a to 101 d are stacked is arranged on a wiring board 120 .

In addition, in this embodiment, the case where the number of stacked semiconductor elements (semiconductor wafers) is mainly four layers will be described. However, the number of stacked semiconductor elements (semiconductor wafers) is not particularly limited. 16 floors, 32 floors, etc. In addition, it may be one layer.

Each of the plurality of semiconductor elements 101a to 101d includes a semiconductor wafer such as a silicon substrate.

The semiconductor element 101a in the uppermost stage does not have through electrodes, and electrode pads (not shown) are formed on one surface thereof.

The semiconductor elements 101b to 101d have through electrodes 102b to 102d, and connection pads (not shown) integrally provided with the through electrodes are provided on both surfaces of each semiconductor element.

The laminated body 101 has a structure in which a semiconductor element 101 a without through electrodes and semiconductor elements 101 b to 101 d having through electrodes 102 b to 102 d are flip-chip connected.

That is, the electrode pad of the semiconductor element 101a without the through electrode and the connection pad on the semiconductor element 101a side of the semiconductor element 101b with the through electrode 102b adjacent thereto are connected by the metal bump 103a such as a solder bump, and have The connection pad on the other side of the semiconductor element 101b of the through electrode 102b and the connection pad on the semiconductor element 101b side of the semiconductor element 101c having the through electrode 102c adjacent thereto are connected by metal bumps 103b such as solder bumps. Similarly, the connection pad on the other side of the semiconductor element 101c having the through-electrode 102c and the connection pad on the semiconductor element 101c side of the semiconductor element 101d having the through-electrode 102d adjacent thereto pass through the metal bump 103c such as a solder bump. And connect.

An underfill layer 110 is formed in a gap between the semiconductor elements 101 a to 101 d , and the semiconductor elements 101 a to 101 d are stacked with the underfill layer 110 interposed therebetween.

The laminated body 101 is arranged on the wiring board 120 .

As the wiring board 120, for example, a multilayer wiring board using an insulating substrate such as a resin substrate, a ceramic substrate, and a glass substrate as a base material is used. As the wiring board 120 to which the resin board is applied, a multilayer copper-clad laminate (multilayer printed wiring board) and the like can be mentioned.

A surface electrode 120 a is provided on one surface of the wiring board 120 .

The insulating film 115 on which the rewiring layer 105 is formed is disposed between the wiring board 120 and the laminate 101 , and the wiring board 120 and the laminate 101 are electrically connected via the rewiring layer 105 . The insulating film 115 is formed using the photosensitive resin composition in the present invention.

That is, one end of the rewiring layer 105 is connected to an electrode pad formed on the surface of the semiconductor element 101d on the rewiring layer 105 side through a metal bump 103d such as a solder bump. Further, the other end of the rewiring layer 105 is connected to the front surface electrode 120a of the wiring board through a metal bump 103e such as a solder bump.

Furthermore, an underfill layer 110 a is formed between the insulating film 115 and the laminated body 101 . Further, an underfill layer 110 b is formed between the insulating film 115 and the wiring board 120 .

The cured film formed from the photosensitive resin composition of the present invention can achieve both high chemical resistance and high elongation at break. The chemical resistance is, for example, preferably 500 nm/min or less, more preferably 300 nm/min or less, and further preferably 100 nm/min or less. The upper limit is not particularly limited, but is actually 50,000 nm/min or less. The elongation at break is, for example, preferably 40% or more, more preferably 55% or more, and further preferably 70% or more. The upper limit is not particularly limited, but is actually 150% or less. The measurement methods of chemical resistance and elongation at break were carried out in accordance with the measurement methods in Examples described later.

In addition to the above-mentioned method, the cured film in the present invention can be widely used in various applications using polyimide or polybenzoxazole.

As a usable field of the cured film of this invention, the insulating film of a semiconductor device, the inter-insulating film for rewiring layers, a stress buffer film, etc. are mentioned. In addition, patterning of sealing films, substrate materials (base films and cover films of flexible printed circuit boards, interlayer insulating films), or insulating films for mounting applications as described above, by etching or the like, etc., can be mentioned. Regarding their uses, for example, you can refer to Science&technology Co., Ltd. "High-functionalization and application technology of polyimide" April 2008, Masaki Kakimoto/Editor-in-chief, CMC Technical library "Basics and Development of Polyimide Materials" "November 2011 issue, Japan Polyimide/Aromatic Polymer Research Association / Edited "Latest Polyimide Fundamentals and Applications" NTS Inc, August 2010, etc.

In addition, the cured film of the present invention can also be used in the production of layouts such as offset printing plates and screen plates, the use of molded parts, the production of protective varnishes and dielectric layers in electronics, especially microelectronics, and the like.

In addition, since polyimide and polybenzoxazole are very heat-resistant, the cured film and the like in the present invention can also be preferably used as transparent plastic substrates for display devices such as liquid crystal displays and electronic paper, automotive parts, heat-resistant Coatings, coating agents, film applications, etc.

Example

Hereinafter, the present invention will be described in further detail by way of examples. Materials, usage amounts, ratios, processing contents, processing steps, and the like shown in the following examples can be appropriately changed within a range that does not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. "Parts" and "%" are based on mass unless otherwise specified.

<Synthesis of Heterocyclic Polymer Precursor Composition (Resin)>

<<Synthesis Example 1>>

[Polyimide precursor derived from 4,4'-oxodiphthalic dianhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate (A-1: having Synthesis of polyimide precursor of radically polymerizable group)]

20.0 g (64.5 mmol) of 4,4'-dioxodiphthalic dianhydride (4,4'-oxodiphthalic acid was dried at 140° C. for 12 hours), 18.6 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 10.7 g of pyridine, 140 g of diglyme (diglyme) were mixed, and the mixture was heated at 60° C. It stirred at temperature for 18 hours, and produced the diester of 4,4'- oxodiphthalic acid and 2-hydroxyethyl methacrylate. Next, the reaction mixture was cooled to -10°C, and 16.12 g (135.5 mmol) of _SOCl2 was added over 10 minutes while maintaining the temperature at -10±4°C. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, 11.08 g (58.7 mmol) of a 4,4'-diaminodiphenyl ether ester solution was dissolved in 100 mL of N-methylpyrrolidone, and the solution was added dropwise to the reaction mixture at 20 to 23° C. over 20 minutes. Next, the reaction mixture was stirred at room temperature for 1 night. Next, the polyimide precursor was precipitated by adding 5 liters of water, and the water-polyimide precursor mixture was stirred at 5000 rpm for 15 minutes. The polyimide precursor was filtered, added to 4 liters of water, added to the water, stirred again for 30 minutes, and filtered again. Next, the polyimide precursor was dried at 45° C. for 3 days in a reduced pressure state to obtain a polyimide precursor (A-1).

[Chemical formula 50]

<<Synthesis Example 2>>

[Polyimide precursor derived from pyromellitic dianhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate (A-2: Synthesis of polyimide precursor)]

14.06 g (64.5 mmol) of pyromellitic dianhydride (the pyromellitic acid was dried at 140° C. for 12 hours), 18.6 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 10.7 g of pyridine, and 140 g of NMP (N-methyl-2-pyrrolidone) were mixed and stirred at 60° C. for 18 hours to produce pyromellitic acid and methyl benzene. Diester of 2-hydroxyethyl acrylate. Next, the reaction mixture was cooled to -10°C, and 16.12 g (135.5 mmol) of _SOCl2 was added over 10 minutes while maintaining the temperature at -10±4°C. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, 11.08 g (58.7 mmol) of a 4,4'-diaminodiphenyl ether solution was dissolved in 100 mL of N-methylpyrrolidone, and it was added dropwise to the reaction mixture at 20 to 23° C. over 20 minutes. Next, the reaction mixture was stirred at room temperature for 1 night. Next, the polyimide precursor was precipitated by adding 5 liters of water, and the water-polyimide precursor mixture was stirred at 5000 rpm for 15 minutes. The polyimide precursor was filtered, added to 4 liters of water, added to the water, stirred again for 30 minutes, and filtered again. Next, the polyimide precursor (A-2) was obtained by drying the polyimide precursor at 45° C. for 3 days in a reduced pressure state.

[Chemical formula 51]

<<Synthesis Example 3>>

[Polyimide precursor derived from 4,4'-oxodiphthalic anhydride, p-phenylenediamine and 2-hydroxyethyl methacrylate (A-3: with radical polymerization Synthesis of Polyimide Precursors of Sexual Groups)]

20.0 g (64.5 mmol) of 4,4'-oxodiphthalic anhydride (oxydiphthalic acid was dried at 140°C for 12 hours), 18.6 g (129 mmol) of methyl 2-Hydroxyethyl acrylate, 0.05 g of hydroquinone, 10.7 g of pyridine, and 140 g of diglyme were mixed and stirred at 60°C for 18 hours to produce 4,4' - Diester of oxodiphthalic acid with 2-hydroxyethyl methacrylate. Next, the reaction mixture was cooled to -10°C, and 16.12 g (135.5 mmol) of _SOCl2 was added over 10 minutes while maintaining the temperature at -10±4°C. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution in which 6.34 g (58.7 mmol) of p-phenylenediamine was dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at 20 to 23° C. over 20 minutes. Next, the reaction mixture was stirred at room temperature for 1 night. Next, the polyimide precursor was precipitated by adding 5 liters of water, and the water-polyimide precursor mixture was stirred at 5000 rpm for 15 minutes. The polyimide precursor was filtered, added to 4 liters of water, added to the water, stirred again for 30 minutes, and filtered again. Next, the polyimide precursor (A-3) was obtained by drying the polyimide precursor at 45° C. for 3 days in a reduced pressure state.

[Chemical formula 52]

<<Synthesis Example 4>>

[Polyimide precursor derived from pyromellitic dianhydride, m-tolidine, and 2-hydroxyethyl methacrylate (A-4: Polyimide precursor having a radically polymerizable group) )Synthesis]

14.06 g (64.5 mmol) of pyromellitic dianhydride (the pyromellitic acid was dried at 140° C. for 12 hours), 18.6 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 10.7 g of pyridine, and 140 g of NMP (N-methyl-2-pyrrolidone) were mixed, and stirred at a temperature of 60 ° C for 18 hours, thereby producing pyromellitic acid and methacrylic acid - Diester of 2-hydroxyethyl ester. Next, the reaction mixture was cooled to -10°C, and 16.12 g (135.5 mmol) of _SOCl2 was added over 10 minutes while maintaining the temperature at -10±4°C. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution in which 12.46 g (58.7 mmol) of m-tolidine was dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at 20 to 23° C. over 20 minutes. Next, the reaction mixture was stirred at room temperature for 1 night. Next, the polyimide precursor was precipitated by adding 5 liters of water, and the water-polyimide precursor mixture was stirred at 5000 rpm for 15 minutes. The polyimide precursor was filtered, added to 4 liters of water, stirred again for 30 minutes, and filtered again. Next, the polyimide precursor (A-4) was obtained by drying the polyimide precursor at 45° C. for 3 days in a reduced pressure state.

[Chemical formula 53]

<<Synthesis Example 5>>

[Synthesis of polyimide precursor composition A-5 derived from 4,4'-diaminodiphenyl ether acid dianhydride, 2-hydroxyethyl methacrylate and the following diamine (a)]

42.4 g of 4,4'-diaminodiphenyl ether dianhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, and 100 mL of tetrahydrofuran were mixed and stirred at 60°C. 4 hours. Next, the reaction mixture was cooled to -10°C, and a solution in which 34.35 g of dicyclohexylcarbodiimide was dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10±5°C over 60 minutes. , and the mixture was stirred for 30 minutes. Next, a solution in which 76.0 g of diamine (a) shown below was dissolved in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10±5°C over 60 minutes, and the mixture was stirred for 1 hour. After that, 20 mL of ethanol and 200 mL of gamma-butyrolactone were added. A reaction liquid was obtained by removing the precipitate formed in the reaction mixture by filtration. 14 L of water was added to the obtained reaction liquid, the polyimide precursor was precipitated, filtered, and dried at 45° C. for 2 days under reduced pressure. The weight average molecular weight of the obtained powdery polyimide precursor was 26500, and the number average molecular weight was 9300. The polymerizable group equivalent is about 95%.

Diamine (a)

[Chemical formula 54]

<<Synthesis Example 6>>

[Synthesis of polybenzoxazole precursor composition A-6 derived from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 4,4'-oxodibenzoyl chloride ]

28.0 g of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was stirred and dissolved in 200 mL of N-methylpyrrolidone. Next, 25.0 g of 4,4'-oxodibenzoyl chloride was added dropwise over 10 minutes while maintaining the temperature at 0 to 5°C, and stirring was continued for 60 minutes. 6 L of water was added to the obtained reaction liquid to precipitate the polybenzoxazole precursor, and the solid was filtered and dried at 45° C. for 2 days under reduced pressure. The weight-average molecular weight of the obtained powdery polybenzoxazole precursor was 28,500, and the number-average molecular weight was 9,800. This polybenzoxazole precursor A-6 is an example which does not have a radically polymerizable group.

<<Synthesis Example A-7>>

The polyimide precursor A-7 was synthesized in the same manner as the synthesis procedure of the polyimide precursor of A-5, except that 2-hydroxyethyl methacrylate was not used. This polyimide precursor A-7 is an example which does not have a radically polymerizable group.

<Preparation of photosensitive resin composition>

The resin and the components described in the following table were mixed to prepare a coating liquid of the photosensitive resin composition as a uniform solution. Each photosensitive resin composition was subjected to pressure filtration through a filter made of UPE having a pore width of 0.8 μm.

＜Chemical resistance＞

After pressure-filtering each photosensitive resin composition through a filter having a pore width of 0.8 μm, a photosensitive resin composition layer was formed on a silicon wafer by a spin coating method. The silicon wafer to which the obtained photosensitive resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes to form a uniform photosensitive resin composition layer with a thickness of 15 μm on the silicon wafer. Using a stepper (Nikon NSR 2005 i9C), the photosensitive resin composition layer on the silicon wafer was exposed at an exposure energy of 500 mJ/cm ² , and the exposed photosensitive resin composition layer (resin layer) was exposed to 10 in a nitrogen atmosphere. The temperature was increased at a temperature increase rate of °C/min, and the cured layer (resin layer) of the photosensitive resin composition layer was obtained by heating at the temperature and time described in Table 1 below.

The obtained resin layer was immersed in the following chemical solution under the following conditions, and the dissolution rate was calculated.

Drug: 90:10 (mass ratio) mixture of dimethyl sulfoxide (DMSO) and 25 mass% tetramethylammonium hydroxide (TMAH) solution

Evaluation conditions: The resin layer was immersed in the solution at 75° C. for 15 minutes, the film thicknesses before and after the immersion were compared, and the dissolution rate (nm/min) was calculated.

<Elongation at break>

The photosensitive resin composition layer was formed on the silicon wafer by spin coating. The silicon wafer to which the obtained photosensitive resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes to form a uniform photosensitive resin composition layer with a thickness of 15 μm on the silicon wafer. The photosensitive resin composition layer on the silicon wafer was exposed at an exposure energy of 500 mJ/cm ² using a stepper (Nikon NSR 2005 i9C). The exposed photosensitive resin composition layer was heated at a temperature increase rate of 10°C/min in a nitrogen atmosphere, and heated at the temperature and time described in Table 1 below to obtain a cured layer of the photosensitive resin composition layer ( resin layer). The resin layer was obtained by immersing the resin layer in a 4.9 volume % hydrofluoric acid solution for 30 minutes, and peeling the resin layer from the silicon wafer.

The elongation at break of the resin layer was set at a crosshead speed of 300 mm/min, a width of 10 mm, and a sample length of 50 mm using a tensile tester (Tensilon) in the longitudinal and width directions of the film at 25° C., Measured according to JIS-K6251 in an environment of 65% RH (relative humidity). In the evaluation, the elongation at break in each of the longitudinal direction and the width direction was measured five times, and the average value of the elongation at break in the longitudinal direction and the width direction was used. In addition, the formula for the elongation at break is, according to JIS, E _b =(L _b -L ₀ )/L ₀ ×100: E _b is the elongation at break (%), and L ₀ is the original length (mm) of the test piece ), L _b is the length (mm) at the time of rupture.

<Curing conditions>

In the above-mentioned tests of chemical resistance and elongation at break, the temperature and time of the cured film obtained by heating and curing the polymer precursor were appropriately determined from the respective Examples and Comparative Examples. The conditions are described in Table 1.

(A) Resin (precursor of heterocycle-containing polymer)

A-1 to A-7: Precursors of heterocycle-containing polymers produced in Synthesis Examples 1 to 7

(B) Polymerizable compound

B-2: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) ... Compound B-2 exemplified above

B-2 is a mixture mixed with a compound in which one hydrogen atom of the acryloyl group is substituted, and the hexafunctional compound is the main component.

In addition, B-1 and B-3 to B-14 are compounds exemplified in the item of the above-mentioned specific radically polymerizable compound.

B-C1: SR-209 (manufactured by Sartomer Company)

[Chemical formula 55]

(C) Photopolymerization initiator

C-1: IRGACURE OXE 01 (manufactured by BASF)

C-2: IRGACURE OXE 02 (manufactured by BASF)

C-3: IRGACURE OXE 04 (manufactured by BASF)

C-4: IRGACURE-784 (manufactured by BASF)

C-5: NCI-831 (manufactured by ADEKA CORPORATION)

(D) Hot alkali generator

D-1: The following compounds

D-2: The following compounds

D-3: The following compounds

[Chemical formula 56]

(E) Inhibitor

E-1: 1,4-Benzoquinone

E-2: 1,4-Methoxyphenol

(F) Migration inhibitor

F-1: 1,2,4-triazole

F-2: 1H-tetrazole

(G) Metal Adhesion Improver (Silane Coupling Agent)

G-1: The following compounds

G-2: The following compounds

G-3: The following compounds

[Chemical formula 57]

(H) Solvent

H-1: γ-Butyrolactone

H-2: dimethyl sulfoxide

H-3: N-methyl-2-pyrrolidone

H-4: Ethyl lactate

Based on the above results, it was found that the specific radically polymerizable compound selected in the present invention was used in combination with a precursor of a radically polymerizable group-containing heterocyclic polymer and a thermal base generator in combination with a photosensitive resin combination. The resulting cured films have high chemical resistance and elongation at break, and are able to achieve both. On the other hand, the compound using the bifunctional radically polymerizable compound that does not satisfy the requirements of the present invention (Comparative Example 3) and the compound not using a thermal base generator (Comparative Examples 1 and 2) were poor in chemical resistance and fractured. Low elongation. In addition, when the polymer precursor does not contain a polymerizable functional group (Comparative Examples 4 and 5), the chemical resistance is remarkably lowered, and the elongation at break also becomes a low value. As described above, in the structure of the present invention, only when a specific radically polymerizable compound, a heterocyclic polymer precursor having a radically polymerizable group, and a thermal alkali generator are used together, both chemical resistance and elongation at break can be achieved simultaneously. The form of rate shows high effects that cannot be obtained when each ingredient is used alone. This is because the above-mentioned three components act as one body in the cyclization reaction system of the polymer precursor, thereby producing a synergistic effect.

<Example 100>

After pressure-filtering the photosensitive resin composition of Example 1 through a filter having a pore width of 0.8 μm, the photosensitive resin composition was applied on a silicon wafer by a spin coating method. The silicon wafer to which the photosensitive resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes to form a uniform photosensitive resin composition layer with a thickness of 15 μm on the silicon wafer. Using a stepper (NiKon NSR 2005 i9C), the photosensitive resin composition layer on the silicon wafer was exposed at an exposure energy of 500 mJ/cm ² , and the exposed photosensitive resin composition layer (resin layer) was developed with cyclopentanone for 60 seconds bell, thereby forming a hole with a diameter of 10 μm. Next, the temperature was increased at a temperature increase rate of 10° C./min in a nitrogen atmosphere to reach the temperatures described in Tables 1 and 2, respectively, and then maintained for the times described in Tables 1 and 2. After cooling to room temperature, a copper thin layer (metal layer) having a thickness of 2 μm was formed on a part of the surface of the photosensitive resin composition layer by vapor deposition so as to cover the hole portion. Furthermore, the same type of photosensitive resin composition was used again on the surfaces of the metal layer and the photosensitive resin composition layer, and the patterned film was heated for 3 hours from filtering the photosensitive resin composition again in the same manner as described above. steps to produce a laminate of resin layer/metal layer/resin layer structure.

This resin layer (interlayer insulating film for rewiring layer) has excellent insulating properties.

Then, as a result of manufacturing a semiconductor device using the interlayer insulating film for rewiring layers, it was confirmed that the operation was normal.

Symbol Description

100-semiconductor device, 101a-101d: semiconductor element, 101: laminate, 102b-102d: through electrode, 103a-103e: metal bump, 105: rewiring layer, 110, 110a, 110b: underfill layer, 115 : insulating film, 120 : wiring board, 120a : surface electrode.

Claims (27)

1. A photosensitive resin composition comprising a precursor of a heterocyclic polymer, a thermobase generator and a radical polymerizable compound,

the precursor of the heterocyclic ring-containing polymer has a radical polymerizable group,

the radical polymerizable compound includes at least 1 radical polymerizable compound selected from the group consisting of a compound having 4 or more polymerizable functional groups and a compound having 3 polymerizable functional groups and having a molecular weight of 400 or less.

2. The photosensitive resin composition according to claim 1,

the polymerizable functional groups are each independently a group selected from a vinylphenyl group, a vinyl group, and a (meth) acryloyl group.

3. The photosensitive resin composition according to claim 1 or 2,

the hot base generator has a cation represented by formula (101) or formula (102),

in the formulae (101) and (102), R¹～R⁶Each independently represents a hydrogen atom or a hydrocarbon group, R⁹Represents a hydrocarbon group.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein,

the precursor of the heterocyclic ring-containing polymer includes a polyimide precursor or a polybenzoxazole precursor.

5. The photosensitive resin composition according to any one of claims 1 to 3, wherein,

the heterocyclic ring polymer-containing precursor includes a polyimide precursor.

6. The photosensitive resin composition according to any one of claims 1 to 5,

the precursor of the heterocycle-containing polymer contains a structural unit represented by the following formula (1),

in the formula (1), A¹And A²Each independently represents an oxygen atom or NH, R¹¹¹Represents an organic radical having a valence of 2, R¹¹⁵Represents an organic group having a valence of 4, R¹¹³And R¹¹⁴Each independently represents a hydrogen atom or a 1-valent organic group.

7. The photosensitive resin composition according to claim 6,

the R is¹¹³And said R¹¹⁴At least 1 of them contains a radical polymerizable group.

8. The photosensitive resin composition according to claim 6 or 7,

the R is¹¹⁵Comprising an aromatic ring.

9. The photosensitive resin composition according to any one of claims 6 to 8,

the R is¹¹¹from-Ar⁰-L⁰-Ar⁰-represents, each Ar⁰Each independently is a 2-valent group containing an aromatic ring, L⁰A single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms optionally substituted with a fluorine atom, -O-, -CO-, -S-, -SO₂-, -NHCO-and a combination of 2 or more of these groups.

10. The photosensitive resin composition according to any one of claims 6 to 9,

the R is¹¹¹Is a group represented by the following formula (51) or formula (61),

in the formula (51), R⁵⁰～R⁵⁷Each independently is a hydrogen atom, a fluorine atom or a 1-valent organic group, R⁵⁰～R⁵⁷At least 1 of which is a fluorine atom, a methyl group, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group,

in the formula (61), R⁵⁸And R⁵⁹Each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group.

11. The photosensitive resin composition according to any one of claims 1 to 10, which contains a photopolymerization initiator.

12. The photosensitive resin composition according to any one of claims 1 to 11,

the mass ratio of the thermokalite generator to the radical polymerizable compound is 1.0-80.

13. The photosensitive resin composition according to any one of claims 1 to 12,

the radical polymerizable compound is used in an amount of 2.5 parts by mass or more and 62.5 parts by mass or less with respect to 100 parts by mass of the precursor of the heterocycle-containing polymer.

14. The photosensitive resin composition according to any one of claims 1 to 13, further containing a solvent.

15. The photosensitive resin composition according to any one of claims 1 to 14, which is used for development by a developer containing 90% by mass or more of an organic solvent.

16. The photosensitive resin composition according to any one of claims 1 to 15, which is used for forming an interlayer insulating film for a rewiring layer.

17. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 16.

18. A laminate having 2 or more layers of the cured film of claim 17.

19. The laminate of claim 18, having a metal layer between the cured films.

20. The laminate of claim 18 or 19, having 3 to 7 layers of said cured film.

21. A method of manufacturing a cured film, comprising: a photosensitive resin composition layer formation step of applying the photosensitive resin composition according to any one of claims 1 to 16 to a substrate to form a photosensitive resin composition layer; and an exposure step of exposing the photosensitive resin composition layer.

22. The method of producing a cured film according to claim 21, further comprising a developing step of developing the photosensitive resin composition layer after the exposure step.

23. The method for producing a cured film according to claim 22,

the developing step is performed using a developer containing 90 mass% or more of an organic solvent.

24. The method for producing a cured film according to claim 22 or 23, which comprises a post-development heating step of heating the photosensitive resin composition layer at a temperature of 50 ℃ to 450 ℃ after the development step.

25. The method for producing a cured film according to claim 24,

the heating temperature is 50-250 ℃.

26. The method for producing a cured film according to any one of claims 21 to 25,

the thickness of the cured film is 1 to 30 μm.

27. A semiconductor device having the cured film of claim 17 or the laminate of any one of claims 18 to 20.

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