阅读说明：本技术 感光性树脂组合物、聚合物前体、固化膜、层叠体、固化膜的制造方法及半导体器件 (Photosensitive resin composition, polymer precursor, cured film, laminate, method for producing cured film, and semiconductor device ) 是由 川端健志 吉田健太 岩井悠 涩谷明规 于 2018-05-28 设计创作，主要内容包括：本发明提供一种感光性树脂组合物、以及聚合物前体、固化膜、层叠体、固化膜的制造方法及半导体器件,所述感光性树脂组合物在成型为固化膜时具有高断裂伸长率,并且保存稳定性优异。所述感光性树脂组合物,其包含选自聚酰亚胺前体及聚苯并噁唑前体中的聚合物前体、光自由基聚合引发剂及溶剂,聚合物前体中所含有的中和点的pH在7.0～12.0的范围的酸基的酸值在2.5～34.0mgKOH/g的范围,聚合物前体具有自由基聚合性基,或者所述感光性树脂组合物包含除了聚合物前体以外的自由基聚合性化合物。(The invention provides a photosensitive resin composition, a polymer precursor, a cured film, a laminated body, a method for manufacturing the cured film and a semiconductor device. The photosensitive resin composition comprises a polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, a photo radical polymerization initiator and a solvent, wherein the acid value of an acid group having a neutralization point in the polymer precursor in the range of 7.0 to 12.0 and a pH value of a neutralization point in the polymer precursor in the range of 2.5 to 34.0mgKOH/g, the polymer precursor has a radical polymerizable group, or the photosensitive resin composition comprises a radical polymerizable compound other than the polymer precursor.)

1. A photosensitive resin composition comprising:

a polymer precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors;

a photo radical polymerization initiator; and

a solvent, a water-soluble organic solvent,

the acid value of the acid group having a pH of 7.0 to 12.0 in the neutralization site contained in the polymer precursor is 2.5mgKOH/g to 34.0mgKOH/g,

the polymer precursor has a radical polymerizable group, or the photosensitive resin composition contains a radical polymerizable compound other than the polymer precursor.

2. The photosensitive resin composition according to claim 1,

the acid value of the acid group having a pH of 7.0 to 12.0 in the neutralization point contained in the polymer precursor is 5.5mgKOH/g to 17.0 mgKOH/g.

3. A photosensitive resin composition comprising a polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, a photo radical polymerization initiator and a solvent, wherein the polymer precursor comprises a carboxyl group, and the polymer precursor has a radical polymerizable group, or the photosensitive resin composition comprises a radical polymerizable compound other than the polymer precursor.

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

the polymer precursor comprises a repeating unit represented by the following formula (1) or a repeating unit represented by the formula (2);

formula (1)

In the formula (1), A¹And A²Each independently represents an oxygen atom or NH,

R¹¹¹represents a 2-valent organic group, R¹¹⁵Represents a 4-valent organic group, R¹¹³And R¹¹⁴Each independently represents a hydrogen atom or a 1-valent organic group;

formula (2)

In the formula (2), R¹²¹Represents a 2-valent organic group, R¹²²Represents a 4-valent organic group, R¹²³And R¹²⁴Each independently represents a hydrogen atom or a 1-valent organic group;

at least one of the repeating units represented by the formula (1) is-C (═ O) a²-R¹¹³and-C (═ O) A¹-R¹¹⁴At least one repeating unit containing an acid group having a pH of 7.0 to 12.0 at the neutralization point,

at least one of the repeating units represented by the formula (2) comprises: -R¹²²-O-R¹²³and-R¹²²-O-R¹²⁴At least one of the above-mentioned neutralization points contains a repeating unit of an acid group having a pH of 7.0 to 12.0.

5. The photosensitive resin composition according to claim 4,

at least one of the repeating units represented by the formula (1) is R¹¹³And R¹¹⁴At least one of which contains a repeating unit of a radical polymerizable group, or,

at least one of the repeating units represented by the formula (2) is R¹²³And R¹²⁴At least one of the above (1) contains a repeating unit of a radical polymerizable group.

6. The photosensitive resin composition according to claim 4 or 5,

the polymer precursor comprises a repeating unit represented by formula (1).

7. The photosensitive resin composition according to any one of claims 1 to 6, further comprising a radical polymerizable compound other than the polymer precursor.

8. The photosensitive resin composition according to any one of claims 1 to 7, further comprising a thermal alkali generator.

9. The photosensitive resin composition according to any one of claims 1 to 8, further comprising a photobase generator.

10. The photosensitive resin composition according to any one of claims 1 to 9, further comprising a polymerization inhibitor.

11. The photosensitive resin composition according to any one of claims 1 to 9, which is used in development using a developer containing an organic solvent.

12. The photosensitive resin composition according to claim 11,

the developer is an organic solvent in an amount of 50% by mass or more.

13. The photosensitive resin composition according to claim 11 or 12,

the developing solution contains an organic solvent with ClogP of-1 to 5.

14. The photosensitive resin composition according to any one of claims 1 to 13, which is used for forming an interlayer insulating film for a rewiring layer.

15. A polymer precursor comprising a repeating unit represented by the following formula (1) or a repeating unit represented by the formula (2);

formula (1)

In the formula (1), A¹And A²Each independently represents an oxygen atom or NH,

R¹¹¹represents a 2-valent organic group, R¹¹⁵Represents a 4-valent organic group, R¹¹³And R¹¹⁴Each independently represents a hydrogen atom or a 1-valent organic group;

formula (2)

In the formula (2), R¹²¹Represents a 2-valent organic group, R¹²²Represents a 4-valent organic group, R¹²³And R¹²⁴Each independently represents a hydrogen atom or a 1-valent organic group;

at least one of the repeating units represented by the formula (1) is-C (═ O) a²-R¹¹³and-C (═ O) A¹-R¹¹⁴At least one repeating unit containing an acid group having a pH of 7.0 to 12.0 at the neutralization point,

at least one of the repeating units represented by the formula (2) comprises: -R¹²²-O-R¹²³and-R¹²²-O-R¹²⁴At least one of the above-mentioned neutralization points contains a repeating unit of an acid group having a pH of 7.0 to 12.0.

16. The polymer precursor according to claim 15,

the acid value of the acid group having a pH of 7.0 to 12.0 in the neutralization point is 5.5mgKOH/g to 17.0 mgKOH/g.

17. The polymer precursor according to claim 15 or 16,

at least one of the repeating units represented by the formula (1) is R¹¹³And R¹¹⁴At least one of which contains a repeating unit of a radical polymerizable group, or,

at least one of the repeating units represented by the formula (2) is R¹²³And R¹²⁴At least one of which contains a free radicalA repeating unit of a radical polymerizable group.

18. A cured film formed from the photosensitive resin composition according to any one of claims 1 to 14.

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

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

21. A method of manufacturing a cured film, comprising: the photosensitive resin composition according to any one of claims 1 to 14 is used.

22. The method for manufacturing a cured film according to claim 21, comprising:

a photosensitive resin composition layer forming step of applying the photosensitive resin composition to a substrate to form a layer;

an exposure step of exposing the photosensitive resin composition layer; and

and a developing treatment step of performing a developing treatment on the exposed photosensitive resin composition layer.

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

the step of heating at 40 ℃ or higher is not included between the exposure step and the development treatment step.

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

the development treatment is performed using a developer containing 50% by mass or more of an organic solvent.

25. The method for producing a cured film according to any one of claims 21 to 24,

the developing treatment is performed by using a developing solution containing an organic solvent having a ClogP of-1 to 5.

26. A semiconductor device having the cured film according to claim 18 or the laminate according to claim 19 or 20.

Technical Field

The invention relates to a photosensitive resin composition, a polymer precursor, a cured film, a laminate, a method for manufacturing the cured film, and a semiconductor device.

Background

Conventionally, polyimide resins having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like have been used for protective films and interlayer insulating films of semiconductor devices. However, in recent years, with the progress of high integration and large-scale growth of semiconductor elements, thinning and miniaturization of sealing resin packages have been required, and surface mounting using LOC (lead on chip) or reflow has been adopted.

In the production of these semiconductor devices, a photosensitive resin composition in which a polyimide precursor and a photo radical polymerizable compound are used is used or a photosensitive is imparted to the polyimide precursor itself. This is because the use of the photosensitive resin composition can simplify the pattern forming step. For example, patent document 1 discloses a negative photosensitive resin composition containing:

(A) the polyamic acid derivative has a plurality of structural units represented by general formula (1), and R in the structural units³A part of which is hydrogen and the remainder is a monovalent organic group,

[ chemical formula 1]

In the formula, R¹Is a tetravalent organic radical, R²Is a divalent organic radical, two R³Independently hydrogen or a monovalent organic group; and

(B) a compound which generates a basic substance by irradiation with radiation.

Prior art documents

Patent document

Patent document 1: japanese patent laid-open publication No. 2014-201695

Disclosure of Invention

Problems to be solved by the invention

However, it is found that the above-mentioned photosensitive resin composition may not have sufficient elongation at break. Further, when the photosensitive resin composition is used for a long time after the photosensitive resin composition is prepared, the storage stability of the photosensitive resin composition itself is also referred to as a problem.

The present invention has been made to solve the above problems, and an object of the present invention is to provide a photosensitive resin composition which has a high elongation at break when formed into a cured film and is excellent in storage stability, a polymer precursor, a cured film, a laminate, a method for producing a cured film, and a semiconductor device.

Means for solving the problems

Based on the above problems, the present inventors have conducted studies and found that both the elongation at break of a cured film and the storage stability of a photosensitive resin composition can be improved by setting the acid value of a polymer precursor used in the photosensitive resin composition to a predetermined range, and have completed the present invention.

Specifically, the above problem is solved by the following means <1>, preferably <2> to <26 >.

<1> a photosensitive resin composition comprising a polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, a photo radical polymerization initiator and a solvent, wherein the acid value of an acid group having a pH of a neutralization point in the polymer precursor in the range of 7.0 to 12.0 is in the range of 2.5 to 34.0mgKOH/g,

the polymer precursor has a radical polymerizable group, or the photosensitive resin composition contains a radical polymerizable compound other than the polymer precursor.

<2> the photosensitive resin composition according to <1>, wherein the acid value of the acid group having a pH of the neutralization point in the polymer precursor in the range of 7.0 to 12.0 is in the range of 5.5 to 17.0 mgKOH/g.

<3> the photosensitive resin composition according to <1> or <2>, wherein the acid group having a pH of the neutralization point contained in the polymer precursor in the range of 7.0 to 12.0 is a carboxyl group.

<3-2> a photosensitive resin composition comprising a polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, a photo radical polymerization initiator and a solvent, wherein the polymer precursor comprises a carboxyl group, and the polymer precursor has a radical polymerizable group, or the photosensitive resin composition comprises a radical polymerizable compound other than the polymer precursor.

<4> the photosensitive resin composition according to any one of <1> to <3-2>, wherein the polymer precursor comprises a repeating unit represented by the following formula (1) or a repeating unit represented by the following formula (2);

formula (1)

[ chemical formula 2]

In the formula (1), A¹And A²Each independently represents an oxygen atom or NH,

R¹¹¹represents a 2-valent organic group, R¹¹⁵Represents a 4-valent organic group, R¹¹³And R¹¹⁴Each independently represents a hydrogen atom or a 1-valent organic group;

formula (2)

[ chemical formula 3]

In the formula (2), R¹²¹Represents a 2-valent organic group, R¹²²Represents a 4-valent organic group, R¹²³And R¹²⁴Each independently represents a hydrogen atom or a 1-valent organic group;

at least one of the repeating units represented by the above formula (1) is — C (═ O) a²-R¹¹³and-C (═ O) A¹-R¹¹⁴At least one repeating unit containing an acid group having a pH of 7.0 to 12.0 at the neutralization point,

at least one of the repeating units represented by the above formula (2) contains-R¹²²-O-R¹²³and-R¹²²-O-R¹²⁴At least one of the above-mentioned neutralization points contains a repeating unit of an acid group having a pH of 7.0 to 12.0.

<5>According to<4>The photosensitive resin composition is characterized in that at least one of the repeating units represented by the formula (1) is R¹¹³And R¹¹⁴At least one of the repeating units containing a radical polymerizable group in (3), or at least one of the repeating units represented by the above formula (2) is R¹²³And R¹²⁴At least one of the above (1) contains a repeating unit of a radical polymerizable group.

<6> the photosensitive resin composition according to <4> or <5>, wherein the polymer precursor comprises a repeating unit represented by formula (1).

<7> the photosensitive resin composition according to any one of <1> to <6>, which further comprises a radical polymerizable compound other than the above-mentioned polymer precursor.

<8> the photosensitive resin composition according to any one of <1> to <7>, which further comprises a thermal alkali generator.

<9> the photosensitive resin composition according to any one of <1> to <8>, which further comprises a photobase generator.

<10> the photosensitive resin composition according to any one of <1> to <9>, which further comprises a polymerization inhibitor.

<11> the photosensitive resin composition according to any one of <1> to <9> for use in development using a developer containing an organic solvent.

<12> the photosensitive resin composition according to <11>, wherein 50% by mass or more of the developing solution is an organic solvent.

<13> the photosensitive resin composition according to <11> or <12>, wherein the developer comprises an organic solvent having a ClogP of-1 to 5.

<14> the photosensitive resin composition according to any one of <1> to <13>, which is used for forming an interlayer insulating film for a rewiring layer.

<15> a polymer precursor comprising a repeating unit represented by the following formula (1) or a repeating unit represented by formula (2);

formula (1)

[ chemical formula 4]

In the formula (1), A¹And A²Each independently represents an oxygen atom or NH,

R¹¹¹represents a 2-valent organic group, R¹¹⁵Represents a 4-valent organic group, R¹¹³And R¹¹⁴Each independently represents a hydrogen atom or a 1-valent organic group;

formula (2)

[ chemical formula 5]

In the formula (2), R¹²¹Represents a 2-valent organic group, R¹²²Represents a 4-valent organic group, R¹²³And R¹²⁴Each independently represents a hydrogen atom or a 1-valent organic group;

at least one of the repeating units represented by the above formula (1) is — C (═ O) a²-R¹¹³and-C (═ O) A¹-R¹¹⁴At least one repeating unit containing an acid group having a pH of 7.0 to 12.0 at the neutralization point,

at least one of the repeating units represented by the above formula (2) contains-R¹²²-O-R¹²³and-R¹²²-O-R¹²⁴At least one of the above-mentioned (B) contains a repeating unit of an acid group having a pH of 7.0 to 12.0 at a neutralization point.

<16> the polymer precursor according to <15>, wherein the acid value of the acid group having a pH of the neutralization point in the range of 7.0 to 12.0 is in the range of 5.5 to 17.0 mgKOH/g.

<17>According to<15>Or<16>The polymer precursor is a polymer precursor in which at least one of the repeating units represented by the above formula (1) is R¹¹³And R¹¹⁴At least one of the repeating units containing a radical polymerizable group or the repeating unit represented by the above formula (2) is R¹²³And R¹²⁴At least one of the above (1) contains a repeating unit of a radical polymerizable group.

<18> a cured film formed from the photosensitive resin composition <1> to <14 >.

<19> a laminate having 2 or more layers of the cured film of <18 >.

<20> the laminate according to <19>, which comprises a metal layer between the cured films.

<21> a method for producing a cured film, which comprises using the photosensitive resin composition of any one of <1> to <14 >.

<22> the method for producing a cured film according to <21>, which comprises:

a photosensitive resin composition layer forming step of applying the photosensitive resin composition to a substrate to form a layer;

an exposure step of exposing the photosensitive resin composition layer; and

and a developing treatment step of performing a developing treatment on the exposed photosensitive resin composition layer.

<23> the method of <22> wherein the step of heating at 40 ℃ or higher is not included between the exposure step and the development treatment step.

<24> the method of <22> or <23>, wherein the developing treatment is performed using a developing solution containing 50% by mass or more of an organic solvent.

<25> the method of producing a cured film according to any one of <21> to <24>, wherein the developing treatment is performed using a developer containing an organic solvent having a ClogP of-1 to 5.

<26> a semiconductor device having the cured film of <18> or the laminate of <19> or <20 >.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a photosensitive resin composition having a high elongation at break when formed into a cured film and excellent storage stability, a polymer precursor, a cured film, a laminate, a method for producing a cured film, and a semiconductor device can be provided.

Drawings

Fig. 1 is a schematic diagram showing a structure of one embodiment of a semiconductor device.

Detailed Description

The present invention will be described in detail below. In the present specification, "to" means that numerical values described before and after the "to" are included as a lower limit value and an upper limit value.

The following description of the constituent elements of the present invention may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

In the present specification, a label of a group (atomic group) is a label which does not describe a substitution or an unsubstituted label and includes both a group having no substituent and a group having a substituent. For example, "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present specification, "exposure" is not particularly limited, and in addition to exposure using light, drawing using a particle beam such as an electron beam or an ion beam is also included in exposure. Examples of the light used for exposure include active rays or radiations such as far ultraviolet rays typified by a bright line spectrum of a mercury lamp and an excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams.

In the present specification, the numerical range represented by "to" means a range in which the numerical values before and after "to" are included as the lower limit value and the upper limit value.

In the present specification, "(meth) acrylate" represents both or either of "acrylate" and "methacrylate", "meth (acrylic acid)" represents both or either of "acrylic acid" and "methacrylic acid", and "(meth) acryloyl group" represents both or either of "acryloyl group" and "methacryloyl group".

In the present specification, the term "step" is included in the term not only for an independent step but also for an effect expected for the step if the step is not clearly distinguished from other steps.

In the present specification, the solid content is a mass percentage of the components other than the solvent in the total mass of the composition. The solid content concentration is a concentration at 25 ℃ unless otherwise specified.

In the present specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as styrene equivalent values based on gel permeation chromatography (GPC measurement). In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined, for example, by using HLC-8220 (manufactured by TOSOH CORPORATION) and using protective columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) as columns. Unless otherwise specified, the elution reagent is measured with THF (tetrahydrofuran). In addition, a 254nm wavelength detector of UV rays (ultraviolet rays) is used for detection unless otherwise specified.

< photosensitive resin composition >

The photosensitive resin composition of the present invention (hereinafter, may be simply referred to as "the composition of the present invention") is characterized by comprising a polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, a photoradical polymerization initiator and a solvent, wherein the acid value of an acid group having a pH of a neutralization point in the range of 7.0 to 12.0 in a neutralization point contained in the polymer precursor is in the range of 2.5 to 34.0mgKOH/g, the polymer precursor has a radical polymerizable group, or the photosensitive resin composition comprises a radical polymerizable compound other than the polymer precursor. With such a structure, a photosensitive resin composition having a high elongation at break and excellent storage stability when molded into a cured film can be provided. That is, the acid value of the polymer precursor is set to a predetermined range, and the radical polymerization initiator is mixed and radical polymerization curing is performed, whereby the elongation at break of the obtained cured film can be improved, and the storage stability of the photosensitive resin composition can be improved. In particular, the presence of a small amount of acid groups in the polymer precursor increases the hydrogen bonding property of the polymer precursor, and thus the durability against external force can be improved. Further, it is presumed that the presence of a radical polymer generated by a radical polymerization initiator increases flexibility to external force, and the elongation at break of the cured film after radical polymerization is good. Further, by setting the amount of the acid group contained in the polymer precursor to a certain amount or less, a photosensitive resin composition having excellent storage stability can be formed.

< Polymer precursor >)

The photosensitive resin composition of the present invention comprises at least one polymer precursor. The polymer precursor preferably contains a polyimide precursor or a polybenzoxazole precursor, more preferably contains a polyimide precursor, and still more preferably contains a repeating unit represented by formula (1) described later.

In the polymer precursor used in the present invention, the acid value of the acid group having a pH of the neutralization point in the range of 7.0 to 12.0 is in the range of 2.5 to 34.0mgKOH/g, preferably 5.5mgKOH/g or more, more preferably 6.0mgKOH/g or more, and preferably 17.0mgKOH/g or less, more preferably 12.0mgKOH/g or less.

In the photosensitive resin composition of the present invention, when the acid value of the entire polymer precursor contained in the composition is in the range of 2.5 to 34.0mgKOH/g, the acid value of each polymer precursor constituting the polymer precursor contained in the composition may be out of the range of 2.5 to 34.0 mgKOH/g. Specifically, two or more types of polymer precursors other than those having a value of 2.5 to 34.0mgKOH/g may be mixed to adjust the acid value of the entire polymer precursor contained in the composition to a value of 2.5 to 34.0 mgKOH/g.

In the photosensitive resin composition of the present invention, the acid value of the polymer precursor contained in the composition is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more, within the range of 2.5 to 34.0mgKOH/g (preferably within the range of 5.5 to 17.0mgKOH/g, and more preferably within the range of 6.0 to 12.0 mgKOH/g).

The acid value in the case where the photosensitive resin composition of the present invention contains two or more polymer precursors can be calculated from the mass ratio of each polymer precursor.

The acid group having a pH of 7.0 to 12.0 at the neutralization point contained in the polymer precursor is a group having a pH of 7.0 to 12.0 in the method for measuring an acid value described in examples described later, and a carboxyl group is exemplified.

The polymer precursor contained in the composition of the present invention may or may not contain an acid group other than an acid group having a pH in the range of 7.0 to 12.0. Among the acid groups contained in the polymer precursor contained in the composition of the present invention, acid groups having a pH in the range of 7.0 to 12.0 are preferably 70 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol% or more.

The acid group having a pH of 7.0 to 12.0 may be bonded to a side chain or a main chain of the polymer precursor. Preferably at least in a bond with the side chains of the polymer precursor.

In addition, the base of the neutralization point can be measured using sodium hydroxide. When it is difficult to measure the neutralization point using sodium hydroxide, the neutralization point is measured using calcium hydroxide, and the neutralization point converted to sodium hydroxide is regarded as the neutralization point measured using sodium hydroxide.

The acid value in the above range can be achieved by appropriately adjusting the reaction conditions.

In the present invention, it is preferable to produce a polymer precursor through a synthesis reaction solution having a water content of 50 to 700 mass ppm. By adopting such a structure, a polymer precursor satisfying a predetermined acid value can be more easily obtained.

The water content of the reaction liquid for synthesizing the polymer precursor in the present invention can be measured by the method described in the examples described later.

< polyimide precursor > > <

The polyimide precursor used in the present invention is not particularly limited in kind and the like, but preferably contains a repeating unit represented by the following formula (1).

Formula (1)

[ chemical formula 6]

In the formula (1), A¹And A²Each independently represents an oxygen atom or NH, R¹¹¹Represents a 2-valent organic group, R¹¹⁵Represents a 4-valent organic group; r¹²³And R¹²⁴Each independently represents a hydrogen atom or a 1-valent organic group.

A in the formula (1)¹And A²Preferably an oxygen atom or NH, more preferably an oxygen atom.

R in the formula (1)¹¹¹Represents a 2-valent organic group. Examples of the 2-valent organic group include groups containing a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, preferably a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof, and more preferably a group containing an aromatic group having 6 to 20 carbon atoms.

R¹¹¹Preferably derived from diamines. The diamine used for producing the polyimide precursor includes a linear or branched aliphatic diamine, a cyclic aliphatic or aromatic diamine, and the like. One diamine may be used alone, or two or more diamines may be used.

Specifically, the diamine is preferably a diamine containing 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 a combination thereof, and more preferably a diamine containing a group consisting of an aromatic group having 6 to 20 carbon atoms. Examples of the aromatic group include the following aromatic groups.

[ chemical formula 7]

In the formula, A is preferably a single bond or selected from aliphatic hydrocarbon groups having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C (═ O) -, -S-, -S (═ O)₂-, -NHCO-and combinations thereof, more preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C (-O) -, -S-, -SO₂-is further preferably selected from the group consisting of-CH₂-、-O-、-S-、-SO₂-、-C(CF₃)₂-and-C (CH)₃)₂A 2-valent radical of the group (A-b).

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-diaminohexane; 1, 2-or 1, 3-diaminocyclopentane, 1, 2-diaminocyclohexane, 1, 3-or 1, 4-diaminocyclohexane, 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 '-diamino-3, 3' -dimethylcyclohexylmethane and isophoronediamine; m-phenylenediamine and p-phenylenediamine, diaminotoluene, 4 '-diaminobiphenyl and 3, 3' -diaminobiphenyl, 4 '-diaminodiphenyl ether, 3' -diaminodiphenyl ether, 4 '-diaminodiphenylmethane and 3, 3' -diaminodiphenylmethane, 4 '-diaminodiphenyl sulfone and 3, 3-diaminodiphenyl sulfone, 4' -diaminodiphenyl sulfide and 3, 3 '-diaminodiphenyl sulfide, 4' -diaminobenzophenone and 3, 3 '-diaminobenzophenone, 3' -dimethyl-4, 4 '-diaminobiphenyl, 2' -dimethyl-4, 4 '-diaminobiphenyl, 3' -dimethoxy-4, 4 ' -diaminobiphenyl, 2-bis (4-aminophenyl) propane, 2-bis (4-aminophenyl) hexafluoropropane, 2-bis (3-hydroxy-4-aminophenyl) propane, 2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2-bis (3-amino-4-hydroxyphenyl) propane, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 4 ' -diaminoterphenyl, 4 ' -bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl ] sulfone, bis (4-aminophenoxy) phenyl) sulfone, bis (4-amino-4-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) propane, 2-bis (4-aminophenyl) hexafluoropropane, 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 ' -dimethyl-4, 4 ' -diaminodiphenyl sulfone, 1, 3-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenyl) benzene, 3 ' -diethyl-4, 4 ' -diaminodiphenylmethane, 3 ' -dimethyl-4, 4 ' -diaminodiphenylmethane, 4 ' -diaminooctafluorobiphenyl, 2-bis [4- (4-aminophenoxy) phenyl ] propane, methyl ether, ethyl ether, 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 9-bis (4-aminophenyl) -10-hydroanthracene, 3 ', 4, 4 ' -tetraaminobiphenyl, 3 ', 4, 4 ' -tetraaminodiphenyl ether, 1, 4-diaminoanthraquinone, 1, 5-diaminoanthraquinone, 3-dihydroxy-4, 4 ' -diaminobiphenyl, 9 ' -bis (4-aminophenyl) fluorene, 4, 4 ' -dimethyl-3, 3 ' -diaminodiphenyl sulfone, 3 ', 5, 5 ' -tetramethyl-4, 4 ' -diaminodiphenylmethane, cumene and 2, 5-diaminocumene, 2, 5-dimethyl-p-phenylenediamine, cumene, toluene, 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, diaminobenzanilide, an ester of diaminobenzoic acid, 1, 5-diaminonaphthalene, diaminobenzotrifluoride, 1, 3-bis (4-aminophenyl) hexafluoropropane, 1, 4-bis (4-aminophenyl) octafluorobutane, 1, 5-bis (4-aminophenyl) decafluoropentane, 1, 7-bis (4-aminophenyl) tetradecafluoroheptane, 2-bis [4- (3-aminophenoxy) phenyl ] hexafluoropropane, 2, 2-bis [4- (2-aminophenoxy) phenyl ] hexafluoropropane, 2-bis [4- (4-aminophenoxy) -3, 5-dimethylphenyl ] hexafluoropropane, 2-bis [4- (4-aminophenoxy) -3, 5-bis (trifluoromethyl) phenyl ] hexafluoropropane, p-bis (4-amino-2-trifluoromethylphenoxy) benzene, 4 '-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4' -bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 4 '-bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4' -bis (3-amino-5-trifluoromethylphenoxy) diphenylsulfone, at least one diamine selected from 2, 2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl ] hexafluoropropane, 3 ', 5, 5 ' -tetramethyl-4, 4 ' -diaminobiphenyl, 4 ' -diamino-2, 2 ' -bis (trifluoromethyl) biphenyl, 2 ', 5, 5 ', 6, 6 ' -hexafluorotolidine and 4, 4 ' -diaminoquaterphenyl.

Also, diamines (DA-1) to (DA-18) shown below are preferable.

[ chemical formula 8]

[ chemical formula 9]

Further, as a preferable example, a diamine having at least two alkylene glycol units in the main chain can be cited. The diamine is preferably a diamine containing two or more ethylene glycol chains or propylene glycol chains in one molecule, or a diamine containing no aromatic ring. Specific examples thereof 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 (product names mentioned above, manufactured by HUNTSMAN Co., Ltd.), 1- (2- (2-aminopropoxy) ethoxy) propoxy) propan-2-amine, and 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propan-2-amine, but the present invention is not limited thereto.

The following shows the structures of 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, and JEFFAMINE (registered trademark) EDR-176.

[ chemical formula 10]

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

From the viewpoint of flexibility of the obtained cured film, R¹¹¹Preferably represented by-Ar-L-Ar-. Wherein Ar is an aromatic hydrocarbon group, L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO₂-or-NHCO-, and groups comprising a combination of two or more of the foregoing. Ar is preferably an phenylene group, L is more preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, or-SO₂-. Among them, the aliphatic hydrocarbon group is preferably an alkylene group.

From the viewpoint of i-ray transmittance, R¹¹¹Preferred is a 2-valent organic group represented by the following formula (51) or formula (61). In particular, the 2-valent organic group represented by formula (61) is more preferable from the viewpoint of i-ray transmittance and ready availability.

Formula (51)

[ chemical formula 11]

In the formula (51), R¹⁰～R¹⁷Each independently is a hydrogen atom, a fluorine atom or a 1-valent organic group, R¹⁰～R¹⁷At least one of which is a fluorine atom, a methyl group, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group.

When R is¹⁰～R¹⁷Examples of the 1-valent organic group include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and the like.

Formula (61)

[ chemical formula 12]

In the formula (61), R¹⁸And R¹⁹Each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group.

Examples of the diamine compound to which the structure of formula (51) or (61) is imparted include dimethyl-4, 4 '-diaminobiphenyl, 2' -bis (trifluoromethyl) -4, 4 '-diaminobiphenyl, 2' -bis (fluoro) -4, 4 '-diaminobiphenyl, and 4, 4' -diaminooctafluorobiphenyl. One of these may be used, or two or more of these may be used in combination.

R in the formula (1)¹¹⁵Represents a 4-valent organic group. The 4-valent organic group is preferably a 4-valent organic group containing an aromatic ring, and more preferably a group represented by the following formula (5) or formula (6).

Formula (5)

[ chemical formula 13]

In the formula (5), R¹¹²Preferably selected from a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO₂-, -NHCO-and combinations thereof, more preferably selected from the group consisting of a single bond, an alkylene group of 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, and-SO₂-further preferably selected from the group consisting of-CH₂-、-C(CF₃)₂-、-C(CH₃)₂-, -O-, -CO-, -S-and-SO₂A 2-valent radical of the group (A-b).

Formula (6)

[ chemical formula 14]

With respect to R in the formula (1)¹¹⁵Specific examples of the 4-valent organic group include tetracarboxylic acid residues remaining after removal of an acid dianhydride group from a tetracarboxylic acid dianhydride. The tetracarboxylic dianhydride may be used alone or in combination of two or more. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (O).

Formula (O)

[ chemical formula 15]

In the formula (O), R¹¹⁵Represents a 4-valent organic group. R¹¹⁵Is defined as in formula (1) and R¹¹⁵The same is true.

Specific examples of the tetracarboxylic acid dianhydride include those selected from the group consisting of pyromellitic acid, pyromellitic acid dianhydride (PMDA), 3, 3 ', 4, 4 ' -biphenyltetracarboxylic acid dianhydride, 3, 3 ', 4, 4 ' -diphenylsulfide tetracarboxylic acid dianhydride, 3, 3 ', 4, 4 ' -diphenylsulfone tetracarboxylic acid dianhydride, 3, 3 ', 4, 4 ' -benzophenonetetracarboxylic acid dianhydride, 3, 3 ', 4, 4 ' -diphenylmethane tetracarboxylic acid dianhydride, 2 ', 3, 3 ' -diphenylmethane tetracarboxylic acid dianhydride, 2, 3, 3 ', 4 ' -biphenyltetracarboxylic acid dianhydride, 2, 3, 3 ', 4 ' -benzophenonetetracarboxylic acid dianhydride, 4, 4 ' -oxydiphthalic acid dianhydride, 2, 3, 6, 7-naphthalenetetracarboxylic acid dianhydride, 1, 4, 5, 7-naphthalenetetracarboxylic acid dianhydride, 1, 4, 7-naphthalenetetracarboxylic acid dianhydride, and mixtures thereof, 2, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 1, 3-diphenylhexafluoropropane-3, 3, 4, 4-tetracarboxylic dianhydride, 1, 4, 5, 6-naphthalenetetracarboxylic dianhydride, 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-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 1, 2, 3, 4-benzenetetracarboxylic dianhydride, and at least one of alkyl derivatives having 1 to 6 carbon atoms and/or alkoxy derivatives having 1 to 6 carbon atoms.

Preferred examples thereof include tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below.

[ chemical formula 16]

In the formula (1), R¹¹³And R¹¹⁴Each independently represents a hydrogen atom or a 1-valent organic group.

In the present invention, at least one of the repeating units represented by formula (1) is preferably — C (═ O) a²-R¹¹³and-C (═ O) A¹-R¹¹⁴At least one of the above-mentioned neutralization points contains a repeating unit of an acid group having a pH of 7.0 to 12.0. Specifically, R can be exemplified¹¹³And R¹¹⁴Containing acid groups or-C (═ O) A²-R¹¹³and-C (═ O) A¹-R¹¹⁴In the case of-COOH, etc., it is preferably-C (═ O) A²-R¹¹³and-C (═ O) A¹-R¹¹⁴In the case of-COOH.

And, the present inventionIn the present invention, at least one of the repeating units represented by the formula (1) is preferably R¹¹³And R¹¹⁴At least one of the above (1) contains a repeating unit of a radical polymerizable group. The radical polymerizable group is a group capable of undergoing a crosslinking reaction by the action of a radical, and a preferable example thereof is a group having an ethylenically unsaturated bond.

As a preferred embodiment, the polyimide precursor used in the present invention includes a polyimide precursor containing — C (═ O) a²-R¹¹³and-C (═ O) A¹-R¹¹⁴At least one (preferably both) of the above-mentioned repeating units (1A) and (R) containing an acid group having a neutralization point pH of 7.0 to 12.0¹¹³And R¹¹⁴At least one (preferably both) of the repeating units (1B) containing a radical polymerizable group contains — C (═ O) a²-R¹¹³and-C (═ O) A¹-R¹¹⁴One of the acid groups contains the above-mentioned neutralization point, R is an acid group having a pH of 7.0 to 12.0¹¹³And R¹¹⁴The other (containing no acid group) of the above-mentioned groups contains a repeating unit (1C) having a radical polymerizable group, and the other contains a repeating unit (1C) and at least one of the repeating unit (1A) and the repeating unit (1B).

In the present invention, the molar ratio of the repeating unit (1A) to the repeating unit (1B) is preferably 99: 1 to 80: 20, and more preferably 98: 2 to 90: 10.

In the present invention, the total of the repeating unit (1A), the repeating unit (1B) and the repeating unit (1C) is preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more of the total repeating units of the polyimide precursor.

In the present invention, the ratio of the number of radical polymerizable groups contained in the polyimide precursor to the number of acid groups having a pH in the range of 7.0 to 12.0 is preferably 80: 20 to 99: 1, and more preferably 90: 10 to 98: 2.

Examples of the group having an ethylenically unsaturated bond include a vinyl group, (meth) allyl group, a group represented by the following formula (III), and the like, and a (meth) acryloyl group is preferable, and a (meth) acryloyloxy group is more preferable.

[ chemical formula 17]

In the formula (III), R²⁰⁰Represents a hydrogen atom or a methyl group, and more preferably a methyl group.

In the formula (III), R²⁰¹An alkylene group having 2 to 12 carbon atoms, -CH₂CH(OH)CH₂-or a C4-30 polyoxyalkylene group.

With respect to R²⁰¹Preferable examples of (A) include ethylene group, propylene group, trimethylene group, tetramethylene group, 1, 2-butylene group, 1, 3-butylene group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group and-CH group₂CH(OH)CH₂-, more preferably ethylene, propylene, trimethylene, -CH₂CH(OH)CH₂-。

Particularly preferred is R²⁰⁰Is methyl, R²⁰¹Is an ethylene group.

As a group consisting of R¹¹³Or R¹¹⁴As the 1-valent organic group, an organic group which increases the solubility of the developer can be preferably used.

When R is¹¹³Or R¹¹⁴Examples of the 1-valent organic group include an aromatic group and an alkyl group having 1, 2, or 3 acid groups, preferably 1 acid group, bonded to the carbon constituting the aryl group. Specifically, the aromatic group has 6 to 20 carbon atoms and has an acidic group, and the aralkyl group has 7 to 25 carbon atoms and has an acidic group. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group are exemplified. The acidic group is preferably an OH group.

From the viewpoint of solubility in an aqueous developer, R¹¹³Or R¹¹⁴More preferred are a hydrogen atom, 2-hydroxybenzyl group, 3-hydroxybenzyl group and 4-hydroxybenzyl group.

From the viewpoint of solubility in organic solvents, R¹¹³Or R¹¹⁴Preferably a 1-valent organic group. The 1-valent organic group is preferably a group containing a linear or branched alkyl group,The cyclic alkyl group and the aromatic group are more preferably alkyl groups substituted with aromatic groups.

The number of carbon atoms of the alkyl group is preferably 1 to 30. The alkyl group may be any of linear, branched, and cyclic. Examples of the straight-chain or branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, an octadecyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 1-ethylpentyl group and a 2-ethylhexyl group. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of the polycyclic cyclic alkyl group include adamantyl, norbornyl, bornyl, camphylenyl, decahydronaphthyl, tricyclodecanyl, tetracyclodecyl, camphoroyl, dicyclohexyl, and sterenyl. Among these, cyclohexyl is most preferable from the viewpoint of achieving both high sensitivity to exposure. The alkyl group substituted with an aromatic group is preferably a straight-chain alkyl group substituted with an aromatic group described later.

The aromatic group is specifically a substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring, tetracene ring, perylene ring, acenaphthylene ring, phenanthrene ring, anthracene ring, perylene ring, acenaphthylene ring, phenanthrene ring, anthracene ring, tetracene ring, perylene ring,

A ring, a triphenylene ring, a fluorene ring, a biphenyl ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an indolizine ring, an indole ring, a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, a quinolizine ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinoxazoline ring, an isoquinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthroline ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxathiin ring, a phenothiazine ring or a phenanthroline ring. Most preferred is a benzene ring.

In the formula (1), when R is¹¹³When it is a hydrogen atom or R¹¹⁴In the case of a hydrogen atom, the polyimide precursor may form a reverse salt with a tertiary amine compound having an ethylenically unsaturated bond. Examples of the tertiary amine compound having such an ethylenically unsaturated bond include N, N-dimethylaminopropyl methacrylate.

Further, the polyimide precursor preferably has a fluorine atom in a structural unit. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

Further, the silicone resin may be copolymerized with an aliphatic group having a siloxane structure for the purpose of improving adhesion to a substrate. Specifically, examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylpentasiloxane.

The repeating unit represented by formula (1) is preferably a repeating unit represented by formula (1-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having a repeating unit represented by the formula (1-a). With such a configuration, the width of the exposure latitude can be further increased.

Formula (1-A)

[ chemical formula 18]

In the formula (1-A), A¹And A²Represents an oxygen atom, R¹¹¹And R¹¹²Each independently represents a 2-valent organic group, R¹¹³And R¹¹⁴Each independently represents a hydrogen atom or a 1-valent organic group.

A¹、A²、R¹¹¹、R¹¹³And R¹¹⁴(containing-C (═ O) A²-R¹¹³and-C (═ O) A¹-R¹¹⁴) Are each independently defined as A in the formula (1)¹、A²、R¹¹¹、R¹¹³And R¹¹⁴(containing-C (═ O) A²-R¹¹³and-C (═ O) A¹-R¹¹⁴) Similarly, the preferred ranges are also the same.

R¹¹²Is defined with R in formula (5)¹¹²Similarly, the preferred ranges are also the same.

In the polyimide precursor, the number of the repeating units represented by the formula (1) may be one, or may be two or more. And may contain structural isomers of the repeating unit represented by formula (1). The polyimide precursor may contain other types of repeating structural units in addition to the repeating unit of formula (1).

As an embodiment of the polyimide precursor in the present invention, a polyimide precursor in which 50 mol% or more, further 70 mol% or more, particularly 90 mol% or more of the total repeating units are repeating units represented by the formula (1) can be exemplified.

The polyimide precursor preferably has a weight average molecular weight (Mw) of 2000 to 500000, more preferably 5000 to 100000, and still more preferably 10000 to 50000. The number average molecular weight (Mn) is preferably 800 to 250000, more preferably 2000 to 50000, and further preferably 4000 to 25000.

The dispersion degree of the polyimide precursor is preferably 1.5 to 2.5.

The polyimide precursor can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, the dicarboxylic acid or dicarboxylic acid derivative is halogenated with a halogenating agent and then reacted with a diamine.

In the method for producing a polyimide precursor, an organic solvent is preferably used when the reaction is carried out. The organic solvent may be one kind or two or more kinds.

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.

In the present invention, as described above, the amine value of the polymer precursor can also be adjusted by adding an amino group to the end of the main chain after the dicarboxylic acid or dicarboxylic acid derivative is reacted with the diamine. As a method of adding an amino group to the end of the main chain, a method of adding an amine compound having an amino group or a hydroxyl group to the end of a repeating unit derived from a dicarboxylic acid or a dicarboxylic acid derivative is preferable.

Examples of the amine compound having a hydroxyl group include 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these may be used, or an amine compound having a plurality of hydroxyl groups may be reacted.

Examples of the amine compound having an amino group include N, N-dimethylethylenediamine, N-diethylethylenediamine, N-dimethylethylenediamine, 1- (2-aminoethyl) piperidine, and 2-morpholinoethylamine. Two or more of these may be used, or an amine compound having a plurality of amino groups may be reacted.

The production of the polyimide precursor preferably includes a step of precipitating a solid. Specifically, the polyimide precursor in the reaction solution is precipitated in water, and the polyimide precursor such as tetrahydrofuran is dissolved in a soluble solvent, whereby solid deposition can be performed.

< < < polybenzoxazole precursor > >)

The polybenzoxazole precursor used in the present invention preferably contains a repeating unit represented by the following formula (2).

Formula (2)

[ chemical formula 19]

In the formula (2), R¹²¹Represents a 2-valent organic group, R¹²²Represents a 4-valent organic group, R¹²³And R¹²⁴Each independently represents a hydrogen atom or a 1-valent organic group.

In the formula (2), R¹²¹Represents a 2-valent organic group. The 2-valent organic group is preferably a group containing at least one of an aliphatic group and an aromatic group. The aliphatic group is preferably a straight-chain aliphatic group. R¹²¹Preferably from 4, 4' -oxodibenzoyl chloride and the like.

In the formula (2), R¹²²Represents a 4-valent organic group. As the 4-valent organic group, the same as defined for R in the above formula (1)¹¹⁵Similarly, the preferred ranges are also the same. R¹²²Preferably from 2, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and the like.

In the formula (2), R¹²³And R¹²⁴Is defined as in formula (1) and R¹¹³And R¹¹⁴Similarly, the preferred ranges are also the same. That is, in the formula (2), R is preferable¹²³And R¹²⁴At least one of them has a radical polymerizable group.

In the present invention, at least one of the repeating units represented by the formula (2) is preferably-R¹²²-O-R¹²³and-R¹²²-O-R¹²⁴At least one of the above-mentioned neutralization points contains a repeating unit of an acid group having a pH of 7.0 to 12.0. Specifically, R can be exemplified¹²³And R¹²⁴In the case of containing acid groups or-R¹²²-O-R¹²³and-R¹²²-O-R¹²⁴In the case where at least one of them contains-COOH, etc., it is preferable that-R is¹²²-O-R¹²³and-R¹²²-O-R¹²⁴At least one of them contains-COOH.

In the present invention, at least one of the repeating units represented by the formula (2) is preferably R¹²³And R¹²⁴At least one of the above (1) contains a repeating unit of a radical polymerizable group. The radical polymerizable group is a group capable of crosslinking reaction by the action of a radical, and a preferable example thereof is a group having an ethylenically unsaturated bond.

As a preferred embodiment, the polyimide precursor used in the present invention includes a polyimide precursor containing-R¹²²-O-R¹²³and-R¹²²-O-R¹²⁴At least one (preferably both) of the repeating units (2A) and R contain an acid group having a pH of 7.0 to 12.0 at the neutralization point¹²³And R¹²⁴At least one (preferably both) of the repeating units (2B) having a radical polymerizable group contains-R¹²²-O-R¹²³and-R¹²²-O-R¹²⁴One of the above-mentioned neutralization sites has a pH of 7.0 to EAcid group in the range of 12.0, R¹²³And R¹²⁴The other (not containing an acid group) of the above-mentioned (meth) acrylic acid ester groups contains a repeating unit (2C) having a radical polymerizable group, and the repeating unit (2C) contains at least one of the repeating unit (2A) and the repeating unit (2B).

In the present invention, the molar ratio of the repeating unit (2A) to the repeating unit (2B) is preferably 99: 1 to 80: 20, and more preferably 98: 2 to 90: 10.

In the present invention, the total of the repeating unit (2A), the repeating unit (2B) and the repeating unit (2C) is preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more of the total repeating units of the polybenzoxazole precursor.

In the present invention, the ratio of the number of radical polymerizable groups contained in the polybenzoxazole precursor to the number of acid groups having a pH in the range of 7.0 to 12.0 is preferably 80: 20 to 99: 1, and more preferably 90: 10 to 98: 2.

The polybenzoxazole precursor may contain other kinds of repeating structural units in addition to the repeating unit of the above formula (2).

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

[ chemical formula 20]

In the formula (SL), Z has a structure a and a structure b, R^1sIs a hydrogen atom or a hydrocarbon group of 1 to 10 carbon atoms, R^2sIs a hydrocarbon group of 1 to 10 carbon atoms, R^3s、R^4s、R^5s、R^6sAt least one of the groups is an aromatic group, and the remainder is a hydrogen atom or an organic group having 1 to 30 carbon atoms, and the groups 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, the a structure is 5 to 95 mol%, the b structure is 95 to 5 mol%, and the a + b is 100 mol%.

In the formula (SL), preferable Z is R in the structure of b^5sAnd R^6sIs phenyl. The molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. The molecular weight can be determined by gel permeation chromatography which is generally used. By setting the molecular weight in the above range, the elasticity of the polybenzoxazole precursor after dehydration ring closure can be reduced, and the effect of suppressing warpage of the cured film and the effect of improving solubility can be both achieved.

When the diamine residue represented by formula (SL) is contained as another kind of repeating structural unit, it is preferable to further contain a tetracarboxylic acid residue remaining after removing the acid dianhydride from the tetracarboxylic acid dianhydride as the repeating structural unit, from the viewpoint that the alkali solubility can be improved. Examples of such tetracarboxylic acid residues include R in the formula (1)¹¹⁵Examples of (3).

The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2000 to 500000, more preferably 5000 to 100000, and further preferably 10000 to 50000. The number average molecular weight (Mn) is preferably 800 to 250000, more preferably 2000 to 50000, and further preferably 4000 to 25000.

The dispersion degree of the polybenzoxazole precursor is preferably 1.5 to 2.5.

The content of the polymer precursor in the photosensitive resin composition of the present invention is preferably 20 to 100% by mass, more preferably 30 to 99% by mass, even more preferably 40 to 98% by mass, even more preferably 50 to 95% by mass, even more preferably 60 to 95% by mass, even more preferably 70 to 95% by mass, based on the total solid content of the composition.

The polymer precursor may contain only one kind, or may contain two or more kinds. When two or more are contained, the total amount is preferably within the above range.

< photo radical polymerization initiator >

The composition of the present invention contains a photo radical polymerization initiator.

The photo radical polymerization initiator that can be used in the present invention is not particularly limited, and can be appropriately selected from known photo radical polymerization initiators. For example, a photo radical polymerization initiator having photosensitivity to light from an ultraviolet region to a visible region is preferable. And may be an active agent that exerts some action with a photo-excited photosensitizer and generates active radicals.

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

When the composition of the present invention contains a photo-radical polymerization initiator, curing by radicals is generated by applying the composition of the present invention to a substrate such as a semiconductor wafer to form a photosensitive resin composition layer and then irradiating the photosensitive resin composition layer with light, and the solubility of a light irradiated portion can be reduced. Therefore, for example, there is an advantage that the regions having different solubilities can be easily produced according to the electrode pattern by exposing the photosensitive resin composition layer through a photomask having a pattern for shielding only the electrode portion.

As the photo radical polymerization initiator, known compounds can be arbitrarily used, and examples thereof include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, and the like), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbisimidazole, oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron arene complexes. For details of these, reference may be made to the descriptions in paragraphs 0165 to 0182 of japanese patent application laid-open No. 2016-027357, which are incorporated herein by reference.

Examples of the ketone compound include those described in paragraph 0087 of Japanese patent application laid-open No. 2015-087611, which are incorporated herein by reference. Among commercially available products, KAYACURE DETX (nippon kayaku co., ltd.) is also preferably used.

As the photo radical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be preferably used. More specifically, for example, an aminoacetophenone-based initiator described in Japanese patent laid-open No. 10-291969 and an acylphosphine oxide-based initiator described in Japanese patent No. 4225898 can be used.

As the hydroxyacetophenone-based initiator, IRGACURE184(IRGACURE, registered trademark), DAROCUR (DAROCUR, registered trademark) 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE127 (product names: manufactured by BASF Co., Ltd.) were used.

As the aminoacetophenone initiator, commercially available IRGACURE 907, IRGACURE369 and IRGACURE379 (trade name: manufactured by BASF) were used.

As the aminoacetophenone-based initiator, a compound described in Japanese patent laid-open publication No. 2009-191179, which has a maximum absorption wavelength matching a light source having a wavelength of 365nm or 405nm, can also be used.

Examples of the acylphosphine initiator include 2, 4, 6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, IRGACURE-819 or IRGACURE-TPO (trade name: manufactured by BASF) can be used as a commercially available product.

Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF corporation).

The photo radical polymerization initiator is more preferably an oxime compound. By using the oxime compound, the exposure latitude can be further effectively improved. The oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also functions as a photobase generator.

Specific examples of the oxime compound include compounds described in Japanese patent application laid-open Nos. 2001-233842, 2000-080068, and 2006-342166.

Preferred examples of the oxime compounds include compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.

[ chemical formula 21]

Among commercially available products, IRGACURE OXE 01, IRGACURE OXE02, IRGACURE OXE03, IRGACURE OXE 04 (manufactured by BASF Co., Ltd.), and ADEKA OPTOMER N-1919 (photo radical polymerization initiator 2 described in ADEKA CORPORATION, Japanese patent application laid-open No. 2012 and 014052) can also be preferably used. Also, TR-PBG-304 (manufactured by Changzhou powerful electronic New Material Co., Ltd.), ADEKAARKLS NCI-831 and ADEKAARKLS NCI-930 (manufactured by ADEKA CORPORATION) can be used. DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can be used.

Further, an oxime compound having a fluorine atom can also be used. Specific examples of these oxime compounds include the compounds described in Japanese patent application laid-open No. 2010-262028, the compounds 24, 36 to 40 described in section 0345 of Japanese patent application laid-open No. 2014-500852, and the compound (C-3) described in section 0101 of Japanese patent application laid-open No. 2013-164471.

Particularly preferred oxime compounds include those having a specific substituent as shown in Japanese patent laid-open Nos. 2007-269779 and 2009-191061.

From the viewpoint of exposure sensitivity, the photo radical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyldimethylketal compounds, α -hydroxyketone compounds, α -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadienyl-benzene-iron complexes and salts thereof, halomethyl oxadiazole compounds, and 3-aryl-substituted coumarin compounds.

Further preferred photo radical polymerization initiators are trihalomethyl triazine compounds, α -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, acetophenone compounds, further preferred are at least one compound selected from the group consisting of trihalomethyl triazine compounds, α -aminoketone compounds, oxime compounds, triarylimidazole dimers, benzophenone compounds, still further preferred are metallocene compounds or oxime compounds, still further preferred are oxime compounds.

Further, as the photo radical polymerization initiator, N ' -tetraalkyl-4, 4 ' -diaminobenzophenone such as benzophenone and N, N ' -tetramethyl-4, 4 ' -diaminobenzophenone (Michler's ketone)), aromatic ketones such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-acetone-1, benzophenones obtained by cyclizing an aromatic ring such as alkylanthraquinone, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkyl benzoin, and benzyl derivatives such as benzyl dimethyl ketal can be used. Further, a compound represented by the following formula (I) can also be used.

[ chemical formula 22]

In the formula (I), R⁵⁰Is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by 1 or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by 1 or more oxygen atoms, or a salt thereofAt least one substituted phenyl or biphenyl group of C1-4 alkyl group, R⁵¹Is a group represented by the formula (II) or with R⁵⁰Same radicals, R⁵²～R⁵⁴Each independently is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen.

[ chemical formula 23]

In the formula, R⁵⁵～R⁵⁷With R of the above formula (I)⁵²～R⁵⁴The same is true.

Further, as the photo radical polymerization initiator, a compound described in paragraphs 0048 to 0055 of International publication WO2015/125469 can be used.

The content of the photo radical polymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 1 to 15% by mass, and even more preferably 1 to 10% by mass, based on the total solid content of the composition of the present invention. The photo radical polymerization initiator may contain only one kind, or may contain two or more kinds. When two or more types of photo radical polymerization initiators are contained, the total amount thereof is preferably in the above range.

< thermal radical polymerization initiator >

The composition of the present invention may contain a thermal radical polymerization initiator within a range not departing from the gist of the present invention.

The thermal radical polymerization initiator is a compound that generates radicals by the energy of heat and initiates or accelerates the polymerization reaction of a compound having polymerizability. By adding the thermal radical polymerization initiator, cyclization of the polymer precursor can be performed, and the polymerization reaction of the polymer precursor can be performed, so that higher heat resistance can be achieved.

Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of Japanese patent application laid-open No. 2008-063554.

When the thermal radical polymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 5 to 15% by mass, based on the total solid content of the composition of the present invention. The thermal radical polymerization initiator may contain only one kind, or may contain two or more kinds. When two or more thermal radical polymerization initiators are contained, the total amount thereof is preferably in the above range.

< solvent >)

The composition of the present invention contains a solvent. The solvent may be any known solvent. 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 the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ -butyrolactone, ε -caprolactone, 6-valerolactone, alkyl alkoxyacetates (for example, methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (for example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxypropionate, etc.), Ethyl 3-ethoxypropionate, etc.)), alkyl esters of 2-alkoxypropionic acid (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl 2-oxobutyrate, etc, Ethyl 2-oxobutyrate, and the like.

Examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.

As the ketone, for example, preferred organic solvents include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like.

As the aromatic hydrocarbon, for example, preferable organic solvents include toluene, xylene, anisole, limonene and the like.

As the sulfoxide, for example, dimethyl sulfoxide is exemplified as a preferable organic solvent.

Examples of the amide include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-dimethylacetamide, and N, N-dimethylformamide as a preferable organic solvent.

In view of improvement of the coating surface shape, it is also preferable to mix two or more types of solvents. Among them, a mixed solution composed of two or more selected from the group consisting of methyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ -butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether and propylene glycol methyl ether acetate is preferable. Particularly preferably, dimethyl sulfoxide and gamma-butyrolactone are used simultaneously.

The content of the solvent is preferably an amount such that the total solid content concentration of the composition of the present invention is 5 to 80% by mass, more preferably an amount such that the total solid content concentration of the composition of the present invention is 5 to 70% by mass, and particularly preferably an amount such that the total solid content concentration of the composition of the present invention is 10 to 60% by mass, from the viewpoint of coatability. The content of the solvent may be adjusted depending on the desired thickness and coating method.

The solvent may contain only one kind, or may contain two or more kinds. When two or more solvents are contained, the total amount thereof is preferably in the above range.

< radically polymerizable Compound >

The composition of the present invention preferably contains a radical polymerizable compound (hereinafter referred to as "polymerizable monomer") other than the polymer precursor. With such a configuration, a cured film having excellent heat resistance can be formed.

As the polymerizable monomer, a compound having a radical polymerizable group can be used. Examples of the radical polymerizable group include groups having an ethylenically unsaturated bond such as a styryl group, a vinyl group, a (meth) acryloyl group, and an allyl group. The radical polymerizable group is preferably a (meth) acryloyl group.

The number of the radical polymerizable groups of the polymerizable monomer may be one or two or more, but the polymerizable monomer preferably has two or more radical polymerizable groups, and more preferably has 3 or more radical polymerizable groups. The upper limit is preferably 15 or less, more preferably 10 or less, and further preferably 8 or less.

The molecular weight of the polymerizable monomer is preferably 2000 or less, more preferably 1500 or less, and further preferably 900 or less. The lower limit of the molecular weight of the polymerizable monomer is preferably 100 or more.

From the viewpoint of developability, the composition of the present invention preferably contains at least one 2-or more-functional polymerizable monomer containing two or more polymerizable groups, and more preferably contains at least one 3-or more-functional polymerizable monomer. Further, a mixture of a 2-functional polymerizable monomer and a polymerizable monomer having 3 or more functions may be used. The number of functional groups of the polymerizable monomer is the number of radical polymerizable groups in 1 molecule.

Specific examples of the polymerizable compound include an unsaturated carboxylic acid (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters and amides thereof, and preferably an ester of an unsaturated carboxylic acid and a polyol compound and an amide of an unsaturated carboxylic acid and a polyamine compound. Further, addition reaction products of unsaturated carboxylic acid esters or amides having an affinity substituent such as a hydroxyl group, an amino group, or a mercapto group with monofunctional or polyfunctional isocyanates or epoxies, dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, and the like can also be preferably used. Further, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituent groups such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having releasable substituent groups such as halogen groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are also preferable. As another example, instead of the unsaturated carboxylic acid, a compound group substituted with an unsaturated phosphonic acid, a vinyl benzene derivative such as styrene, a vinyl ether, an allyl ether, or the like can be used. As a specific example, reference can be made to the descriptions in paragraphs 0113 to 0122 of Japanese patent laid-open No. 2016-027357, which are incorporated herein by reference.

Further, a compound in which the polymerizable monomer has a boiling point of 100 ℃ or higher under normal pressure is also preferable. Examples thereof include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tris (acryloyloxyethyl) isocyanurate, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylating the resulting mixture, JP-B-48-041708, JP-B-50-006034, carbamates of (meth) acrylic acid disclosed in JP-B-51-037193, esters of (meth) acrylic acid, and mixtures thereof, The polyester acrylates described in JP-A-48-064183, JP-A-49-043191 and JP-A-52-030490, and the polyfunctional acrylates or methacrylates such as epoxy acrylates as a reaction product of an epoxy resin and (meth) acrylic acid, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of Japanese patent laid-open No. 2008-292970 are also preferable. Further, there can be mentioned a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group and an ethylenically unsaturated group such as glycidyl (meth) acrylate.

Further, as another preferable polymerizable monomer, a compound having a fluorene ring and having 2 or more ethylenically unsaturated bond-containing groups or a cardo (cardo) resin described in japanese patent application laid-open nos. 2010-160418, 2010-129825, 4364216, and the like can be used.

Further, as other examples, specific unsaturated compounds described in Japanese patent publication No. 46-043946, Japanese patent publication No. 1-040337, and Japanese patent publication No. 1-040336, vinylphosphonic acid-based compounds described in Japanese patent publication No. 2-025493, and the like can be cited. Furthermore, a compound containing a perfluoroalkyl group as described in Japanese patent application laid-open No. 61-022048 can also be used. Further, compounds described as photocurable monomers and oligomers in the Journal of the additive Society of Japan, vol.20, No.7, pages 300 to 308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese patent application laid-open No. 2015-034964 can be preferably used, and these contents are incorporated in the present specification.

Further, compounds described as the formula (1) and the formula (2) in jp-a-10-062986 and specific examples thereof, which are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylating, can also be used as the polymerizable monomer.

Further, it is also possible to use the compounds described in paragraphs 0104 to 0131 of Japanese patent application laid-open No. 2015-187211 as the polymerizable monomers, and these contents are incorporated in the present specification.

As the polymerizable monomer, dipentaerythritol triacrylate (KaYARAD-330; Nippon Kayaku Co., manufactured by Ltd. as a commercially available product), dipentaerythritol tetraacrylate (KaYARAD-320; Nippon Kayaku Co., manufactured by Ltd. as a commercially available product, A-TMMT: Shin-Nakamura Chemical Co., manufactured by Ltd.), dipentaerythritol penta (meth) acrylate (KaYARAD-310; Nippon Kayaku Co., manufactured by Ltd. as a commercially available product), dipentaerythritol hexa (meth) acrylate (KAYARAD DPHA; Nippon Kayaku Co., manufactured by Ltd. as a commercially available product, A-DPH; Shin-Nakamura Chemical Co., manufactured by Ltd. as a commercially available product) and a structure in which these (meth) acryloyl groups are bonded via ethylene glycol residues and propylene glycol residues are preferable. These oligomer types can also be used.

Commercially available products of polymerizable monomers include, for example, SR-494 which is a 4-functional acrylate having 4 ethylene oxide chains manufactured by Sartomer Company, Inc, SR-209 manufactured by Sartomer Company, Inc, DPCA-60 which is a 6-functional acrylate having 6 ethylene oxide chains manufactured by Ltd, TPA-330 which is a 3-functional acrylate having 3 isobutoxy chains, NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200(Shin-Nakamura Co., Ltd.), DPHA-40H (Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (Shateal Co., Ltd., shya, Ltd.), ltd, manufactured), BLEMMER PME400 (manufactured by NOF corporation), and the like.

As the polymerizable monomer, urethane acrylates such as those disclosed in JP-B-48-041708, JP-A-51-037193, JP-B-2-032293 and JP-B-2-016765, and urethane compounds having an ethylene oxide skeleton such as those disclosed in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417 and JP-B-62-039418 are preferable. Further, as the polymerizable monomer, compounds having an amino group structure or a sulfide structure in the molecule as described in Japanese patent application laid-open Nos. 63-277653, 63-260909 and 1-105238 can be used.

The polymerizable monomer may be a polymerizable monomer having an acid group such as a carboxyl group, a sulfo group, or a phosphoric acid group. Among the polymerizable monomers having an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a polymerizable monomer having an acid group by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride is more preferable. In particular, among the polymerizable monomers having an acid group by reacting an unreacted hydroxyl group of an aliphatic polyhydric compound with a non-aromatic carboxylic acid anhydride, the aliphatic polyhydric compound is preferably a compound of pentaerythritol and/or dipentaerythritol. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by TOAGOSEICO., Ltd.

The polymerizable monomer having an acid group may be used alone or in combination of two or more. If necessary, a polymerizable monomer having no acid group and a polymerizable monomer having an acid group may be used together.

The acid value of the polymerizable monomer having an acid group is preferably 0.1 to 40mgKOH/g, and particularly preferably 5 to 30 mgKOH/g. When the acid value of the polymerizable monomer is within the above range, the production and handling properties are excellent, and the developability is excellent. Further, the polymerizability is good.

From the viewpoint of good polymerizability and heat resistance, the content of the polymerizable monomer is preferably 1 to 50% by mass relative to the total solid content of the composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 30% by mass or less. The polymerizable monomer may be used alone or in combination of two or more.

The mass ratio of the polymer precursor to the polymerizable monomer (polymer precursor/polymerizable monomer) is preferably 98/2 to 10/90, more preferably 95/5 to 30/70, and still more preferably 90/10 to 50/50. When the mass ratio of the polymer precursor to the polymerizable monomer is within the above range, a cured film having further excellent polymerizability and heat resistance can be formed.

The composition of the present invention can preferably use a monofunctional polymerizable monomer from the viewpoint of suppressing warpage due to control of the modulus of elasticity of the cured film. As the monofunctional polymerizable monomer, N-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, (meth) acrylic acid derivatives such as glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allyl glycidyl ether, diallyl phthalate and triallyl trimellitate. The monofunctional polymerizable monomer is preferably a compound having a boiling point of 100 ℃ or higher under normal pressure in order to suppress volatilization before exposure.

< other polymerizable Compound >

The composition of the present invention may further contain other polymerizable compounds than the above-mentioned polymer precursor and radical polymerizable compound. Examples of the other polymerizable compound include compounds having a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl group; an epoxy compound; an oxetane compound; a benzoxazine compound.

(Compound having hydroxymethyl group, alkoxymethyl group or acyloxymethyl group)

As the compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, a compound represented by the following formula (AM1) is preferable.

[ chemical formula 24]

(wherein t represents an integer of 1 to 20, R⁴Represents a t-valent organic group having 1 to 200 carbon atoms, R⁵Is represented by-OR⁶or-OCO-R⁷A group represented by R⁶R represents a hydrogen atom or an organic group having 1 to 10 carbon atoms⁷Represents an organic group having 1 to 10 carbon atoms. )

The content of the compound represented by the formula (AM1) is preferably 5 to 40 parts by mass with respect to 100 parts by mass of the polymer precursor. More preferably 10 to 35 parts by mass. The total amount of the other polymerizable compounds is 10 to 90% by mass of the compound represented by the following formula (AM4), and preferably 10 to 90% by mass of the compound represented by the following formula (AM 5).

[ chemical formula 25]

(in the formula, R⁴Represents a 2-valent organic group having 1 to 200 carbon atoms, R⁵Is represented by-OR⁶or-OCO-R⁷A group represented by R⁶R represents a hydrogen atom or an organic group having 1 to 10 carbon atoms⁷Represents an organic group having 1 to 10 carbon atoms. )

[ chemical formula 26]

(wherein u represents an integer of 3 to 8, R⁴Represents a u-valent organic group having 1 to 200 carbon atoms, R⁵Is represented by-OR⁶or-OCO-R⁷A group represented by R⁶R represents a hydrogen atom or an organic group having 1 to 10 carbon atoms⁷Represents an organic group having 1 to 10 carbon atoms. )

By using the compound having a methylol group or the like, the occurrence of cracks can be more effectively suppressed when the composition of the present invention is applied to a substrate having irregularities. Further, a cured film having excellent pattern processability and high heat resistance, in which the temperature at which the mass loss is 5% is 350 ℃ or higher, more preferably 380 ℃ or higher, can be formed. Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (trade name: ASAHI YUKIZAI CORPORATION), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylBISOC-P, DML-PFP, DML-PSBP, DML-MTry PC (trade name: Honshu Chemical Industry Co., manufactured by Ltdy.), NIKALAC MX-290 (trade name: Sanwa Chemical Co., manufactured by Ltd.), 2, 6-dimethylymethyl-4-t-butylmethylphenol (2, 6-dimethoxymethyl-4-t-butylphenol), 2, 6-dimethylymethyl-4-dimethoxycresol (2, 6-dimethoxymethyl-4-t-butylphenol), 2, 6-dimethylymethyl-cresol (2, 6-dimethoxymethyl-2-cresol (2, 6-dimethylymethyl-cresol), 6-diacetoxymethyl-p-cresol), and the like.

Specific examples of the compound represented by the formulｃA (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by ASAHIYUKIZAI CORATION), NIKALAMX-280, NIKALAC MX-270, and NIKALAC MW-100LM (trade name, manufactured by SanwｃA Chemical Co., Ltd.).

(epoxy Compound (Compound having epoxy group))

As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferable. The epoxy group undergoes a crosslinking reaction at 200 ℃ or less, and it is difficult to cause film shrinkage since a dehydration reaction derived from crosslinking is not caused. Therefore, by containing the epoxy compound, low-temperature curing of the composition and warpage of the cured film can be effectively suppressed.

The epoxy compound preferably contains a polyethylene oxide group. This further reduces the elastic modulus and suppresses warpage. The polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and preferably 2 to 15.

Examples of the epoxy compound include, but are not limited to, bisphenol a type epoxy resins, bisphenol F type epoxy resins, alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether, polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether, epoxy group-containing silicones such as polymethyl (glycidoxypropyl) siloxane, and the like. Specifically, EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4850-150, EPICLON (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822 (trade names, DICON) RIKARESIN (registered trademark) BEO-60E (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822 (trade names, DIC-S, EP, NEICLON (registered trademark) EXA-40052, EPICLON, manufactured by ADEKA CORPORATION), and the like. Among them, an epoxy resin containing a polyethylene oxide group is preferable in terms of suppressing warpage and excellent heat resistance. For example, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, and RIKARESIN (registered trademark) BEO-60E contain a polyethylene oxide group, and are therefore preferable.

The content of the epoxy compound is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and still more preferably 10 to 40 parts by mass, based on 100 parts by mass of the heterocycle-containing polymer precursor. The content of the epoxy compound is 5 parts by mass or more, whereby warpage of the obtained cured film can be suppressed, and 50 parts by mass or less, whereby pattern embedding due to reflow during curing can be further suppressed.

(Oxetane Compound (Compound having an Oxetanyl group))

Examples of the oxetane compound include a compound having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxyoxetane, 1, 4-bis { [ (3-ethyl-3-oxetanyl) methoxy ] methyl } benzene, 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1, 4-benzenedicarboxylic acid-bis [ (3-ethyl-3-oxetanyl) methyl ] ester, and the like. As a specific example, TOAGOSEI co, a series of ARON oxoetane (for example, OXT-121, OXT-221, OXT-191, and OXT-223) made by ltd can be preferably used, and these may be used alone or two or more kinds may be used in combination.

The content of the oxetane compound is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and still more preferably 10 to 40 parts by mass, based on 100 parts by mass of the polymer precursor.

(benzoxazine Compound (Compound having polybenzoxazole group))

The benzoxazine compound is preferable because the crosslinking reaction due to the ring-opening addition reaction does not generate degassing during curing, and further, the heat shrinkage is reduced to suppress the generation of warpage.

Preferable examples of the benzoxazine compound include B-a type benzoxazine, B-m type benzoxazine (hereinafter, trade name: Shikoku Chemicals Corporation), a benzoxazine adduct of polyhydroxystyrene resin, and a novolak type dihydrobenzoxazine compound. These may be used alone or two or more kinds may be mixed.

The content of the benzoxazine compound is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and still more preferably 10 to 40 parts by mass, based on 100 parts by mass of the polymer precursor.

< migration inhibitor >)

The photosensitive resin composition preferably further comprises a migration inhibitor. By including the migration inhibitor, it is possible to effectively inhibit the metal ions originating from the metal layer (metal wiring) from migrating into the photosensitive resin composition layer.

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

Further, an ion scavenger that scavenges anions such as halogen ions can also be used.

As other migration inhibitors, there can be used rust inhibitors described in paragraph 0094 of Japanese patent application laid-open No. 2013-015701, compounds described in paragraphs 0073-0076 of Japanese patent application laid-open No. 2009-283711, compounds described in paragraph 0052 of Japanese patent application laid-open No. 2011-059656, compounds described in paragraphs 0114, 0116 and 0118 of Japanese patent application laid-open No. 2012-194520, and the like.

Specific examples of the migration inhibitor include the following compounds.

[ chemical formula 27]

When the photosensitive resin composition contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and still more preferably 0.1 to 1.0% by mass, based on the total solid content of the photosensitive resin composition.

The migration inhibitor may be one kind only, or two or more kinds. When the number of migration inhibitors is two or more, the total amount thereof is preferably within the above range.

< polymerization inhibitor >)

The compositions of the invention preferably contain a polymerization inhibitor.

As the polymerization inhibitor, for example, hydroquinone, 1, 4-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, p-t-butylcatechol, 1, 4-benzoquinone, diphenyl-p-benzoquinone, 4 '-thiobis (3-methyl-6-t-butylphenol), 2' -methylenebis (4-methyl-6-t-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1, 2-cyclohexanediaminetetraacetic acid, glycoletherdiamine tetraacetic acid, 2, 6-di-t-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, and the like can be preferably used, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxylamine ammonium salt, bis (4-hydroxy-3, 5-tert-butyl) phenylmethane and the like. Further, the polymerization inhibitor described in paragraph 0060 of Japanese patent laid-open publication No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International publication WO2015/125469 can also be used.

The following compound (Me is methyl) can be used.

[ chemical formula 28]

When the composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass relative to the total solid content of the composition of the present invention.

The polymerization inhibitor may be used alone or in combination of two or more. When the polymerization inhibitor is two or more, the total amount thereof is preferably in the above range.

< Metal adhesion improver >)

The composition of the present invention preferably contains a metal adhesion improving agent for improving adhesion to a metal material used for an electrode, a wiring, or the like. Examples of the metal adhesion improver include a silane coupling agent.

Examples of the silane coupling agent include compounds described in paragraphs 0062 to 0073 of Japanese patent application laid-open No. 2014-191002, compounds described in paragraphs 0063 to 0071 of International publication No. WO201I/080992A1, compounds described in paragraphs 0060 to 0061 of Japanese patent application laid-open No. 2014-191252, compounds described in paragraphs 0045 to 0052 of Japanese patent application laid-open No. 2014-041264, and compounds described in paragraphs 0055 of International publication No. WO 2014/097594. Further, it is preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of Japanese patent application laid-open No. 2011-128358. Further, the following compounds are preferably used as the silane coupling agent. In the following formula, Et represents an ethyl group.

[ chemical formula 29]

The metal adhesion improver can also be a compound described in paragraphs 0046 to 0049 of Japanese patent application laid-open No. 2014-186186 or a sulfide described in paragraphs 0032 to 0043 of Japanese patent application laid-open No. 2013-072935.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, and more preferably 0.5 to 15 parts by mass, based on 100 parts by mass of the polymer precursor. When the amount is 0.1 parts by mass or more, the adhesion between the cured film and the metal layer after the curing step is good, and when the amount is 30 parts by mass or less, the heat resistance and mechanical properties of the cured film after the curing step are good. The metal adhesion improver may be one kind only, or two or more kinds. When two or more kinds are used, the total amount thereof is preferably in the above range.

< agent for generating alkali >)

The composition used in the present invention may contain an alkali generating agent. The alkali generating agent can be a thermal alkali generating agent or a photoalkali generating agent.

[ thermal alkali-producing agent ]

The kind of the thermal alkali generator is not particularly limited, and preferably the thermal alkali generator contains at least one selected from an acidic compound generating an alkali when heated to 40 ℃ or higher, and an ammonium salt having an anion having a pKa1 of 0 to 4 and an ammonium cation. Wherein pKa1 represents the logarithmic sign (-Log) of the dissociation constant (Ka) of the first proton of the polyacid₁₀Ka)。

By blending these compounds, the cyclization reaction of the polymer precursor can be performed at a low temperature, and a composition having further excellent stability can be obtained. Further, since the thermal alkali generator does not generate an alkali unless heated, the thermal alkali generator can suppress cyclization of the polymer precursor during storage even in the presence of the polymer precursor, and has excellent storage stability.

The thermal alkali generator of the present invention comprises at least one selected from the group consisting of an acidic compound (A1) which generates an alkali when heated to 40 ℃ or higher, and an ammonium salt (A2) having an anion with a pKa1 of 0 to 4 and an ammonium cation.

Since the acidic compound (a1) and the ammonium salt (a2) generate a base upon heating, the base generated from these compounds can promote the cyclization reaction of the polymer precursor and can cause the cyclization of the polymer precursor at a low temperature. Further, even if these compounds coexist with a polymer precursor cyclized and cured by an alkali, since the cyclization of the polymer precursor hardly proceeds unless heated, a photosensitive resin composition having excellent stability can be produced.

In the present specification, the term "acidic compound" means that 1g of the compound is collected in a container, and 50mL of a mixed solution of ion-exchanged water and tetrahydrofuran (water/tetrahydrofuran: 1/4 by mass) is added thereto. Stirred at room temperature for 1 hour. A compound having a value of less than 7 as measured on the solution at 20 ℃ with a pH meter.

In the present invention, the alkali generation temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40 ℃ or higher, and more preferably 120 to 200 ℃. The upper limit of the alkali generation temperature is preferably 190 ℃ or lower, more preferably 180 ℃ or lower, and still more preferably 165 ℃ or lower. The lower limit of the alkali generation temperature is preferably 130 ℃ or more, more preferably 135 ℃ or more.

Since the alkali generation temperature of the acidic compound (a1) and the ammonium salt (a2) is 120 ℃ or higher, the alkali is not easily generated during storage, and thus a photosensitive resin composition having excellent stability can be prepared. When the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 200 ℃ or lower, the cyclization temperature of the polymer precursor and the like can be lowered. The alkali generation temperature can be measured, for example, by heating the compound to 250 ℃ at 5 ℃/min in a pressure-resistant capsule using a differential scanning calorimeter, reading the peak temperature of the lowest-temperature exothermic peak, and determining the peak temperature as the alkali generation temperature.

In the present invention, the base generated by the thermal base generator is preferably a secondary amine or a tertiary amine, and more preferably a tertiary amine. The tertiary amine is highly basic, and therefore can lower the cyclization temperature of the polymer precursor. The boiling point of the alkali generated by the thermal alkali generator is preferably 80 ℃ or higher, more preferably 100 ℃ or higher, and still more preferably 140 ℃ or higher. The molecular weight of the base is preferably 80 to 2000. The lower limit is preferably 100 or more. The upper limit is preferably 500 or less. The value of the molecular weight is a theoretical value determined from the structural formula.

In the present invention, the acidic compound (a1) preferably contains at least one selected from an ammonium salt and a compound represented by formula (101) or (102) described later.

In the present invention, the ammonium salt (a2) is preferably an acidic compound. The ammonium salt (A2) may be a compound containing an acidic compound which generates a base when heated to 40 ℃ or higher (preferably 120 to 200 ℃), or may be a compound other than an acidic compound which generates a base when heated to 40 ℃ or higher (preferably 120 to 200 ℃).

< ammonium salt > >)

In the present invention, the ammonium salt is a salt of an ammonium cation represented by the following formula (101) or formula (102) and an anion. The anion may be bonded to any portion of the ammonium cation by a covalent bond and may be present outside the molecule of the ammonium cation, but is preferably present outside the molecule of the ammonium cation. The presence of an anion outside the molecule of the ammonium cation means that the ammonium cation and the anion are not bonded to each other by a covalent bond. Hereinafter, the intermolecular anion of the cation portion is also referred to as an anion.

Formula (101) formula (102)

[ chemical formula 30]

In the formula R¹～R⁶Each independently represents a hydrogen atom or a hydrocarbon group, R⁷Represents a hydrocarbon group. R¹And R²、R³And R⁴、R⁵And R⁶、R⁵And R⁷May be bonded to form a ring.

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

[ chemical formula 31]

In the formulae (Y1-1) to (Y1-5), R¹⁰¹Represents an n-valent organic group, R¹And R⁷Is defined with R in formula (101) or formula (102)¹And R⁷The same is true. n represents an integer of 1 or more, and m represents an integer of 0 to 5.

In the formula (Y1-4), Ar¹⁰¹And Ar¹⁰²Each independently represents an aryl group.

In the present embodiment, the ammonium salt is preferably an anion having a pKa1 of 0 to 4 and an ammonium cation. 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 more preferably 0.5 or more, and still more preferably 1.0 or more. When the pKa1 of the anion is within the above range, the polymer precursor or the like can be cyclized at a lower temperature, and the stability of the composition can be improved. When pKa1 is 4 or less, the thermal alkali generator has good stability, and the composition has good stability by suppressing generation of alkali without heating. When pKal is 0 or more, the generated base is not easily neutralized, and the cyclization efficiency of the polymer precursor or the like is good.

The kind of anion is preferably one selected from the group consisting of a carboxylic acid anion, a phenol anion, a phosphoric acid anion and a sulfuric acid anion, and a carboxylic acid anion is preferable from the viewpoint of compatibility between the stability of the salt and the thermal decomposability. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylic acid anion.

The carboxylic acid anion is preferably an anion of a 2-valent or higher carboxylic acid having 2 or more carboxyl groups, and more preferably an anion of a 2-valent carboxylic acid. According to this aspect, a thermal alkali generator can be provided which can further improve the stability, curability, and developability of the composition. In particular, the use of an anion of a 2-valent carboxylic acid can further improve the stability, curability, and developability of the composition.

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

The pKa1 represents the logarithm of the reciprocal of the dissociation constant of the first proton of the acid and can be referred to the values described in Determination of Organic Structures by Physical Methods (authors: Brown, H.C., McDaniel, D.H., Hafliger, O.A., Nachod, F.C.; editions: Braude, E.A., Nachod, F.C.; academic Press, New York, 1955), Data for Biochemical Research (authors: Dawson, R.M.C.et al; Oxford, Clarendon Press, 1959). As for the compounds not described in these documents, values calculated from the structural formulae using software of ACD/pKa (manufactured by ACD/Labs) were used.

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

[ chemical formula 32]

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

In this embodiment, the electron-withdrawing group means that the hammett substituent constant σ m represents a positive value. Among them, σ m is described in detail in general, Journal of Synthetic Organic Chemistry, Japan, Vol.23, No. 8 (1965), p.631-642. The electron-withdrawing group in the present embodiment is not limited to the substituents described in the above documents.

Examples of the substituent in which σ m represents a positive value include CF₃Base (. sigma.m.0.43), CF₃CO group (σ m ═ 0.63), HC ≡ C group (σ m ≡ 0.21), CH group₂CH (σ m) group 0.06, Ac (σ m) group 0.38, MeOCO (σ m) group 0.37, MeCOCH (σ m) CH group 0.21, PhCO (σ m) group 0.34, H2NCOCH₂And a group (σ m ═ 0.06). Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (hereinafter, the same applies).

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

[ chemical formula 33]

In the formulae (EWG-1) to (EWG-6), R^x1～R^x3Each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group or a carboxyl group, and Ar represents an aromatic group.

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

Formula (XA)

[ chemical formula 34]

In the formula (XA), L¹⁰Represents a single bond or is selected from alkylene, alkyleneAlkenyl, aromatic radical, -NR^XAnd 2-valent linking groups in these combinations, R^XRepresents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group.

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

The thermal alkali generator can be described in paragraphs 0021 to 0077 of Japanese patent application laid-open No. 2016-027357, and the contents thereof are incorporated herein.

Examples of the thermal alkali generator include the following compounds.

[ chemical formula 35]

[ chemical formula 36]

[ chemical formula 37]

[ chemical formula 38]

When the thermal alkali generator is used, the content of the thermal alkali generator in the composition is preferably 0.1 to 50% by mass based on the total solid content of the composition. The lower limit is more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less.

One or more than two kinds of the thermal alkali-producing agents can be used. When two or more are used, the total amount is preferably in the above range.

[ photobase generator > ]

The photosensitive resin composition used in the present invention may contain a photobase generator. The photobase generator generates a base by exposure and does not exhibit activity under normal temperature and pressure conditions, but is not particularly limited as long as it generates a base (basic substance) when electromagnetic waves are irradiated and heated as an external stimulus. The base generated by exposure acts as a catalyst when the polymer precursor is cured by heating, and therefore can be preferably used for the negative type.

In the present invention, a known photobase generator can be used. For example, as m.shirai, and m.tsunooka, prog.polym.sci., 21, 1 (1996); jiaokang Zhenghong, polymer processing, 46, 2 (1997); c.kutal, coord.chem.rev., 211, 353 (2001); y.kaneko, a.sarker, and d.neckers, chem.mater., 11, 170 (1999); h.tachi, m.shirai, and m.tsunooka, j.photopolym.sci.technol., 13, 153 (2000); m.winkle, and k.graziano, j.photopolym.sci.technol., 3, 419 (1990); m.tsunooka, h.tachi, and s.yoshitaka, j.phopolym.sci.technol., 9, 13 (1996); examples of the alkali component include transition metal compound complexes, compounds having a structure such as ammonium salts, ionic compounds in which an amidino moiety is latent by forming a carboxylic acid or a salt, and nonionic compounds in which an alkali component is latent by forming a salt, urethane bonds or oxime bonds, such as urethane derivatives, oxime ester derivatives, and acyl compounds, as described in k.suyama, h.araki, m.shirai, j.photopolym.sci.technol., 19, 81 (2006).

The basic substance generated by the photobase generator is not particularly limited, and examples thereof include compounds having an amino group, and in particular, polyamines such as monoamines and diamines, amidines, and the like.

The generated basic substance is preferably a compound having an amino group with higher basicity. The reason for this is that the polymer precursor has a strong catalytic action on the dehydration condensation reaction or the like in the imidization, and the catalyst effect in the dehydration condensation reaction or the like at a lower temperature can be exhibited with a smaller amount of addition. That is, since the catalytic effect of the generated alkali substance is large, the sensitivity of the appearance as a negative photosensitive resin composition is improved.

From the viewpoint of the catalytic effect, amidines and aliphatic amines are preferable.

The photobase generator used in the present invention is preferably a compound containing an aromatic ring and generating a basic substance having an amino group.

Examples of the photobase generator according to the present invention include photobase generators having a cinnamamide structure as disclosed in japanese patent laid-open publication No. 2009-080452 and international publication No. 2009/123122, photobase generators having a carbamate structure as disclosed in japanese patent laid-open publication nos. 2006-189591 and 2008-247747, and photobase generators having an oxime structure or a carbamoyl oxime structure as disclosed in japanese patent laid-open publication nos. 2007-249013 and 2008-003581, but the photobase generators are not limited thereto, and in addition, photobase generators having a known structure may be used.

Examples of the photobase generator include compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 of Japanese patent laid-open No. 2012 and 093746, compounds described in paragraphs 0022 to 0069 of Japanese patent laid-open No. 2013 and 194205, compounds described in paragraphs 0026 to 0074 of Japanese patent laid-open No. 2013 and 204019, and compounds described in paragraph 0052 of International publication No. WO 2010/064631.

As commercially available photobase generators, it is also possible to use WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-027, PBG-018, WPGB-015, WPBG-041, WPGB-172, WPGB-174, WPBG-166, WPGB-158, WPGB-025, WPGB-168, WPGB-167 and WPBG-082 (manufactured by Wako Pure Chemical Industries, Ltd.).

Further, the following compounds can be exemplified as the photobase generator.

[ chemical formula 39]

When a photobase generator is used, the content of the photobase generator in the resin composition of the present invention is preferably 0.1 to 50% by mass based on the total solid content of the composition. The lower limit is more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less.

The photobase generator can be used alone or in combination of two or more. When two or more are used, the total amount is preferably within the above range.

< other additives >

The composition of the present invention can contain, as necessary, various additives, for example, a thermal acid generator, a sensitizing dye, a chain transfer agent, a surfactant, a higher fatty acid derivative, inorganic particles, a curing agent, a curing catalyst, a filler, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, and the like, as long as the effects of the present invention are not impaired. When these additives are blended, the total blending amount thereof is preferably 3% by mass or less of the solid content of the composition.

< thermal acid Generator > >)

The compositions of the present invention may contain a thermal acid generator. The thermal acid generator generates an acid by heating, and promotes cyclization of the polymer precursor to further improve mechanical properties of the cured film. As the thermal acid generator, compounds described in paragraph 0059 of Japanese patent laid-open publication No. 2013-167742, and the like can be mentioned.

The content of the thermal acid generator is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more, per 100 parts by mass of the polymer precursor. The inclusion of 0.01 parts by mass or more of the thermal acid generator promotes the crosslinking reaction and the cyclization of the polymer precursor, and therefore the mechanical properties and chemical resistance of the cured film can be further improved. 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, from the viewpoint of electrical insulation of the cured film.

The thermal acid generator may be used alone or in combination of two or more. When two or more are used, the total amount is preferably within the above range.

< sensitizing dye > >)

The compositions of the present invention may contain sensitizing dyes. The sensitizing dye absorbs a specific active radiation to become an electron excited state. The sensitizing dye in an electron excited state is brought into contact with a thermal alkali generator, a thermal radical polymerization initiator, a radical polymerization initiator, or the like to generate an action such as electron transfer, energy transfer, heat generation, or the like. Thereby, the thermal alkali generator, the thermal radical polymerization initiator, and the radical polymerization initiator are chemically changed and decomposed to generate radicals, acids, or bases. For details of the sensitizing dye, reference can be made to the descriptions in paragraphs 0161 to 0163 of Japanese patent application laid-open No. 2016-027357, which is incorporated herein by reference.

When the 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 still more preferably 0.5 to 10% by mass, based on the total solid content of the composition of the present invention. The sensitizing dye can be used singly or in combination of two or more.

< chain transfer agent > > > <

The composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in page 683-684 of The third edition of The Polymer dictionary (The Society of Polymer Science, Japan, 2005). Examples of the chain transfer agent include compounds having SH, PH, SiH, and GeH in the molecule. These radicals can be generated by supplying hydrogen to a low-activity radical to generate a radical, or by deprotonation after oxidation. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptopolybenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, and the like) can be preferably used.

When the composition of the present invention contains 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, and still more preferably 1 to 5 parts by mass, per 100 parts by mass of the total solid content of the composition of the present invention. The chain transfer agent may be one kind or two or more kinds. When the chain transfer agent is two or more, the total range thereof is preferably within the above range.

< surfactant > >)

Various surfactants may be added to the composition of the present invention in order to further improve coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. Further, the following surfactants are also preferable.

[ chemical formula 40]

When the composition of the present invention has a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, relative to the total solid content of the composition of the present invention. The surfactant may be one kind only, or two or more kinds. When the number of the surfactants is two or more, the total range is preferably within the above range.

< higher fatty acid derivative > >)

In order to prevent inhibition of polymerization by oxygen, a higher fatty acid derivative such as behenic acid or behenamide may be added to the composition of the present invention so as to be biased toward the surface of the composition during drying after coating.

When the composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass based on the total solid content of the composition of the present invention. The higher fatty acid derivative may be one kind or two or more kinds. When the number of the higher fatty acid derivatives is two or more, the total range thereof is preferably within the above range.

< restrictions concerning other contained substances >)

From the viewpoint of coating surface shape, the moisture content of the 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.

The metal content of the composition of the present invention is preferably less than 5 mass ppm (part per million), more preferably less than 1 mass ppm, and particularly preferably less than 0.5 mass ppm, from the viewpoint of insulation properties. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, and nickel. When a plurality of metals are contained, the total of these metals is preferably in the above range.

As a method for reducing metal impurities unexpectedly contained in the composition of the present invention, there can be mentioned a method in which a raw material having a small metal content is selected as a raw material constituting the composition of the present invention, the raw material constituting the composition of the present invention is subjected to filter filtration, and the inside of the apparatus is lined with polytetrafluoroethylene to distill under conditions in which contamination is suppressed as much as possible.

From the viewpoint of corrosion of wiring, the content of the halogen atom in the composition of the present invention is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and particularly preferably less than 200 mass ppm. Among these, the halogen atom present in the state of a halogen ion is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and still more preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. The total of chlorine atoms and bromine atoms or chlorine ions and bromine ions is preferably in the above-mentioned range.

As the container for the composition of the present invention, a conventionally known container can be used. Further, as the container, for the purpose of suppressing the contamination of impurities into the raw material or the composition, it is also preferable to use a multilayer bottle in which the inner wall of the container is composed of 6 kinds of 6-layer resins or a bottle in which 6 kinds of resins are formed into a 7-layer structure. Examples of such a container include those described in Japanese patent laid-open publication No. 2015-123351.

< preparation of composition >)

The composition of the present invention can be prepared by mixing the above-mentioned respective components. The mixing method is not particularly limited, and can be performed by a conventionally known method.

For the purpose of removing foreign matter such as dust and fine particles in the composition, it is preferable to mix the components and then perform filtration using a filter. The pore diameter of the filter is preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be one previously washed with an organic solvent. In the filtration step of the filter, a plurality of filters may be used in parallel or in series. When a plurality of filters are used, filters having different pore sizes and/or different materials may be used in combination. Also, various materials may be filtered multiple times. When the filtration is performed a plurality of times, it may be a circulation filtration. Also, filtration may be performed after pressurization. When the filtration is performed after the pressurization, the pressure for the pressurization is preferably 0.05MPa or more and 0.3MPa or less.

In addition to filtration using a filter, an impurity removal treatment using an adsorbent may be performed. It is also possible to combine filter filtration and impurity removal treatment using an adsorption material. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

< cured film, laminate, semiconductor device, method for producing cured film, and method for producing laminate >

Next, the cured film, the laminate, the semiconductor device, the method for producing the cured film, and the method for producing the laminate of the present invention will be described.

The cured film of the present invention is formed from the composition of the present invention. The thickness of the cured film of the present invention can be set to, for example, 0.5 μm or more and 1 μm or more. The upper limit value may be 100 μm or less, and may be 30 μm or less.

A laminate having 2 or more layers of the cured film of the present invention may be used. The laminate having 2 or more cured films of the present invention is preferably a laminate having a metal layer between the cured films. Such a metal layer can be preferably used as a metal wiring such as a rewiring layer.

Examples of the field to which the cured film of the present invention can be applied include an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, and the like. In particular, since the resolution is good, it can be preferably used for an interlayer insulating film for a rewiring layer in a three-dimensional mounted device.

The cured film in the present invention can also be used for an electron resist, an electrochemical (electrolytic) resist, an etching resist, a solder resist (solder top resist), and the like.

The cured film of the present invention can also be used for manufacturing a printing plate such as an offset printing plate or a screen printing plate, etching a molded member, manufacturing a protective varnish for electronics, particularly microelectronics, and a dielectric layer.

The method for producing a cured film of the present invention comprises using the composition of the present invention. Preferably, the method for producing a cured film comprises: a photosensitive resin composition layer forming step of applying the photosensitive resin composition of the present invention to a substrate to form a layer; an exposure step of exposing the photosensitive resin composition layer; and a developing treatment step of performing a developing treatment on the exposed photosensitive resin composition layer (resin layer). The photosensitive resin composition of the present invention can be preferably used in the case of performing development, particularly negative development using an organic solvent.

The method for producing a laminate of the present invention includes the method for producing a cured film of the present invention. In the method for producing a laminate of the present invention, it is preferable that, after the cured film is formed, the photosensitive resin composition layer forming step, the exposure step, and the development treatment step are further performed in this order. In particular, it is preferable that the photosensitive resin composition layer forming step, the exposure step, and the development treatment step are further performed 2 to 5 times (i.e., 3 to 6 times in total) in this order. By laminating the cured films in this manner, a laminate can be obtained. In the present invention, it is particularly preferable that a metal layer is provided in a portion which has been removed with a developer after a cured film is provided and developed.

These details are explained below.

< photosensitive resin composition layer Forming step >)

The method for producing a laminate of the present invention includes a photosensitive resin composition layer forming step of applying a photosensitive resin composition to a substrate to form a layer.

The type of the substrate may be appropriately set according to the application, but is not particularly limited, and examples thereof include a semiconductor substrate such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon, a semiconductor substrate such as quartz, glass, an optical film, a ceramic material, a vapor deposited film, a magnetic film, a reflective film, a metal substrate such as Ni, Cu, Cr, and Fe, paper, sog (spin On glass), a TFT (thin film transistor) array substrate, and an electrode plate of a Plasma Display Panel (PDP). In the present invention, a semiconductor substrate is particularly preferable, and a silicon substrate is more preferable.

When the photosensitive resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer serves as a substrate.

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

Specifically, examples of the application method include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, a slit coating method, an ink jet method, and the like. From the viewpoint of 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 the solid content concentration and the coating conditions appropriately according to the method, a resin layer having a desired thickness can be obtained. The coating method can be appropriately selected according to the shape of the substrate, and as long as a circular substrate such as a wafer is used, a spin coating method, a spray coating method, an ink jet method, and the like are preferable, and as long as a rectangular substrate, a slit coating method, a spray coating method, an ink jet method, and the like are preferable. In the case of the spin coating method, the method can be applied at a rotation speed of, for example, 500 to 2000rpm for about 10 seconds to 1 minute.

< drying Process >)

The method for producing a laminate of the present invention may further include a step of drying the photosensitive resin composition layer to remove the solvent after the formation of the photosensitive resin composition layer. The preferable drying temperature is 50 to 150 ℃, more preferably 70 to 130 ℃, and further preferably 90 to 110 ℃. The drying time is, for example, 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.

< Exposure Process >

The method for producing a laminate of the present invention includes an exposure step of exposing the photosensitive resin composition layer. The exposure dose is not particularly limited in the range capable of curing the photosensitive resin composition, and for example, it is preferable to irradiate the photosensitive resin composition with 100 to 10000mJ/cm in terms of exposure energy at a wavelength of 365nm²More preferably, the irradiation is 200 to 8000mJ/cm²。

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

In the present invention, it is preferable that a step of heating at 40 ℃ or higher is not included between the exposure step and the development step.

< developing treatment Process >

The method for producing a laminate of the present invention includes a development treatment step of performing a development treatment on the exposed photosensitive resin composition layer. By performing development, an unexposed portion (unexposed portion) is removed. The developing method is not particularly limited as long as a desired pattern can be formed, and for example, a developing method such as paddle stirring, spraying, dipping, or ultrasonic waves can be used.

Development is performed using a developer. The developing solution can be used without particular limitation as long as the unexposed portion (unexposed portion) can be removed. The developer preferably comprises an organic solvent. In the present invention, the developer preferably contains an organic solvent having a ClogP of-1 to 5, and more preferably contains an organic solvent having a ClogP of 0 to 3. ClogP can be calculated as a calculated value by inputting the structural formula by chembidraw (chemibiological diagram).

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

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

The developer is preferably an organic solvent in an amount of 50% by mass or more, more preferably an organic solvent in an amount of 70% by mass or more, and still more preferably an organic solvent in an amount of 90% by mass or more. Also, 100% by mass of the developing solution may be an organic solvent.

The developing time is preferably 10 seconds to 5 minutes. The temperature during development is not particularly limited, and can be usually carried out at 20 to 40 ℃.

After the treatment with the developer, rinsing may be further performed. The rinsing is preferably carried out with a different solvent than the developer. For example, the solvent contained in the photosensitive resin composition can be used for rinsing. The rinsing time is preferably 5 seconds to 1 minute.

< heating Process >)

The method for producing a laminate of the present invention preferably includes a step of heating after development. In the heating step, a cyclization reaction of the polymer precursor proceeds. When the composition of the present invention contains a radical polymerizable compound other than the polymer precursor, curing or the like of an unreacted radical polymerizable compound other than the polymer precursor is also performed. The heating temperature (maximum heating temperature) is preferably 50 to 450 ℃, more preferably 140 to 400 ℃, and still more preferably 160 to 350 ℃.

The heating is preferably performed at a temperature rise rate of 1 to 12 ℃/min, more preferably 2 to 10 ℃/min, and still more preferably 3 to 10 ℃/min, from the temperature at the start of heating to the maximum heating temperature. The temperature increase rate is set to 1 ℃/min or more, whereby excessive volatilization of the amine can be prevented while ensuring productivity, and the temperature increase rate is set to 12 ℃/min or less, whereby the residual stress of the cured film can be reduced.

The temperature at the start of heating is preferably 20 to 150 ℃, more preferably 20 to 130 ℃, and still more preferably 25 to 120 ℃. The temperature at the start of heating is the temperature at the start of the heating step to the maximum heating temperature. For example, when the photosensitive resin composition is applied to a substrate and then dried, the temperature after drying is preferably increased gradually from the boiling point- (30 to 200 ℃) of the solvent contained in the photosensitive resin composition.

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

In particular, in the case of forming a multilayer laminate, from the viewpoint of adhesion between the layers of the cured film, the heating is preferably performed at a heating temperature of 180 to 320 ℃, and more preferably at 180 to 260 ℃. The reason is not clear, but is considered to be because the ethynyl groups of the polymer precursors between the layers are crosslinked with each other by setting the temperature to this temperature.

The heating may be performed in stages. For example, the treatment step may be carried out before the temperature is raised to 25 to 180 ℃ at 3 ℃/min, the mixture is left at 180 ℃ for 60 minutes, the temperature is raised to 180 to 200 ℃ at 2 ℃/min, and the mixture is left at 200 ℃ for 120 minutes. The heating temperature in the pretreatment step is preferably 100 to 200 ℃, more preferably 110 to 190 ℃, and still more preferably 120 to 185 ℃. In this pretreatment step, it is also preferable to perform treatment while irradiating ultraviolet rays as described in U.S. Pat. No. 9159547. The film characteristics can be improved by such a pretreatment step. The pretreatment step may be performed in a short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be carried out in two or more stages, and for example, the pretreatment step 1 may be carried out at a temperature of 100 to 150 ℃ and the pretreatment step 2 may be carried out at a temperature of 150 to 200 ℃.

The heating and cooling may be performed after the heating, and the cooling rate in this case is preferably 1 to 5 ℃/min.

In the heating step, it is preferable to perform the heating step in an environment of low temperature concentration by flowing an inert gas such as nitrogen, helium, or argon, in order to prevent decomposition of the polymer precursor. The oxygen concentration is preferably 50ppm (by volume) or less, more preferably 20ppm (by volume) or less.

< Process for Forming Metal layer >)

The method for producing a laminate 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 conventional metal species can be used, and examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten, more preferably copper and aluminum, and still more preferably copper.

The method for forming the metal layer is not particularly limited, and conventional methods can be applied. For example, the methods described in Japanese patent laid-open Nos. 2007-157879, 2001-521288, 2004-214501 and 2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, a method of combining these, and the like can be considered. More specifically, a patterning method in which sputtering, photolithography, and etching are combined, and a patterning method in which photolithography and electrolytic plating are combined are given.

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

< lamination Process >)

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

The laminating step is a series of steps including a step of forming the photosensitive resin composition layer, a step of exposing the photosensitive resin composition layer, and a step of developing the photosensitive resin composition layer in this order. Of course, the laminating step may include the drying step, the heating step, or the like.

When the lamination step is performed after the lamination step, the surface activation treatment step may be further performed after the exposure step or after the metal layer formation step. As the surface activation treatment, plasma treatment can be exemplified.

The laminating step is preferably performed 2 to 5 times, and more preferably 3 to 5 times.

For example, a structure in which the resin layer is 3 layers or more and 7 layers or less, such as resin layer/metal layer/resin layer/metal layer, is preferable, and 3 layers or more and 5 layers or less is more preferable.

That is, in the present invention, it is particularly preferable that after the metal layer is provided, the photosensitive resin composition layer forming step, the exposure step, and the development treatment step are further performed in this order so as to cover the metal layer. The photosensitive resin composition layer (resin layer) and the metal layer can be alternately laminated by alternately performing the laminating step of laminating the photosensitive resin composition layer (resin) and the metal layer forming step.

Also disclosed is a semiconductor device comprising the cured film or laminate of the invention. An embodiment of a semiconductor device in which the composition of the present invention is used for forming an interlayer insulating film for a rewiring layer will be described.

A semiconductor device 100 shown in fig. 1 is a so-called three-dimensional mounted device, and a multilayer body 101 in which a plurality of semiconductor elements (semiconductor chips) 101a to 101d are stacked is arranged on a wiring board 120. In this embodiment, although the case where the number of stacked semiconductor elements (semiconductor chips) is 4 has been described, the number of stacked semiconductor elements (semiconductor chips) is not particularly limited, and may be, for example, 2 layers, 8 layers, 16 layers, 32 layers, or the like. And may be 1 layer.

Each of the plurality of semiconductor elements 101a to 101d is formed of a semiconductor wafer such as a silicon substrate. The uppermost semiconductor element 101a does not have a through electrode, and an electrode pad (not shown) is formed on one surface thereof. The semiconductor elements 101b to 101d have through electrodes 102b to 102d, and connection pads (not shown) provided integrally with the through electrodes are provided on both surfaces of each semiconductor element.

The laminate 101 has a structure in which a semiconductor element 101a having no through electrode and semiconductor elements 101b to 101d having through electrodes 102b to 102d are flip-chip connected. That is, the electrode pad of the semiconductor element 101a having no through electrode and the adjacent connection pad on the semiconductor element 101a side of the semiconductor element 1O1b having the through electrode 102b are connected by the metal bump 103a such as a solder bump, and the other connection pad of the semiconductor element 101b having the through electrode 102b and the connection pad on the semiconductor element 101b side of the semiconductor element 101c having the through electrode 102c connected thereto are connected by the metal bump 103b such as a solder bump. Similarly, the other connection pad of the semiconductor element 101c having the through electrode 102c and the adjacent connection pad of the semiconductor element 101c having the semiconductor element 101d having the through electrode 102d are connected by a metal bump 103c such as a solder bump.

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

The laminate 101 is laminated on the wiring board 120. As the wiring board 120, for example, a multilayer wiring board of an insulating substrate such as a resin substrate, a ceramic substrate, or a glass substrate used as a base material can be used. As the wiring board 120 to which the resin substrate is applied, a multilayer copper-clad laminate (multilayer printed circuit board) and the like can be given.

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

An insulating film 115 forming a rewiring layer 105 is disposed between the wiring substrate 120 and the laminate 101, and the wiring substrate 120 and the laminate 101 are electrically connected via the rewiring layer 105. The insulating film 115 is an insulating film formed using the composition of 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 via a metal bump 103d such as a solder bump. The other end of the rewiring layer 105 is connected to the surface electrode 120a of the wiring board via a metal bump 103e such as a solder bump.

Further, a bottom filling 110a is formed between the insulating film 115 and the stacked body 101. Further, a underfill 11Ob is formed between the insulating film 115 and the wiring board 120.