KR20220008885A - A curable resin composition, a cured film, a laminated body, the manufacturing method of a cured film, a semiconductor device, and a polyimide, or a polyimide precursor - Google Patents

Abstract

Curable resin composition comprising at least one resin selected from the group consisting of polyimide and polyimide precursor having a polyalkyleneoxy group and a polymerizable group, a polymerization initiator, a polymerizable compound, and a solvent, and curing the curable resin composition It is related with the cured film formed by making, the laminate containing the said cured film, the manufacturing method of the said cured film, the semiconductor device containing the said cured film or the said laminated body, and a polyimide or a polyimide precursor.

Description

A curable resin composition, a cured film, a laminated body, the manufacturing method of a cured film, a semiconductor device, and a polyimide, or a polyimide precursor

The present invention relates to a curable resin composition, a cured film, a laminate, a method for producing a cured film, a semiconductor device, and a polyimide or a polyimide precursor.

Since polyimide is excellent in heat resistance and insulation, it is applied to various uses. Although it does not specifically limit as said use, When the semiconductor device for mounting is mentioned as an example, use as a material of an insulating film or sealing material, or use as a protective film is mentioned. Moreover, it is used also as a base film, a coverlay, etc. of a flexible board|substrate.

For example, the use mentioned above WHEREIN: A polyimide may be used with the form of curable resin composition containing a polyimide, and may be used with the form of curable resin composition containing a polyimide precursor. The said precursor is cyclized by heating etc., and turns into a polyimide, for example.

Since these curable resin compositions can be applied to a substrate or the like by a known coating method or the like, for example, the curable resin composition to be applied has a high degree of freedom in designing the shape, size, and application position, etc. can do.

Industrial application development for a curable resin composition containing polyimide and at least one resin selected from the group consisting of polyimide precursors from the viewpoint of excellent manufacturing adaptability in addition to the high performance of polyimide is gradually expected.

For example, in patent document 1, curable polyimide of the structure which has a specific polymeric group is described.

Patent Document 1: International Publication No. 2018/237377

Curable resin composition containing at least 1 sort(s) of resin selected from the group which consists of polyimide or a polyimide precursor WHEREIN: Provision of the curable resin composition excellent in the applicability|paintability of a composition is desired.

One embodiment of the present invention provides a curable resin composition excellent in applicability, a cured film formed by curing the curable resin composition, a laminate including the cured film, a method for manufacturing the cured film, and the cured film or the laminate An object of the present invention is to provide a semiconductor device comprising a.

Moreover, another one embodiment of this invention aims at providing a novel polyimide or a polyimide precursor.

Hereinafter, examples of representative embodiments of the present invention will be described.

<1> at least one resin selected from the group consisting of polyimides and polyimide precursors having a polyalkyleneoxy group and a polymerizable group;

polymerization initiator,

a polymerizable compound, and

solvent containing

Curable resin composition.

<2> Curable resin composition as described in <1> containing the structure represented by following formula (1-1) as a structure which has the said polyalkyleneoxy group and the said polymeric group.

[Formula 1]

In formula (1-1), ^{each R 1} independently represents a hydrogen atom or an alkyl group, Z ¹ represents a group containing a polymerizable group, n represents an integer of 2 or more, m represents an integer of 2 or more, * indicates a binding site with another structure.

<3> wherein Z ¹ is, as the polymerizable group, an ethylenically unsaturated group, including a cyclic ether group, and a group of at least one member selected from the group consisting of methylol, the curable resin composition according to <2>.

<4> Curable resin composition as described in <2> or <3> in which the said resin is a structure containing the structure represented by the said Formula (1-1), and containing the structure represented by following formula (1-2).

[Formula 2]

In formula (1-2), L ¹ represents a b+2-valent linking group, X ² represents an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond, and L ² is a single bond or a+1 represents a valent linking group, X ¹ represents the structure represented by the above formula (1-1), a represents an integer of 1 or more, b represents an integer of 1 or more, and X ² , L ² , X ¹ or a plurality of In this case, a plurality of X ² , L ² , X ¹ or a may be the same or different.

<5> Curable resin composition in any one of <2>-<4> containing the repeating unit represented by following formula (1-3) as a repeating unit containing the structure represented by said formula (1-1) .

[Formula 3]

In formula (1-3), L ¹ represents a b+2-valent linking group, X ² represents an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond, and L ² represents a single bond or a+1 represents a valent linking group, X ¹ represents a structure represented by the above formula (1-1), a represents an integer of 1 or more, b represents an integer of 1 or more, and L ⁴ represents the following formula (L4-1) or formula ( L4-2), when ^two or more X 2 , L ² , X ¹ or a exists, a plurality of X ² , L ² , X ¹ or a may be the same or different.

[Formula 4]

In the formula (L4-1) or (L4-2), R ¹¹⁵ represents a tetravalent organic group, A ¹ and A ² each independently represent an oxygen atom or —NH—, and R ¹¹³ and R ¹¹⁴ are, Each independently represents a hydrogen atom or a monovalent organic group.

<6> ^{Curable resin according to <4> or <5>, wherein L 1} includes a structure represented by at least one selected from the group consisting of structures represented by the following formulas (A-1) to (A-5). composition.

[Formula 5]

In formulas (A-1) to (A-5), R ^A11 to R ^A14 , R ^A21 to R ^A24 , R ^A31 to R ^A38 , R ^A41 to R ^A48 and R ^A51 to R ^A58 are each independently a hydrogen atom , an alkyl group, a cyclic alkyl group, an alkoxy group, a hydroxy group, a cyano group, a halogenated alkyl group, a halogen atom, or a bond with ^{X 2 in the formula (1-2) or (1-3)} represents a moiety, and L ^A31 and L ^A41 are each independently a single bond, a carbonyl group, a sulfonyl group, a divalent saturated hydrocarbon group, a divalent unsaturated hydrocarbon group, a hetero atom, a heterocyclic group, or a halogenated alkylene group represents a group, and among R ^A11 to R ^A14 , R ^A21 to R ^A24 , R ^A31 to R ^A38 , R ^A41 to R ^A48 and R ^A51 to R ^A58 , each b is the formula (1-2) or the formula (1) ^{It is a binding site with X 2} in -3), and * each independently represents a binding site with another structure.

<7> Curable resin composition in any one of <1>-<6> used for formation of the interlayer insulating film for redistribution layers.

<8> A cured film formed by curing the curable resin composition according to any one of <1> to <7>.

<9> The laminated body which has two or more layers of cured films as described in <8>, and has a metal layer between cured films.

<10> The manufacturing method of a cured film including the film-forming process of applying the curable resin composition in any one of <1> to <7> to a base material, and forming a film|membrane.

<11> The manufacturing method of the cured film as described in <10> including the exposure process of exposing the said film|membrane, and the image development process of developing the said film|membrane.

<12> The manufacturing method of the cured film as described in <10> or <11> including the process of heating the said film|membrane at 50-450 degreeC.

<13> A semiconductor device comprising the cured film according to <8> or the laminate according to <9>.

The polyimide or polyimide precursor containing the structure represented by <14> following formula (1-1).

[Formula 6]

In formula (1-1), ^{each R 1} independently represents a hydrogen atom or an alkyl group, Z ¹ represents a group containing a polymerizable group, n represents an integer of 2 or more, m represents an integer of 2 or more, * indicates a binding site with another structure.

According to one embodiment of the present invention, a curable resin composition excellent in applicability, a cured film formed by curing the curable resin composition, a laminate including the cured film, a method for manufacturing the cured film, and the cured film or the laminate A semiconductor device including a sieve is provided.

Further, according to another embodiment of the present invention, a novel polyimide, or a polyimide precursor is provided.

1 is a schematic diagram of a stepped substrate used in Examples.

EMBODIMENT OF THE INVENTION Hereinafter, main embodiment of this invention is described. However, the present invention is not limited to the specified embodiment.

In this specification, the numerical range indicated by using the symbol "to" means a range including the numerical value described before and after "to" as a lower limit and an upper limit, respectively.

As used herein, the term "process" is meant to include not only independent processes, but also processes that cannot be clearly distinguished from other processes as long as the desired action of the process can be achieved.

In the description of the group (atomic group) in this specification, the description which does not describe substitution and unsubstituted includes a group (atomic group) having a substituent together with a group (atomic group) having no 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" includes not only exposure using light, but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Moreover, as light used for exposure, actinic rays or radiations, such as a bright-line spectrum of a mercury lamp, and the far ultraviolet, extreme ultraviolet (EUV light), X-ray, and an electron beam, typified by an excimer laser.

In this specification, "(meth)acrylate" means both, or either of "acrylate" and "methacrylate", and "(meth)acryl" is "acryl" and "methacrylic" It means both, or either of ", and "(meth)acryloyl" means both, or either of "acryloyl" and "methacryloyl".

In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

In this specification, total solid means the total mass of the component except the solvent from all the components of a composition. In addition, in this specification, solid content concentration is the mass percentage of the other component except a solvent with respect to the total mass of a composition.

In this specification, a weight average molecular weight (Mw) and a number average molecular weight (Mn) are defined as polystyrene conversion values according to a gel permeation chromatography (GPC measurement) unless otherwise indicated. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) use, for example, HLC-8220GPC (manufactured by Tosoh Corporation), and as a column, a guard column HZ-L, TSKgel Super HZM- It can obtain|require by using M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (made by Tosoh Corporation). Unless otherwise specified, those molecular weights are measured using THF (tetrahydrofuran) as the eluent. In addition, detection in a GPC measurement shall use the wavelength 254nm detector of UV rays (ultraviolet rays) unless it demonstrates in particular.

In the present specification, when "upper" or "lower" is described with respect to the positional relationship of each layer constituting the laminate, another layer is above or below the reference layer among the plurality of layers of interest. should have this That is, a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer and the other layer do not need to be in contact with each other. In addition, unless otherwise specified, the direction in which the layers are laminated with respect to the substrate is referred to as "upper", or in the case of a photosensitive layer, the direction from the substrate to the photosensitive layer is referred to as "up", and vice versa. The direction is called "down". In addition, the setting of such an up-down direction is for convenience in this specification, and in an actual aspect, the "upward" direction in this specification may differ from a vertically upward direction in some cases.

In this specification, unless otherwise indicated, a composition may contain 2 or more types of compounds corresponding to the component as each component contained in a composition. In addition, unless there is a special description, content of each component in a composition means the total content of all the compounds corresponding to the component.

In the present specification, unless otherwise specified, the temperature is 23°C and the atmospheric pressure is 101,325 Pa (1 atm).

In this specification, the combination of a preferable aspect is a more preferable aspect.

(Curable resin composition)

The curable resin composition of the present invention (hereinafter also simply referred to as "the composition of the present invention") is at least one resin selected from the group consisting of polyimides and polyimide precursors having a polyalkyleneoxy group and a polymerizable group ( Hereinafter, it is also referred to as "specific resin."), a polymerization initiator, a polymerizable compound, and a solvent.

It is preferable that curable resin composition of this invention further contains the thermal base generator or onium salt mentioned later. In particular, when specific resin is a polyimide precursor, it is preferable that curable resin composition of this invention further contains the below-mentioned thermal base generator or onium salt.

Curable resin composition of this invention is excellent in applicability|paintability.

In this specification, the excellent applicability|paintability of a composition means that the film thickness difference is small in the coating film formed after application and drying, and there are few defects, such as application|coating nonuniformity by foam|bubble and unevenness.

Although the mechanism by which the said effect is acquired is not certain, it is thought that specific resin is excellent in the solubility to a solvent because specific resin contains a polyalkyleneoxy group and a polymerizable group.

By using a specific resin excellent in solubility as described above, even at a stage where the solvent is volatilized during coating and drying of the composition, it is difficult to precipitate the specific resin. , it is also considered that defects are less likely to occur.

Moreover, even when the curable resin composition of this invention is used for the base material which has a level|step difference, for example, it is thought that a flat film|membrane is easy to be obtained.

Moreover, since a rigid polyimide structure and a flexible polyalkyleneoxy structure coexist in the cured film obtained after hardening of a coating film, it is thought that the intensity|strength (for example, breaking elongation) of a cured film improves easily.

Here, in patent document 1, neither description nor suggestion is made about resin containing a polyalkyleneoxy group. Moreover, in the curable resin composition in patent document 1, there existed a problem that applicability|paintability was low.

<Specific resin>

Curable resin composition of this invention contains specific resin.

Specific resin has a polyalkyleneoxy group and a polymerizable group.

Although specific resin may have a polyalkyleneoxy group in a principal chain, it is preferable to have in the side chain of specific resin from a viewpoint of the film strength of the cured film obtained.

In the present specification, the "main chain" refers to the relatively longest bonding chain among molecules of the polymer compound constituting the resin, and the "side chain" refers to other bonding chains.

Moreover, it is preferable that specific resin has a side chain which has a polyalkyleneoxy group and a polymeric group as a side chain.

[polyalkyleneoxy group]

In the present invention, the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the some alkyleneoxy group contained in a polyalkyleneoxy group may be same or different, respectively.

When the polyalkyleneoxy group contains a plurality of types of alkyleneoxy groups from which the alkylene groups are different, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, a block arrangement, or the like. It may be an array having a pattern of .

It is preferable that carbon number of the said alkylene group (when an alkylene group has a substituent, carbon number of a substituent is included), it is preferable that it is 2 or more, It is more preferable that it is 2-50, It is more preferable that it is 2-30, It is 2-10 It is more preferably, it is more preferably 2-6, It is especially preferable that it is 2-4, It is most preferable that it is 2 or 3.

Moreover, the said alkylene group may have a substituent. As a preferable substituent, an alkyl group, an aryl group, a halogen atom, etc. are mentioned.

Moreover, 2-100 are preferable, as for the number (repetition number of polyalkyleneoxy group) of the alkyleneoxy groups contained in a polyalkyleneoxy group, 2-50 are more preferable, 2-30 are still more preferable, 2- 10 is particularly preferred, and 3 to 10 are most preferred.

As the polyalkyleneoxy group, from the viewpoint of coexistence of solvent solubility and chemical resistance, a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups The bonded group is preferable, and a polyethyleneoxy group or a polypropyleneoxy group is more preferable. In the group in which the plurality of ethyleneoxy groups and the plurality of propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be arranged at random, may be arranged in blocks, or may be arranged in a pattern such as alternating. The preferable aspect of the repeating number, such as an ethyleneoxy group in these groups, is as above-mentioned.

[Polymerizable group]

As the polymerizable group contained in the specific resin, a group containing an ethylenically unsaturated group, a cyclic ether group or a methylol group is preferable, and a vinyl group, (meth)allyl group, (meth)acrylamide group, (meth)acryloxy group, A maleimide group, a vinylphenyl group, an epoxy group, an oxetanyl group, or a methylol group is more preferable, and a (meth)acryloxy group, an epoxy group, or a methylol group is more preferable.

As one preferable aspect of this invention, the aspect in which the polymeric group contained in specific resin is directly couple|bonded with one terminal of the polyalkyleneoxy group mentioned above is mentioned. That is, it is preferable that specific resin has one terminal of the above-mentioned polyalkyleneoxy group, and the side chain which the polymeric group couple|bonded.

[Structure represented by Formula (1-1)]

It is preferable that specific resin contains the structure represented by following formula (1-1) as a structure which has the said polyalkyleneoxy group and the said polymeric group.

It is preferable that specific resin contains two or more structures represented by following formula (1-1). When specific resin contains two or more structures represented by Formula (1-1), the structure represented by some Formula (1-1) may be same or different.

[Formula 7]

In formula (1-1), ^{each R 1} independently represents a hydrogen atom or an alkyl group, Z ¹ represents a group containing a polymerizable group, n represents an integer of 2 or more, m represents an integer of 2 or more, * indicates a binding site with another structure.

-R ¹ -

In formula (1-1), R ¹ is each independently preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, still more preferably a hydrogen atom or a methyl group .

-Z ¹ -

In Formula (1-1), Z<^1> represents group containing a polymeric group.

Z ¹ is the polymerizable group and preferably contains at least one group selected from the group consisting of an ethylenically unsaturated group, a cyclic ether group, and a methylol group, a vinyl group, a (meth)allyl group, (meth) It is more preferable to include acrylamide group, (meth)acryloxy group, maleimide group, vinylphenyl group, epoxy group, oxetanyl group, or methylol group, (meth)acryloxy group, epoxy group, or methylol group It is more preferable to include

Moreover, as for Z<^1> , group represented by a following formula (Z-1) is preferable.

[Formula 8]

In formula (Z-1), L represents a single bond or an nz+1 valent coupling group, nz represents an integer of 1 or more, Z ² represents a polymerizable group, and * represents an oxygen atom in formula (1-1) Represents a binding site.

In formula (Z-1), L is a single bond, or an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an ether bond (-O-), a carbonyl group (-C(=O)-), a thioether bond ( -O-), a sulfonyl group (-S(=O) ₂ -), -NR ^N -, or a group which these two or more couple|bonded is preferable, and a single bond, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group is more preferable. . R ^N represents a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aryl group, still more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

As said aliphatic hydrocarbon group, a C1-C20 hydrocarbon group is preferable, and a C1-C10 hydrocarbon group is more preferable. Moreover, as said aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group is more preferable.

As said aromatic hydrocarbon group, a C6-C20 aromatic hydrocarbon group is more preferable, A C6-C12 aromatic hydrocarbon group is more preferable, A C6 aromatic hydrocarbon group is more preferable.

In formula (Z-1), it is preferable that nz is an integer of 1-10, It is preferable that it is an integer of 1-4, It is more preferable that it is 1 or 2, It is especially preferable that it is 1.

In formula (Z-1), nz is 1, and L is a single bond, or an alkylene group, an arylene group, an ether bond (-O-), a carbonyl group (-C(=O)-), and It is preferable that an ether bond (-O-), a sulfonyl group (-S(=O) ₂ -), -NR ^N -, or a group in which two or more of these bonds are bonded, nz is 1, and L is a single bond; Alternatively, an alkylene group having 1 to 10 carbon atoms, a phenylene group, an ether bond (-O-), a carbonyl group (-C(=O)-), a thioether bond (-O-), a sulfonyl group (-S (= O) ₂ -), -NR ^N -, or a group in which two or more of these are bonded is more preferable.

In formula (Z-1), Z ² is a vinyl group, (meth)allyl group, (meth)acrylamide group, (meth)acryloxy group, maleimide group, vinylphenyl group, epoxy group, oxetanyl group, or methyl An ol group is more preferable, and a (meth)acryloxy group, an epoxy group, or a methylol group is more preferable.

-n-

In formula (1-1), n is each independently preferably an integer of 2-100, more preferably an integer of 2-50, still more preferably an integer of 2-30, and particularly that it is an integer of 2-10. Preferably, it is the most preferable that it is an integer of 3-10.

-m-

In formula (1-1), m is each independently preferably an integer of 2 to 50, more preferably an integer of 2 to 30, still more preferably an integer of 2 to 10, further preferably an integer of 2 to 6 It is preferable, and it is especially preferable that it is an integer of 2-4, and it is most preferable that it is 2 or 3.

Specific resin is a structure represented by Formula (1-1), The structure represented by a following formula (1-1-1), a structure represented by a following formula (1-1-2), and a following formula (1-1-3) It is preferable to include at least one type of structure selected from the group consisting of structures represented by

[Formula 9]

In formulas (1-1-1) to (1-1-3), n and Z ^{1 have the same meanings as n and Z 1} in formula (1-1), respectively, and preferred embodiments are also the same.

In formulas (1-1-1) to (1-1-3), * represents a binding site with another structure.

[Structure represented by Formula (1-2)]

It is preferable that specific resin is a structure containing the structure represented by said Formula (1-1), and it is preferable to include the structure represented by following formula (1-2).

It is preferable that specific resin contains the structure represented by Formula (1-2) in a principal chain. That is, it is preferable that the structure represented by ^L<1> in Formula (1-2) is contained in the principal chain of specific resin.

It is preferable that specific resin contains two or more structures represented by Formula (1-2). When specific resin contains two or more structures represented by Formula (1-2), the structure represented by some Formula (1-2) may be same or different.

[Formula 10]

In formula (1-2), L ¹ represents a b+2-valent linking group, X ² represents an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond, and L ² is a single bond or a+1 represents a valent linking group, X ¹ represents the structure represented by the above formula (1-1), a represents an integer of 1 or more, b represents an integer of 1 or more, and X ² , L ² , X ¹ or a plurality of In this case, a plurality of X ² , L ² , X ¹ or a may be the same or different.

-L ¹ -

L ¹ represents a linking group having a valence of b+2, and at least one of an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or at least one of these groups and an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, and -NR ^N - It is preferable that one is a bonded group. R ^N represents a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aryl group, still more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

As said aliphatic hydrocarbon group, a C2-C30 aliphatic saturated hydrocarbon group is preferable, and a C2-C10 aliphatic saturated hydrocarbon group is more preferable.

Moreover, as said aliphatic hydrocarbon group, the saturated aliphatic hydrocarbon ring group whose reduction number is 6-20 is preferable.

As said aromatic hydrocarbon group, a C6-C20 aromatic hydrocarbon group is preferable, a C6-C12 aliphatic hydrocarbon group is preferable, and a C6 aromatic hydrocarbon group is more preferable.

Among these, from the viewpoint of solvent solubility, L ¹ is preferably a group containing an aliphatic hydrocarbon ring group or an aromatic hydrocarbon ring group, and more preferably a group containing an aromatic hydrocarbon ring group.

Moreover, it is preferable that L<^1> contains at least 1 sort(s) of structure selected from the group which consists of a structure represented by any one of following formula (A-1) - following formula (A-5), following formula (A-1) It is more preferable that it is a structure represented by any one of - following formula (A-5).

[Formula 11]

In formulas (A-1) to (A-5), R ^A11 to R ^A14 , R ^A21 to R ^A24 , R ^A31 to R ^A38 , R ^A41 to R ^A48 and R ^A51 to R ^A58 are each independently a hydrogen atom , an alkyl group, a cyclic alkyl group, an alkoxy group, a hydroxy group, a cyano group, a halogenated alkyl group, a halogen atom, or a bond with ^{X 2 in the formula (1-2) or (1-3)} represents a moiety, and L ^A31 and L ^A41 are each independently a single bond, a carbonyl group, a sulfonyl group, a divalent saturated hydrocarbon group, a divalent unsaturated hydrocarbon group, a hetero atom, a heterocyclic group, or a halogenated alkylene group represents a group, and among R ^A11 to R ^A14 , R ^A21 to R ^A24 , R ^A31 to R ^A38 , R ^A41 to R ^A48 and R ^A51 to R ^A58 , each b is represented by Formula (1-2) or Formula (1) to be described later ^{It is a binding site with X 2} in -3), and * each independently represents a binding site with another structure.

^{It is preferable that L<1>} is a structure represented by a formula (A-1), a formula (A-2), a formula (A-3), or a formula (A-4) among these from a chemical-resistance viewpoint.

In formula (A-1), R ^A11 to R ^A14 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, cyano group It is preferable to represent a group, a halogenated alkyl group having 1 to 3 carbon atoms, or a halogen atom, and from the viewpoint of solvent solubility, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a carbon number A 1-3 halogenated alkyl group is more preferable, and a hydrogen atom or a C1-C6 alkyl group is more preferable.

In addition, ^{b of R A11} to R ^A14 is a binding site with ^{X 2} in Formula (1-2) or Formula (1-3) to be described later ^{, and R A13} is a binding site with ^{X 2 , or R} It is preferred that ^A12 and R ^A14 are ^{binding sites with X 2 .}

Examples ^{of the halogen atom or the halogen atom in the halogenated alkyl group for R A11} to R ^A14 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom or a bromine atom is preferred.

In the formula (A-2), R ^A21 to R ^{A24 have the same meanings as R A11} to R ^A14 in the formula (A-1), respectively, and their preferred embodiments are also the same.

Moreover, ^{b of R A21} -R ^A24 is a binding site with ^{X 2} in Formula (1-2) or Formula (1-3) mentioned later.

In formula (A-3), R ^A31 to R ^A38 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxy group, cyano group It is preferable to represent a group, a halogenated alkyl group having 1 to 3 carbon atoms, or a halogen atom, and from the viewpoint of solvent solubility, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a carbon number A 1-3 halogenated alkyl group is more preferable, and a hydrogen atom or a C1-C6 alkyl group is more preferable.

Examples ^{of the halogen atom or the halogen atom in the halogenated alkyl group for R A31} to R ^A38 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom or a bromine atom is preferred.

In addition, ^{b of R A31} to R ^A38 is a binding site with ^{X 2} in Formula (1-2) or Formula (1-3) to be described later ^{, and R A31} and R ^A36 are a bonding site with ^{X 2 .} desirable.

In formula (A-3), L ^A31 is a single bond, a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, a divalent unsaturated hydrocarbon group having 5 to 24 carbon atoms, -O-, -S-, -NR ^N -, a heterocyclic group, or preferably a halogenated alkylene group having 1 to 6 carbon atoms, preferably a single bond, a saturated hydrocarbon group having 1 to 6 carbon atoms, -O- or a heterocyclic group, a single bond Or -O- is more preferable.

R ^N represents a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aryl group, still more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

Although the said divalent unsaturated hydrocarbon group may be a divalent aliphatic unsaturated hydrocarbon group or a divalent aromatic hydrocarbon group may be sufficient as it, it is preferable that it is a bivalent aromatic hydrocarbon group.

As the heterocyclic group, for example, a group obtained by removing two hydrogen atoms from an aliphatic or aromatic heterocycle is preferable, and a group obtained by removing two hydrogen atoms from an aliphatic or aromatic heterocycle is preferable, and a pyrrolidine ring, a tetrahydrofuran ring, A group obtained by removing two hydrogen atoms from a ring structure such as a tetrahydrothiophene ring, a pyrrole ring, a furan ring, a thiophene ring, a piperidine ring, a tetrahydropyran ring, a pyridine ring and a morpholine ring is more preferable. These heterocycles may have another heterocyclic ring or a hydrocarbon ring, and a condensed ring.

It is preferable that it is 5-10, and, as for the reduction number of the said heterocyclic ring, it is more preferable that it is 5 or 6.

Moreover, as a hetero atom in the said heterocyclic group, it is preferable that they are an oxygen atom, a nitrogen atom, or a sulfur atom.

A fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned as a halogen atom in the said halogenated alkylene group, A chlorine atom or a bromine atom is preferable.

In the formula (A-4), R ^A41 to R ^{A48 have the same meaning as R A31} to R ^A38 in the formula (A-3), respectively, and their preferred embodiments are also the same.

In addition, ^{b among R A41} to R ^A48 is a binding site with ^{X 2} in Formula (1-2) or Formula (1-3) to be described later ^{, and R A41} and R ^A48 are a binding site with ^{X 2 .} desirable.

In Formula (A-4), L ^{A41 has the same meaning as L A31} in Formula (A-3), and a preferable aspect is also the same.

In the formula (A-5), R ^A51 to R ^{A58 have the same meanings as R A11} to R ^A14 in the formula (A-1), respectively, and their preferred embodiments are also the same.

Moreover, in Formula (A-1) - Formula (A-5), it is preferable that * is each independently a binding site|part with the main chain in resin.

-X ² -

In formula (1-2), X ² represents an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond, and is preferably an ester bond or an ether bond.

In addition, what is necessary is just to determine ^{X<2> after considering a synthesis method etc.}

If X ² is ester bond, and may be combined with the carbon atom L ¹ of the ester bond, it may be combined with an oxygen atom L ^1.

When X ² is a urethane bond, it is preferable that the oxygen atom of the urethane bond ^{bonds with L 1 .}

When X ² is an amide bond, it is preferable that a carbon atom of the amide bond is ^{bonded to L 1 .}

-L ² -

In formula (1-2), L ² represents a single bond or an a+1 valent linking group, a single bond or an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, - NR ^N - or the group which these two or more couple|bonded is preferable, and a single bond, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group is more preferable. R ^N represents a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aryl group, still more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

As said aliphatic hydrocarbon group, a C1-C20 hydrocarbon group is preferable, and a C1-C10 hydrocarbon group is more preferable. Moreover, as said aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group is more preferable.

As said aromatic hydrocarbon group, a C6-C20 aromatic hydrocarbon group is more preferable, A C6-C12 aromatic hydrocarbon group is more preferable, A C6 aromatic hydrocarbon group is more preferable.

-X ¹ -

In Formula (1-2), X<^1> represents the structure represented by said Formula (1-1), and a preferable aspect is as having described in description of Formula (1-1).

-a-

In formula (1-2), a represents an integer of 1 or more, it is preferable that it is an integer of 1-10, It is more preferable that it is 1-4, It is more preferable that it is 1 or 2, It is especially preferable that it is 1.

-b-

In formula (1-2), b represents an integer of 1 or more, it is preferable that it is an integer of 1-10, It is more preferable that it is 1-4, It is more preferable that it is 1 or 2, It is especially preferable that it is 1.

[repeating unit represented by formula (1-3)]

It is preferable that specific resin contains the repeating unit represented by following formula (1-3) as a repeating unit containing the structure represented by Formula (1-1).

Moreover, it is preferable that specific resin has the repeating unit represented by Formula (1-3) in a principal chain.

[Formula 12]

In formula (1-3), L ¹ represents a b+2-valent linking group, X ² represents an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond, and L ² represents a single bond or a+1 represents a valent linking group, X ¹ represents a structure represented by the above formula (1-1), a represents an integer of 1 or more, b represents an integer of 1 or more, and L ⁴ represents the following formula (L4-1) or formula ( L4-2), when ^two or more X 2 , L ² , X ¹ or a exists, a plurality of X ² , L ² , X ¹ or a may be the same or different.

[Formula 13]

In the formula (L4-1) or (L4-2), R ¹¹⁵ represents a tetravalent organic group, A ¹ and A ² each independently represent an oxygen atom or —NH—, and R ¹¹³ and R ¹¹⁴ are, Each independently represents a hydrogen atom or a monovalent organic group.

-L ¹ , X ² , L ² , X ¹ , a and b-

Equation (1-3) of the, ^{L 1, X 2, L 2} , X 1, a and b are, respectively, the formula (1-2) in ^{L 1, X 2, L 2} , X 1, is equal to a and b meaning, and preferred embodiments are also the same.

-L ⁴ -

<<Formula (L4-1)>>

In the formula (L4-1), R ^115, it is more preferably a group represented by the tetravalent organic group is preferably the following formula (5) or (6) containing an aromatic ring.

[Formula 14]

R ¹¹² is a divalent linking group, a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -S (= O) ₂ -, -NHC(=O)-, or a group combining two or more of these, preferably a single bond, an alkylene group having 1 to 3 carbon atoms optionally substituted with a fluorine atom, -O-, -C (= It is more preferably a group selected from O)-, -S- and S(=O) _{2 -, -CH 2} -, -O-, -S-, -S(=O) ₂ -, -C(CF ₃ ) It is more preferable that it is a divalent group selected from the group which _{consists of 2} -, and -C(CH ₃ ) _{2 -.} * each independently represents a binding site with another structure.

^{Specific examples of the tetravalent organic group represented by R 115} in the formula (L4-1) include the tetracarboxylic acid residue remaining after removing the acid dianhydride group from the tetracarboxylic acid dianhydride. As for tetracarboxylic dianhydride, only 1 type may be used and 2 or more types may be used for it. As for tetracarboxylic dianhydride, the compound represented by following formula (7) is preferable.

[Formula 15]

R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ and R ¹¹⁵ are as defined in formula (L4-1).

Specific examples of tetracarboxylic dianhydride include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-di Phenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4 '-diphenylmethanetetracarboxylic acid dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, 2,3 ,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride, 2,3,6,7 -naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3- Dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4 -tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride Water, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis (2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and these carbon atoms 1 At least 1 sort(s) selected from a -6 alkyl derivative and a C1-C6 alkoxy derivative is illustrated.

Moreover, tetracarboxylic dianhydride (DAA-1) - (DAA-5) shown below are also mentioned as a preferable example.

[Formula 16]

<<Formula (L4-2)>>

In formula (L4-2), A ¹ and A ² each independently represent an oxygen atom or -NH-, and it is preferable that it is an oxygen atom.

In formula (L4-2), R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, ^{and it is preferable that at least one of R 113} and R ¹¹⁴ contains a polymerizable group, both of which are polymerizable groups It is more preferable to include

As the polymerizable group in R ¹¹³ or R ^114, there may be mentioned the same groups as the polymerizable group in Z ¹ in the above formula (1-1).

It ^{is also preferable that R 113} or R ¹¹⁴ is a vinyl group, an allyl group, a (meth)acryloyl group, or a group represented by the following formula (III).

[Formula 17]

In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and a methyl group is preferable.

In formula (III), R ²⁰¹ is an alkylene group having 2 to 12 carbon atoms, —CH ₂ CH(OH)CH ₂ — or a (poly)alkyleneoxy group having 4 to 30 carbon atoms (the alkylene group preferably has 1 to 12 carbon atoms. and 1 to 6 are more preferable, and 1 to 3 are particularly preferable; the number of repetitions is preferably 1 to 12, more preferably 1 to 6, particularly preferably 1 to 3). In addition, the (poly)alkyleneoxy group means an alkyleneoxy group or a polyalkyleneoxy group.

Examples of suitable R ²⁰¹ are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butanediyl group, 1,3-butanediyl group, pentamethylene group, hexamethylene group, octamethylene group , dodecamethylene group, -CH ₂ CH(OH)CH ₂ - are mentioned, and ethylene group, propylene group, trimethylene group, and -CH ₂ CH(OH)CH ₂ - are more preferable.

Particularly preferably, R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethylene group.

In formula (III), * represents a binding site with another structure.

As a preferred embodiment, as the ^{monovalent organic group of R 113} or R ¹¹⁴ in formula (L4-2), an aliphatic group, an aromatic group and an arylalkyl group having 1, 2 or 3, preferably 1 acid group and the like. Specific examples thereof include an aromatic group having 6 to 20 carbon atoms having an acid group and an arylalkyl group having 7 to 25 carbon atoms having an acid group. More specifically, the phenyl group which has an acidic radical, and the benzyl group which has an acidic radical are mentioned. As for an acidic radical, a hydroxyl group is preferable. That is, R ¹¹³ or R ¹¹⁴ is preferably a group having a hydroxyl group.

As the ^{monovalent organic group represented by R 113} or R ¹¹⁴ , a substituent for improving the solubility of the developer is preferably used.

It is more preferable that R ¹¹³ or R ¹¹⁴ is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl from the viewpoint of solubility in an aqueous developer solution.

From the viewpoint of solubility in the organic solvent, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. As a monovalent organic group, a linear or branched alkyl group, a cyclic alkyl group, and an aromatic group are preferable, and the alkyl group substituted by the aromatic group is more preferable.

As for carbon number of an alkyl group, 1-30 are preferable (3 or more in the case of a cyclic|annular form). The alkyl group may be linear, branched, or cyclic. Examples of the linear 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, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, and 2-ethylhexyl group are mentioned. 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 a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic cyclic alkyl group include adamantyl group, norbornyl group, bornyl group, campenyl group, decahydronaphthyl group, tricyclodecanyl group, tetracyclodecanyl group, camphoroyl group, dicyclohexyl group and pinenyl group. can be heard Moreover, as the alkyl group substituted with an aromatic group, the straight-chain alkyl group substituted with the aromatic group demonstrated below is preferable.

Specific examples of the aromatic group include a substituted or unsubstituted aromatic hydrocarbon group (as a cyclic structure constituting the group, a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentaene ring, an indene ring, an azulene ring, a heptalene ring) , an indacene ring, a perylene ring, a pentacene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, a chrysene ring, a triphenylene ring, etc.), or a substituted or unsubstituted aromatic heterocyclic group (constituting the group) Examples of the cyclic structure include a fluorene 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, Benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolizine ring, quinoline ring, phthalazine ring, naphthylidene ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, a cridine ring, phenanthroline ring, cyanthrene ring, chromene ring, xanthene ring, phenoxathiazine ring, phenothiazine ring or phenazine ring).

Moreover, it is also preferable that a polyimide precursor has a fluorine atom in a repeating unit. 10 mass % or more is preferable and, as for content of the fluorine atom in a polyimide precursor, 20 mass % or more is more preferable. Although there is no upper limit in particular, 50 mass % or less is practical.

Moreover, the aliphatic group which has a siloxane structure may be copolymerized with specific resin for the purpose of improving adhesiveness with a base material. Specific examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane and bis(paraaminophenyl)octamethylpentasiloxane.

In formula (L4-2), R ^{115 has the same meaning as R 115} in formula (L4-1), and a preferred aspect thereof is also the same.

-Resin species-

Equation (1-3) of the case, the structure of the group represented by L ⁴ represented the formula (L4-1), the specific resin is preferably a polyimide.

Equation (1-3) of, when the structure is a group represented by L ⁴ represented the formula (L4-2), the specific resin is preferably a polyimide precursor.

-content-

When the specific resin contains the repeating unit represented by the formula (1-3), the content of the repeating unit represented by the formula (1-3) is preferably 0.1 to 80 mass% with respect to the total mass of the specific resin, It is more preferable that it is 0.5-70 mass %, and it is still more preferable that it is 1-60 mass %.

Specific resin may contain only 1 type, and may contain 2 or more types of repeating units represented by Formula (1-3).

[Structure represented by Formula (1-1B)]

The aspect which has a polymeric group in the other site|part of specific resin including the structure represented by following formula (1-1B) may be sufficient as specific resin.

Although specific resin may have in a principal chain the structure represented by following formula (1-1B), and may have it in a side chain, it is preferable to have in a principal chain from a viewpoint of film strength. Moreover, from a viewpoint of applicability|paintability, it is preferable to have in a side chain.

[Formula 18]

In formula (1-1B), ^{each R B1} independently represents a hydrogen atom or an alkyl group, nB represents an integer of 2 or more, mB represents an integer of 2 or more, and * each independently represents a binding site with another structure indicates

-R ^B1 -

In formula (1-1B), R ^B1 is each independently preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, still more preferably a hydrogen atom or a methyl group .

-nB-

In formula (1-1B), nB is each independently preferably an integer of 2 to 100, more preferably an integer of 2 to 50, still more preferably an integer of 2 to 30, particularly that it is an integer of 2 to 10 Preferably, it is the most preferable that it is an integer of 3-10.

-mB-

In formula (1-1B), m is each independently preferably an integer of 2 to 50, more preferably an integer of 2 to 30, still more preferably an integer of 2 to 10, further preferably an integer of 2 to 6 Preferably, it is an integer of 2 to 4, particularly preferably, 2 or 3 is most preferable.

Specific resin is a structure represented by Formula (1-1B), A structure represented by a following formula (1-1B-1), a structure represented by a following formula (1-1B-2), and a following formula (1-1B-3) It is preferable to include at least one type of structure selected from the group consisting of structures represented by

[Formula 19]

In formulas (1-1B-1) to (1-1B-3), nB has the same meaning as nB in formula (1-1B), respectively, and a preferable aspect is also the same.

In formulas (1-1B-1) to (1-1B-3), each independently represents a binding site with another structure.

[Formula (1-2B) or Formula (1-2C)]

It is preferable that specific resin contains a structure represented by a following formula (1-2B) as a structure containing Formula (1-1B), or a structure represented by a following formula (1-2C).

When specific resin contains the structure represented by following formula (1-2B), it is preferable that specific resin contains the structure represented by following formula (1-2B) in a principal chain.

When the specific resin includes a structure represented by the following formula (1-2C), the specific resin preferably includes the structure represented by the following formula (1-2C) in the main chain terminal or side chain, and more preferably in the side chain desirable.

It is preferable that specific resin contains two or more structures represented by the structure represented by Formula (1-2B), or Formula (1-2C). When specific resin contains a plurality of structures represented by formula (1-2B) or structures represented by formula (1-2C), the structures represented by a plurality of formulas (1-2B) or structures represented by formula (1-2C) are They may be the same or different.

[Formula 20]

In Formula (1-2B), L ^B1 and L ^B2 each independently represent a single bond or a divalent coupling group, and L ^X represents the structure represented by Formula (1-1B) mentioned above.

In the formula (1-2C), L ^B3 represents a single bond or a divalent linking group, L ^X represents a structure represented by the above formula (1-1B), and R ^B2 represents a hydrogen atom, or a polymerizable group represents a substituent having no

In formula (1-2B), L ^B1 and L ^B2 are each independently a single bond, or an alkylene group, an arylene group, an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, -NR ^N -, or The group which these two or more couple|bonded is preferable, a single bond, an alkylene group, or an arylene group is more preferable, A single bond or an alkylene group is more preferable. R ^N represents a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aryl group, still more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

As said alkylene group, a C2-C10 alkylene group is preferable, A C2-C4 alkylene group is more preferable, An ethylene group or a propylene group is more preferable.

In Formula (1-2B), L ^X represents the structure represented by Formula (1-1B) mentioned above, and a preferable aspect is as having described in description in Formula (1-1B) mentioned above.

Equation (1-2C) during, L ^B3 are as defined, or L ^B1 L ^B2 in the above-described formula (1-2B), it is also the same preferred embodiment.

In Formula (1-2C), L ^X represents the structure represented by Formula (1-1B) mentioned above, and a preferable aspect is as having described in the description in Formula (1-1B) mentioned above.

In formula (1-2C), R ^B2 may be a hydrogen atom or a known substituent such as an alkyl group, an aryl group, or a halogen atom, preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group , an alkyl group is more preferable.

As said alkyl group, a C1-C20 alkyl group is preferable, A C1-C10 alkyl group is more preferable, A C1-C4 alkyl group is still more preferable.

As said aryl group, a C6-C20 alkyl group is preferable, A C6-C12 alkyl group is more preferable, A C1-C4 alkyl group is still more preferable.

[Repeating unit represented by formula (1-3B)]

When specific resin contains the structure represented by Formula (1-2B), it is preferable that specific resin contains the repeating unit represented by following formula (1-3B).

[Formula 21]

In the formula (1-3B), L ^B1 and L ^B2 each independently represent a single bond or a divalent linking group, L ^X represents the structure represented by the above-mentioned formula (1-1B), and LB ⁴ is the above-mentioned formula The structure represented by Formula (L4-1) or Formula (L4-2) in (1-3) is shown.

Formula (1-3B) of the, L ^B1, L ^B2 and L are each ^X, formula (1-2B) is as defined in L ^B1, L ^B2 and L ^X, it is also the same preferred embodiment.

In Formula (1-3B), L ^{B4 has the same meaning as L 4} in Formula (1-3) mentioned above, and a preferable aspect is also the same.

-Resin species-

Formula (1-3B) of the case, the structure L ^B4 appears group represented by the formula (L4-1), the specific resin is preferably a polyimide.

Formula (1-3B) of the case, the structure L ^B4 appears group represented by the formula (L4-2), the specific resin is preferably a polyimide precursor.

-content-

When the specific resin contains the repeating unit represented by the formula (1-3B), the content of the repeating unit represented by the formula (1-3B) is preferably 0.1 to 80 mass% with respect to the total mass of the specific resin, It is more preferable that it is 10-70 mass %, and it is still more preferable that it is 20-60 mass %.

Specific resin may contain only 1 type, and may contain 2 or more types of repeating units represented by Formula (1-3B).

[Structure represented by formula (1-3C)]

When the specific resin contains a structure represented by the formula (1-2C), the specific resin is a structure including the structure represented by the formula (1-2C), and includes a structure represented by the following formula (1-3C) desirable.

It is preferable that specific resin contains the structure represented by Formula (1-3C) in a principal chain. That is, the structure represented by L ^B5 in the formula (1-3C), preferably included in the main chain of the specific resin.

It is preferable that specific resin contains two or more structures represented by Formula (1-3C). When specific resin contains two or more structures represented by Formula (1-3C), the structure represented by several Formula (1-3C) may be same or different.

[Formula 22]

In formula (1-3C), L ^B5 represents an nB2+2-valent linking group, X ^B2 represents an ester bond, a urethane bond, a urea bond, an amide bond, or an ether bond, and X ^B1 represents the above-mentioned formula (1- 2C) represents a structure represented by, nB2 represents an integer of 1 or more, if there are X X ^B1 or ^B2 plurality, and the plurality of X X ^B1 or ^B2 will be the same or different.

In Formula (1-3C), L ^{B5 has the same meaning as L 1} in Formula (1-2) mentioned above, and a preferable aspect is also the same.

When Formula L ^B5 contains any one of the structures represented by Formulas (A-1) to (A-5), "R ^A11 to R" in the description of Formulas (A-1) to (A-5) ^{Among A14} , R ^A21 to R ^A24 , R ^A31 to R ^A38 , R ^A41 to R ^A48 and R ^A51 to R ^A58 , each b is X in Formula (1-2) or Formula (1-3) to be described later ^{2 is} a binding site with, ", "R ^A11 to R ^A14 , R ^A21 to R ^A24 , R ^A31 to R ^A38 , R ^A41 to R ^A48 and R ^A51 to R ^A58 , each of nB2 is a formula (2-1 ), which is a binding site with ^{X B2 in "."}

In Formula (1-3C), X ^{B2 has the same meaning as X 2} in Formula (1-2) mentioned above, and a preferable aspect is also the same.

In Formula (1-3C), X ^B1 represents the structure represented by Formula (1-2C) mentioned above, and a preferable aspect is as having described in the description of Formula (1-2C) mentioned above.

In Formula (1-3C), nB2 has the same meaning as b in Formula (1-2) mentioned above, and a preferable aspect is also the same.

[Repeating unit represented by formula (1-4C)]

When specific resin contains the structure represented by Formula (1-2C) or the structure represented by Formula (1-3C), it is preferable that specific resin contains the repeating unit represented by following formula (1-4C).

[Formula 23]

In formula (1-4C), L ^B5 represents an nB2+2-valent linking group, X ^B2 represents an ester bond, a urethane bond, a urea bond, an amide bond, or an ether bond, and X ^B1 represents the above-mentioned formula (1- 2C), nB2 represents an integer of 1 or more, L ^B4 represents a structure represented by Formula (L4-1) or Formula (L4-2) in Formula (1-3) above, X ^{When two} or more ^{B1 or X B2} exist, a plurality of X ^B1 or X ^B2 may be the same or different.

Equation (1-4C) during, L ^B5, and the same meaning as X ^B2, X ^B1 and ^B5 nB2 is L, X ^B2, X ^B1 and nB2 in each of the above-described formula (1-3C), a preferred embodiment Fig. same.

In Formula (1-4C), L ^{B4 has the same meaning as L 4} in Formula (1-3) mentioned above, and a preferable aspect is also the same.

-Resin species-

Equation (1-4C) if one or more of, the structure L ^B4 appears group represented by the formula (L4-1), the specific resin is preferably a polyimide.

Equation (1-4C) if one or more of, the structure L ^B4 appears group represented by the formula (L4-2), the specific resin is preferably a polyimide precursor.

-content-

When the specific resin contains the repeating unit represented by the formula (1-4C), the content of the repeating unit represented by the formula (1-4C) is preferably 0.1 to 80% by mass based on the total mass of the specific resin, It is more preferable that it is 10-80 mass %, and it is still more preferable that it is 20-75 mass %.

Specific resin may contain only 1 type, and may contain 2 or more types of repeating units represented by Formula (1-4C).

[Repeating unit represented by Formula (2-1)]

Specific resin may further contain the repeating unit represented by following formula (2-1).

Moreover, when specific resin contains the structure represented by Formula (1-2B) or Formula (1-2C), specific resin has a structure other than the structure represented by Formula (1-2B) or Formula (1-2C). contains a polymerizable group.

When the specific resin is a polyimide, the specific resin is a repeating unit having a polymerizable group, which is a repeating unit represented by the following formula (2-1) and further includes a repeating unit in which ^{L 21 is the formula (L4-1).} desirable.

When the specific resin is a polyimide precursor, the specific resin is a polymerizable group in the formula L ^B4 of the repeating unit represented by L ^B4, or the formula (1-4C) in the repeating unit represented by (1-3B) It is a repeating unit which contains or is represented by following formula (2-1), It is preferable to further include the repeating unit whose ^{L 21 is formula (L4-2).} If the formula includes a polymerizable group in L ^B4 of the repeating unit represented by L ^B4, or the formula (1-4C) in the repeating unit represented by (1-3B), said L ^B4 the formula (L4-2 ), and it is preferable to include a polymerizable group in at least one ^{of R 113} and R ¹¹⁴ in formula (L4-2).

[Formula 24]

In formula (2-1), L ²¹ represents a b2+2-valent linking group, X ²² represents an ester bond, a urethane bond, a urea bond, an amide bond, or an ether bond, and X ²¹ represents a group containing a polymerizable group , X ²¹ and X ²² are groups not containing a polyalkyleneoxy group, b2 represents an integer of 1 or more, and L ⁴ is a formula (L4-1) or a formula (L4-1) in the above-mentioned formula (1-3) ( the structure appears to L4-2), X ²² or X ²¹ if a plurality is present, and the plurality of X ²² or X ²¹ may be the same or different.

In Formula (2-1), L ²¹ , X ²² , b2 and L ^{4 each have the same meaning as L 1} , X ² , b and L ⁴ in Formula (1-3) described above, and a preferred embodiment is also the same

When formula L ²¹ includes any one of the structures represented by formulas (A-1) to (A-5), “R ^A11 to R” in the description of formulas (A-1) to (A-5) ^{Among A14} , R ^A21 to R ^A24 , R ^A31 to R ^A38 , R ^A41 to R ^A48 and R ^A51 to R ^A58 , each b is X in Formula (1-2) or Formula (1-3) to be described later ^{2 is} a binding site with "," means "R ^A11 to R ^A14 , R ^A21 to R ^A24 , R ^A31 to R ^A38 , R ^A41 to R ^{A48 ,} and R ^A51 to R ^A58 , and each b2 is a formula (2-1 ), which is a binding site with ^{X 22 in "."}

In Formula (2-1), X ²¹ represents group containing a polymerizable group, and group represented by Formula (Z-1) mentioned above is preferable.

-Resin species-

Formula (2-1) wherein L ⁴ is a structure that appears group represented by the formula (L4-1), the specific resin is preferably a polyimide.

Formula (2-1) wherein L ⁴ is a structure that appears group represented by the formula (L4-2), the specific resin is preferably a polyimide precursor.

-content-

When the specific resin contains a repeating unit represented by formula (2-1), the content of the repeating unit represented by formula (1-4C) is preferably 0.1 to 80 mass% with respect to the total mass of the specific resin, It is more preferable that it is 10-80 mass %, and it is still more preferable that it is 20-75 mass %.

Specific resin may contain only 1 type, and may contain 2 or more types of repeating units represented by Formula (2-1).

[Other repeat units]

-Repeating unit represented by formula (4)-

Specific resin may further contain the repeating unit represented by following formula (4).

When specific resin contains the repeating unit represented by following formula (4), it is preferable that specific resin is a polyimide.

When specific resin contains the repeating unit represented by following formula (4), it is preferable that specific resin contains the repeating unit represented by following formula (4) in a principal chain.

[Formula 25]

In Formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group.

Examples of the divalent organic group represented by R ^{131 include the same groups as those of R 111} in Formula (1) to be described later, and the preferable ranges are also the same. As the ^{tetravalent organic group represented by R 132 , the same group as R 115} in the above formula (L4-1) is exemplified, and the preferable range is also the same.

If R ¹ in the structure represented by formula (1-1) in the specific resin is a substituent that does not contain a polymerizable group, and if the at least one of R ¹³¹ and R ¹³² include a polymerizable group, the terminal of the polyimide You may have a structure containing a polymeric group in it.

When the specific resin contains the repeating unit represented by formula (4) (for example, when the specific resin is a polyimide), the specific resin contains the repeating unit represented by the formula (4) with respect to the total mass of the specific resin, It is preferable to contain 1-80 mass %, It is more preferable to contain 10-70 mass %, It is more preferable to contain 20-60 mass %.

Moreover, when specific resin is a polyimide, specific resin can also be set as the aspect which does not contain the repeating unit represented by Formula (4) substantially, In such an aspect, content of the repeating unit represented by Formula (4) It is preferable that it is 5 mass % or less with respect to the total mass of specific resin, and, as for silver, it is more preferable that it is 1 mass % or less.

Moreover, when specific resin is a polyimide, the repeating unit represented by Formula (1-3), the repeating unit represented by Formula (1-3B), and the repeating unit represented by Formula (1-4C) contained in specific resin. and the total content of the repeating unit represented by the formula (2-1) and the repeating unit represented by the formula (4) (a repeating unit not contained among the repeating units may be included) with respect to the total mass of the specific resin. , It is preferable that it is 50-100 mass %, It is more preferable that it is 60-99 mass %, It is more preferable that it is 70-95 mass %.

-Repeating unit represented by formula (1)-

Specific resin may further contain the repeating unit represented by following formula (1).

When specific resin contains the repeating unit represented by following formula (1), it is preferable that specific resin is a polyimide precursor.

When specific resin contains the repeating unit represented by following formula (1), it is preferable that specific resin contains the repeating unit represented by following formula (1) in a principal chain.

[Formula 26]

A ¹ and A ² each independently represents an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, R ¹¹³ and R ¹¹⁴ each independently represents a hydrogen atom or a monovalent organic group.

Formula (1) ^{of, A 1, A 2, R} 113, R 114 and R ¹¹⁵ are each independently a, A ^1, of the above formula ^{(L4-2) A 2, R 113} , R 114 and R ^115, respectively It has the same meaning, and a preferable aspect is also the same.

In Formula (1), R ¹¹¹ represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group combining two or more thereof, and a linear aliphatic group having 2 to 20 carbon atoms and 3 carbon atoms. A branched aliphatic group having ~20, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group combining two or more thereof is preferable, and an aromatic group having 6 to 20 carbon atoms is more preferable.

Of R ¹¹¹ in formula (1) it is preferably derived from a diamine. As diamine used for manufacture of a polyimide precursor, linear or branched aliphatic, cyclic aliphatic, or aromatic diamine etc. are mentioned. Only 1 type may be used for diamine, and 2 or more types may be used for it.

Specifically, diamine is 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 group combining two or more thereof. It is preferable, and it is more preferable that it is a diamine containing a C6-C20 aromatic group. Examples of the aromatic group include the following.

[Formula 27]

In the formula, A is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) ₂ -, -NHC(=O)-, or a group combining two or more of these is preferable, A single bond, a C1-C3 alkylene group which may be substituted by the fluorine atom, -O-, -C(=O)- , -S- and S(=O) ₂ - are more preferred, -CH ₂ -, -O-, -S-, -S(=O) ₂ -, -C(CF ₃ ) ₂ It is more preferable that it is a divalent group selected from the group consisting of -, and -C(CH ₃ ) _{2 -.}

Specifically as diamine, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexene three; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane phosphorus or isophoronediamine; Meta or paraphenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether , 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenylsulfone, 4,4'- or 3,3'-diaminodi Phenylsulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'- Diaminobiphenyl (4,4'-diamino-2,2'-dimethylbiphenyl), 3,3'-dimethoxy-4,4'-diaminobiphenyl, bis(4-amino-3 -Carboxyphenyl) methane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-hydroxy-4 -Aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2, 2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4, 4'-diaminoparaterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy) )phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3 '-Dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis( 4-Aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4 '-Diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoro Propane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ter, 1, 4 -Diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4, 4'-Dimethyl-3,3'-diaminodiphenylsulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2-(3', 5' -Diaminobenzoyloxy)ethyl methacrylate, 2,4- or 2,5-diaminocumene, 2,5-dimethyl-paraphenylenediamine, acetoguanamine, 2,3,5,6-tetra Methyl-paraphenylenediamine, 2,4,6-trimethyl metaphenylenediamine, 4,6-dihydroxy-1,3-phenylenediamine, bis(3-aminopropyl)tetramethyldisilox Sein, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, diaminobenzoic acid, 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, 2,2-bis[4-(3-aminophenoxy)phenyl]hexa Fluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl ]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, parabis(4-amino-2 -Trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethyl Phenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy) Diphenylsulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4 '-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, and at least one diamine selected from 2,2',5,5',6,6'-hexafluorotolidine and 4,4'-diaminoquaterphenyl.

Moreover, the diamines (DA-1) - (DA-18) shown below are also preferable.

[Formula 28]

[Formula 29]

Moreover, the diamine which has at least two alkylene glycol units in a main chain is also mentioned as a preferable example. Preferably, it is a diamine containing two or more of either or both of an ethylene glycol chain and a propylene glycol chain in 1 molecule, More preferably, it is a diamine which does not contain an aromatic ring. Specific examples include Jeffamine (registered trademark) KH-511, Jeffamine (registered trademark) ED-600, Jeffamine (registered trademark) ED-900, Jeffamine (registered trademark) ED-2003, Jeffamine (registered trademark) EDR -148, Jeffamine (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (trade names above, manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy) ) ethoxy) propoxy) propane-2-amine and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propane-2-amine, and these is not limited to

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, The structure of Jeffamine (registered trademark) EDR-176 is shown below.

[Formula 30]

In the above, x, y, and z are arithmetic mean values.

It is preferable that ^{R 111} in Formula (1) is represented ^{by -Ar 0} -L ⁰ -Ar ⁰ - from a viewpoint of the softness|flexibility of the cured film obtained. Ar ⁰ is each independently an aromatic hydrocarbon group (C6-C22 is preferable, 6-18 are more preferable, and 6-10 are especially preferable), and a phenylene group is preferable. L ⁰ is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) ₂ -; -NHCO- or the group which combined these 2 or more is shown. The preferable range of L ^{0 has} the same meaning as A above.

^{It is preferable that R 111} in Formula (1) is a divalent organic group represented by following formula (51) or Formula (61) from a viewpoint of i line|wire transmittance. In particular, it is more preferable that it is a divalent organic group represented by Formula (61) from a viewpoint of i line|wire transmittance and the easiness of an acquisition.

[Formula 31]

In formula (51), R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom, or a monovalent organic ^{group, and at least one of R 50} to R ⁵⁷ is a fluorine atom, a methyl group, a fluoromethyl group, or a difluoromethyl group. , or a trifluoromethyl group, and * each independently represents a binding site with another structure.

Examples of the monovalent organic group for R ⁵⁰ to R ⁵⁷ 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. can

[Formula 32]

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

Examples of the diamine compound giving the structure of Formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-di aminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. are mentioned. You may use 1 type of these, or may use it in combination of 2 or more type.

When the specific resin contains the repeating unit represented by Formula (1) (for example, when the specific resin is a polyimide precursor), the specific resin contains the repeating unit represented by Formula (1) with respect to the total mass of the specific resin. , It is preferable to contain 1-90 mass %, It is more preferable to contain 10-80 mass %, It is more preferable to contain 20-70 mass %.

Moreover, when specific resin is a polyimide precursor, specific resin can also be set as the aspect which does not contain the repeating unit represented by Formula (1) substantially, and in such an aspect, the repeating unit represented by Formula (1) It is preferable that it is 5 mass % or less with respect to the total mass of specific resin, and, as for content, it is more preferable that it is 1 mass % or less.

Moreover, when specific resin is a polyimide precursor, the repeating unit represented by Formula (1-3), the repeating unit represented by Formula (1-3B), and the repeating represented by Formula (1-4C) which are contained in specific resin. The total content of the unit, the repeating unit represented by the formula (2-1), and the repeating unit represented by the formula (1) (in the repeating units, an uncontained repeating unit may be included) is determined by the total mass of the specific resin. With respect to it, it is preferable that it is 50-100 mass %, It is more preferable that it is 60-99 mass %, It is more preferable that it is 70-95 mass %.

〔content〕

From the viewpoint of improving the elongation at break of the cured film obtained, the content of the specific resin in the curable resin composition of the present invention is preferably 20 mass % or more, more preferably 30 mass % or more with respect to the total solid content of the curable resin composition. and 40 mass % or more is more preferable.

As an upper limit of the said content, from a viewpoint of improving the resolution of curable resin composition, it is preferable that it is 99.5 mass % or less, It is more preferable that it is 99 mass % or less, It is more preferable that it is 98 mass % or less, It is still more preferable that it is 97 mass % or less. It is preferable, and it is still more preferable that it is 95 mass % or less.

[Physical properties of specific resins]

-Molecular Weight-

It is preferable that it is 2,000-500,000, as for the weight average molecular weight (Mw) of specific resin, it is more preferable that it is 5,000-100,000, It is more preferable that it is 10,000-50,000.

It is preferable that it is 800-250,000, as for the number average molecular weight (Mn) of specific resin, it is more preferable that it is 2,000-50,000, It is more preferable that it is 4,000-25,000.

1.5-3.5 are preferable and, as for the dispersion degree of molecular weight of specific resin, 2-3 are more preferable.

In this specification, the dispersion degree of molecular weight means the value (weight average molecular weight/number average molecular weight) obtained by dividing the weight average molecular weight by the number average molecular weight.

-acid-

When using curable resin composition for the solvent image development mentioned later, it is preferable that it is 1 mmol/g or less, as for the acid value of specific resin, it is more preferable that it is 0.5 mmol/g or less, It is still more preferable that it is 0.3 mmol/g. The lower limit of the said acid value is not specifically limited, What is necessary is just 0 mmol/g or more.

When using curable resin composition for the alkali image development mentioned later, it is preferable that it is 1.2-7 mmol/g, as for the acid value of specific resin, it is more preferable that it is 1.5-6 mmol/g, It is more preferable that it is 2-5 mmol/g .

In the present invention, the acid value means the amount (mmol) of the acid group contained in 1 g of the specific resin.

The said acidic radical means the group neutralized by the alkali (for example, sodium hydroxide) of pH 12 or more. Moreover, it is preferable that the said acidic radical is group whose pKa is 10 or less.

The said acid value is measured by a well-known method, for example, it is measured by the method of JISK0070:1992.

[Preferred aspect of specific resin]

Specific resin is at least 1 sort(s) of resin chosen from the group which consists of a polyimide and a polyimide precursor.

In the following description, a repeating unit represented by Formula (1-3), wherein L ⁴ is Formula (L4-1), is referred to as a repeating unit PI-1.

A repeating unit represented by formula (1-3B), is referred to as L ^B4 the formula repeating unit PI-2 in the repeating unit (L4-1).

A repeating unit represented by the formula (1-4C), is referred to as L ^B4 the formula (L4-1) of repeating unit repeating unit of PI-3.

A repeating unit represented by Formula (2-1), wherein L ⁴ is Formula (L4-1), is referred to as a repeating unit PI-4.

A repeating unit represented by Formula (1-3), wherein L ⁴ is Formula (L4-2), is referred to as a repeating unit PIP-1.

A repeating unit represented by formula (1-3B), is referred to as L ^B4 the formula repeating unit PIP-2 in the repeating unit (L4-2).

A repeating unit represented by the formula (1-4C), is referred to as L ^B4 the formula (L4-2) of the repeating unit PIP-3 repeating units.

A repeating unit represented by Formula (2-1), wherein L ⁴ is Formula (L4-2), is referred to as a repeating unit PIP-4.

-Polyimide-

When specific resin is a polyimide, it is preferable that specific resin is a polyimide in any one of following PI1 - following PI3.

PI1: polyimide comprising repeating unit PI-1

PI2: a polyimide comprising a repeating unit PI-2, and a repeating unit PI-4

PI3: a polyimide comprising a repeating unit PI-3, and a repeating unit PI-4

The polyimide described in PI1 may further include a repeating unit PIP-1.

The polyimide as described in said PI2 may further contain at least 1 sort(s) selected from the group which consists of repeating unit PIP-2 and repeating unit PIP-4.

The polyimide as described in said PI3 may further contain at least 1 sort(s) selected from the group which consists of repeating unit PIP-3 and repeating unit PIP-4.

The polyimide described in PI1 may further include a repeating unit PI-4. The polyimide described in PI1 may further include a repeating unit PI-4.

The polyimide as described in said PI1-PI3 may further contain other repeating units, such as a repeating unit represented by Formula (4). When the polyimide of said PI1-PI3 contains the repeating unit represented by Formula (4), it may further contain the repeating unit represented by Formula (1).

Moreover, when specific resin is a polyimide, it is preferable that it is 70 % or more, as for the ring closure rate of specific resin, it is more preferable that it is 80 % or more, It is more preferable that it is 90 % or more.

The exchange rate of specific resin in the case of specific resin being a polyimide is a value represented by following formula CR(PI).

Expression CR(PI):

Ring closure rate (%) of specific resin = (molar amount of imide ring in specific resin) / (molar amount of imide ring in specific resin + molar amount of structure capable of forming imide ring by ring closure in specific resin) x 100

For example, when the specific resin is a resin comprising a repeating unit PI-1, a repeating unit PIP-1, a repeating unit represented by the formula (4), and a repeating unit represented by the formula (1), the ring closure rate is It is a value represented by the following formula CR(PI)1.

Formula CR(PI)1:

Closing rate (%) of specific resin = (molar amount of repeating unit PI-1 + molar amount of repeating unit represented by formula (4))/(molar amount of repeating unit PI-1 + molar amount of repeating unit PIP-1 + formula (4) ) of the repeating unit represented by the molar amount + the molar amount of the repeating unit represented by the formula (1))

-Polyimide precursor-

When specific resin is a polyimide precursor, it is preferable that specific resin is a polyimide in any one of following PIP1 - following PIP5.

PIP1: polyimide precursor comprising repeating unit PIP-1

PIP2: PIP2 containing a repeating unit and the formula (1-3B) of the L ^B4 the formula (L4-2), and the formula containing R ¹¹³ and R ¹¹⁴ at least one of the polymerizable group of (L4-2) polyimide precursor

PIP3: polyimide precursor comprising a repeating unit PIP-2, and a repeating unit PIP-4

PIP4: repeating units included in the PIP-3, formula (1-3B) of the L ^B4 the formula (L4-2), and the formula containing R ¹¹³ and R ¹¹⁴ at least one of the polymerizable group of (L4-2) polyimide precursor

PIP5: polyimide precursor comprising a repeating unit PIP-3, and a repeating unit PIP-4

[Specific Example]

As a specific example of specific resin, the specific resin used in the Example mentioned later is mentioned.

[Synthesis method]

A specific resin is synthesized, for example, by the synthesis method shown in the synthesis example in the Example mentioned later.

When specific resin is the polyimide as described in said PI1, specific resin is synthesize|combined by performing the process as described in following (1)-(2) sequentially, for example.

(1) A diamine having a functional group such as a carboxy group, a hydroxyl group, or an amino group is reacted with a dicarboxylic acid or a dicarboxylic acid derivative, and after the reaction, thermal imidization or chemical imidization (for example, by reacting a catalyst) Acceleration of cyclization reaction), the process of forming an imide ring by a method such as to obtain a polyimide

(2) With respect to the functional group in the polyimide obtained in the above (1), a group capable of bonding with the functional group (for example, a hydroxyl group, a halogenated carboxy group, an isocyanate group, etc.) ) and a polyalkyleneoxy group and a compound having a polymerizable group (eg, polyalkylene glycol-monomethacrylate, etc.)

A commercially available compound may be used as a compound having a group capable of bonding with the functional group, a polyalkyleneoxy group, and a polymerizable group, and as a commercially available compound, Blemmer PE-90, PE-200, PE-350, PP-1000, PP-500, PP-800, AE-90U, AE-200, AE-400, AP-200, AP-400, AP-550, AP-800 (all are made by Nichiyu Corporation), etc. are mentioned.

When specific resin is the polyimide as described in said PI2, specific resin is synthesize|combined by performing the process of following (3)-(4) sequentially, for example.

(3) a diamine having a polyalkyleneoxy group (for example, bis(2-(3-aminopropoxy)ethyl)ether, etc.) and a diamine having a functional group such as a carboxy group, a hydroxy group, and an amino group; , dicarboxylic acid or a dicarboxylic acid derivative is reacted to form an imide ring by a method such as thermal imidization or chemical imidization (for example, promotion of cyclization reaction by reacting a catalyst) after the reaction to form a polyimide process of getting

(4) With respect to the functional group in the polyimide obtained in the above (1), a group capable of bonding with the functional group (for example, a hydroxyl group, a halogenated carboxy group, an isocyanate group, etc.) ) and a compound having a polymerizable group (eg, methacrylic acid chloride, etc.)

When specific resin is the polyimide as described in said PI3, specific resin is synthesize|combined by performing the process of following (5)-(6) sequentially, for example.

(5) A diamine having a functional group such as a carboxy group, a hydroxyl group, or an amino group is reacted with a dicarboxylic acid or a dicarboxylic acid derivative, and after the reaction, thermal imidization or chemical imidization (eg, by reacting a catalyst) Acceleration of cyclization reaction), the process of forming an imide ring by a method such as to obtain a polyimide

(6) With respect to the functional group in the polyimide obtained in the above (1), a group capable of bonding with the functional group (for example, a hydroxyl group, a halogenated carboxy group, an isocyanate group, etc.) ), a compound having a polyalkyleneoxy group (eg, polyalkylene glycol monoalkylene ether, etc.), and a group capable of bonding with the functional group (eg, a hydroxy group, halogenated A step of reacting a compound having a polymerizable group (for example, hydroxyethyl methacrylate, etc.) with an optional carboxy group, isocyanate group, etc.)

As a synthesis method when specific resin is a polyimide precursor, the method of making diamine and the dicarboxylic acid derivative which at least one of a polyalkyleneoxy group and a polymeric group introduce|transduced into a part of carboxylic acid react is mentioned, for example.

As said diamine, you may use the diamine which has a polyalkyleneoxy group.

<Other resins>

The curable resin composition of the present invention may contain other resins different from the above-mentioned specific resins (hereinafter, simply referred to as "other resins").

As other resin, a polyimide of a different kind from specific resin, a polyimide precursor, etc. are mentioned.

When the specific resin is a polyimide, it is preferable that the other resin is a polyimide.

When a specific resin is a polyimide precursor, it is preferable that other resin is a polyimide precursor.

[Polyimide (Other Resin)]

It is preferable that the polyimide which is another resin from a viewpoint of the film strength of the cured film obtained has a repeating unit represented by Formula (4) mentioned above.

Polyimide WHEREIN: Although 1 type may be sufficient as the repeating unit represented by Formula (4), 2 or more types may be sufficient as it. Moreover, polyimide may also contain the repeating unit of another type other than the repeating unit of said Formula (4).

As one embodiment of the polyimide in this invention, 50 mol% or more of all repeating units, Furthermore, 70 mol% or more, and especially 90 mol% or more are illustrated polyimide precursors which are repeating units represented by Formula (4) . As an upper limit, 100 mol% or less is practical.

The weight average molecular weight (Mw) of a polyimide becomes like this. Preferably it is 2,000-500,000, More preferably, it is 5,000-100,000, More preferably, it is 10,000-50,000. Moreover, the number average molecular weight (Mn) becomes like this. Preferably it is 800-250,000, More preferably, it is 2,000-50,000, More preferably, it is 4,000-25,000.

1.5-3.5 are preferable and, as for the dispersion degree of molecular weight of a polyimide, 2-3 are more preferable.

A polyimide is obtained by cyclizing the polyimide precursor which is another resin mentioned later by heating etc., for example.

[Polyimide precursor (other resin)]

It is preferable that a polyimide precursor has the repeating unit represented by Formula (1) mentioned above from a viewpoint of the film strength of the cured film obtained.

Polyimide precursor WHEREIN: 1 type may be sufficient as the repeating unit represented by Formula (1), but 2 or more types may be sufficient as it. Moreover, the structural isomer of the repeating unit represented by Formula (1) may be included. Moreover, a polyimide precursor may also contain the repeating unit of another type other than the repeating unit of said Formula (1).

As one Embodiment of the polyimide precursor in this invention, 50 mol% or more of all repeating units, Furthermore, 70 mol% or more, and especially 90 mol% or more are illustrated polyimide precursors which are repeating units represented by Formula (1) do. As an upper limit, 100 mol% or less is practical.

The weight average molecular weight (Mw) of a polyimide precursor becomes like this. Preferably it is 2,000-500,000, More preferably, it is 5,000-100,000, More preferably, it is 10,000-50,000. Moreover, the number average molecular weight (Mn) becomes like this. Preferably it is 800-250,000, More preferably, it is 2,000-50,000, More preferably, it is 4,000-25,000.

1.5-3.5 are preferable and, as for the dispersion degree of the molecular weight of a polyimide precursor, 2-3 are more preferable.

A polyimide precursor is obtained by making dicarboxylic acid or a dicarboxylic acid derivative and diamine react. Preferably, it is obtained by halogenating dicarboxylic acid or a dicarboxylic acid derivative using a halogenating agent, followed by reaction with diamine.

In the manufacturing method of a polyimide precursor, it is preferable to use the organic solvent in the case of reaction. The number of organic solvents may be one, and 2 or more types may be sufficient as them.

Although it can determine suitably as an organic solvent according to a raw material, Pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone are illustrated.

In the case of manufacture of a polyimide precursor, it is preferable that the process of depositing solid is included. Specifically, solid deposition can be achieved by precipitating the polyimide precursor in the reaction solution in water and dissolving the polyimide precursor such as tetrahydrofuran in a soluble solvent.

When the curable resin composition of the present invention contains another resin, the content of the other resin is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and 1% by mass or more with respect to the total solid content of the curable resin composition. It is more preferable, it is still more preferable that it is 2 mass % or more, It is still more preferable that it is 5 mass % or more, It is still more preferable that it is 10 mass % or more. Further, in the curable resin composition of the present invention, the content of the other resin is preferably 80% by mass or less, more preferably 75% by mass or less, and more preferably 70% by mass or less, with respect to the total solid content of the curable resin composition. It is preferable, and it is still more preferable that it is 60 mass % or less, It is still more preferable that it is 50 mass % or less.

The curable resin composition of this invention may contain 1 type of other resin, and may contain it 2 or more types. When 2 or more types are included, it is preferable that a total amount becomes the said range.

<Polymerization Initiator>

Curable resin composition of this invention contains a polymerization initiator.

As a polymerization initiator, a photoinitiator is preferable.

(Photoinitiator)

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

It is preferable that a photoinitiator is a photoradical polymerization initiator. There is no restriction|limiting in particular as a photoradical polymerization initiator, It can select suitably from well-known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light in the visible region from the ultraviolet region is preferable. Moreover, the activator which generate|occur|produces an active radical by generating a certain action with the photo-excited sensitizer may be sufficient.

The photoradical polymerization initiator preferably contains at least one compound having a molar extinction coefficient of ^{at least about 50L·mol -1·} cm ^-1 within the range of about 300 to 800 nm (preferably 330 to 500 nm). do. The molar extinction coefficient of a compound can be measured using a well-known method. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) at a concentration of 0.01 g/L using ethyl acetate.

As a photoradical polymerization initiator, a well-known compound can be used arbitrarily. For example, acylphosphine compounds such as halogenated hydrocarbon derivatives (eg, a compound having a triazine skeleton, a compound having an oxadiazole skeleton, a compound having a trihalomethyl group, etc.) and acylphosphine oxide , hexaarylbiimidazole, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds, A metallocene compound, an organic boron compound, an iron arene complex, etc. are mentioned. For these details, Paragraph 0165 - 0182 of Unexamined-Japanese-Patent No. 2016-027357, Paragraph 0138 - Description of 0151 of International Publication No. 2015/199219 can be considered into consideration, and this content is integrated in this specification.

As a ketone compound, the compound of Paragraph 0087 of Unexamined-Japanese-Patent No. 2015-087611 is illustrated, for example, This content is integrated in this specification. In a commercial item, Gayacure DETX (made by Nippon Kayaku Co., Ltd.) is also used suitably.

In one embodiment of the present invention, as the photoradical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be suitably used. More specifically, the aminoacetophenone-type initiator of Unexamined-Japanese-Patent No. 10-291969 and the acylphosphine oxide-type initiator of Unexamined-Japanese-Patent No. 4225898 can be used, for example.

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

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

As the aminoacetophenone-based initiator, a compound described in Japanese Patent Application Laid-Open No. 2009-191179 in which an absorption maximum wavelength is matched to a wavelength light source such as 365 nm or 405 nm can also be used.

Examples of the acylphosphine-based initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. In addition, commercially available IRGACURE-819 and IRGACURE-TPO (trade names: all manufactured by BASF) can be used.

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

As a photoradical polymerization initiator, More preferably, an oxime compound is mentioned. By using an oxime compound, it becomes possible to improve an exposure latitude more effectively. An oxime compound has a wide exposure latitude (exposure margin), and since it also acts as a photocuring accelerator, it is especially preferable.

As a specific example of an oxime compound, the compound of Unexamined-Japanese-Patent No. 2001-233842, the compound of Unexamined-Japanese-Patent No. 2000-080068, and the compound of Unexamined-Japanese-Patent No. 2006-342166 can be used.

Preferred oxime compounds include, for example, compounds of the following structures, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy) ) iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, and the like. In the curable resin composition of this invention, it is especially preferable to use an oxime compound (oxime type photoinitiator) as a photoradical polymerization initiator. An oxime-type photoinitiator has a coupling group of >C=N-O-C(=O)- in a molecule|numerator.

[Formula 33]

Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKA, Inc., the optical radical described in Japanese Patent Application Laid-Open No. 2012-014052) Polymerization initiator 2) is also used suitably. In addition, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), Adeca Arcles NCI-831 and Adeca Arcles NCI-930 (Co., Ltd.) ADEKA) can also be used. Moreover, DFI-091 (made by Daito Chemix Co., Ltd.) can be used.

Moreover, it is also possible to use the oxime compound which has a fluorine atom. As a specific example of such an oxime compound, the compound described in Unexamined-Japanese-Patent No. 2010-262028, the compound 24, 36-40 which are described in Paragraph 0345 of Unexamined-Japanese-Patent No. 2014-500852, Unexamined-Japanese-Patent No. 2013- The compound (C-3) described in Paragraph 0101 of 164471, etc. are mentioned.

As a most preferable oxime compound, the oxime compound which has a specific substituent shown in Unexamined-Japanese-Patent No. 2007-269779, the oxime compound which has a thioaryl group shown in Unexamined-Japanese-Patent No. 2009-191061, etc. are mentioned.

A photoradical polymerization initiator is a trihalomethyltriazine compound, a benzyldimethyl ketal compound, (alpha)-hydroxyketone compound, (alpha)-amino ketone compound, an acylphosphine compound, a phosphine oxide compound, a metal from a viewpoint of exposure sensitivity. Rosene compound, oxime compound, triarylimidazole dimer, onium salt compound, benzothiazole compound, benzophenone compound, acetophenone compound and derivatives thereof, cyclopentadiene-benzene-iron complex and salts thereof, halomethyloxa A compound selected from the group consisting of a diazole compound and a 3-aryl substituted coumarin compound is preferred.

A more preferable photoradical polymerization initiator is a trihalomethyltriazine compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, and an onium salt compound. , a benzophenone compound, an acetophenone compound, and at least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound. It is preferable, and it is still more preferable to use a metallocene compound or an oxime compound, and an oxime compound is still more preferable.

Moreover, a photoradical polymerization initiator is N,N'- tetraalkyl-4,4'- diamino, such as benzophenone and N,N'- tetramethyl-4,4'- diamino benzophenone (Michler's ketone) Benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morphopoly Aromatic ketones such as no-propanone-1, quinones condensed with aromatic rings such as alkylanthraquinone, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, benzyldi Benzyl derivatives, such as methyl ketal, etc. can also be used. Moreover, the compound represented by following formula (I) can also be used.

[Formula 34]

In formula (I), R ^I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, 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 and an alkyl group having 1 to 4 carbon atoms interrupted by one or more oxygen atoms is a phenyl group substituted with at least one of, or biphenyl, R ^I01 is a group represented by Formula (II), or is the same group as ^{R I00 , and R I02} to R ^I04 are each independently an alkyl having 1 to 12 carbon atoms, 1 carbon number It is an alkoxy group of ~12 or halogen.

[Formula 35]

Wherein, R ~ R ^{I05 I07} is the same as R ^I02 ~ ^I04 R of the formula (I).

Moreover, as a photo-radical polymerization initiator, the compound of Paragraph 0048 - 0055 of International Publication No. 2015/125469 can also be used.

When a photoinitiator is included, it is preferable that the content is 0.1-30 mass % with respect to the total solid of curable resin composition of this invention, More preferably, it is 0.1-20 mass %, More preferably, it is 0.5-15 mass %. It is mass %, More preferably, it is 1.0-10 mass %. The photoinitiator may contain only 1 type, and may contain it 2 or more types. When containing 2 or more types of photoinitiators, it is preferable that the sum total is the said range.

[Polymerization Initiator]

The curable resin composition of this invention may contain a thermal-polymerization initiator as a polymerization initiator, and may also contain especially a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound which generate|occur|produces a radical by the energy of heat, and initiates or accelerates|stimulates the polymerization reaction of the compound which has polymerizability. By adding the thermal radical polymerization initiator, when the specific resin is a polyimide precursor, the polymerization reaction of the specific resin and the polymerizable compound can be advanced along with the cyclization of the precursor, so that higher heat resistance can be achieved.

As a thermal radical polymerization initiator, the compound specifically described in Paragraph 0074 of Unexamined-Japanese-Patent No. 2008-063554 - 0118 is mentioned.

When a thermal polymerization initiator is included, it is preferable that the content is 0.1-30 mass % with respect to the total solid of curable resin composition of this invention, More preferably, it is 0.1-20 mass %, More preferably, it is 5- 15 mass %. The thermal polymerization initiator may contain only 1 type, and may contain it 2 or more types. When two or more types of thermal-polymerization initiators are contained, it is preferable that the sum total is the said range.

<Polymerizable compound>

[Radically Polymerizable Compound]

Curable resin composition of this invention contains a polymeric compound.

As the polymerizable compound, a radical polymerizable compound can be used. A radically polymerizable compound is a compound which has a radically polymerizable group. As a radically polymerizable group, group which has ethylenically unsaturated bonds, such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth)acryloyl group, is mentioned. A (meth)acryloyl group is preferable and, as for a radically polymerizable group, a (meth)acryloxy group is more preferable from a reactive viewpoint.

One or two or more may be sufficient as the number of the radically polymerizable group which a radically polymerizable compound has, However, It is preferable to have two or more radically polymerizable groups, and, as for a radically polymerizable compound, it is more preferable to have three or more. 15 or less are preferable, as for an upper limit, 10 or less are more preferable, and 8 or less are still more preferable.

2,000 or less are preferable, as for the molecular weight of a radically polymerizable compound, 1,500 or less are more preferable, 900 or less are still more preferable. As for the minimum of the molecular weight of a radically polymerizable compound, 100 or more are preferable.

It is preferable that curable resin composition of this invention contains at least 1 sort(s) of a bifunctional or more than radically polymerizable compound which contains two or more radically polymerizable groups from a developable viewpoint, It is at least 1 sort(s) of a trifunctional or more than radically polymerizable compound. It is more preferable to include Moreover, the mixture of a bifunctional radically polymerizable compound and trifunctional or more than trifunctional radically polymerizable compound may be sufficient. For example, the number of functional groups of a bifunctional or more than bifunctional polymerizable monomer means that the number of radically polymerizable groups in 1 molecule is two or more.

Specific examples of the radically polymerizable compound include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters and amides thereof, preferably , esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group, or a sulfanyl group, and monofunctional or polyfunctional isocyanates or epoxies, or monofunctional or polyfunctional carboxylic acid A dehydration-condensation reaction product or the like is also suitably used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines, and thiols, and a halogeno group or tosyloxy group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a monofunctional or polyfunctional alcohol, amine, or thiol is also suitable. In addition, as another example, it is also possible to use a group of compounds substituted with vinyl benzene derivatives such as unsaturated phosphonic acid and styrene, vinyl ether, allyl ether, etc. instead of the above unsaturated carboxylic acid. As a specific example, Paragraph 0113 of Unexamined-Japanese-Patent No. 2016-027357 - description of 0122 can be considered into consideration, and these content is integrated in this specification.

Moreover, as for a radically polymerizable compound, the compound which has a boiling point of 100 degreeC or more 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, trimethylol propane tri (acryloyloxy) After adding ethylene oxide or propylene oxide to polyfunctional alcohol such as propyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin or trimethylolethane, (meth) acrylated compound, Japanese publication Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, Japanese Unexamined Patent Publication No. 51-037193 Urethane (meth)acrylates as described in each publication, Japanese Patent Application Laid-Open No. Epoxy acrylate, which is a reaction product of polyester acrylates and epoxy resins and (meth)acrylic acid described in each publication, No. 48-064183, Japanese Patent Publication No. 49-043191, and Japanese Publication No. No. 52-030490 Polyfunctional acrylates and methacrylates, such as a compound, and mixtures thereof are mentioned. Moreover, the compound of Paragraph 0254 of Unexamined-Japanese-Patent No. 2008-292970 - 0257 is also suitable. Moreover, polyfunctional (meth)acrylate obtained by making polyfunctional carboxylic acid react with cyclic ether groups, such as glycidyl (meth)acrylate, and the compound which has an ethylenically unsaturated bond, etc. are mentioned.

Moreover, it has a fluorene ring and is ethylenic as described in Unexamined-Japanese-Patent No. 2010-160418, Unexamined-Japanese-Patent No. 2010-129825, Unexamined-Japanese-Patent No. 4364216 etc. as a preferable radically polymerizable compound other than what was mentioned above. It is also possible to use a compound having two or more groups having an unsaturated bond, or a cardo resin.

In addition, as other examples, the specific unsaturated compounds described in Japanese Patent Application Laid-Open No. 46-043946, Japanese Unexamined Patent Publication No. Hei 01-040337, and Japanese Unexamined Patent Publication No. Hei 01-040336, and Japanese Patent Application Laid-Open No. Hei 02-025493 and the vinylphosphonic acid-based compounds described in the preceding paragraph. Moreover, the compound containing the perfluoroalkyl group described in Unexamined-Japanese-Patent No. 61-022048 can also be used. Also, the Journal of the Japan Adhesive Association vol. 20, No. 7, pages 300 to 308 (1984), those introduced as photopolymerizable monomers and oligomers 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 and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used, the contents of which are incorporated herein by reference. .

Moreover, after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described with the specific example as Formula (1) and Formula (2) in Unexamined-Japanese-Patent No. 10-062986 (meth)acrylated, A compound can also be used as a radically polymerizable compound.

In addition, the compound of Paragraph 0104 - 0131 of Unexamined-Japanese-Patent No. 2015-187211 can also be used as another radically polymerizable compound, These content is integrated in this specification.

As a radically polymerizable compound, dipentaerythritol triacrylate (as a commercial item, KAYARAD D-330; Nippon Kayaku Co., Ltd. product), dipentaerythritol tetraacrylate (as a commercial item, KAYARAD D-320; Nippon Kayaku Co., Ltd.) ) agent, A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (Meth) acrylate (as a commercial product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.), and (meth)acryloyl groups thereof are ethylene glycol residues or propylene glycol A structure bonding through a call residue is preferable. These oligomeric types can also be used.

As a commercial item of a radically polymerizable compound, SR-494 which is a tetrafunctional acrylate which has four ethyleneoxy chains by Sartomer, for example, SR- which is a bifunctional methacrylate which has four ethyleneoxy chains, manufactured by Sartomer Co., Ltd. 209, 231, 239, manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having 6 pentyleneoxy chains, TPA-330, which is a trifunctional acrylate having 3 isobutyleneoxy chains, oil Retain oligomer UAS-10, UAB-140 (manufactured by Nippon Seishi Corporation), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical), Blemmer PME400 (Ni) Healing Co., Ltd.) and the like.

As the radically polymerizable compound, as described in Japanese Patent Application Laid-Open No. 48-041708, Japanese Unexamined Patent Publication No. 51-037193, Japanese Unexamined Patent Publication No. Hei 02-032293, and Japanese Unexamined Patent Publication No. Hei 02-016765. Ethylene described in the same urethane acrylates, Japanese Patent Publication No. 58-049860, Japanese Publication No. 56-017654, Japanese Publication No. 62-039417, and Japanese Publication No. 62-039418 Also suitable are urethane compounds having an oxide-based skeleton. Moreover, as a radically polymerizable compound, it has an amino structure or a sulfide structure in a molecule|numerator, which is described in Unexamined-Japanese-Patent No. 63-277653, Unexamined-Japanese-Patent No. 63-260909, and Unexamined-Japanese-Patent No. Hei 01-105238. A compound may also be used.

A radically polymerizable compound which has acidic radicals, such as a carboxy group and a phosphoric acid group, may be sufficient as a radically polymerizable compound. The radically polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and is radically polymerizable in which an acid group is given by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A compound is more preferable. Particularly preferably, in the radically polymerizable compound in which an acid group is given by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of the aliphatic polyhydroxy compound, the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. It is a phosphorus compound. As a commercial item, M-510, M-520, etc. are mentioned, for example as a polybasic acid modified|denatured acrylic oligomer made from Toagosei Corporation.

The preferable acid value of the polymeric compound which has an acidic radical is 0.1-40 mgKOH/g, Especially preferably, it is 5-30 mgKOH/g. When the acid value of a radically polymerizable compound is the said range, it is excellent in the handleability on manufacture, and by extension, it is excellent in developability. Moreover, polymerizability is favorable. The said acid value is measured based on description of JISK0070:1992.

The curable resin composition of this invention can use a monofunctional radically polymerizable compound suitably as a radically polymerizable compound from a viewpoint of the curvature suppression accompanying elastic modulus control of a cured film. Examples of the monofunctional radically polymerizable compound include 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, glycidyl (meth) acrylate, polyethylene glycol (meth)acrylic acid derivatives such as lycol mono(meth)acrylate and polypropylene glycol mono(meth)acrylate; N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam; Allyl compounds, such as cydyl ether, diallyl phthalate, and triallyl trimellitate, etc. are used preferably. As a monofunctional radically polymerizable compound, in order to suppress volatilization before exposure, the compound which has a boiling point of 100 degreeC or more under normal pressure is also preferable.

[Polymerizable compounds other than the radically polymerizable compound mentioned above]

Curable resin composition of this invention can contain polymeric compounds other than the radically polymerizable compound mentioned above further. Examples of the polymerizable compound other than the radical polymerizable compound described above include a compound having a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl group; epoxy compounds; oxetane compounds; and benzoxazine compounds.

-A compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group-

As a compound which has a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl group, the compound represented by a following formula (AM1), (AM4), or (AM5) is preferable.

[Formula 36]

(Wherein, t represents an integer of 1 to 20, R ¹⁰⁴ represents an organic group having a t valency of 1 to 200 carbon atoms, R ^{105 represents a group represented by -OR 106} or -OCO-R ¹⁰⁷ , R ¹⁰⁶ Silver represents a hydrogen atom or an organic group ^{having 1 to 10 carbon atoms, and R 107} represents an organic group having 1 to 10 carbon atoms.)

[Formula 37]

(Wherein, R ⁴⁰⁴ represents a divalent organic group having 1 to 200 carbon atoms, R ⁴⁰⁵ represents a group represented by -OR ⁴⁰⁶ or -OCO-R ⁴⁰⁷ , R ⁴⁰⁶ is a hydrogen atom or an organic group having 1 to 10 carbon atoms group, and R ⁴⁰⁷ represents an organic group having 1 to 10 carbon atoms.)

[Formula 38]

(Wherein, u represents an integer of 3 to 8, R ⁵⁰⁴ represents an organic group having a valence of 1 to 200 carbon atoms, R ^{505 represents a group represented by -OR 506} or -OCO-R ⁵⁰⁷ , R ⁵⁰⁶ is, A hydrogen atom or an organic group ^{having 1 to 10 carbon atoms is represented, and R 507} is an organic group having 1 to 10 carbon atoms.)

As a specific example of the compound represented by Formula (AM4), 46DMOC, 46DMOEP (above, a brand name, Asahi Yukizai Kogyo Co., Ltd. product), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML -PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (above, trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 ( brand name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, and the like.

Moreover, as a specific example of the compound represented by Formula (AM5), TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP , HMOM-TPPHBA, HMOM-TPHAP (above, brand name, manufactured by Honshu Chemical Co., Ltd.), TM-BIP-A (brand name, manufactured by Asahi Yukizai Kogyo Co., Ltd.), NIKALAC MX-280, NIKALAC MX-270 , NIKALAC MW-100LM (above, a brand name, manufactured by Sanwa Chemical Co., Ltd.) is mentioned.

-Epoxy compound (compound having an epoxy group)-

As an epoxy compound, it is preferable that it is a compound which has two or more epoxy groups in 1 molecule. The epoxy group undergoes a crosslinking reaction at 200° C. or less, and since a dehydration reaction resulting from crosslinking does not occur, film shrinkage hardly occurs. For this reason, containing an epoxy compound is effective in low-temperature hardening of curable resin composition, and suppression of curvature.

It is preferable that an epoxy compound contains a polyethylene oxide group. Thereby, an elastic modulus falls more and curvature can be suppressed. The polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and it is preferable that the number of repeating units is 2-15.

As an example of an epoxy compound, Bisphenol A epoxy resin; bisphenol F-type epoxy resin; alkylene glycol-type epoxy resins such as propylene glycol diglycidyl ether; polyalkylene glycol-type epoxy resins such as polypropylene glycol diglycidyl ether; Although epoxy group containing silicones, such as polymethyl (glycidyloxypropyl) siloxane, etc. are mentioned, It is not limited to these. Specifically, Epiclone (registered trademark) 850-S, Epiclone (registered trademark) HP-4032, Epiclone (registered trademark) HP-7200, Epiclone (registered trademark) HP-820, Epiclone (registered trademark) HP-4700, Epiclone (registered trademark) EXA-4710, Epiclone (registered trademark) HP-4770, Epiclone (registered trademark) EXA-859CRP, Epiclone (registered trademark) EXA-1514, Epiclone (registered trademark) EXA-4880, Epiclone (registered trademark) EXA-4850-150, Epiclone EXA-4850-1000, Epiclone (registered trademark) EXA-4816, Epiclone (registered trademark) EXA-4822 (more than trade names, DIC) ), Rika Resin (registered trademark) BEO-60E (trade name, Shin-Nippon Rica Co., Ltd.), EP-4003S, EP-4000S (above brand name, ADEKA Co., Ltd. make), etc. are mentioned. Among these, the epoxy resin containing a polyethylene oxide group is preferable at the point excellent in suppression of curvature and heat resistance. For example, Epiclone (registered trademark) EXA-4880, Epiclone (registered trademark) EXA-4822, and Likaresin (registered trademark) BEO-60E are preferable because they contain a polyethylene oxide group.

-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-hydroxymethyloxetane, 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, etc. are mentioned. . As a specific example, Toagosei Co., Ltd. Aaron Oxetane series (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be used suitably, These may be used individually or in mixture of 2 or more types do.

-benzoxazine compound (compound having a benzoxazolyl group)-

A benzoxazine compound is preferable at the point that degassing does not generate|occur|produce at the time of hardening because of the crosslinking reaction derived from a ring-opening addition reaction, and makes thermal contraction small and generation|occurrence|production of curvature is suppressed.

Preferred examples of the benzoxazine compound include Ba-type benzoxazine, Bm-type benzoxazine (above, trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, phenol novolac-type dihydrobenz and oxazine compounds. These may be used independently or may mix 2 or more types.

It is preferable that content of a polymeric compound is more than 0 mass % and 60 mass % or less with respect to the total solid of curable resin composition of this invention. As for a minimum, 5 mass % or more is more preferable. It is more preferable that it is 50 mass % or less, and, as for an upper limit, it is still more preferable that it is 30 mass % or less.

Although a polymeric compound may be used individually by 1 type, it may mix and use 2 or more types. When using 2 or more types together, it is preferable that the total amount becomes said range.

<solvent>

Curable resin composition of this invention contains a solvent. As a solvent, a well-known solvent can be used arbitrarily. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.

As the esters, for example, 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, δ-valerolactone, alkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate; ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionic acid alkyl esters (eg, 3-alkyloxypropionate methyl, 3-alkyloxypropionate ethyl, etc.) (For example, 3-methoxypropionate methyl, 3-methoxypropionate ethyl, 3-ethoxypropionate methyl, 3-ethoxypropionate ethyl, etc.), 2-alkyloxypropionic acid alkyl esters (eg, 2 -Methyl alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-ethoxy methyl propionate, 2-ethoxypropionate ethyl)), 2-alkyloxy-2-methylpropionate, and 2-alkyloxy-2-methylpropionate ethyl (eg, 2-methoxy-2-methylpropionate, 2 -ethoxy-2-methylpropionate etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. are mentioned as suitable.

As the ethers, for example, 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, propylene glycol monomethyl ether acetate , propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. are mentioned as suitable.

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

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

As sulfoxides, for example, dimethyl sulfoxide is mentioned as a suitable thing.

Suitable amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide.

The form in which a solvent mixes 2 or more types from viewpoints, such as improvement of coated surface properties, is also preferable.

In the present invention, 3-ethoxy methyl propionate, 3-ethoxy propionate ethyl, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxy methyl propionate, 2-heptane one, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and One type of solvent selected from propylene glycol methyl ether acetate, or a mixed solvent composed of two or more types is preferable. A combination of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

The content of the solvent is preferably such that the total solids concentration of the curable resin composition of the present invention is 5-80% by mass, more preferably 5-75% by mass, from the viewpoint of applicability, It is more preferable to set it as the quantity used as 10-70 mass %, and it is still more preferable to set it as 40-70 mass %. What is necessary is just to adjust solvent content according to the desired thickness of a coating film, and an application|coating method.

The solvent may contain only 1 type, and may contain it 2 or more types. When containing 2 or more types of solvents, it is preferable that the sum total is the said range.

<Thermal acid generator>

It is preferable that curable resin composition of this invention contains a thermal acid generator.

The thermal acid generator generates an acid by heating, and at least one compound selected from a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxetane compound, and a benzoxazine compound, or specific There is an effect of accelerating the crosslinking reaction of the methylol group contained in the resin.

Moreover, when curable resin composition of this invention contains a thermal acid generator, it is preferable that specific resin contains a methylol group as a polymeric group.

50 degreeC - 270 degreeC are preferable and, as for the thermal decomposition start temperature of a thermal acid generator, 50 degreeC - 250 degreeC are more preferable. In addition, no acid is generated during drying (pre-baking: about 70 to 140 ° C.) after the curable resin composition is applied to the substrate, and the final heating after patterning by exposure and development (cure: about 100 to 400 ° C) It is preferable to select a thermal acid generator that generates an acid to the surface, since a decrease in sensitivity at the time of development can be suppressed.

The thermal decomposition start temperature is obtained as the peak temperature of the exothermic peak with the lowest temperature when the thermal acid generator is heated to 500°C at 5°C/min in the pressure-resistant capsule.

Q2000 (made by TA Instruments) etc. are mentioned as an apparatus used when measuring the thermal decomposition start temperature.

The acid generated from the thermal acid generator is preferably a strong acid, for example, an arylsulfonic acid such as p-toluenesulfonic acid or benzenesulfonic acid, an alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid or butanesulfonic acid A haloalkyl sulfonic acid, such as a phonic acid or a trifluoromethanesulfonic acid, etc. is preferable. As an example of such a thermal acid generator, the thing of Paragraph 0055 of Unexamined-Japanese-Patent No. 2013-072935 is mentioned.

Among them, it is more preferable to generate an alkylsulfonic acid having 1 to 4 carbon atoms or a haloalkylsulfonic acid having 1 to 4 carbon atoms from the viewpoint that there is little residual in the cured film and it is difficult to reduce the properties of the cured film, methanesulfonic acid (4- Hydroxyphenyl)dimethylsulfonium, methanesulfonic acid (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium, methanesulfonate benzyl (4-hydroxyphenyl)methylsulfonium, methanesulfonic acid benzyl (4-((methoxycarbonyl)oxy)phenyl)methylsulfonium, methanesulfonic acid (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)sulfonium, trifluoromethanesulfonic acid (4-hydro Roxyphenyl)dimethylsulfonium, trifluoromethanesulfonic acid (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium, trifluoromethanesulfonic acid benzyl (4-hydroxyphenyl)methylsulfonium , trifluoromethanesulfonic acid benzyl (4-((methoxycarbonyl) oxy) phenyl) methylsulfonium, trifluoromethanesulfonic acid (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium , 3-(5-(((propylsulfonyl)oxy)imino)thiophene-2(5H)-iriden)-2-(o-tolyl)propanenitrile, 2,2-bis(3- (methanesulfonylamino)-4-hydroxyphenyl)hexafluoropropane is preferable as the thermal acid generator.

Moreover, the compound of Paragraph 0059 of Unexamined-Japanese-Patent No. 2013-167742 is also preferable as a thermal acid generator.

0.01 mass part or more is preferable with respect to 100 mass parts of specific resin, and, as for content of a thermal acid generator, 0.1 mass part or more is more preferable. By containing 0.01 mass part or more, since crosslinking reaction is accelerated|stimulated, the mechanical characteristic and chemical-resistance of a cured film can be improved more. Moreover, from a viewpoint of the electrical insulation of a cured film, 20 mass parts or less are preferable, 15 mass parts or less are more preferable, and 10 mass parts or less are still more preferable.

<Onium salt>

It is preferable that curable resin composition of this invention contains an onium salt.

In particular, when specific resin is a polyimide precursor, it is preferable that curable resin composition contains an onium salt.

Although the kind of onium salt is not specifically defined, An ammonium salt, an iminium salt, a sulfonium salt, an iodonium salt, or a phosphonium salt is mentioned preferably.

Among these, an ammonium salt or an iminium salt is preferable from a viewpoint of high thermal stability, and a sulfonium salt, an iodonium salt, or a phosphonium salt is preferable from a viewpoint of compatibility with a polymer.

Moreover, an onium salt is a salt of the cation and anion which have an onium structure, The said cation and anion may couple|bond via a covalent bond, and it is not necessary to couple|bond together via a covalent bond.

That is, the onium salt may be an intramolecular salt having a cation moiety and an anion moiety in the same molecular structure, or may be an intermolecular salt in which a cation molecule and an anion molecule, which are separate molecules, are ionically bonded, but is preferably an intermolecular salt. Moreover, curable resin composition of this invention WHEREIN: The said cation part or a cation molecule, and the said anion part or an anion molecule may couple|bond by an ionic bond, and may dissociate.

The cation in the onium salt is preferably an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation, and is selected from the group consisting of a tetraalkylammonium cation, a sulfonium cation and an iodonium cation. At least 1 type of cation is more preferable.

A thermal base generator may be sufficient as the onium salt used in this invention.

A thermal base generator means the compound which generate|occur|produces a base by heating, for example, the acidic compound etc. which generate|occur|produce a base when heated at 40 degreeC or more are mentioned.

[Ammonium Salt]

In the present invention, an ammonium salt means a salt of an ammonium cation and an anion.

-ammonium cation-

As the ammonium cation, a quaternary ammonium cation is preferable.

Moreover, as an ammonium cation, the cation represented by following formula (101) is preferable.

[Formula 39]

In formula (101), R ¹ to R ⁴ each independently represent a hydrogen atom or a hydrocarbon group, and ^{at least two of R 1} to R ⁴ may be bonded to each other to form a ring.

In formula (101), R ¹ to R ⁴ are each independently preferably a hydrocarbon group, more preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms. . R ¹ to R ⁴ may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group and the like.

When ^{at least two of R 1} to R ⁴ are bonded to each other to form a ring, the ring may contain a hetero atom. A nitrogen atom is mentioned as said hetero atom.

It is preferable that an ammonium cation is represented by either of following formula (Y1-1) and (Y1-2).

[Formula 40]

In the formula (Y1-1) and (Y1-2), R ¹⁰¹ is, represents an n-valent organic, R ¹ is the same meaning as that of R ¹ in the formula ^(101), Ar 101 and Ar ¹⁰² are each independently , represents an aryl group, and n represents an integer of 1 or more.

In the formula (Y1-1), R ¹⁰¹ is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from the structure to which they are bonded, a saturated aliphatic hydrocarbon having 2 to 30 carbon atoms, benzene or It is more preferable that it is the group which removed n hydrogen atoms from naphthalene.

In formula (Y1-1), it is preferable that n is 1-4, It is more preferable that it is 1 or 2, It is more preferable that it is 1.

In formula (Y1-2), Ar ¹⁰¹ and Ar ¹⁰² are each independently preferably a phenyl group or a naphthyl group, more preferably a phenyl group.

-anion-

As the anion in the ammonium salt, one selected from a carboxylate anion, a phenol anion, a phosphate anion and a sulfate anion is preferable, and a carboxylate anion is more preferable from the viewpoint of achieving both stability and thermal decomposition of the salt. That is, as for an ammonium salt, the salt of an ammonium cation and a carboxylate anion is more preferable.

The anion of divalent or more carboxylic acid which has two or more carboxy groups is preferable, and, as for a carboxylate anion, the anion of divalent carboxylic acid is more preferable. According to this aspect, stability, sclerosis|hardenability, and developability of curable resin composition can be improved more. In particular, by using the anion of divalent carboxylic acid, stability, curability, and developability of the curable resin composition can be further improved.

It is preferable that a carboxylate anion is represented by a following formula (X1).

[Formula 41]

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

In this embodiment, an electron withdrawing group means that Hammett's substituent constant (sigma)m shows a positive value. Here, σm is, Editorial by Yuho Tsuno, Journal of the Association of Organic Synthetic Chemistry, Vol. 23, No. 8 (1965) p. 631-642 are described in detail. In addition, the electron withdrawing group in this embodiment is not limited to the substituent described in the said document.

Examples of the substituent in which σm is positive include CF ₃ group (σm=0.43), CF ₃ C(=O) group (σm=0.63), HC≡C group (σm=0.21), CH ₂ =CH group ( σm=0.06), Ac group (σm=0.38), MeOC(=O) group (σm=0.37), MeC(=O)CH=CH group (σm=0.21), PhC(=O) group (σm=0.34) ), H ₂ NC(=O)CH ₂ group (σm=0.06), and the like. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (hereinafter the same).

It is preferable that EWG is group represented by following formula (EWG-1) - (EWG-6).

[Formula 42]

In formulas (EWG-1) to (EWG-6), R ^x1 to R ^x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxy group or a carboxy group, and Ar represents an aromatic group.

In this invention, it is preferable that a carboxylate anion is represented by a following formula (XA).

[Formula 43]

In formula (XA), L ¹⁰ represents a single bond or a divalent linking group selected from the group consisting of an alkylene group, an alkenylene group, an aromatic group, -NR ^X -, and combinations thereof, and R ^X is, A hydrogen atom, an alkyl group, an alkenyl group, or an aryl group is represented.

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

The onium salt in the present invention contains an ammonium cation as a cation, and the onium salt is an anion, It is preferable that the anion whose pKa (pKaH) of a conjugated acid is 2.5 or less is included, and it is more preferable that the anion whose pKa (pKaH) is 1.8 or less is included.

Although the lower limit of the said pKa is not specifically limited, It is preferable that it is -3 or more, and it is more preferable that it is -2 or more from a viewpoint of making it hard to neutralize the base which generate|occur|produced, and making cyclization efficiency of specific resin etc. favorable.

As the pKa, Determination of Organic Structures by Physical Methods (Author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; Compiled: Braude, EA, Nachod, FC; Academic Press, New York, 1955) or , Data for Biochemical Research (Author: Dawson, RMC et al; Oxford, Clarendon Press, 1959) may be referred to. For compounds not described in these documents, the value calculated from the structural formula using ACD/pKa (manufactured by ACD/Labs) is assumed to be used.

Specific examples of the ammonium salt include the following compounds, but the present invention is not limited thereto.

[Formula 44]

[Iminium salt]

In the present invention, the iminium salt means a salt of an iminium cation and an anion. As an anion, the thing similar to the anion in the above-mentioned ammonium salt is illustrated, and a preferable aspect is also the same.

-iminium cation

As the iminium cation, a pyridinium cation is preferable.

Moreover, as an iminium cation, the cation represented by following formula (102) is also preferable.

[Formula 45]

In formula (102), R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, R ⁷ represents a hydrocarbon group, and ^{at least two of R 5} to R ⁷ may be bonded to each other to form a ring. .

In Formula (102), R ⁵ and R ^{6 have the same meanings as R 1} to R ⁴ in Formula (101) described above, and their preferred embodiments are also the same.

In formula (102), R ⁷ is preferably combined with at least one of R ⁵ and R ^{6 to form a ring.} The ring may contain a hetero atom. A nitrogen atom is mentioned as said hetero atom. Moreover, as said ring, a pyridine ring is preferable.

It is preferable that an iminium cation is what is represented by any one of following formula (Y1-3) - (Y1-5).

[Formula 46]

In the formula (Y1-3) ~ according to (Y1-5), R ¹⁰¹ is, represents an n-valent organic, R ⁵ is the same meaning as R ⁵ in the formula (102), R ⁷ has the formula (102) It has the ^{same meaning as R 7} in R 7 , n represents an integer of 1 or more, and m represents an integer of 0 or more.

In the formula (Y1-3), R ¹⁰¹ is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from the structure to which they are bonded, a saturated aliphatic hydrocarbon having 2 to 30 carbon atoms, benzene or It is more preferable that it is the group which removed n hydrogen atoms from naphthalene.

In formula (Y1-3), it is preferable that n is 1-4, It is more preferable that it is 1 or 2, It is more preferable that it is 1.

In formula (Y1-5), it is preferable that m is 0-4, It is more preferable that it is 1 or 2, It is more preferable that it is 1.

Specific examples of the iminium salt include the following compounds, but the present invention is not limited thereto.

[Formula 47]

[sulfonium salt]

In the present invention, a sulfonium salt means a salt of a sulfonium cation and an anion. As an anion, the thing similar to the anion in the above-mentioned ammonium salt is illustrated, and a preferable aspect is also the same.

-sulfonium cation-

As the sulfonium cation, a tertiary sulfonium cation is preferable, and a triarylsulfonium cation is more preferable.

Moreover, as a sulfonium cation, the cation represented by following formula (103) is preferable.

[Formula 48]

In the formula (103), R ⁸ to R ¹⁰ each independently represent a hydrocarbon group.

R ⁸ to R ¹⁰ are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and a phenyl group It is more preferable that

R ⁸ to R ¹⁰ may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group and the like. Among these, it is preferable to have an alkyl group or an alkoxy group as a substituent, it is more preferable to have a branched alkyl group or an alkoxy group, It is more preferable to have a C3-C10 branched alkyl group or a C1-C10 alkoxy group.

R ⁸ ~ R ¹⁰ being the same contribution, but different contributions, in the viewpoint of synthesis suitability, preferably the same group.

[iodonium salt]

In the present invention, an iodonium salt means a salt of an iodonium cation and an anion. As an anion, the thing similar to the anion in the above-mentioned ammonium salt is illustrated, and a preferable aspect is also the same.

-iodonium cation-

As the iodonium cation, a diaryliodonium cation is preferable.

Moreover, as an iodonium cation, the cation represented by following formula (104) is preferable.

[Formula 49]

In formula (104), R ¹¹ and R ¹² each independently represent a hydrocarbon group.

R ¹¹ and R ¹² are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, more preferably a phenyl group It is more preferable that

R ¹¹ and R ¹² may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group and the like. Among these, as a substituent, it is preferable to have an alkyl group or an alkoxy group, It is more preferable to have a branched alkyl group or an alkoxy group, It is more preferable to have a C3-C10 branched alkyl group or a C1-C10 alkoxy group.

Although R ¹¹ and R ¹² may contribute the same or may be different, it is preferable that they are the same group from the viewpoint of synthetic aptitude.

[phosphonium salt]

In the present invention, a phosphonium salt means a salt of a phosphonium cation and an anion. As an anion, the thing similar to the anion in the above-mentioned ammonium salt is illustrated, and a preferable aspect is also the same.

-phosphonium cation

As a phosphonium cation, a quaternary phosphonium cation is preferable and a tetraalkyl phosphonium cation, a triaryl monoalkyl phosphonium cation, etc. are mentioned.

Moreover, as a phosphonium cation, the cation represented by following formula (105) is preferable.

[Formula 50]

In formula (105), each of R ¹³ to R ¹⁶ independently represents a hydrogen atom or a hydrocarbon group.

R ¹³ to R ¹⁶ are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and a phenyl group It is more preferable that

R ¹³ to R ¹⁶ may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group and the like. Among these, as a substituent, it is preferable to have an alkyl group or an alkoxy group, It is more preferable to have a branched alkyl group or an alkoxy group, It is more preferable to have a C3-C10 branched alkyl group or a C1-C10 alkoxy group.

Although R ¹³ to R ¹⁶ may contribute the same or make a different contribution, it is preferable that they are the same group from the viewpoint of synthetic aptitude.

When curable resin composition of this invention contains an onium salt, 0.1-50 mass % of content of onium salt is preferable with respect to the total solid of curable resin composition of this invention. As for a minimum, 0.5 mass % or more is more preferable, 0.85 mass % or more is still more preferable, 1 mass % or more is still more preferable. As for an upper limit, 30 mass % or less is more preferable, 20 mass % or less is more preferable, 10 mass % or less is still more preferable, 5 mass % or less may be sufficient, and 4 mass % or less may be sufficient as it.

As an onium salt, 1 type(s) or 2 or more types can be used. When using 2 or more types, it is preferable that a total amount is the said range.

<Thermal base generator>

Curable resin composition of this invention may also contain a thermal base generator.

In particular, when specific resin is a polyimide precursor, it is preferable that curable resin composition contains a heat base generator.

The thermal base generator may be a compound corresponding to the onium salt described above, or may be a thermal base generator other than the onium salt described above.

As another heat base generator, a nonionic heat base generator is mentioned.

As a nonionic thermal base generator, the compound represented by Formula (B1) or Formula (B2) is mentioned.

[Formula 51]

In formulas (B1) and (B2), Rb ¹ , Rb ^{2 ,} and Rb ³ are each independently an organic group having no tertiary amine structure, a halogen atom, or a hydrogen atom. However, Rb ¹ and Rb ² do not simultaneously become hydrogen atoms. In addition, Rb ^1, Rb ² and Rb ³ is not the case both having carboxyl group. In addition, as used herein, the tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Accordingly, the case where the bonded carbon atom is a carbon atom constituting a carbonyl group, that is, a case where an amide group is formed together with a nitrogen atom is excluded.

Formula (B1), (B2) of, Rb ^1, Rb ^2, Rb ^3, and is, at least one of which is preferably including a cyclic structure, it is more preferable to contain at least two of the cyclic structure. As a cyclic structure, either monocyclic or condensed ring may be sufficient, and the condensed ring which monocyclic or monocyclic two condensed is preferable. A 5-membered ring or a 6-membered ring is preferable and, as for a monocyclic ring, a 6-membered ring is preferable. A cyclohexane ring and a benzene ring are preferable and, as for a monocyclic ring, a cyclohexane ring is more preferable.

More specifically, Rb ¹ and Rb ² are a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms) , 2-18 are more preferable, and 3-12 are more preferable), an aryl group (C6-C22 is preferable, 6-18 are more preferable, and 6-10 are still more preferable), or an arylalkyl group ( It is preferable that carbon number is 7-25, 7-19 are more preferable, and 7-12 are more preferable). These groups may have a substituent within the range which shows the effect of this invention. Rb ¹ and Rb ² may be bonded to each other to form a ring. As a ring to be formed, a 4- to 7-membered nitrogen-containing heterocycle is preferable. Rb ¹ and Rb ² are particularly preferably a straight-chain, branched, or cyclic alkyl group optionally having a substituent (C1-C24 is preferable, 2-18 are more preferable, and 3-12 are still more preferable), , It is more preferable that it is a cycloalkyl group which may have a substituent (C3-C24 is preferable, 3-18 are more preferable, and 3-12 are still more preferable), and the cyclohexyl group which may have a substituent is still more preferable. do.

As Rb ³ , an alkyl group (C1-C24 is preferable, 2-18 are more preferable, and 3-12 are still more preferable), an aryl group (C6-22 are preferable, 6-18 are more preferable, 6-10 are more preferable), an alkenyl group (C2-C24 is preferable, 2-12 are more preferable, and 2-6 are still more preferable), an arylalkyl group (C7-23 are preferable, 7- 19 is more preferable, and 7-12 are more preferable), an aryl alkenyl group (C1-C24 is preferable, 8-20 are more preferable, and 8-16 are still more preferable), an alkoxyl group (C1-C4) 24 are preferable, 2-18 are more preferable, 3-12 are still more preferable), an aryloxy group (C6-C22 is preferable, 6-18 are more preferable, 6-12 are still more preferable) Or an arylalkyloxy group (C7-C23 is preferable, 7-19 are more preferable, and 7-12 are still more preferable) are mentioned. Especially, a cycloalkyl group (C3-C24 is preferable, 3-18 are more preferable, and 3-12 are still more preferable), an arylalkenyl group, and an arylalkyloxy group are preferable. Rb ³ is which may have a substituent in the range of the effect of the present invention.

It is preferable that the compound represented by a formula (B1) is a compound represented by a following formula (B1-1) or a following formula (B1-2).

[Formula 52]

In the formula, Rb ¹¹ and Rb ¹² , and Rb ³¹ and Rb ³² are the same as ^{Rb 1} and Rb ² in the formula (B1), respectively.

Rb ¹³ is an alkyl group (C1-C24 is preferable, 2-18 are more preferable, and 3-12 are still more preferable), an alkenyl group (C2-24 are preferable, 2-18 are more preferable, 3 -12 are more preferable), an aryl group (C6-C22 is preferable, 6-18 are more preferable, and 6-12 are still more preferable), an arylalkyl group (C7-23 are preferable, 7-19 are preferable. is more preferable, and 7 to 12 are more preferable), and may have a substituent within the range showing the effect of the present invention. Among them, Rb ¹³ is preferably an arylalkyl group.

Rb ³³ and Rb ³⁴ are each independently a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms). and 2-8 are more preferable, 2-3 are more preferable), an aryl group (C6-C22 is preferable, 6-18 are more preferable, 6-10 are still more preferable), an arylalkyl group ( C7-23 are preferable, 7-19 are more preferable, and 7-11 are still more preferable), and a hydrogen atom is preferable.

Rb ³⁵ is an alkyl group (C1-C24 is preferable, 1-12 are more preferable, and 3-8 are still more preferable), an alkenyl group (C2-C12 is preferable, 2-12 are more preferable, 3-8 are more preferable), an aryl group (C6-C22 is preferable, 6-18 are more preferable, and 6-12 are still more preferable), an arylalkyl group (C7-23 are preferable, 7- 19 is more preferable, and 7-12 are more preferable), and an aryl group is preferable.

As for the compound represented by a formula (B1-1), the compound represented by a formula (B1-1a) is also preferable.

[Formula 53]

Rb ¹¹ and Rb ¹² have the same meanings as Rb ¹¹ and Rb ¹² in the formula (B1-1).

Rb ¹⁵ and Rb ¹⁶ are a hydrogen atom, an alkyl group (having a carbon number of 1-12 it is preferable, and 1 to 6 are more preferable, and 1 to 3 is more preferred), an alkenyl group (having a carbon number of 2 to 12 preferably 2 to 6 More preferably, 2-3 are more preferable), an aryl group (C6-C22 is preferable, 6-18 are more preferable, and 6-10 are still more preferable), an arylalkyl group (C7-23 are Preferably, 7-19 are more preferable, 7-11 are still more preferable), and a hydrogen atom or a methyl group is preferable.

Rb ¹⁷ is an alkyl group (C1-C24 is preferable, 1-12 are more preferable, and 3-8 are still more preferable), an alkenyl group (C2-C12 is preferable, 2-12 are more preferable, 3 -8 are more preferable), an aryl group (C6-C22 is preferable, 6-18 are more preferable, and 6-12 are still more preferable), an arylalkyl group (C7-23 are preferable, 7-19 are preferable. is more preferable, and 7 to 12 are more preferable), and among these, an aryl group is preferable.

It is preferable that it is 800 or less, as for the molecular weight of a nonionic thermal base generator, it is more preferable that it is 600 or less, It is more preferable that it is 500 or less. As a minimum, it is preferable that it is 100 or more, It is more preferable that it is 200 or more, It is more preferable that it is 300 or more.

The following compounds are mentioned as a specific example of the compound which is a thermal base generator among the above-mentioned onium salts, or as a specific example of another thermal base generator.

[Formula 54]

[Formula 55]

[Formula 56]

As for content of a heat base generator, 0.1-50 mass % is preferable with respect to the total solid of curable resin composition of this invention. As for a minimum, 0.5 mass % or more is more preferable, and 1 mass % or more is still more preferable. 30 mass % or less is more preferable, and, as for an upper limit, 20 mass % or less is still more preferable. A heat base generator can use 1 type or 2 or more types. When using 2 or more types, it is preferable that a total amount is the said range.

<Migration inhibitor>

It is preferable that curable resin composition of this invention contains a migration inhibitor further. By including a migration inhibitor, it becomes possible to suppress effectively that the metal ion derived from a metal layer (metal wiring) moves into curable resin composition layer.

Although there is no restriction|limiting in particular as a migration inhibitor, A heterocyclic ring (pyrrole ring, furan ring, thiophen ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine a compound having a ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), thiourea and sulfanyl group compounds having , hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole-based compounds such as 1,2,4-triazole and benzotriazole, and tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

Alternatively, an ion trapping agent that traps anions such as halogen ions may be used.

As other migration inhibitors, the compound of Paragraph 0094 of Unexamined-Japanese-Patent No. 2013-015701 Paragraph 0094, Paragraph 0073 of Unexamined-Japanese-Patent No. 2009-283711 - Paragraph 0076, The compound of Paragraph 0052 of Unexamined-Japanese-Patent No. 2011-059656, The compound of Paragraph 0114 of Unexamined-Japanese-Patent No. 2012-194520, 0116, and 0118, the compound of Paragraph 0166 of International Publication No. 2015/199219, etc. can be used.

As a specific example of a migration inhibitor, the following compound is mentioned.

[Formula 57]

When curable resin composition has a migration inhibitor, it is preferable that content of a migration inhibitor is 0.01-5.0 mass % with respect to the total solid of curable resin composition, It is more preferable that it is 0.05-2.0 mass %, It is 0.1-1.0 mass % is more preferable.

The number of migration inhibitors may be one, and 2 or more types may be sufficient as them. When there are 2 or more types of migration inhibitors, it is preferable that the sum total is the said range.

<Polymerization inhibitor>

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

Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl- p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitroso -N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol Etherdiamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1 -Naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxyamine ammonium salt, bis(4-hydroxy- 3,5-tert-butyl)phenylmethane etc. are used suitably. Moreover, the polymerization inhibitor of Paragraph 0060 of Unexamined-Japanese-Patent No. 2015-127817, and the compound of Paragraph 0031 - 0046 of International Publication No. 2015/125469 can also be used.

Moreover, the following compound can be used (Me is a methyl group).

[Formula 58]

When curable resin composition of this invention has a polymerization inhibitor, it is preferable that content of a polymerization inhibitor is 0.01-5 mass % with respect to the total solid of curable resin composition of this invention, It is 0.02-3 mass % It is more preferable, and it is still more preferable that it is 0.05-2.5 mass %.

The number of polymerization inhibitors may be one, and 2 or more types may be sufficient as them. When the polymerization inhibitor is two or more types, it is preferable that the sum total is the said range.

<Metal adhesion improving agent>

It is preferable that curable resin composition of this invention contains the metal adhesiveness improving agent for improving adhesiveness with the metal material used for an electrode, wiring, etc. A silane coupling agent etc. are mentioned as a metal adhesiveness improving agent.

As an example of a silane coupling agent, the compound of paragraph 0167 of International Publication No. 2015/199219, the compound of paragraphs 0062 - 0073 of Unexamined-Japanese-Patent No. 2014-191002, Paragraph 0063 - 0071 of International Publication No. 2011/080992 The compound described, the compound described in paragraphs 0060 to 0061 of JP 2014-191252 , the compound described in paragraphs 0045 to 0052 of JP 2014-041264 , the compound described in paragraph 0055 of International Publication No. 2014/097594 can Moreover, as described in Paragraph 0050 - 0058 of Unexamined-Japanese-Patent No. 2011-128358, it is also preferable to use 2 or more types of different silane coupling agents. Moreover, it is also preferable to use the following compound as a silane coupling agent. In the following formulas, Et represents an ethyl group.

[Formula 59]

Moreover, as a metal adhesive improving agent, the compound of Paragraphs 0046 - 0049 of Unexamined-Japanese-Patent No. 2014-186186, Paragraph 0032 - 0043 of Unexamined-Japanese-Patent No. 2013-072935 A sulfide type compound can also be used.

To [ content of metal adhesive improving agent / 100 mass parts of specific resin ], Preferably it is 0.1-30 mass parts, More preferably, it is the range of 0.5-15 mass parts, More preferably, it is the range of 0.5-5 mass parts. By using more than the said lower limit, the adhesiveness of the cured film and a metal layer after a hardening process becomes favorable, and the heat resistance and mechanical properties of the cured film after a hardening process become favorable by using below the said upper limit. The number of metal adhesive improving agents may be one, and 2 or more types may be sufficient as them. When using 2 or more types, it is preferable that the sum total is the said range.

<Other additives>

The curable resin composition of the present invention may contain, if necessary, various additives, for example, a sensitizer such as N-phenyldiethanolamine, 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, etc. can be mix|blended. When mix|blending these additives, it is preferable that the total compounding quantity shall be 3 mass % or less of solid content of curable resin composition.

[sensitizer]

The curable resin composition of this invention may contain the sensitizer. A sensitizer absorbs specific actinic radiation and becomes an electron excited state. The sensitizer used in the electron excited state comes into contact with a thermosetting accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, etc., and effects, such as electron transfer, energy transfer, and heat_generation|fever, arise. Thereby, the thermal curing accelerator, thermal radical polymerization initiator, and photoradical polymerization initiator cause a chemical change and decompose to generate radicals, acids or bases.

As a sensitizer, sensitizers, such as N-phenyldiethanolamine, are mentioned.

Moreover, as a sensitizer, you may use a sensitizing dye.

About the detail of a sensitizing dye, Paragraph 0161 of Unexamined-Japanese-Patent No. 2016-027357 - description of 0163 can be considered into consideration, and this content is integrated in this specification.

When the curable resin composition of this invention contains a sensitizer, it is preferable that content of a sensitizer is 0.01-20 mass % with respect to the total solid of curable resin composition of this invention, It is more that it is 0.1-15 mass % It is preferable, and it is more preferable that it is 0.5-10 mass %. A sensitizer may be used individually by 1 type, and may use 2 or more types together.

[Chain Transfer Agent]

The curable resin composition of this invention may contain a chain transfer agent. The chain transfer agent is defined, for example, on pages 683-684 of the Polymer Dictionary 3rd Edition (Edited by the Society of Polymers, 2005). As a chain transfer agent, the compound group which has SH, PH, SiH, and GeH in a molecule|numerator is used, for example. These can generate a radical by donating hydrogen to a radical with low activity to generate a radical, or by deprotonation after being oxidized. In particular, a thiol compound can be preferably used.

Moreover, the compound of Paragraph 0152 - 0153 of International Publication No. 2015/199219 can also be used as a chain transfer agent.

When the curable resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, with respect to 100 parts by mass of the total solids of the curable resin composition of the present invention, , more preferably 1 to 5 parts by mass. The number of chain transfer agents may be one, and 2 or more types may be sufficient as them. When two or more types of chain transfer agents are, it is preferable that the sum total is the said range.

〔Surfactants〕

You may add various types of surfactant to curable resin composition of this invention from a viewpoint of improving applicability|paintability more. As surfactant, each type of surfactant, such as a fluorine type surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone type surfactant, can be used. Moreover, the following surfactant is also preferable. In the following formula, parentheses indicating the repeating units of the main chain indicate the content (mol%) of each repeating unit, and parentheses indicating the repeating units of the side chain indicate the number of repetitions of each repeating unit, respectively.

[Formula 60]

Moreover, as surfactant, Paragraph 0159 of International Publication No. 2015/199219 - the compound of 0165 can also be used.

When curable resin composition of this invention has surfactant, it is preferable that content of surfactant is 0.001-2.0 mass % with respect to the total solid of curable resin composition of this invention, More preferably, it is 0.005-1.0 mass %. to be. One type may be sufficient as surfactant, and 2 or more types may be sufficient as it. When there are 2 or more types of surfactant, it is preferable that the sum total is the said range.

[Higher Fatty Acid Derivatives]

In the curable resin composition of the present invention, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent oxygen-induced polymerization inhibition, and may be localized on the surface of the curable resin composition during drying after application.

Further, as the higher fatty acid derivative, the compound described in paragraph 0155 of International Publication No. 2015/199219 can also be used.

When curable resin composition of this invention has a higher fatty acid derivative, it is preferable that content of a higher fatty acid derivative is 0.1-10 mass % with respect to the total solid of curable resin composition of this invention. The number of higher fatty acid derivatives may be one, and 2 or more types may be sufficient as them. When there are two or more types of higher fatty acid derivatives, it is preferable that the sum total is the said range.

<Restrictions on other contained substances>

From the viewpoint of coating surface properties, the moisture content of the curable resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and still more preferably less than 0.6% by mass.

From an insulating viewpoint, less than 5 mass ppm (parts per million) is preferable, as for metal content of curable resin composition of this invention, less than 1 mass ppm is more preferable, and its less than 0.5 mass ppm is still more preferable. As a metal, sodium, potassium, magnesium, calcium, iron, chromium, nickel, etc. are mentioned. When two or more metals are included, it is preferable that the sum total of these metals is the said range.

In addition, as a method of reducing the metallic impurities unintentionally contained in the curable resin composition of the present invention, a raw material having a low metal content is selected as a raw material constituting the curable resin composition of the present invention, or the curable resin composition of the present invention is constituted Methods, such as performing filter filtration with respect to the raw material to be used, or carrying out distillation under conditions in which contamination was suppressed as much as possible by lining the inside of an apparatus with polytetrafluoroethylene etc. are mentioned.

When the use as a semiconductor material is considered, the curable resin composition of this invention is less than 500 mass ppm from a viewpoint of wiring corrosiveness, and, as for content of a halogen atom, less than 300 mass ppm is more preferable, It is less than 200 mass ppm. This is more preferable. Especially, less than 5 mass ppm is preferable, as for what exists in a halogen ion state, less than 1 mass ppm is more preferable, and its less than 0.5 mass ppm is still more preferable. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of a chlorine atom and a bromine atom, or a chlorine ion and a bromine ion is each in the said range.

As a container for the curable resin composition of this invention, a conventionally well-known container can be used. In addition, for the purpose of suppressing the mixing of impurities into the raw material or the curable resin composition as the container for storage, a multi-layer bottle in which the inner wall of the container is composed of 6 types of 6 layers of resin, or a bottle with 7 layers of 6 types of resins is used. It is also desirable As such a container, the container of Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

<Preparation of curable resin composition>

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

Moreover, in order to remove foreign substances, such as dust and microparticles|fine-particles in curable resin composition, it is preferable to perform filtration using a filter. 1 micrometer or less is preferable, as for a filter pore diameter, 0.5 micrometer or less is more preferable, and 0.1 micrometer or less is still more preferable. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon. As a filter, you may use what wash|cleaned previously with the organic solvent. In a filter filtration process, you may connect and use several types of filters in series or parallel. When using multiple types of filters, you may use combining filters from which a pore diameter or a material differs. Moreover, you may filter various materials multiple times. When filtering multiple times, circulation filtration may be sufficient. Moreover, you may filter by pressurizing. When performing filtration by pressurizing, as for the pressure to pressurize, 0.05 Mpa or more and 0.3 Mpa or less are preferable.

In addition to the filtration using a filter, you may perform the removal process of the impurity using the adsorbent. You may combine filter filtration and the impurity removal process using an adsorbent. 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.

<Use of curable resin composition>

It is preferable that curable resin composition of this invention is used for formation of the interlayer insulating film for rewiring layers.

Moreover, it can be used also for formation of the insulating film of a semiconductor device, formation of a stress buffer film, etc. other than that.

(Cured film, laminated body, semiconductor device, and their manufacturing method)

Next, a cured film, a laminated body, a semiconductor device, and those manufacturing methods are demonstrated.

The cured film of this invention is formed by hardening|curing curable resin composition of this invention. The film thickness of the cured film of this invention can be made into 0.5 micrometer or more, and can be made into 1 micrometer or more. Moreover, as an upper limit, it can be set as 100 micrometers or less, and can also be set as 30 micrometers or less.

It is good also as a laminated body by laminating|stacking 2 or more layers of the cured film of this invention, Furthermore, 3-7 layers are laminated|stacked. It is preferable that the laminated body of this invention has two or more layers of cured films, and it is a laminated body which has a metal layer between cured films. Moreover, the aspect in which the laminated body of this invention contains two or more layers of cured films, and contains a metal layer between any one of the said cured films is preferable. For example, the laminated body containing at least the layer structure in which three layers of a 1st cured film, a metal layer, and a 2nd cured film were laminated|stacked in this order is mentioned preferably. The said 1st cured film and the said 2nd cured film are both the cured film of this invention, For example, all of the said 1st cured film and the said 2nd cured film are the film|membrane formed by hardening|curing the curable resin composition of this invention. are preferably mentioned. The curable resin composition of the present invention used for formation of the first cured film and the curable resin composition of the present invention used for formation of the second cured film may have the same composition or different compositions. From a viewpoint, it is preferable that the composition is the same composition. Such a metal layer is preferably used as metal wiring, such as a redistribution layer.

As an applicable field|area of the cured film of this invention, the insulating film of a semiconductor device, the interlayer insulating film for redistribution layers, a stress buffer film, etc. are mentioned. In addition, pattern formation of a sealing film, a board|substrate material (a base film, a coverlay of a flexible printed circuit board, an interlayer insulating film), or the insulating film for a mounting use as mentioned above by etching etc. is mentioned. Regarding their use, for example, Science & Technology Co., Ltd. "High-functionalization and application technology of polyimide" April 2008, Masaaki Kagimoto/supervision, CMC Technical Library "Basics and development of polyimide materials" November 2011 Publication, Japan Polyimide/Aromatic Polymer Research Society/Edition "Latest Polyimide Basics and Applications" N.T.S, August 2010, etc. can be referred to.

In addition, the cured film in the present invention is used for production of plate surfaces such as an offset plate surface or a screen plate surface, use in etching of molded parts, and production of protective lacquers and dielectric layers in electronics, particularly microelectronics, etc. may be

It is preferable that the manufacturing method of the cured film of this invention (hereinafter also simply referred to as "the manufacturing method of the present invention") includes a film forming step of applying the curable resin composition of the present invention to a substrate to form a film.

Moreover, the manufacturing method of the cured film of this invention includes the said film-forming process, It is more preferable to further include the exposure process of exposing the said film|membrane, and the developing process of developing the said film|membrane (it develops with respect to the said film|membrane) desirable.

Moreover, it is more preferable that the manufacturing method of the cured film of this invention includes the said film-forming process (and the said image development process as needed), and further includes the heating process of heating the said film|membrane at 50-450 degreeC. .

Specifically, it is also preferable to include the steps of the following (a) to (d).

(a) a film forming process of forming a film (curable resin composition layer) by applying a curable resin composition to a substrate

(b) an exposure step of exposing the film after the film forming step

(c) a developing step of performing a developing treatment on the exposed film

(d) heating process of heating the developed film at 50 ~ 450 ℃

By heating in the said heating process, the resin layer hardened|cured by exposure can further be hardened. In this heating process, for example, the above-mentioned thermal base generator is decomposed|disassembled, and sufficient sclerosis|hardenability is obtained.

The manufacturing method of the laminated body which concerns on preferable embodiment of this invention includes the manufacturing method of the cured film of this invention. After the manufacturing method of the laminated body of this embodiment forms a cured film according to the manufacturing method of said cured film, further again, the process of (a), or the process of (a)-(c), or (a ) to (d) are performed. In particular, it is preferable to perform each of the above steps in order a plurality of times, for example, 2 to 5 times (ie, 3 to 6 times in total). Thus, by laminating|stacking a cured film, it can be set as a laminated body. In this invention, it is preferable to provide a metal layer in the top of the part which provided the cured film especially, between cured films, or both. In addition, in manufacture of a laminated body, it is not necessary to repeat all the processes of (a)-(d), As mentioned above, at least (a), Preferably (a)-(c) or (a)- By performing the process of (d) in multiple times, the laminated body of a cured film can be obtained.

<Film formation process (layer formation process)>

The production method according to a preferred embodiment of the present invention includes a film formation step (layer formation step) in which a curable resin composition is applied to a substrate to form a film (layered).

Although the type of the substrate can be appropriately determined depending on the application, semiconductor production substrates such as silicon, silicon nitride, polysilicon, silicon oxide and amorphous silicon, quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film, A reflective film, a metal substrate such as Ni, Cu, Cr, Fe, paper, spin on glass (SOG), a thin film transistor (TFT) array substrate, an electrode plate of a plasma display panel (PDP), etc. are not particularly limited. In this invention, especially, a semiconductor manufacturing base material is preferable, and a silicon base material is more preferable.

Moreover, as a base material, a plate-shaped base material (substrate) is used, for example.

Moreover, when forming a curable resin composition layer in the surface of a resin layer or the surface of a metal layer, a resin layer and a metal layer become a base material.

As a means for applying the curable resin composition to the substrate, application is preferred.

Specifically, as a means to be applied, a dip coat method, an air knife coat method, a curtain coat method, a wire bar coat method, a gravure coat method, an extrusion coat method, a spray coat method, a spin coat method, a slit coat method, and The inkjet method etc. are illustrated. From a viewpoint of the uniformity of the thickness of curable resin composition layer, More preferably, they are the spin coating method, the slit coating method, the spray coating method, and the inkjet method. A resin layer of a desired thickness can be obtained by adjusting an appropriate solid content concentration and application|coating conditions according to a method. In addition, the coating method can be appropriately selected depending on the shape of the substrate. If it is a circular substrate such as a wafer, the spin coating method, spray coating method, inkjet method, etc. are preferable, and if it is a rectangular substrate, the slit coating method, spray coating method, inkjet method, etc. This is preferable. In the case of the spin coating method, for example, at a rotation speed of 500 to 2,000 rpm (revolutions per minute), about 10 seconds to 1 minute can be applied.

Moreover, the method of transferring on a base material the coating film previously provided and formed in accordance with the said provision method on a provisional support body can also be applied.

Regarding the transcription|transfer method, Paragraph 0023 of Unexamined-Japanese-Patent No. 2006-023696, Paragraph 0036 - 0051, and Paragraph 0096 - 0108 of Unexamined-Japanese-Patent No. 2006-047592 The manufacturing method described in it can be used suitably also in this invention.

<Drying process>

The manufacturing method of this invention may include the process of drying in order to remove a solvent after forming the said film|membrane (curable resin composition layer) and after a film-forming process (layer formation process). A preferable drying temperature is 50-150 degreeC, 70 degreeC - 130 degreeC are more preferable, and 90 degreeC - 110 degreeC are still more preferable. As drying time, 30 second - 20 minutes are illustrated, 1 minute - 10 minutes are preferable, and 3 minutes - 7 minutes are more preferable.

<Exposure process>

The manufacturing method of this invention may also include the exposure process of exposing the said film|membrane (curable resin composition layer). Although the exposure amount is not particularly determined as long as the curable resin composition can be cured, for example, 100 to 10,000 mJ/cm ² irradiated in terms of exposure energy at a wavelength of 365 nm is preferable, and 200 to 8,000 mJ/cm ² irradiated. It is more preferable to

An exposure wavelength can be suitably determined in the range of 190-1,000 nm, and 240-550 nm is preferable.

The exposure wavelength is, in relation to the light source, (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-line (wavelength 436 nm), h Line (wavelength 405 nm), i-line (wavelength 365 nm), broad (3 wavelengths of g, h, and i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet; EUV (wavelength 13.6 nm), (6) electron beam, etc. are mentioned. About the curable resin composition of this invention, especially exposure by a high-pressure mercury-vapor lamp is preferable, and especially, exposure by i line|wire is preferable. Thereby, particularly high exposure sensitivity can be obtained.

<Development process>

The manufacturing method of this invention may also include the image development process of performing a developing process with respect to the exposed film|membrane (curable resin composition layer). By developing, the unexposed part (unexposed part) is removed. The developing method is not particularly limited as long as a desired pattern can be formed, and for example, developing methods such as puddle, spray, immersion, and ultrasonic waves are employable.

Development is performed using a developing solution. The developer can be used without any particular limitation as long as the unexposed portion (unexposed portion) is removed.

In the present invention, the case where an alkaline developer is used as the developer is referred to as alkali development, and the case where a developer containing 50% by mass or more of an organic solvent is used as the developer is referred to as solvent development.

In alkali development, the content of the organic solvent in the developer is preferably 10 mass% or less, more preferably 5 mass% or less, more preferably 1 mass% or less, with respect to the total mass of the developer, and does not contain an organic solvent It is particularly preferable not to.

As for the developing solution in alkali image development, the aqueous solution whose pH is 9-14 is more preferable.

As an alkali compound contained in the developing solution in alkali image development, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, potassium metasilicate, for example. , ammonia or an amine. Examples of the amine include ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, quaternary Ammonium hydroxide, tetramethylammonium hydroxide (TMAH) or tetraethylammonium hydroxide, tetrabutylammonium hydroxide, etc. are mentioned. Among them, an alkali compound containing no metal is preferable, and an ammonium compound is more preferable.

The number of alkali compounds may be one, and 2 or more types may be sufficient as them. When an alkali compound is 2 or more types, it is preferable that the sum total is the said range.

Solvent development WHEREIN: It is more preferable that a developing solution contains 90% or more of organic solvents. In this invention, it is preferable that ClogP value contains the organic solvent of -1-5, and, as for a developing solution, it is more preferable that ClogP value contains the organic solvent of 0-3. A ClogP value can be calculated|required as a calculated value by inputting a structural formula into ChemBioDraw.

The organic solvent is an ester, for example, 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, alkyloxyacetate (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, alkyloxyacetic acid butyl (e.g. methoxyacetic acid) methyl, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionate alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.) (For example, 3-methoxypropionate methyl, 3-methoxypropionate ethyl, 3-ethoxypropionate methyl, 3-ethoxypropionate ethyl, etc.), 2-alkyloxypropionic acid alkyl esters (eg 2-alkyl Methyl oxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate) , 2-ethoxypropionate ethyl)), 2-alkyloxy-2-methylpropionate methyl and 2-alkyloxy-2-methylpropionate ethyl (eg, 2-methoxy-2-methylpropionate methyl, 2-e ethyl oxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like, and ethers, for example For example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol Colmonomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol mono Ethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as ketones, for example, methyl ethyl ketone, cyclohexane One, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc.; Dimethyl sulfoxide is suitably mentioned as sulfoxides.

In this invention, especially cyclopentanone and (gamma)-butyrolactone are preferable, and cyclopentanone is more preferable.

It is preferable that 50 mass % or more of a developing solution is an organic solvent, It is more preferable that 70 mass % or more is an organic solvent, It is more preferable that 90 mass % or more is an organic solvent. Moreover, 100 mass % of an organic solvent may be sufficient as a developing solution.

As image development time, 10 second - 5 minutes are preferable. Although the temperature of the developing solution at the time of image development is not specifically defined, Usually, it can carry out at 20-40 degreeC.

After the treatment using the developer, further rinsing may be performed.

In the case of solvent development, it is preferable to perform rinsing using the organic solvent different from a developing solution.

In the case of alkali development, it is preferable to perform rinsing using pure water.

As for rinsing time, 5 second - 1 minute are preferable.

<Heating process>

It is preferable that the manufacturing method of this invention includes the process (heating process) of heating the said developed film|membrane at 50-450 degreeC.

It is preferable that a heating process is included after a film formation process (layer formation process), a drying process, and a developing process.

Although the curable resin composition of the present invention contains a polymerizable compound other than a specific resin, a curing reaction of an unreacted polymerizable compound other than a specific resin, a curing reaction of an unreacted polymerizable group in a specific resin, etc. are performed in this step. can proceed.

Moreover, when specific resin is a polyimide precursor and curable resin composition contains a thermal base generator, in a heating process, for example, a base is generated by decomposing|disassembling a thermal base generator, and the cyclization reaction of a polyimide precursor is carried out proceeds

The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50°C or higher, more preferably 80°C or higher, still more preferably 140°C or higher, particularly preferably 150°C or higher, and 160°C or higher. It is still more preferable, and it is most preferable that it is 170 degreeC or more. As an upper limit, it is preferable that it is 450 degrees C or less, It is more preferable that it is 350 degrees C or less, It is more preferable that it is 250 degrees C or less, It is especially preferable that it is 220 degrees C or less.

It is preferable to perform heating at the temperature increase rate of 1-12 degreeC/min from the temperature at the time of a heating start to maximum heating temperature, 2-10 degreeC/min is more preferable, 3-10 degreeC/min is still more preferable. Excessive volatilization of an amine can be prevented, ensuring productivity by making a temperature increase rate 1 degreeC/min or more, and the residual stress of a cured film can be relieved by making a temperature increase rate 12 degrees C/min or less.

20 degreeC - 150 degreeC are preferable, as for the temperature at the time of a heating start, 20 degreeC - 130 degreeC are more preferable, and 25 degreeC - 120 degreeC are still more preferable. The temperature at the time of heating start means the temperature at the time of starting the process of heating to the highest heating temperature. For example, after applying the curable resin composition on the substrate and then drying, it is the temperature of the film (layer) after this drying, for example, a temperature 30 to 200° C. lower than the boiling point of the solvent contained in the curable resin composition. It is preferable to raise the temperature gradually from

It is preferable that it is 10-360 minutes, as for heating time (heating time at the highest heating temperature), it is more preferable that it is 20-300 minutes, It is more preferable that it is 30-240 minutes.

When forming a multilayer laminated body especially, it is preferable to heat at 180 degreeC - 320 degreeC, and, as for heating temperature, it is more preferable to heat at 180 degreeC - 260 degreeC from a viewpoint of the adhesiveness between the layers of a cured film. Although the reason is not certain, it is thought that it is for the polymeric groups in specific resin between layers to advance the crosslinking reaction by setting it as this temperature.

Heating may be performed in stages. For example, a pretreatment process such as raising the temperature from 25°C to 180°C at 3°C/min, holding at 180°C for 60 minutes, and increasing the temperature from 180°C to 200°C at 2°C/min, maintaining at 200°C for 120 minutes may be done 100-200 degreeC is preferable, as for the heating temperature as a pretreatment process, it is more preferable that it is 110-190 degreeC, It is more preferable that it is 120-185 degreeC. In this pretreatment process, it is also preferable to process while irradiating an ultraviolet-ray as described in US Patent No. 9159547. It is possible to improve the properties of the film by such a pretreatment process. What is necessary is just to perform a pretreatment process in the short time of about 10 second - 2 hours, and 15 second - 30 minutes are more preferable. The pretreatment may be a step of two or more steps, for example, the pretreatment step 1 may be performed in the range of 100 to 150°C, and then the pretreatment step 2 may be performed in the range of 150 to 200°C.

Moreover, you may cool after heating, and as a cooling rate in this case, it is preferable that it is 1-5 degreeC/min.

The heating step is preferably performed in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon to prevent decomposition of the specific resin. 50 ppm (volume ratio) or less is preferable and, as for oxygen concentration, 20 ppm (volume ratio) or less is more preferable.

<Metal layer forming process>

It is preferable that the manufacturing method of this invention includes the metal layer formation process of forming a metal layer on the surface of the film|membrane (curable resin composition layer) after development.

The metal layer is not particularly limited, and an existing metal species can be used, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are exemplified, with copper and aluminum being more preferable, and copper being more preferable. .

The method of forming the metal layer is not particularly limited, and an existing method can be applied. For example, the method described in Unexamined-Japanese-Patent No. 2007-157879, Unexamined-Japanese-Patent No. 2001-521288, Unexamined-Japanese-Patent No. 2004-214501, and Unexamined-Japanese-Patent No. 2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, a method combining these, etc. are conceivable. More specifically, the patterning method which combined sputtering, photolithography, and etching, and the patterning method which combined photolithography and electroplating are mentioned.

As thickness of a metal layer, 0.1-50 micrometers is preferable in the thickest part, and 1-10 micrometers is more preferable.

<Lamination process>

It is preferable that the manufacturing method of this invention further includes a lamination|stacking process.

The lamination process is again, (a) film-forming process (layer-forming process), (b) exposure process, (c) developing process, (d) heating process on the surface of a cured film (resin layer) or metal layer, this It is a series of processes that include performing sequentially. However, the aspect which repeats only the film-forming process of (a) may be sufficient. Moreover, the (d) heating process is good also as an aspect performed collectively in the last or middle of lamination|stacking. That is, it is good also as an aspect which hardens the laminated|stacked curable resin composition layer collectively by repeating the process of (a)-(c) a predetermined number of times, and heating (d) after that. Further, after the (c) developing step, (e) the metal layer forming step may be included, and even at this time, the heating of (d) may be performed each time, and after laminating a predetermined number of times, the heating of (d) is collectively performed. also be It cannot be overemphasized that the said drying process, a heating process, etc. may be included suitably further in a lamination|stacking process.

When performing a lamination|stacking process further after a lamination|stacking process, you may perform a surface activation treatment process further after the said heating process, after the said exposure process, or after the said metal layer formation process. As the surface activation treatment, plasma treatment is exemplified.

It is preferable to perform 2-5 times, and, as for the said lamination|stacking process, it is more preferable to perform 3-5 times.

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

In this invention, especially after providing a metal layer, the aspect which forms the cured film (resin layer) of the said curable resin composition so that the said metal layer may be covered further is preferable. Specifically, (a) film formation process, (b) exposure process, (c) development process, (e) metal layer formation process, (d) heating process are repeated in this order, or (a) film formation process , (b) exposure process, (c) image development process, and (e) metal layer formation process are repeated in order, and the aspect which provides (d) heating process collectively is mentioned in the last or the middle. By alternately performing the lamination process of laminating|stacking curable resin composition layer (resin layer), and the metal layer formation process, curable resin composition layer (resin layer) and a metal layer can be laminated|stacked alternately.

This invention also discloses the semiconductor device containing the cured film or laminated body of this invention. As a specific example of a semiconductor device in which the curable resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer, reference may be made to the description of paragraphs 0213 to 0218 of JP-A-2016-027357 and the description of FIG. is incorporated herein by reference.

(polyimide, or polyimide precursor)

It is preferable that the polyimide of this invention or a polyimide precursor contains the structure represented by following formula (1-1).

[Formula 61]

In formula (1-1), ^{each R 1} independently represents a hydrogen atom or an alkyl group, Z ¹ represents a group containing a polymerizable group, n represents an integer of 2 or more, m represents an integer of 2 or more, * indicates a binding site with another structure.

The said formula (1-1) has the same meaning as Formula (1-1) in specific resin, and a preferable aspect is also the same.

The polyimide or polyimide precursor of this invention has the same meaning as the polyimide in the specific resin mentioned above, or a polyimide precursor except making said Formula (1-1) essential, and a preferable aspect is also same.

<Use>

It is preferable that the polyimide of this invention or a polyimide precursor is used as resin contained in curable resin composition.

Further, for example, in a composition in which a conventional polyimide or a polyimide precursor is used, such as a composition for an interlayer insulating film, a part or all of a conventional polyimide or a polyimide precursor is used in the present invention without particular limitation. of polyimide, or a polyimide precursor may be used.

Since the composition containing the polyimide or polyimide precursor of the present invention is excellent in applicability, the polyimide or polyimide precursor of the present invention can be applied to, for example, a composition for forming an insulating film. The composition used for the use which forms a coating film by this WHEREIN: It is thought that it is used suitably.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. Materials, amounts of use, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Hereinafter, "part" and "%" are based on mass unless otherwise specified.

(Synthesis of specific resins)

<Synthesis Example 1: Synthesis of polyimide (PI-1)>

In a dry reactor equipped with a flat-bottom joint equipped with a stirrer, condenser and internal thermometer, 15.21 g (100 mmol) of 3,5-diaminobenzoic acid was added to 130.0 g of N-methylpyrrolidone (NMP) while removing moisture. was dissolved in Then, 31.02 g (100 mmol) of oxydiphthalic dianhydride was added, and it stirred at the temperature of 40 degreeC for 2 hours. Subsequently, after adding 50 mL of toluene, the temperature was raised to 180 degreeC, and it stirred for 4 hours, flowing nitrogen of the flow volume of 200 ml/min. After cooling the reaction solution to 25° C., Blemmer PE-200 (manufactured by Nichiyu Co., Ltd.) 28.4 g (100 mmol), N,N'-dimethylaminopyridine 0.61 g (5 mmol), p-methyl 0.06 g of oxyphenol and 130.0 g of N-methylpyrrolidone were added, dissolved, and cooled to 0°C. Next, 12.6 g (100 mmol) of diisopropylcarbodiimide was added, the mixture was stirred at 10°C or lower for 5 hours, and the temperature was raised to room temperature. Then, the polyimide was precipitated in 2 liters of water, and the water-polyimide mixture was stirred at a speed of 2,000 rpm for 30 minutes. The polyimide precursor resin was removed by filtration, and the mixture was stirred again with 1.5 liters of methanol for 30 minutes, followed by filtration. Next, the obtained polyimide was dried under reduced pressure at 40 degreeC for 1 day, and PI-1 was obtained. The weight average molecular weight (Mw) of PI-1 was 29,500, and the number average molecular weight (Mn) was 13,500.

It is estimated that the structure of PI-1 is a structure represented by the following formula (PI-1).

In addition, the subscripts in each parenthesis represent the content ratio (molar ratio) of each repeating unit, and m=91, q=9.

[Formula 62]

<Synthesis Example 2: Synthesis of polyimide (PI-2)>

In a dry reactor equipped with a flat-bottom joint equipped with a stirrer, condenser and internal thermometer, 15.21 g (100 mmol) of 3,5-diaminobenzoic acid was added to 130.0 g of N-methylpyrrolidone (NMP) while removing moisture. was dissolved in Then, 31.02 g (100 mmol) of oxydiphthalic dianhydride was added, and it stirred at the temperature of 40 degreeC for 2 hours. Subsequently, after adding 50 mL of toluene, the temperature was raised to 180 degreeC, and it stirred for 4 hours, flowing nitrogen of the flow volume of 200 ml/min. After cooling the reaction solution to 25° C., Blemmer AP-400 (manufactured by Nichiyu Co., Ltd.) 33.6 g (80 mmol), N,N'-dimethylaminopyridine 0.61 g (5 mmol), p-methyl 0.06 g of oxyphenol and 130.0 g of N-methylpyrrolidone were added, dissolved, and cooled to 0°C. Next, 12.6 g (90 mmol) of diisopropylcarbodiimide was added, stirred at 10°C or lower for 5 hours, and the temperature was raised to room temperature. Then, the polyimide was precipitated in 2 liters of water, and the water-polyimide mixture was stirred at a speed of 2,000 rpm for 30 minutes. The polyimide precursor resin was removed by filtration, and the mixture was stirred again with 1.5 liters of methanol for 30 minutes, followed by filtration. Next, the obtained polyimide was dried under reduced pressure at 40 degreeC for 1 day, and PI-2 was obtained. The weight average molecular weight (Mw) of PI-2 was 25,100, and the number average molecular weight (Mn) was 12,100.

It is estimated that the structure of PI-2 is a structure represented by the following formula (PI-2).

In addition, the subscripts in square brackets show the content ratio (molar ratio) of each repeating unit, and are m=85 and q=15.

[Formula 63]

In (PI-2), _{the substrate of C 3} H ₆ includes a 1-methylethylene group (below (P1)) and a 2-methylethylene group (below (P2)) at random. In the following formulas (P1) and (P2), * ¹ is bonded to the structure on the carbonyl group side in the formula (PI-2), and * ² is the acryloxy group side in the formula (PI-7). combined with the structure.

[Formula 64]

<Synthesis Example 3: Synthesis of polyimide (PI-3)>

14.3 g (50 mmol) of bis(4-amino-3-carboxyphenyl)methane was mixed with N-methylpyrrolidone (NMP ) was dissolved in 100.0 g. Subsequently, 9.31 g (30 mmol) of oxydiphthalic dianhydride and 8.88 g (20 mmol) of 4,4'-(hexafluoroisopropylidene) diphthalic dianhydride were added, followed by stirring at a temperature of 40°C for 2 hours. . Then, after adding 50 mL of toluene, the temperature was raised to 180 degreeC, and it stirred for 5 hours, flowing nitrogen of the flow volume of 200 ml/min. After cooling the reaction solution to 25°C, Blemmer PE-200 (manufactured by Nichiyu Co., Ltd.) 14.2 g (50 mmol), N,N'-dimethylaminopyridine 0.61 g (5 mmol), p-Me 0.06 g of oxyphenol and 130.0 g of N-methylpyrrolidone were added and dissolved, and it cooled to 0 degreeC. Next, 6.3 g (50 mmol) of diisopropylcarbodiimide was added, followed by stirring at 10°C or lower for 5 hours, and the temperature was raised to room temperature. Then, the polyimide was precipitated in 2 liters of water, and the water-polyimide mixture was stirred at a speed of 2,000 rpm for 30 minutes. The polyimide precursor resin was removed by filtration, and the mixture was stirred again with 1.5 liters of methanol for 30 minutes, followed by filtration. Next, the obtained polyimide was dried under reduced pressure at 40 degreeC for 1 day, and PI-3 was obtained. The weight average molecular weight (Mw) of PI-3 was 31,000, and the number average molecular weight (Mn) was 13,900.

It is estimated that the structure of PI-3 is a structure represented by the following formula (PI-3). In formula (PI-3), * represents a bonding site with the oxygen atom to which R is bonded.

[Formula 65]

<Synthesis Example 4: Synthesis of polyimide (PI-4)>

In a dry reactor equipped with a flat-bottom joint equipped with a stirrer, condenser and internal thermometer, 15.21 g (100 mmol) of 3,5-diaminobenzoic acid was added to 130.0 g of N-methylpyrrolidone (NMP) while removing moisture. was dissolved in Subsequently, 15.51 g (50 mmol) of oxydiphthalic dianhydride and 22.1 g (50 mmol) of 4,4'-(hexafluoroisopropylidene) diphthalic dianhydride were added, and 2 at a temperature of 40°C time was stirred. Subsequently, after adding 50 mL of toluene, the temperature was raised to 180 degreeC, and it stirred for 4 hours, flowing nitrogen of the flow volume of 200 ml/min. After cooling the reaction solution to 25°C, 7.80 g (60 mmol) of 2-hydroxyethyl methacrylate, 13.6 g (40 mmol) of hexaethylene glycol monomethyl ether, N,N'-dimethylamino 0.61 g (5 mmol) of pyridine, 0.06 g of p-methoxyphenol, and 130.0 g of N-methylpyrrolidone were added, dissolved, and cooled to 0°C. Next, 12.6 g (100 mmol) of diisopropylcarbodiimide was added, the mixture was stirred at 10°C or lower for 5 hours, and the temperature was raised to room temperature. Then, the polyimide was precipitated in 2 liters of water, and the water-polyimide mixture was stirred at a speed of 2,000 rpm for 30 minutes. The polyimide precursor resin was removed by filtration, and the filtrate was mixed with 1.5 liters of methanol, stirred again for 30 minutes, and filtered again. Next, the obtained polyimide was dried under reduced pressure at 40 degreeC for 1 day, and PI-4 was obtained. The weight average molecular weight (Mw) of PI-4 was 28 and 300, and the number average molecular weight (Mn) was 13,000.

It is estimated that the structure of PI-4 is a structure represented by the following formula (PI-4). In formula (PI-4), * represents a bonding site with the oxygen atom to which _{R 1 is bonded.}

In addition, the subscripts in square brackets show the content ratio (molar ratio) of each repeating unit, and are m=50 and q=50.

[Formula 66]

<Synthesis Example 5: Synthesis of polyimide (PI-5)>

In a dry reactor equipped with a flat-bottom joint equipped with a stirrer, condenser and internal thermometer, 15.21 g (100 mmol) of 3,5-diaminobenzoic acid was added to 130.0 g of N-methylpyrrolidone (NMP) while removing moisture. was dissolved in Subsequently, 15.5 g (50 mmol) of oxydiphthalic dianhydride and 13.3 g (30 mmol) of 4,4'-(hexafluoroisopropylidene) diphthalic dianhydride were added, and the mixture was stirred at a temperature of 40°C for 2 hours. did. Subsequently, after adding 50 mL of toluene, the temperature was raised to 180 degreeC, and it stirred for 4 hours, flowing nitrogen of the flow volume of 200 ml/min. After cooling the reaction solution to 25° C., Blemmer AP-400 (manufactured by Nichiyu Co., Ltd.) 21.3 g (50 mmol), 1-hydroxy-2,3-epoxypropane 2.22 g (30 mmol), 0.61 g (5 mmol) of N,N'-dimethylaminopyridine, 0.06 g of p-methoxyphenol, and 130.0 g of N-methylpyrrolidone were added, dissolved, and cooled to 0°C. Next, 12.6 g (100 mmol) of diisopropylcarbodiimide was added, the mixture was stirred at 10°C or lower for 5 hours, and the temperature was raised to room temperature. Then, the polyimide was precipitated in 2 liters of water, and the water-polyimide mixture was stirred at a speed of 2,000 rpm for 30 minutes. The polyimide precursor resin was removed by filtration, and the filtrate was mixed with 1.5 liters of methanol, stirred again for 30 minutes, and filtered again. Next, the obtained polyimide was dried under reduced pressure at 40 degreeC for 1 day, and PI-5 was obtained. The weight average molecular weight (Mw) of PI-5 was 33,300, and the number average molecular weight (Mn) was 15,000.

It is estimated that the structure of PI-5 is a structure represented by the following formula (PI-5). In formula (PI-5), * represents the bonding site|part with the oxygen atom which _{R<1> couple|bonds.}

[Formula 67]

In (PI-5), _{the substrate of C 3} H ₆ includes a 1-methylethylene group ((P1) above) and a 2-methylethylene group ((P2) above) at random. In the formulas (P1) and (P2), * ¹ is bonded to the structure on the acrylate group side in _{R 1} ^{in the formula (PI-5), and * 2} _{is R 1} in the formula (PI-5). Combines with the structure on the * side of

<Synthesis Example 6: Synthesis of polyimide (PI-6)>

6.91 g (30 mmol) bis(2-(3-aminopropoxy)ethyl)ether, 2,2-bis(3 -Amino-4-hydroxyphenyl) hexafluoropropane 25.6 g (70 mmol) was dissolved in 100.0 g of N-methylpyrrolidone (NMP). Subsequently, 310.2 g (100 mmol) of oxydiphthalic dianhydride and 13.3 g (30 mmol) of 4,4'-(hexafluoroisopropylidene) diphthalic dianhydride were added, and the mixture was stirred at a temperature of 40°C for 2 hours. did. Then, after adding 50 mL of toluene, the temperature was raised to 180 degreeC while nitrogen flowed at a flow rate of 200 ml/min, and it stirred for 5 hours, and cooled the reaction liquid to 25 degreeC. 12.1 g (120 mmol) of triethylamine, 0.06 g of p-methoxyphenol, and 80.0 g of N-methylpyrrolidone were added, dissolved, and cooled to 0°C. Next, 10.4 g (100 mmol) of methacrylic acid chloride was added dropwise over 1 hour, followed by stirring at 25°C or lower for 4 hours. Then, the polyimide was precipitated in 2 liters of water, and the water-polyimide mixture was stirred at a speed of 2,000 rpm for 30 minutes. The polyimide precursor resin was removed by filtration, and the filtrate was mixed with 1.5 liters of methanol, stirred again for 30 minutes, and filtered again. Next, the obtained polyimide was dried under reduced pressure at 40 degreeC for 1 day, and PI-6 was obtained. The weight average molecular weight (Mw) of PI-6 was 29,900, and the number average molecular weight (Mn) was 14,300.

It is estimated that the structure of PI-6 is a structure represented by the following formula (PI-6). In formula (PI-6), * represents a bonding site with the oxygen atom to which R is bonded.

[Formula 68]

<Synthesis Example 7: Synthesis of polyimide (PI-7)>

Instead of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane used in the synthesis of PI-6, the same molar amount of 4,6-dihydroxy-1,3-phenylenedia PI-7 was synthesized in the same manner as for PI-6 except that min was used. The weight average molecular weight (Mw) of PI-7 was 27, 400, and the number average molecular weight (Mn) was 13, 300.

It is estimated that the structure of PI-7 is a structure represented by the following formula (PI-7). In formula (PI-7), * represents a bonding site with the oxygen atom to which R is bonded.

[Formula 69]

<Synthesis Example 8: Synthesis of polyimide (PI-8)>

Instead of 2-hydroxyethyl methacrylate and hexaethylene glycol monomethyl ether used in the synthesis of PI-4, glycerin dimethacrylate (manufactured by Nichiyu Co., Ltd.) 30 (mmol) and Blemmer PE PI-8 was synthesized in the same manner as PI-4 except that -200 (manufactured by Nichiyu Co., Ltd.) (70 mmol) was used. The weight average molecular weight (Mw) of PI-8 was 25,900, and the number average molecular weight (Mn) was 12,900.

It is estimated that the structure of PI-8 is a structure represented by the following formula (PI-8). In formula (PI-8), * represents the bonding site|part with the oxygen atom which _{R<1> couple|bonds.}

[Formula 70]

<Synthesis Example 9: Synthesis of polyimide (PI-9)>

4.56 g (30 mmol) 3,5-diaminobenzoic acid, and 9,9-bis(4-amino-3- 7.53 g (20 mmol) of methylphenyl)fluorene was dissolved in 80.0 g of N-methylpyrrolidone (NMP). Then, 15.51 g (50 mmol) of oxydiphthalic dianhydride was added, and it stirred at the temperature of 40 degreeC for 2 hours. Then, after adding 30 mL of toluene, the temperature was raised to 180 degreeC, flowing nitrogen at a flow rate of 200 ml/min, and it stirred for 5 hours. After cooling the reaction solution to 25°C, Blemmer PE-200 (manufactured by Nichiyu Co., Ltd.) 14.2 g (50 mmol), N,N'-dimethylaminopyridine 0.61 g (5 mmol), p-Me 0.06 g of oxyphenol and 130.0 g of N-methylpyrrolidone were added, dissolved, and cooled to 0°C. Next, 6.3 g (50 mmol) of diisopropylcarbodiimide was added, stirred at 10°C or lower for 5 hours, and the temperature was raised to room temperature. Next, this was cooled to 25°C, precipitated in 1.5 liters of water/methanol = 75/25 (volume ratio), and stirred at a speed of 2,000 rpm for 30 minutes. The precipitated polyimide resin was filtered off, washed with 1 liter of water, and the filtrate was mixed with 1.5 liters of methanol, stirred for 30 minutes again, and filtered again. The obtained polyimide was dried under reduced pressure at 40 degreeC for 1 day, and PI-9 was obtained. The weight average molecular weight (Mw) of PI-9 was 31,600, and the number average molecular weight (Mn) was 11,500.

It is estimated that the structure of PI-9 is a structure represented by the following formula (PI-9).

It is estimated that the structure of PI-9 is a structure represented by the following formula (PI-9). In formula (PI-9), * represents a bonding site with the oxygen atom to which _{R 1 is bonded.}

In addition, the subscripts in square brackets show the content ratio (molar ratio) of each repeating unit, and are m=3, q=2.

[Formula 71]

<Synthesis Example 10: Synthesis of polyimide precursor (PA-1)>

20.0 g (64.5 mmol) of oxydiphthalic dianhydride was suspended in 140 mL of diglyme while removing moisture in a dry reactor equipped with a flat bottom joint equipped with a stirrer, condenser and internal thermometer. 2-hydroxyethyl methacrylate 10.1 g (77 mmol), Blemmer AP-400 (manufactured by Nichiyu Co., Ltd.) 12.6 g (39 mmol), hydroquinone 0.05 g and pyridine 10.7 g (135 mmol) were successively added It was added and stirred at the temperature of 60 degreeC for 18 hours. Then, after the mixture was cooled to -20°C, 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. Then, the mixture was warmed to room temperature and stirred for 2 hours, then 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to obtain a clear solution. Then, to the obtained transparent solution, 11.7 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added dropwise over 1 hour. While adding the diamine, the viscosity increased. Next, 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added, and the mixture was stirred for 2 hours. Then, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes. The polyimide precursor resin was removed by filtration, and the mixture was stirred again for 30 minutes in 4 liters of water, followed by filtration. Next, the obtained polyimide precursor resin was dried under reduced pressure at 45 degreeC for 1 day. The molecular weight of this polyimide precursor PA-1 was Mw=25,100 and Mn=13,200.

The structure of PA-1 is estimated to be a structure represented by following formula (PA-1). In formula (PA-1), * represents a bonding site with the oxygen atom to which R is bonded.

[Formula 72]

In the above (PA-1), the C ₃ H ₆ substrate contains a 1-methylethylene group ((P1) above) and a 2-methylethylene group ((P2) above) at random. In formulas (P1) and (P2), * ¹ is bonded to the structure on the acryloxy group side in R in ^{formula (PA-1), and *2} is * in R in formula (PA-1). combined with the structure of the side.

<Synthesis Example 11: Synthesis of polyimide (A-1) for comparative example>

While removing moisture in a dry reactor equipped with a flat bottom joint equipped with a stirrer, condenser and internal thermometer, 31.0 g (100 mmol) of 4,4'-diaminodiphenyl ether was added to N-methylpyrrolidone (NMP) 180.0 g was dissolved. Then, 44.4 g (100 mmol) of 4,4'-(hexafluoroisopropylidene) diphthalic dianhydride was added, and it stirred at the temperature of 40 degreeC for 2 hours. After 50 mL of toluene was then added, the temperature was raised to 180°C while flowing nitrogen at a flow rate of 200 ml/min, stirred for 6 hours, and cooled to room temperature. Then, 130.0 g of N-methylpyrrolidone was added and diluted, and the polyimide was precipitated in 2 liters of water, and the water-polyimide mixture was stirred at a speed of 2000 rpm for 30 minutes. The polyimide precursor resin was removed by filtration, and the filtrate was mixed with 1.5 liters of methanol, stirred again for 30 minutes, and filtered again. Next, the obtained polyimide was dried under reduced pressure at 40 degreeC for 1 day, and A-1 was obtained. The weight average molecular weight (Mw) of A-1 was 30,100, and the number average molecular weight (Mn) was 14,500.

The structure of A-1 is estimated to be a structure represented by following formula (A-1).

The polyimide precursor (A-1) for a comparative example does not contain a polyalkyleneoxy group and a polymeric group, and does not correspond to specific resin.

[Formula 73]

<Synthesis Example 12: Synthesis of Polyimide (A-2) for Comparative Example>

155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a separable flask, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added. A reaction mixture was obtained by adding 79.1 g of pyridine while stirring at room temperature. After completion of the exotherm by the reaction, it was allowed to cool to room temperature and left still for 16 hours.

Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture while stirring for 40 minutes. Subsequently, a suspension in which 93.0 g of 4,4'-diaminodiphenyl ether was suspended in 350 ml of γ-butyrolactone was added while stirring for 60 minutes. Furthermore, after stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added, and it stirred for 1 hour. After that, 400 ml of γ-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.

The obtained reaction liquid was added to 3 liters of ethyl alcohol, and the precipitate which consists of a crude polymer was produced|generated. The produced crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dripped at 28 liters of water, a polymer was precipitated, and the powdery polyimide precursor (A-2) for comparative examples was obtained by vacuum-drying after filtering the obtained deposit. It was 20,000 when the weight average molecular weight (Mw) of the polyimide precursor (A-2) for comparative examples was measured.

<Synthesis Example 13: Synthesis of polyimide precursor (A-3) for comparative example>

The method described in Synthesis Example 18, except that in Synthesis Example 12, 147.1 g of 3,3′,4,4′-biphenyltetracarboxylic dianhydride was used instead of 155.1 g of 4,4′-oxydiphthalic dianhydride. The polyimide precursor (A-3) for comparative examples was obtained by carrying out similarly to and reacting. It was 22,000 when the weight average molecular weight (Mw) of the polyimide precursor (A-3) for comparative examples was measured.

Polyimide precursors (A-2) and (A-3) for comparative examples do not contain a polyalkyleneoxy group, and do not correspond to specific resin.

<Examples and Comparative Examples>

In each Example, the components shown in Table 1 below were respectively mixed, and each curable resin composition was obtained. Moreover, in each comparative example, the components of following Table 1 were mixed, respectively, and each comparative composition was obtained. The obtained curable resin composition and the composition for comparison were filtered under pressure by passing through a filter made from polytetrafluoroethylene having a micropore width of 0.8 µm.

In Table 1, the numerical value in the column of "mass part" has shown content (mass part) of each component.

In Table 1, for example, descriptions such as "PI-1/PI-2" in the "Type" column and "16/16" in the "mass part" column refer to PI-1 as 16 parts by mass and PI-2 shows that 16 parts by mass of each was used.

In addition, in Table 1, description of "-" has shown that the corresponding component is not contained.

[Table 1]

Details of each component listed in Table 1 are as follows.

[Specific resin or comparative resin]

PI-1 to PI-8: PI-1 to PI-8 synthesized above

PA-1: PA-1 synthesized above

・A-1 to A-3: A-1 to A-3 synthesized above

〔solvent〕

DMSO: dimethyl sulfoxide

·GBL: γ-butyrolactone

・Ethyl lactate

·NMP: N-methylpyrrolidone

In Table 1, description of DMSO/GBL has shown that DMSO and GBL were mixed in the ratio of DMSO:GBL=20:80 (mass ratio).

In Table 1, the description of NMP/ethyl lactate shows that NMP and ethyl lactate are mixed in a ratio of NMP:ethyl lactate = 80:20 (mass ratio).

[Polymerization Initiator]

・OXE-01: IRGACURE OXE 01 (manufactured by BASF)

・OXE-02: IRGACURE OXE 02 (manufactured by BASF)

[Polymerizable compound]

・SR-209: SR-209 (manufactured by Sartomer)

・SR-231: SR-231 (manufactured by Sartomer)

・SR-239: SR-239 (manufactured by Sartomer)

・SR-268: SR-268 (manufactured by Sartomer)

・A-DPH: dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[Polymerization inhibitor]

F-1: 1,4-benzoquinone

F-2: 4-methoxyphenol

F-3: 1,4-dihydroxybenzene

・F-4: 2-nitroso-1-naphthol (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

[Metal adhesion improving agent]

·G-1 to G-4: A compound of the following structure. In the following structural formulas, Et is an ethyl group.

[Formula 74]

[Migration inhibitor]

·H-1: 1H-tetrazole

H-2: 1,2,4-triazole

·H-3: 5-phenyltetrazole

[Thermal base generator]

I-1: a compound of the following structure

[Formula 75]

〔additive〕

·J-1: N-phenyldiethanolamine (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

<Evaluation>

In each Example and comparative example, applicability|paintability and film strength (elongation at break) were evaluated using the curable resin composition or the composition for comparison respectively prepared.

The detail of the evaluation method in each evaluation is described below.

[Applicability]

It was set as the silicon|silicone level|step difference board|substrate in which a total of 10 steps|steps 100 micrometers in length, 20 micrometers in width, and 5 micrometers in depth were formed on one side of a 4 inch diameter silicon substrate.

1 is a schematic diagram of a formed stepped substrate.

In Fig. 1, on the surface of a silicon substrate 1, a total of 10 steps 2 are formed in 5 columns and 2 rows.

In FIG. 1 , a step 2 is a step having a depth of 5 μm with respect to the surface of a portion of the silicon substrate 1 where no step is formed. In addition, in each of the 10 steps, the depth of the step is substantially uniform.

In Fig. 1, A indicates the vertical length of the step 2, and is 100 µm.

In FIG. 1, B represents the horizontal length of the step 2, and is 20 micrometers.

In FIG. 1 , the intervals between the five steps arranged in the horizontal direction are all 1 mm.

In FIG. 1 , an interval between two steps arranged in the vertical direction is 2 mm in both cases.

With respect to the step substrate shown in Fig. 1, each curable resin composition or composition for comparison prepared in Examples and Comparative Examples was respectively applied by spin coating to form a curable resin composition layer.

The silicon wafer to which the obtained curable resin composition layer was applied was dried at 100 degreeC for 5 minutes on a hotplate, and the curable resin composition layer with a uniform thickness of about 15 micrometers was obtained on the silicon wafer.

The surface of the curable resin composition layer after drying was observed by AFM (atomic force microscope), and the difference in height of the film|membrane measured by following formula FL was computed.

Formula FL: film height difference = (maximum height of curable resin composition layer) - (minimum height of curable resin composition layer)

Moreover, the surface of the curable resin composition layer after drying was observed with the optical microscope defect inspection apparatus KLA2360 (made by APPLID MATERIALS) and review SEM Vision G3 (made by APPLID MATERIALS), and the number of defects per ^{cm<2> was computed.}

Using the said film thickness difference and the said number of defects as indicators, applicability|paintability was evaluated according to the following evaluation criteria. The evaluation result was described in the "applicability" column of Table 1. It can be said that the composition is excellent in applicability|paintability, so that the height difference of a film|membrane is small, and there are few defects.

-Evaluation standard-

A: The height difference of the film|membrane was less than 0.3 micrometer, and the number of defects was less than ^{5 pieces/cm<2>.}

B: The difference in height of the film was less than 0.3 µm, and the number of defects was 5/cm ² or more and less than 10 pieces/cm ^{2 .}

C: The film|membrane height difference was 0.3 micrometer or more and less than 0.5 micrometer, and the number of defects was less than ^{10 pieces/cm<2>.}

D: At least one of the conditions of a film height difference of 0.5 µm or more and the number of defects of 10 pieces/cm ^{2 or more was satisfied.}

[film strength (elongation at break)]

Each curable resin composition or the composition for comparison prepared in each Example and the comparative example was respectively applied on a silicon wafer by the spin coating method, and the curable resin composition layer was formed.

The silicon wafer to which the obtained curable resin composition layer was applied was dried at 100 degreeC for 5 minutes on a hotplate, and the curable resin composition layer with a uniform thickness of about 15 micrometers was obtained on the silicon wafer.

The obtained curable resin composition layer (resin layer) was heated at a temperature increase rate of 10° C./min in a nitrogen atmosphere to reach the temperature described in the “curing conditions” column of Table 1, followed by heating at this temperature for 3 hours.

The resin layer (cured film) after hardening was immersed in 4.9 mass % hydrofluoric acid aqueous solution, and the cured film was peeled from a silicon wafer. The peeled cured film was punched out using the punching machine, and the test piece of width 3mm and sample length 30mm was produced. About the obtained test piece, using a tensile tester (tensilon), in the environment of a crosshead speed of 300 mm/min, 25 degreeC, 65%RH (relative humidity), based on JIS-K6251, the film in the longitudinal direction of a film The elongation at the time of fracture|rupture (break elongation rate) was measured. Evaluation was performed 5 times in each Example or comparative example, and the arithmetic mean value of the measured value of the elongation at break in 5 times of measurement was made into a landmark value.

About the said landmark value, evaluation was performed according to the following evaluation criteria, and the evaluation result was described in Table 1.

-Evaluation standard-

A: The above landmark value was 60% or more.

B: The above landmark values were 55% or more and less than 60%.

C: The sign value was 50% or more and less than 55%.

D: The sign value was less than 50%.

From the above result, it turns out that the curable resin composition containing specific resin which concerns on this invention is excellent in applicability|paintability.

The composition for comparison according to Comparative Examples 1-2 does not contain specific resin. It turns out that the composition for comparison which concerns on this Comparative Examples 1-2 is inferior in applicability|paintability.

<Example 101>

The curable resin composition described in Example 1 was applied by spinning so that the film thickness might be set to 20 µm on the surface of the copper foil layer in the resin substrate in which the copper foil layer was formed on the surface. After drying the curable resin composition apply|coated to the resin base material at 100 degreeC for 2 minutes, it exposed using the stepper (made by Nikon, NSR1505 i6). The exposure was performed through a mask of a square pattern (a square pattern of 100 µm in length and width each, the number of repetitions of 10) at a wavelength of 365 nm at ^{an exposure amount of 400 mJ/cm 2} to create a square negative pattern. After exposure, it developed for 30 second with cyclopentanone, rinsed for 20 second with PGMEA, and obtained the pattern.

Subsequently, the temperature was raised at a temperature increase rate of 10° C./min in a nitrogen atmosphere to reach the temperature described in the “curing conditions” column of Table 1, followed by heating at this temperature for 3 hours to form an interlayer insulating film for a redistribution layer. This interlayer insulating film for a redistribution layer was excellent in insulation. Moreover, as a result of manufacturing a semiconductor device using these interlayer insulating films for redistribution layers, it was confirmed that it operates without a problem.

1 silicon substrate
2 steps
A step length
B step width

Claims (14)

Curable resin composition containing at least 1 sort(s) of resin selected from the group which consists of polyimide and polyimide precursor which has a polyalkyleneoxy group and a polymeric group, a polymerization initiator, a polymeric compound, and a solvent. The method according to claim 1,
Curable resin composition containing the structure represented by following formula (1-1) as a structure which has the said polyalkyleneoxy group and the said polymeric group.
[Formula 1]

In formula (1-1), R ¹ each independently represents a hydrogen atom or an alkyl group, Z ¹ represents a group containing a polymerizable group, n represents an integer of 2 or more, m represents an integer of 2 or more, * indicates a binding site with another structure. 3. The method according to claim 2,
Curable resin composition in which said Z<^1> contains at least 1 sort(s) of group selected from the group which consists of an ethylenically unsaturated group, a cyclic ether group, and a methylol group as said polymeric group. 4. The method according to claim 2 or 3,
Curable resin composition in which the said resin is a structure containing the structure represented by the said Formula (1-1), Comprising: The structure represented by following formula (1-2) is included.
[Formula 2]

In formula (1-2), L ¹ represents a b+2-valent linking group, X ² represents an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond, and L ² is a single bond or a+1 represents a valent linking group, X ¹ represents a structure represented by the above formula (1-1), a represents an integer of 1 or more, b represents an integer of 1 or more, and X ² , L ² , X ¹ or a plurality of a is present. In this case, a plurality of X ² , L ² , X ¹ or a may be the same or different. 5. The method according to any one of claims 2 to 4,
Curable resin composition containing the repeating unit represented by following formula (1-3) as a repeating unit containing the structure represented by said Formula (1-1).
[Formula 3]

In formula (1-3), L ¹ represents a b+2-valent linking group, X ² represents an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond, and L ² is a single bond or a+1 represents a valent linking group, X ¹ represents a structure represented by the above formula (1-1), a represents an integer of 1 or more, b represents an integer of 1 or more, and L ⁴ represents the following formula (L4-1) or formula ( When a structure represented by L4-2) is shown and ^two or more X 2 , L ² , X ¹ or a exists, a plurality of X ² , L ² , X ¹ or a may be the same or different.
[Formula 4]

In formula (L4-1) or formula (L4-2), R ¹¹⁵ represents a tetravalent organic group, A ¹ and A ² each independently represent an oxygen atom or —NH-, R ¹¹³ and R ¹¹⁴ are, Each independently represents a hydrogen atom or a monovalent organic group. 6. The method according to claim 4 or 5,
Curable resin composition in which said L<^1> contains the structure represented by at least 1 sort(s) selected from the group which consists of structures represented by following formula (A-1) - (A-5).
[Formula 5]

In formulas (A-1) to (A-5), R ^A11 to R ^A14 , R ^A21 to R ^A24 , R ^A31 to R ^A38 , R ^A41 to R ^A48 and R ^A51 to R ^A58 are each independently a hydrogen atom , an alkyl group, a cyclic alkyl group, an alkoxy group, a hydroxyl group, a cyano group, a halogenated alkyl group, a halogen atom, or a bond with ^{X 2 in the formula (1-2) or (1-3)} represents a moiety, and L ^A31 and L ^A41 are each independently a single bond, a carbonyl group, a sulfonyl group, a divalent saturated hydrocarbon group, a divalent unsaturated hydrocarbon group, a hetero atom, a heterocyclic group, or a halogenated alkylene group represents a group, and among R ^A11 to R ^A14 , R ^A21 to R ^A24 , R ^A31 to R ^A38 , R ^A41 to R ^A48 and R ^A51 to R ^A58 , each b is the formula (1-2) or the formula (1) ^{It is a binding site with X 2} in -3), and * each independently represents a binding site with another structure. 7. The method according to any one of claims 1 to 6,
The curable resin composition used for formation of the interlayer insulating film for redistribution layers. The cured film formed by hardening|curing the curable resin composition in any one of Claims 1-7. The laminated body which has two or more layers of cured films of Claim 8, and has a metal layer between cured films. The manufacturing method of a cured film including the film-forming process of applying the curable resin composition of any one of Claims 1-7 to a base material, and forming a film|membrane. 11. The method of claim 10,
The manufacturing method of the cured film including the exposure process of exposing the said film|membrane, and the developing process of developing the said film|membrane. 12. The method according to claim 10 or 11,
The manufacturing method of the cured film including the process of heating the said film|membrane at 50-450 degreeC. The semiconductor device containing the cured film of Claim 8, or the laminated body of Claim 9. The polyimide or polyimide precursor containing the structure represented by following formula (1-1).
[Formula 6]

In formula (1-1), R ¹ each independently represents a hydrogen atom or an alkyl group, Z ¹ represents a group containing a polymerizable group, n represents an integer of 2 or more, m represents an integer of 2 or more, * indicates a binding site with another structure.

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