JP2022135427A - Negative type photosensitive resin composition and use of the same - Google Patents

Abstract

To provide a negative type photosensitive resin composition from which a cured product such as a film that is excellent in mechanical strength such as elongation and chemical resistance can be obtained.SOLUTION: A negative type photosensitive resin composition contains (A) polyimide having a double bond in a side chain, (B) a crosslinking agent containing a (meth)acrylate compound having a fluorene skeleton, and (C) a polymerization initiator.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a negative photosensitive resin composition and uses thereof.

Polyimide resin has high mechanical strength, heat resistance, insulation, and solvent resistance, so it is widely used as a protective material for liquid crystal display elements and semiconductors, as an insulating material, and as a thin film for electronic materials such as color filters. there is

US Pat. No. 5,300,000 discloses a polyimide precursor containing a dianhydride, a diamine, and 1,3-bis(3-aminophenoxy)benzene.
Patent Documents 2 to 4 disclose photosensitive resin compositions containing polyimide precursors having a predetermined structure.

Patent Document 5 discloses a curable composition containing a (meth)acrylate having a fluorene skeleton and a polymerization initiator.
Patent Document 6 discloses (A) a compound having a carbon-carbon unsaturated bond, (B) an epoxy resin, (C) a photoinitiator, and (D) at least a soluble polymer soluble in an alkaline aqueous solution or an organic solvent. A photosensitive adhesive composition is disclosed. In this document, a resin containing a fluorene skeleton is exemplified as the component (A), and a polyimide resin is exemplified as the component (D).
Patent Document 7 discloses a resin composition containing a polyimide resin having a predetermined structure.

JP 2013-241607 A JP 2013-95894 A JP 2014-172994 A WO2010/110335 JP 2012-206968 A JP 2012-162676 A JP 2018-070829 A

However, in the conventional techniques described in Patent Documents 1 to 7, there is room for improvement in mechanical strength such as elongation and chemical resistance in films containing polyimide obtained from resin compositions. When the type and amount of resin added are adjusted in order to improve the elongation of a cured film such as a film, the chemical resistance tends to decrease, and there is a trade-off between them.

The present inventors have found that the above problems can be solved by combining a given polyimide with a (meth)acrylate compound having a specific structure, and have completed the present invention.
That is, the present invention can be shown below.

According to the invention,
(A) a polyimide having a double bond in its side chain;
(B) a cross-linking agent containing a (meth)acrylate compound having a fluorene skeleton;
(C) a polymerization initiator;
Including, it is possible to provide a negative photosensitive resin composition.

According to the invention,
A cured product of the negative photosensitive resin composition can be provided.

According to the invention,
A cured film comprising the cured product can be provided.

According to the invention,
A semiconductor device comprising a resin film containing the cured product can be provided.

EFFECTS OF THE INVENTION The negative photosensitive resin composition of the present invention is excellent in mechanical strength such as elongation, and can provide cured products such as films with excellent chemical resistance.

1 is a schematic cross-sectional view of a semiconductor device according to an embodiment; FIG.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described with reference to the drawings. In addition, in all the drawings, the same constituent elements are denoted by the same reference numerals, and the description thereof will be omitted as appropriate. In addition, "~" represents "more than" to "less than" unless otherwise specified.

The negative photosensitive resin composition of the present embodiment includes (A) a polyimide having a double bond in the side chain, (B) a cross-linking agent containing a (meth)acrylate compound having a fluorene skeleton, and (C) polymerization initiation and an agent.
In the present embodiment, by using a combination of a polyimide (A) having a double bond in a side chain and a cross-linking agent (B) containing a (meth)acrylate compound having a fluorene skeleton, mechanical strength such as elongation is excellent. At the same time, a cured product such as a film having excellent chemical resistance can be obtained.
Each component will be described below.

[Polyimide (A) having a double bond in the side chain]
Polyimide (A) having a double bond in the side chain (hereinafter also simply referred to as polyimide (A)) is a known polyimide having a double bond in the side chain within the scope of the effect of the present invention. can be done.
In this embodiment, the polyimide (A) preferably contains a compound having a structural unit (a) represented by the following general formula (1-1) and having a double bond in its side chain.

In general formula (1-1), Y represents a divalent organic group.
Although the divalent organic group is not particularly limited, groups represented by the following general formula (1a), the following general formula (1b), or the following general formula (1c) can be mentioned.

In general formula (1a), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having ¹ to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms; The R ² groups present may be the same or different.
From the viewpoint of the effects of the present invention, R ¹ and R ² are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

R ³ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and a plurality of R ³ may be the same or different.
From the viewpoint of the effects of the present invention, R ³ is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
* indicates a bond.

In general formula (1b), R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to ³ carbon atoms, or an alkoxy group having 1 to 3 carbon atoms; ^R5s present may be the same or different.

From the viewpoint of the effects of the present invention, R ⁴ and R ⁵ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably at least one of R ⁴ and at least one of R ⁵ an alkyl group having 1 to 3 carbon atoms, more preferably three R ⁴ are alkyl groups having 1 to 3 carbon atoms, one R ⁴ is a hydrogen atom, and three R ⁵ are alkyl groups having 1 to 3 carbon atoms and one R ⁵ is a hydrogen atom, particularly preferably three R ⁴ are methyl groups and one R ⁴ is a hydrogen atom, and three R ⁵ are methyl groups and one R ⁵ is It is a hydrogen atom.
* indicates a bond.

In general formula (1c), Z represents an alkylene group having 1 to 5 carbon atoms or a divalent aromatic group.
* indicates a bond.

The polyimide (A) of the present embodiment contains a compound (polymer) having a group represented by the general formula (1a), the general formula (1b) and the general formula (1c) in the main chain in Y In addition, the main chain of the polymer can withstand deformation, and the slippage between the polymer chains is improved, so the elongation is significantly improved, and the mechanical strength is excellent. A cured product such as an excellent film can be obtained.

Although the reason why such an effect is obtained is not clear, it is presumed that the strong packing between polymer chains suppresses breakage due to sliding of the polymer chains, improves elongation, and provides excellent flexibility.

The polyimide (A) of the present embodiment has double bonds (groups having double bonds) in side chains.
Polyimide (A) has a double bond in the side chain, so that in the exposure step, these groups and the cross-linking agent (B) polymerize and become insoluble in the solvent, and ring closure does not occur during subsequent curing. Therefore, it is possible to obtain a cured product such as a film in which cure shrinkage is suppressed and excellent in dimensional stability.

Examples of groups having a double bond include alkenyl groups such as a vinyl group, an allyl group, and an isopropenyl group; alkenyl carbonate groups such as an allyl carbonate group; vinyl aromatic groups such as a vinylphenyl group; (Meth)acryloyl group is preferred.

Polyimide (A) includes a compound having a structural unit (a) represented by the general formula (1-1) and a structural unit (b) represented by the following general formula (1-2). is preferred.

In general formula (1-2), Q represents a divalent to tetravalent organic group having 1 to 10 carbon atoms, and multiple Qs may be the same or different.

Examples of the divalent to tetravalent organic group having 1 to 10 carbon atoms include an ester group, a divalent to tetravalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and a divalent to tetravalent carbon number of 3 to 10. Alicyclic hydrocarbon groups and the like may be mentioned, and these hydrocarbon groups may contain heteroatoms such as oxygen, nitrogen, and sulfur atoms, and have structures such as ester bonds, thioester bonds, urethane bonds, and thiourethane bonds. You may have it inside.

R represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and multiple R may be the same or different. R is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
m1 and m2 each independently represent an integer of 1 to 3;

X represents a single bond, —SO ₂ —, —C(=O)—, a linear or branched alkylene group having 1 to 5 carbon atoms, or a linear or branched fluoroalkylene group having 1 to 5 carbon atoms; Multiple X's may be the same or different.
From the viewpoint of the effect of the present invention, X is preferably a linear or branched alkylene group having 1 to 5 carbon atoms or a linear or branched fluoroalkylene group having 1 to 5 carbon atoms.
The molar ratio (b/a) between the structural unit (a) and the structural unit (b) is 0.01/1 or more and 1/1 or less, preferably 0.20/1 or more, from the viewpoint of the effects of the present invention. , 0.90/1 or less.

The polyimide (A) of the present embodiment is a structural unit (a) represented by the general formula (1-1), a structural unit (b) represented by the following general formula (1-2), and the following general A compound having a structural unit (c) represented by formula (1-3) can be included.

In general formula (1-3), Z ¹ and Z ² each independently represent an alkoxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, preferably a fluoroalkyl group having 1 to 3 carbon atoms. group, more preferably a fluoroalkyl group having 1 to 3 carbon atoms.

In this embodiment, the polyimide (A) preferably contains a compound having a structural unit represented by the following general formula (1).

In general formula (1), Q, R, m1, m2, and X are synonymous with general formula (1-2), and Y is synonymous with general formula (1-1).

The polyimide (A) of the present embodiment contains a compound having the above structural unit, and the compound may further partially contain a compound having the following structural unit.

The polyimide (A) of the present embodiment has a weight average molecular weight of 10,000 to 300,000, preferably 15,000 to 200,000.
From the viewpoint of the effect of the present invention, the negative photosensitive resin composition of the present embodiment preferably contains 20 parts by mass or more and 90 parts by mass or less of polyimide (A) in 100 parts by mass of non-volatile components excluding the solvent described later. can be contained in an amount of 30 to 80 parts by mass, more preferably 40 to 75 parts by mass.

In addition, since the polyimide (A) of the present embodiment has excellent solubility in solvents and does not need to be varnished in a precursor state, a varnish containing the polyimide (A) can be prepared. A cured product such as a film having excellent dimensional stability can be obtained from the varnish.

<Method for producing polyimide (A)>
A method for producing the polyimide (A) (negative photosensitive polymer) of the present embodiment will be described using a polyimide having a structural unit represented by general formula (1) as an example.

The method for producing polyimide (A) is
A bisaminophenol (a) represented by the following general formula (a) and an acid anhydride (b) represented by the following general formula (b) are imidated at a temperature of 100° C. or higher and 250° C. or lower. a step a;
Step b of introducing a group containing a (meth)acrylate group by reacting the hydroxyl group of the polyhydroxyimide obtained in step a with a compound having a (meth)acrylate group;
including.
According to this embodiment, a polyimide (A) having excellent solubility in organic solvents can be synthesized by a simple method.

In general formula (a), X has the same meaning as in general formula (1).

In general formula (b), Y represents a divalent organic group.
Although the divalent organic group is not particularly limited, it can be selected from groups represented by the following general formulas (1a), (1b) and (1c).

In general formula (1a), R ¹ , R ² and R ³ have the same meanings as R ¹ , R ² and R ³ in general formula (1a) for Y in general formula (1), and in general formula (1b) , R ⁴ and R ⁵ are synonymous with R ⁴ and R ⁵ of general formula (1b) in Y of general formula (1), and in general formula (1c), Z is It has the same meaning as Z in the general formula (1c). * indicates a bond.

In order to control the molecular weight of the resulting polyhydroxyimide, it is also possible to add a small amount of acid anhydride (b) or aromatic amine as an end-capping agent to carry out the reaction.

Examples of the acid anhydride (b), which is an end-capping agent, include phthalic anhydride, maleic anhydride, and nadic anhydride. Examples of the aromatic amine include p-methylaniline, p-methoxyaniline, p-phenoxyaniline, and the like. mentioned. It is preferable that the amount of the acid anhydride (b) or the aromatic amine added as the end-capping agent is 5 mol % or less. If it exceeds 5 mol %, the molecular weight of the resulting polyhydroxyimide is significantly lowered, causing problems in heat resistance and mechanical properties.

The equivalent ratio of acid anhydride (b) and bisaminophenol (a) in the imidization reaction of step a is an important factor that determines the molecular weight of the resulting polyhydroxyimide. In general, it is well known that there is a correlation between the molecular weight and mechanical properties of polymers, the higher the molecular weight the better the mechanical properties. Therefore, in order to obtain a polyhydroxyimide having practically excellent strength, it is necessary to have a high molecular weight to some extent. In the present invention, the equivalent ratio of the acid anhydride (b) and bisaminophenol (a) to be used is not particularly limited, but the equivalent ratio of the acid anhydride (b) to the bisaminophenol (a) is 0.90 to It is preferably in the range of 1.06. If it is less than 0.90, the molecular weight is low and the material becomes brittle, resulting in low mechanical strength. On the other hand, if it exceeds 1.06, unreacted carboxylic acid may be decarboxylated during heating to cause gas generation and foaming, which is not preferable. That is, when the equivalent ratio is within the above range, excellent mechanical strength and excellent production stability are achieved.

From the viewpoint of improving the mechanical properties, even if the equivalent ratio of the acid anhydride (b) to the bisaminophenol (a) is outside the above range, the apparent molecular weight can be reduced by side-chain cross-linking the resin. can also be raised.

In step a, the bisaminophenol (a), the acid anhydride (b), and the diaminobiphenyl (c) represented by the following general formula (c) can also be reacted for imidization.

In general formula (c), Z ¹ and Z ² have the same meanings as in general formula (1-3).

Step a (imidization reaction step) can be performed in an organic solvent by a known method.
Examples of organic solvents include aprotic polar solvents such as γ-butyl lactone (GBL), N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, cyclohexanone, and 1,4-dioxane. , and one type or two or more types may be used in combination. At this time, a nonpolar solvent compatible with the aprotic polar solvent may be mixed and used. Examples of nonpolar solvents include aromatic hydrocarbons such as toluene, ethylbenzene, xylene, mesitylene and solvent naphtha, and ether solvents such as cyclopentyl methyl ether. The ratio of the non-polar solvent in the mixed solvent is set arbitrarily according to the resin properties such as the stirring device capacity and solution viscosity, as long as the solubility of the solvent decreases and the polyamic acid resin obtained by the reaction does not precipitate. can do.

The reaction temperature is 0° C. or higher and 100° C. or lower, preferably 20° C. or higher and 80° C. or lower, for about 30 minutes to 2 hours. React for some time.

A polyhydroxyimide containing the following structural units can be obtained by step a. In step a, the polyhydroxyimide can be purified by a known method. can be done.

In step b, the hydroxyl groups of the polyhydroxyimide obtained in step a are reacted with a compound having a (meth)acrylate group to introduce a cross-linking group containing a (meth)acrylate group.
The cross-linking group introduced into the polyimide (A) reacts with the cross-linking agent (B) described later in the exposure step, and the exposed area becomes insoluble in the organic solvent.

Compounds having a (meth)acrylate group include 2-isocyanatoethyl (meth)acrylate, 2-(2-(meth)acryloyloxyethyloxy)ethyl isocyanate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate , glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, and the like.

In order to introduce a cross-linking group containing a (meth)acrylate group into polyhydroxyimide, polyhydroxyimide and a compound having a (meth)acrylate group are mixed in an organic solvent at 60° C. to 150° C. for 2 hours. React for about 10 hours. Although the reaction is not particularly limited, it can be carried out at normal pressure.

The compound having a (meth)acrylate group can be appropriately selected according to the amount of cross-linking groups to be introduced into the polyhydroxyimide. It can be added in double amounts, preferably equimolar. In addition, when the polyhydroxyimide has a group capable of introducing a cross-linking group, the group can be added in a molar amount.

Examples of organic solvents include aprotic polar solvents such as γ-butyl lactone (GBL), N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, cyclohexanone, and 1,4-dioxane. , and one type or two or more types may be used in combination. At this time, a nonpolar solvent compatible with the aprotic polar solvent may be mixed and used. Examples of non-polar solvents include aromatic hydrocarbons such as toluene, ethylbenzene, xylene, mesitylene and solvent naphtha, and ether solvents such as cyclopentyl methyl ether.
A base such as triethylamine or 1,1,3,3-tetramethylguanidine may be added during the reaction.

In step b, the polyhydroxyimide obtained by purifying the reaction solution containing polyhydroxyimide obtained in step a by reprecipitation or the like can be used. can be used.

[Crosslinking agent (B)]
The cross-linking agent (B) can contain a (meth)acrylate compound (b1) having a fluorene skeleton. The compound (b1) is more excellent in chemical resistance due to having a fluorene skeleton.
The (meth)acrylate compound (b1) is at least one selected from compounds represented by the following general formula (A).

In general formula (A), ring A represents a benzene ring or a condensed polycyclic aromatic hydrocarbon ring.

Examples of the condensed polycyclic aromatic hydrocarbon ring include condensed bicyclic hydrocarbon rings (e.g., C8-20 condensed bicyclic hydrocarbon rings such as indene and naphthalene rings), condensed tricyclic hydrocarbon rings ( For example, anthracene ring, phenanthrene ring, etc.) can be exemplified. Preferred ring A is a condensed bicyclic hydrocarbon ring such as naphthalene ring from the viewpoint of refractive index, heat resistance and the like. The types of the two rings A substituted at the 9-position of fluorene may be different, but usually they are the same. Further, the substitution position of the ring A substituted at the 9-position of fluorene is not particularly limited. A 2-naphthyl group is particularly preferred.

^R1 represents a halogen atom or an alkyl group. A plurality of R ¹ may be the same or different.

Examples of the halogen atom include fluorine, chlorine, and bromine atoms.
Examples of the alkyl group include alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and t-butyl group. The substitution position of R ¹ with respect to the benzene ring constituting fluorene is not particularly limited.
m representing the number of bonds in R ¹ is an integer of 0 to 4, preferably 0 or 1, more preferably 0. Multiple m may be the same or different.

^R2 represents a halogen atom, a hydrocarbon group, a hydroxyl group, an alkoxy group, a cycloalkoxy group, an aryloxy group, or an aralkyloxy group. A plurality of R ² may be the same or different.

Examples of the halogen atom include fluorine, chlorine, and bromine atoms.
Examples of the hydrocarbon group include alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and t-butyl group; C6-C10 aryl groups such as phenyl, alkylphenyl (methylphenyl, dimethylphenyl, etc.) and naphthyl groups; aralkyl groups such as benzyl;

Examples of the alkoxy group include alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, propoxy, n-butoxy, isobutoxy, and t-butoxy. A cycloalkyloxy group having 5 to 10 carbon atoms such as a hexyloxy group can be mentioned. Examples of aryloxy groups include aryloxy groups having 6 to 10 carbon atoms such as a phenoxy group. , a benzyloxy group, and the like.

n representing the number of bonds in R ² is 0 or an integer of 1 or more, preferably 0 or an integer of 1 to 6, more preferably 0. A plurality of n may be the same or different.

^R3 represents a hydrogen atom or a methyl group. A plurality of R ³ may be the same or different.

p is an integer of 1 or more, preferably an integer of 1 to 4, more preferably 1; A plurality of p may be the same or different.

X is a group represented by the following general formula (a) or general formula (b). A plurality of X's may be the same or different. From the viewpoint of obtaining a cured product such as a film having excellent mechanical strength such as elongation, it is more preferable that the linear chain of the group is long.

In general formula (a), q represents an integer of 1-15, preferably an integer of 1-12, more preferably an integer of 1-10.
In general formula (b), R ⁴ represents an alkylene group, preferably an alkylene group having 1 to 5 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms.
r represents an integer of 0 or 1 or more, preferably 0 or an integer of 1-5, more preferably 0 or an integer of 1-3.
* indicates a bond.

As the (meth)acrylate compound having a fluorene skeleton represented by the general formula (A), a (meth)acrylate compound represented by the following general formula (A1) or the following general formula (A2) is preferably used. , and one or a mixture of two or more selected from these can be used. From the viewpoint of the effects of the present invention, it is also preferable to use a combination of a (meth)acrylate compound represented by the following general formula (A1) and a (meth)acrylate compound represented by the following general formula (A2).

In general formula (A1), R ¹ , R ² , R ³ , X, m and p have the same meanings as in general formula (A). n1 is an integer of 0 to 4, preferably 0 or 1, more preferably 0; A plurality of n1's may be the same or different. X is preferably a group represented by the general formula (a).

Specific examples of the compound represented by the general formula (A1) include compounds represented by the following general formula.

In the above general formula, q represents an integer of 1-15, preferably an integer of 1-12, more preferably an integer of 1-10.

In general formula (A2), R ¹ , R ² , R ³ , X, m and p have the same meanings as in general formula (A). n2 is an integer of 0 to 3, preferably 0 or 1, more preferably 0. A plurality of n2's may be the same or different. n3 is an integer of 0 to 3, preferably 0 or 1, more preferably 0; A plurality of n3's may be the same or different. X is preferably a group represented by the general formula (b).

The cross-linking agent (B) can further contain a polyfunctional (meth)acrylate compound (b2) other than the compound (b1) together with the (meth)acrylate compound (b1) having a fluorene skeleton.

The polyfunctional (meth)acrylate compound (b2) is a compound having two or more (meth)acryloyl groups, and conventionally known compounds can be used as long as the effects of the present invention can be exhibited.

Examples of the polyfunctional (meth) acrylic compound (b2) include, for example, compounds represented by the following general formula (1b-p), compounds represented by the general formula (1c-p), and general formula (1d- Examples include, but are not limited to, compounds represented by p).

In the general formula (1b-p),
k is 2 or 3,
R is a hydrogen atom or a methyl group, multiple R may be the same or different,
X ¹ is a single bond, an alkylene group having 1 to 6 carbon atoms or a group represented by -ZX- (where Z is -O- or -OCO- and X is an alkylene group having 1 to 6 carbon atoms ), and multiple X ¹ may be the same or different,
X ¹ ' is a single bond, an alkylene group having 1 to 6 carbon atoms or a group represented by -X'-Z'- (X' is an alkylene group having 1 to 6 carbon atoms, Z' is -O- or -COO-),
X ² is a k+1 valent organic group having 1 to 12 carbon atoms.
R is preferably a hydrogen atom from the viewpoint of further improvement of sensitivity (ease of polymerization).
Although k may be 2 or 3, it is preferably 3 from the standpoints of availability of raw materials and further improvement of sensitivity.

In general formula (1c-p), k, R, Y, X ¹ and X ² each have the same meaning as in general formula (1b-p) above, and multiple Rs may be the same or different. a plurality of X ¹ may be the same or different,
X ³ is a divalent organic group having 1 to 6 carbon atoms,
X ⁴ and X ⁵ are each independently a single bond or a divalent organic group having 1 to 6 carbon atoms,
X ⁶ is a divalent organic group having 1 to 6 carbon atoms.
Y is a hydrogen atom or a (meth)acryloyl group.

In general formula (1dp), Y is a hydrogen atom or a (meth)acryloyl group.
n is an integer from 1 to 5;

Specific examples of the polyfunctional (meth)acrylic compound represented by general formula (1b-p) include, but are not limited to, compounds having the following structures. In the compounds below, Y represents a hydrogen atom, a (meth)acryloyl group, or a combination thereof.

Specific examples of the polyfunctional (meth)acrylic compound represented by general formula (1c-p) include, but are not limited to, the following compounds.

The amount of the cross-linking agent (B) with respect to 100 parts by mass of the polyimide (A) is 10 parts by mass or more and 80 parts by mass or less, preferably 20 parts by mass or more and 70 parts by mass or less, preferably 30 parts by mass, from the viewpoint of the effect of the present invention. parts or more and 60 parts by mass or less. Within this range, elongation is further improved.

The amount of the (meth)acrylate compound (b1) having a fluorene skeleton in 100 parts by mass of the cross-linking agent (B) is 5 parts by mass or more and 100 parts by mass or less, preferably 10 parts by mass or more, from the viewpoint of the effects of the present invention. It can be 100 parts by mass or less, more preferably 15 parts by mass or more and 100 parts by mass or less.

The amount of the polyfunctional (meth)acrylate compound (b2) in 100 parts by mass of the cross-linking agent (B) is 0 parts by mass or more and 95 parts by mass or less, preferably 0 parts by mass or more and 90 parts by mass, from the viewpoint of the effects of the present invention. Below, more preferably 0 mass parts or more and 85 mass parts or less.

[Polymerization initiator (C)]
As the polymerization initiator (C), conventionally known polymerization initiators can be used as long as the effects of the present invention can be exhibited, and examples thereof include thermal radical generators and photo-radical generators.

Examples of the thermal radical generator include 1,1-bis(t-butylperoxy)2-methylcyclohexane, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1 -bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2 -bis(4,4-di-butylperoxycyclohexyl)propane, 1,1-bis(t-butylperoxy)cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t- Butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di(m-toluoylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexylmonocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butylperoxyacetate, 2,2- Bis(t-butylperoxy)butane, t-butylperoxybenzoate, n-butyl-4,4-bis(t-butylperoxy)valerate, di-t-butylperoxyisophthalate, α, α'- Bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butylperoxide , p-menthane hydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3,3 - organic peroxides such as tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide and benzoyl peroxide; and azobisisobutyronitrile, 1,1' -azobis(cyclohexane-1-carbonitrile), 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, azodi-t-octane, azodi-t-butane and 2,2′-azobis[N-(2- azo compounds such as propenyl)-2-methylpropionamide]; Also, the organic peroxide can be combined with a reducing agent to cause a redox reaction.

Examples of the photoradical generator include alkylphenone type initiators, oxime ester type initiators, acylphosphine oxide type initiators, and the like. For example, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1[4-(methylthio)phenyl]-2-morifolinopropan-1-one , 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, bis (2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)), ethanone, 1-[9- Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime), 2-(dimethylamino)-1-(4-(4-morpholino)phenyl)- 2-(phenylmethyl)-1-butanone, Irgacure Oxe01 (BASF Japan Ltd.), Irgacure Oxe02 (BASF Japan Ltd.), Irgacure Oxe03 (BASF Japan Ltd.), Irgacure Oxe04 (BASF Japan Ltd.), N-1919T (ADEKA Corporation), NCI-730 (ADEKA Corporation), NCI-831E (ADEKA Corporation), NCI-930 (ADEKA Corporation), and the like. Any one or more of these can be used.
Among these, the oxime ester type initiator is preferable from the viewpoint of the effect of the present invention and from the viewpoint of producing a resin film composed of a photosensitive resin composition having excellent exposure sensitivity.

The amount of the polymerization initiator (C) added is not particularly limited, but it is preferably about 0.3 to 10% by mass of 100% by mass of the non-volatile components excluding the solvent of the negative photosensitive resin composition, and 0.5% by mass. It is more preferably about 7.5% by mass, more preferably about 1 to 5% by mass. By setting the addition amount of the polymerization initiator (C) within the above range, the patterning property of the photosensitive resin layer containing the negative photosensitive resin composition is enhanced, and the long-term storage stability of the negative photosensitive resin composition is improved. can be improved.

[Other ingredients]
The negative photosensitive resin composition according to the present embodiment can contain other components such as a solvent, a surfactant, an adhesion aid, and an antioxidant.

(solvent)
The negative photosensitive resin composition according to this embodiment can contain a solvent. Thereby, a uniform photosensitive resin film can be formed on various substrate surfaces.

An organic solvent is preferably used as the solvent. Specifically, one or more of ketone-based solvents, ester-based solvents, ether-based solvents, alcohol-based solvents, lactone-based solvents, carbonate-based solvents, and the like can be used.

Examples of solvents include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, methyl isobutyl carbinol (MIBC), gamma-butyrolactone (GBL), N-methylpyrrolidone (NMP), methyl- Mention may be made of n-amyl ketone (MAK), diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, or mixtures thereof.
The amount of solvent used is not particularly limited. For example, it is used in such an amount that the concentration of non-volatile components is, for example, 10 to 70% by mass, preferably 15 to 60% by mass.

(Surfactant)
The negative photosensitive resin composition according to this embodiment may further contain a surfactant.

The surfactant is not limited, and specifically polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, polyoxyethylene Polyoxyethylene aryl ethers such as nonylphenyl ether; Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Ftop EF301, Ftop EF303, Ftop EF352 (manufactured by Shin-Akita Kasei), Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F444, Megafac F470, Megafac F471, Megafac F475, Megafac F482, Megafac F477 (DIC Corporation) manufactured), Florado FC-430, Florard FC-431, Novec FC4430, Novec FC4432 (manufactured by 3M Japan), Surflon S-381, Surflon S-382, Surflon S-383, Surflon S-393, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106, commercially available fluorine-based surfactants (manufactured by AGC Seimi Chemical Co., Ltd.); Combined KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); (meth)acrylic acid-based copolymer Polyflow No. 57, 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

Among these, it is preferable to use a fluorine-based surfactant having a perfluoroalkyl group. Among the specific examples of the perfluoroalkyl group-containing fluorosurfactant, Megafac F171, Megafac F173, Megafac F444, Megafac F470, Megafac F471, Megafac F475, Megafac F482, and Megafac One or more selected from F477 (manufactured by DIC), Surflon S-381, Surflon S-383, Surflon S-393 (manufactured by AGC Seimi Chemical Co., Ltd.), Novec FC4430 and Novec FC4432 (manufactured by 3M Japan) is preferably used.

As the surfactant, a silicone-based surfactant (for example, polyether-modified dimethylsiloxane) can also be preferably used. Specific examples of silicone surfactants include SH series, SD series and ST series from Dow Corning Toray Co., Ltd., BYK series from BYK Chemie Japan, KP series from Shin-Etsu Chemical Co., Ltd., Disfoam from NOF CORPORATION ( (registered trademark) series, TSF series of Toshiba Silicone Co., Ltd., and the like.

The upper limit of the content of the surfactant in the negative photosensitive resin composition is preferably 1% by mass (10000 ppm) or less with respect to the entire negative photosensitive resin composition (including the solvent), It is more preferably 0.5% by mass (5000 ppm) or less, and even more preferably 0.1% by mass (1000 ppm) or less.

In addition, although there is no particular lower limit for the content of the surfactant in the negative photosensitive resin composition, from the viewpoint of sufficiently obtaining the effect of the surfactant, for example, the negative photosensitive resin composition It is 0.001% by mass (10 ppm) or more with respect to the whole (including the solvent).
Applicability and uniformity of the coating film can be improved while maintaining other properties by appropriately adjusting the amount of the surfactant.

(adherence aid)
The negative photosensitive resin composition according to this embodiment may further contain an adhesion aid.
Examples of adhesion aids that can be used include silane coupling agents such as aminosilane, epoxysilane, (meth)acrylsilane, mercaptosilane, vinylsilane, ureidosilane, acid anhydride-functional silane, and sulfidesilane. Silane coupling agents may be used alone or in combination of two or more. Among these, epoxysilanes (i.e., compounds containing both an epoxy moiety and a group that generates a silanol group by hydrolysis in one molecule) or anhydride-functional silanes (i.e., in one molecule, an anhydride and a group that generates a silanol group by hydrolysis) are preferred.

Examples of aminosilanes include bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-amino propylmethyldimethoxysilane, N-β (aminoethyl)γ-aminopropyltrimethoxysilane, N-β (aminoethyl)γ-aminopropyltriethoxysilane, N-β (aminoethyl)γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, N-phenyl-γ-amino-propyltrimethoxysilane, and the like.

Examples of epoxysilanes include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and γ-glycidylpropyltrimethoxysilane. Silane etc. are mentioned.

Examples of acrylic silanes include γ-(methacryloxypropyl)trimethoxysilane, γ-(methacryloxypropyl)methyldimethoxysilane, γ-(methacryloxypropyl)methyldiethoxysilane, and the like.
Mercaptosilanes include, for example, 3-mercaptopropyltrimethoxysilane.

Vinylsilanes include, for example, vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, and the like.
Ureidosilanes include, for example, 3-ureidopropyltriethoxysilane.

Examples of the acid anhydride-functional silane include X-12-967C (product name: 3-trimethoxysilylpropylsuccinic anhydride) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

Examples of sulfide silanes include bis(3-(triethoxysilyl)propyl)disulfide and bis(3-(triethoxysilyl)propyl)tetrasulfide.
The amount of the adhesion aid added is not particularly limited, but is 0.1 to 5% by mass, preferably 0.5 to 3% by mass, based on the total solid content of the negative photosensitive resin composition.

(Antioxidant)
The negative photosensitive resin composition according to this embodiment may further contain an antioxidant. As the antioxidant, one or more selected from phenol-based antioxidants, phosphorus-based antioxidants and thioether-based antioxidants can be used. The antioxidant can suppress oxidation of the resin film formed from the negative photosensitive resin composition.

Phenolic antioxidants include pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,9-bis{2-[3-(3 -t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}2,4,8,10-tetraoxaspiro[5,5]undecane, octadecyl-3-(3, 5-di-t-butyl-4-hydroxyphenyl)propionate, 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 1,3,5 -trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t -butyl-4-ethylphenol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-t-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-t -butyl-4-hydroxybenzyl)phosphonate, thiodiethylene glycol bis[(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 4,4'-thiobis(6-t-butyl-m-cresol) , 2-octylthio-4,6-di(3,5-di-t-butyl-4-hydroxyphenoxy)-s-triazine, 2,2′-methylenebis(4-methyl-6-t-butyl-6- butylphenol), 2,-2'-methylenebis(4-ethyl-6-t-butylphenol), bis[3,3-bis(4-hydroxy-3-t-butylphenyl)butyric acid]glycol ester, 4, 4'-butylidenebis(6-t-butyl-m-cresol), 2,2'-ethylidenebis(4,6-di-t-butylphenol), 2,2'-ethylidenebis(4-s-butyl-6 -t-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, bis[2-t-butyl-4-methyl-6-(2-hydroxy- 3-t-butyl-5-methylbenzyl)phenyl]terephthalate, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-t-butylbenzyl)isocyanurate, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5-tri Su[(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane , 2-t-butyl-4-methyl-6-(2-acryloyloxy-3-t-butyl-5-methylbenzyl)phenol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)- 2,4-8,10-tetraoxaspiro[5,5]undecane-bis[β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate], triethylene glycol-bis[β-( 3-t-butyl-4-hydroxy-5-methylphenyl)propionate], 1,1′-bis(4-hydroxyphenyl)cyclohexane, 2,2′-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 2,2'-methylenebis(6-(1-methylcyclohexyl)-4-methylphenol), 4,4'-butylidenebis(3-methyl -6-t-butylphenol), 3,9-bis(2-(3-t-butyl-4-hydroxy-5-methylphenylpropionyloxy)1,1-dimethylethyl)-2,4,8,10- Tetraoxaspiro(5,5)undecane, 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-bis(3,5-di-t-butyl-4-hydroxybenzyl) Sulfide, 4,4'-thiobis(6-t-butyl-2-methylphenol), 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 2-t-butyl-6 -(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2,4-dimethyl-6-(1-methylcyclohexyl, styreneated phenol, 2,4-bis(( octylthio)methyl)-5-methylphenol, and the like.
Phosphorus antioxidants include bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, tris(2,4-di-t-butylphenylphosphite), tetrakis(2 ,4-di-t-butyl-5-methylphenyl)-4,4′-biphenylenediphosphonite, 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, bis-(2,6 -dicumylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-t-butylphenyl)octylphosphite, tris(mixed mono and di-nonylphenylphosphite), bis(2, 4-di-t-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-methoxycarbonylethyl-phenyl)pentaerythritol diphosphite, bis(2,6-di-t -Butyl-4-octadecyloxycarbonylethylphenyl)pentaerythritol diphosphite and the like.

Thioether antioxidants include dilauryl-3,3′-thiodipropionate, bis(2-methyl-4-(3-n-dodecyl)thiopropionyloxy)-5-t-butylphenyl)sulfide , distearyl-3,3′-thiodipropionate, pentaerythritol-tetrakis(3-lauryl)thiopropionate, and the like.

(Preparation of negative photosensitive resin composition)
A method for preparing the negative photosensitive resin composition in the present embodiment is not limited, and a known method can be used depending on the components contained in the negative photosensitive resin composition.
For example, it can be prepared by mixing and dissolving the above components in a solvent.

(Negative photosensitive resin composition)
The negative photosensitive resin composition according to the present embodiment is formed by applying the negative photosensitive resin composition to a surface comprising a metal such as Al or Cu, and then pre-baking to dry it to form a resin film. Then, the resin film is patterned into a desired shape by exposure and development, and then the resin film is cured by post-baking to form a cured film.

In addition, when producing the said permanent film, as conditions of a pre-baking, it can be set as the heat processing for 30 seconds or more and 1 hour or less at the temperature of 90 degreeC or more and 130 degrees C or less, for example. The post-baking conditions are, for example, heat treatment at a temperature of 150° C. to 250° C. for 30 minutes to 10 hours, preferably about 170° C. for 1 to 6 hours.

The negative photosensitive resin composition of this embodiment is excellent in low-temperature curability.
For example, the cured product obtained by curing the negative photosensitive resin composition of the present embodiment at 170°C for 4 hours has a glass transition temperature (Tg) of 200°C or higher, preferably 210°C or higher, more preferably 220°C. °C or higher.

Furthermore, the cured product obtained by curing the negative photosensitive resin composition of the present embodiment at 170° C. for 4 hours has a storage elastic modulus E′ at 200° C. of 0.5 GPa or more, preferably 0.7 GPa or more. More preferably, it can be 0.8 GPa or more.

The viscosity of the negative photosensitive resin composition according to this embodiment can be appropriately set according to the desired thickness of the resin film. The viscosity of the negative photosensitive resin composition can be adjusted by adding a solvent.

The film obtained from the negative photosensitive resin composition of the present embodiment has a maximum elongation of 15 to 200%, preferably 20 to 150%, and an average elongation of 10 as measured by a tensile test using a Tensilon tester. ~150%, preferably 15-120%.

A cured product such as a film obtained from the negative photosensitive resin composition of the present embodiment has excellent chemical resistance.
Specifically, the film is immersed in a solution of less than 99% by mass of dimethyl sulfoxide and less than 2% by mass of tetramethylammonium hydroxide at 40° C. for 10 minutes, then thoroughly washed with isopropyl alcohol and air-dried. to measure. The film thickness change rate between the film thickness after treatment and the film thickness before treatment is calculated from the following formula and evaluated as the reduction rate of the film.
Formula: Film reduction rate (%) {(film thickness after immersion - film thickness before immersion) / film thickness before immersion x 100 (%)}

The film thickness change rate is preferably 40% or less, more preferably 30% or less. As a result, even when the cured film is subjected to a step of being immersed in dimethylsulfoxide, the film thickness hardly decreases. Therefore, a cured film that can maintain its functions even after being subjected to such steps can be obtained.

The negative photosensitive resin composition of the present embodiment has suppressed curing shrinkage, and is spin-coated on the surface of a silicon wafer so that the film thickness after drying becomes 10 μm, pre-baked at 120° C. for 3 minutes, and placed under a high-pressure mercury lamp. When a film is prepared by exposing to 600 mJ / cm ² and then post-baking at 170 ° C. for 120 minutes in a nitrogen atmosphere, the film thickness after the pre-baking is the film thickness A, and the film after the post-baking Assuming that the film thickness is film thickness B, the curing shrinkage rate calculated from the following formula is preferably 12% or less, more preferably 10% or less.
Formula: Cure shrinkage rate [%] = {(film thickness A - film thickness B) / film thickness A} x 100

The negative photosensitive resin composition of the present embodiment has high heat resistance, and the resulting film has a weight loss temperature (Td5) measured by simultaneous thermogravimetric differential thermal measurement of 200° C. or higher, preferably 300° C. or higher. be able to.

Curing shrinkage of the film made of the negative photosensitive resin composition of the present embodiment is suppressed, and the coefficient of linear thermal expansion (CTE) can be 200 ppm or less, preferably 100 ppm or less.

(Application)
The negative photosensitive resin composition of the present embodiment is used for forming resin films for semiconductor devices such as permanent films and resists. Among these, from the viewpoint of expressing in a well-balanced manner the improvement in adhesion between the negative photosensitive resin composition and the Al pad after prebaking and the suppression of the generation of residues of the negative photosensitive resin composition during development, after postbaking From the viewpoint of improving the adhesion between the cured film of the negative photosensitive resin composition and the metal, in addition, from the viewpoint of improving the chemical resistance of the negative photosensitive resin composition after post-baking, a permanent film It is preferably used for the intended use.

In addition, in this embodiment, the resin film includes a cured film of a negative photosensitive resin composition. That is, the resin film according to this embodiment is obtained by curing a negative photosensitive resin composition.

The permanent film is a resin film obtained by pre-baking, exposing, and developing a negative photosensitive resin composition, patterning it into a desired shape, and post-baking it to cure it. Permanent films can be used as protective films, interlayer films, dam materials, and the like for semiconductor devices.

The above-mentioned resist can be obtained, for example, by applying a negative photosensitive resin composition to an object to be masked by the resist by a method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, and negative photosensitive resin composition. It is composed of a resin film obtained by removing the solvent from a flexible resin composition.

An example of a semiconductor device according to this embodiment is shown in FIG.
The semiconductor device 100 according to this embodiment can be a semiconductor device including the resin film. Specifically, one or more of the group consisting of the passivation film 32, the insulating layer 42, and the insulating layer 44 in the semiconductor device 100 can be a resin film containing the cured product of the present embodiment. Here, the resin film is preferably the permanent film described above.

Semiconductor device 100 is, for example, a semiconductor chip. In this case, for example, a semiconductor package is obtained by mounting the semiconductor device 100 on the wiring substrate via the bumps 52 .

The semiconductor device 100 includes a semiconductor substrate provided with semiconductor elements such as transistors, and a multilayer wiring layer (not shown) provided on the semiconductor substrate. An interlayer insulating film 30 and a top layer wiring 34 provided on the interlayer insulating film 30 are provided in the uppermost layer of the multilayer wiring layers. The uppermost layer wiring 34 is made of aluminum Al, for example. A passivation film 32 is provided on the interlayer insulating film 30 and the uppermost layer wiring 34 . A portion of the passivation film 32 is provided with an opening through which the uppermost layer wiring 34 is exposed.

A rewiring layer 40 is provided on the passivation film 32 . The rewiring layer 40 includes an insulating layer 42 provided on the passivation film 32, a rewiring 46 provided on the insulating layer 42, an insulating layer 44 provided on the insulating layer 42 and the rewiring 46, have An opening connected to the uppermost layer wiring 34 is formed in the insulating layer 42 . The rewiring 46 is formed on the insulating layer 42 and in openings provided in the insulating layer 42 and connected to the uppermost layer wiring 34 . The insulating layer 44 is provided with an opening connected to the rewiring 46 .

A bump 52 is formed in the opening provided in the insulating layer 44 via a UBM (Under Bump Metallurgy) layer 50, for example. Semiconductor device 100 is connected to a wiring substrate or the like via bumps 52, for example.
Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can be employed within the scope that does not impair the effects of the present invention.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these.
In Synthesis Example 1, the following compounds were used.

2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter also referred to as BAFA) represented by the following formula

4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (hereinafter also referred to as TFMB) represented by the following formula

4-[4-(1,3-dioxoisobenzofuran-5-ylcarbonyloxy)-2,3,5-trimethylphenyl]-2,3,6-trimethylphenyl 1,3 represented by the following formula -dioxoisobenzofuran-5-carboxylate (hereinafter also referred to as TMPBP-TME)

[Synthesis Example 1]
First, 37.62 g (102.7 mmol) of BAFA, 32.89 g (102.7 mmol) of TFMB, and 151.29 g (244.6 mmol) of TMPBP-TME were added to an appropriately sized reaction vessel equipped with a stirrer and condenser. I put it in. An additional 598.86 g of GBL was then added to the reaction vessel.
After bubbling nitrogen for 10 minutes, the temperature was raised to 60° C. while stirring, and the reaction was allowed to proceed for 1.5 hours. Thereafter, the reaction was further carried out at 180° C. for 3 hours to polymerize the bisaminophenol and the acid anhydride to prepare a polymerization solution.
The resulting polymerization solution was diluted with acetone to prepare a diluted solution, and then the diluted solution was added dropwise to a mixed solution of water/methanol=3/1 to precipitate a white solid. The resulting white solid was collected and vacuum dried at 120° C. to obtain 205.55 g of polymer.
GPC measurement of the polymer revealed a weight average molecular weight Mw of 18200 and a polydispersity (weight average molecular weight Mw/number average molecular weight Mn) of 1.82.
When the polymer was subjected to IR measurement, peaks derived from amide groups around 1480, 1550 and 1670 cm ⁻¹ disappeared, confirming that imidization was completed.
Further, when ¹ H-NMR measurement was performed, a peak was confirmed in the aromatic region (6.9 ppm to 8.9 ppm) with an area ratio corresponding to the number of protons.
Next, 197.16 g of the obtained polyimide (182.6 mmol in terms of hydroxyl group) and 2-isocyanatoethyl acrylate (hereinafter also referred to as AOI, manufactured by Showa Denko Co., Ltd.) were placed in an appropriately sized reaction vessel equipped with a stirrer and a cooling tube. ) and 737.08 g of γ-butyl lactone (GBL) were added. After that, the temperature was raised to 120° C. while stirring, and the reaction was carried out for 6 hours.
The resulting reaction solution was diluted with acetone to prepare a diluted solution, and then the diluted solution was added dropwise to a mixed solution of water/methanol=2/1 to precipitate a white solid. The resulting white solid was collected and vacuum dried at a temperature of 40° C. to obtain 183.99 g of polymer.
GPC measurement of the polymer revealed a weight average molecular weight Mw of 20,400 and a polydispersity (weight average molecular weight Mw/number average molecular weight Mn) of 1.80.
From the results of ¹ H-NMR measurement, it was confirmed that cross-linking groups were introduced into the polymer. A part of the polymer into which the cross-linking group was introduced contained the following repeating units.
Moreover, the introduction rate of the cross-linking group was 60% from the measurement results of gas chromatography.

The following ingredients were used in the examples.
[Crosslinking agent]
Acrylate compound 1: a polyfunctional acrylate compound represented by the following chemical formula (manufactured by Shin-Nakamura Chemical Co., Ltd., A-DPH)

Acrylate compound 2: a bifunctional acrylate compound having a fluorene skeleton (manufactured by Osaka Gas Chemicals Co., Ltd., GA-5060P)
Acrylate compound 3: a bifunctional acrylate compound having a fluorene skeleton (manufactured by Osaka Gas Chemicals, GA-2800)

Acrylate compound 4: a bifunctional acrylate compound represented by the following chemical formula (q = 1) (Shin-Nakamura Chemical Co., Ltd., A-BPEF-2)

[Synthesis Example 2]
(Synthesis of acrylate compound 5)
9,9-bis(4-hydroxypentaethoxyphenyl) obtained by adding 10 mol of ethylene oxide to 1 mol of 9,9-bis(4-hydroxyphenyl)-fluorene (manufactured by JEF Chemical Co.) was placed in a 5-liter four-necked flask. 180 g of fluorene, 320 g of toluene, 75 g of acrylic acid, 0.1 g of hydroquinone, and 6 g of sulfuric acid were added, and the reaction was carried out for 4 hours while stirring at 120° C. to azeotropically remove by-produced water with toluene. After the reaction, 130 g of toluene was added, washed with alkaline water, and the toluene was distilled off under reduced pressure to obtain acrylate compound 5 represented by q=5 in the chemical formula of acrylate compound 4. The structure was identified by ¹ H-NMR and MS measurements.

[Synthesis Example 3]
(Synthesis of acrylate compound 6)
9,9-bis(4-hydroxydecaethoxyphenyl) obtained by adding 20 mol of ethylene oxide to 1 mol of 9,9-bis(4-hydroxyphenyl)-fluorene (manufactured by JEF Chemical Co.) was placed in a 5-liter four-necked flask. 281 g of fluorene, 400 g of toluene, 75 g of acrylic acid, 0.1 g of hydroquinone, and 6 g of sulfuric acid were added and reacted for 4 hours while stirring at 120° C. to azeotropically remove by-produced water with toluene. After the reaction, 300 g of toluene was added, washed with alkaline water, and the toluene was distilled off under reduced pressure to obtain an acrylate compound 6 represented by q=10 in the chemical formula of the acrylate compound 4. The structure was identified by ¹ H-NMR and MS measurements.

Acrylate compound 7: 1,6-hexanediol diacrylate (Viscoat 230, manufactured by Osaka Organic Chemical Industry Co., Ltd.)

[Polymerization initiator]
・Polymerization initiator 1: O-acyloxime compound (NCI-730, manufactured by ADEKA)
・Polymerization initiator 2: Dicumyl peroxide (Perkadox BC, peroxide, manufactured by Kayaku Akzo Co., Ltd.)

[Adhesion aid]
Adhesion aid 1: 3-trimethoxysilylpropyl succinic anhydride (X-12-967C (manufactured by Shin-Etsu Chemical Co., Ltd.)

[Surfactant]
・Surfactant 1: Surfactant having a fluorocarbon chain (FC-4432, manufactured by Sumitomo 3M)

[solvent]
- Solvent 1: propylene glycol monomethyl ether acetate (PGMEA)
・ Solvent 2: γ-butyl lactone (GBL)

[Examples 1 to 16, Comparative Examples 1 to 2]
The cross-linking group-introduced polyhydroxyimide obtained in Synthesis Example 1 and the components shown in Table 1 were mixed in a solvent to prepare a negative photosensitive resin composition.
The obtained negative photosensitive resin composition was spin-coated on the surface of a silicon wafer so that the film thickness after drying was 10 μm, prebaked at 120° C. for 3 minutes, and then exposed to light at 600 mJ/cm ² with a high-pressure mercury lamp. After that, post-baking was performed at 170° C. for 120 minutes in a nitrogen atmosphere to prepare a film.
Cure shrinkage, storage modulus E′, glass transition temperature (Tg), linear thermal expansion coefficient (CTE), 5% weight loss temperature (Td5), elongation, resistance Chemical properties were measured.

(curing shrinkage)
The film thickness after pre-baking of the films obtained in Examples and Comparative Examples is film thickness A, and the film thickness after post-baking is film thickness B. Substituting film thickness A and film thickness B into the following equation, cure shrinkage rate was calculated. Table 1 shows the results.
Cure shrinkage rate [%] = {(film thickness A - film thickness B) / film thickness A} x 100

(Glass transition temperature, storage modulus E')
A test piece of 8 mm × 40 mm was cut out from the films obtained in Examples and Comparative Examples, and the test piece was subjected to dynamic viscoelasticity measurement (DMA device, TA Instruments, Q800), and the temperature was raised. A dynamic viscoelasticity measurement was performed at a rate of 5°C/min and a frequency of 1 Hz to calculate the storage modulus E'. The glass transition temperature was defined as the temperature at which the loss tangent tan δ showed the maximum value.

(Coefficient of linear thermal expansion (CTE))
A strip-shaped test piece having a length of 13 mm and a width of 5 mm was cut from the films obtained in Examples and Comparative Examples. A thermomechanical measurement in tensile mode was performed at a chuck-to-chuck distance of 10 mm, and an average linear thermal expansion coefficient (CTE, 50° C. to 100° C.) was obtained from the thermal expansion curve. Table 1 shows the results.

(5% weight loss temperature (Td5))
The films obtained in Examples and Comparative Examples were measured by thermogravimetric differential thermal simultaneous measurement. The measurement conditions were a nitrogen stream of 30 ml/min and a heating rate of 10° C./min. The temperature at which the weight decreased by 5% from the initial stage was measured and defined as the 5% weight decrease temperature (Td5). Table 1 shows the results.

(Growth rate)
A tensile test (stretching speed: 5 mm/min) was performed in a 23° C. atmosphere on test pieces (6.5 mm×60 mm×10 μm thick) cut out from the films obtained in Examples and Comparative Examples. The tensile test was performed using a tensile tester (Tensilon RTC-1210A) manufactured by Orientec. The strength was obtained by measuring five test pieces and averaging the stress at the breaking point. The tensile elongation was calculated from the breaking distance and the initial distance, and the maximum value of the elongation was obtained. Table 1 shows the results.

(chemical resistance)
The films obtained in Examples and Comparative Examples were immersed in a solution of less than 99% by mass of dimethyl sulfoxide and less than 2% by mass of tetramethylammonium hydroxide at 40°C for 10 minutes, then thoroughly washed with isopropyl alcohol, air-dried, and treated. After film thickness was measured. The film thickness change rate between the film thickness after treatment and the film thickness before treatment was calculated from the following formula and used as the reduction rate of the cured product.
Formula: reduction rate of cured product (%) {(film thickness after immersion - film thickness before immersion) / film thickness before immersion x 100 (%)}

As shown in Table 1, the negative photosensitive resin compositions of Examples according to the present invention were excellent in both elongation and chemical resistance in a well-balanced manner, and were also excellent in other physical properties.

30 Interlayer insulating film 32 Passivation film 34 Top layer wiring 40 Rewiring layer 42 Insulating layer 44 Insulating layer 46 Rewiring 50 UBM layer 52 Bump 100 Semiconductor device

Claims (16)

(A) a polyimide having a double bond in its side chain;
(B) a cross-linking agent containing a (meth)acrylate compound having a fluorene skeleton;
(C) a polymerization initiator;
A negative photosensitive resin composition comprising: The negative photosensitive resin composition according to claim 1, wherein the (meth)acrylate compound having a fluorene skeleton is at least one selected from compounds represented by the following general formula (A).

(In general formula (A), ring A represents a benzene ring or a condensed polycyclic aromatic hydrocarbon ring, R ¹ represents a halogen atom or an alkyl group, R ² represents a halogen atom, a hydrocarbon group, or a hydroxyl group. , an alkoxy group, a cycloalkoxy group, an aryloxy group or an aralkyloxy group, R ³ represents a hydrogen atom or a methyl group, m is an integer of 0 to 4, n is an integer of 0 or 1 or more, p is It is an integer of 1 or more.
X is a group represented by the following general formula (a) or general formula (b).

(In general formula (a), q represents an integer of 1 to 15, and in general formula (b), R ⁴ represents an alkylene group, r represents an integer of 0 or 1 or more. * represents a bond. .)) 3. The negative photosensitive resin composition according to claim 1, wherein the polyimide (A) contains a compound having a structural unit (a) represented by the following general formula (1-1).

(In general formula (1-1), Y represents a divalent organic group.) Polyimide (A) comprises a compound having a structural unit (a) represented by the general formula (1-1) and a structural unit (b) represented by the following general formula (1-2). 3. The negative photosensitive resin composition according to 3.

(In general formula (1-2), Q represents a divalent to tetravalent organic group having 1 to 10 carbon atoms, and multiple Qs may be the same or different.
R represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and multiple R may be the same or different.
m1 and m2 each independently represent an integer of 1 to 3;
X represents a single bond, —SO ₂ —, —C(=O)—, a linear or branched alkylene group having 1 to 5 carbon atoms, or a linear or branched fluoroalkylene group having 1 to 5 carbon atoms; Multiple X's may be the same or different. ) wherein the divalent organic group of Y in the general formula (1-1) is selected from groups represented by the following general formula (1a), the following general formula (1b) and the following general formula (1c); 5. The negative photosensitive resin composition according to 3 or 4.

(in general formula (1a), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having ¹ to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms; A plurality of R ² may be the same or different, R ³ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and a plurality of R ³ being present are the same. * indicates a bond.
In general formula (1b), R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to ³ carbon atoms, or an alkoxy group having 1 to 3 carbon atoms; ^R5s present may be the same or different. * indicates a bond.
In general formula (1c), Z represents an alkylene group having 1 to 5 carbon atoms or a divalent aromatic group.
* indicates a bond. ) The cross-linking agent (B) further comprises a polyfunctional (meth) acrylate compound (excluding the (meth) acrylate compound having a fluorene skeleton), the negative photosensitive resin composition according to any one of claims 1 to 5. . The negative photosensitive resin composition according to any one of claims 1 to 6, wherein the polymerization initiator (C) is an oxime ester polymerization initiator. The negative photosensitive resin composition according to any one of claims 1 to 7, wherein the amount of the cross-linking agent (B) is 10 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the polyimide (A). The negative photosensitive resin composition according to any one of claims 1 to 8, wherein the polyimide (A) contains a compound having a structural unit represented by the following general formula (1).

(In general formula (1), Y is synonymous with general formula (1-1), and Q, R, m1, m2, and X are synonymous with general formula (1-2).) The negative photosensitive resin composition according to any one of claims 1 to 9, wherein a cured product obtained by curing at 170°C for 4 hours has a glass transition temperature (Tg) of 200°C or higher. The negative photosensitive resin composition according to any one of claims 1 to 10, wherein the cured product obtained by curing at 170°C for 4 hours has a storage elastic modulus E' at 200°C of 0.5 GPa or more. The negative photosensitive resin composition according to any one of claims 1 to 11, which is used for forming a rewiring layer. A cured product of the negative photosensitive resin composition according to any one of claims 1 to 12. A cured film comprising the cured product according to claim 13 . A semiconductor device comprising a resin film containing the cured product according to claim 13 . an interlayer insulating film;
A resin film containing the cured product according to claim 13 provided on the interlayer insulating film;
a rewiring embedded in the resin film;
16. The semiconductor device according to claim 15, comprising:

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