WO2017033633A1 - Resin composition, photosensitive resin composition, resin film and electronic device - Google Patents

Abstract

This resin composition comprises a phenol resin, and a polymer including a repeating unit represented by formula (1). (In formula (1), R_X, R_Y are each independently hydrogen or an organic group having 1 to 3 carbon atoms.)

Description

Resin composition, photosensitive resin composition, resin film and electronic device

The present invention relates to a resin composition, a photosensitive resin composition, a resin film, and an electronic device.

Phenolic resin is excellent in resolution and has high heat resistance and mechanical strength, and therefore, application to resin films constituting various electronic devices has been studied.

For example, Patent Document 1 discloses a positive photoresist that can be applied as a resist for ultra-fine processing used in the manufacture of elements such as IC and LSI. More specifically, a composition comprising a metacresol novolac resin, a resin mixture comprising an orthocresol novolac resin, and a 1,2-quinonediazide compound is disclosed.
Moreover, according to the said literature, it is supposed that the positive type photoresist excellent in the sensitivity, the remaining film rate, and adhesiveness with a support body can be provided by employ | adopting such a structure.

Further, in recent years, a positive photoresist composition containing a novolak type phenol resin obtained by condensing a phenol compound having a specific structure and an aliphatic aldehyde compound as an essential component has been proposed (for example, Patent Documents). 2).

JP-A-2-55359 JP 2013-174702 A

However, the heat resistance required for the resin film constituting the electronic device is required to be higher, and a resin composition containing a phenol resin that has conventionally existed cannot satisfy this requirement. .
In addition, with such a background, there is also a fact that there is a delay in the development of photosensitive resin compositions containing phenolic resins.

In view of such circumstances, the present invention provides a resin composition that is excellent in heat resistance, and can exhibit excellent sensitivity and high heat resistance in a well-balanced manner when, for example, a photosensitive resin composition is used. is there.

According to the present invention,
Phenolic resin,
A polymer containing a repeating unit represented by the following formula (1):
A resin composition is provided.

(In the formula (1), R _X and R _Y are each independently hydrogen or an organic group having 1 to 3 carbon atoms.)

Moreover, according to the present invention,
There is provided a resin composition comprising an ester compound in which an acid anhydride moiety of a polymer containing a repeating unit represented by the following formula (1) and a phenolic hydroxyl group provided in a phenol resin constitute an ester bond.

(In the formula (1), R _X and R _Y each independently represent hydrogen or an organic group having 1 to 3 carbon atoms.)

Moreover, according to the present invention,
The above resin composition;
A photosensitizer,
A photosensitive resin composition is provided.

Moreover, according to the present invention, a resin film made of the above resin composition is provided.

Moreover, according to the present invention, a resin film comprising the above-described photosensitive resin composition is provided.

Moreover, according to the present invention, an electronic device including the above resin film is provided.

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in heat resistance, for example, when it is set as the photosensitive resin composition, the resin composition which can express the outstanding sensitivity and high heat resistance in good balance, the resin film using the same, and an electronic device Can be provided.

The above-described object and other objects, features, and advantages will be further clarified by a preferred embodiment described below and the following drawings attached thereto.

It is sectional drawing which shows an example of the electronic device which concerns on this embodiment. It is the infrared absorption spectrum chart of the polymer 2 used in the Example, and the composition which modified | denatured this.

Hereinafter, embodiments will be described with reference to the drawings as appropriate. In all the drawings, the same reference numerals are given to the same components, and the description will be omitted as appropriate. Further, “˜” represents the following from the above unless otherwise specified.

[Resin composition]
First, the resin composition of this embodiment is demonstrated.
The resin composition of this embodiment is shown below.
Phenolic resin,
A polymer containing a repeating unit represented by the following formula (1):
A resin composition comprising:

(In the formula (1), R _X and R _Y are each independently hydrogen or an organic group having 1 to 3 carbon atoms.)

The resin composition of this embodiment can express higher heat resistance than a resin composition containing a conventional phenol resin.
Although the detailed mechanism is not clear, for example, it includes a phenol resin and a polymer containing a repeating unit represented by the above formula (1), but the phenolic hydroxyl group provided in the phenol resin is represented by the formula (1). It acts on the structural unit, and as a result, it is considered that the polymer and the phenol resin have a close connection structure.
Such a resin composition of this embodiment can be suitably used for a photosensitive resin composition. The photosensitive resin composition can include a resin composition and a photosensitive agent.

Hereinafter, each component constituting the resin composition of the present embodiment will be described.

(Phenolic resin)
First, the phenol resin contained about the resin composition of this embodiment is demonstrated.
A conventionally well-known thing can be used for the phenol resin which concerns on this embodiment. Although it does not specifically limit as said phenol resin, For example, a novolak type phenol resin, a resol type phenol resin, an aryl alkylene type phenol resin etc. are mentioned. As a phenol resin, one of these may be used alone, two or more having different weight average molecular weights may be used in combination, and one or two or more thereof and a prepolymer thereof may be used in combination. May be. Among these, it is preferable to use a novolac type phenol resin.

The novolac-type phenol resin can be appropriately selected according to the use as long as it is a resin obtained by reacting phenols and aldehydes in the presence of no catalyst or acidic catalyst. For example, a random novolac type or high ortho novolac type phenol resin can also be used.
This novolak type phenol resin can be usually obtained by reacting after controlling the molar ratio of aldehydes to phenols (aldehydes / phenols) to 0.5 to 1.0.

Specific examples of phenols used in preparing this novolak type phenol resin include, for example, phenol, o-cresol, m-cresol, p-cresol, xylenol, alkylphenols, catechol, resorcin and the like. In addition, you may use these phenols individually or in mixture of 2 or more types.

Examples of the aldehydes used in preparing the novolac type phenol resin include aldehyde compounds such as formaldehyde, paraformaldehyde, benzaldehyde, substances that generate these aldehyde compounds, or solutions of these aldehyde compounds. Etc. can be used. In addition, you may use these aldehydes individually or in mixture of 2 or more types.

As molecular weight of the phenol resin of this embodiment, it is preferable that it is 300 or more as a weight average molecular weight (Mw), for example, it is more preferable that it is 1000 or more, It is further more preferable that it is 2000 or more, It is 3000 or more It is particularly preferable. When the weight average molecular weight (Mw) is at least the lower limit, the mechanical strength and heat resistance of the resin composition and the resin film obtained from the resin composition can be improved.
As a molecular weight of this phenol resin, it is preferable that it is 20000 or less as a weight average molecular weight (Mw), for example, it is more preferable that it is 18000 or less, and it is further more preferable that it is 15000 or less. When the weight average molecular weight (Mw) is not more than the above upper limit, it is possible to improve workability when producing the resin composition and improve moldability when obtaining a resin film from the resin composition.
Furthermore, it is possible to improve the sensitivity of the resin composition and the resin film obtained from the resin composition and reduce the amount of precipitated insoluble components.
Further, this weight average molecular weight can be calculated by gel permeation chromatography (GPC) based on a calibration curve created using a polystyrene standard substance, as in the polymer described later.

(polymer)
The polymer according to the present embodiment includes a repeating unit represented by the above formula (1). That is, the polymer according to the present embodiment is a polymer containing units derived from an unsaturated carboxylic acid anhydride having a cyclic structure in the molecule. For example, a copolymer of an unsaturated carboxylic acid anhydride and another monomer It is a coalescence. In this embodiment, the unsaturated carboxylic acid anhydride having a cyclic structure in the molecule may be selected from the group comprising maleic anhydride, citraconic anhydride, dimethylmaleic anhydride, or derivatives thereof. It may be selected from the group consisting of citraconic anhydride and dimethylmaleic anhydride. These may be used alone or in combination of two or more.

Examples of the unit derived from the unsaturated carboxylic acid anhydride having a cyclic structure in the molecule of the polymer according to this embodiment include an unsaturated carboxylic acid anhydride having a cyclic structure in the molecule represented by the following formula (1). A unit derived from a product may be used, and a unit derived from maleic anhydride represented by the following formula (6) may be used.

(In the formula (1), R _X and R _Y are each independently hydrogen or an organic group having 1 to 3 carbon atoms.)

In the present embodiment, in the above formula (1), R _X and R _Y are preferably each independently, for example, hydrogen or an organic group having 1 to 3 carbon atoms, and each independently represents hydrogen or 1 carbon atom. It is more preferable that R _X is hydrogen and R _Y is hydrogen or an organic group having 1 carbon atom, and it is more preferable that R _X and R _Y are hydrogen.

In the present embodiment, in the above formula (1), examples of the organic group constituting R _X and R _Y include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, a cycloalkyl group, and a heterocyclic group.
Examples of the alkyl group include a methyl group, an ethyl group, and an n-propyl group. Examples of the alkenyl group include an allyl group and a vinyl group. An ethynyl group is mentioned as an alkynyl group. Examples of the alkylidene group include a methylidene group and an ethylidene group. Examples of the cycloalkyl group include a cyclopropyl group. Examples of the heterocyclic group include an epoxy group and an oxetanyl group.

The other monomer to be copolymerized with the unsaturated carboxylic acid anhydride having a cyclic structure in the molecule can be appropriately selected according to the application to which the resin composition is applied.
More specific examples include norbornene, norbornadiene, bicyclo [2.2.1] -hept-2-ene (common name: 2-norbornene), 5-methyl-2-norbornene, 5-ethyl-2-norbornene. 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-allyl-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (1- Norbornene monomers such as methyl-4-pentenyl) -2-norbornene, 5-ethynyl-2-norbornene, 5-benzyl-2-norbornene, 5-phenethyl-2-norbornene; indene, 2-methylindene, 3-methyl Indene monomers such as indene; 1,5,9-cyclododecatriene, cis-trans-trans-1,5 9-cyclododecatriene, trans-trans-trans-1,5,9-cyclododecatriene, trans-cis-cis-1,5,9-cyclododecatriene, cis-cis-cis-1,5,9- Cycloaliphatic monomers such as cyclododecatriene; styrene monomers such as styrene, vinyltoluene and α-methylstyrene; vinyl monomers such as vinyl chloride and vinylidene chloride; fluorine such as perfluoroethylene, perfluoropropylene and vinylidene fluoride -Containing vinyl monomers; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; amide group-containing vinyl monomers such as acrylamide and methacrylamide; acetic acid Vinyl, propio Vinyl esters such as vinyl acetate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; Alkenes such as ethylene and propylene; Conjugated dienes such as butadiene and isoprene; Allyl monomers such as allyl chloride and allyl alcohol; Maleimide N-alkylmaleimide, N-ethylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-isobutylmaleimide, Nt-butylmaleimide, etc .; N-cyclohexylmaleimide, N N-cycloalkylmaleimides such as cyclopentylmaleimide, N-norbornylmaleimide, N-cyclohexylmethylmaleimide, N-cyclopentylmethylmaleimide; N-phenylmaleimide, N-chlorophenylmaleimide, N-me N-arylmaleimides such as ruphenylmaleimide, N-naphthylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, etc .; N-alkylmaleimide, N-cycloalkylmaleimide In addition to N-arylmaleimide, maleimide monomers such as N-hydroxymaleimide; One of these may be used alone, or two or more different types may be used in combination.

As the other monomer, a norbornene monomer, a styrene monomer, an indene monomer, and a maleimide monomer can be preferably used among the alicyclic monomers. That is, the polymer of this embodiment is a unit derived from a norbornene monomer represented by the formula (2), a unit derived from a styrene monomer represented by the formula (3), and a unit derived from an indene monomer represented by the formula (7). And at least one unit selected from the group consisting of units derived from maleimide monomers represented by formula (8). These may include one alone or may include two or more different units.
When a polymer contains these units, the heat resistance of the resin composition of this embodiment and the resin film obtained from the resin composition can be improved.

(In Formula (2), R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or an organic group having 1 to 30 carbon atoms. N is 0, 1 or 2)

(In Formula (3), each R _a is independently an organic group having 1 to 30 carbon atoms. M is an integer of 0 or more and 5 or less.)

(In formula (7), R ₅ to R ₁₁ are each independently hydrogen or an organic group having 1 to 3 carbon atoms.)

(In Formula (8), R ₁₂ is independently hydrogen or an organic group having 1 to 10 carbon atoms.)

In the present embodiment, in the above formula (2), R ₁ to R ₄ are, for example, each independently hydrogen or an organic group having 1 to 30 carbon atoms, and each independently hydrogen or 1 to 10 carbon atoms. It is preferably an organic group, more preferably independently hydrogen or an organic group having 1 to 3 carbon atoms, and further preferably each independently hydrogen or an organic group having 1 carbon atom. Moreover, in said formula (2), n is 0, 1 or 2, for example, it is preferable that it is 0 or 1, and it is more preferable that it is 0.

In the present embodiment, in the above formula (3), R _a is, for example, each independently hydrogen or an organic group having 1 to 30 carbon atoms, and each independently hydrogen or an organic group having 1 to 10 carbon atoms. It is preferable that they are each independently hydrogen or an organic group having 1 to 3 carbon atoms, more preferably hydrogen or an organic group having 1 carbon atom. In the above formula (3), m is, for example, an integer of 0 or more and 5 or less, preferably an integer of 0 or more and 3 or less, and more preferably an integer of 0 or more and 1 or less.

In the present embodiment, in the above formula (7), R ₅ to R ₁₁ are, for example, each independently hydrogen or an organic group having 1 to 3 carbon atoms, and each independently hydrogen or an organic group having 1 carbon atom. It is preferable that each is independently hydrogen.

In the present embodiment, in the above formula (8), R ₁₂ is, for example, independently hydrogen or an organic group having 1 to 10 carbon atoms, and independently hydrogen or an organic group having 1 to 5 carbon atoms. It is preferably independently hydrogen or an organic group having 1 to 3 carbon atoms, more preferably independently hydrogen or an organic group having 1 carbon atom.

The organic group having 1 to 30 carbon atoms constituting R ₁ to R ₄ and R _a may contain one or more atoms selected from O, N, S, P and Si in the structure. Further, the organic group having 1 to 3 carbon atoms constituting R ₅ to R ₁₁ may contain one or more atoms selected from O, N, S, P and Si in the structure. Good. In addition, the organic group having 1 to 10 carbon atoms constituting R ₁₂ may contain one or more atoms selected from O, N, S, P and Si in the structure. In addition, any of the organic groups constituting R ₁ to R ₄ , R _a , R ₅ to R ₁₁ and R ₁₂ may have no acidic functional group. Thereby, control of the acid value in a polymer can be made easy.

In this embodiment, examples of the organic group constituting R ₁ to R ₄ and R _a include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkaryl group, a cycloalkyl group, and a heterocyclic ring. Groups.
Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, An octyl group, a nonyl group, and a decyl group are mentioned. Examples of the alkenyl group include allyl group, pentenyl group, and vinyl group. An ethynyl group is mentioned as an alkynyl group. Examples of the alkylidene group include a methylidene group and an ethylidene group. Examples of the aryl group include a tolyl group, a xylyl group, a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the heterocyclic group include an epoxy group and an oxetanyl group.

In the present embodiment, examples of the organic group constituting R ₅ to R ₁₁ include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, a cycloalkyl group, and a heterocyclic group.
Examples of the alkyl group include a methyl group, an ethyl group, and an n-propyl group. Examples of the alkenyl group include an allyl group and a vinyl group. An ethynyl group is mentioned as an alkynyl group. Examples of the alkylidene group include a methylidene group and an ethylidene group. Examples of the cycloalkyl group include a cyclopropyl group. Examples of the heterocyclic group include an epoxy group and an oxetanyl group.

In the present embodiment, the organic group constituting R _12, for example, hydrogen and, among the exemplified organic groups in the above _{R 1 ~ R 4, R a} , may be used an organic group having 1 to 10 carbon atoms .

Further, the alkyl group, alkenyl group, alkynyl group, alkylidene group, aryl group, aralkyl group, alkaryl group, cycloalkyl group, and heterocyclic ring constituting R ₁ to R ₄ , R _a , R ₅ to R ₁₁ and R ₁₂ In the group, one or more hydrogen atoms may be substituted with a halogen atom. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. Among these, a haloalkyl group in which one or more hydrogen atoms of the alkyl group are substituted with a halogen atom is preferable. When at least one of R ₁ to R ₄ , R _a , R ₅ to R ₁₁ , and R ₁₂ is a haloalkyl group, when a cured film is formed using a polymer, the dielectric constant of the cured film is Can be reduced. In addition, by using a haloalkyl alcohol group, not only the solubility in an alkali developer can be appropriately adjusted, but also the heat discoloration can be improved.
From the viewpoint of increasing the light transmittance of the film comprising the polymer, it is preferable that any of R ₁ to R ₄ , R _a , R ₅ to R ₁₁ and R ₁₂ is hydrogen, for example, When the structural unit of the formula (2) is adopted, it is preferable that all of R ₁ to R ₄ are hydrogen. For example, when adopting the structural unit of the formula (3), R _a is preferably hydrogen. For example, when the structural unit of the formula (7) is employed, it is preferable that R ₅ to R ₁₁ are hydrogen. For example, when the structural unit of the formula (8) is employed, R ₁₂ is preferably hydrogen.

A chain transfer agent can be appropriately used to adjust the molecular weight of the polymer. Examples of chain transfer agents include stearyl-3-mercaptopropionate, pentaerythritol tetrakis (3-mercaptopropionate), β-mercaptopropionic acid, methoxybutyl-3-mercaptopropionate, stearyl-3-mercapto. Β-mercaptopropionic acids such as propionate, trimethylolpropane tris (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate; 2-hydroxy-1,4-naphthoquinone Naphthoquinones such as 1,4-naphthoquinone; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, thioglycolic acid, mercaptopropionic acid; Xanthate disulfide, xanthogen such as diisopropyl xanthogen disulfide and the like; triethoxysilane, mention may be made of terpinolene, the α- methylstyrene dimer.

In the molecular weight distribution curve obtained by, for example, GPC (Gel Permeation Chromatography), the peak area at a molecular weight of 1000 or less may be 3% or less or 2% or less of the polymer before the reaction with the phenol resin in the present embodiment. .
Thus, the pattern shape of the film | membrane consisting of the resin composition containing a polymer can be made favorable by making the ratio of the peak area in the molecular weight 1000 or less of the molecular weight distribution curve obtained by GPC into the said range. Therefore, it is possible to improve the operation reliability of an electronic device such as a liquid crystal display device or a solid-state imaging device that includes the film as a permanent film.
In addition, the minimum of the quantity of the low molecular weight component in a polymer is not specifically limited. However, the polymer in this embodiment allows a case where the peak area at a molecular weight of 1000 or less is 0.01% or more of the whole in the molecular weight distribution curve obtained by GPC.

The polymer before reacting with the phenol resin in the present embodiment has, for example, Mw (weight average molecular weight) / Mn (number average molecular weight) of 1.5 or more and 2.5 or less. Mw / Mn is a degree of dispersion indicating the width of the molecular weight distribution.
The present inventor has found that, by controlling the molecular weight distribution in a polymer within a certain range, the deformation of the pattern during curing can be suppressed for a film formed from the polymer. For this reason, the shape of the film | membrane which consists of a resin composition containing a polymer can be made favorable by making Mw / Mn of a polymer into the said range. Such an effect is particularly noticeable when the low molecular weight component of the polymer is simultaneously reduced as described above.
The polymer Mw (weight average molecular weight) is, for example, from 1,500 to 30,000.

For the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn), for example, a polystyrene conversion value obtained from a standard polystyrene (PS) calibration curve obtained by GPC measurement is used. The measurement conditions are, for example, as follows.
Tosoh gel permeation chromatography device HLC-8320GPC
Column: Tosoh TSK-GEL Supermultipore HZ-M
Detector: RI detector for liquid chromatogram Measurement temperature: 40 ° C
Solvent: THF
Sample concentration: 2.0 mg / milliliter In addition, the amount of low molecular weight components in the polymer is based on the data on the molecular weight obtained by GPC measurement, for example. It is calculated from the ratio.

(Method for producing polymer)
The polymer according to this embodiment can be obtained by copolymerizing an unsaturated carboxylic acid anhydride having a cyclic structure in the molecule and another monomer. This manufacturing method may be a conventionally known method. Hereinafter, a method for producing a polymer containing the repeating unit represented by the above formula (2) will be described as an example.

(Polymerization step (Process S1))
First, a norbornene type monomer represented by the following formula (2a) and maleic anhydride as a monomer are prepared. In the norbornene-type monomer represented by the formula (2a), n and R ₁ to R ₄ can be the same as those in the above formula (2).

Specific examples of the norbornene-type monomer represented by the formula (2a) include bicyclo [2.2.1] -hept-2-ene (common name: 2-norbornene), which further has an alkyl group. As those having an alkenyl group, such as 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, etc. Are those having an alkynyl group, such as 5-allyl-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (1-methyl-4-pentenyl) -2-norbornene, and the like, Examples of those having an aralkyl group such as -2-norbornene include 5-benzyl-2-norbornene and 5-phenethyl-2-norbol Such as emissions, and the like.
In addition, examples of the norbornene-type monomer include functional groups such as a group having a crosslinkability or a group containing a halogen atom such as fluorine in the structure of R ₁ , R ₂ , R ₃ , R _{4 in} the formula (2a). It is possible to adopt one including
Any one or more of these can be used as the norbornene-type monomer. Of these, bicyclo [2.2.1] -hept-2-ene (common name: 2-norbornene) is preferably used from the viewpoint of the balance between heat resistance and light transmittance of the polymer.

Next, the norbornene type monomer represented by the formula (2a) and maleic anhydride are subjected to addition polymerization. Here, a copolymer (copolymer 1) of the norbornene-type monomer represented by the formula (2a) and maleic anhydride is formed by radical polymerization.
The molar ratio of the norbornene-type monomer represented by the formula (2a) to maleic anhydride (mole number of the compound represented by formula (2a): mole number of maleic anhydride) is 0.5: 1 to 1: 0. .5 is preferable. Among these, from the viewpoint of controlling the molecular structure, it is preferable that the number of moles of the norbornene-type monomer represented by the formula (2a): the number of moles of maleic anhydride = 0.8: 1 to 1: 0.8.
In addition, in this addition polymerization, a monomer that can be copolymerized in addition to the above-described norbornene-type monomer and maleic anhydride may be added. Examples of such a monomer include compounds containing a group having an ethylenic double bond in the molecule. Here, specific examples of the group having an ethylenic double bond include an allyl group, an acrylic group, a methacryl group, a maleimide group, and an aromatic vinyl group such as a styryl group and an indenyl group.
Instead of the maleic anhydride, an unsaturated carboxylic acid anhydride having a cyclic structure in another molecule may be used.

As the polymerization method, for example, a polymerization method using a radical polymerization initiator and, if necessary, a chain transfer agent is suitable. In this case, methods such as suspension polymerization, solution polymerization, dispersion polymerization, and emulsion polymerization can be employed. Among these, solution polymerization is preferable. In the solution polymerization, all the monomers may be charged all at once, or a part of them may be charged into a reaction vessel and the rest may be dropped.

For example, the norbornene-type monomer represented by the formula (2a), the maleic anhydride, and the polymerization initiator are dissolved in a solvent, and then heated for a predetermined time, whereby the norbornene-type monomer represented by the formula (2a), Solution polymerization is performed with maleic anhydride. The heating temperature is, for example, 50 to 80 ° C., and the heating time is 10 to 20 hours.

As the solvent used for the polymerization, for example, any one or more of diethyl ether, tetrahydrofuran, toluene, methyl ethyl ketone, ethyl acetate and the like can be used.

As the radical polymerization initiator, any one or more of an azo compound and an organic peroxide can be used.
Examples of the azo compound include azobisisobutyronitrile (AIBN), dimethyl 2,2′-azobis (2-methylpropionate), 1,1′-azobis (cyclohexanecarbonitrile) (ABCN), Any one or more of these can be used.
Examples of organic peroxides include hydrogen peroxide, ditertiary butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), and methyl ethyl ketone peroxide (MEKP). Any one or more of them can be used.

The amount (number of moles) of the radical polymerization initiator is preferably 1% to 10% of the total number of moles of the norbornene-type monomer represented by the formula (2a) and maleic anhydride. By appropriately setting the amount of the polymerization initiator within the above range and appropriately setting the reaction temperature, the reaction time, and the amount of the chain transfer agent, the weight average molecular weight (Mw) of the obtained polymer is adjusted to an appropriate range. can do.

By this polymerization step (treatment S1), the copolymer 1 having the repeating unit represented by the above formula (1) and the repeating unit represented by the formula (2) can be polymerized.
However, in the copolymer 1, R _{1 in} the structure of the formula (2) is preferably common to each repeating unit, but may be different for each repeating unit. The same applies to R ₂ to R ₄ .

In the copolymer 1, the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) may be randomly arranged, or may be alternately arranged. There may be. Moreover, the norbornene-type monomer represented by the formula (2a) and maleic anhydride may be block copolymerized. However, from the viewpoint of ensuring the uniformity of solubility of the resin composition using the polymer produced in this embodiment, the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) It is preferable that the structure is arranged alternately. That is, for example, when the norbornene monomer and maleic anhydride are copolymerized, the copolymer 1 preferably has a repeating unit represented by the following formula (4).

(In Formula (4), n and R ₁ to R ₄ are the same as those in Formula (2) above. That is, n is 0, 1, or 2. R ₁ to R ₄ are hydrogen or An organic group having 1 to 30 carbon atoms, R ₁ to R ₄ may be the same or different, and a is an integer of 10 or more and 200 or less.)

Here, R _{1 in} the structure of the formula (4) is preferably common to each repeating unit, but may be different for each repeating unit. The same applies to R ₂ to R ₄ .

(Low molecular weight component removal step (Process S2))
Next, if necessary, in addition to a large amount of a poor solvent such as hexane or methanol, the copolymer 1 and an organic layer containing low molecular weight components such as residual monomers and oligomers The polymer containing coalescence 1 is coagulated and precipitated. Here, as a low molecular weight component, a residual monomer, an oligomer, a polymerization initiator, and the like are included. Next, filtration is performed, and the obtained coagulum is dried. Thereby, the polymer which has the copolymer 1 from which the low molecular weight component was removed as a main component (main product) can be obtained.

In the resin composition of the present embodiment, the polymer content is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and more preferably 15 parts by mass or more with respect to 100 parts by mass of the aforementioned phenol resin. More preferably, it is more preferably 20 parts by mass or more.
In the resin composition of the present embodiment, the polymer content is preferably 100 parts by mass or less, more preferably 70 parts by mass or less, and 50 parts by mass with respect to 100 parts by mass of the phenol resin described above. More preferably, it is more preferably 35 parts by mass or less.
By setting to such a range, it is possible to bring about an appropriate interaction with the above-mentioned phenol resin, and to contribute to further improvement of heat resistance.

For example, even when the above-described polymer includes a repeating unit represented by the above formula (7), the repeating unit of the formula (2) can be obtained by using an indene monomer represented by the following formula (7a). It can be produced in the same manner as the monomer and polymer containing it.

(In formula (7a), R ₅ to R ₁₁ are the same as in formula (7).)

The resin composition of the present embodiment includes the above-described phenol resin and a polymer, but the structural unit represented by the formula (6) in the polymer (that is, maleic anhydride unit) and the phenolic provided in the phenol resin. It is preferable that the compound (ester compound) which the hydroxyl group couple | bonded through the ester bond is included.
In the resin composition of this embodiment, it can be considered that a half ester represented by the following formula (5) is given by adding this phenolic hydroxyl group to maleic anhydride. Due to the ester bond in the formula (5), the resin composition and the resin film of this embodiment can exhibit high heat resistance.
Furthermore, it is thought that the half ester in Formula (5) contains a carboxyl group, and this can improve the sensitivity when a photosensitive resin composition is prepared.
Instead of the maleic anhydride, an unsaturated carboxylic acid anhydride having a cyclic structure in another molecule may be used.

(In Formula (5), R is an atomic group derived from a phenol resin.)

In addition, it is possible that the resin composition of this embodiment gives half ester as shown by Formula (5) as mentioned above. Since the effects such as heat resistance are thereby exhibited, the content ratio of the above-mentioned half ester can be increased by heating the resin composition before being subjected to various uses.
The heating condition is, for example, in the range of 50 to 100 ° C.
Further, for example, when used for an application that undergoes a heating step in the process, the above-mentioned phenol resin and polymer can be mixed at room temperature and used without heating.
In this heating, a catalyst can be appropriately added from the viewpoint of promoting the reaction, and for example, a base catalyst or an acid catalyst can be added.
As the base catalyst, hydroxy compounds such as sodium hydroxide and potassium hydroxide, alkylamines such as pyridine and triethylamine, amine compounds such as dimethylaniline, urotropine and dimethylaminopyridine, metal salts such as sodium acetate, ammonia and the like are used. be able to. These may be used alone or in combination of two or more kinds of base catalysts in order to further increase the reactivity.
As the acid catalyst, mineral acids such as sulfuric acid and hydrochloric acid, organic acids such as p-toluenesulfonic acid, Lewis acids such as boron fluoride etherate, and the like can be used.
Instead of the maleic anhydride, an unsaturated carboxylic acid anhydride having a cyclic structure in another molecule may be used.

Moreover, the resin composition of this embodiment comprises an ester compound in which the acid anhydride portion of the polymer containing the repeating unit represented by the above formula (1) and the phenolic hydroxyl group provided in the phenol resin constitute an ester bond. It may be included. In this case, in the resin composition of the present embodiment, all of the acid anhydride (eg, maleic anhydride) of the polymer may be ring-opened and / or the phenolic hydroxyl group provided in the phenol resin. All may have an ester bond. Thereby, heat resistance can be improved further.

[Photosensitive resin composition]
More specific applications of the above-described resin composition include applications as a photosensitive resin composition shown below.
The photosensitive resin composition of this embodiment can contain the said phenol resin, the polymer containing the repeating unit shown by said Formula (1), and a photosensitive agent. That is, the photosensitive resin composition of this embodiment may contain the above resin composition and a photosensitive agent.
Here, about the phenol resin and polymer used with the photosensitive resin composition of this embodiment, the thing similar to the above-mentioned thing is employable. Hereinafter, components other than these will be described.

(Photosensitive agent)
The photosensitive resin composition of this embodiment contains a photosensitive agent.
Examples of the photosensitive agent include diazoquinone compounds, diaryliodonium salts, onium salts such as triarylsulfonium salts or sulfonium borate salts, 2-nitrobenzyl ester compounds, N-iminosulfonate compounds, imide sulfonate compounds, 2,6-bis. A (trichloromethyl) -1,3,5-triazine compound or a dihydropyridine compound can be used. Among these, it is particularly preferable to use a diazoquinone compound having excellent sensitivity and solvent solubility. As the diazoquinone compound, for example, those shown below can be used.

(N2 is an integer of 1 or more and 5 or less)

In each of the above compounds, Q is one of the structures shown in the following (a) to (c) or a hydrogen atom. However, at least one of Q of each compound has one of the structures shown in the following (a) to (c).

In this embodiment, for example, an ester of a phenol compound and 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid is used as the diazoquinone compound. It is more preferable.
The photosensitive resin composition of the present embodiment can be a so-called positive type, and the photosensitive agent remaining in the relief pattern in the unexposed area is considered to decompose by heat at the time of curing and generate an acid, thereby promoting the reaction. This photosensitive agent also plays an important role as an agent. As the diazoquinone compound having such a role, it is particularly preferable to use an ester of 1,2-naphthoquinone-2-diazide-4-sulfonic acid which is more easily decomposed by heat.

Although content of the photosensitive agent in the photosensitive resin composition of this embodiment is not specifically limited, It is preferable that it is 5 mass parts or more with respect to 100 mass parts of phenol resins, and is 8 mass parts or more. More preferably. Moreover, it is preferable that it is 80 mass parts or less with respect to 100 mass parts of phenol resins, and, as for content of the photosensitive agent in the photosensitive resin composition, it is more preferable that it is 60 mass parts or less. When the content of the photosensitive agent is within the above range, good patterning performance can be exhibited.

(solvent)
The resin composition and the photosensitive resin composition described in this embodiment can be used as a varnish by dissolving the above-described components in a solvent.
Examples of such solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol Monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, and ethyl and methyl pyruvate -3-Methoxypropionate and the like.
Of these compounds, γ-butyrolaclone, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether are among these compounds from the viewpoint of significantly suppressing the occurrence of cracks in the resin film. It is preferable to use a compound selected from the group consisting of propylene glycol monomethyl ether acetate.

The content of the solvent in the resin composition and the photosensitive resin composition of the present embodiment is not particularly limited, but is preferably 100 parts by mass or more and 150 parts by mass with respect to 100 parts by mass of the phenol resin. More preferably, it is at least part.
Moreover, it is preferable that it is 1000 mass parts or less with respect to 100 mass parts of phenol resins, and, as for content of the solvent in the resin composition and photosensitive resin composition of this embodiment, it is more preferable that it is 800 mass parts or less. preferable. When the content of the solvent is within the above range, an appropriate handling property can be provided.

(Other ingredients)
In addition to the components described above, the resin composition and the photosensitive resin composition of the present embodiment can contain various components in accordance with the application.
For example, as an alkali-soluble resin, an acrylic resin such as a phenol resin, a phenol aralkyl resin, a hydroxystyrene resin, a methacrylic acid resin, or a methacrylic ester resin, a cyclic olefin resin, or the like can be separately added.
In addition, additives such as an antioxidant, a filler, a silane coupling agent, a surfactant, an adhesion assistant, a terminal blocking agent, and a sensitizer may be added as necessary.
In addition, the quantity which can add these is arbitrary.

(Use)
The resin composition and photosensitive resin composition of this embodiment are used for forming a resin film such as a resist or a permanent film. Such an application is suitable from the viewpoint of heat resistance.
The resist is, for example, a resin film obtained by applying a photosensitive resin composition by a method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, etc., and removing the solvent. Composed.
The permanent film is composed of a cured film obtained by exposing and developing the resin film, patterning it into a desired shape, and curing it by heat treatment or the like. The permanent film can be used, for example, as a protective film, an interlayer film, or a dam material.

Next, an example of the electronic device 100 to which the resin composition or the photosensitive resin composition of the present embodiment is applied will be described.
The electronic device 100 of this embodiment can include the resin film.
An electronic device 100 shown in FIG. 1 is, for example, a semiconductor chip. In this case, for example, a semiconductor package can be obtained by mounting the electronic device 100 on the wiring board via the bumps 52. The electronic device 100 includes a semiconductor substrate provided with a semiconductor element such as a transistor, and a multilayer wiring layer provided on the semiconductor substrate (not shown). An interlayer insulating film 30 and an uppermost layer wiring 34 provided on the interlayer insulating film 30 are provided in the uppermost layer of the multilayer wiring layer. The uppermost layer wiring 34 is made of, for example, Al. Further, a passivation film 32 is provided on the interlayer insulating film 30 and the uppermost layer wiring 34. An opening through which the uppermost layer wiring 34 is exposed is provided in a part of the passivation film 32.

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 an opening provided in the insulating layer 42, and is connected to the uppermost layer wiring 34. The insulating layer 44 is provided with an opening connected to the rewiring 46.
In the present embodiment, at least one of the passivation film 32, the insulating layer 42, and the insulating layer 44 is configured by a resin film formed by curing the above-described resin composition or photosensitive resin composition. Can do. In this case, for example, the coating film formed of the photosensitive resin composition is exposed to ultraviolet rays and developed to perform patterning, followed by heat curing, whereby the passivation film 32, the insulating layer 42, or the insulating layer 44. Is formed.

In the opening provided in the insulating layer 44, for example, a bump 52 is formed via a UBM (Under Bump Metallurgy) layer 50. The electronic device 100 is connected to a wiring board or the like via bumps 52, for example.

It should be noted that the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.
Hereinafter, examples of the reference form will be added.
1.
Novolac type phenolic resin,
A polymer containing a repeating unit represented by the following formula (6):
A resin composition comprising:

2.
1. The resin composition according to claim 1,
The resin composition whose weight average molecular weights of the said novolak-type phenol resin are 300-20000.
3.
1. Or 2. The resin composition according to claim 1,
The resin composition containing the compound which the acid anhydride site | part with which the repeating unit shown by said Formula (6) is equipped, and the phenolic hydroxyl group with which the said novolak-type phenol resin is couple | bonded through the ester bond.
4).
1. Or 3. A resin composition according to any one of
The polymer further includes a repeating unit represented by the following formula (2) or a repeating unit represented by the following formula (3).

(In Formula (2), R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or an organic group having 1 to 30 carbon atoms. N is 0, 1 or 2)

(In Formula (3), each R _a is independently an organic group having 1 to 30 carbon atoms. M is an integer of 0 or more and 5 or less.)
5).
Novolac type phenolic resin,
A polymer containing a repeating unit represented by the following formula (6):
A photosensitizer,
A photosensitive resin composition comprising:

6).
5). The photosensitive resin composition according to claim 1,
The photosensitive resin composition whose said photosensitive agent is a diazoquinone compound.
7).
5). Or 6. The photosensitive resin composition according to claim 1,
The photosensitive resin composition whose weight average molecular weights of the said novolak-type phenol resin are 300-20000.
8).
5). Or 7. A photosensitive resin composition according to any one of
The photosensitive resin composition containing the compound which the acid anhydride site | part with which the repeating unit shown by the said Formula (6) is equipped, and the phenolic hydroxyl group with which the said novolak-type phenol resin is couple | bonded through the ester bond.
9.
5). Or 8. A photosensitive resin composition according to any one of
The polymer further includes a repeating unit represented by the following formula (2) or a repeating unit represented by the following formula (3).

(In Formula (2), R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or an organic group having 1 to 30 carbon atoms. N is 0, 1 or 2)

(In Formula (3), each R _a is independently an organic group having 1 to 30 carbon atoms. M is an integer of 0 or more and 5 or less.)
10.
5). Or 9. A resin film composed of a cured product of the photosensitive resin composition according to any one of the above.
11.
10. An electronic device comprising the resin film described in 1.

Next, examples of the present invention will be described.
First, each material used in the examples was prepared as shown below.

(Novolac type phenolic resin 1)
Phenol in which m-cresol and p-cresol were mixed in a molar ratio (m-cresol: p-cresol) = 5: 5 in a 3 L 4-neck flask equipped with a stirrer, thermometer and heat exchanger To 1000 parts of the product, 526 parts of a 37% formalin aqueous solution (formaldehyde / phenol molar ratio = 0.70) and 10 parts of oxalic acid were charged and reacted under reflux for 6 hours. Thereafter, dehydration was carried out under normal pressure up to an internal temperature of 170 ° C., and further, the temperature was raised to 230 ° C. under reduced pressure of 8.0 kPa, followed by dehydration under reduced pressure, weight average molecular weight 11,000, dispersity 9.0, unreacted 1050 parts of a novolak type phenolic resin containing 0.5% of phenols was obtained.

(Polymer 1)
Into a suitably sized reaction vessel equipped with a stirrer and condenser, maleic anhydride (735 g, 7.5 mol), 2-norbornene (706 g, 7.5 mol) and dimethyl 2,2′-azobis (2-methylpro) Pionate) (69 g, 0.3 mol) was weighed and dissolved in methyl ethyl ketone and toluene. This dissolved solution was subjected to heat treatment under conditions of 60 ° C. and 15 hours with stirring, after removing dissolved oxygen in the system by nitrogen bubbling. As a result, a copolymer of 2-norbornene and maleic anhydride was obtained. Subsequently, after re-precipitating the said melt | dissolution solution cooled to room temperature using a lot of methanol, the deposit was filtered and dried with the vacuum dryer, and 1100g of white solid was obtained.
The polymer thus obtained had a weight average molecular weight (Mw) of 10,000 and a dispersity (Mw / Mn) of 2.1.

(Polymer 2)
A styrene / maleic anhydride copolymer SMA-1000-P (Cray ValleyUSA, LLC) was prepared. The polymer had a weight average molecular weight (Mw) of 3,600 and a dispersity (Mw / Mn) of 2.3.

(Polymer 3)
In a suitably sized reaction vessel equipped with a stirrer and condenser, indene (870 g, 7.5 mol) and dimethyl 2,2′-azobis (2-methylpropionate) (11.5 g, 0.05 mol) Was weighed and dissolved in methyl ethyl ketone. The dissolved oxygen in the system was removed from the solution by nitrogen bubbling, and after reaching 70 ° C. with stirring, maleic anhydride (735 g, 7.5 mol) methyl ethyl ketone solution, n-dodecyl mercaptan (20.2 g, (0.10 mol) Methyl ethyl ketone solution was sequentially added from each of the mouths over 5 hours, followed by further heat treatment for 2 hours. Thereby, a copolymer of indene and maleic anhydride was obtained.

(Polymer 4)
In a suitably sized reaction vessel equipped with stirrer and condenser, indene (870 g, 7.5 mol) and dimethyl 2,2′-azobis (2-methylpropionate) (23.0 g, 0.1 mol) Was weighed and dissolved in methyl ethyl ketone. After removing dissolved oxygen in the system by nitrogen bubbling to this solution, after reaching 75 ° C. with stirring, a citraconic anhydride (840 g, 7.5 mol) methyl ethyl ketone solution was sequentially added over 6 hours. Further heat treatment was performed for 3 hours. As a result, a copolymer of indene and citraconic anhydride was obtained.

(Polymer 5)
In a suitably sized reaction vessel equipped with a stirrer and condenser, indene (870 g, 7.5 mol) and dimethyl 2,2′-azobis (2-methylpropionate) (11.5 g, 0.05 mol) Was weighed and dissolved in methyl ethyl ketone. The dissolved oxygen in the system was removed by nitrogen bubbling with respect to this solution, and after reaching 70 ° C. with stirring, maleic anhydride (662 g, 6.75 mol) and maleimide (72.8 g, 0.75 mol) were added. The mixed methyl ethyl ketone solution and n-dodecyl mercaptan (20.2 g, 0.10 mol) methyl ethyl ketone solution were sequentially added from each mouth over 5 hours, and then further heat-treated for 2 hours. As a result, a copolymer of indene, maleic anhydride, and maleimide was obtained.

(Polymer 6)
In a suitably sized reaction vessel equipped with stirrer and condenser, indene (696 g, 6.0 mol), 2-norbornene (141 g, 1.5 mol) and dimethyl 2,2′-azobis (2-methylpropionate) ) (11.5 g, 0.05 mol) was weighed and dissolved in methyl ethyl ketone. The dissolved oxygen in the system was removed from the solution by nitrogen bubbling, and after reaching 70 ° C. with stirring, maleic anhydride (735 g, 7.5 mol) methyl ethyl ketone solution, n-dodecyl mercaptan (20.2 g, (0.10 mol) Methyl ethyl ketone solution was sequentially added from each port over 7 hours, and further heat-treated for 5 hours. Thereby, a copolymer of indene, norbornene and maleic anhydride was obtained.

(Phenol compound 1)
A phenol compound represented by the following formula (product name, Tris P-PA, manufactured by Honshu Chemical Co., Ltd.) was prepared.

(Photosensitive agent 1)
A photosensitive agent represented by the following formula (B-1) (product name PA-28 manufactured by Daito Chemix Co., Ltd.) was prepared.

Note that Q in the formula (B-1) is represented by a hydrogen atom or the above formula (B-2), and 90% of the total Q is the above formula (B-2).

(Surfactant 1)
Fluorosurfactant Megafac F-556 (manufactured by DIC Corporation) was prepared.

[Preparation of photosensitive resin composition]
For each example and each comparative example, the raw materials in the amounts shown in Table 1 and Table 2 were prepared, dissolved in PGMEA (propylene glycol monomethyl ether acetate), and then filtered with a fluororesin filter having a pore size of 0.2 μm. Filtration was performed to obtain a photosensitive resin composition.
In preparing the photosensitive resin compositions of Examples and Comparative Examples, PGMEA (propylene glycol monomethyl ether acetate) has a resin component content (total of novolac type phenol resin and polymer or phenol compound) of 25. % Was adjusted.
In addition, about each Example, about Example 1 and 2, after adding methyl ethyl ketone and adding 5 mass parts of pyridine to the methyl ethyl ketone solution of a novolak-type phenol resin and the polymer 1, and heating at 70 degreeC for 2 days, After removing the solvent and pyridine, the mixture was filtered and prepared.
For Examples 6 to 11, 5 parts by mass of methyl ethyl ketone and pyridine were further added to the methyl ethyl ketone solution of the novolac type phenolic resin and polymer 3 solution, and reacted at 70 ° C. for 3 days. Then, the reaction solvent and pyridine were removed. did.
For Examples 13, 14, and 15, 5 parts by mass of methyl ethyl ketone and pyridine were further added to the novolak-type phenol resin and the polymer solutions 4, 5, and 6 corresponding to the respective examples, and reacted at 70 ° C. for 3 days. Thereafter, the reaction solvent, pyridine, was removed.
Further, Examples 3 to 5, 12 and Comparative Examples 1 and 2 differ from the above-described Examples 1 to 2, 6 to 11, and 13 to 15, and before dissolving each raw material in PGMEA, the novolac type phenol resin is used. And the polymer was not reacted.
The photosensitive resin composition obtained as described above is evaluated according to the following items.

(sensitivity)
Each of the photosensitive resin compositions obtained above was applied onto a 4-inch silicon wafer using a spin coater and then pre-baked at 110 ° C. for 2 minutes on a hot plate to obtain a coating film having a thickness of about 2 μm. . An i-line stepper (manufactured by Nikon Corporation, NSR-) is passed through this coating film through a mask made by Toppan Printing Co., Ltd. (test chart No. 1: a remaining pattern of 0.88 to 50 μm in width and a removal pattern is drawn). 4425i) was used for irradiation with varying exposure.
Next, a 2.38% tetramethylammonium hydroxide aqueous solution is used as a developing solution, and the developing time is adjusted so that the difference between the film thickness after pre-baking and the film thickness after developing is 1.0 μm, and paddle twice. The exposed portion was dissolved and removed by developing, and then rinsed with pure water for 10 seconds. The value of the minimum exposure amount at which a 100 μm square via hole pattern was formed was evaluated as sensitivity. The results are shown in Tables 1 and 2.

(Heat resistance evaluation)
Each of the photosensitive resin compositions obtained above was applied onto a 4-inch silicon wafer using a spin coater and then pre-baked at 110 ° C. for 2 minutes on a hot plate to obtain a coating film having a thickness of about 2 μm. . Through this mask, a mask made by Toppan Printing Co., Ltd. (a 1 mm square pattern) was used, and exposure was carried out with a fixed exposure time of 40 seconds using a mask aligner MA8 manufactured by SSUS. Next, the exposed portion was dissolved and removed by immersing in a 2.38% tetramethylammonium hydroxide aqueous solution, and then rinsed with pure water for 30 seconds. At this time, the amount of film reduction in the unexposed area was about 0.02 μm. About the unexposed part which carried out the said pattern process, it dried on 100 degreeC 1 minute conditions, and obtained the resin film.
This resin film was subjected to heat treatment at 140 ° C. for 3 minutes, and observation was made using a metal microscope as to whether or not the shape of the resin film changes. In addition, the evaluation criteria in this test are as follows. The results are shown in Tables 1 and 2.
(Double-circle): The shape change of a pattern is not observed.
○: Slight deformation is observed at the corners of the pattern, but there is no practical problem.
X: Change in pattern shape is observed.

As shown in Tables 1 and 2, in each Example, a resin film that can withstand high temperatures was obtained. Moreover, it is recognized that the various photosensitive resin compositions obtained in each Example have high sensitivity and high utility as a photoresist.
Of each example, it was confirmed that for example 1 and example 4, the pattern shape was sufficiently retained even when the conditions of the heat resistance test were changed to 150 ° C. for 3 minutes.

In addition, about the photosensitive resin composition of a present Example showing high heat resistance, a novolak-type phenol resin and the specific polymer containing the unsaturated carboxylic anhydride unit which has a cyclic structure in a molecule | numerator are an ester bond. It is thought that this is one of the causes of this heat resistance expression.
In FIG. 2, the FT-IR spectrum of the above-mentioned polymer 2 (FIG. 2 (a)), polymer 2 and a novolac type phenol resin are dissolved in a ratio of 25:75 in methyl ethyl ketone, and at 70 ° C. in the presence of pyridine. The FT-IR spectrum (FIG. 2 (b)) of the composition obtained after reacting for 1 day and then removing the solvent and pyridine is shown. As can be seen from a comparison between FIG. 2 (a) and FIG. 2 (b), in FIG. 2 (b), an absorption peak near 1700 cm ⁻¹ peculiar to the ester bond is observed.
That is, in this invention, it is suggested that the coupling | bonding of such a phenol resin and the unsaturated carboxylic anhydride unit which has a cyclic structure in a molecule | numerator has influenced the contribution of heat resistance.

The resin composition of the present invention can exhibit high heat resistance due to the interaction between the phenol resin and the polymer having a specific structural unit. For example, when a photosensitive resin composition is used, the resin composition has excellent sensitivity. And high heat resistance can be expressed in a well-balanced manner.
Moreover, even if the resin composition of the present invention is used for applications other than such a photosensitive resin composition, it can be applied to applications requiring heat resistance as appropriate.

This application claims priority based on Japanese Patent Application No. 2015-163438 filed on August 21, 2015, the entire disclosure of which is incorporated herein.

Claims (10)

1. Phenolic resin,
   A polymer containing a repeating unit represented by the following formula (1):
   A resin composition comprising:
   

   

   (In the formula (1), R _X and R _Y each independently represent hydrogen or an organic group having 1 to 3 carbon atoms.)
2. The resin composition according to claim 1,
   The resin composition whose weight average molecular weights of the said phenol resin are 300-20,000.
3. The resin composition according to claim 1 or 2,
   The resin composition containing the compound which the acid-anhydride site | part with which the repeating unit shown by said Formula (1) is equipped, and the phenolic hydroxyl group with which the said phenol resin is equipped couple | bonded through an ester bond.
4. The resin composition according to any one of claims 1 to 3,
   The polymer is a unit derived from a norbornene monomer represented by the following formula (2), a unit derived from a styrene monomer represented by formula (3), a unit derived from an indene monomer represented by formula (7), and a formula ( A resin composition further comprising at least one unit selected from the group consisting of units derived from a maleimide monomer represented by 8).
   

   

   (In Formula (2), R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or an organic group having 1 to 30 carbon atoms. N is 0, 1 or 2)
   

   

   (In Formula (3), each R _a is independently an organic group having 1 to 30 carbon atoms. M is an integer of 0 or more and 5 or less.)
   

   

   (In formula (7), R ₅ to R ₁₁ are each independently hydrogen or an organic group having 1 to 3 carbon atoms.)
   

   

   (In Formula (8), R ₁₂ is independently hydrogen or an organic group having 1 to 10 carbon atoms.)
5. The resin composition containing the ester compound in which the acid anhydride part of the polymer containing the repeating unit shown by following formula (1), and the phenolic hydroxyl group with which a phenol resin is equipped comprise an ester bond.
   

   

   (In the formula (1), R _X and R _Y each independently represent hydrogen or an organic group having 1 to 3 carbon atoms.)
6. A resin composition according to any one of claims 1 to 5;
   A photosensitizer,
   A photosensitive resin composition comprising:
7. The photosensitive resin composition according to claim 6,
   The photosensitive resin composition whose said photosensitive agent is a diazoquinone compound.
8. A resin film comprising the resin composition according to any one of claims 1 to 5.
9. A resin film comprising the photosensitive resin composition according to claim 6 or 7.
10. An electronic device comprising the resin film according to claim 8 or 9.

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