KR20190101460A - Negative photosensitive resin composition, resin film and electronic device - Google Patents

Abstract

The negative photosensitive resin composition of this invention contains the polymer which is a copolymer, a crosslinking agent, and a photosensitive agent. Here, the copolymer is a norbornene-type structural unit substituted by a functional group containing a terminal unsaturated carbon double bond, a norbornene-type structural unit substituted by a carboxyl group, maleic anhydride, maleic anhydride derivative, maleimide or maleic Structural units derived from the mid derivatives.

Description

Negative photosensitive resin composition, resin film and electronic device

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

In the field of the negative photosensitive resin composition up to now, various techniques are developed for the purpose of high definition of a resist pattern according to the refinement | miniaturization of a pattern. As this kind of technique, the technique of patent document 1 is mentioned, for example. According to this document, a radiation sensitive resin composition containing a polymer [A] and an acid generator [B] is described. And since the polymer [A] has a structural unit (I) and a structural unit (II), it is excellent in the line width roughness (LWR) performance and defect suppression which show that the line width nonuniformity is small. It is described (paragraph 0012 of patent document 1).

Here, the structural unit (I) is N- (t-butyloxycarbonylmethyl) maleimide, N- (1-methyl-1-cyclopentyloxycarbonylmethyl) maleimide, or N- (2-ethyl- It is described that it is a structural unit derived from 2-adamantyloxycarbonylmethyl) maleimide. Moreover, it is described that structural unit (II) is a structural unit derived from 2-norbornene.

Patent Document 1: Japanese Patent Application Publication No. 2015-184458

This inventor produced the resin film which consists of a negative photosensitive resin composition, and examined the developability like the heat resistance of the resin film, the durability like solvent resistance, and the residual film rate after image development. As a result, it turned out that the resin film which consists of a radiation sensitive resin composition of patent document 1 has room for further improvement from a durability and developability viewpoint.

Therefore, an object of this invention is to provide the negative photosensitive resin composition which can improve durability and developability in a favorable balance, without impairing alkali developability.

MEANS TO SOLVE THE PROBLEM This inventor examined the structural unit which the polymer which is a copolymer has in order to improve the heat resistance of the resin film which consists of negative photosensitive resin composition, durability, such as solvent resistance, and developability, such as the residual film rate after image development. As a result, the copolymer is a norbornene-type structural unit substituted by a functional group containing a terminal carbon unsaturated double bond, a norbornene-type structural unit substituted by a carboxyl group, maleic anhydride, maleic anhydride derivative, maleimide or maleic By providing the structural unit derived from a medi derivative, it turned out that durability and developability can be improved in a favorable balance, without impairing alkali developability.

As mentioned above, when this inventor included the copolymer containing a specific structural unit, it discovered that the durability and developability of the resin film using the negative photosensitive resin composition can be improved, without impairing alkali developability. The present invention has been completed.

According to the invention,

The polymer which is a copolymer represented by following formula (1),

With a crosslinking agent,

There is provided a negative photosensitive resin composition comprising a photosensitive agent.

(In formula (1),

l and m represent the molar content in the polymer,

l + m = 1,

A is a structural unit represented by the following formula (A1),

It includes the structural unit represented by the following formula (A2),

B contains at least 1 or more of the structural units represented by following formula (B1), following formula (B2), following formula (B3), following formula (B4), following formula (B5), or following formula (B6). .)

(In formula (A1), R <_1> , R <_2> , R <_3> and R <_4> are respectively independently hydrogen or the C1-C30 organic group, At least 1 terminal unsaturation to R <_1> , R <_2> , R <_3> and R <_4> . Carbon double bonds, where n is 0, 1 or 2.

(In formula (A2), R <_5> , R <_6> and R <_7> are respectively independently hydrogen or an organic group of 1-30 carbon atoms, n is 0, 1, or 2.

(In formula (B1), R <_8> is a C1-C30 organic group independently.)

(In formula (B2), R <_9> and R <_10> is a C1-C30 organic group each independently.)

(In formula (B6), R <_11> is a C1-C30 organic group independently.)

Moreover, according to this invention, the resin film which consists of said negative photosensitive resin composition is provided.

Moreover, according to this invention, the electronic device provided with the said resin film is provided.

According to this invention, the negative photosensitive resin composition which can improve the durability of a resin film which consists of a negative photosensitive resin composition, and developability is not impaired alkali developability.

The above-mentioned objects and other objects, features, and advantages are further clarified by the following preferred embodiments and the accompanying drawings.
1 is a cross-sectional view showing an example of an electronic device according to the present embodiment.

EMBODIMENT OF THE INVENTION Hereinafter, this embodiment is described suitably using drawing. In all the drawings, the same components are denoted by the same reference numerals, and description thereof is omitted. In addition, in this embodiment, A-B intends A or more and B or less.

The outline | summary of the negative photosensitive resin composition of this embodiment is demonstrated.

The negative photosensitive resin composition of this embodiment is

The polymer which is a copolymer represented by following formula (1),

With a crosslinking agent,

Contains a photosensitizer.

(In formula (1),

l and m represent the molar content in the polymer,

l + m = 1,

A is a structural unit represented by the following formula (A1),

It includes the structural unit represented by the following formula (A2),

B contains at least 1 or more of the structural units represented by following formula (B1), following formula (B2), following formula (B3), following formula (B4), following formula (B5), or following formula (B6). .)

(In formula (A1), R <_1> , R <_2> , R <_3> and R <_4> are respectively independently hydrogen or the C1-C30 organic group, At least 1 terminal unsaturation to R <_1> , R <_2> , R <_3> and R <_4> . Carbon double bonds, where n is 0, 1 or 2.

(In formula (A2), R <_5> , R <_6> and R <_7> are respectively independently hydrogen or an organic group of 1-30 carbon atoms, n is 0, 1, or 2.

(In formula (B1), R <_8> is a C1-C30 organic group independently.)

(In formula (B2), R <_9> and R <_10> is a C1-C30 organic group each independently.)

(In formula (B6), R <_11> is a C1-C30 organic group independently.)

According to this embodiment, the copolymer is a norbornene-type structural unit substituted by a functional group containing a terminal unsaturated carbon double bond, a norbornene-type structural unit substituted by a carboxyl group, maleic anhydride, maleic anhydride derivative, and maleic acid. Structural units derived from mid or maleimide derivatives.

The negative photosensitive resin composition which concerns on this embodiment hardens | cures by the photosensitive agent generate | occur | producing a radical by exposure, and a radical chain reaction occurring. In the negative photosensitive resin composition which concerns on this embodiment, it is thought that the terminal unsaturated carbon double bond of the norbornene side chain of a copolymer contributes to a radical chain reaction. Thereby, although the detailed mechanism is not certain, compared with the conventional negative photosensitive resin composition, the negative photosensitive resin composition which concerns on this embodiment can improve the crosslinking density of the crosslinked structure formed by radical chain reaction, It is speculated that the mobility of the molecular chain can be more limited. Therefore, the durability, such as heat resistance of the cured film of a negative photosensitive resin composition, solvent resistance, and developability, such as the residual film rate after image development, can be improved.

Moreover, the negative photosensitive resin composition which concerns on this embodiment exposes and hardens | cures a part as mentioned above, for example, but does not harden | cure a part without exposing. And the unexposed part which is not hardened can be removed by alkaline solution, and it can use for a desired use.

In the copolymer according to the present embodiment, the norbornene-type structural unit substituted by a functional group containing a terminal unsaturated carbon double bond is formed by replacing a part of the norbornene-type structural unit substituted by a carboxyl group. And the norbornene-type structural unit substituted by some carboxyl group remains in a copolymer as it is. Thereby, the copolymer which concerns on this embodiment contains the norbornene-type structural unit provided with a carboxyl group. Thereby, alkali solubility can be improved when removing an unexposed part.

In addition, the copolymer can suitably control alkali solubility by including the structural unit derived from maleic anhydride, maleic anhydride derivative, maleimide, or maleimide derivative.

In the conventional negative photosensitive resin composition, when improving the durability and developability of the cured film of a negative photosensitive resin composition, there existed a problem that alkali solubility falls only by setting it as the structure which is easy to crosslink easily. However, the negative photosensitive resin composition which concerns on this embodiment is a norbornene-type structural unit by which the copolymer was substituted by the functional group containing a terminal unsaturated carbon double bond, the norbornene-type structural unit substituted by the carboxyl group, and anhydrous. By including the structural unit derived from a maleic acid, a maleic anhydride derivative, a maleimide, or a maleimide derivative, the durability and developability of a cured film can be improved, without reducing alkali solubility.

As mentioned above, the negative photosensitive resin composition which concerns on this embodiment can improve the durability and developability of the resin film which consists of a negative photosensitive resin composition, without impairing alkali developability.

Hereinafter, each component of the negative photosensitive resin composition of this embodiment is demonstrated.

The negative photosensitive resin composition which concerns on this embodiment contains a polymer, a crosslinking agent, and a photosensitive agent.

(Polymer)

First, the polymer which concerns on this embodiment is demonstrated.

The polymer which concerns on this embodiment is a copolymer represented by following formula (1). In addition, following formula (1) does not limit the arrangement | positioning of a copolymer. As an arrangement of a copolymer, a random copolymer, an alternating copolymer, a block copolymer, a periodic copolymer, etc. can be selected, for example.

(In formula (1),

l and m represent the molar content in the polymer,

l + m = 1,

A is a structural unit represented by the following formula (A1),

It includes the structural unit represented by the following formula (A2),

B contains at least 1 or more of the structural units represented by following formula (B1), following formula (B2), following formula (B3), following formula (B4), following formula (B5), or following formula (B6). .)

The composition ratio of the structural unit of said A and the structural unit of said B in a copolymer is demonstrated. When the molar content (mol%) of the structural unit of A is l, the molar content (mol%) of the structural unit of B is m, and l + m = 1, the numerical range of l is 0.1≤ l≤0.9. Moreover, the numerical range of m is 0.1 <= m <= 0.9. Thereby, by fully including the structural unit of A and the structural unit of B, it is possible to realize improvement in heat resistance, improvement in solvent resistance, and improvement in residual film ratio after development.

In the copolymer represented by the formula (1), A is a structural unit derived from a norbornene-type monomer substituted by a functional group containing a terminal unsaturated carbon double bond represented by the following formula (A1), and the following formula: The structural unit derived from the norbornene-type monomer substituted by the carboxyl group represented by (A2) is included.

By including the structural unit represented by following formula (A1), a copolymer can improve the heat resistance, solvent resistance, and residual film rate after image development when it is set as a negative photosensitive resin composition.

Moreover, the alkali solubility at the time of making a negative photosensitive resin composition can be adjusted as above-mentioned by including a structural unit represented by a following formula (A2).

(In formula (A1), R <_1> , R <_2> , R <_3> and R <_4> are respectively independently hydrogen or the C1-C30 organic group, At least 1 terminal unsaturation to R <_1> , R <_2> , R <_3> and R <_4> . Carbon double bonds, where n is 0, 1 or 2.

(In formula (A2), R <_5> , R <_6> and R <_7> are respectively independently hydrogen or an organic group of 1-30 carbon atoms, n is 0, 1, or 2.

In the present embodiment, the formula (A1) of the R ₁ ~ R _4, and the formula (A2) of the R ₅ ~ R organic group of hydrogen or 1 to 30 carbon atoms constituting the _7, the structure O, N, One or more atoms selected from S, P and Si may be included.

In addition, in this embodiment, all the organic groups which comprise R <_1> , R <_2> , R <_3> and R <_4> may be made to have no acidic functional group. Thereby, control of the acid value in a polymer can be made easy.

In addition, in this embodiment, R <_1> -R <_{4> in} said Formula (A1) and R <_5> -R <_7> in said Formula (A2) are respectively independently hydrogen or a C1-C30 organic group, respectively. It is preferable that they are independently hydrogen or a C1-C10 organic group, It is more preferable that they are each independently hydrogen or a C1-C5 organic group, It is more preferable that they are each independently hydrogen or a C1-C3 organic group.

In the present embodiment, the formula (A1) of the R ₁ ~ R _4, and as the organic group constituting R ₅ ~ R ₇ in the formula (A2), for example, alkyl group, alkenyl group, alkynyl group, alkyl A lidene group, an aryl group, an aralkyl group, an alkaryl group, a cycloalkyl group, and a heterocyclic group.

As the alkyl group, for example, 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 , Octyl group, nonyl group, and decyl group. As an alkenyl group, an allyl group, a pentenyl group, and a vinyl group are mentioned, for example. As an alkynyl group, an ethynyl group is mentioned. As an alkylidene group, a methylidene group and an ethylidene group are mentioned, for example. As an aryl group, a tolyl group, a xylyl group, a phenyl group, a naphthyl group, and anthracenyl group is mentioned, for example. As an aralkyl group, a benzyl group and a phenethyl group are mentioned, for example. As a cycloalkyl group, an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group are mentioned, for example. As a heterocyclic group, an epoxy group and an oxetanyl group are mentioned, for example.

In this embodiment, in said Formula (A1), R <_1> , R <_2> , R <_3> and R <_4> contain at least 1 terminal unsaturated carbon double bond. Thereby, in the negative photosensitive resin composition, the structural unit which radicalizes at the time of exposure and contributes to a crosslinked structure can be increased. In addition, although the detailed mechanism is not certain, since the side chain of a norbornene-type structural unit contributes to a crosslinked structure, the movement | movement of a polymer chain can be firmly restricted. Thereby, the heat resistance, solvent resistance, and residual film rate after image development of a negative photosensitive resin composition can be improved with a favorable balance.

In addition, in this embodiment, it does not specifically limit that R <_1> , R <_2> , R <_3> and R <_4> contain 2 or more terminal unsaturated carbon double bond. R ₁ ~ R ₄ wherein it comprises a terminal unsaturated carbon-carbon double bond is preferably at least one of R ₁ ~ R _4. Thereby, functional groups containing terminal unsaturated carbon double bonds do not become steric hindrance, and are preferable at the point which can form an appropriate crosslinked structure.

In said Formula (A1) and Formula (A2), n is 0, 1 or 2 each independently, n is 0 or 1, n is 0.

Since R <_1> , R <_2> , R <_3> and R <_4> contain a terminal unsaturated carbon double bond, it is preferable to include the structure represented by following formula (E1). It is more preferable to include the structure represented by a following formula (E2) among the structures represented by Formula (E1). Thereby, a suitable crosslinked structure can be formed. Therefore, the heat resistance, solvent resistance, and residual film rate after image development of a negative photosensitive resin composition can be improved with a favorable balance.

(In formula (E1), R _e is independently hydrogen or an organic group having 1 to 10 carbon atoms.)

(In formula (E2), R _e is independently hydrogen or an organic group having 1 to 10 carbon atoms.)

In the formulas (E1) and (E2), R _e is independently hydrogen or an organic group having 1 to 10 carbon atoms, preferably hydrogen or an organic group having 1 to 7 carbon atoms, and hydrogen or an organic group having 1 to 5 carbon atoms. It is more preferable that it is a group, It is still more preferable that it is hydrogen or a C1-C3 organic group, It is especially preferable that it is hydrogen or a C1-C organic group.

As a specific example of R <_1> , R <_2> , R <_3> and R <_4> containing a terminal unsaturated carbon double bond, a vinyl group, vinylidene group, an acryl group, a methacryl group, an acrylate group, a methacrylate group, etc. are mentioned. . Among these, it is preferable that R <_1> , R <_2> , R <_3> and R <_4> containing a terminal unsaturated carbon double bond are 1 or more types chosen from the group which consists of an acryl group, a methacryl group, an acrylate group, and a methacrylate group, It is more preferable that it is an acrylate group or a methacrylate group.

It is preferable that it is 0.1 mol or more with respect to 1 mol of structural units represented by said Formula (A2), and, as for the minimum of content of the structural unit represented by said Formula (A1) in a copolymer, it is more preferable that it is 0.2 mol or more. . Thereby, a suitable crosslinked structure can be formed.

Moreover, it is preferable that the upper limit of content of the structural unit represented by said Formula (A1) in a copolymer is 3.0 mol or less with respect to 1 mol of structural units represented by said Formula (A2), and it is further 2.0 mol or less. It is preferable, it is more preferable that it is 1.0 mol or less, and it is especially preferable that it is 0.7 mol or less. Thereby, alkali solubility can be expressed suitably.

In addition, in this embodiment, content of the structural unit represented by said Formula (A1) with respect to 1 mol of structural units represented by said Formula (A1) in a polymer is a nuclear magnetic resonance apparatus (for example, It can evaluate by <^1> H-NMR measurement using Nippon Denshi Corporation.

Moreover, in the copolymer represented by said Formula (1), B is a following formula (B1), following formula (B2), following formula (B3), following formula (B4), following formula (B5), or following formula At least one or more of the structural units represented by (B6) is included.

Among these, it is preferable to include the structural unit represented by following formula (B5) or following formula (B6). Thereby, alkali solubility can be improved and developability can be improved.

Moreover, it is more preferable to include following formula (B6) also among following formula (B5) or following formula (B6). Thereby, alkali solubility at the time of setting it as negative photosensitive resin composition can be adjusted, and heat resistance can be improved.

(In formula (B1), R <_8> is a C1-C30 organic group independently.)

(In formula (B2), R <_9> and R <_10> is a C1-C30 organic group each independently.)

(In formula (B6), R <_11> is a C1-C30 organic group independently.)

In this embodiment, it is preferable that B further includes the structural unit represented by said formula (B5) in addition to the structural unit represented by said formula (B6). By including together the structural unit represented by said Formula (B6) and said Formula (B5), when it is set as negative photosensitive resin composition, alkali solubility can be improved and a sensitivity can be improved. Thereby, when it is set as a negative photosensitive resin composition, in addition to the improvement of heat resistance, solvent resistance, and the residual film rate after image development, maintaining excellent sensitivity can be compatible.

In this embodiment, the C1-C30 organic group which comprises R <_8> -R <_11> in said Formula (B1), Formula (B2), and Formula (B6) is O, N, S, P, and Si in the structure. One or more atoms selected from may be included.

In addition, in this embodiment, all the organic groups which comprise R <_8> -R <_11> do not have an acidic functional group. Thereby, control of the acid value in a polymer can be made easy.

Moreover, in this embodiment, R <_8> -R <_11> in said Formula (B1), Formula (B2), and Formula (B6) is a C1-C30 organic group each independently, and is each independently C1-C It is preferable that it is a 10 organic group, It is more preferable that it is a C1-C5 organic group each independently, It is still more preferable that it is a C1-C3 organic group each independently.

In this embodiment, the above formula (B1), formula (B2) and the equation (B6) As the organic group constituting of R ₈ ~ R _11, the formula R ₁ ~ R _4, and the formula of (A1) ( The same organic group as the organic group which comprises R <_5> -R <_7> in A2) can be used.

The upper limit of Mw (weight average molecular weight) of the polymer which concerns on this embodiment is 30000 or less, for example, it is preferable to set it as 20000 or less, It is more preferable to set it to 14000 or less, It is more preferable to set it to 10000 or less. . As a result, the mobility of the molecular chain is improved, whereby a more appropriate crosslinked structure can be made.

Moreover, the lower limit of polymer Mw is 1500 or more, for example, it is preferable to set it as 2000 or more, and it is more preferable to set it as 3000 or more. Thereby, when exposing a negative photosensitive resin composition, it becomes possible to form a crosslinked structure quickly. Therefore, the sensitivity of the negative photosensitive resin composition can be improved.

Moreover, the upper limit of the dispersion degree of the polymer concerning this embodiment, ie, Mw (weight average molecular weight) / Mn (number average molecular weight) is 2.5 or less, for example, it is preferable to set it to 2.2 or less, and to set it to 2.0 or less. More preferred. Thereby, the width | variety of the molecular weight distribution of a polymer can be narrowed and the same crosslinked structure can be formed in the whole negative photosensitive resin composition. Therefore, physical properties can be made uniform in the whole hardened | cured material of a negative photosensitive resin composition.

In addition, the lower limit of Mw / Mn may be 1.0 or more, for example, and may be 1.5 or more. Further, Mw / Mn is closer to monodispersion.

In addition, Mw / Mn is a dispersion degree which shows the width | variety of molecular weight distribution. By making Mw / Mn of a polymer into the said range, the shape of the resin film which consists of a resin composition containing a polymer can be made favorable. This effect is particularly remarkable when the low molecular weight component of the polymer is simultaneously reduced as described above.

In addition, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw / Mn) use the polystyrene conversion value calculated | required from the analytical curve of the standard polystyrene (PS) obtained by GPC measurement, for example. Measurement conditions are as follows, for example.

Tosoh gel permeation chromatography apparatus HLC-8320GPC

Column: TSK-GEL Supermultipore HZ-M manufactured by Tosoh Corporation

Detector: RI detector for liquid chromatogram

Measuring temperature: 40 ℃

Solvent: THF

Sample concentration: 2.0 mg / milliliter

The alkali dissolution rate of the polymer in this embodiment is 500 kPa / sec or more and 20,000 kPa / sec or less, for example. The alkali dissolution rate of the polymer is, for example, by dissolving the polymer in propylene glycol monomethyl ether acetate and applying a polymer solution adjusted to a solid content of 20% by weight on a silicon wafer by spin method, and at 110 ° C. The polymer film obtained by soft-baking for 100 seconds is impregnated in 2.38% of tetramethylammonium hydroxide aqueous solution at 23 degreeC, and is computed by measuring the time until the said polymer film is visually erased.

By setting the alkali dissolution rate of the polymer to 500 kPa / sec or more, the throughput in the developing step with the alkaline developer can be made good. Moreover, the residual film rate after the image development process by alkaline developing solution can be improved by making the alkali dissolution rate of a polymer into 20,000 kPa / sec or less. For this reason, it becomes possible to suppress the film reduction by a lithography process.

(Method of producing a polymer)

The polymer which concerns on this embodiment is manufactured as follows, for example.

The polymerization process (process S1) which superposes | polymerizes monomer A and monomer B, and superposes copolymer 1, and then substitutes the carboxyl group derived from monomer A of copolymer 1 by the compound which has a terminal unsaturated carbon double bond, At least the substitution process (process S2) which obtains copolymer 2, and the low molecular weight removal process (process S3) which removes a low molecular weight component from copolymer 2 and obtains a polymer.

When the monomer B contains maleic anhydride, after the polymerization step (treatment S1) and before the low molecular weight removal process (treatment S3), a ring-opening step (treatment S'1) which opens a part of the repeating unit derived from maleic anhydride, and then You may also include the washing | cleaning process (process S'2) which removes a residual metal component.

Hereinafter, the detail of each process is demonstrated.

(Polymerization Process (Process S1))

First, a norbornene-type monomer substituted with a carboxyl group and maleic anhydride, maleimide or maleimide derivative are prepared.

In the copolymer represented by the formula (1), the norbornene-type monomer (hereinafter referred to as monomer A) substituted with the carboxyl group is derived from the structural unit represented by A. In addition, one or two or more monomers (hereinafter referred to as monomer B) selected from the group consisting of maleic anhydride, maleimide and maleimide derivatives are derived from the structural unit represented by B.

Monomer A is represented by following formula (2). In following formula (2), R <_5> -R <_7> can be made the same as that of Formula (A2) mentioned above.

(In formula (2), R <_5> , R <_6> and R <_7> is respectively independently hydrogen or an organic group of 1-30 carbon atoms, n is 0, 1, or 2.

As a norbornene-type monomer substituted by the carboxyl group represented by said Formula (2), 5-norbornene-2-carboxylic acid, 5-norbornene-2,3-dicarboxylic acid, tetracyclo dodecene carboxylic acid, etc. are mentioned specifically, Can be.

As a norbornene-type monomer substituted by the carboxyl group, 1 type, or 2 or more types of these can be used. Especially, it is preferable to use 5-norbornene-2-carboxylic acid from a viewpoint of heat resistance improvement.

The monomer B is one or two or more monomers selected from the group consisting of maleic anhydride, maleimide and maleimide derivatives, and preferably one or two or more monomers selected from the group consisting of maleimide and maleimide derivatives. . By using a maleimide derivative, heat resistance, residual film rate after hardening, and solvent resistance can be improved. Moreover, by using a maleimide and a maleimide derivative together, the alkali dissolution rate of a negative photosensitive resin composition can be improved and a sensitivity can also be improved.

As said maleimide derivative, it shows by following formula (3).

(In formula (3), R <_11> is a C1-C30 organic group independently.)

As a maleimide derivative represented by said Formula (3), For example, N-linear alkylmaleimide, such as N-methyl maleimide and N-ethyl maleimide; N-branched alkylmaleimides such as N-isopropylmaleimide; N-cycloalkyl maleimide, such as N-cyclohexyl maleimide; N-aryl maleimide, such as N-phenyl maleimide and N-naphthyl maleimide, etc. are mentioned. Among these, it is preferable to use linear N-alkyl maleimide, branched alkyl maleimide, or N-cycloalkyl maleimide, and it is still more preferable to contain N-cycloalkyl maleimide. As N-cycloalkyl maleimide, it is preferable to use N-cyclohexyl maleimide. Thereby, heat resistance, residual film rate after hardening, and solvent resistance can be improved.

Subsequently, copolymerization 1 is synthesized by addition polymerization of monomer A and monomer B.

Although it does not specifically limit as a method of addition polymerization, In this embodiment, the copolymer 1 is synthesize | combined by radical polymerization.

By addition polymerization, the copolymer 1 which has a structural unit derived from monomer A and a structural unit derived from monomer B can be synthesize | combined.

Here, the structural unit derived from monomer A is shown to following formula (A2).

Moreover, the copolymer 1 which has a structural unit derived from following formula (B3), following formula (B5), and following formula (B6) can be obtained by using maleic anhydride, a maleimide, and a maleimide derivative as monomer B, respectively. have.

(In formula (A2), R <_5> , R <_6> and R <_7> are respectively independently hydrogen or an organic group of 1-30 carbon atoms, n is 0, 1, or 2.

(In formula (B6), R <_11> is a C1-C30 organic group independently.)

It is preferable that the molar ratio of monomer A and monomer B is 0.5: 1-1: 0.5. Especially, it is preferable from a viewpoint of molecular structure control that molar ratio is 1: 1.

The addition polymerization is advanced by dissolving the monomer A, the monomer B, and the polymerization initiator in a solvent, and heating the predetermined time thereafter. Heating temperature is 50-80 degreeC, for example, and a heat time is 10 to 20 hours.

As a polymerization initiator, 1 type, or 2 or more types of azo compound and an organic peroxide can be used.

Examples of the azo compound include azobisisobutyronitrile (AIBN), dimethyl 2,2'-azobis (2-methylpropionate), and 1,1'-azobis (cyclohexanecarbonitrile). (ABCN) is mentioned, Any 1 or more types of these can be used.

In addition, examples of the organic peroxide include hydrogen peroxide, dieteryl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), and methyl ethyl ketone peroxide (MEKP). 1 or more types can be used.

The amount (molar number) of the polymerization initiator is 1% to 10% of the total moles of the norbornene-type monomer substituted by the carboxyl group derived from the structural unit of A and the monomer derived from the structural unit of B. It is preferable. By setting the quantity of a polymerization initiator suitably within the said range, and setting reaction temperature and reaction time suitably, the weight average molecular weight (Mw) of the polymer obtained can be adjusted to 5000-30000.

As a solvent, 1 type, or 2 or more types can be used among diethyl ether, tetrahydrofuran, toluene, etc., for example.

By this polymerization process, copolymer 1 which is a copolymer of monomer A and monomer B can be polymerized. The arrangement of the copolymer 1 is not particularly limited, and any of a random copolymer, an alternating copolymer, a block copolymer, and a periodic copolymer may be used.

Copolymer 1 has a structural unit represented by following formula (4), for example, when using the monomer represented by said Formula (2) as monomer A, and using the monomer represented by said Formula (3) as monomer B. Copolymer is formed.

(In Formula (4), R <_5> -R <_7> is the same as said Formula (A2). Moreover, R <_11> is the same as said Formula (3).)

In the copolymer 1, the functional group of R <_5> -R <_7> derived from monomer A may differ in each repeating unit, and may be common. It is preferable that it is common among these. Thereby, the patterning precision of a negative photosensitive resin composition can be improved.

(Substitution step (S2))

Next, in the obtained copolymer 1, the carboxyl group of the structural unit represented by some said Formula (A2) is substituted by the compound which has a terminal unsaturated carbon double bond, and it is set as copolymer 2.

Although it does not specifically limit about the method of replacing copolymer 1 and synthesize | combining copolymer 2, For example, it can carry out by the following method.

The copolymer 1 and the compound having a terminal unsaturated carbon double bond are dissolved in a solvent and heated for a predetermined time to proceed with a substitution reaction to synthesize copolymer 2. Here, heating temperature is 50-100 degreeC, for example, and heating time is 2 to 20 hours.

Thereby, in the structural unit of A, the copolymer 2 provided with the repeating unit derived from the monomer A, the repeating unit substituted by the compound in which monomer A has a terminal unsaturated carbon double bond, and the structural unit derived from monomer B You can get it.

The structural unit substituted with the compound which monomer A has a terminal unsaturated carbon double bond is shown by following formula (A1).

(In formula (A1), R <_1> , R <_2> , R <_3> and R <_4> are respectively independently hydrogen or the C1-C30 organic group, At least 1 terminal unsaturation to R <_1> , R <_2> , R <_3> and R <_4> . Carbon double bonds, where n is 0, 1 or 2.

As a compound which has the said terminal unsaturated carbon double bond, it is preferable to use an acryl compound.

As an acryl compound, glycidyl methacrylate (glycidyl methacrylate), glycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether, hydroxyethyl methacrylate, etc. are mentioned, for example. have. Among these, it is preferable to use glycidyl methacrylate.

As a solvent, 1 type, or 2 or more types can be used among diethyl ether, tetrahydrofuran, toluene, etc., for example.

In copolymer 2, it is preferable to replace the 5 mol% or more structural unit with the structural unit represented by said Formula (A1) with respect to all the structural units represented by A, for example, and it is more preferable to substitute 10 mol% or more. More preferably at least 15 mol%, even more preferably at least 20 mol%. By setting a substitution rate in this way, the terminal unsaturated carbon double bond derived from a norbornene unit can be bridge | crosslinked suitably. Thereby, heat resistance, residual film ratio, and solvent resistance of the negative photosensitive resin composition containing copolymer 2 can be improved.

Here, the thing which substituted a part of repeating units among the repeating units derived from the norbornene-type monomer substituted by the carboxyl group can be identified by the spectral data of a ¹ H-NMR measurement.

In addition, the substitution rate which substituted the carboxyl group by the acryl compound can be measured as follows.

About the polymer solution of copolymer 2, ¹ H-NMR measurement is carried out. ^With respect to the spectral data obtained by ¹ H-NMR measurement, the signal integral value X per unit proton derived from the carboxyl group and the signal integral value Y per unit proton derived from the terminal unsaturated carbon double bond formed by the added acrylic compound To calculate. The substitution rate can be calculated by the following formula using the said signal integral value.

Substitution rate (%) = Y / (X + Y) × 100

(Low Molecular Weight Removal Process (S3))

Next, after copolymerizing and the said organic layer containing low molecular weight components, such as a residual monomer and an oligomer, it concentrates, and it dissolves again in organic solvents, such as THF. And hexane and methanol are added to this solution, and the polymer containing copolymer 2 is coagulated and precipitated. Here, as a low molecular weight component, a residual monomer, an oligomer, and also a polymerization initiator etc. are contained. Subsequently, filtration is carried out and the coagulated product is dried. Thereby, the polymer which has copolymer 2 in which the low molecular weight component was removed as a main component (main product) can be obtained.

In this embodiment, in the said low molecular weight component removal process (process S3), it is preferable to repeat an extraction operation until the low-nuclide content rate of the molecular weight 1000 or less in copolymer 2 becomes 1% or less. Thereby, the quantity of the low molecular weight component in a 1st polymer can be reduced to a sufficient degree in order to suppress the pattern deformation of the film | membrane at the time of hardening.

In addition, when monomer B contains maleic anhydride, you may perform a ring-opening process (S'1) and a washing process (S'2) after the said polymerization process (S1) and before the said low molecular weight component removal process (S3). It demonstrates below.

(Opening process (S'1))

In the maleic anhydride of the obtained copolymer 1 or copolymer 2, the remaining repeating unit is ring-opened while leaving some repeating units closed. Thereby, the quantity of the carboxyl group in copolymer 1 can be adjusted. That is, control of the acid value in the polymer manufactured is attained.

In this embodiment, in the repeating unit derived from maleic anhydride of copolymer 1 or copolymer 2, it does not ring-open 50% or more repeating units, for example, ring-opens the cyclic structure (anhydrous ring) of the said remaining repeating units. . That is, the ring-opening ratio of copolymer 1 is less than 50%, for example. Especially, it is preferable not to ring-open 60% or more and 90% or less of repeating units of the total number of the repeating units of the cyclic structure derived from maleic anhydride of copolymer 1.

Here, the ring-opening ratio of the repeating unit derived from maleic anhydride can be measured as follows.

IR absorption intensity (A1) of (C = O) in the acid anhydride structure of the copolymer 1 or copolymer 2 before ring-opening was measured, and IR absorption intensity of (C = O) in the acid anhydride structure after ring opening ( The ring-opening ratio is computed from the following formula from A2).

Ring opening rate (%) = ((A1-A2) / A1) * 100

In addition, acetonitrile is used as an internal standard.

Specifically,

(A) metal alkoxides as bases

(B) Alkali metal hydroxides as alcohols and bases

In the polymerization step, any one of them is added to the reaction solution in which the copolymer 1 is polymerized, and an organic solvent such as methyl ethyl ketone (MEK) is further added, and at 1 to 5 hours at 40 to 50 ° C. Stirring obtains reaction liquid L1. In reaction liquid L1, the anhydrous ring of a part of the repeating unit derived from maleic anhydride of copolymer 1 ring-opens, and the terminal part of the terminal formed by ring-opening is esterified. In addition, the remaining terminal is not esterified and becomes a metal salt structure.

In this embodiment, it is preferable that the number-of-moles of the hydroxide of a metal alkoxide or an alkali metal shall be 50% or less of the number-of-moles of maleic anhydride used at the superposition | polymerization process. Especially, the number-of-moles of the hydroxide of a metal alkoxide or an alkali metal are preferably 40% or less, 10% or more of the number-of-moles of maleic anhydride used at the superposition | polymerization process, Furthermore, it is preferable to set it as 30% or less. By doing in this way, the quantity of metal alkoxide or hydroxide of an alkali metal can be reduced, and the alkali metal concentration in the polymer finally obtained can be reduced.

By reducing the alkali metal concentration in the polymer, when a device using this polymer is formed, migration of metal ions can be suppressed.

Examples of the aforementioned metal alkoxides, this will appear as M (OR ₈₎ (M is a monovalent metal, R ₈ is an organic group having a carbon number being 1 to 18) are preferred. Alkali metal is mentioned as metal M, Especially, sodium is preferable from a viewpoint of handleability. As R <_8> , the same thing as R <_8> in said Formula (B1) is mentioned, for example.

In addition, as a metal alkoxide, you may use 2 or more types of different things. However, it is preferable to use 1 type of metal alkoxide from a viewpoint of manufacture stability.

In addition, as above-mentioned, you may ring-open the structure derived from maleic anhydride of copolymer 1 or copolymer 2 in presence of the (B) alcohol and the hydroxide of an alkali metal as a base.

As hydroxide of an alkali metal, sodium hydroxide is preferable from a viewpoint of handleability.

As the alcohol, it is preferred monovalent alcohol (R ₈ OH). R _{8 which} is an organic group can use the above-mentioned thing. In addition, R ₈ is preferably 30 or less carbon atoms.

The repeating unit derived from maleic anhydride ring-opened at this ring-opening process (process S'1) turns into a structure represented by following formula (6), and becomes a structure which has a salt part of a carboxyl group.

In addition, when the copolymer is ring-opened with (A) a metal alkoxide as a base, or (B) an alcohol and a hydroxide of an alkali metal as a base, a structure is formed slightly but represented by the following formula (8) and the following formula (B2). There is. In addition, in following formula (B2), R <_9> , R <_10> may be the same as said R <_8> .

Subsequently, by adding an acidic aqueous solution such as hydrochloric acid or formic acid to the reaction solution L1, the copolymer 1 or copolymer 2 is acid treated to replace the metal ions (Na +) with protons (H +).

The structural units represented by the formulas (6) and (8) are each structural units represented by the following (B1) and (B4) by proton substitution.

In this ring-opening process (process S'1), it is preferable not to ring-open 50% or more of repeating units derived from maleic anhydride of copolymer 1 or copolymer 2. In the copolymer 2, as mentioned above, although a metal (for example, Na) is couple | bonded with one terminal formed by the ring opening of anhydrous maleic ring, it is contained in the polymer which is a product which does not ring-open 50% or more of repeating units. The amount of metal that can be reduced can be reduced. Thereby, the quantity of the alkali metal in the polymer finally obtained by this embodiment can be reduced, and the desired characteristic can be exhibited in the negative photosensitive resin composition using this polymer.

(Cleaning process (process S'2))

When the ring-opening step (treatment S'1) is performed, the solution containing copolymer 1 or copolymer 2 after ring-opening obtained by the step is washed with a mixture of water and an organic solvent (for example, methyl ethyl ketone). , Remove residual metal components. The copolymer 1 or copolymer 2, the residual monomer, and the oligomer after ring opening move to an organic layer. Thereafter, the aqueous layer is removed (first washing).

Then, the mixture of water and an organic solvent (for example, methyl ethyl ketone) is added to the organic layer again, and it wash | cleans (2nd washing).

In this embodiment, the above washing process (process S'2) is repeated 5 times or more, for example, 10 times more preferably. Moreover, by adjusting the addition amount of water and an organic solvent used for a washing | cleaning process, it is preferable to remove 85% or more of remaining sodium by one washing process, and it is more preferable to remove 90% or more. Thereby, the density | concentration of the alkali metal in the copolymer 1 or copolymer 2 after ring-opening can fully be reduced.

Moreover, it is preferable to repeat a washing process (process S3) so that alkali metal concentration in the copolymer 1 or copolymer 2 after ring-opening may be 10 ppm or less, Preferably it is 5 ppm or less.

In this embodiment, the negative photosensitive resin composition can contain the said polymer, a photosensitive agent, and a crosslinking agent. Moreover, a solvent and additives, such as an adhesion improving agent and surfactant, can be included.

The upper limit of content of a polymer in this embodiment is 80 mass parts or less with respect to 100 mass parts of total solids of a negative photosensitive resin composition, It is preferable that it is 75 mass parts or less, It is more preferable that it is 70 mass parts or less. .

Moreover, the lower limit of content of a polymer is 5 mass parts or more with respect to 100 mass parts of total solids of a negative photosensitive resin composition, It is preferable that it is 10 mass parts or more, It is more preferable that it is 20 mass parts or less.

When content of a polymer exists in the range of the said upper limit and the minimum, it becomes possible to form a suitable crosslinked structure by exposing the negative photosensitive resin composition.

(Photosensitive agent)

In this embodiment, an optical radical polymerization initiator can be used for a photosensitive agent.

As an optical radical polymerization initiator, an alkyl phenone type initiator, an oxime ester type initiator, an acyl phosphine oxide type initiator, etc. are mentioned specifically ,. As an optical radical polymerization initiator, it can use 1 type or in combination of 2 or more types in the said specific example. Among these, it is preferable to use the oxime ester type radical photopolymerization initiator. Thereby, a photosensitive agent can be radicalized by low exposure amount, and a sensitivity can be raised.

As a specific radical photopolymerization initiator, for example, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1 [4- (methylcy O) phenyl] -2-morpholinopropane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 1,2-octane ion, 1- [4- (Phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- ( O-acetyl oxime) etc. are mentioned. Among these, you may use 1 type, or 2 or more types.

1 mass part or more may be sufficient with respect to 100 mass parts of polymers, and, as for the upper limit of content of the photosensitive agent in this embodiment, it is preferable that it is 1.5 mass parts or more, and it is more preferable that it is 2 mass parts or more. Thereby, in the negative photosensitive resin composition, the reaction speed by exposure can be improved. Therefore, the sensitivity can be improved.

The lower limit of the content of the photosensitive agent is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less. Thereby, in the negative photosensitive resin composition, appropriate reactivity can be expressed with respect to a polymer.

(Bridge)

In this embodiment, a well-known crosslinking agent can be used as a crosslinking agent. As a crosslinking agent, it is preferable to use the acrylic crosslinking agent containing a (meth) acryl group, for example. An acrylic crosslinking agent is a polyfunctional acrylic compound, for example. Here, a polyfunctional acrylic compound is a compound which has two or more (meth) acryl groups.

In addition, in this embodiment, a (meth) acryl group represents an acryl group or methacryl group, ie, methacryl group. In addition, an acryl group contains an acrylate group. In addition, a methacryl group contains a methacrylate group, ie, a methacrylate group.

Here, as a combination of the crosslinking agent and the terminal unsaturated carbon double bond of a copolymer, a crosslinking agent is an acryl-type crosslinking agent, and the functional group provided with the terminal unsaturated carbon double bond of a copolymer is the said General formula (E1) or general formula ( It is preferable to include the structure represented by E2). Thereby, the reactivity of the radical chain reaction of a crosslinking agent and a copolymer can be maintained to the same extent. Therefore, an appropriate crosslinked structure can be formed.

Specific polyfunctional acrylic compounds include trifunctional (meth) acrylates such as trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and ditry 6 functional (meth) acrylates, such as tetrafunctional (meth) acrylates, such as methylol propane tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate, are mentioned. Among these, you may use 1 type, or 2 or more types.

In addition, in this embodiment, a (meth) acrylate group represents an acrylate group or a methacrylate group.

20 mass parts or more may be sufficient with respect to 100 mass parts of polymers, as for the minimum of content of a crosslinking agent in this embodiment, it is preferable that it is 25 mass parts or more, and it is more preferable to set it as 30 weight part or more. Thereby, a crosslinked structure can be formed in addition to the crosslinked structure derived from the terminal unsaturated carbon double bond of a norbornene-type structural unit. Therefore, improvement of heat resistance, solvent resistance, and improvement of the residual film ratio after image development can be implement | achieved.

Moreover, as for the upper limit of content of a crosslinking agent, 80 mass parts or less may be sufficient with respect to 100 mass parts of polymers, It is preferable that it is 75 mass parts or less, It is more preferable that it is 70 mass parts or less. Thereby, excessive contribution of a crosslinking agent to a crosslinked structure can be prevented, and the motility of a norbornene-type structural unit can be suppressed suitably. Therefore, improvement of heat resistance, solvent resistance, and improvement of the residual film ratio after image development can be implement | achieved.

(menstruum)

The negative photosensitive resin composition of this embodiment can be used as a varnish by melt | dissolving each component mentioned above in a solvent.

Examples of such a solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, and diethylene glycol Cold diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate , Lactic acid butyl, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate and methyl-3-methoxypropionate, and the like. Can be mentioned.

From the viewpoint of significantly suppressing cracking of the resin film, among these compounds, γ-butyrolactone, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and die It is a preferred embodiment to use a compound selected from the group consisting of ethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate. .

(Other additives)

In this embodiment, the negative photosensitive resin composition may contain additives, such as an adhesion improving agent, surfactant, antioxidant, a filler, a sensitizer, a silane coupling agent, and a terminal sealing agent, as needed.

The resin film which concerns on this embodiment consists of hardened | cured material of negative photosensitive resin composition.

The resin film of this embodiment consists of said negative photosensitive resin composition, and can be comprised by these dry films or cured films.

The negative photosensitive resin composition of this embodiment is used in order to form resin films, such as a resist and a permanent film. Such a use is suitable from a heat resistant viewpoint.

Moreover, the said resist is comprised from the resin film obtained by apply | coating a negative photosensitive resin composition by methods, such as a spin coat, a roll coat, a flow coat, a dip coat, a spray coat, a doctor coat, etc., for example, and removing a solvent.

The said permanent film is comprised with the cured film obtained by performing exposure and image development with respect to said resin film, patterning it in a desired shape, and hardening by heat processing etc. The permanent film can be used, for example, a protective film, an interlayer film, a dam material or the like.

The said resin film is used for the electronic device which concerns on this embodiment.

The electronic device 100 of the present embodiment can be provided with the above resin film.

The electronic device 100 shown in FIG. 1 is a semiconductor chip, for example. In this case, for example, the semiconductor package is 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 semiconductor elements such as a transistor and a multilayer wiring layer provided on the semiconductor substrate (not shown). The interlayer insulating film 30 and the uppermost wiring 34 provided on the interlayer insulating film 30 are provided in the uppermost layer of a multilayer wiring layer. The uppermost wiring 34 is made of aluminum (Al), for example. The passivation film 32 is provided on the interlayer insulating film 30 and the uppermost wiring 34. A part of the passivation film 32 is provided with an opening through which the uppermost wiring 34 is exposed.

On the passivation film 32, the redistribution layer 40 is provided. The redistribution layer 40 includes the insulating layer 42 provided on the passivation film 32, the redistribution 46 provided on the insulating layer 42, the insulating layer 42, and the redistribution 46. It has the insulating layer 44 provided in it. In the insulating layer 42, an opening connected to the uppermost wiring 34 is formed. The redistribution 46 is formed in the opening provided in the insulating layer 42 and the insulating layer 42, and is connected to the uppermost wiring 34. As shown in FIG. The insulating layer 44 is provided with an opening connected to the rewiring 46.

In this embodiment, one or more of the passivation film 32, the insulating layer 42, and the insulating layer 44 can be comprised by the resin film formed by hardening | curing the negative photosensitive resin composition mentioned above, for example. have. In this case, for example, the passivation film 32, the insulating layer 42, or the insulation is patterned by exposing ultraviolet rays to a coating film formed of a negative photosensitive resin material and performing development, followed by heat curing. Layer 44 is formed.

In the opening provided in the insulating layer 44, the bump 52 is formed through the under bump metallurgy (UBM) layer 50, for example. The electronic device 100 is connected to a wiring board or the like through the bump 52, for example.

In addition, this invention is not limited to embodiment mentioned above, The deformation | transformation, improvement, etc. in the range which can achieve the objective of this invention are included in this invention.

Example

Next, the Example of this invention is described.

First, about each material used by the Example, preparation was performed as shown below.

Synthesis Example 1

A polymer which is a copolymer by introducing 5-norbornene-2-carboxylic acid and N-cyclohexylmaleimide and using a mol ratio of 50/50 to prepare a copolymer, and adding glycidyl methacrylate to the copolymer Was synthesize | combined and it was set as the synthesis example 1. The details will be described below.

5-norbornene-2-carboxylic acid (NC, manufactured by Honshu Chemical Co., Ltd., 87.7 g, 0.630 mol) and dimethyl 2,2'-azobis in a reaction vessel of a suitable size equipped with a stirrer and a cooling tube. (2-Methyl propionate) (V-601, manufactured by Wako Junyaku Kogyo Co., Ltd., 14.5 g, 63 mmol) was weighed and dissolved in methyl ethyl ketone (MEK, 58.0 g) to prepare a solution. Nitrogen was passed through the solution for 10 minutes to remove oxygen, and then the mixture was reacted at 70 ° C for 6 hours while stirring. In the reaction of 6 hours, a mixed liquid of N-cyclohexylmaleimide (CMI, manufactured by Nihon Shokubai Co., Ltd., 112.9 g, 0.630 mol) and MEK 127.5 g was continuously added to the reaction vessel for 6 hours. After the addition of the mixed solution of CMI was completed, the mixture was further reacted at 70 ° C for 3 hours. MEK 266.7g was added to the reaction mixture to dilute it, and then a large amount of methanol / water mixture (8/2 by weight) was added dropwise to precipitate a solid. The solid collected by filtration was dried for 16 hours at 50 degreeC by the vacuum dryer, and the polymer which is a copolymer of 5-norbornene-2-carboxylic acid and N-cyclohexyl maleimide was obtained. The yield was 128.1 g, Mw was 4,700 and Mw / Mn was 1.63.

A polymer (60.0 g), which is a copolymer of the 5-norbornene-2-carboxylic acid and N-cyclohexylmaleimide, was weighed in a reaction vessel of a suitable size equipped with a stirrer and a cooling tube, and PGMEA (140.0 g). Dissolved in. Furthermore, glycidyl methacrylate (GMA, Tokyo Kasei Kogyo Co., 20.7g, 0.146mol) and triethylamine (1.8g) were added, and it heated at 80 degreeC for 5 hours. Formic acid was added to the reaction solution, followed by acid treatment, followed by dropwise addition to a large amount of methanol / water mixture (weight ratio 8/2) to precipitate the polymer of Synthesis Example 1. The solid obtained by filtration was dried at 40 degreeC for 40 hours with the vacuum dryer, and the polymer of the synthesis example 1 was obtained. The yield was 50.5 g, Mw was 5,500 and Mw / Mn was 1.65.

The obtained polymer of Synthesis Example 1 was dissolved in heavy DMSO, and subjected to ¹ H-NMR measurement by a nuclear magnetic resonance apparatus manufactured by Nippon Denshi Corporation. ^{From the} spectrum obtained by <^1> H-NMR measurement, the signal derived from the methacryloyl group of GMA added to δ5.68 and δ6.07 was confirmed, and the signal derived from the carboxyl group in a polymer was confirmed by δ12.13, respectively.

Moreover, it was confirmed from the integral ratio of each signal that mol ratio of a carboxyl group and a methacryloyl group is 1: 0.3.

Thereby, it was confirmed that the carboxyl group in some structural units derived from 5-norbornene-2-carboxylic acid is substituted by glycidyl methacrylate. Therefore, in the synthesis example 1, it was confirmed that the copolymer which has each structural unit represented by following formula (9) is obtained.

Synthesis Example 2

5-norbornene-2-carboxylic acid, maleimide, and N-cyclohexylmaleimide were introduced to prepare a copolymer using a mol ratio of 50/15/35, and glycidyl methacrylate was added to the copolymer. By adding, the polymer which is a copolymer was synthesize | combined and it was set as the synthesis example 2. The details will be described below.

5-norbornene-2-carboxylic acid (NC, manufactured by Honshu Chemical Co., Ltd., 70.8 g, 0.512 mol), N-cyclohexyl maleimide (CMI, Nihon Shokubai Co., Ltd., 14.23 g, 0.079 mol) and dimethyl 2,2'-azobis (2-methylpropionate) (V-601, manufactured by Wako Junyaku Kogyo Co., Ltd., 11.8 g, 51 mmol) ) Was weighed and dissolved in methyl ethyl ketone (MEK, 47.2 g) to prepare a solution. Nitrogen was passed through the solution for 10 minutes to remove oxygen, and then the mixture was reacted at 70 ° C for 6 hours while stirring. During this 6 hour reaction, a mixture of maleimide (14.9 g, 0.154 mol), CMI (50.1 g, 0.279 mol) and MEK 91.0 g was continuously added to the reaction vessel for 6 hours. After the addition of the solution was completed, the solution was further reacted at 70 ° C for 3 hours. After diluting and adding 200 g of MEK to the reaction solution, a solid was precipitated by dropwise adding a large amount of methanol / water mixture (weight ratio 5/5). The solid collected by filtration was dried at 50 degreeC for 64 hours by the vacuum dryer, and the polymer which is a copolymer of 5-norbornene-2-carboxylic acid, maleimide, and N-cyclohexyl maleimide was obtained. The yield was 124.3 g, Mw was 4,500 and Mw / Mn was 1.75.

A polymer (50.0 g) which is a copolymer of the 5-norbornene-2-carboxylic acid, maleimide, and N-cyclohexyl maleimide was weighed in a reaction vessel of a suitable size equipped with a stirrer and a cooling tube, and PGMEA ( 100.0 g). Furthermore, glycidyl methacrylate (GMA, Tokyo Kasei Kogyo Co., 24.3g, 0.171mol) and triethylamine (1.5g) were added, and it heated at 90 degreeC for 4 hours. Formic acid was added to the reaction solution, followed by acid treatment, followed by dropwise addition to a large amount of methanol / water mixture (weight ratio 5/5) to precipitate the polymer of Synthesis Example 2. The solid obtained by filtration was dried at 40 degreeC for 40 hours with the vacuum dryer, and the polymer of the synthesis example 2 was obtained. The yield was 31.2 g, Mw was 4,900 and Mw / Mn was 1.72.

The obtained polymer of Synthesis Example 2 was dissolved in heavy DMSO and subjected to ¹ H-NMR measurement by a nuclear magnetic resonance apparatus manufactured by Nippon Denshi Corporation. In the same manner as in Synthesis example 1, the peak derived from the carboxyl group and the peak derived from the structure of the methacryloyl group were confirmed. Thereby, it was confirmed that the carboxyl group in some structural units derived from 5-norbornene-2-carboxylic acid is substituted by glycidyl methacrylate. Therefore, in the synthesis example 2, it was confirmed that the copolymer which has each structural unit represented by following formula (10) is obtained.

Synthesis Example 3

A copolymer was prepared by introducing 2-norbornene and maleic anhydride and using a molar ratio of 50/50. The structural unit derived from maleic anhydride of the copolymer was ring-opened with sodium acetate to form glycidyl methacrylate. By adding, the polymer which is a copolymer was synthesize | combined and it was set as the synthesis example 3. The details will be described below.

Maleic anhydride (122.4 g, 1.25 mol), 2-norbornene (75 wt% toluene solution, Maruzen Sekiyu Chemical Co., Ltd., 156.8 g) in a reaction vessel of a suitable size equipped with a stirrer and a cooling tube. , 1.25 mol) and dimethyl 2,2'-azobis (2-methylpropionate) (V-601, manufactured by Wako Junyaku Kogyo Co., Ltd., 11.5 g, 50 mmol) were weighed, and methyl ethyl ketone (MEK, 150.8 g) was measured. ) And toluene (38.5 g) to prepare a solution. Nitrogen was vented through this solution for 10 minutes to remove oxygen, and then it heated at 60 degreeC, stirring. After 16 h, MEK (320 g) was added to dilute and cool. The reaction mixture was added dropwise to a large amount of methanol, and a solid was precipitated, filtered using Nutsche, further washed with methanol, and the solid was collected by filtration. The obtained solid was vacuum dried at 70 degreeC, and the copolymer of 2-norbornene and maleic anhydride was obtained. The yield was 208.1 g, the weight average molecular weight (Mw) was 11,100, and the dispersion degree (Mw / Mn) was 2.25.

The copolymer (10.0g) of 2-norbornene mentioned above and maleic anhydride was measured and dissolved in MEK (30.0g) in the reaction container of the appropriate size provided with the stirrer and the cooling tube. Furthermore, 2-hydroxyethyl methacrylate (HEMA, Nippon Shokubai Co., 8.5 g, 65 mmol) and sodium acetate (1.0 g) were added, and it heated at 70 degreeC for 8 hours. To this reaction solution, glycidyl methacrylate (GMA, 1.5 g, 10 mmol) was added, and further stirred at 70 ° C. for 16 hours. Formic acid was added to the reaction solution, followed by acid treatment, followed by dropwise addition to a large amount of pure water to precipitate a polymer. The solid collected by filtration was dried at 40 ° C. for 16 hours in a vacuum dryer to obtain a polymer of Synthesis Example 3. The yield was 11.5 g, Mw was 14,100 and Mw / Mn was 2.30.

In the synthesis example 3, the copolymer which has each structural unit represented by following formula (13) was obtained.

(Acid value)

About each synthesis example, the acid value of the obtained polymer was computed as follows.

About 0.2 g of the synthesized polymer was weighed and dissolved in 50 mL of a solution of THF / methanol = 1/1 (v / v). Potentiometric titration was performed about the obtained solution using the sodium methoxide / methanol solution of concentration 0.1M. In potentiometric titration, the acid value of the polymer was evaluated according to the amount of reagent added up to the inflection point of the potential generated at the electrode.

(Alkali dissolution rate)

About each synthesis example, the alkali dissolution rate of the obtained polymer was measured as follows.

The polymer was dissolved in PGMEA to prepare a solution having a solid concentration of 25%. This polymer solution was applied onto a silicon wafer by spin method, and softbaked at 100 ° C. for 120 seconds to form a polymer film having a thickness H of about 2.0 μm. The silicon wafer on which this polymer film was formed was impregnated with 2.38% of 23 degreeC tetramethylammonium hydroxide aqueous solution, and the time T until the polymer film was visually erased was measured. From H and T, the alkali dissolution rate was calculated from the following formula.

(Alkali dissolution rate) [ms / sec] = (film thickness H) / (time T until the polymer film is erased)

About the polymer of each synthesis example, the evaluation result of an acid value and alkali dissolution rate is shown in the following Table 1.

TABLE 1

(Photosensitive agent)

Photosensitive agent 1: The radical photopolymerization initiator (Irgacure OXE02 by BASF Corporation) represented by following formula (11) was used.

(Bridge)

Crosslinking agent 1: The acrylic crosslinking agent (DPHA made from Daicel Cytec Co., Ltd.) represented by following formula (12) was used.

(Adhesion improver)

Adhesion improver 1: 3-glycidoxypropyl trimethoxysilane (KBM-403 made by Shin-Etsu Chemical Co., Ltd.)

(Surfactants)

Surfactant 1: Megapak F-556 (made by DIC Corporation)

Next, the negative photosensitive resin composition produced by the Example of this invention is demonstrated.

(Adjustment of the negative photosensitive resin composition of Example 1, 2 and Comparative Example 1)

About each Example and each comparative example, in the compounding quantity shown in Table 2, the 20% PGMEA solution of the polymer produced by the synthesis examples 1-3, the photosensitizer, the crosslinking agent, the adhesion improving agent, and surfactant were melt | dissolved in the appropriate amount of PGMEA, and it stirred. . After stirring, it filtered with a 0.2 micrometer filter and prepared the negative resin composition.

In addition, in preparing the negative photosensitive resin composition of each Example and each comparative example, PGMEA adjusted so that content (total of a phenol resin and a polymer) of a resin component might be 30%.

(5% weight loss temperature)

About each Example and each comparative example, 5% weight loss temperature in the temperature increase process after hardening was evaluated using the obtained negative photosensitive resin composition as follows.

First, after apply | coating a negative photosensitive resin composition to a 6-inch wafer, the desolvent was performed by heat-processing on 80 degreeC and 90 second conditions. Subsequently, heat treatment was performed with respect to the negative photosensitive resin composition in oven, and the photosensitive resin composition was hardened. In the heat treatment, the inside of the oven where the wafer is placed is replaced with nitrogen at 30 ° C. for 30 minutes, and the temperature is raised to a curing temperature (200 ° C.) at a temperature increase rate of 5 ° C./min, and then 30 minutes at the curing temperature (200 ° C.). By keeping. After the heat treatment, the temperature in the oven was lowered to 70 ° C or lower at a temperature-fall rate of 5 ° C / min, and the wafer was taken out. Subsequently, the cured film of the photosensitive resin composition was peeled from the said wafer using hydrofluoric acid, and it dried on 60 degreeC and the conditions of 10 hours. Thus, the cured film hardened | cured by the curing temperature of 200 degreeC was obtained about each of each Example and each comparative example.

The 5% weight loss temperature (° C.) of the sample was then measured. The measurement was performed on a sample obtained by weighing 10 mg of the cured film, using a thermogravimetric / differential thermal measurement apparatus (TG / DTA), under conditions of a start temperature of 30 ° C., a measurement temperature range of 30 to 500 ° C., and a temperature increase rate of 5 ° C./min. It was done under. The temperature at the time when the weight of the weighed sample decreased 5% was made into the 5% weight reduction temperature.

(Residual ratio after curing)

About each Example and each comparative example, the residual film rate after hardening was evaluated using the obtained negative photosensitive resin composition as follows.

The resulting negative photosensitive resin composition was spun onto a 4 inch silicon wafer treated with hexamethyldisilazane (HMDS, Hexamethyldisilazane), and baked at 110 ° C. for 100 seconds to obtain a thin film A having a thickness of about 3.0 μm. The thin film A was used with a g + h + i line mask aligner (PLA-501F) manufactured by Canon Corporation with a mask having a width of 1: 1 for a line of 10 μm and a width of 1: 1. A line having a 1: 1 width and a line width by exposing g + h + i rays at an optimum exposure dose of 50: 1 (50mJ / cm ² ) and developing them at 23 ° C. for 90 seconds with a 2.38% by mass aqueous tetramethylammonium hydroxide solution. Thin film B having a & space pattern was obtained.

From the film thicknesses of the thin film A and thin film B obtained by said method, the residual film ratio was computed from the following formula | equation.

Residual film rate (%) after curing = {(film thickness (μm) of thin film B) / (film thickness (μm) of thin film A))} × 100

(Solvent resistance)

About each Example and each comparative example, solvent resistance was evaluated as follows using the obtained negative photosensitive resin composition.

The obtained negative photosensitive resin composition was spin-coated on the 1737 glass substrate made by Corning Corporation of length 100mm and width 100mm, and baked by 110 degreeC and the hotplate for 100 second, and the glass substrate with a thin film of about 3.0 micrometers thickness was obtained.

The glass substrate with the thin film was immersed in N-methylpyrrolidone (Kanto Chemical Co., Ltd.) for 10 minutes at room temperature (25 ° C), followed by pure water rinsing. The film thickness change rate defined by the following formula was calculated.

Film thickness change rate (%) = [{(film thickness after solvent immersion)-(film thickness before solvent immersion)} / (film thickness before solvent immersion)] × 100

(Sensitivity)

About each Example and each comparative example, the sensitivity was evaluated as follows using the obtained negative photosensitive resin composition.

The resulting negative photosensitive resin composition was spun onto a 4-inch silicon wafer treated with hexamethyldisilazane (HMDS, Hexamethyldisilazane), and baked at 90 ° C. for 120 seconds to obtain a thin film having a thickness of about 3.0 μm. The thin film was exposed to light using a g + h + i line mask aligner (PLA-501F) manufactured by Canon Corporation using a mask having a 1: 1 width of a 10 μm line and space. Subsequently, after baking by a 110 degreeC hotplate for 120 second, the resist pattern formed by developing at 23 degreeC and 60 second with 2.38 mass% tetramethylammonium hydroxide aqueous solution for 10 micrometers of line width: space width = 1: 1 mJ / cm ² ) as the sensitivity.

TABLE 2

As shown in Table 1, the synthesis examples 1 and 2 were confirmed to be a copolymer which maintained the appropriate acid value and alkali dissolution rate.

Moreover, as shown in Table 2, compared with the negative photosensitive resin composition of the comparative example 1, the negative photosensitive resin composition of Example 1 was able to confirm that heat resistance, residual film rate after hardening, and solvent resistance improve. Moreover, compared with the negative photosensitive resin composition of the comparative example 1, the negative photosensitive resin composition of Example 2 was able to confirm that heat resistance, residual film rate after hardening, and solvent resistance improve and maintain sensitivity.

This application claims the priority based on Japanese Patent Application No. 2017-002022 for which it applied in Japan on January 10, 2017, and uses all the indication here.

Claims (13)

The polymer which is a copolymer represented by following formula (1),
With a crosslinking agent,
A negative photosensitive resin composition containing a photosensitive agent.

(In formula (1),
l and m represent the molar content in the polymer,
l + m = 1,
A is a structural unit represented by the following formula (A1),
It includes the structural unit represented by the following formula (A2),
B contains at least 1 or more of the structural units represented by following formula (B1), following formula (B2), following formula (B3), following formula (B4), following formula (B5), or following formula (B6). .)

(In formula (A1), R <_1> , R <_2> , R <_3> and R <_4> are respectively independently hydrogen or the C1-C30 organic group, At least 1 terminal unsaturation to R <_1> , R <_2> , R <_3> and R <_4> . Carbon double bonds, where n is 0, 1 or 2.

(In formula (A2), R <_5> , R <_6> and R <_7> are respectively independently hydrogen or an organic group of 1-30 carbon atoms, n is 0, 1, or 2.

(In formula (B1), R <_8> is a C1-C30 organic group independently.)

(In formula (B2), R <_9> and R <_10> is a C1-C30 organic group each independently.)

(In formula (B6), R <_11> is a C1-C30 organic group independently.) The method according to claim 1,
The negative photosensitive resin composition in which the structural unit represented by said B of the said copolymer contains the structural unit represented by said Formula (B6). The method according to claim 1 or 2,
The structural unit represented by said B of the said copolymer is a negative photosensitive resin composition containing the structural unit represented by the said Formula (B6), and the structural unit represented by the said Formula (B5). The method according to any one of claims 1 to 3,
Of the structural units represented by the formula (A1) of the copolymer, at least one of R ₁ , R ₂ , R _3, and R ₄ is a terminal unsaturated carbon double bond, and represents a structural unit represented by the following general formula (E1). A negative photosensitive resin composition containing.

(In formula (E1), R _e is independently hydrogen or an organic group having 1 to 10 carbon atoms.) The method according to any one of claims 1 to 4,
The said crosslinking agent is an acrylic photosensitive resin composition which is an acrylic crosslinking agent containing a (meth) acryl group. The method according to any one of claims 1 to 5,
Content of the said crosslinking agent is 20 mass parts or more and 80 mass parts or less with respect to 100 mass parts of said polymers, The negative photosensitive resin composition. The method according to any one of claims 1 to 6,
The negative photosensitive resin composition whose content of the said polymer is 5 mass parts or more and 80 mass parts or less with respect to 100 mass parts of total solids of the said negative photosensitive resin composition. The method according to any one of claims 1 to 7,
The negative photosensitive resin composition whose content of the structural unit represented by said Formula (A1) of the said copolymer is 0.1 mol or more and 3.0 mol or less with respect to 1.0 mol of structural units represented by said Formula (A2). The method according to any one of claims 1 to 8,
The said photosensitive agent is a negative photosensitive resin composition which is an optical radical polymerization initiator. The method according to any one of claims 1 to 9,
The weight average molecular weight of the said polymer is 1500 or more and 30000 or less, The negative photosensitive resin composition characterized by the above-mentioned. The method according to any one of claims 1 to 10,
The negative photosensitive resin composition whose dispersion degree of the said polymer is 1.0 or more and 2.5 or less. The resin film which consists of hardened | cured material of the negative photosensitive resin composition of any one of Claims 1-11. The electronic device using the resin film of Claim 12.

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