JP2019137762A - Polymer, photosensitive resin composition, photosensitive resin film, pattern, organic electroluminescent element, method for producing substrate including pattern and method for producing polymer - Google Patents

Abstract

To provide a material that has high liquid repellency of an organic solvent and can be suitably used as, for example, a partition wall forming material of an organic EL element.SOLUTION: The present invention provides a polymer containing a structural unit represented by general formula (A1) (containing a cyclic olefin structure), and at least one selected from the group consisting of a structural unit represented by general formula (B1) and a structural unit represented by general formula (B2) (where, a siloxane structure is introduced into a maleic anhydride structure), and a method for producing the polymer. There are also provided: a photosensitive resin composition containing the polymer and a photosensitizer; a photosensitive resin film formed from the photosensitive resin composition; a pattern obtained by exposing and developing the photosensitive resin film and a method for producing the same; and an organic electroluminescent element including the pattern.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a polymer, a photosensitive resin composition, a photosensitive resin film, a pattern, an organic electroluminescence element, a method for producing a substrate provided with a pattern, and a method for producing a polymer.

  In the periphery of the light emitting portion of the organic electroluminescence element (hereinafter also referred to as an organic EL element), a partition wall (bank, pixel separation film, pixel definition film, element separation) is provided for electrical insulation from other elements and wiring. (Also referred to as a membrane).

As a known technique related to the “partition wall”, for example, Patent Document 1 can be cited.
For example, in FIG. 2 of Patent Document 1, a material liquid that is a source of an organic layer is applied (injected) into a region surrounded by a partition on a substrate, and then the organic solvent in the material liquid is dried. Forming an organic layer.
However, in Patent Document 1, there is no detailed and specific description regarding the partition wall forming material to the extent that “fluorine-containing resin” is described as a material (partition wall forming material) for forming the partition wall.

On the other hand, Patent Document 2 describes a resin composition containing a cyclic olefin polymer having a protic polar group as a material used for forming a partition wall of an organic EL device.
Specifically, in the example of Patent Document 1, 8-carboxytetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ] dodec-3-ene, N-phenyl- (5-norbornene-2,3-dicarboximide) and 1,5-hexadiene as raw materials monomers, polymer by ring-opening metathesis polymerization The hydride 1C was obtained by subjecting this polymer to treatment such as hydrogenation. Moreover, it describes that the resin composition was prepared using this hydride 1C.

Japanese Patent No. 4621818 Japanese Patent No. 5401835

  As described in Patent Document 1, in the manufacture of an organic EL element, a material liquid that is a source of an organic layer may be applied (injected) into a region surrounded by a partition on a substrate. Since the material liquid is usually a solution in which various components are dissolved or dispersed in an organic solvent, the partition wall “repells” the organic solvent (the liquid repellency of the organic solvent, hereinafter also referred to simply as liquid repellency). It is preferable to have. By having this property, it is possible to suppress problems such as the material liquid applied (injected) in the region surrounded by the partition wall creeping up the partition wall and exuding to an unintended region.

  However, according to the knowledge of the present inventors, the partition formed by a conventional partition wall forming material has room for improvement in terms of liquid repellency.

  The present invention has been made in view of such circumstances. That is, it is an object of the present invention to provide a material having high liquid repellency that can be preferably used as a partition wall forming material for an organic EL element, for example.

  As a result of the study, the present inventors have found that the above-described problems can be achieved by making the invention provided below.

  According to the present invention, the following polymers are provided.

A structural unit represented by the following general formula (A1);
A polymer comprising a structural unit represented by the following general formula (B1) and at least one structural unit selected from the group consisting of a structural unit represented by the following general formula (B2).

一般式（Ａ１）において、
Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は、それぞれ独立して、水素または炭素数１〜３０の有機基であり、
ａ_１は０、１または２である。

In general formula (A1),
R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen or an organic group having 1 to 30 carbon atoms,
a ₁ is 0, 1 or 2.

一般式（Ｓ１）において、
複数のＲは、それぞれ独立に、アルキル基、シクロアルキル基、アルケニル基、アリール基またはアラルキル基であり、
Ｒ^５は、水素原子、ヒドロキシル基、アルキル基、シクロアルキル基、アルケニル基、アリール基またはアラルキル基であり、
Ｘは、炭素数１〜３０の二価の有機基であり、
ｋは、１以上の整数を表す。 In general formula (B1) and general formula (B2),
R ^S is, NH ₂ moiety excluding a monovalent group of the compound represented by the following general formula (S1) or a monovalent excluding the NH ₂ moiety of the compound represented by the following general formula (S2) It is a group.

In general formula (S1):
Plural Rs are each independently an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group,
R ⁵ is a hydrogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group,
X is a C1-C30 divalent organic group,
k represents an integer of 1 or more.

In general formula (S2):
Plural Rs are each independently an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group,
R ⁶ and R ⁷ are each independently a hydrogen atom, hydroxyl group, alkyl group, cycloalkyl group, alkenyl group, aryl group or aralkyl group;
X ′ is a divalent organic group having 1 to 30 carbon atoms,
l and m each independently represent an integer of 1 or more.

Moreover, according to the present invention,
There is provided a photosensitive resin composition comprising the above polymer and a photosensitive agent.

Moreover, according to the present invention,
A photosensitive resin film formed from the above-described photosensitive resin composition is provided.

Moreover, according to the present invention,
A pattern obtained by exposing and developing the photosensitive resin film is provided.

Moreover, according to the present invention,
An organic electroluminescence device having the above pattern is provided.

Moreover, according to the present invention,
A film forming step of forming a photosensitive resin film on a substrate using the photosensitive resin composition;
There is provided a method for producing a substrate having a pattern, including a pattern forming step of obtaining a pattern by exposing and developing the photosensitive resin film.

Moreover, according to the present invention,
A method for producing the above polymer,
The raw material polymer containing the structural unit represented by the general formula (A1) and the structural unit represented by the following formula (D1) is converted into a compound represented by the general formula (S1) and / or the general formula ( Provided is a method for producing a polymer, which comprises a step of reacting with a compound represented by S2).

Moreover, according to the present invention,
A method for producing the above polymer,
A raw material polymer containing a structural unit represented by the general formula (A1) and a structural unit represented by the following formula (D1), in the presence of an alcohol, a compound represented by the general formula (S1) and A method for producing a polymer comprising a step of reacting with the compound represented by the general formula (S2) is provided.

  According to the present invention, a material having high liquid repellency is provided. This material can be preferably used as, for example, a partition wall forming material for an organic EL element.

3 is a ¹ H-NMR chart of the polymer obtained in Synthesis Example 2. FIG.

  Hereinafter, embodiments of the present invention will be described in detail.

In the present specification, the notation “ab” in the description of the numerical range represents a range from a to b unless otherwise specified. For example, “1 to 5% by mass” means “1 to 5% by mass”.
In the notation of a group (atomic group) in this specification, the notation which does not describe substitution or non-substitution includes both those having no substituent and those having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
The notation “(meth) acryl” in the present specification represents a concept including both acrylic and methacrylic. The same applies to similar notations such as “(meth) acrylate”.

<Polymer>
The polymer of this embodiment is
A structural unit represented by the following general formula (A1);
And at least one structural unit selected from the group consisting of a structural unit represented by the following general formula (B1) and a structural unit represented by the following general formula (B2).

In general formula (A1),
R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen or an organic group having 1 to 30 carbon atoms,
a ₁ is 0, 1 or 2.

一般式（Ｂ１）および一般式（Ｂ２）において、
Ｒ^Ｓは、下記一般式（Ｓ１）で表される化合物のＮＨ_２部分を除いた一価の基、または、下記一般式（Ｓ２）で表される化合物のＮＨ_２部分を除いた一価の基である。

In general formula (B1) and general formula (B2),
R ^S is, NH ₂ moiety excluding a monovalent group of the compound represented by the following general formula (S1) or a monovalent excluding the NH ₂ moiety of the compound represented by the following general formula (S2) It is a group.

In general formula (S1):
Plural Rs are each independently an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group,
R ⁵ is a hydrogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group,
X is a C1-C30 divalent organic group,
k represents an integer of 1 or more.

(In general formula (S2),
Plural Rs are each independently an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group,
R ⁶ and R ⁷ are each independently a hydrogen atom, hydroxyl group, alkyl group, cycloalkyl group, alkenyl group, aryl group or aralkyl group;
X ′ is a divalent organic group having 1 to 30 carbon atoms,
l and m each independently represent an integer of 1 or more. )

The polymer, by having a silicon-containing group of R ^s, would indicate desired liquid repellency (liquid repellency against an organic solvent such as anisole). Therefore, the partition wall is formed of this polymer (or an appropriate composition containing this polymer), whereby the liquid repellency of the partition wall can be improved.
In addition, since the polymer includes a rigid structural unit represented by the general formula (A1), the shape of the partition wall is not easily deformed by a preferable performance as a partition wall forming material other than liquid repellency, for example, heat. It is thought that there are performances such as.

The polymer production method (synthetic method) of this embodiment will be described in detail separately.
(I) First, a polymer including a structural unit represented by the general formula (A1) and a structural unit derived from maleic anhydride (a structural unit represented by the following formula (D1)) is prepared,
(Ii) Next, the structural unit derived from maleic anhydride of the polymer is obtained by a reaction in which the amino group (—NH ₂ site) of the compound represented by the general formula (S1) or (S2) is attacked. be able to.

  Details of the general formula (A1) and the like will be described below.

Examples of the organic group having 1 to 30 carbon atoms of R ¹ , R ² , R ³ and R ^{4 in} the general formula (A1) include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, and an alkaryl group. , Cycloalkyl group, alkoxy group, heterocyclic group, carboxyl group and the like.
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, a decyl group, etc. are mentioned.
Examples of the alkenyl group include allyl group, pentenyl group, and vinyl group.
Examples of the alkynyl group include an ethynyl 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 alkaryl group include a tolyl group and a xylyl group.
Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, s-butoxy group, isobutoxy group, t-butoxy group, n-pentyloxy group, and neopentyloxy group. , N-hexyloxy group and the like.
Examples of the heterocyclic group include an epoxy group and an oxetanyl group.

R ¹ , R ² , R ³ and R ⁴ in the general formula (A1) are preferably hydrogen or an alkyl group, and more preferably hydrogen.
The ^hydrogen atom in the organic group R ^1, R 2, ^{R 3} and a carbon number of ^{R 4} 1 to 30 may be substituted with any atom group. For example, it may be substituted with a fluorine atom, a hydroxyl group, a carboxyl group or the like. More specifically, a fluorinated alkyl group or the like may be selected as the organic group having 1 to 30 carbon atoms of R ¹ , R ² , R ³ and R ⁴ .

In the general formula (A1), a ₁ is preferably 0 or 1, more preferably 0.

  The ratio of the structural unit represented by the general formula (A1) in all the structural units of the polymer of the present embodiment is preferably 35 to 65 mol%, more preferably 40 to 60 mol%.

As described above, in the general formulas (B1) and (B2), R ^s is a monovalent group excluding the NH ₂ moiety of the compound represented by the above general formula (S1), or the above general It is a monovalent group excluding the NH ₂ portion of the compound represented by the formula (S2).
Hereinafter, the general formula (S1) and the general formula (S2) will be described.

・ General formula (S1)
As the alkyl group for R, 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, A heptyl group, an octyl group, a nonyl group, a decyl group, etc. are mentioned.
Examples of the cycloalkyl group of R include monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group. Moreover, polycyclic cycloalkyl groups, such as a norbornyl group and an adamantyl group, can also be mentioned.
Examples of the alkenyl group for R include an allyl group, a pentenyl group, and a vinyl group.
Examples of the aryl group of R include a tolyl group, a xylyl group, a phenyl group, a naphthyl group, and an anthracenyl group.
Examples of the aralkyl group for R include a benzyl group and a phenethyl group.

Carbon number of R becomes like this. Preferably it is 1-12, More preferably, it is 1-10, More preferably, it is 1-6.
R is particularly preferably a methyl group or a phenyl group, and most preferably a methyl group.

When R ⁵ is an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or an aralkyl group, specific examples of these groups include the same as those described above as specific examples of R.
R ⁵ preferably has 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 6 carbon atoms.
R ⁵ is preferably an alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group.

Examples of the divalent organic group having 1 to 30 carbon atoms of X include an alkylene group (straight or branched), a cycloalkylene group, an arylene group, and a group in which two or more of these groups are linked. it can.
A part of the carbon chain constituting the divalent organic group may be replaced by an ether bond, a carbonyl bond, an ester bond, or the like. For example, a structure such as —CH ₂ —O—CH ₂ — in which the central CH ₂ site of the propylene group —CH ₂ —CH ₂ —CH ₂ — is replaced with an ether bond may be used.

Examples of the alkylene group for X include a divalent group obtained by removing one arbitrary hydrogen atom from the groups exemplified as the alkyl group for R.
Examples of the cycloalkylene group for X include a divalent group obtained by removing one arbitrary hydrogen atom from the groups exemplified as the cycloalkyl group for R.
Examples of the arylene group for X include a divalent group obtained by removing one arbitrary hydrogen atom from the group exemplified as the aryl group for R.

  X is preferably a linear or branched alkylene group having 1 to 6 carbon atoms, more preferably a linear alkylene group having 1 to 6 carbon atoms, and a methylene group, an ethylene group, a propylene group or a butylene group. More preferably it is.

  k may be an integer of 1 or more, preferably 1 to 100, more preferably 3 to 50, and further preferably 5 to 20.

・ General formula (S2)
Specific examples and preferred embodiments of R are the same as R in the general formula (S1).
When R ⁶ and R ⁷ are an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group, specific examples and preferred embodiments of these groups are the same as those for R ^{5 in the} general formula (S1). Particularly preferred is a methyl group.
Specific examples and preferred embodiments of the divalent organic group having 1 to 30 carbon atoms of X ′ are the same as X in the general formula (S1).
Although 1 should just be an integer greater than or equal to 1, Preferably it is 1-1000, More preferably, it is 3-500, More preferably, it is 5-200.
Although m should just be an integer greater than or equal to 1, Preferably it is 1-10, More preferably, it is 1-5, More preferably, it is 1-2.
Note that when m is an integer of 2 or more, two or more —NH ₂ exists, and a structure excluding one of them is R ^{s in the} general formula (B1) or the general formula (B2). Become.

It is preferable that the polymer of this embodiment contains the structural unit represented by general formula (B1) among the structural unit represented by general formula (B1) and the structural unit represented by general formula (B2).
According etc. to the findings of the present inventors, more of the structural unit represented by the general formula (B1) is, than the structure represented by the general formula (B2), hardly portion of R ^s and thermal decomposition or dissociation . That is, when the polymer of this embodiment is used as the partition wall forming material, it is preferable because the resin is stably present even by exposure or heating.
Whether or not the structural unit represented by the general formula (B1) is present in the polymer is determined by, for example, infrared spectroscopy (FT-IR analysis) at a wave number of 1600 cm ⁻¹ (N—H change of the amide group). The presence or absence of absorption near (angular vibration) is one clue.

  The ratio of the structural unit represented by the general formula (B1) and the structural unit represented by the general formula (B2) in all the structural units of the polymer of the present embodiment (total of two structural units) is preferably 1 It is -30 mol%, More preferably, it is 1-20 mol%, More preferably, it is 1-15 mol%, Especially preferably, it is 1-6 mol%, Most preferably, it is 1-3 mol%. By appropriately adjusting this value, the transparency of the resin can be increased. And when the polymer of this embodiment is used for the photosensitive resin composition, the turbidity of a composition can be suppressed. That is, it is preferable in terms of light transmittance during exposure.

  As described above, in the present embodiment, the structural unit represented by the general formula (B1) is more preferable than the structural unit represented by the general formula (B2). Therefore, as an example, the proportion of the structural unit represented by the general formula (B1) in all the structural units of the polymer of the present embodiment is preferably 1 to 30 mol%, more preferably 1 to 15 mol%, Preferably it is 1-10 mol%, Most preferably, it is 1-6 mol%, Most preferably, it is 1-3 mol%.

  It is preferable that the polymer of the present embodiment further includes a structural unit represented by the following general formula (C1).

In General Formula (C1), R ^A represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or an aralkyl group.

  It is thought that the effect of the alkali solubility improvement of a polymer is acquired because the polymer of this embodiment contains this structural unit. That is, for example, when a photosensitive resin composition is prepared using the polymer of the present embodiment due to the —COOH structure, the developability with respect to an alkaline developer can be improved.

Moreover, it is thought that the solubility of the polymer in an organic solvent can be increased by including the structural unit in the polymer of the present embodiment. That is, since the hydrocarbon structure of ^RA is compatible with an organic solvent, when preparing a composition by mixing the polymer of the present embodiment and an organic solvent, a composition with reduced residual residue and the like is prepared. It is thought that it is easy to obtain. In particular, when the polymer has a silicone-containing structure, the solubility in an organic solvent may be lowered. Therefore, the solubility in an organic solvent is preferably ensured by the hydrocarbon structure of ^RA .

Specific examples of the alkyl group, cycloalkyl group, alkenyl group, aryl group and aralkyl group of R ^A include, for example, the alkyl groups, cycloalkyl groups, alkenyl groups, and aryls mentioned as specific examples of R in formula (S1). And aralkyl groups.
The carbon number of R ^A is preferably 1 to 12, more preferably 2 to 10, and further preferably 2 to 8. By adjusting the carbon number of ^RA , it is possible to achieve both high solubility in an organic solvent and high solubility in an alkali developer.

Although the method for introducing the structural unit represented by the general formula (C1) into the polymer will be described in detail separately, for example, a structural unit derived from maleic anhydride (formula (D1) described later) It can be obtained by a reaction in which an alcohol represented by R ^A —OH (R ^A has the same meaning as in the general formula (C1)) is attacked with respect to the structural unit represented.

  When the polymer of this embodiment contains the structural unit represented by the general formula (C1), the content (ratio to the total structural unit) is preferably 10 to 40 mol%, more preferably 15 to 35 mol%, More preferably, it is 20-30 mol%. By adjusting the content of the structural unit represented by the general formula (C1), the developability with respect to the alkali development and the solubility with respect to the organic solvent can be further enhanced.

The polymer of this embodiment may further contain a structural unit represented by the following formula (D1).
The polymer of the present embodiment is represented by, for example, a compound (a compound represented by the general formula (S1) and / or a general formula (S2) that is reacted with a raw material polymer in a production method (synthesis method) described in detail separately. This structural unit may be included depending on the amount of the compound) charged and the reactivity of the alcohol represented by the general formula (C1-m) described later with maleic anhydride.

  It is thought that there exists a merit when forming a cured film using a polymer because a polymer contains the structural unit represented by Formula (D1). For example, it is considered that the structural unit represented by the formula (D1) can react with a crosslinkable component (for example, an epoxy group-containing compound) to form a crosslinked structure and increase the strength of the cured film.

  Moreover, it is thought that the solubility with respect to an alkali developing solution can be appropriately adjusted because a polymer contains the structural unit represented by Formula (D1) as another viewpoint.

  When the polymer of this embodiment contains the structural unit represented by the general formula (D1), the content (ratio to the total structural unit) is preferably 1 to 40 mol%, more preferably 5 to 35 mol%, More preferably, it is 10-30 mol%.

The weight average molecular weight Mw of the polymer of this embodiment becomes like this. Preferably it is 2000-50000, More preferably, it is 5000-25000, More preferably, it is 7500-15000. By appropriately adjusting the weight average molecular weight, solubility in an alkali developer, solubility in an organic solvent, and the like can be adjusted.
Moreover, the polydispersity (weight average molecular weight Mw / number average molecular weight Mn) of the polymer of the present embodiment is preferably 1.0 to 3.0, more preferably 1.0 to 2.5, and still more preferably 1. 0-2.0. By appropriately adjusting the polydispersity, the physical properties of the polymer can be made uniform, which is preferable.
These values can be obtained by gel permeation chromatography (GPC) measurement using polystyrene as a standard substance.

The content (ratio) of each structural unit contained in the polymer of the present embodiment is the amount of raw material charged at the time of polymer synthesis (molar amount), the amount of raw material remaining after synthesis, and the peak areas of various spectra (for example, ¹ H-NMR peak area) and the like.

<Method for producing polymer>
The polymer production method (synthesis method) of the present embodiment is not particularly limited, and as an example, a structural unit represented by the above general formula (A1), a structural unit represented by the above formula (D1), and Can be obtained by reacting a compound represented by the above general formula (S1) and / or a compound represented by the above general formula (S2).
Hereinafter, the compound represented by the general formula (S1) and / or the compound represented by the general formula (S2) is also referred to as “aminated silicone compound”.

First, the method for obtaining the raw material polymer here will be described.
The raw material polymer can be obtained by polymerizing (addition polymerization) a monomer represented by the following general formula (2) and maleic anhydride.

In general formula (2), R ¹ , R ² , R ³ , R ⁴ and a ₁ are respectively synonymous with R ¹ , R ² , R ³ R ⁴ and a ₁ in general formula (A1).
Examples of the monomer represented by the general formula (2) 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-methyl-4-pentenyl) -2-norbornene, 5-ethynyl-2-norbornene, 5-benzyl-2-norbornene, 5-phenethyl-2-norbornene, 2-acetyl-5-norbornene, Examples include methyl 5-norbornene-2-carboxylate and 5-norbornene-2,3-dicarboxylic acid anhydride.
In the polymerization, only one monomer represented by the general formula (2) may be used, or two or more monomers may be used in combination.

Although the polymerization method is not limited, radical polymerization using a radical polymerization initiator is preferred.
As a polymerization initiator, an azo compound, an organic peroxide, etc. can be used, for example.
Specific examples of the azo compound include azobisisobutyronitrile (AIBN), dimethyl 2,2′-azobis (2-methylpropionate), 1,1′-azobis (cyclohexanecarbonitrile) (ABCN), and the like. Can be mentioned.
Examples of the organic peroxide include hydrogen peroxide, ditertiary butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), and methyl ethyl ketone peroxide (MEKP).
About a polymerization initiator, only 1 type may be used and it may be used in combination of 2 or more type.

  As the polymerization solvent, for example, an organic solvent such as diethyl ether, tetrahydrofuran, toluene, methyl ethyl ketone, or the like can be used. The polymerization solvent may be a single solvent or a mixed solvent.

The monomer represented by the general formula (2), maleic anhydride, and a polymerization initiator are dissolved in a solvent, charged into a reaction vessel, and then heated to cause addition polymerization. The heating temperature is, for example, 50 to 80 ° C., and the heating time is, for example, 5 to 20 hours.
The molar ratio of the monomer represented by the general formula (2) and maleic anhydride when charged into the reaction vessel is preferably 0.5: 1 to 1: 0.5. From the viewpoint of molecular structure control, the molar ratio is preferably 1: 1.
Through such a process, a “raw polymer” can be obtained.
The raw material polymer may be any of a random copolymer, an alternating copolymer, a block copolymer, a periodic copolymer, and the like.

After the synthesis of the raw material polymer, a step of removing low molecular weight components such as unreacted monomers, oligomers, and remaining polymerization initiator may be performed.
Specifically, the synthesized organic layer containing the raw material polymer and the low molecular weight component is concentrated, and then mixed with an organic solvent such as tetrahydrofuran (THF) to obtain a solution. And this solution is mixed with poor solvents, such as methanol, and a monomer is precipitated. The purity of the raw material polymer can be increased by filtering this precipitate and drying it.

Next, a method for reacting the raw material polymer with an aminated silicone compound will be described. This method can be performed, for example, in the following steps (1) and (2).
(1) The starting polymer is a suitable organic solvent (alcohol solvent described later and / or a single solvent or mixed solvent such as propylene glycol monomethyl ether acetate (PGMEA), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP)) Prepare a solution dissolved in). While stirring this, an aminated silicone compound diluted with an organic solvent is added dropwise. Thereby, the structural unit derived from the maleic anhydride of the raw material polymer is reacted with the —NH ₂ site of the aminated silicone compound to form an amide bond while opening the structural unit. When the structural unit derived from maleic anhydride is ring-opened, a carboxyl group is generated in addition to the amide bond.
(2) After completion of the dropwise addition, the solution is heated at 80 to 200 ° C. for 1 to 24 hours (such as reflux). Thereby, the carboxyl group produced | generated by ring-opening of the structural unit derived from maleic anhydride in said process (1) and an amide bond react, and it dehydrates, and an imide ring structure is formed.

  In other words, the structural unit represented by the general formula (B2) (a structural unit in which the maleic anhydride structure is opened) can be introduced into the raw material polymer by the above step (1). Moreover, the structural unit represented by the general formula (B1) (an imide structure-containing unit in which the structural unit represented by the general formula (B2) is closed) can be introduced by performing the step (2). it can.

  The step (1) is preferably performed in the presence of alcohol. In other words, the polymer production method (synthesis method) of the present embodiment is preferably a raw material polymer containing a structural unit represented by the general formula (A1) and a structural unit represented by the formula (D1). It can be obtained by reacting with a compound represented by the general formula (S1) and / or a compound represented by the general formula (S2) in the presence of an alcohol. By doing so, a structural unit having a ring-opened structural unit derived from maleic anhydride as represented by the general formula (C1) can be introduced into the polymer. That is, the structural unit derived from maleic anhydride and the hydroxyl group of the alcohol can react to generate a structural unit represented by the general formula (C1).

  The reaction between maleic anhydride and an alcohol such as butanol is considered a reversible reaction. Therefore, in the usually applied reaction conditions (for example, reaction conditions in Examples described later), even if the alcohol is used in an amount (excess amount) larger than the molar amount of the structural unit derived from maleic anhydride, The structural unit is not converted to the structural unit of the general formula (C1).

  Here, as a specific method of performing the above step (1) “in the presence of alcohol”, (i) using alcohol as an organic solvent for dissolving the raw material polymer, (ii) diluting the aminated silicone compound Alcohol is used as the organic solvent, (iii) both of these can be employed.

The alcohol used here preferably includes an alcohol represented by the following general formula (C1-m).
R ^A —OH (C1-m)

In the formula (C1-m), ^{R A} has the same meaning as ^{R A} in the general formula (C1). That is, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or an aralkyl group. The same applies to specific examples and preferred embodiments of ^RA .

  In addition, about aminated silicone compound (The compound represented by general formula (S1) or the compound represented by general formula (S2)), a commercial item can be used suitably. For example, those sold as “modified silicone oil” by Shin-Etsu Chemical Co., Ltd., sold as “organic modified silicone oil” by Toray Dow Corning, and sold as “REACTIVE SILICONES” by Gelest. Can be used.

The polymer of this embodiment can be used as a raw material of the photosensitive resin composition described below, for example. In addition, the polymer alone of this embodiment may be used for any application, or a non-photosensitive composition obtained by mixing the polymer of this embodiment and any component may be prepared and applied to any application. Good.
The polymer of this embodiment is considered to have not only the liquid repellency of an organic solvent but also performances such as water repellency, antifouling property, releasability, lubricity, and low stress by including a silicone structure. In other words, it can be applied to technical fields that require these performances.

<Photosensitive resin composition>
The photosensitive resin composition of the present embodiment includes the polymer described above (hereinafter also referred to as “specific polymer”) and a photosensitive agent. In addition to these components, various optional components may be included.
Hereinafter, these photosensitive agents and optional components will be described.

-Photosensitive agent The photosensitive resin composition of this embodiment contains a photosensitive agent.
Preferred examples of the photosensitive agent include acid generators, that is, compounds that generate an acid upon irradiation with actinic rays (for example, g-line or i-line).

  Specific examples of the photosensitive agent include photosensitive diazoquinone compounds, onium salts (sulfonium salts, iodonium salts, etc.), sulfonic acid ester compounds, triazine compounds, oxime sulfonate compounds, diazodisulfone compounds, 2-nitrobenzyl ester compounds, N- Examples include imino sulfonate compounds, imide sulfonate compounds, 2,6-bis (trichloromethyl) -1,3,5-triazine compounds, and dihydropyridine compounds.

In particular, when the photosensitive resin composition is positive (the exposed portion dissolves when developed with an alkaline developer after pattern exposure), the photosensitive agent preferably contains a diazoquinone compound. By using a diazoquinone compound, sensitivity, resolution, developability and the like can be improved.
As the diazoquinone compound, for example, those shown below can be used.

In each of the above diazoquinone compounds, Q is any one of the structures represented by the following formula (a), the following formula (b), and the following formula (c), or a hydrogen atom. However, at least one of Q of each diazoquinone compound is one of structures represented by the following formula (a), the following formula (b), and the following formula (c). Moreover, n is an integer of 1-5.
The Q of the diazoquinone compound preferably includes the following formula (a) or the following formula (b). Thereby, the transparency of the photosensitive resin composition can be improved. Therefore, the appearance of the photosensitive resin composition can be improved.

The photosensitive resin composition of this embodiment may contain only 1 type of photosensitive agents, and may contain 2 or more types.
The content of the photosensitizer is usually 10 to 80 parts by mass, preferably 30 to 60 parts by mass, and more preferably 40 to 50 parts by mass when the amount of the specific polymer in the composition is 100 parts by mass. By setting it within this range, sufficient sensitivity can be obtained, and other performance and sensitivity can be compatible.

-Crosslinking agent The photosensitive resin composition of this embodiment preferably contains a crosslinking agent as one aspect. The crosslinking agent typically has a group (crosslinkable group) capable of forming a covalent bond between the specific polymer and the crosslinking agent, or between the crosslinking agents. The crosslinking reaction proceeds by the action of the acid generated from the photosensitizer and / or heating.

The cross-linking agent typically contains 2 or more (preferably 2-6, more preferably 2-4) crosslinkable groups in one molecule.
Preferred examples of the crosslinking agent (C) include the following compounds (1) to (5).

(1) A crosslinking agent having an alkoxymethyl group and / or a methylol group (—CH ₂ OH): for example, benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, Bis (hydroxymethyl) benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis (hydroxymethyl) biphenyl, dimethylbis (hydroxymethyl) biphenyl, bis (methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxy Benzene, bis (methoxymethyl) diphenyl ether, bis (methoxymethyl) benzophenone, methoxymethylphenyl benzoate, bis (methoxymethyl) Phenyl, dimethylbis (methoxymethyl) biphenyl; commercial products include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170 , 1174, UFR65, 300 (manufactured by Mitsui Cytec Co., Ltd.), Nicarax MX-270, -280, -290, Nicarak MS-11, Nicarak MW-30, -100, -300, -390, -750 (Sanwa) Chemical Co.), 1,4-bis (methoxymethyl) benzene, 4,4′-biphenyldimethanol, 4,4′-bis (methoxymethyl) biphenyl, commercially available 26DMPC, 46DMOC, DM-BIPC-F , DM-BIOC-F, TM-BIP-A (Asahi Organic Materials Co., Ltd.) , DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, DML-OC, dimethylol-Bis-C, dimethylol-BisOC -P, DML-BisOC-Z, DML-BisOCHP-Z, DML-PFP, DML-PSBP, DML-MB25, DML-MTrisPC, DML-Bis25X-34XL, DML-Bis25X-PCHP, 2,6-dimethoxymethyl- 4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymer-p-cresol, TriML-P, TriML-35XL, TriML-TrisCR-HAP, HML-TPPHBA, HML-TPHAP , MOM-TPPHBA, HMOM-TPHAP (manufactured by Honshu Chemical Industry Co.) and the like.

(2) Compound having an epoxy group: for example, n-butyl glycidyl ether, 2-ethoxyhexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether Glycerol polyglycidyl ether, sorbitol polyglycidyl ether, glycidyl ether of bisphenol A (or F), polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, pentaerythritol poly Glycidyl ether (for example, pentaerythritol tea) Lag glycidyl ether) glycidyl ether, and the like can be given.

  Further, glycidyl esters such as adipic acid diglycidyl ester and o-phthalic acid diglycidyl ester, 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexane) carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl ( 3,4-epoxy-6-methylcyclohexane) carboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, dicyclopentanediene oxide, bis (2,3-epoxycyclopentyl) ether, etc. Can do.

  Furthermore, Daicel Corporation's Celoxide 2021, Celoxide 2081, Celoxide 2083, Celoxide 2085, Celoxide 8000, Epoxide GT401 and other cycloaliphatic epoxy compounds, Printtech's TECHMORE VG3101L-containing aromatic heat-resistant trifunctional epoxy Compounds, Epolite 100MF manufactured by Kyoeisha Chemical Industry Co., Ltd., aliphatic polyglycidyl ethers such as Epiol TMP manufactured by NOF Corporation, DMS-E09 manufactured by Gelest Co., etc.

(3) Compounds having an oxetanyl group: for example, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, bis [1-ethyl (3-oxetanyl)] methyl ether, 4,4′- Bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl, 4,4′-bis (3-ethyl-3-oxetanylmethoxy) biphenyl, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, diethylene glycol Bis (3-ethyl-3-oxetanylmethyl) ether, bis (3-ethyl-3-oxetanylmethyl) diphenoate, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl- 3-Oxetanylmethyl) ete , Poly [[3-[(3-ethyl-3-oxetanyl) methoxy] propyl] silasesquioxane] derivatives, oxetanyl silicate, phenol novolac oxetane, 1,3-bis [(3-ethyloxetan-3-yl) And methoxy] benzene.

(4) Compound having an isocyanate group: for example, 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, 1,3-phenylene bismethylene diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, etc. Is mentioned.

(5) Compounds having a bismaleimide group: for example, 4,4′-diphenylmethane bismaleimide, phenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3′-dimethyl-5,5′-diethyl -4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, 4,4'-diphenyl ether bismaleimide, Examples include 4,4′-diphenylsulfone bismaleimide, 1,3-bis (3-maleimidophenoxy) benzene, 1,3-bis (4-maleimidophenoxy) benzene, and the like.

  In addition, a well-known epoxy resin can also be mentioned as a compound which has (2) epoxy group. Specifically, phenol novolac type epoxy resin, cresol novolac type epoxy resin, cresol naphthol type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, phenoxy resin, naphthalene skeleton type epoxy resin, bisphenol A type epoxy resin, bisphenol A diglycidyl ether type epoxy resin, bisphenol F type epoxy resin, bisphenol F diglycidyl ether type epoxy resin, bisphenol S diglycidyl ether type epoxy resin, glycidyl ether type epoxy resin, cresol novolac type epoxy resin, aromatic polyfunctional epoxy resin And aliphatic epoxy resins, aliphatic polyfunctional epoxy resins, alicyclic epoxy resins, polyfunctional alicyclic epoxy resins, and the like.

When using a crosslinking agent, it may be used independently and may be used in combination of multiple types.
When the photosensitive resin composition contains a crosslinking agent, the content thereof is usually 10 to 70 parts by mass, preferably 20 to 50 parts by mass, when the amount of the specific polymer in the composition is 100 parts by mass.

-Adhesion assistant The photosensitive resin composition may contain an adhesion assistant. Thereby, the adhesiveness with the board | substrate of the resin film and pattern formed with the photosensitive resin composition can be improved.
The adhesion aid that can be used is not particularly limited. For example, silane coupling agents such as amino silane, epoxy silane, acrylic silane, mercapto silane, vinyl silane, ureido silane, acid anhydride functional silane, and sulfide silane can be used. A silane coupling agent may be used individually by 1 type, and may use 2 or more types together. Among these, epoxy silane (that is, a compound containing both an epoxy moiety and a group that generates a silanol group by hydrolysis) or an acid anhydride functional silane (that is, acid anhydride in one molecule). A compound containing both a physical group and a group capable of generating a silanol group by hydrolysis is preferred.

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

  Examples of the epoxy silane include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-glycidylpropyltrimethoxy. Silane etc. are mentioned.

  Examples of the acrylic silane include γ- (methacryloxypropyl) trimethoxysilane, γ- (methacryloxypropyl) methyldimethoxysilane, and γ- (methacryloxypropyl) methyldiethoxysilane.

  Examples of mercaptosilane include 3-mercaptopropyltrimethoxysilane.

  Examples of vinyl silane include vinyl tris (β-methoxyethoxy) silane, vinyl triethoxy silane, and vinyl trimethoxy silane.

  Examples of ureidosilane include 3-ureidopropyltriethoxysilane.

  Examples of the acid anhydride functional silane include 3-trimethoxysilylpropyl succinic anhydride.

  Examples of the sulfide silane include bis (3- (triethoxysilyl) propyl) disulfide, bis (3- (triethoxysilyl) propyl) tetrasulfide, and the like.

When using the adhesion assistant, only one type may be used, or two or more types may be used in combination.
The content of the adhesion assistant is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, when the amount of the specific polymer in the composition is 100 parts by mass. By setting it as this range, it is thought that "adhesion" which is an effect of the adhesion assistant can be sufficiently obtained while balancing with other performances.

-Surfactant The photosensitive resin composition may contain a surfactant. Thereby, the uniformity of the thickness at the time of apply | coating the photosensitive resin composition on a board | substrate can be improved.
The surfactant is preferably a nonionic surfactant containing at least one of a fluorine atom and a silicon atom. Commercially available products include, for example, F-251, F-253, F-281, F-430, F-477, F-551, F-552, and F-553 of "Megafac" series manufactured by DIC Corporation. F-554, F-555, F-556, F-557, F-558, F-559, F-560, F-561, F-562, F-563, F-565, F-568, F -569, F-570, F-572, F-574, F-575, F-576, R-40, R-40-LM, R-41, R-94, etc. Surfactants, fluorine-containing nonionic surfactants such as Footage 250 and Footage 251 manufactured by Neos Co., Ltd., SILFOAM (registered trademark) series manufactured by Wacker Chemie (for example, SD 100 TS, SD 670, D 850, SD 860, SD 882) silicone surfactant and the like.

When using surfactant, only 1 type may be used and 2 or more types may be used together.
Content of surfactant is 0.01-10 mass parts normally, when the quantity of the specific polymer in a composition is 100 mass parts, Preferably it is 0.05-5 mass parts. By setting it as this range, it is thought that effects, such as the improvement of the uniformity of the thickness of a resin film, are fully acquired, balancing with other performance.

-Solvent It is preferable that the photosensitive resin composition contains a solvent.
The solvent that can be used is typically an organic solvent. Specifically, ketone solvents, ester solvents, ether solvents, alcohol solvents, lactone solvents, carbonate solvents, and the like can be used.

  More specifically, acetone, methyl ethyl ketone, toluene, propylene glycol methyl ethyl ether, propylene glycol dimethyl ether, propylene glycol 1-monomethyl ether 2-acetate, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, benzyl alcohol And organic solvents such as propylene carbonate, ethylene glycol diacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, anisole, N-methylpyrrolidone, cyclohexanone, cyclopentanone, dipropylene glycol methyl-n-propyl ether. it can.

When using a solvent, only 1 type may be used and 2 or more types may be used.
When the solvent is used, the amount used is not particularly limited, but it is used in such an amount that the concentration of the nonvolatile component is, for example, 10 to 70% by mass, preferably 15 to 60% by mass.

-Other component The photosensitive resin composition of this embodiment may contain various components other than the above. For example, a basic compound, a curing accelerator, an antioxidant, a filler such as silica, a sensitizer, a filming agent, a dissolution accelerator, a dissolution inhibitor, and the like may be included.
Among the above, for the basic compound, various amine compounds (for example, primary amine, secondary amine, tertiary amine, etc.) can be specifically mentioned.
Among the above, specific examples of the curing accelerator include a nitrogen-containing heterocyclic compound containing an amidine skeleton or a salt thereof (specifically, diazabicycloundecene or a salt thereof).

Moreover, the photosensitive resin composition of this embodiment may contain a polymer different from the specific polymer. For example, the structural unit represented by the general formula (A1), the general formula (C1) and / or the formula (D1) is included, but the structural unit represented by the general formula (B1) and the general formula (B2) You may use together the polymer which does not contain the structural unit represented with a specific polymer.
Furthermore, the photosensitive resin composition of the present embodiment may include two or more kinds of polymers corresponding to the specific polymer.

-Supplementary matter etc. The photosensitive resin composition of this embodiment may be a positive type or a negative type. Any pattern can be designed according to the pattern shape to be obtained. In addition, typically, the strength of the acid generated from the photosensitizer and the reactivity of the cross-linking agent (whether the cross-linking reaction proceeds by the acid generated from the photosensitizer) or the like are appropriately adjusted to make the photosensitive resin The composition can be designed to be either positive or negative.

  The amount of the specific polymer in the photosensitive resin composition is preferably 3 to 60% by mass, more preferably 5 to 40% by mass, and still more preferably, based on the total amount of non-volatile components in the composition (100% by mass). It is 10-30 mass%.

<Photosensitive resin film, pattern, method for producing substrate with pattern, organic EL element>
A photosensitive resin film can be formed using the photosensitive resin composition described above. In addition, the photosensitive resin film can be exposed to light and developed to form a pattern, a substrate having a pattern can be manufactured, and an organic EL element can be manufactured.
Hereinafter, formation of the photosensitive resin film, exposure / development of the photosensitive resin film, and the like will be specifically described.

-Formation of photosensitive resin film The photosensitive resin film can be obtained, for example, by applying the photosensitive resin composition described above on an arbitrary substrate and drying it as necessary.

The board | substrate which apply | coats a composition is not specifically limited, For example, a glass substrate, a silicon wafer, a ceramic substrate, an aluminum substrate, a SiC wafer, a GaN wafer, a copper clad laminated board etc. are mentioned. When manufacturing an organic EL element, the photosensitive resin film is typically formed on a glass substrate.
The substrate may be an unprocessed substrate or a substrate on which electrodes and elements are formed. You may surface-treat for the improvement of adhesiveness.

  The coating method of the photosensitive resin composition is not particularly limited, and can be performed by spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, an inkjet method, or the like.

  The photosensitive resin composition coated on the substrate is typically dried by heat treatment with a hot plate, hot air, oven, or the like. The heating temperature is usually 80 to 140 ° C, preferably 90 to 120 ° C. The heating time is usually 30 to 600 seconds, preferably about 30 to 300 seconds.

  The film thickness of the photosensitive resin film is not particularly limited, and may be appropriately adjusted according to the pattern to be finally obtained. As an example, when it is going to finally obtain the partition of an organic EL element, the film thickness of the photosensitive resin film is 0.5-10 micrometers normally, Preferably it is 1-5 micrometers. In addition, a film thickness can be adjusted with content of the solvent in the photosensitive resin composition, a coating method, etc.

-Exposure Exposure is typically performed by applying an actinic ray to the photosensitive resin film through an appropriate photomask.
Examples of actinic rays include X-rays, electron beams, ultraviolet rays, and visible rays. In terms of wavelength, light of 200 to 500 nm is preferable. From the viewpoint of pattern resolution and handleability, the light source is preferably g-line, h-line or i-line of a mercury lamp, and i-line is particularly preferable. Two or more light beams may be mixed and used. As the exposure apparatus, a contact aligner, mirror projection or stepper is preferable.
The amount of exposure light may be appropriately adjusted depending on the amount of the photosensitive agent in the photosensitive resin film, and is, for example, about 100 to 500 mJ / cm ² .

  In addition, after the exposure, the photosensitive resin film may be heated again as necessary (post-exposure bake). The temperature is, for example, 70 to 150 ° C, preferably 90 to 120 ° C. The time is, for example, 30 to 600 seconds, preferably 30 to 300 seconds.

-Development By developing the exposed photosensitive resin film with an appropriate developer, a pattern can be obtained, and a substrate provided with the pattern can be produced. And the board | substrate provided with these patterns thru | or a pattern is applied preferably to an organic EL element, for example.

  In the development step, development can be performed using a suitable developer, for example, by a method such as an immersion method, a paddle method, or a rotary spray method. By development, an exposed portion (in the case of a positive type) or an unexposed portion (in the case of a negative type) of the photosensitive resin film is eluted and removed, and a pattern is obtained.

The developer that can be used is not particularly limited. For example, an alkaline aqueous solution or an organic solvent can be used.
Specific examples of the alkaline aqueous solution include (i) an inorganic alkaline aqueous solution such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia; (ii) an organic amine aqueous solution such as ethylamine, diethylamine, triethylamine, and triethanolamine; (iii) Examples thereof include aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide.
Specific examples of the organic solvent include ketone solvents such as cyclopentanone, ester solvents such as propylene glycol monomethyl ether acetate (PGMEA) and butyl acetate, ether solvents such as propylene glycol monomethyl ether, and the like.
For example, a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added to the developer.

  In the present embodiment, it is preferable to use an aqueous tetramethylammonium hydroxide solution as the developer. The concentration of tetramethylammonium hydroxide in this aqueous solution is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass.

  Through the above steps, a pattern can be obtained / a substrate with a pattern can be manufactured, but various processes may be performed after development.

  For example, after development, the pattern and the substrate may be washed with a rinse solution. Examples of the rinsing liquid include distilled water, methanol, ethanol, isopropanol, and propylene glycol monomethyl ether. These may be used alone or in combination of two or more.

  Further, the obtained pattern may be heated and cured. The heating temperature is typically 150 to 400 ° C, preferably 160 to 300 ° C, more preferably 200 to 250 ° C. Although heating time is not specifically limited, For example, it exists in the range of 15 to 300 minutes. This heat treatment can be performed by a hot plate, an oven, a temperature rising oven capable of setting a temperature program, or the like. The atmospheric gas for performing the heat treatment may be air or an inert gas such as nitrogen or argon. Moreover, you may heat under reduced pressure.

The obtained pattern is applicable to the partition of an organic EL element.
Moreover, the board | substrate provided with the manufactured pattern is applicable to an organic EL element. In other words, the organic EL element is formed by forming a pattern to be a partition on an appropriate substrate, applying (injecting) the material liquid that is the source of the organic layer to the partition and drying it, and other known processes. Can be manufactured. For the method for producing the organic EL element, the method for forming the light emitter of the organic EL element, and the like, see, for example, the description in Patent Document 1 (Japanese Patent No. 4621818).

  In addition, the board | substrate provided with the pattern obtained and the pattern manufactured is applicable also to various products other than an electrical / electronic device other than an organic EL element, and an electrical / electronic device. In other words, various technical fields that can take advantage of the benefits of including a specific polymer (not only the liquid repellency of organic solvents, but also water repellency, antifouling properties, release properties, lubricity, and low stress). Application to is considered.

  As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and can employ | adopt various structures other than the above. Further, the present invention is not limited to the above-described embodiment, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.

  Embodiments of the present invention will be described in detail based on examples and comparative examples. In addition, this invention is not limited to an Example.

(Synthesis of raw material polymer)
First, in a suitably sized reaction vessel equipped with a stirrer and a condenser tube, 353.02 g (3.6 mol) of maleic anhydride (hereinafter also referred to as MA) and 2-norbornene (hereinafter also referred to as NB) 338. 94 g (3.6 mol) and 41.45 g (180.0 mmol) of dimethyl 2,2′-azobis (2-methylpropionate) were added, 579.0 g of methyl ethyl ketone (hereinafter also referred to as MEK), and toluene 113. It dissolved in the mixed solvent which consists of 0g, and produced the solution.
Nitrogen was bubbled through the solution for 20 minutes to remove oxygen. Next, MA and NB were polymerized by heating at a temperature of 65 ° C. for 6 hours with stirring to prepare a polymerization solution. The obtained polymerization solution was diluted with 712.9 g of MEK to prepare a dilution liquid, and then the dilution liquid was added dropwise to 8553.1 g of methanol to precipitate a white solid. The white solid thus obtained was vacuum-dried at a temperature of 50 ° C. to obtain 604.64 g of a raw material polymer containing a structural unit derived from NB and a structural unit derived from MA.
As a result of GPC measurement of the obtained raw material polymer, the weight average molecular weight Mw was 12300, and the polydispersity (weight average molecular weight Mw / number average molecular weight Mn) was 1.86.

(Synthesis Example 1)
400.0 g (5.4 mol) of butanol was added to 100 g (0.52 mol of MA conversion) of the above raw material polymer. While stirring this, 7.65 g of aminated silicone diluted with 30.6 g (0.41 mol) of butanol (manufactured by Shin-Etsu Chemical Co., Ltd., product number X-22-9643, 0.0078 mol, functional group (—NH ₂ )) Equivalent 980 g / mol) was added dropwise at room temperature. After completion of the dropwise addition, the mixture was heated and heat-treated (Reflux) at a temperature of 110 ° C. for 4 hours. As described above, a structure derived from butanol or aminated silicone was introduced into the maleic anhydride structure in the raw polymer. (Note that the aminated silicone used corresponds to the above general formula (S1) (R is a methyl group, k is about 10, X is a linear alkylene group having 1 to 6 carbon atoms, and R ⁵ is carbon. 1-6 alkyl groups)).
Thereafter, solvent evaporation and dilution of the obtained solution were repeated to obtain 268.1 g of a 40 mass% PGMEA (propylene glycol monomethyl ether acetate, hereinafter the same) solution of the polymer of Synthesis Example 1.
As a result of GPC measurement of the obtained polymer of Synthesis Example 1, the weight average molecular weight Mw was 13200, and the polydispersity (weight average molecular weight Mw / number average molecular weight Mn) was 1.80. Further, as a result of GPC measurement, the peak corresponding to the raw material aminated silicone disappeared. Furthermore, as a result of infrared spectroscopic analysis, no significant absorption was confirmed near a wave number of 1600 cm ⁻¹ (N—H bending vibration of an amide group), and a structural unit represented by the general formula (B1) was formed. Was confirmed.

(Synthesis Example 2)
400.0 g (5.4 mol) of butanol was added to 100 g (0.52 mol of MA conversion) of the above raw material polymer. While stirring this, 15.3 g of aminated silicone diluted with 61.2 g (0.83 mol) of butanol (manufactured by Shin-Etsu Chemical Co., Ltd., product number X-22-9643, 0.0156 mol, functional group (—NH ₂ )) Equivalent 980 g / mol) was added dropwise at room temperature. After completion of the dropwise addition, the mixture was heated and heat-treated (Reflux) at a temperature of 110 ° C. for 4 hours. As described above, a structure derived from butanol or aminated silicone was introduced into the maleic anhydride structure in the raw polymer.
Then, 263.4g of 40 mass% PGMEA solutions of the polymer of the synthesis example 2 were obtained by repeating solvent distillation and dilution of the obtained solution.

As a result of GPC measurement of the obtained polymer of Synthesis Example 2, the weight average molecular weight Mw was 13700, and the polydispersity (weight average molecular weight Mw / number average molecular weight Mn) was 1.84. Further, as a result of GPC measurement, the peak corresponding to the raw material aminated silicone disappeared. From this result (all the aminated silicone was consumed) and the charged amount of the raw material, it was considered that 3 mol% in the MA structural unit of the raw polymer reacted with the aminosilicone.
Furthermore, as a result of infrared spectroscopic analysis, no significant absorption was confirmed near a wave number of 1600 cm ⁻¹ (N—H bending vibration of an amide group), and a structural unit represented by the general formula (B1) was formed. Was confirmed.

For the solid content of the polymer of Synthesis Example 2, ¹ H-NMR measurement was also performed. This chart is shown in FIG.
In this measurement, a complex peak that was not confirmed when only butanol was allowed to react with the raw material polymer or raw material polymer was observed in the vicinity of 0.0 to 0.2 ppm (the peak “D” in FIG. 1). This confirmed that a silicone chain was introduced into the polymer of Synthesis Example 2. That is, it was confirmed that the polymer of Synthesis Example 2 was obtained by reacting an aminated silicone with a structural unit derived from maleic anhydride.
In this measurement, a peak derived from a structure in which butanol and a structural unit derived from maleic anhydride are reacted (“A” in FIG. 1), or a characteristic derived from an aminated silicone other than “D” described above. Typical peaks ("B" and "C" in FIG. 1) were also confirmed.
From the area ratio between the peak of “B” in FIG. 1 (corresponding to 3 mol% of the MA structural unit of the raw polymer reacting with aminosilicone) and the peak of “A”, the MA structure in the raw polymer It was thought that a structure derived from butanol was introduced in about 50 mol% of the unit (and the MA unit (formula (D1)) in which neither aminated silicone nor butanol was introduced remained as it was).

(Synthesis Example 3)
400.0 g (5.4 mol) of butanol was added to 100 g (0.52 mol of MA conversion) of the above raw material polymer. While stirring this, 31.2 g of aminated silicone diluted with 122.4 g (1.65 mol) of butanol (manufactured by Shin-Etsu Chemical Co., Ltd., product number X-22-9643, 0.0312 mol, functional group (—NH ₂ )) Equivalent 980 g / mol) was added dropwise at room temperature. After completion of the dropwise addition, the mixture was heated and heat-treated (Reflux) at a temperature of 110 ° C. for 4 hours. As described above, a structure derived from butanol or aminated silicone was introduced into the maleic anhydride structure in the raw polymer.
Thereafter, solvent evaporation and dilution of the obtained solution were repeated to obtain 322.1 g of a 40 mass% PGMEA solution of the polymer of Synthesis Example 3.
As a result of GPC measurement of the obtained polymer of Synthesis Example 3, the weight average molecular weight Mw was 14700, and the polydispersity (weight average molecular weight Mw / number average molecular weight Mn) was 1.81. Further, as a result of GPC measurement, the peak corresponding to the raw material aminated silicone disappeared. Furthermore, as a result of infrared spectroscopic analysis, no significant absorption was confirmed near a wave number of 1600 cm ⁻¹ (N—H bending vibration of an amide group), and a structural unit represented by the general formula (B1) was formed. Was confirmed.

(Synthesis Example 4)
40.0 g (0.54 mol) of butanol was added to 10 g of the above raw material polymer (0.052 mol in terms of MA). While stirring this, 5.1 g of aminated silicone diluted with 20.4 g (0.275 mol) of butanol (manufactured by Shin-Etsu Chemical Co., Ltd., product number X-22-9643, 0.0052 mol, functional group (—NH ₂ )) Equivalent 980 g / mol) was added dropwise at room temperature. After completion of the dropwise addition, the mixture was heated and heat-treated (Reflux) at a temperature of 110 ° C. for 4 hours. As described above, a structure derived from butanol or aminated silicone was introduced into the maleic anhydride structure in the raw polymer.
Then, the solvent evaporation and dilution of the obtained solution were repeated, and 32.4 g of 40 mass% PGMEA solutions of the polymer of the synthesis example 4 were obtained.
As a result of GPC measurement of the obtained polymer of Synthesis Example 4, the weight average molecular weight Mw was 16000, and the polydispersity (weight average molecular weight Mw / number average molecular weight Mn) was 1.89.

(Synthesis Example 5)
40.0 g (0.54 mol) of butanol was added to 10 g of the above raw material polymer (0.052 mol in terms of MA). While stirring this, 10.2 g of aminated silicone diluted with 40.8 g (0.55 mol) of butanol (manufactured by Shin-Etsu Chemical Co., Ltd., product number X-22-9643, 0.0104 mol, functional group (—NH ₂ )) Equivalent 980 g / mol) was added dropwise at room temperature. After completion of the dropwise addition, the mixture was heated and heat-treated (Reflux) at a temperature of 110 ° C. for 4 hours. As described above, a structure derived from butanol or aminated silicone was introduced into the maleic anhydride structure in the raw polymer.
Then, the solvent distillation and dilution of the obtained solution were repeated to obtain 40.2 g of a 40% by mass PGMEA solution of the polymer of Synthesis Example 5.
As a result of GPC measurement of the obtained polymer of Synthesis Example 5, the weight average molecular weight Mw was 19300, and the polydispersity (weight average molecular weight Mw / number average molecular weight Mn) was 1.90.

(Synthesis Example 6)
40.0 g (0.54 mol) of butanol was added to 10 g of the above raw material polymer (0.052 mol in terms of MA). While stirring this, 3.2 g of aminated silicone diluted with 12.8 g (0.17 mol) of butanol (manufactured by Shin-Etsu Chemical Co., Ltd., product number KF-868 (corresponding to the above general formula (S2)), 0.00036 mol , Functional group (—NH ₂ ) equivalent 8800 g / mol) was added dropwise at room temperature. After completion of the dropwise addition, the mixture was heated and heat-treated (Reflux) at a temperature of 110 ° C. for 4 hours. As described above, a structure derived from butanol or aminated silicone was introduced into the maleic anhydride structure in the raw polymer.
Then, the solvent distillation and dilution of the obtained solution were repeated to obtain 31.7 g of a 40 mass% PGMEA solution of the polymer of Synthesis Example 6.
As a result of GPC measurement of the obtained polymer of Synthesis Example 6, the weight average molecular weight Mw was 14400, and the polydispersity (weight average molecular weight Mw / number average molecular weight Mn) was 1.93.

(Comparative Synthesis Example 1)
As Comparative Synthesis Example 1, a polymer obtained by ring-opening a polymer comprising a structural unit derived from NB and a structural unit derived from MA using butanol was synthesized. Details will be described below.
First, 125.0 g (1.7 mol) of butanol was added to 25 g of the raw material polymer used in Synthesis Examples 1 to 6 (MA conversion: 0.13 mol), followed by heat treatment (Reflux) at a temperature of 110 ° C. for 4 hours. This caused a reaction to ring-open the MA structural unit in the raw polymer with butanol. Thereafter, the polymer was precipitated with heptane.
Through the above steps, 26.15 g of the polymer of Comparative Synthesis Example 1 was obtained in which a polymer comprising a structural unit derived from NB and a structural unit derived from MA was opened using butanol.
As a result of GPC measurement of the obtained polymer of Comparative Synthesis Example 1, the weight average molecular weight Mw was 12700, and the polydispersity (weight average molecular weight Mw / number average molecular weight Mn) was 1.78.

<Preparation of photosensitive resin composition>
A photosensitive resin composition (Composition 1) was prepared by uniformly mixing the following components and filtering through a filter as appropriate.
-Polymer of Synthesis Example 1: 100 parts by mass in terms of solid content-Cross-linking agent (Printtech VG3101L, epoxy compound described later): 25 parts by mass-Photosensitizer (Dai-Tokemix GPA-200, quinonediazide compound described later): 50 parts by mass · Fluorosurfactant (3M FC 4432): 1 part by mass · Adhesion aid (Shin-Etsu Chemical Co., Ltd. KBM-403E, 3-glycidoxypropyltrimethoxysilane): 5 parts by mass · Organic solvent ( PGMEA): adjusted so that the concentration of the non-volatile component is 30% by mass

  Further, in composition 1, a photosensitive resin composition (composition 2 to composition 2) prepared in the same manner except that the polymer was not the polymer of synthesis example 1 but the polymer of synthesis examples 2 to 6 or comparative example synthesis example 1. 6 and comparative composition 1) were also prepared.

<Evaluation of liquid repellency>
About the film | membrane produced with the photosensitive resin composition prepared above, liquid repellency was evaluated by measuring the contact angle of an anisole solvent. Specifically, it was as follows.

First, the photosensitive resin composition prepared above was spin-coated on a silicon wafer and dried at 100 ° C. for 3 minutes to form a resin film having a thickness of 4 μm. Thereafter, using an oven, the resin film was heated at 230 ° C. for 60 minutes (Air atmosphere) to cure the resin film.
Thus, a resin film for evaluation was obtained.

A contact angle was measured by dropping 2 μL of anisole droplets onto the evaluation resin film. For the measurement of the contact angle, a portable contact angle meter PCA-1 manufactured by Kyowa Interface Chemical Co., Ltd. was used, and the dropped droplets were recorded with a camera. In addition, the company's multifunctional integrated analysis software FAMAS was used as analysis software.
After the anisole was dropped, the contact angle was measured 5 times per second, and the average value of the measurement for 5 seconds was defined as the contact angle. The same dropping and measurement were repeated 5 times, and the average value of the contact angles of these 5 times is shown in Table 1.

<Evaluation of water repellency>
In the measurement of the contact angle, the same evaluation as the above <Evaluation of liquid repellency> was performed except that pure water was dropped instead of dropping anisole. This result is also shown in Table 1.

  As shown in Table 1, the compositions of Examples 1 to 6 including the polymers of Synthesis Examples 1 to 6 are more excellent in the liquid repellency and water repellency of anisole than Comparative Composition 1 including the polymer of Comparative Synthesis Example 1. The results were significantly better. From these results, it was shown that the polymer and the photosensitive resin composition of the present embodiment can be preferably applied as a partition material for organic EL and other materials requiring liquid repellency / water repellency.

<Thermal stability of polymer>
The polymer of Synthesis Example 3 was diluted in a 25% by mass PGMEA solution, spin-coated on a silicon wafer, and dried at 150 ° C. for 2 minutes to form an excessively heated resin film.
When the obtained resin film was subjected to GPC measurement, no aminated silicone, which was a thermally desorbed product of silicone, was observed, and there was no change in the peak when heated at 100 ° C. for 2 minutes.
From the above results, it was shown that the polymer of the present embodiment is less likely to be decomposed and volatilized by heating, and can be preferably applied to a process that requires heating in a manufacturing process such as a manufacturing process of an electronic device.

<Transparency of polymer>
Each of the polymers of Synthesis Examples 1 to 6 was used as a 25 mass% PGMEA solution. This solution was spin-coated on a silicon wafer and dried at 100 ° C. for 2 minutes to form a resin film having a thickness of 2 μm.
When the presence or absence of turbidity of the obtained resin film was visually confirmed, the polymer resin films of Synthesis Examples 1 to 3 were transparent, but the polymer resin films of Synthesis Examples 4 to 6 were slightly turbid. It was. This is presumably because the amount of aminated silicone introduced into the polymers of Synthesis Examples 4 to 6 was larger than the polymers of Synthesis Examples 1 to 3.
From this result, it was found that it is desirable to appropriately adjust the introduction amount of the aminated silicone from the viewpoint of light transmittance of the composition when preparing the photosensitive resin composition.

<Dissolution rate in alkaline developer>
The polymers of Synthesis Examples 2 and 3 and Comparative Synthesis Example 1 were each used as a 25 mass% PGMEA solution. This solution was spin-coated on a silicon wafer and dried at 100 ° C. for 2 minutes to form a resin film having a thickness of 2 μm.
Next, the formed resin film was immersed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution together with the silicon wafer, and the dissolution rate in the alkaline developer was calculated from the time required for the resin film to completely dissolve.
The results are shown in the table below. Note that it is preferable that the dissolution rate is not too high (appropriately small) from the viewpoint of easy formation of a fine pattern and redundancy with respect to variations in patterning conditions.

  From the above results, it was shown that the dissolution rate of the polymer of the present embodiment is a moderately smaller value than that of the polymer of Comparative Synthesis Example 1, which is desirable for forming a fine pattern.

<PGMEA solubility>
It was confirmed whether a 40 mass% PGMEA solution of the polymers of Synthesis Examples 1 to 6 could be prepared (whether there was no undissolved residue). As a result, it was possible to prepare solutions with all polymers. That is, it was shown that the polymer of this embodiment has good organic solvent solubility despite the fact that it contains a silicone structure, which is desirable for application to various compositions.

Claims (12)

A structural unit represented by the following general formula (A1);
A polymer comprising a structural unit represented by the following general formula (B1) and at least one structural unit selected from the group consisting of a structural unit represented by the following general formula (B2).

In general formula (A1),
R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen or an organic group having 1 to 30 carbon atoms,
a ₁ is 0, 1 or 2.

In general formula (B1) and general formula (B2),
R ^S is, NH ₂ moiety excluding a monovalent group of the compound represented by the following general formula (S1) or a monovalent excluding the NH ₂ moiety of the compound represented by the following general formula (S2) It is a group.

In general formula (S1):
Plural Rs are each independently an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group,
R ⁵ is a hydrogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group,
X is a C1-C30 divalent organic group,
k represents an integer of 1 or more.

In general formula (S2):
Plural Rs are each independently an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group,
R ⁶ and R ⁷ are each independently a hydrogen atom, hydroxyl group, alkyl group, cycloalkyl group, alkenyl group, aryl group or aralkyl group;
X ′ is a divalent organic group having 1 to 30 carbon atoms,
l and m each independently represent an integer of 1 or more. The polymer of claim 1,
The polymer containing the structural unit represented by the said general formula (B1). The polymer according to claim 1 or 2, wherein
Furthermore, the polymer containing the structural unit represented by the following general formula (C1).

In general formula (C1):
R ^A is an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or an aralkyl group. The polymer according to any one of claims 1 to 3,
Furthermore, the polymer containing the structural unit represented by a following formula (D1).

  The photosensitive resin composition containing the polymer of any one of Claims 1-4, and a photosensitive agent.   The photosensitive resin film formed with the photosensitive resin composition of Claim 5.   The pattern obtained by exposing and developing the photosensitive resin film of Claim 6.   The organic electroluminescent element provided with the pattern of Claim 7. A film forming step of forming a photosensitive resin film on a substrate using the photosensitive resin composition according to claim 5;
And a pattern forming step of obtaining a pattern by exposing and developing the photosensitive resin film. A method for producing the polymer according to any one of claims 1 to 4,
The raw material polymer containing the structural unit represented by the general formula (A1) and the structural unit represented by the following formula (D1) is converted into a compound represented by the general formula (S1) and / or the general formula ( The manufacturing method of the polymer including the process made to react with the compound represented by S2).

A method for producing the polymer according to any one of claims 1 to 4,
A raw material polymer containing a structural unit represented by the general formula (A1) and a structural unit represented by the following formula (D1), in the presence of an alcohol, a compound represented by the general formula (S1) and // A method for producing a polymer comprising a step of reacting with the compound represented by the general formula (S2).

A method for producing a polymer according to claim 11, comprising:
The manufacturing method of the polymer in which the said alcohol contains the alcohol represented by the following general formula (C1-m).
R ^A —OH (C1-m)
In general formula (C1-m),
R ^A is an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or an aralkyl group.

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