JP6958402B2 - Polymer, photosensitive resin composition, photosensitive resin film, pattern, organic electroluminescence element, method for producing a substrate having a pattern, and method for producing a polymer. - Google Patents

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 having a pattern, and a method for producing a polymer.

Around the light emitting body of an organic electroluminescent element (hereinafter, also referred to as an organic EL element), a partition wall (bank, pixel separation film, pixel definition film, element separation) is provided to electrically insulate from other elements and wiring. (Also called a membrane or the like) may be provided.

As a known technique related to this "partition wall", for example, Patent Document 1 can be mentioned.
In, for example, FIG. 2 of Patent Document 1, a material liquid that is the source of an organic layer is applied (injected) into a region surrounded by a partition wall on a substrate, and then the organic solvent in the material liquid is dried. It is described that an organic layer is formed.
However, Patent Document 1 only describes "fluorine-containing resin" as a material for forming a partition wall (partition wall forming material), and does not provide a detailed and specific description about the partition wall forming material.

On the other hand, Patent Document 2 describes a resin composition containing a cyclic olefin polymer having a protonic polar group as a material used for forming a partition wall of an organic EL device.
Specifically, in the examples of Patent Document 1, 8-carboxytetracyclo [4.4.0.1 ^2,5 . ^17,10 ] Dodeca-3-ene, N-phenyl- (5-norbornene-2,3-dicarboxyimide), and 1,5-hexadiene are used as raw material monomers to form a polymer by ring-opening metathesis polymerization. It is described that the polymer was subjected to a treatment such as hydrogenation to obtain a hydride 1C. It is also described that a 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 wall on a substrate. Since the material liquid is usually obtained by dissolving or dispersing various components in an organic solvent, the partition wall has the property of "repelling" the organic solvent (the liquid repellency of the organic solvent, hereinafter also simply referred to as the liquid repellency). It is preferable to have. By having this property, it is possible to suppress problems such as the material liquid applied (injected) into the region surrounded by the partition wall crawls up the partition wall and exudes to an unintended region.

However, according to the findings of the present inventors, there is room for improvement in the liquid repellent property of the partition wall formed by the conventional partition wall forming material.

The present invention has been made in view of such circumstances. That is, one of the objects of the present invention is to provide a material having high liquid repellency, which 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 inventions provided below can be achieved and the above-mentioned problems can be achieved.

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

The structural unit represented by the following general formula (A1) and
A polymer containing 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).

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 the general formula (A1)
R ¹ , R ² , R ³ and R ⁴ are independently hydrogen or organic groups 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 the general formula (B1) and the 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 base.

In the general formula (S1)
The plurality of Rs are independently alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups or aralkyl groups, respectively.
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 divalent organic group having 1 to 30 carbon atoms.
k represents an integer of 1 or more.

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

Further, according to the present invention.
A photosensitive resin composition containing the above polymer and a photosensitive agent is provided.

Further, according to the present invention.
A photosensitive resin film formed by the above-mentioned photosensitive resin composition is provided.

Further, according to the present invention.
A pattern obtained by exposing and developing the above-mentioned photosensitive resin film is provided.

Further, according to the present invention.
An organic electroluminescent device having the above pattern is provided.

Further, according to the present invention.
A film forming step of forming a photosensitive resin film on a substrate using the above photosensitive resin composition, and
Provided is a method for manufacturing a substrate having a pattern, which comprises a pattern forming step of exposing and developing the photosensitive resin film to obtain a pattern.

Further, according to the present invention.
The above-mentioned polymer manufacturing method.
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 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 the compound represented by S2).

Further, according to the present invention.
The above-mentioned polymer manufacturing method.
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 subjected to the compound represented by the general formula (S1) and the raw material polymer in the presence of alcohol. / Or a method for producing a polymer, which comprises a step of reacting with a 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, for example, as a partition wall forming material for an organic EL element.

^{6 is a 1} H-NMR chart of the polymer obtained in Synthesis Example 2.

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

In the present specification, the notation "a to b" in the description of the numerical range means a or more and b or less unless otherwise specified. For example, "1 to 5% by mass" means "1% by mass or more and 5% by mass or less".
In the notation of a group (atomic group) in the present specification, the notation that does not indicate whether it is substituted or unsubstituted 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) acrylic" herein represents a concept that includes both acrylic and methacryl. The same applies to similar notations such as "(meth) acrylate".

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

In the general formula (A1)
R ¹ , R ² , R ³ and R ⁴ are independently hydrogen or organic groups 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 the general formula (B1) and the 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 base.

In the general formula (S1)
The plurality of Rs are independently alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups or aralkyl groups, respectively.
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 divalent organic group having 1 to 30 carbon atoms.
k represents an integer of 1 or more.

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

It is considered that this polymer exhibits desirable liquid repellency (liquid repellency to an organic solvent such as anisole) by having a silicon-containing group of ^{R s.} Therefore, by forming the partition wall with this polymer (or an appropriate composition containing this polymer), the liquid repellency of the partition wall can be improved.
Further, since this polymer contains a rigid structural unit represented by the general formula (A1), the shape of the partition wall is not easily deformed by preferable performance as a partition wall forming material other than liquid repellency, for example, heat. It is also considered to play the performance such as.

The polymer production method (synthesis method) of the present embodiment will be described in detail separately, but will be briefly described.
(I) First, a polymer containing a structural unit represented by the general formula (A1) and a structural unit derived from maleic anhydride (a structural unit represented by the formula (D1) described later) is prepared.
(Ii) Next, the structural unit derived from maleic anhydride of the polymer is obtained by a reaction of attacking _{the amino group (-NH 2} site) of the compound represented by the general formula (S1) or the general formula (S2). 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 alkalil group. , Cycloalkyl group, alkoxy group, heterocyclic group, carboxyl group and the like.
Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group and a heptyl group. Examples thereof include an octyl group, a nonyl group and a decyl group.
Examples of the alkenyl group include an allyl group, a pentenyl group, a vinyl group and the like.
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 xsilyl group, a phenyl group, a naphthyl group, and an anthrasenyl group.
Examples of the aralkyl group include a benzyl group and a phenethyl group.
Examples of the alkaline group include a tolyl group and a xylyl group.
Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group and the like.
Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an s-butoxy group, an isobutoxy group, a t-butoxy group, an n-pentyloxy group and a neopentyloxy group. , N-hexyloxy group and the like.
Examples of the heterocyclic group include an epoxy group and an oxetanyl group.

Preferably a hydrogen or an alkyl group as ^{R 1,} R 2, ^{R 3} and ^{R 4} in the general formula (A1), hydrogen is more preferable.
The hydrogen atoms in the organic groups having 1 to 30 carbon atoms of R ¹ , R ² , R ³ and R ^{4 may be substituted with arbitrary atomic groups.} For example, it may be substituted with a fluorine atom, a hydroxyl group, a carboxyl group, or the like. More specifically, an alkyl fluoride 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 formula (A1), _{a 1} is preferably 0 or 1, more preferably 0.

The proportion of the structural unit represented by the general formula (A1) in the total 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 formula (B1) and the general formula (B2), R ^s _{is a monovalent group excluding the NH 2} portion of the compound represented by the above-mentioned general formula (S1), or the above-mentioned 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)
Examples of the alkyl group of R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, and a hexyl group. Examples thereof include a heptyl group, an octyl group, a nonyl group and a decyl group.
Examples of the cycloalkyl group of R include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group. In addition, polycyclic cycloalkyl groups such as norbornyl group and adamantyl group can also be mentioned.
Examples of the alkenyl group of R include an allyl group, a pentenyl group, a vinyl group and the like.
Examples of the aryl group of R include a tolyl group, a xsilyl group, a phenyl group, a naphthyl group, an anthrasenyl group and the like.
Examples of the aralkyl group of R include a benzyl group and a phenethyl group.

The carbon number of R is preferably 1 to 12, more preferably 1 to 10, and even more preferably 1 to 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 those similar to those mentioned as specific examples of R.
The number of carbon atoms in R ⁵ is preferably 1 to 12, more preferably 1 to 10, more preferably from 1 to 6.
R ⁵ is preferably an alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms, and even 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 (linear or branched), a cycloalkylene group, an arylene group, and a group in which two or more of these groups are linked. 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, the structure may be such that the central CH ₂ site of the propylene group −CH ₂ −CH ₂ −CH ₂ − is replaced with an ether bond −CH ₂ −O−CH _2−.

Examples of the alkylene group of X include a divalent group obtained by removing one arbitrary hydrogen atom from the group exemplified as the alkyl group of R.
Examples of the cycloalkylene group of X include a divalent group obtained by removing one arbitrary hydrogen atom from the group exemplified as the cycloalkyl group of R.
Examples of the arylene group of X include a divalent group obtained by removing one arbitrary hydrogen atom from the group exemplified as the aryl group of 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 is a methylene group, an ethylene group, a propylene group or a butylene group. It is more preferable to have.

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

・ General formula (S2)
Specific examples and preferred embodiments of R are the same as those of 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 of R ⁵ of the general formula (S1). Particularly preferably, it 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 those of X in the general formula (S1).
l may be an integer of 1 or more, but is preferably 1 to 1000, more preferably 3 to 500, and even more preferably 5 to 200.
m may be an integer of 1 or more, but is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 2.
When m is an integer of 2 or more, two or more -NH ₂ ^{exists, but the structure excluding one of them is R s of the} general formula (B1) or the general formula (B2). Become.

The polymer of the present embodiment preferably contains the structural unit represented by the general formula (B1) among the structural unit represented by the general formula (B1) and the structural unit represented by the general formula (B2).
According to the findings of the present inventors, the structural unit represented by the general formula (B1) is less likely to be thermally decomposed or dissociated in the ^{R s portion than the structure represented by the general formula (B2).} .. That is, when the polymer of the present 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 spectroscopic measurement (FT-IR analysis) and a wave number of 1600 cm ^-1 (NH variation of the amide group). The presence or absence of absorption near (angle 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) (the sum of the two structural units) to the total structural units of the polymer of the present embodiment is preferably 1. ~ 30 mol%, more preferably 1-20 mol%, still more preferably 1-15 mol%, particularly preferably 1-6 mol%, most preferably 1-3 mol%. By appropriately adjusting this value, the transparency of the resin can be improved. Then, when the polymer of the present embodiment is used in the photosensitive resin composition, turbidity of the composition can be suppressed. That is, it is preferable in terms of light transmission during exposure.

As described above, in the present embodiment, the structural unit represented by the general formula (B1) is preferable to 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 the total structural units of the polymer of the present embodiment is preferably 1 to 30 mol%, more preferably 1 to 15 mol%, and further. It is preferably 1 to 10 mol%, particularly preferably 1 to 6 mol%, and most preferably 1 to 3 mol%.

The polymer of the present embodiment further preferably contains a structural unit represented by the following general formula (C1).

In the general formula (C1), ^RA is an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group.

It is considered that the effect of improving the alkali solubility of the polymer can be obtained by including this structural unit in the polymer of the present embodiment. That is, due to the −COOH structure, for example, when a photosensitive resin composition is prepared using the polymer of the present embodiment, the developability with respect to an alkaline developer can be improved.

Further, it is considered that the solubility of the polymer in an organic solvent can be improved by including this structural unit in the polymer of the present embodiment. That is, since ^{the hydrocarbon structure of RA} is compatible with the organic solvent, when the polymer of the present embodiment and the organic solvent are mixed to prepare a composition, a composition in which undissolved residue and the like are reduced can be obtained. It is considered easy to obtain. In particular, when the polymer has a silicone-containing structure, the solubility in an organic solvent may decrease. Therefore, it is preferable that the hydrocarbon structure of ^{RA ensures the solubility in an organic solvent.}

^{Specific examples of the alkyl group, cycloalkyl group, alkenyl group, aryl group and aralkyl group of RA} include the alkyl group, cycloalkyl group, alkenyl group and aryl given as specific examples of R in the general formula (S1). Groups and arylkill groups can be mentioned.
^{The carbon number of RA} is preferably 1 to 12, more preferably 2 to 10, and even more preferably 2 to 8. ^{By adjusting the carbon number of RA} , it is possible to achieve both solubility in an organic solvent and solubility in an alkaline developer.

The method of introducing the structural unit represented by the general formula (C1) into the polymer will be described in detail separately, but to explain it very briefly, for example, the structural unit derived from maleic anhydride (in the formula (D1) described later). It can be obtained by a reaction of attacking an alcohol represented by ^RA- OH ( ^RA is synonymous with that in the general formula (C1)) with respect to the represented structural unit).

When the polymer of the present embodiment contains a structural unit represented by the general formula (C1), its content (ratio to all structural units) is preferably 10 to 40 mol%, more preferably 15 to 35 mol%. More preferably, it is 20 to 30 mol%. By adjusting the content of the structural unit represented by the general formula (C1), the above-mentioned developability for alkaline development and solubility in organic solvents can be further enhanced.

The polymer of the present 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 reacts with the raw material polymer in the 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 considered that the inclusion of the structural unit represented by the formula (D1) in the polymer has an advantage in forming a cured film using the polymer. For example, it is considered that the structural unit represented by the formula (D1) can form a crosslinked structure by reacting with a crosslinkable component (for example, an epoxy group-containing compound) to increase the strength of the cured film.

Further, from another viewpoint, it is considered that the solubility in the alkaline developer can be appropriately adjusted by including the structural unit represented by the formula (D1) in the polymer.

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

The weight average molecular weight Mw of the polymer of the present embodiment is preferably 2000 to 50,000, more preferably 5000 to 25000, and even more preferably 7500 to 15000. By appropriately adjusting the weight average molecular weight, the solubility in an alkaline developer, the solubility in an organic solvent, and the like can be adjusted.
The degree of 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 even more preferably 1. It is 0 to 2.0. By appropriately adjusting the degree of 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 includes the amount of raw material charged (molar amount) at the time of polymer synthesis, the amount of raw material remaining after synthesis, and the peak area of various spectra (for example, ^1). It can be estimated / calculated from the peak area of H-NMR).

<Polymer manufacturing method>
The polymer production method (synthesis method) of the present embodiment is not particularly limited, but as an example, a structural unit represented by the above-mentioned general formula (A1) and a structural unit represented by the above-mentioned formula (D1) are used. The raw material polymer containing the above can be obtained by reacting with the compound represented by the above-mentioned general formula (S1) and / or the compound represented by the above-mentioned general formula (S2).
In the following, the compound represented by the general formula (S1) and / or the compound represented by the general formula (S2) will also be referred to as “aminoized silicone compound”.

First, a 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 the general formula (2), R ¹ , R ² , R ³ , R ⁴ and a ₁ are synonymous with ^{R 1} , R ² , R ³ R ⁴ and a _{1 in} the general formula (A 1), respectively.
Examples of the monomer represented by the general formula (2) include norbornene, norbornene, bicyclo [2.2.1] -hept-2-ene (common name: 2-norbornene), 5-methyl-2-norbornene, and the like. 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 thereof include methyl 5-norbornene-2-carboxylate and 5-norbornene-2,3-dicarboxylic acid anhydride.
At the time of polymerization, only one type of monomer represented by the general formula (2) may be used, or two or more types may be used in combination.

The method of polymerization is not limited, but radical polymerization using a radical polymerization initiator is preferable.
As the polymerization initiator, for example, an azo compound, an organic peroxide, or the like can be used.
Specific examples of the azo compound include azobisisobutyronitrile (AIBN), dimethyl 2,2'-azobis (2-methylpropionate), and 1,1'-azobis (cyclohexanecarbonitrile) (ABCN). Can be mentioned.
Examples of the organic peroxide include hydrogen peroxide, di-tert-butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), methyl ethyl ketone peroxide (MEKP) and the like.
As the polymerization initiator, only one type may be used, or two or more types may be used in combination.

As the polymerization solvent, for example, an organic solvent such as diethyl ether, tetrahydrofuran, toluene, or methyl ethyl ketone 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 the polymerization initiator are dissolved in a solvent and charged into a reaction vessel, and then heated to allow the addition polymerization to proceed. 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) to maleic anhydride when charged in the reaction vessel is preferably 0.5: 1 to 1: 0.5. From the viewpoint of controlling the molecular structure, the molar ratio is preferably 1: 1.
By such a step, a "raw material 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 synthesizing the above-mentioned raw material polymer, a step of removing low molecular weight components such as unreacted monomers, oligomers, and residual polymerization initiator may be performed.
Specifically, an organic layer containing the synthesized raw material polymer and a low molecular weight component is concentrated, and then mixed with an organic solvent such as tetrahydrofuran (THF) to obtain a solution. Then, this solution is mixed with a poor solvent such as methanol to precipitate the monomer. By collecting and drying this precipitate, the purity of the raw material polymer can be increased.

Next, a method of reacting the raw material polymer with the amination silicone compound will be described. This method can be performed, for example, in the following steps (1) and (2).
(1) The raw material polymer is an appropriate organic solvent (alcohol-based solvent described later and / or a single solvent such as propylene glycol monomethyl ether acetate (PGMEA), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), or a mixed solvent. ) Prepare a solution dissolved in. While stirring this, the amination silicone compound diluted with an organic solvent is added dropwise. As a result, the structural unit derived from maleic anhydride of the raw material polymer is reacted with the -NH ₂ moiety of the amination silicone compound, and an amide bond is formed 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 dropping, the solution is heated at 80 to 200 ° C. for 1 to 24 hours (reflux, etc.). As a result, the carboxyl group generated by ring-opening of the structural unit derived from maleic anhydride in the above step (1) reacts with the amide bond and dehydrates to form an imide ring structure.

In other words, the structural unit represented by the general formula (B2) (the structural unit in which the maleic anhydride structure is ring-opened) can be introduced into the raw material polymer by the above step (1). Further, by continuously performing the step (2), it is possible to introduce a 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 ring-closed). can.

The above step (1) is preferably performed in the presence of alcohol. In other words, the polymer production method (synthesis method) of the present embodiment preferably comprises 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, it is possible to introduce into the polymer a structural unit in which the structural unit derived from maleic anhydride is ring-opened, as represented by the general formula (C1). That is, the structural unit derived from maleic anhydride reacts with the hydroxyl group of the alcohol to generate a structural unit as shown in the general formula (C1).

The reaction between maleic anhydride and an alcohol such as butanol is considered to be a reversible reaction. Therefore, under normally applied reaction conditions (for example, the reaction conditions of Examples described later), even if alcohol is used in an amount (excess amount) larger than the molar amount of the structural unit derived from maleic anhydride, all the relevant substances are concerned. 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) alcohol is used as an organic solvent for dissolving the raw material polymer, and (ii) an amination silicone compound is diluted. Alcohol is used as the organic solvent, (iii) both of these, and the like can be adopted.

The alcohol used here preferably contains an alcohol represented by the following general formula (C1-m).
^RA- OH (C1-m)

In the general formula (C1-m), ^RA is synonymous with ^RA in the general formula (C1). That is, it 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.

As for the amination silicone compound (the compound represented by the general formula (S1) or the compound represented by the general formula (S2)), a commercially available product can be appropriately used. For example, one sold as "modified silicone oil" by Shin-Etsu Chemical Co., Ltd., one sold as "organic modified silicone oil" by Toray Dow Corning, and one sold as "REACIVE SILICONES" by Gelest. You can use what you have.

The polymer of the present embodiment can be used, for example, as a raw material for the photosensitive resin composition described below. Further, the polymer of the present embodiment may be used alone for some purpose, or a non-photosensitive composition obtained by mixing the polymer of the present embodiment with an arbitrary component may be prepared and applied to any use. good.
Since the polymer of the present embodiment contains a silicone structure, it is considered that not only the liquid repellency of the organic solvent but also the performances such as water repellency, antifouling property, releasability, lubricity, and stress reduction are exhibited. That is, it can be applied to technical fields where these performances are required.

<Photosensitive resin composition>
The photosensitive resin composition of the present embodiment contains 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 contained.
Hereinafter, these photosensitizers and optional components will be described.

-Photosensitizer The photosensitive resin composition of the present embodiment contains a photosensitive agent.
As the photosensitive agent, an acid generator, that is, a compound that generates an acid by irradiation with an active ray (for example, g-ray or i-ray) can be preferably mentioned.

Specifically, as the photosensitizer, a photosensitive diazoquinone compound, onium salt (sulfonium salt, iodonium salt, etc.), sulfonic acid ester compound, triazine compound, oxime sulfonate compound, diazodisulfone compound, 2-nitrobenzyl ester compound, N- Examples thereof include iminosulfonate compounds, imidesulfonate compounds, 2,6-bis (trichloromethyl) -1,3,5-triazine compounds, dihydropyridine compounds and the like.

In particular, when the photosensitive resin composition is of the positive type (when developed with an alkaline developer after pattern exposure, the exposed portion dissolves), the photosensitive agent preferably contains a diazoquinone compound. By using the diazoquinone compound, sensitivity, resolving power, 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 of the structures represented by the following formulas (a), the following formula (b) and the following formula (c), or a hydrogen atom. However, at least one of the Qs of each diazoquinone compound is any of the structures represented by the following formulas (a), the following formula (b) and the following formula (c). Further, n is an integer of 1 to 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 the present embodiment may contain only one type of photosensitizer, or may contain two or more types of photosensitizer.
The content of the photosensitive agent 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. Within this range, sufficient sensitivity can be obtained, and other performance and sensitivity can be compatible with each other.

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

The cross-linking agent typically contains 2 or more (preferably 2 to 6, more preferably 2 to 4) cross-linking groups in one molecule.
Preferred cross-linking agent (C) includes, for example, the following compounds (1) to (5).

(1) Cross-linking 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 methoxymethylbenzoate, bis (methoxymethyl) biphenyl, dimethylbis (methoxymethyl) biphenyl; as commercial products, 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.), Nicarac MX-270,- 280, 290, Nicarac MS-11, Nicarac MW-30, -100, -300, -390, -750 (manufactured by Sanwa Chemical Co., Ltd.), 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 (manufactured by Asahi Organic Materials Industry 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-diacetoximel-p-cresol, TriML-P, TriML-35XL, TriML-TrisCR-HAP, HML-TPPHBA, HML- TPHA P, HMOM-TPPHBA, HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.) and the like can be mentioned.

(2) Compounds 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. , Gglycerol polyglycidyl ether, sorbitol polyglycidyl ether, bisphenol A (or F) glycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylol ethanetriglycidyl ether, pentaerythritol poly Examples thereof include glycidyl ethers such as glycidyl ethers (for example, pentaerythritol tetraglycidyl ethers).

In addition, glycidyl esters such as adipic acid diglycidyl ester and o-phthalic acid diglycidyl ester, 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexane) carboxylate, and 3,4-epoxy-6-methylcyclohexylmethyl (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 be done.

Furthermore, alicyclic epoxy compounds such as Celoxide 2021, Celoxide 2081, Celoxide 2083, Celoxide 2085, Celoxide 8000, and Epolide GT401 manufactured by Daicel Co., Ltd., and aromatic group-containing highly heat-resistant trifunctional epoxy such as TECHMORE VG3101L manufactured by Printec Co., Ltd. Examples thereof include compounds, Epolite 100MF manufactured by Kyoeisha Chemical Industry Co., Ltd., aliphatic polyglycidyl ethers such as Epiol TMP manufactured by Nichiyu Co., Ltd., and DMS-E09 manufactured by Gerest Co., Ltd.

(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, trimethylpropanthris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-) 3-Oxetanylmethyl) ether, poly [[3-[(3-ethyl-3-oxetanyl) methoxy] propyl] silaseskioxane] derivative, oxetanyl silicate, phenol novolac type oxetane, 1,3-bis [(3-ethyl) Oxetane-3-yl) methoxy] benzene and the like can be mentioned.

(4) Compounds 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 and the like. Can be 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 thereof include 4,4'-diphenylsulphonbismaleimide, 1,3-bis (3-maleimidephenoxy) benzene, and 1,3-bis (4-maleimidephenoxy) benzene.

In addition, as (2) a compound having an epoxy group, a known epoxy resin can also be mentioned. 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 , An aliphatic epoxy resin, an aliphatic polyfunctional epoxy resin, an alicyclic epoxy resin, a polyfunctional alicyclic epoxy resin and the like.

When a cross-linking agent is used, it may be used alone or in combination of two or more.
When the photosensitive resin composition contains a cross-linking 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 aid The photosensitive resin composition may contain an adhesion aid. This makes it possible to improve the adhesion of the resin film or pattern formed of the photosensitive resin composition to the substrate.
The adhesive aid that can be used is not particularly limited. For example, silane coupling agents such as aminosilane, epoxysilane, acrylicsilane, mercaptosilane, vinylsilane, ureidosilane, acid anhydride functional silane, and sulfidesilane can be used. One type of silane coupling agent may be used alone, or two or more types may be used in combination. Among these, epoxysilane (ie, a compound containing both an epoxy moiety and a group that generates a silanol group by hydrolysis in one molecule) or acid anhydride functional silane (ie, acid anhydride in one molecule). A compound containing both a physical group and a group that generates a silanol group by hydrolysis) is preferable.

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, Examples thereof include N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane and N-phenyl-γ-amino-propyltrimethoxysilane.

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

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

Examples of the mercaptosilane include 3-mercaptopropyltrimethoxysilane.

Examples of vinylsilane include vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, and the like.

Examples of the ureidosilane include 3-ureidopropyltriethoxysilane and the like.

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 the adhesion aid is used, only one type may be used, or two or more types may be used in combination.
The content of the adhesion aid 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. Within this range, it is considered that "adhesion", which is the effect of the adhesion aid, can be sufficiently obtained while balancing with other performances.

-Surfactant The photosensitive resin composition may contain a surfactant. Thereby, the uniformity of the thickness when the photosensitive resin composition is applied onto the 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 the "Mega Fuck" series manufactured by DIC Co., Ltd. , 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 Fluorine-containing oligomeric structures such as -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 Neos Co., Ltd.'s Futagent 250 and Futagent 251's SILFOAM® series (eg SD 100 TS, SD 670, SD 850, SD 850, Wacker Chemie) Examples thereof include silicone-based surfactants such as SD 860 and SD 882).

When a surfactant is used, only one type may be used, or two or more types may be used in combination.
The content of the surfactant 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. Within this range, it is considered that the effect of improving the uniformity of the thickness of the resin film can be sufficiently obtained while balancing with other performances.

-Solvent The photosensitive resin composition preferably contains a solvent.
The solvent that can be used is typically an organic solvent. Specifically, a ketone solvent, an ester solvent, an ether solvent, an alcohol solvent, a lactone solvent, a carbonate solvent 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. , Propylene Glycol Diacetate, Propylene Glycol Diacetate, Propylene Glycol Monomethyl Ether Acetate, Anisol, N-Methylpyrrolidone, Cyclohexanone, Cyclopentanone, Dipropylene Glycolmethyl-n-propyl Ether and other organic solvents. can.

When a solvent is used, only one type may be used, or two or more types may be used.
When a solvent is used, the amount used is not particularly limited, but the solvent is used in such an amount that the concentration of the non-volatile component is, for example, 10 to 70% by mass, preferably 15 to 60% by mass.

-Other components The photosensitive resin composition of the present embodiment may contain various components other than the above. For example, it may contain 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.
Among the above, as the basic compound, various amine compounds (for example, primary amine, secondary amine, tertiary amine, etc.) can be specifically mentioned.
Among the above, as the curing accelerator, a nitrogen-containing heterocyclic compound containing an amidine skeleton or a salt thereof (specifically, diazabicycloundecene or a salt thereof) can be specifically mentioned.

Further, the photosensitive resin composition of the present embodiment may contain a polymer different from the specific polymer. For example, the structural units represented by the above-mentioned general formula (A1), general formula (C1) and / or formula (D1) are included, but the structural units represented by the general formula (B1) and the general formula (B2) are used. A polymer containing no structural unit represented may be used in combination with a specific polymer.
Further, the photosensitive resin composition of the present embodiment may contain two or more kinds of polymers corresponding to the specific polymer.

-Supplementary information, etc. The photosensitive resin composition of the present embodiment may be of a positive type or a negative type. Any can be designed depending on the pattern shape to be obtained. Typically, the photosensitive resin is typically adjusted by appropriately adjusting the strength of the acid generated from the photosensitive agent and the reactivity of the cross-linking agent (whether or not the cross-linking reaction proceeds due to the acid generated from the photosensitive agent). The composition can be designed in either positive or negative form.

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, still more preferably 5 to 40% by mass, based on the total amount of the non-volatile components in the composition (100% by mass). It is 10 to 30% by mass.

<Photosensitive resin film, pattern, manufacturing method of substrate with pattern, organic EL element>
A photosensitive resin film can be formed by using the above-mentioned photosensitive resin composition. Further, the photosensitive resin film can be exposed and developed to form a pattern, a substrate having the pattern can be manufactured, or an organic EL element can be manufactured.
Hereinafter, the formation of the photosensitive resin film, the exposure / development of the photosensitive resin film, and the like will be specifically described.

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

The substrate on which the composition is applied is not particularly limited, and examples thereof include a glass substrate, a silicon wafer, a ceramic substrate, an aluminum substrate, a SiC wafer, a GaN wafer, and a copper-clad laminate. When manufacturing an organic EL device, 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 on the surface. It may be surface-treated to improve the adhesiveness.

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

Drying of the photosensitive resin composition applied on the substrate is typically carried out by heat treatment with a hot plate, hot air, an oven or the like. The heating temperature is usually 80 to 140 ° C, preferably 90 to 120 ° C. The heating time is usually about 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 finally obtaining a partition wall of an organic EL element, the film thickness of the photosensitive resin film is usually 0.5 to 10 μm, preferably 1 to 5 μm. The film thickness can be adjusted by adjusting the content of the solvent in the photosensitive resin composition, the coating method, and the like.

-Exposure Exposure is typically performed by irradiating the photosensitive resin film with active light rays through an appropriate photomask.
Examples of active rays include X-rays, electron beams, ultraviolet rays, visible rays and the like. In terms of wavelength, light having a wavelength 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. Further, two or more light rays may be mixed and used. As the exposure apparatus, a contact aligner, a mirror projection or a stepper is preferable.
The amount of light for exposure may be appropriately adjusted depending on the amount of the photosensitive agent in the photosensitive resin film and the like, and is, for example, about ^{100 to 500 mJ / cm 2.}

After the exposure, the photosensitive resin film may be heated again if necessary (heating after exposure: 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 developing solution, a pattern can be obtained and a substrate having the pattern can be manufactured. Then, the pattern or the substrate provided with the pattern is preferably applied to, for example, an organic EL element.

In the developing step, development can be carried out using a suitable developer, for example, by a method such as a dipping method, a paddle method, or a rotary spray method. By development, the exposed portion (in the case of the positive type) or the unexposed portion (in the case of the 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, and (iii). Examples thereof include an aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide.
Specific examples of the organic solvent include a ketone solvent such as cyclopentanone, an ester solvent such as propylene glycol monomethyl ether acetate (PGMEA) and butyl acetate, and an ether solvent such as propylene glycol monomethyl ether.
A water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added to the developing solution.

In this embodiment, it is preferable to use an aqueous solution of tetramethylammonium hydroxide as a developing solution. 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.

By the above steps, a pattern can be obtained / a substrate having the pattern can be produced, but various processes may be performed after the development.

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

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

The obtained pattern can be applied to the partition wall of the organic EL element.
Further, the substrate having the manufactured pattern can be applied to an organic EL element. That is, the organic EL element is formed by a step of forming a pattern to be a partition wall on an appropriate substrate, applying (injecting) a material liquid which is a source of an organic layer to the partition wall portion and drying, and other known steps. Can be manufactured. For a method of manufacturing an organic EL element, a method of forming a light emitting body of an organic EL element, and the like, refer to, for example, the above-mentioned description of Patent Document 1 (Patent No. 4621818).

The substrate having the obtained pattern or the manufactured pattern can be applied to various electric / electronic devices other than the organic EL element and various products not limited to the electric / electronic device. In other words, various technical fields that can take advantage of the inclusion of a specific polymer (not only the liquid repellency of organic solvents, but also water repellency, antifouling property, mold release property, lubricity, low stress, etc. are expected). Can be applied to.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted. Further, the present invention is not limited to the above-described embodiment, and modifications, improvements, and the like within the range in which the object of the present invention can be achieved are included in the present invention.

Embodiments of the present invention will be described in detail based on Examples and Comparative Examples. The present invention is not limited to the examples.

(Synthesis of raw material polymer)
First, in an appropriately sized reaction vessel equipped with a stirrer and a cooling 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, and 579.0 g of methyl ethyl ketone (hereinafter, also referred to as MEK) and toluene 113. A solution was prepared by dissolving in a mixed solvent consisting of 0 g.
The solution was aerated with nitrogen for 20 minutes to remove oxygen. Then, by heating at a temperature of 65 ° C. for 6 hours with stirring, MA and NB were polymerized to prepare a polymerization solution. The obtained polymerization solution was diluted with MEK 712.9 g to prepare a dilution solution, and then the dilution solution was added dropwise to methanol 8553.1 g 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 degree of 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 of the above raw material polymer (0.52 mol in terms of MA). While stirring this, 7.65 g of amination 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 dropping, 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 amination silicone was introduced into the maleic anhydride structure portion of the raw material polymer. (Note that the amination 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 a carbon. Alkyl groups of numbers 1 to 6)).
Then, by repeating solvent distillation and dilution of the obtained solution, 268.1 g of a 40% by mass PGMEA (propylene glycol monomethyl ether acetate, the same applies hereinafter) solution of the polymer of Synthesis Example 1 was obtained.
As a result of GPC measurement of the obtained polymer of Synthesis Example 1, the weight average molecular weight Mw was 13200, and the degree of polydispersity (weight average molecular weight Mw / number average molecular weight Mn) was 1.80. Moreover, as a result of GPC measurement, the peak corresponding to the raw material amination silicone disappeared. Furthermore, as a result of infrared spectroscopic analysis ^{, no significant absorption was confirmed near the wave number of 1600 cm -1} (NH variable angular vibration of the amide group), and the 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 of the above raw material polymer (0.52 mol in terms of MA). While stirring this, 15.3 g of amination 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 dropping, 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 amination silicone was introduced into the maleic anhydride structure portion of the raw material polymer.
Then, by repeating solvent distillation and dilution of the obtained solution, 263.4 g of a 40% by mass PGMEA solution of the polymer of Synthesis Example 2 was obtained.

As a result of GPC measurement of the obtained polymer of Synthesis Example 2, the weight average molecular weight Mw was 13700, and the degree of polydispersity (weight average molecular weight Mw / number average molecular weight Mn) was 1.84. Moreover, as a result of GPC measurement, the peak corresponding to the raw material amination silicone disappeared. From this result (all the amination silicone was consumed) and the amount of the raw material charged, it was considered that 3 mol% of the MA structural unit of the raw material polymer reacted with the amino silicone.
Furthermore, as a result of infrared spectroscopic analysis ^{, no significant absorption was confirmed near the wave number of 1600 cm -1} (NH variable angular vibration of the amide group), and the structural unit represented by the general formula (B1) was formed. Was confirmed.

For the solid content of the polymer of Synthesis Example 2, ^{1 1} H-NMR measurement was also performed. This chart is shown in FIG.
In this measurement, a complicated peak that was not confirmed when only butanol was reacted with the raw material polymer or the raw material polymer was confirmed in the vicinity of 0.0 to 0.2 ppm (peak of “D” in FIG. 1). From this, it was confirmed that the silicone chain was introduced into the polymer of Synthesis Example 2. That is, it was confirmed that the polymer of Synthesis Example 2 was a reaction of the amination silicone and the structural unit derived from maleic anhydride.
In this measurement, the peak derived from the structure obtained by the reaction of butanol and the structural unit derived from maleic anhydride (“A” in FIG. 1) and the characteristics derived from the amination silicone other than the above-mentioned “D”. Peaks (“B” and “C” in FIG. 1) were also confirmed.
From the area ratio of the peak of "B" in FIG. 1 (corresponding to the reaction of 3 mol% in the MA structural unit of the raw material polymer with aminosilicone) and the peak of "A", the MA structure in the raw material polymer It was considered that a butanol-derived structure 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 of the above raw material polymer (0.52 mol in terms of MA). 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 dropping, 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 amination silicone was introduced into the maleic anhydride structure portion of the raw material polymer.
Then, by repeating solvent distillation and dilution of the obtained solution, 322.1 g of a 40% by mass PGMEA solution of the polymer of Synthesis Example 3 was obtained.
As a result of GPC measurement of the obtained polymer of Synthesis Example 3, the weight average molecular weight Mw was 14700, and the degree of polydispersity (weight average molecular weight Mw / number average molecular weight Mn) was 1.81. Moreover, as a result of GPC measurement, the peak corresponding to the raw material amination silicone disappeared. Furthermore, as a result of infrared spectroscopic analysis ^{, no significant absorption was confirmed near the wave number of 1600 cm -1} (NH variable angular vibration of the amide group), and the structural unit represented by the general formula (B1) was formed. Was confirmed.

(Synthesis Example 4)
To 10 g of the above raw material polymer (0.052 mol in terms of MA), 40.0 g (0.54 mol) of butanol was added. 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 dropping, 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 amination silicone was introduced into the maleic anhydride structure portion of the raw material polymer.
Then, by repeating solvent distillation and dilution of the obtained solution, 32.4 g of a 40% by mass PGMEA solution of the polymer of Synthesis Example 4 was 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 degree of polydispersity (weight average molecular weight Mw / number average molecular weight Mn) was 1.89.

(Synthesis Example 5)
To 10 g of the above raw material polymer (0.052 mol in terms of MA), 40.0 g (0.54 mol) of butanol was added. While stirring this, 10.2 g of amination 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 dropping, 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 amination silicone was introduced into the maleic anhydride structure portion of the raw material polymer.
Then, by repeating solvent distillation and dilution of the obtained solution, 40.2 g of a 40% by mass PGMEA solution of the polymer of Synthesis Example 5 was obtained.
As a result of GPC measurement of the obtained polymer of Synthesis Example 5, the weight average molecular weight Mw was 19300, and the degree of polydispersity (weight average molecular weight Mw / number average molecular weight Mn) was 1.90.

(Synthesis Example 6)
To 10 g of the above raw material polymer (0.052 mol in terms of MA), 40.0 g (0.54 mol) of butanol was added. 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 dropping, 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 amination silicone was introduced into the maleic anhydride structure portion of the raw material polymer.
Then, by repeating solvent distillation and dilution of the obtained solution, 31.7 g of a 40% by mass PGMEA solution of the polymer of Synthesis Example 6 was obtained.
As a result of GPC measurement of the obtained polymer of Synthesis Example 6, the weight average molecular weight Mw was 14400, and the degree of 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 having a structural unit derived from NB and a structural unit derived from MA was ring-opened with butanol to synthesize a polymer. The 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 (0.13 mol in terms of MA), and heat treatment (Reflux) was performed at a temperature of 110 ° C. for 4 hours. This caused a reaction in which the MA structural unit in the raw material polymer was ring-opened with butanol. The polymer was then precipitated with heptane.
Through the above steps, 26.15 g of the polymer of Comparative Synthesis Example 1 was obtained by ring-opening a polymer having a structural unit derived from NB and a structural unit derived from MA 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 degree of polydispersity (weight average molecular weight Mw / number average molecular weight Mn) was 1.78.

<Preparation of photosensitive resin composition>
The following components were uniformly mixed and appropriately filtered through a filter to prepare a photosensitive resin composition (composition 1).
-Polymer of Synthesis Example 1: 100 parts by mass in terms of solid content-Cross-linking agent (Printec VG3101L, epoxy compound described below): 25 parts by mass-Photosensitizer (Daito Chemix GPA-200, quinone diazide compound described below): 50 parts by mass, fluorine-based surfactant (FC4432 from 3M): 1 part by mass, adhesion aid (KBM-403E, 3-glycidoxypropyltrimethoxysilane): 5 parts by mass, organic solvent (organic solvent) PGMEA): Adjusted so that the concentration of the non-volatile component is 30% by mass.

Further, in the composition 1, the photosensitive resin composition (compositions 2 to 2) prepared in the same manner except that the polymer was replaced with the polymer of Synthesis Examples 2 to 6 or Comparative Example Synthesis 1 instead of the polymer of Synthesis Example 1. 6 and the comparative composition 1) were also prepared.

<Evaluation of liquid repellency>
The liquid repellency of the film prepared from the photosensitive resin composition prepared above was evaluated by measuring the contact angle of the 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 film thickness of 4 μm. Then, using an oven, the resin film was heated at 230 ° C. for 60 minutes (Air atmosphere) to cure the resin film.
From the above, a resin film for evaluation was obtained.

A droplet of 2 μL of anisole was dropped onto the above resin film for evaluation, and the contact angle was measured. For the measurement of the contact angle, a portable contact angle meter PCA-1 manufactured by Kyowa Surface Chemistry 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 the analysis software.
After dropping the anisole, the contact angle was measured 5 times every 1 second, and the average value of the measurements for 5 seconds was taken 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 containing the polymers of Synthesis Examples 1 to 6 were compared with Comparative Composition 1 containing the polymer of Comparative Synthesis Example 1 in the liquid repellency and water repellency of anisole. The result was significantly better. From this result, 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 with 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 GPC measurement of the obtained resin film was performed, no amination silicone, which is a thermal desorbed product of silicone, was observed, and there was no change in the peak from the case of heating at 100 ° C. for 2 minutes.
From the above results, it was shown that the polymer of the present embodiment has less decomposition and volatilization due to heating, and can be preferably applied to a process requiring heating in the manufacturing process such as a manufacturing process of an electronic device.

<Polymer transparency>
The polymers of Synthesis Examples 1 to 6 were used as 25% by mass PGMEA solutions, respectively. This solution was spin-coated on a silicon wafer and dried at 100 ° C. for 2 minutes to form a resin film having a film thickness of 2 μm.
When the presence or absence of turbidity of the obtained resin film was visually confirmed, the resin film of the polymer of Synthesis Examples 1 to 3 was transparent, but the resin film of the polymer of Synthesis Examples 4 to 6 was slightly turbid. Was done. It is presumed that this is because the polymers of Synthesis Examples 4 to 6 introduce a larger amount of amination silicone than the polymers of Synthesis Examples 1 to 3.
From this result, it was found that it is desirable to appropriately adjust the amount of the amination silicone introduced from the viewpoint of the 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 used as 25% by mass PGMEA solutions, respectively. This solution was spin-coated on a silicon wafer and dried at 100 ° C. for 2 minutes to form a resin film having a film 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 an alkaline developer was calculated from the time during which the resin film was completely dissolved.
The results are shown in the table below. From the viewpoint of ease of forming fine patterns and redundancy against fluctuations in patterning conditions, it is preferable that the dissolution rate is not too high (moderately low).

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

<PGMEA solubility>
It was confirmed whether a 40% by mass PGMEA solution of the polymers of Synthesis Examples 1 to 6 could be prepared (whether there was any undissolved residue). As a result, it was possible to prepare a solution with all the polymers. That is, it was shown that the polymer of the present embodiment has good organic solvent solubility even though it contains a silicone structure, and is desirable for application to various compositions.

Claims (12)

The structural unit represented by the following general formula (A1) and
A polymer containing 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 the general formula (A1)
R ¹ , R ² , R ³ and R ⁴ are independently hydrogen or organic groups having 1 to 30 carbon atoms.
a ₁ is 0, 1 or 2.

In the general formula (B1) and the 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 base.

In the general formula (S1)
The plurality of Rs are independently alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups or aralkyl groups, respectively.
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 divalent organic group having 1 to 30 carbon atoms.
k represents an integer of 1 or more.

In the general formula (S2)
Each of the plurality of Rs is independently an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group.
R ⁶ and R ⁷ are independently hydrogen atoms, hydroxyl groups, alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups or aralkyl groups, respectively.
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 according to claim 1.
A polymer containing a structural unit represented by the general formula (B1). The polymer according to claim 1 or 2.
Further, a polymer containing a structural unit represented by the following general formula (C1).

In the general formula (C1)
^RA 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.
Further, a polymer containing a structural unit represented by the following formula (D1).

A photosensitive resin composition containing the polymer according to any one of claims 1 to 4 and a photosensitive agent. A photosensitive resin film formed by the photosensitive resin composition according to claim 5. A pattern obtained by exposing and developing the photosensitive resin film according to claim 6. An organic electroluminescence device having the pattern according to claim 7. A film forming step of forming a photosensitive resin film on a substrate by using the photosensitive resin composition according to claim 5.
A method for manufacturing a substrate having a pattern, which comprises a pattern forming step of exposing and developing the photosensitive resin film to obtain a pattern. The method for producing a 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 a compound represented by the general formula (S1) and / or the general formula ( A method for producing a polymer, which comprises a step of reacting with the compound represented by S2).

The method for producing a 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 subjected to the compound represented by the general formula (S1) and the raw material polymer in the presence of alcohol. / Or a method for producing a polymer, which comprises a step of reacting with a compound represented by the general formula (S2).

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

Images