JP7383921B2 - Polymer-containing compositions, polymers and methods for producing polymers - Google Patents

Description

The present invention relates to polymer-containing compositions, polymers, and methods of making polymers.

Several attempts are known to improve polymers by reacting amino group-containing compounds with polymers containing structural units (acid anhydride rings) derived from maleic anhydride monomers.

As an example, in Table 5 and Synthesis Example 40 of Patent Document 1, 4-aminobutanoic acid is added to bicyclo[2,2,1]hepta-2,5-diene-maleic anhydride copolymer at 80°C. It is described that the acid anhydride ring was partially opened to an amide by the reaction described below.

As another example, in the example of Patent Document 2, a dimethylacetamide solution of a copolymer of norbornene and maleic anhydride is reacted with a dimethylacetamide solution of a diamine at room temperature, and a coating solution containing polyamic acid is prepared. It is stated that it was obtained. Further, in the example of Patent Document 2, this coating liquid is applied onto a substrate, dried at 100°C for 1 hour to obtain a film, and the film is heated at 200°C for 24 hours to form an imide crosslinked resin. It states that it was obtained.

As yet another example, the claims of U.S. Pat. and compositions thereof are disclosed. In this polymer, at least a portion of the maleic anhydride type repeat units are ring-opened or converted to maleimide repeat units.

Japanese Patent Application Publication No. 2-146045 International Publication No. 2017/195728 Special Publication No. 2016-531191

Polymers may be applied in electronic device manufacturing, as described, for example, in US Pat. Specifically, polymers or polymer-containing compositions may be used to form permanent films (protective films, insulating films, etc.) in electronic devices.

In forming a permanent film, a photolithography method may be applied. In this case, the polymer or polymer-containing composition is required to have appropriate solubility in the alkaline developer.
Furthermore, in forming a permanent film, cracking may become a problem. Electronic devices can be placed in various environments during and after their manufacture, and for example, when a permanent film is rapidly cooled, cracks may occur in the film and its function as a permanent film may be impaired.

The present invention has been made in view of these circumstances. One of the objects of the present invention is to provide a polymer-containing composition or polymer that has appropriate solubility in an alkaline developer and is less likely to crack when formed into a film.

As a result of intensive studies, the present inventors completed the invention provided below and solved the above problem.

According to the invention,
A polymer-containing composition containing a polymer having a structure represented by the following general formula (CL) and a solvent is provided.

In the general formula (CL), X represents a divalent atomic group containing an ether bond (C--O--C).

Further, according to the present invention,
A polymer including a structure represented by the following general formula (CL) is provided.

In the general formula (CL), X represents a divalent atomic group containing an ether bond (C--O--C).

Further, according to the present invention,
A raw material polymer containing a structural unit represented by the following formula (MA) and a diamine compound represented by the following general formula (am-1) are reacted in a liquid phase, and the following is represented by the general formula (CL). A method for producing a polymer is provided, comprising a crosslinking reaction step to obtain a polymer comprising a structure.

In the general formulas (am-1) and (CL), X represents a divalent atomic group containing an ether bond (C-O-C).

According to the present invention, there is provided a polymer-containing composition or polymer that has appropriate solubility in an alkaline developer and is less likely to cause cracks when formed into a film.

1 is an infrared absorption spectrum of the polymer of Synthesis Example 1. Infrared absorption spectrum of reference polymer.

Embodiments of the present invention will be described in detail below with reference to the drawings.
In all the drawings, similar components are denoted by the same reference numerals, and description thereof will be omitted as appropriate.
To avoid complication, (i) if there are multiple identical components in the same drawing, only one of them will be given a reference numeral and not all of them, or (ii) especially 2 and subsequent parts, components similar to those in FIG. 1 may not be labeled again.
All drawings are for illustrative purposes only. The shapes and dimensional ratios of each member in the drawings do not necessarily correspond to the actual product.

In the present specification, the notation "X to Y" in the description of numerical ranges refers to not less than X and not more than Y, unless otherwise specified. For example, "1 to 5% by mass" means "1 to 5% by mass".

In the description of a group (atomic group) in this specification, a description that does not indicate whether it is substituted or unsubstituted includes both those without a substituent and those with a substituent. For example, the term "alkyl group" includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
The term "organic group" as used herein means an atomic group obtained by removing one or more hydrogen atoms from an organic compound, unless otherwise specified. For example, a "monovalent organic group" refers to an atomic group obtained by removing one hydrogen atom from an arbitrary organic compound.
In this specification, the term "electronic device" refers to an element to which electronic engineering technology is applied, such as a semiconductor chip, semiconductor element, printed wiring board, electric circuit display device, information communication terminal, light emitting diode, physical battery, or chemical battery. , devices, final products, etc.

<Polymer-containing composition/polymer>
The polymer-containing composition of the present embodiment includes a polymer having a structure represented by the following general formula (CL) and a solvent.
Moreover, the polymer of this embodiment includes a structure represented by the following general formula (CL).

In the general formula (CL), X represents a divalent atomic group containing an ether bond (C--O--C).

As a design guideline for polymers, it is possible to introduce a crosslinked structure between polymer chains in order to reduce cracks. It is thought that by doing so, a three-dimensional network is formed in the formed film, thereby suppressing the occurrence of cracks.
However, crosslinking increases the effective molecular weight of the polymer. Furthermore, the introduction of a crosslinked structure reduces the molecular mobility of polymer chains. These are disadvantageous in terms of polymer solubility in alkaline developers.

In this regard, in the polymer of this embodiment, X (crosslinked structure) in the general formula (CL) includes an ether bond (C-O-C), which is a flexible chemical skeleton, so that the molecular movement of the polymer chain is It is thought that the performance will not decrease excessively. It is thought that appropriate solubility in an alkaline developer can be obtained.
Furthermore, it is considered that the presence of the crosslinked structure represented by the general formula (CL) suppresses the occurrence of cracks.

By the way, the inclusion of a flexible ether bond (C-O-C) in X (crosslinked structure) in the general formula (CL) increases the ``ease of stretching'' when formed into a film, and increases the ``curing shrinkage''. It is also possible to reduce the "rate".

The description regarding the polymer of this embodiment and the polymer-containing composition of this embodiment will be continued.

(X in general formula (CL))
X in the general formula (CL) is not particularly limited as long as it is a divalent atomic group containing an ether bond (C--O--C).
From the viewpoint of heat resistance, it is preferable that X contains an aryl ether skeleton. That is, one or both of the two carbon atoms sandwiching an oxygen atom in the ether bond represented by C--O--C is preferably a carbon atom in an aryl group.
"Aryl" in the aryl ether skeleton is preferably phenyl (benzene ring).

More preferably, X is represented by the following general formula (x).

In general formula (x),
If there are multiple A's, each one is independently selected from the group consisting of a single bond, a linear or branched alkylene group, an ether group, a carbonyl group, an ester group, and a group in which two or more of these are connected. is the basis of
B is any group selected from the group consisting of a single bond, a linear or branched alkylene group, an ether group, a carbonyl group, an ester group, and a group in which two or more of these are connected;
At least one of A and B is an ether group (-O-),
R ¹ , R ² and R ³ are each independently a monovalent organic group, a hydroxyl group or a halogen atom, when a plurality of them exist;
k, l and m are each independently an integer of 0 to 4,
n is an integer greater than or equal to 0,
* represents a bond with the nitrogen atom in the general formula (CL).

When A and/or B are linear or branched alkylene groups, the linear or branched alkylene group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms.

Preferably, all of A and B in general formula (x) are ether groups (-O-).

Monovalent organic groups for R ¹ , R ² and R ³ include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkaryl groups, cycloalkyl groups, alkoxy groups, heterocyclic groups, and carboxyl groups. Examples include groups.
Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, Examples include octyl group, nonyl group, and decyl group.
Examples of the alkenyl group include an allyl group, a pentenyl group, and a vinyl group.
Examples of the alkynyl group include ethynyl group.
Examples of the alkylidene group include a methylidene group and an ethylidene group.
Examples of the aryl group include tolyl group, xylyl group, phenyl group, naphthyl group, and anthracenyl group.
Examples of the aralkyl group include benzyl group and phenethyl group.
Examples of the alkaryl group include tolyl group and 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, etc.
Examples of the heterocyclic group include an epoxy group and an oxetanyl group.
The total number of carbon atoms in the monovalent organic groups R ¹ , R ² and R ³ is, for example, 1 to 30, preferably 1 to 20, more preferably 1 to 10, particularly preferably 1 to 6.

k, l and m are each independently preferably an integer of 0 or 1.
In one aspect, k, l and m are all 0.
n is preferably 0-3, more preferably 0-2.

Incidentally, in the benzene ring drawn at the center in general formula (x), it is preferable that the bonding site of A and the bonding site of B be in a meta-position relationship from the viewpoint of appropriate solubility. It is presumed that this is related to the fact that the presence of a bent structure in the polymer reduces crystallinity.
Of course, the relationship between the binding site of A and the binding site of B may be the para position or the ortho position.

Further, X in the general formula (CL) preferably contains 2 to 5 benzene rings, more preferably 2 to 4 benzene rings. More specifically, in the general formula (x), n is preferably 0 to 3, more preferably 0 to 2.

(Structural unit represented by general formula (CO))
It is preferable that the polymer of this embodiment further includes a structural unit represented by the following general formula (CO). Thereby, for example, the heat resistance of the polymer can be improved.

In the general formula (CO),
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 the general formula (CO), the organic groups having 1 to 30 carbon atoms for R ¹ , R ² , R ³ and R ⁴ 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, carboxy group, etc.

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, Examples include octyl group, nonyl group, and decyl group.
Examples of the alkenyl group include an allyl group, a pentenyl group, and a vinyl group.
Examples of the alkynyl group include ethynyl group.
Examples of the alkylidene group include a methylidene group and an ethylidene group.
Examples of the aryl group include tolyl group, xylyl group, phenyl group, naphthyl group, and anthracenyl group.
Examples of the aralkyl group include benzyl group and phenethyl group.
Examples of the alkaryl group include tolyl group and 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, sec-butoxy group, isobutoxy group, tert-butoxy group, n-pentyloxy group, and neopentyloxy group. , n-hexyloxy group, etc.
Examples of the heterocyclic group include an epoxy group and an oxetanyl group.

R ¹ , R ² , R ³ and R ⁴ in general formula (CO) are preferably hydrogen or an alkyl group, and more preferably hydrogen.
The hydrogen atom in the organic group having 1 to 30 carbon atoms in R ¹ , R ² , R ³ and R ⁴ may be substituted with any atomic 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 for R ¹ , R ² , R ³ and R ⁴ .
In the general formula (CO), a ₁ is preferably 0 or 1, more preferably 0.

(Structural unit represented by general formula (IM-1))
The polymer of this embodiment may further include a structural unit represented by the following general formula (IM-1). This structural unit may make it possible to better balance the heat resistance and alkali solubility of the polymer.

In general formula (IM-1), R is a monovalent organic group.
The monovalent organic group is not particularly limited. Specific examples of the monovalent organic group include those listed as the monovalent organic groups of R ¹ , R ² and R ³ in the above-mentioned general formula (x).

R in general formula (IM-1) preferably contains an acid group. In other words, R is preferably a monovalent organic group having an acid group (substituted with an acid group). This facilitates making the solubility in an alkaline developer more appropriate.

Examples of the acid group include a carboxy group, a phenolic hydroxy group, a sulfonic acid group, and a hexafluoroisopropanol group (-C(CF ₃ ) ₂ OH). Of course, acid groups are not limited to these.
The acid group is preferably a carboxy group from the viewpoint of ease of preparation of the compound and compatibility with developing solutions commonly used in electronic device manufacturing.
Incidentally, from the viewpoints of ease of introduction, solubility of the final polymer in organic solvents, solubility in alkaline developing solutions, etc., R preferably has only an acid group as a substituent, and preferably has no substituents other than acid groups. It has no group. More preferably, R is an alkyl group having only an acid group as a substituent and no substituents other than an acid group.

(Other structural units)
The polymer of this embodiment may include any structural unit other than the above.
As an example, the polymer of this embodiment can include a structural unit represented by the formula (MA) below. The structural unit represented by formula (MA) is a structure derived from a raw material polymer in the method for producing a polymer described below.
As another example, the polymer of this embodiment can include a structural unit represented by the following general formula (IM-2). The definition and specific examples of R in general formula (IM-2) are the same as R in general formula (IM-1).

(Weight average molecular weight, etc.)
The weight average molecular weight Mw of the polymer of this embodiment is preferably 15,000 to 50,000, more preferably 20,000 to 40,000. When the Mw is 15,000 or more, it is possible to improve the mechanical properties and heat resistance when the polymer is used as a film. It is thought that Mw of 50,000 or less has advantages such as suppressing gelation of the polymer or polymer-containing composition, making it easy to wash with water during synthesis, and making it easy to obtain sufficient film formability. Further, by having an Mw of 50,000 or less, it is easy to appropriately increase the solubility in an alkaline aqueous solution.
The degree of dispersion (weight average molecular weight Mw/number average molecular weight Mn) of the polymer of this embodiment is preferably 1.0 to 5.0, more preferably 1.0 to 4.0. By appropriately adjusting the degree of dispersion, for example, the mechanical properties of a polymer film may be improved.
Mw and Mw/Mn can be determined by gel permeation chromatography (GPC) measurement using polystyrene as a standard substance. For example, THF (tetrahydrofuran) can be used as the developing solvent.
Incidentally, although it depends on the amount (density) of the crosslinked structure, the polymer of this embodiment tends to be easily dissolved in THF. The polymer of this embodiment can preferably be made into a 0.5% by mass THF solution (a solution with no undissolved residue).

(solvent)
The polymer-containing composition of this embodiment includes a solvent. In other words, the polymer-containing composition of this embodiment has a polymer dissolved or dispersed in a solvent. Since the polymer-containing composition of this embodiment contains a solvent, it can be easily applied to film formation in electronic device manufacturing (a uniform resin film can be provided on a substrate by coating and drying).
The polymer-containing composition of the present embodiment is preferably in the form of a varnish containing a solvent, and the polymer exists in a state dissolved in the solvent (substantially no undissolved polymer exists in the composition). The solubility of the polymer-containing composition of this embodiment in organic solvents (for example, propylene glycol monomethyl ether acetate) is usually good.

The solvent is typically an organic solvent. Specific examples of the organic solvent include ketone solvents, ester solvents, ether solvents, alcohol solvents, lactone solvents, and carbonate solvents.
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. , γ-butyrolactone, propylene carbonate, ethylene glycol diacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, anisole, N-methylpyrrolidone, cyclohexanone, cyclopentanone, dipropylene glycol methyl-n-propyl ether, and other organic solvents. can be mentioned.

The polymer-containing composition of this embodiment may contain only one solvent, or may contain two or more solvents.
The amount of solvent used is not particularly limited. The solvent is used in an amount such that the concentration of non-volatile components of the polymer-containing composition is, for example, from 10 to 70% by weight, preferably from 15 to 60% by weight.

(Components other than polymer in polymer-containing composition)
The polymer-containing composition of the present embodiment may contain components other than the above-mentioned polymer (a polymer having a structure represented by general formula (CL)) and a solvent.
For example, the polymer-containing composition of this embodiment includes a photosensitizer, a crosslinking agent (epoxy resin, etc.), an adhesion aid, a surfactant, a basic compound, a curing accelerator, an antioxidant, a filler such as silica, and an additive. It may contain one or more of a sensitizer, a film-forming agent, a dissolution promoter, a dissolution inhibitor, various dyes (dyes, pigments), and the like.

Photosensitive agents 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-iminosulfonate compounds. , imidosulfonate compounds, 2,6-bis(trichloromethyl)-1,3,5-triazine compounds, and dihydropyridine compounds.

The crosslinking agent typically contains two or more (preferably 2 to 6, more preferably 2 to 4) crosslinking groups in one molecule. Preferred crosslinking agents include (1) a crosslinking agent having an alkoxymethyl group and/or a methylol group (-CH ₂ OH), (2) a compound having an epoxy group, (3) a compound having an oxetanyl group, and (4) an isocyanate. (5) a compound having a bismaleimide group, and the like. (2) Examples of compounds having epoxy groups include known epoxy resins.

In particular, by using a compound having an epoxy group (such as an epoxy resin), a cured film that has good elongation and is difficult to break can be obtained. Furthermore, a composition that uses the polymer of this embodiment in combination with a compound having an epoxy group tends to have a relatively small curing shrinkage rate.

Examples of the epoxy resin include phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, biphenylaralkyl type epoxy resin, bisphenol A type epoxy resin, bisphenol A diglycidyl ether type epoxy resin, and 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, aliphatic epoxy resin, aliphatic polyfunctional epoxy resin, Examples include alicyclic epoxy resin and polyfunctional alicyclic epoxy resin.

The epoxy resin preferably includes a polyfunctional epoxy resin having three or more functionalities (a polyfunctional epoxy resin having three or more epoxy groups in one molecule). By this, the film is sufficiently cured, and for example, the heat resistance and durability as a permanent film can be improved. Of course, the epoxy resin may be a bifunctional or less functional epoxy resin.

When using epoxy resins, only one epoxy resin may be used, or two or more epoxy resins may be used in combination.
When using an epoxy resin, the amount thereof is, for example, 1 to 100 parts by weight, preferably 1 to 100 parts by weight, and more preferably 30 to 80 parts by weight, based on 100 parts by weight of the polymer of the present embodiment.

Examples of the adhesion aid include various silane coupling agents. Silane coupling agents can be obtained from Shin-Etsu Chemical Co., Ltd., Asahi Kasei Wacker Silicone Co., Ltd., Tokyo Kasei Kogyo Co., Ltd., Dow-Toray Co., Ltd., etc.

The surfactant that can be used is not particularly limited, but preferably a nonionic surfactant containing at least one of a fluorine atom and a silicon atom. Commercially available products include, for example, fluorine-containing oligomer structure surfactants such as the "Megafac" series manufactured by DIC Corporation, and fluorine-containing nonionic surfactants such as the "Ftergent" series manufactured by Neos Corporation. , and the SILFOAM (registered trademark) series manufactured by Wacker Chemie.

<Polymer manufacturing method>
The method for producing a polymer of the present embodiment involves reacting a raw material polymer containing a structural unit represented by the general formula (MA) below with a diamine compound represented by the general formula (am-1) in a liquid phase. , a crosslinking reaction step for obtaining a polymer having a structure represented by the following general formula (CL).

In the general formulas (am-1) and (CL), X represents a divalent atomic group containing an ether bond (C-O-C). Specific examples and preferred embodiments of X are as described above.

The polymer described in the section <Polymer-containing composition/polymer> above is preferably produced by the polymer production method described herein.
Hereinafter, an example of a specific procedure of the method for producing a polymer of this embodiment, including a crosslinking reaction step, will be explained.

(Preparation of raw material polymer)
In carrying out the crosslinking reaction step, a raw material polymer containing a structural unit represented by formula (MA) is prepared.
The raw material polymer contains at least a structural unit represented by the above-mentioned formula (MA).
In addition to the structural unit represented by formula (MA), the raw material polymer may contain one or more other structural units. For example, the raw material polymer preferably contains a structural unit represented by the above-mentioned general formula (CO) in addition to the structural unit represented by the formula (MA).

The raw material polymer can be "prepared" by any method. If there is a commercially available product, it may be used. Alternatively, it may be synthesized using appropriate monomers and initiators.

For reference, the method for synthesizing the raw material polymer will be briefly described below. Of course, the method for synthesizing the raw material polymer is not limited to the following method. For the synthesis of the raw material polymer, known techniques in the technical field of polymer synthesis can be appropriately utilized. The synthesis of a raw material polymer containing a structural unit represented by the formula (MA) and a structural unit represented by the general formula (CO) will be described below, but this will jeopardize the generality of the method for producing the raw material polymer. It's not something you can do.

The raw material polymer can be obtained, for example, by polymerizing (addition polymerization) a monomer represented by the following general formula (CO-m) and maleic anhydride.
The definitions of R ¹ , R ² , R ³ and R ⁴ and a ₁ in general formula (CO-m) are the same as those in general formula (CO). The same applies to preferred embodiments.

Examples of monomers represented by the general formula (CO-m) include 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, 5- Examples include methyl norbornene-2-carboxylate, 5-norbornene-2,3-dicarboxylic anhydride, and norbornadiene.
During polymerization, only one type of monomer represented by the general formula (CO-m) may be used, or two or more types may be used in combination.

The polymerization method is not limited. Radical polymerization using a radical polymerization initiator is preferred.
As the polymerization initiator, for example, an azo compound, an organic peroxide, etc. can be used.
Specific examples of azo compounds include azobisisobutyronitrile (AIBN), dimethyl-2,2'-azobis(2-methylpropionate), 1,1'-azobis(cyclohexanecarbonitrile) (ABCN), etc. can be mentioned.
Examples of the organic peroxide include hydrogen peroxide, di-tert-butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), and methyl ethyl ketone peroxide (MEKP).
Regarding 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, organic solvents such as diethyl ether, tetrahydrofuran, toluene, methyl ethyl ketone, and ethyl acetate can be used. The polymerization solvent may be a single solvent or a mixed solvent.

A monomer represented by the general formula (CO-m), maleic anhydride, and a polymerization initiator are dissolved in a solvent and charged into a reaction vessel, and then heated to proceed with 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 (CO-m) 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 the steps described above, a "raw material polymer" can be obtained.
The raw material polymer may be a random copolymer, an alternating copolymer, a block copolymer, a periodic copolymer, or the like. Typically, it is a random copolymer or an alternating copolymer (maleic anhydride is generally known as a monomer with strong alternating copolymerizability).

The amount of the structural unit represented by formula (MA) in the raw material polymer is preferably 10 to 90 mol%, more preferably 30 to 70 mol%, and even more preferably 40 to 60 mol%, based on the total structural units of the polymer.
When the raw material polymer contains a structural unit represented by the general formula (CO), the amount thereof is preferably 10 to 90 mol%, more preferably 30 to 70 mol%, and even more preferably 40 to 60 mol% of the total structural units of the polymer. %.
By appropriately adjusting these proportions, it is easy to obtain appropriate solubility in an alkaline developer and improve heat resistance as a permanent film in the final polymer.

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

(Monoamine reaction step)
The method for producing a polymer according to the present embodiment may include a monoamine reaction step in which a monoamine is added to the reaction system and the polymer (raw material polymer) is reacted with the monoamine. This allows the structural unit represented by general formula (IM-1) to be included in the final polymer.

Monoamines are, for example, compounds represented by the general formula R—NH ₂ . In this general formula, R is a monovalent organic group. Specific examples and preferred embodiments of R are the same as R in general formula (IM-1).
Preferably, the monoamine contains an acid group. That is, in the above general formula, R preferably contains an acid group. When the acid group is a carboxy group, the compound represented by the general formula (am) is an "amino acid". That is, a commercially available amino acid compound can be used as the monoamine.

The monoamine reaction step is preferably carried out in the liquid phase (in a solvent). There are no particular limitations on the solvent that can be used. A material that can sufficiently dissolve or disperse both the polymer (raw material polymer) and monoamine and does not excessively inhibit the intended reaction may be selected as appropriate. Only one solvent may be used, or two or more solvents may be used in combination.

Examples of solvents that can be selected include the following.
・Alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol ・Ethers such as tetrahydrofuran, cyclopentyl methyl ether, diethyl ether ・Acetone, acetylacetone, ethyl methyl ketone, 2-heptanone , 3-heptanone, 4-heptanone, 2-pentanone, 3-pentanone, and other ketones; benzene, toluene, ethylbenzene, o-xylene, m-xylene, p-xylene, and other aromatic hydrocarbons; and acetonitrile and other nitriles.・Organic acids (carboxylic acids) such as formic acid, acetic acid, propionic acid, and butyric acid ・Halogen-containing solvents such as carbon tetrachloride, dichloromethane, chloroform, 1,2-dichloroethane, and chlorobenzene ・Others, N,N'-dimethylformamide , dimethyl sulfoxide, hexamethylphosphotriamide, water, etc.

In the monoamine reaction step, the reaction system is preferably heated to 100°C or higher.
According to the findings of the present inventors, when the heating temperature is less than 100° C., a ring-opened structure in which a maleic anhydride skeleton is ring-opened by a monoamine, as shown in the above-mentioned general formula (IM-2), is obtained. However, it is difficult for the reaction to proceed until this ring-opened structure undergoes "ring closure" and reaches the imide ring-closing reaction represented by general formula (IM-1).
(On the other hand, it is also conceivable to intentionally react a monoamine at a temperature below 100°C to actively form a ring-opened structure such as the general formula (IM-2) in the polymer in the hope of improving some performance.)

In the monoamine reaction step, the temperature is more preferably 100 to 150°C, even more preferably 110 to 130°C. When the temperature is appropriately high, the reaction can proceed sufficiently. In addition, since the temperature is not too high, it is easy to prevent runaway reactions, side reactions, and the generation of unintended impurities.

(Crosslinking reaction step)
As described above, in the crosslinking reaction step, the polymer (raw material polymer) and the diamine compound represented by the general formula (am-1) are reacted in a liquid phase (in the presence of a solvent). Then, a polymer containing a structure represented by the general formula (CL) (a structure in which two imide ring structures are connected via an atomic group X) is obtained.

The temperature (heating temperature) of the crosslinking reaction step can be about the same as the temperature of the above-mentioned "step of reacting monoamine", preferably 100 ° C. or higher, more preferably 100 to 150 ° C., even more preferably 110 to 130 ° C. It is ℃.
The time of the crosslinking reaction step (the time during which the reaction system is heated in the coexistence of the raw material polymer and the diamine compound) is preferably 1 to 24 hours, more preferably 4 to 16 hours.
The solvent used in the crosslinking reaction step can be the same as the solvent mentioned in the above "step of reacting a monoamine".

The diamine compound represented by general formula (am-1) preferably contains an aryl ether skeleton. That is, it is preferable that X in general formula (am-1) contains an aryl ether skeleton.

More preferably, the diamine compound represented by general formula (am-1) is a diamine compound represented by general formula (am-2) below.

The definitions and specific examples of A, B, R ¹ , R ² , R ³ , k, l, m and n in general formula (am-2) are as explained in general formula (x).

Specific examples of diamine compounds are shown below. Of course, usable diamine compounds are not limited to the following.

(Post-processing (polymer purification, etc.)
The polymer (usually in the form of a polymer solution) obtained through the crosslinking reaction process is preferably purified by an appropriate method.

As an example, unreacted raw materials and reaction solvent are reduced as much as possible by "washing with water". The water washing procedure can be, for example, the following procedures (1) to (3).
(1) First, a washing liquid containing water and a polymer solution (usually separated into a polymer layer and an aqueous layer) are placed in the same container and stirred vigorously. The washing liquid may be water itself or a mixture of water and an organic solvent (methyl ethyl ketone, toluene, etc.). By appropriately using a mixed solution of water and an organic solvent, it is possible to wash the polymer with water without precipitating it.
(2) After stirring, let stand for a while, and then remove the aqueous layer.
(3) Usually, the above (1) and (2) are repeated multiple times.

Moreover, apart from washing with water, solvent replacement (distillation and dilution of the solvent) may be performed once or multiple times to reduce unreacted raw materials and reaction solvent.

To be sure, the method for stopping the reaction and the method for purifying the polymer are not limited to the methods described above. Methods known in the field of polymer synthesis can be applied as appropriate.

(Supplementary information regarding the process of reacting monoamines and the crosslinking reaction process)
When the method for producing a polymer of the present embodiment includes both a monoamine reaction step and a crosslinking reaction step, these steps are preferably performed continuously. "Continuously" specifically means that (i) first, a monoamine is added to the reaction system, and the raw material is The polymer and the monoamine are reacted, and (ii) a diamine compound represented by the general formula (am-1) is then added to the reaction system to react the diamine compound with the raw material polymer (represented by the formula (MA)). Some of the structural units in the monoamine are reacted with the monoamine).

The time of the monoamine reaction step and the time of the crosslinking reaction step are determined by the amount of monoamine or diamine used, the structural unit expressed by the general formula (IM-1) and the general formula (CL) desired in the final polymer. It may be adjusted as appropriate based on the amount of structure to be used.
By way of example only, the time for the monoamine reaction step is about 10 minutes to 6 hours, and the time for the crosslinking reaction step is about 1 to 24 hours. The temperature in each reaction step is as described above.

Incidentally, according to the findings of the present inventor, in the reaction at the above-mentioned temperature and time, all of the structural units represented by the formula (MA) in the raw material polymer have the structure of the formula (CL) or the general formula ( It is not converted to the structure of IM-1). It is thought that some of the structural units represented by formula (MA) in the raw material polymer remain unreacted with the structure represented by formula (MA). And/or it is considered that some of the structural units represented by formula (MA) in the raw material polymer are converted into ring-opened structures represented by general formula (IM-2).
As a finding of the present inventor, normally, in the reaction at the above-mentioned temperature and time, for example, 50 to 98 mol%, preferably 50 to 95 mol% of the structural units represented by formula (MA) in the raw material polymer are (CL) or the structure (imide ring structure) of general formula (IM-1). On the other hand, of the structural units represented by formula (MA) in the raw material polymer, for example, 2 to 50 mol%, preferably 5 to 50 mol%, do not react with diamines or monoamines and are represented by formula (MA). It is considered that the structure remains as a structure or is converted into an open ring structure (for example, a structure represented by the general formula (IM-2)).

The order of the monoamine reaction step and the crosslinking reaction step is not limited. However, from the viewpoint of precise control of the reaction, ease of purification of the polymer, etc., it is preferable that the crosslinking reaction step is performed after the monoamine reaction step.

<Application>
The polymer of this embodiment and/or the polymer-containing composition of this embodiment are preferably applied to electronic device manufacturing from the viewpoint of appropriate solubility in an alkaline developer and resistance to cracking when formed into a film. .

Specifically, by forming a resin film in an electronic device using the polymer of this embodiment and/or the polymer-containing composition of this embodiment, a highly reliable electronic device can be obtained (film Since cracks are less likely to occur, defects can be easily suppressed). The resin film here is typically a permanent film such as an insulating film, a flattening film, a buffer coat layer, or a dam material.
Further, for example, when the polymer-containing composition of the present embodiment is photosensitive, the resin film can be easily patterned into a desired form by a lithography process (due to the appropriate solubility of the polymer in an alkaline developer). In the current situation where electronic devices are becoming increasingly finer and more complex, good patterning performance through lithography processes is desirable.

The polymer of this embodiment and/or the polymer-containing composition of this embodiment can be used for forming color filters and black matrices, in addition to insulating films, flattening films, buffer coat layers, dam materials, etc. It is also considered to be preferable and applicable.
That is, it is effective to apply the polymer of this embodiment and/or the polymer-containing composition of this embodiment to form a color filter or black matrix in an image sensor such as a flat panel display, CCD, or CMOS. Conceivable. This is because color filters and black matrices are often formed by a lithography process.

Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and the present invention includes modifications, improvements, etc. within a range that can achieve the purpose of the present invention.
Reference embodiments of the present invention are additionally described below.
1.
A polymer-containing composition comprising a polymer having a structure represented by the above general formula (CL) and a solvent.
In the general formula (CL), X represents a divalent atomic group containing an ether bond (C--O--C).
2.
1. The polymer-containing composition described in
The above X is a polymer-containing composition containing an aryl ether skeleton.
3.
1. or 2. The polymer-containing composition described in
The above-mentioned X is a polymer-containing composition represented by the above-mentioned general formula (x).
In general formula (x),
If there are multiple A's, each one is independently selected from the group consisting of a single bond, a linear or branched alkylene group, an ether group, a carbonyl group, an ester group, and a group in which two or more of these are connected. is the basis of
B is any group selected from the group consisting of a single bond, a linear or branched alkylene group, an ether group, a carbonyl group, an ester group, and a group in which two or more of these are connected;
At least one of A and B is an ether group,
R ¹ , R ² and R ³ are each independently a monovalent organic group, a hydroxyl group or a halogen atom, when a plurality of them exist;
k, l and m are each independently an integer of 0 to 4,
n is an integer greater than or equal to 0,
* represents a bond with the nitrogen atom in the general formula (CL).
4.
1. ~3. The polymer-containing composition according to any one of
A polymer-containing composition in which the polymer further includes a structural unit represented by the above general formula (CO).
In the general formula (CO),
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.
5.
1. ~4. The polymer-containing composition according to any one of
Furthermore, a polymer-containing composition containing a structural unit represented by the above-mentioned general formula (IM-1).
In general formula (IM-1), R is a monovalent organic group.
6.
5. The polymer-containing composition described in
The above R is a polymer-containing composition containing an acid group.
7.
1. ~6. The polymer-containing composition according to any one of
A polymer-containing composition wherein the polymer has a weight average molecular weight of 15,000 to 50,000.
8.
1. ~7. The polymer-containing composition according to any one of
Furthermore, a polymer-containing composition containing a compound having an epoxy group.
9.
A polymer containing a structure represented by the above general formula (CL).
In the general formula (CL), X represents a divalent atomic group containing an ether bond (C--O--C).
10.
9. The polymer described in
The above X is a polymer containing an aryl ether skeleton.
11.
9. or 10. The polymer described in
Said X is a polymer represented by the following general formula (x).
In general formula (x),
If there are multiple A's, each one is independently selected from the group consisting of a single bond, a linear or branched alkylene group, an ether group, a carbonyl group, an ester group, and a group in which two or more of these are connected. is the basis of
B is any group selected from the group consisting of a single bond, a linear or branched alkylene group, an ether group, a carbonyl group, an ester group, and a group in which two or more of these are connected;
At least one of A and B is an ether group,
R ¹ , R ² and R ³ are each independently a monovalent organic group, a hydroxyl group or a halogen atom, when a plurality of them exist;
k, l and m are each independently an integer of 0 to 4,
n is an integer greater than or equal to 0,
* represents a bond with the nitrogen atom in the general formula (CL).
12.
9. ~11. The polymer according to any one of
Furthermore, a polymer containing a structural unit represented by the above-mentioned general formula (CO).
In the general formula (CO),
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.
13.
9. ~12. The polymer according to any one of
Furthermore, a polymer containing a structural unit represented by the above-mentioned general formula (IM-1).
In general formula (IM-1), R is a monovalent organic group.
14.
9. ~13. The polymer according to any one of
The above R is a polymer containing an acid group.
15.
9. ~14. The polymer according to any one of
A polymer having a weight average molecular weight of 15,000 to 50,000.
16.
A raw material polymer containing a structural unit represented by the above formula (MA) and a diamine compound represented by the above general formula (am-1) are reacted in a liquid phase to form a compound having the above general formula (CL). A method for producing a polymer, comprising a crosslinking reaction step to obtain a polymer having the structure represented.
In the general formulas (am-1) and (CL), X represents a divalent atomic group containing an ether bond (C-O-C).
17.
16. A method for producing a polymer according to
The method for producing a polymer, wherein the crosslinking reaction step is performed by heating the raw material polymer and the diamine compound at 100 to 150° C. for 1 to 24 hours.
18.
16. or 17. A method for producing a polymer according to
The method for producing a polymer in which the diamine compound includes an aryl ether skeleton.
19.
16. ~18. A method for producing a polymer according to any one of
The method for producing a polymer in which the diamine compound is represented by the above general formula (am-2).
If there is more than one A, each independently selected from the group consisting of a single bond, a linear or branched alkylene group, an ether group, a carbonyl group, an ester group, and a group in which two or more of these are connected. is the basis of
B is any group selected from the group consisting of a single bond, a linear or branched alkylene group, an ether group, a carbonyl group, an ester group, and a group in which two or more of these are connected;
At least one of A and B is an ether group,
R ¹ , R ² and R ³ are each independently a monovalent organic group, a hydroxyl group, or a halogen atom, if there are a plurality of them;
k, l and m are each independently an integer of 0 to 4,
n is an integer greater than or equal to 0.
20.
16. ~19. A method for producing a polymer according to any one of
The method for producing a polymer in which the raw material polymer further includes a structural unit represented by the above-mentioned general formula (CO).
In the general formula (CO),
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.
21.
16. ~20. A method for producing a polymer according to any one of
Furthermore, the method for producing a polymer includes a monoamine reaction step of reacting a raw material polymer with a monoamine.
22.
21. A method for producing a polymer according to
The method for producing a polymer, wherein the monoamine is a monoamine containing an acid group.

Embodiments of the present invention will be described in detail based on Examples and Comparative Examples. It should be noted that the present invention is not limited only to the embodiments.

<Synthesis of raw material polymer>
First, 209.41 g (2.1 mol) of maleic anhydride (hereinafter also referred to as MA) and 201.0 g (hereinafter also referred to as NB) of 2-norbornene (hereinafter also referred to as NB) are placed in a reaction vessel of an appropriate size equipped with a stirrer and a cooling tube. 06 g (2.1 mol) and 21.85 g (94.9 mmol) of dimethyl 2,2'-azobis(2-methylpropionate) were added. These were dissolved in a mixed solvent consisting of 316.7 g of methyl ethyl ketone (hereinafter also referred to as MEK) and 163.1 g of toluene. In this way, a solution was prepared.
The lysate was bubbled with nitrogen for 20 minutes to remove oxygen.

Thereafter, MA and NB were polymerized by heating the solution at a temperature of 65° C. for 6 hours while stirring, to obtain a polymerization solution.
A diluted solution was prepared by diluting the obtained polymerization solution with 456.1 g of MEK. A white solid was precipitated by dropping the diluted solution into 5418.1 g of methanol. The obtained white solid was vacuum-dried at a temperature of 50° C. to obtain 334.94 g of a raw material polymer containing a structural unit derived from NB and a structural unit derived from MA.
The obtained raw material polymer was measured by GPC. The weight average molecular weight Mw was 10,800, and the polydispersity (weight average molecular weight Mw/number average molecular weight Mn) was 1.97.

<Polymer synthesis>
(Synthesis example 1)
First, 70.00 g (MA equivalent: 0.364 mol) of the above raw material polymer and 75.29 g (0.350 mol) of 12-aminolauric acid were heat-treated at 115° C. for 1 hour in the presence of a solvent. As a result, 12-aminolauric acid was reacted with the maleic anhydride structure in the raw material polymer.
Thereafter, 4.26 g (14.6 mmol) of 1,3-bis(4-aminophenoxy)benzene dissolved in a solvent was added as a diamine compound, and the mixture was further reacted at 115° C. for 6 hours.
After the reaction was completed, unreacted raw materials were removed from the resulting solution by repeating acid extraction and water washing, and solvent distillation and dilution were repeated. In this way, 269.46 g of a 35% by mass propylene glycol monomethyl ether acetate (hereinafter also referred to as PGMEA) solution of the polymer of Synthesis Example 1 was obtained.

The obtained polymer of Synthesis Example 1 was subjected to GPC measurement. The weight average molecular weight Mw was 30,400, and the polydispersity (weight average molecular weight Mw/number average molecular weight Mn) was 3.37 (Mw was larger compared to Comparative Example 1, which will be described later, which did not contain diamine).

(Reference synthesis example: Synthesis of reference polymer (only monoamine reacts, ring-opened structure))
40.0 g (MA equivalent: 0.21 mol) of raw material polymer and 44.8 g (0.21 mol) of 12-aminolauric acid were heat-treated (refluxed) at 80° C. for 4 hours in the presence of a solvent. As a result, the amino group of 12-aminolauric acid was reacted with the maleic anhydride structure in the raw material polymer.

Thereafter, unreacted raw materials were removed by repeatedly washing the obtained solution with water, and 125.2 g of a 35% by mass PGMEA solution of the reference polymer was obtained by repeating solvent distillation and dilution.

(Infrared spectroscopy)
The polymer of Synthesis Example 1 and the reference polymer were subjected to infrared spectroscopic analysis. The obtained spectra are shown in FIGS. 1 and 2.
In the polymer of Synthesis Example 1, absorption derived from an aromatic ring was observed at a wave number of around 1510 cm ⁻¹ , which was not observed before the diamine compound was reacted, confirming the introduction of a diamine component.
Furthermore, in the polymer of Synthesis Example 1 and the reference polymer, absorption at a wave number of around 1600 cm ⁻¹ (NH bending vibration of the amide group), which was not observed in the raw material polymer, was confirmed.

When the peak area ratio of the reference polymer represented by the following formula is 100, the peak area ratio of the polymer of Synthesis Example 1 was 21.

(The "peak area ratio" can be said to be a value corresponding to the amount of structural units derived from MA ring-opened with monoamines or diamines in the polymer.In addition, in the "reference polymer", It is thought that almost all of the structural units derived from MA are ring-opened by monoamines.)

As mentioned above, since the peak area ratio of the polymer of Synthesis Example 1 was 21, about 79 mol% of the MA-derived structural units in the raw polymer were ring-opened and then closed to form an imide ring structure (general formula (CL)). or the structure represented by general formula (IM-1)). Furthermore, it was confirmed that about 21 mol% of the MA-derived structural units in the raw material polymer remained unreacted or had an open ring structure.
Furthermore, from the charging ratio of raw materials, the molar ratio of the structure represented by general formula (CL) and the structure represented by general formula (IM-1) present in the polymer of Synthesis Example 1 is approximately 96:4. It is thought that.

(Comparative synthesis example 1)
125.0 g (1.7 mol) of butanol was added to 25 g (MA equivalent: 0.13 mol) of the raw material polymer, and heat-treated at a temperature of 115° C. for 4 hours. As a result, the maleic anhydride structural unit of the copolymer was ring-opened with butanol. The polymer was then reprecipitated with heptane.
Through the above steps, 25.43 g of Comparative Polymer 1 was obtained, in which a copolymer comprising a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride was ring-opened using butanol.
Comparative Polymer 1 was measured by GPC. The weight average molecular weight Mw was 12,900, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.77.

(Evaluation of alkali solubility)
The polymer (PGMEA solution) of Synthesis Example 1 or Comparative Synthesis Example 1 was appropriately diluted with PGMEA to adjust the viscosity for spin coating. Each polymer solution whose viscosity had been adjusted was spin-coated onto a wafer and prebaked at 100° C. for 2 minutes to form a resin film with a thickness of 2.5 μm.
The alkali dissolution rate of this resin film was measured at 23° C. using a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution. Specifically, the alkali dissolution rate was calculated from the initial thickness of the resin film and the time required for the resin film to completely dissolve when the resin film was immersed in the TMAH aqueous solution.

(Crack resistance evaluation)
The polymer of Synthesis Example 1 or Comparative Synthesis Example 1 was spin-coated onto a wafer to a film thickness of 20 μm, and prebaked at 120° C. for 4 minutes to form a resin film. Thereafter, the resin film together with the wafer was rapidly cooled on a stainless steel (SUS) plate. After quenching, the presence or absence of cracks in the resin film was visually observed.

The evaluation results are summarized in Table 1.

As shown in Table 1, the polymer of Synthesis Example 1 had appropriate solubility in alkali, although it contained a crosslinked structure. Furthermore, when the polymer of Synthesis Example 1 was used as a film, the occurrence of cracks was suppressed.

<Preparation of a composition containing a compound having an epoxy group>
(Example 1)
Each component was uniformly stirred and mixed according to the formulation shown in Table 2 below. Thereafter, a composition was prepared by filtering through a filter with a pore size of 0.2 μm.

(Comparative example 1)
A photosensitive resin composition was obtained in the same manner as in Example 1, except that the raw materials were changed as shown in Table 2 below.

Details of each component shown in Table 2 are as follows.
・Polymer Polymer 1: Synthesized in Synthesis Example 1 Polymer 2: Synthesized in Comparative Synthesis Example 1

・Crosslinking agent Epoxy 1: VG3101L (manufactured by Printec Co., Ltd., structure below)

<Evaluation of a composition containing a compound having an epoxy group>
1. Preparation of cured film The following procedure was performed.
(1) A silicon wafer having a size of 8 inches and a thickness of 725 μm was prepared.
(2) The composition was applied onto this silicon wafer using a spin coater to form a liquid film.
(3) Using a hot plate, the liquid film was dried at 110° C. for 3 minutes to obtain a coating film.
(4) The entire surface of the obtained coating film was exposed to light at 700 mJ/cm ² using an exposure device (ORC HMW 201GX) manufactured by Oak Seisakusho Co., Ltd.
(5) PEB (Post Exposure Bake) was performed on the exposed coating film at 110° C. for 5 minutes.
(6) A silicon wafer having a cured film was obtained by heating at 200° C. for 90 minutes.

2. Evaluation of elongation First, from the silicon wafer having the cured film described above, the cured film was peeled off using an aqueous hydrofluoric acid solution, washed with water, and cut into a piece of 6.5 mm wide x 20 mm long to obtain a sample for elongation evaluation. Ta.
At a temperature of 25°C and a humidity of 55%, the sample was pulled until it broke using a tensile tester (Tensilon RTA-100) manufactured by Orientec Co., Ltd. at a tensile speed of 5 mm/min, and the tensile elongation rate was determined. (%) was measured. The measurement was carried out five times in each of the examples and comparative examples, and the average value was adopted as the elongation value.

3. Evaluation of curing shrinkage rate 1 above. A cured film was provided on a silicon wafer as described in (1) to (6) above. At this time, the film thickness of the coating film before curing, that is, after completing (3), and the film thickness of the cured film after curing, that is, after completing (6), were measured, and the curing shrinkage rate (%) was determined from the following formula. . For measuring the film thickness, an optical interference film thickness system VM-1030 manufactured by Olympus Corporation was used.
Formula: {(thickness of resin film before curing - thickness of cured film)/thickness of resin film before curing} x 100

The above is summarized in Table 2.

As shown in Table 2, the elongation of the composition of Example 1 was greater than that of Comparative Example 1, indicating that it was difficult to break. Further, the curing shrinkage rate of the composition of Example 1 was smaller than that of the composition of Comparative Example 1, indicating that it was difficult to shrink upon curing. From these results as well, the usefulness of the polymer containing the structure represented by the general formula (CL) can be understood (especially the usefulness of the composition used in combination with an epoxy resin).

Claims (21)

A polymer-containing composition comprising a polymer having a structure represented by the following general formula (CL) and a solvent ,
Furthermore, a polymer-containing composition in which the polymer contains a structural unit represented by the following general formula (IM-1) .

In the general formula (CL), X represents a divalent atomic group containing an ether bond (C--O--C).

In the general formula (IM-1), R is a monovalent organic group containing an acid group. A polymer-containing composition comprising a polymer having a structure represented by the following general formula (CL) and a solvent,
Furthermore, a polymer-containing composition containing a compound having an epoxy group.

In the general formula (CL), X represents a divalent atomic group containing an ether bond (C--O--C). A polymer-containing composition comprising a polymer having a structure represented by the following general formula (CL) and a solvent,
A polymer-containing composition that can be patterned by a photolithographic process.

In the general formula (CL), X represents a divalent atomic group containing an ether bond (C--O--C). A polymer-containing composition comprising a polymer having a structure represented by the following general formula (CL) and a solvent,
Polymer-containing compositions for forming permanent films inside electronic devices.

In the general formula (CL), X represents a divalent atomic group containing an ether bond (C--O--C). The polymer-containing composition according to any one of claims 1 to 4 ,
The above X is a polymer-containing composition containing an aryl ether skeleton. The polymer-containing composition according to any one of claims 1 to 5 ,
Said X is a polymer-containing composition represented by the following general formula (x).

In general formula (x),
If there are multiple A's, each one is independently selected from the group consisting of a single bond, a linear or branched alkylene group, an ether group, a carbonyl group, an ester group, and a group in which two or more of these are connected. is the basis of
B is any group selected from the group consisting of a single bond, a linear or branched alkylene group, an ether group, a carbonyl group, an ester group, and a group in which two or more of these are connected;
At least one of A and B is an ether group,
R ¹ , R ² and R ³ are each independently a monovalent organic group, a hydroxyl group or a halogen atom, when a plurality of them exist;
k, l and m are each independently an integer of 0 to 4,
n is an integer greater than or equal to 0,
* represents a bond with the nitrogen atom in the general formula (CL). The polymer-containing composition according to any one of claims 1 to 6 ,
The polymer is a polymer-containing composition further including a structural unit represented by the following general formula (CO).

In the general formula (CO),
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. The polymer-containing composition according to any one of claims 2 to 4,
A polymer- containing composition in which the polymer further contains a structural unit represented by the following general formula (IM-1).

In general formula (IM-1), R is a monovalent organic group. 9. The polymer-containing composition according to claim 8 ,
The above R is a polymer-containing composition containing an acid group. The polymer-containing composition according to any one of claims 1 to 9 ,
A polymer-containing composition wherein the polymer has a weight average molecular weight of 15,000 to 50,000. 5. The polymer-containing composition according to claim 1 , 3 or 4 ,
Furthermore, a polymer-containing composition containing a compound having an epoxy group. A polymer containing a structure represented by the following general formula (CL) ,
Furthermore, a polymer containing a structural unit represented by the following general formula (IM-1) .

In the general formula (CL), X represents a divalent atomic group containing an ether bond (C--O--C).

In the general formula (IM-1), R is a monovalent organic group containing an acid group. 13. The polymer according to claim 12 ,
The above X is a polymer containing an aryl ether skeleton. The polymer according to claim 12 or 13 ,
Said X is a polymer represented by the following general formula (x).

In general formula (x),
If there are multiple A's, each one is independently selected from the group consisting of a single bond, a linear or branched alkylene group, an ether group, a carbonyl group, an ester group, and a group in which two or more of these are connected. is the basis of
B is any group selected from the group consisting of a single bond, a linear or branched alkylene group, an ether group, a carbonyl group, an ester group, and a group in which two or more of these are connected;
At least one of A and B is an ether group,
R ¹ , R ² and R ³ are each independently a monovalent organic group, a hydroxyl group or a halogen atom, when a plurality of them exist;
k, l and m are each independently an integer of 0 to 4,
n is an integer greater than or equal to 0,
* represents a bond with the nitrogen atom in the general formula (CL). The polymer according to any one of claims 12 to 14 ,
Furthermore, a polymer containing a structural unit represented by the following general formula (CO).

In the general formula (CO),
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. The polymer according to any one of claims 12 to 15 ,
A polymer having a weight average molecular weight of 15,000 to 50,000. A raw material polymer containing a structural unit represented by the following formula (MA) and a diamine compound represented by the following general formula (am-1) are reacted in a liquid phase, and the following is represented by the general formula (CL). a crosslinking reaction step to obtain a polymer containing the structure ;
A method for producing a polymer, comprising a monoamine reaction step of reacting the raw material polymer with a monoamine containing an acid group .

In the general formulas (am-1) and (CL), X represents a divalent atomic group containing an ether bond (C-O-C). A method for producing the polymer according to claim 17 , comprising:
The method for producing a polymer, wherein the crosslinking reaction step is performed by heating the raw material polymer and the diamine compound at 100 to 150° C. for 1 to 24 hours. A method for producing the polymer according to claim 17 or 18 ,
The method for producing a polymer in which the diamine compound includes an aryl ether skeleton. A method for producing the polymer according to any one of claims 17 to 19 , comprising:
The diamine compound is a method for producing a polymer represented by the following general formula (am-2).

If there are multiple A's, each one is independently selected from the group consisting of a single bond, a linear or branched alkylene group, an ether group, a carbonyl group, an ester group, and a group in which two or more of these are connected. is the basis of
B is any group selected from the group consisting of a single bond, a linear or branched alkylene group, an ether group, a carbonyl group, an ester group, and a group in which two or more of these are connected;
At least one of A and B is an ether group,
R ¹ , R ² and R ³ are each independently a monovalent organic group, a hydroxyl group or a halogen atom, when a plurality of them exist;
k, l and m are each independently an integer of 0 to 4,
n is an integer greater than or equal to 0. A method for producing the polymer according to any one of claims 17 to 20 , comprising:
The raw material polymer further includes a structural unit represented by the following general formula (CO).

In the general formula (CO),
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.

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