JP2009132820A - Crosslinkable prepolymer, method for producing the same and its application - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a crosslinkable prepolymer having a low relative dielectric constant and high heat resistance and capable of forming a cured product having good elongation characteristic. <P>SOLUTION: The crosslinkable prepolymer is a polymer having a fluorine-containing polyaryl ether structure in a main chain, has a crosslinkable functional group, and also has a side chain represented by R'-O- (wherein R' is a ≥11C organic group having no fluorine atom). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a crosslinkable prepolymer having a fluorine-containing polyarylether structure and a method for producing the same, a cured product of the crosslinkable prepolymer, a coating composition containing the crosslinkable prepolymer, and a coating composition comprising the coating composition. Cured film, article having the cured film, negative photosensitive composition containing the crosslinkable prepolymer, cured film pattern using the negative photosensitive composition and method for forming the same, and cured film pattern It relates to an article having.

  In the electronics field, dielectric materials are widely used in semiconductors, interposers, flat panel displays, interlayer insulating films such as multichip modules, bumping of redistribution layers, passivation films, stress relaxation layers, and build-up layers of printed wiring boards. ing. Conventionally, many dielectric materials have been proposed, but organic dielectric materials have been actively developed because semiconductors and the like are easy to manufacture.

As an organic low dielectric constant material, a polymer having a polyaryl ether structure in the main chain is considered promising.
For example, in Patent Document 1, a first monomer having a benzene ring to which a hydroxyl group is bonded and a second monomer having a benzene ring to which a halogen atom is bonded are polymerized to obtain a low dielectric constant and heat resistance. Describes a method for producing an organic insulating film material that satisfies the above.
Patent Document 2 describes a fluorine-containing polyarylether resin that is produced using a specific fluorine-containing aromatic compound having a branched structure and has both a low dielectric constant and a high Tg.

Patent Document 3 discloses that a compound having a crosslinkable functional group, a fluorine-containing aromatic compound, and a compound having three or more phenolic hydroxyl groups are subjected to a condensation reaction, thereby having a branched structure and a crosslinkable functional group. A method for producing a fluorine-containing polyarylether resin (crosslinkable prepolymer) is described. Since the crosslinkable prepolymer has a fluorine-containing polyarylether structure, it has a low dielectric constant, and since it has a crosslinkable functional group, it has an advantage of high heat resistance in a cured product.
Japanese Patent Laid-Open No. 10-247646 International Publication No. 03/8484 Pamphlet International Publication No. 2005/30837 Pamphlet

The conventional polyaryl ether resins described in Patent Documents 1 to 3 all have a low dielectric constant, and the cured product has high heat resistance, but has a problem of low elongation physical properties. If the stretched physical properties are low, cracks are likely to occur upon impact and sufficient reliability may not be ensured.
Therefore, in addition to a low dielectric constant and high heat resistance, an organic material having high toughness represented by elongation physical properties is strongly demanded. The material is not known.

  The present invention has been made in view of the above circumstances, and provides a crosslinkable prepolymer capable of forming a cured product having low dielectric constant and high heat resistance and good elongation characteristics, a method for producing the same, and use thereof The purpose is to do.

The present invention has the following gist.
[1] A polymer having a fluorine-containing polyaryl ether structure in the main chain, having a crosslinkable functional group, and R′—O— (where R ′ does not have a fluorine atom and has 11 carbon atoms) A crosslinkable prepolymer having a side chain represented by the above-mentioned organic group.
[2] The crosslinkable prepolymer according to [1], wherein the side chain is represented by the following general formula (I).

[Wherein, R represents an organic group having 10 or more carbon atoms which does not have a fluorine atom. ]

[3] The main chain has a halogen-substituted aromatic ring in which some or all of the hydrogen atoms bonded to the aromatic ring are substituted with halogen atoms, and the side chain is bonded to the halogen-substituted aromatic ring The crosslinkable prepolymer according to the above [1] or [2].
[4] Compound (Y-1) having a crosslinkable functional group and a phenolic hydroxyl group; Compound having a crosslinkable functional group and “an aromatic ring substituted with a fluorine atom capable of reacting with a phenolic hydroxyl group” (Y— 2) and either or both, a fluorine-containing aromatic compound (B) represented by the following general formula (1), and having 3 or more phenolic hydroxyl groups without having a crosslinkable functional group The crosslinkable prepolymer according to [3] above, wherein the side chain is introduced into a precursor (P21) obtained by subjecting compound (C) to a condensation reaction in the presence of a dehydrofluorinating agent.

[Wherein, n represents an integer of 0 to 2; a and b each independently represents an integer of 0 to 3; Rf ¹ and Rf ² each independently represents a fluorine-containing alkyl group having 8 or less carbon atoms; When a plurality of Rf ¹ or Rf ² are present, they may be the same or different from each other; F in the aromatic ring indicates that all the hydrogen atoms bonded to the aromatic ring are substituted with fluorine atoms. To express. ]

[5] Obtained by subjecting a fluorine-containing aromatic compound (B) represented by the above formula (1) and a compound (C) having three or more phenolic hydroxyl groups to a condensation reaction in the presence of a dehydrofluorinating agent. The crosslinkable prepolymer according to the above [3], wherein the precursor (P11) is introduced with the side chain and a crosslinkable functional group.
[6] Compound (Y-1) having a crosslinkable functional group and a phenolic hydroxyl group as a crosslinkable functional group; a crosslinkable functional group and “an aromatic ring substituted with a fluorine atom capable of reacting with a phenolic hydroxyl group” The crosslinkable prepolymer according to the above [5], which is a crosslinkable functional group derived from any one or both of the compound (Y-2) having:

[7] A polymer having a fluorine-containing polyarylether structure in the main chain, having a crosslinkable functional group, and having “an aromatic ring substituted with a halogen atom capable of reacting with a phenolic hydroxyl group” in the main chain And a precursor (P2) having a compound (Q ′) represented by R′OH (where R ′ represents an organic group having 11 or more carbon atoms not having a fluorine atom) A method for producing a crosslinkable prepolymer, characterized by reacting in the presence of an agent.
[8] The method for producing a crosslinkable prepolymer according to the above [7], wherein the compound (Q ′) is an alcohol (Q) represented by the following general formula (II).

[Wherein, R represents an organic group having 10 or more carbon atoms which does not have a fluorine atom. ]

[9] Compound (Y-1) having a crosslinkable functional group and a phenolic hydroxyl group as a precursor (P2); a crosslinkable functional group and an “aromatic ring substituted with a fluorine atom capable of reacting with a phenolic hydroxyl group” Any one or both of the compound (Y-2), and the fluorine-containing aromatic compound (B) represented by the above formula (1), which has no crosslinkable functional group and is phenolic The crosslinkable prepolymer according to [7] or [8] above, which uses a precursor (P21) obtained by subjecting a compound (C) having three or more hydroxyl groups to a condensation reaction in the presence of a dehydrofluorinating agent. Manufacturing method.

[10] a precursor (P1) which is a polymer having a fluorine-containing polyaryl ether structure in the main chain and having “an aromatic ring substituted with a halogen atom capable of reacting with a phenolic hydroxyl group” in the main chain; A compound (Q ′) represented by R′OH (where R ′ represents an organic group having 11 or more carbon atoms having no fluorine atom) is reacted in the presence of a dehydrofluorinating agent; A method for producing a crosslinkable prepolymer, further comprising introducing a crosslinkable functional group.
[11] The method for producing a crosslinkable prepolymer according to the above [10], wherein the compound (Q ′) is an alcohol (Q) represented by the above formula (II).
[12] As the precursor (P1), a fluorine-containing aromatic compound (B) represented by the above formula (1) and a compound (C) having no crosslinkable functional group and having 3 or more phenolic hydroxyl groups And a precursor (P11) obtained by a condensation reaction in the presence of a dehydrofluorinating agent. The method for producing a crosslinkable prepolymer according to the above [10] or [11].
[13] A method of introducing a crosslinkable functional group includes a compound (Y-1) having a crosslinkable functional group and a phenolic hydroxyl group; and a crosslinkable functional group and a “fluorine atom capable of reacting with a phenolic hydroxyl group” Any one or both of the compound (Y-2) having an “aromatic ring” and a condensation reaction in the presence of a dehydrofluorinating agent is described in any one of [10] to [12] above. A method for producing the crosslinkable prepolymer as described.

[14] A fluorinated aromatic compound (B) represented by the above formula (1) and a compound (C) having no crosslinkable functional group and having 3 or more phenolic hydroxyl groups are defluorinated. A step (S1) of performing a condensation reaction in the presence of a hydrogen agent; a compound (Y-1) having a crosslinkable functional group and a phenolic hydroxyl group; a crosslinkable functional group and “substituted with a fluorine atom capable of reacting with a phenolic hydroxyl group; A compound (Y-2) having a “aromatic ring” and a step (S2) in which one or both of them are subjected to a condensation reaction in the presence of a dehydrofluorinating agent to introduce a crosslinkable functional group; A compound (Q ′) represented by OH (wherein R ′ represents an organic group having 11 or more carbon atoms having no fluorine atom) is reacted in the presence of a dehydrofluorinating agent, and the side chain is And a step (S3) of introducing, Method of manufacturing a mer.
[15] The method for producing a crosslinkable prepolymer according to the above [14], wherein the compound (Q ′) is an alcohol (Q) represented by the following general formula (II).

[16] A cured product formed by curing the crosslinkable prepolymer according to any one of [1] to [6].
[17] A coating composition comprising the crosslinkable prepolymer according to any one of [1] to [6] and a solvent.
[18] The coating composition according to [17] is applied to a substrate to form a wet film, the solvent in the wet film is removed, and the wet film is removed after or simultaneously with the removal of the solvent. A cured film obtained by curing the crosslinkable prepolymer in the film.
[19] An article having the cured film as described in [18] above.
[20] A negative photosensitive composition containing the crosslinkable prepolymer according to any one of [1] to [6] above, a photosensitive agent, and a solvent.
[21] The negative photosensitive composition as described in [20] above, wherein the photosensitive agent comprises a photoinitiator or a photocrosslinking agent.
[22] A step of forming a coating film on the substrate from the negative photosensitive composition as described in [20] or [21], and selectively exposing a part of the coating film, A method of forming a cured film pattern, comprising: an exposure step for causing a reaction of the crosslinkable functional group; and a step of developing after the exposure step.
[23] A cured film pattern obtained by the formation method described in [22] above.
[24] An article having the cured film pattern according to [23].

According to the present invention, a crosslinkable prepolymer having a low relative dielectric constant and high heat resistance and capable of forming a cured product having good elongation characteristics can be obtained.
The coating composition of the present invention can be used to form a cured film having low dielectric constant and high heat resistance and good elongation characteristics.
The negative photosensitive composition of the present invention can be used to form a cured film pattern having low dielectric constant and high heat resistance and good elongation characteristics.

<Crosslinkable prepolymer>
The crosslinkable prepolymer of the present invention (hereinafter sometimes simply referred to as prepolymer) is a polymer having a fluorinated polyarylether structure in the main chain, having a crosslinkable functional group, and the above R It has a side chain represented by '-O-.

[Main chain]
In the present invention, the “polyaryl ether structure” means a polymer structure formed by repeating a structure in which two aromatic rings are bonded via an ether bond (—O—). The “aromatic ring” in the present invention means a ring structure in a cyclic organic compound having aromaticity, and includes those having an arbitrary substituent unless otherwise specified. In particular, a structure in which at least a part of the aromatic ring of the polyaryl ether structure has a substituent containing a fluorine atom is referred to as a fluorine-containing polyaryl ether structure.
“Having a polyaryl ether structure in the main chain” means that in each aromatic ring constituting the polyaryl ether structure, two or more carbon atoms constituting the ring are carbon chains constituting the main chain (however, 2 The ether bond between the two aromatic rings is regarded as a part of the carbon chain constituting the main chain, that is, the ether bond may be interposed between the two aromatic rings, and so on. It means that.
In the crosslinkable prepolymer of the present invention, the carbon chain constituting the main chain may be branched. In the present invention, even a branched carbon chain (branched chain) includes a portion containing a polyaryl ether structure, or a portion containing "an aromatic ring in which two or more carbon atoms are carbon atoms in the carbon chain". Is regarded as a part of the main chain, and the terminal part not including these structures is referred to as a “side chain”. However, when it has a structure represented by “R′—O— (R ′ represents an organic group having 11 or more carbon atoms not having a fluorine atom)” at the terminal, the “R′—O—” "Is a side chain, which is not included in the main chain.

Halogen in which one of two aromatic rings bonded via an ether bond in the polyaryl ether structure of the main chain is substituted with a halogen atom for some or all of the hydrogen atoms bonded to the aromatic ring A substituted aromatic ring is preferred.
The halogen atom in the halogen-substituted aromatic ring is preferably a fluorine atom. The halogen-substituted aromatic ring is preferably a perfluoroaromatic ring in which all of the hydrogen atoms bonded to the aromatic ring are substituted with halogen atoms, and all of the hydrogen atoms are substituted with fluorine atoms. More preferred.
The main chain may have another aromatic ring other than the aromatic ring constituting the polyaryl ether structure. For example, an aromatic ring bonded to an adjacent aromatic ring only through a single bond corresponds to the other aromatic ring. The other aromatic ring is preferably the halogen-substituted aromatic ring, and more preferably the perfluoroaromatic ring.

[Crosslinkable functional group]
The crosslinkable functional group in the present invention does not substantially react at the time of producing the prepolymer, and gives external energy at the time of producing a cured product such as a film, a film or a molded product, or at any time after production. A reactive functional group that reacts to cause cross-linking or chain extension between prepolymer molecules.
Examples of the external energy include heat, light, and electron beam. These may be used in combination. When heat is used as external energy, a reactive functional group that reacts at a temperature of 40 ° C to 500 ° C is preferable. If the reaction temperature is too low, stability during storage of the prepolymer or the composition containing the prepolymer cannot be ensured, and if it is too high, thermal decomposition of the prepolymer itself occurs during the reaction. It is preferable. More preferably, it is 60 degreeC-400 degreeC, and 70 degreeC-350 degreeC is the most preferable.
Moreover, when using light (actinic radiation) as external energy, it is preferable to contain a photosensitizer in the prepolymer or the composition containing the prepolymer. In this case, the prepolymer in the exposed portion can be made high molecular weight by selectively irradiating actinic radiation in the exposure process, and external energy such as actinic radiation or heat can be applied after the exposure and development processes as necessary. The prepolymer can be further increased in molecular weight.

Specific examples of the crosslinkable functional group include vinyl group, allyl group, methacryloyl (oxy) group, acryloyl (oxy) group, vinyloxy group, trifluorovinyl group, trifluorovinyloxy group, ethynyl group, 1-oxocyclopenta Examples include -2,5-dien-3-yl group, cyano group, alkoxysilyl group, diarylhydroxymethyl group, hydroxyfluorenyl group, cinnamyl group and the like. A vinyl group, a methacryloyl (oxy) group, an acryloyl (oxy) group, a trifluorovinyloxy group, and an ethynyl group are preferable in terms of high reactivity and high crosslink density, and the resulting cured product has good heat resistance. The vinyl group and the ethynyl group are most preferable from the viewpoint of having them. The methacryloyl (oxy) group means a methacryloyl group or a methacryloyloxy group, and the same applies to an acryloyl (oxy) group.
All of the examples of the crosslinkable functional groups listed above are functional groups that can react both when irradiated with actinic radiation in the presence of a photosensitizer or when heated at a temperature of 40-500 ° C. is there.

The crosslinkable functional group may be in the main chain or in the side chain. “The crosslinkable functional group is present in the main chain” means that one or more carbon atoms constituting the crosslinkable functional group (which may contain an etheric oxygen atom) are bonded to the main chain. It means a carbon atom in the constituting carbon chain.
From the viewpoint of easy availability of the raw material, it is preferable that the crosslinkable functional group is in the side chain and the main chain does not have the crosslinkable functional group.

  The content of the crosslinkable functional group in the prepolymer of the present invention is preferably from 0.1 to 4 mmol, more preferably from 0.2 to 3 mmol, based on 1 g of the prepolymer. By setting the content to 0.1 mmol or more, the heat resistance and solvent resistance of the cured product can be increased, and by setting the content to 4 mmol or less, brittleness can be easily reduced.

[Side chain]
The prepolymer of the present invention has a side chain represented by R′—O—. R ′ represents an organic group having 11 or more carbon atoms that does not have a fluorine atom. The upper limit of the carbon number of R ′ is preferably 1000 or less, more preferably 500 or less, from the viewpoint of reactivity and heat resistance during production.
Examples of R ′ include R—CH ₂ — and R—Ph— (where Ph represents a phenylene group. R is the same as R in “R—CH ₂ —” described later). In particular, it is preferable that R′— is R—CH ₂ — in that the obtained cured product is excellent in elongation property and therefore excellent in flexibility.
Since R ′ does not have a fluorine atom, that is, has a long side chain that does not contain a fluorine atom, the resulting cured product has excellent stretch properties and therefore excellent flexibility. The reason is presumed that a micro sea island structure is formed in the polymer structure by the interaction between the side chain and the aromatic ring having a substituent containing a fluorine atom in the main chain. The existence of this micro-island structure is considered to produce high flexibility.

The position at which the side chain represented by R′—O— is introduced is not particularly limited, but it is preferable in production that the side chain is bonded to the halogen-substituted aromatic ring in the main chain. That is, it is preferable that a halogen-substituted aromatic ring is present in the main chain, and a side chain represented by R′—O— is bonded to the aromatic ring.
The halogen-substituted aromatic ring to which the side chain is bonded may be an aromatic ring constituting a polyaryl ether structure, or may be another aromatic ring other than that. From the viewpoint of easy production of the prepolymer, it is more preferable that a side chain represented by R′—O— is bonded to the latter, that is, a halogen-substituted aromatic ring that does not constitute a polyaryl ether structure. The halogen-substituted aromatic ring to which the side chain is bonded is more preferably a perfluoroaromatic ring.

The “side chain represented by R′—O—” present in one molecule of the prepolymer may be one type or two or more types.
The content of the “side chain represented by R′—O—” in the prepolymer of the present invention is preferably 0.01 to 0.5 g, more preferably 0.02 to 0.3 g, with respect to 1 g of the prepolymer. . When the content is not less than the lower limit of the above range, the effect of improving the flexibility in the cured product is easily obtained, and when the content is not more than the upper limit, good heat resistance is easily obtained.

[Side Chain Represented by Formula (I)]
The side chain represented by R′—O— is preferably a side chain (R—CH ₂ —O—) represented by the above formula (I).
In the above formula (I), R represents an organic group having 10 or more carbon atoms that does not have a fluorine atom. The carbon number of R is preferably 15 or more, more preferably 20 or more, and particularly preferably 30 or more. When the carbon number of R is 10 or more, the flexibility of the obtained cured film tends to be high. The upper limit of the carbon number of R is preferably 1000 or less, more preferably 500 or less, from the viewpoints of reactivity and heat resistance during production.
The organic group as R in the side chain (R—CH ₂ —O—) is preferably linear or branched from the viewpoint of increasing the flexibility of the resulting cured film. When R in the side chain is a branched chain, the branched chain preferably has 10 or less carbon atoms. The organic group as R in the side chain may contain an etheric oxygen atom (—O—) in the main skeleton chain (the main skeleton chain of R in the side chain). A siloxane chain (—Si—O—) may be included, and the main skeleton chain may include an aromatic ring. The inclusion of an aromatic ring in the main skeleton chain means that two or more carbon atoms constituting the aromatic ring are carbon atoms in the carbon chain constituting the main skeleton chain. The organic group as R may have a functional group such as a hydroxyl group, a carboxy group, and an amino group.

The organic group as R is preferably an alkyl group which may contain an etheric oxygen atom or an alkyl group having a polysiloxane chain in which a chain alkyl group is bonded to a silicon atom.
For example, a monovalent group having at least one chain selected from a polyoxyalkylene chain, a polyolefin chain, and a polyalkylsiloxane chain is preferable.
Examples of the polyoxyalkylene chain include a polyoxyethylene chain, a polyoxypropylene chain, a polyoxybutylene chain, and a polyoxytetramethylene chain.
Examples of the polyolefin chain include a polyethylene chain, a polypropylene chain, a polybutadiene chain, and a polyisoprene chain.
Examples of the polyalkylsiloxane chain include a polydimethylsiloxane chain, a polymethylphenylsiloxane chain, and a polydiphenylsiloxane chain.
A preferred specific example of the side chain represented by the above formula (I) is a monovalent group obtained by removing hydrogen from one hydroxyl group in the alcohol (Q) described later.

<Prepolymer production method>
The prepolymer of the present invention comprises a fluorine-containing aromatic compound (B) represented by the above formula (1) and a compound (C) having no crosslinkable functional group and having 3 or more phenolic hydroxyl groups. A step (S1) of performing a condensation reaction in the presence of a dehydrofluorinating agent, a compound (Y-1) having a crosslinkable functional group and a phenolic hydroxyl group; a crosslinkable functional group and “fluorine capable of reacting with a phenolic hydroxyl group” Step (S2) of introducing a crosslinkable functional group by subjecting one or both of the compound (Y-2) having an “aromatic ring substituted with an atom” to a condensation reaction in the presence of a dehydrofluorinating agent. And a compound (Q ′) represented by R′OH (wherein R ′ represents an organic group having 11 or more carbon atoms not having a fluorine atom) are reacted in the presence of a dehydrofluorinating agent. A step of introducing a side chain (S3). It can be produced. In the following description, the compound (Y-1) and the compound (Y-2) may be collectively referred to as the compound (Y).

  More specifically, the method of performing the step (S3) after performing the step (S1) and the step (S2), or the step (S2) after performing the step (S1) and the step (S3). The method of carrying out is preferred. However, performing step (S1) and step (S2) may be performed after step (S1) is performed, step (S2) may be performed, and step (S1) and step (S2) are performed simultaneously. Also good. The same applies to the steps (S1) and (S3).

  Steps (S1), (S2), and (S3) are all condensation reactions performed in the presence of a dehydrofluorinating agent (hereinafter also referred to as a deHF agent). In addition, all of these condensation reactions may be reacted in one step, or may be performed in multiple steps. Moreover, after reacting a specific compound preferentially among the reaction raw materials, another compound may be subsequently reacted. When the condensation reaction is performed in multiple stages, the intermediate product obtained in the middle may be separated from the reaction system and purified, and then used for the subsequent reaction (condensation reaction). In the reaction field, the raw material compounds may be charged all at once, may be charged continuously, or may be charged intermittently.

[Production method using precursor (P1)]
Further, as a method for producing the prepolymer of the present invention, a polymer having a fluorinated polyarylether structure in the main chain and having “an aromatic ring substituted with a halogen atom capable of reacting with a phenolic hydroxyl group” in the main chain. It is possible to use a method in which the precursor (P1) having the compound and the compound (Q ′) represented by R′OH are reacted in the presence of a dehydrofluorinating agent and a crosslinkable functional group is further introduced. . Specifically, the precursor (P1) is obtained by performing the step (S1), the precursor (P1) and the compound (Q ′) are subjected to a condensation reaction, and then the compound (Y) is subjected to a condensation reaction. Thus, the prepolymer of the present invention is obtained.
In this production method, the molecular weight of the prepolymer is easily controlled by producing the precursor (P1) first. Moreover, when the reactivity of compound (Q ') is low compared with compound (Y), it is suitable for reacting a desired amount of compound (Q'). That is, it is preferable in that the introduction of a desired amount of the side chain represented by R′—O— is easily controlled. Depending on the selection of the raw material, when a crosslinkable functional group is introduced, the storage stability of the prepolymer may decrease due to the progress of the crosslinking reaction. In this case, the intermediate product may be stored at a stage where the crosslinkable functional group is not introduced, and it may be expected that the yield of the prepolymer is improved.
More specifically, as the precursor (P1), the fluorine-containing aromatic compound (B) represented by the above formula (1) and 3 or more phenolic hydroxyl groups that do not have a crosslinkable functional group. It is preferable to use a precursor (P11) obtained by subjecting compound (C) to a condensation reaction in the presence of a dehydrofluorinating agent. That is, after the step (S1) is performed, the step (S3) is performed to introduce the side chain represented by R′—O—, and then the step (S2) is performed to introduce a crosslinkable functional group. preferable.
For introducing the crosslinkable functional group, it is preferable to use the compound (Y).

[Production method using precursor (P2)]
As another production method of the prepolymer of the present invention, a polymer having a fluorine-containing polyaryl ether structure in the main chain, having a crosslinkable functional group and having “a halogen atom capable of reacting with a phenolic hydroxyl group” in the main chain The precursor (P2) having an “aromatic ring substituted with” and the compound (Q ′) represented by R′OH are preferably reacted in the presence of a dehydrofluorinating agent. Specifically, the step (S1) and the step (S2) are performed to obtain a precursor (P2), and the precursor (P2) and the compound (Q ′) are subjected to a condensation reaction to thereby produce the prepolymer of the present invention. Is obtained. This production method is preferable in that the production process of the prepolymer is easily simplified by producing the precursor (P2) first.
More specifically, as the precursor (P2), the compound (Y-1) having a crosslinkable functional group and a phenolic hydroxyl group, the crosslinkable functional group, and “a fluorine atom capable of reacting with a phenolic hydroxyl group are substituted. Either or both of the compound (Y-2) having an “aromatic ring”, the fluorine-containing aromatic compound (B) represented by the above formula (1), and a phenolic compound having no crosslinkable functional group It is preferable to use a precursor (P21) obtained by subjecting a compound (C) having three or more hydroxyl groups to a condensation reaction in the presence of a dehydrofluorinating agent. That is, it is preferable to implement a step (S3) and introduce a side chain after carrying out the steps (S1) and (S2) to introduce a crosslinkable functional group. The precursor (P2) can also be obtained by reacting the compound (Y) after obtaining the precursor (P1).

The precursor (P21) is produced by either or both of the following methods (i) and (ii).
(I) A method in which the compound (B), the compound (C) and the compound (Y-1) are subjected to a condensation reaction in the presence of a deHF agent.
(Ii) A method in which the compound (B), the compound (C) and the compound (Y-2) are subjected to a condensation reaction in the presence of a deHF agent.
In addition, when manufacturing a precursor (P21) by both said (i) and (ii), a fluorine-containing aromatic compound (B), a compound (C), a compound (Y-1), and a compound (Y-2) ) In the presence of a deHF agent.
When the side chain represented by the above R′—O— is introduced into the precursor (P21), “a part or all of the hydrogen atoms bonded to the aromatic ring are substituted with fluorine atoms in the main chain” And a side chain represented by R′—O— is bonded to the fluorine-containing aromatic ring.

The “aromatic ring substituted with a halogen atom capable of reacting with a phenolic hydroxyl group” is preferably an aromatic ring in which two or more of the hydrogen atoms bonded to the aromatic ring are substituted with a halogen atom, It is preferred that all of the hydrogen atoms are substituted with halogen atoms. The halogen atom is preferably a fluorine atom, and the “aromatic ring substituted with a halogen atom capable of reacting with a phenolic hydroxyl group” is most preferably a perfluoroaromatic ring. Examples of the perfluoroaromatic ring include perfluorophenyl and perfluorobiphenyl.
Further, the “aromatic ring substituted with a halogen atom capable of reacting with a phenolic hydroxyl group” is introduced into the prepolymer by the fluorine-containing aromatic compound (B) or the compound (Y-2). Therefore, the side chain represented by R′—O— is introduced into the aromatic ring derived from the fluorine-containing aromatic compound (B) or the compound (Y-2).

  In the condensation reaction in the method for producing a prepolymer of the present invention, as represented by the following formula (2), a phenoxy group derived from a phenolic hydroxyl group is bonded to a fluorine atom of the fluorinated aromatic compound (B). An ether bond is generated by a reaction mechanism that attacks a carbon atom to which a carbon atom and / or a fluorine atom (or halogen atom) of (Y-2) is bonded, and then the fluorine atom is eliminated. When the compound (C) and / or (Y-1) has two phenolic hydroxyl groups in the ortho positional relationship, the dioxin skeleton is represented by the same reaction mechanism as shown in the following formula (3). May generate. Heat resistance can be improved by introducing a dioxin skeleton.

In addition, the reaction between the “aromatic ring substituted with a halogen atom capable of reacting with a phenolic hydroxyl group” and the compound (Q ′) is similar to the reaction represented by the formula (2) in the compound (Q ′). The alkoxy group or phenoxy group derived from the hydroxyl group of this attacks the carbon atom to which the halogen atom of the “aromatic ring substituted with a halogen atom capable of reacting with a phenolic hydroxyl group” is bonded, and then the halogen atom is eliminated. An ether bond is generated depending on the reaction mechanism.
By this reaction, a side chain in which hydrogen is removed from the hydroxyl group of compound (Q ′), that is, a side chain represented by R′—O— is introduced.

By using the compound (Y-1) or (Y-2) having a crosslinkable functional group as a monomer for producing the prepolymer of the present invention, a prepolymer having a crosslinkable functional group introduced therein can be obtained. As a result, when the prepolymer of the present invention is cured, the crosslinking or chain extension reaction between the prepolymer molecules proceeds, and the heat resistance is greatly improved. Moreover, the effect that the solvent resistance of hardened | cured material improves by using the compound (Y-1) or (Y-2) which has a crosslinkable functional group is also acquired.
Moreover, by using the compound (C) having no crosslinkable functional group and having 3 or more phenolic hydroxyl groups, a prepolymer having a branched structure introduced into the polymer chain and a three-dimensional molecular structure can be obtained. .
Furthermore, the flexibility in the cured product can be improved by using the fluorine-containing aromatic compound (B) represented by the above formula (1). The prepolymer using the compound (B) as a monomer has a higher ether bond density than a fluorine-containing aromatic polymer produced using a fluorine-containing aromatic compound having a branched structure as a monomer. The flexibility of the main chain is improved. Thereby, good flexibility is obtained in the cured product of the prepolymer of the present invention. Further, the good flexibility of the cured product is particularly advantageous when the cured product is in the form of a cured film.

[Fluorine-containing aromatic compound (B)]
The fluorine-containing aromatic compound (B) is a fluorine-containing aromatic compound represented by the above formula (1). That is, the fluorine-containing aromatic compound (B) is a compound having “an aromatic ring substituted with a fluorine atom capable of reacting with a phenolic hydroxyl group”. The fluorine-containing aromatic compound (B) is also a compound having an aromatic ring to which the side chain represented by R′—O— can be bonded in the condensation reaction with the compound (Q ′).
In this formula (1), Rf ¹ and Rf ² each independently represents a fluorine-containing alkyl group having 8 or less carbon atoms, preferably 3 or less carbon atoms. When a plurality of Rf ¹ are present in one kind of fluorine-containing aromatic compound (B), they may be the same or different. Similarly, when there are a plurality of Rf ² , they may be the same or different.
The fluorine-containing alkyl group as Rf ¹ or Rf ² means one in which part or all of the hydrogen atoms bonded to the carbon atom of the alkyl group are substituted with fluorine atoms. From the viewpoint of heat resistance, a perfluoroalkyl group is preferred. Specific examples include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group.

When Rf ¹ and Rf ² are increased, it becomes difficult to produce the fluorine-containing aromatic compound (B). Accordingly, the number of Rf ¹ (a in the formula) is 0 to 3, preferably 0 to 2, and most preferably 0.
The number of Rf ² (n b in the formula) is 0 to 6, preferably 0 to 2, and most preferably 0.
In the above formula (1), n is an integer of 0 to 2, preferably 0 or 1, and most preferably 1.

As specific examples of the fluorine-containing aromatic compound (B), the following compounds can be preferably exemplified.
perfluorobenzene, perfluorotoluene, perfluoroxylene when n = 0; perfluorobiphenyl when n = 1; perfluoroterphenyl when n = 2; perfluoro (1, 3, 3 when n = 3 5-triphenylbenzene) and perfluoro (1,2,4-triphenylbenzene). In particular, perfluorobenzene, perfluorobiphenyl, perfluoro (1,3,5-triphenylbenzene), and perfluoro (1,2,4-triphenylbenzene) are preferable. These may be used alone or in combination of two or more. In the case of n = 3, a branched structure is introduced into the prepolymer, so that the heat resistance of the cured product can be improved.
Perfluorobiphenyl is most preferred as the fluorinated aromatic compound (B) in that the cured product obtained has an excellent balance between the dielectric constant and heat resistance and the flexibility of the cured product is increased.

[Compound (C)]
The compound (C) is a compound having no crosslinkable functional group and having 3 or more phenolic hydroxyl groups. In the present invention, those having a crosslinkable functional group are not included in the compound (C).
Specific examples of the compound (C) include trihydroxybenzene, trihydroxybiphenyl, trihydroxynaphthalene, 1,1,1-tris (4-hydroxyphenyl) ethane, tris (4-hydroxyphenyl) benzene, tetrahydroxybenzene, Examples thereof include tetrahydroxybiphenyl, tetrahydroxybinaphthyl, tetrahydroxyspiroindanes and the like. Since the flexibility of the obtained cured film becomes high, the compound (C) is preferably a compound having three phenolic hydroxyl groups. Among these, 1,1,1-tris (4-hydroxyphenyl) ethane and trihydroxybenzene are more preferable.

[Compound (Y-1)]
The compound (Y-1) has a crosslinkable functional group and a phenolic hydroxyl group. The compound (Y-1) does not have “an aromatic ring substituted with a fluorine atom capable of reacting with a phenolic hydroxyl group”.
As the compound (Y-1), a compound (Y-1-1) having one phenolic hydroxyl group and a compound (Y-1-2) having two phenolic hydroxyl groups are preferable. (Y-1-1) works as a monofunctional compound, and when this is used, a prepolymer having a crosslinkable functional group in the side chain is obtained. (Y-1-2) works as a bifunctional compound, and when used, a precursor prepolymer having a crosslinkable functional group in the main chain is obtained. Both (Y-1-1) and (Y-1-2) may be used, in which case a prepolymer having a crosslinkable functional group in the main chain and side chain is obtained.
In addition, you may generate | occur | produce the phenolic hydroxyl group in a compound (Y-1) in a reaction system. Specifically, a protected phenolic hydroxyl group that undergoes hydrolysis in the presence of an alkali to form a phenolic hydroxyl group is considered to be the same as the phenolic hydroxyl group. More specifically, a compound such as an ester that gives a phenolic hydroxyl group in the presence of a dehydrofluorinating agent is also included in (Y-1).
As described above, the prepolymer of the present invention preferably has a crosslinkable functional group only in the side chain, and therefore it is more preferable to use only (Y-1-1).
The number of crosslinkable functional groups in each of (Y-1-1) and (Y-1-2) is preferably 1.

Specific examples of the compound (Y-1-1) include phenols having a reactive double bond such as 4-hydroxystyrene, 2-allylphenol, 4-hydroxychalcone, 3-ethynylphenol, 4-phenylethynylphenol. And ethynylphenols such as 4- (4-fluorophenyl) ethynylphenol. Moreover, 4-acetoxystyrene etc. are mentioned as a specific example of the compound by which the phenolic hydroxyl group was protected. These may be used alone or in combination of two or more. An aromatic compound having a vinyl group or an ethynyl group as the crosslinkable functional group is preferable, and an aromatic compound having a vinyl group is more preferable.
Note that 4- (4-fluorophenyl) ethynylphenol has an aromatic ring in which one hydrogen atom bonded to the aromatic ring is substituted with a fluorine atom. This fluorine atom is substantially phenolic. Does not react with hydroxyl groups. Thus, even if it is a compound which the fluorine atom couple | bonded with the aromatic ring, what this fluorine atom does not react with a phenolic hydroxyl group is contained in a compound (Y-1-1).

  Specific examples of the compound (Y-1-2) include 2,2′-bis (phenylethynyl) -5,5′-dihydroxybiphenyl, 2,2′-bis (phenylethynyl) -4,4′-dihydroxy. Examples thereof include bis (phenylethynyl) dihydroxybiphenyls such as biphenyl, and dihydroxydiphenylacetylenes such as 4,4′-dihydroxytolane and 3,3′-dihydroxytolane. These may be used alone or in combination of two or more.

[Compound (Y-2)]
The compound (Y-2) has a crosslinkable functional group and “an aromatic ring substituted with a fluorine atom capable of reacting with a phenolic hydroxyl group”. Compound (Y-2) does not have a phenolic hydroxyl group.
In the compound (Y-2), the “aromatic ring substituted with a fluorine atom capable of reacting with a phenolic hydroxyl group” preferably has two or more hydrogen atoms bonded to the aromatic ring substituted with a fluorine atom. A perfluoroaromatic ring that is an aromatic ring and in which all of the hydrogen atoms are substituted with fluorine atoms is more preferred. Examples of the perfluoroaromatic ring include perfluorophenyl and perfluorobiphenyl.
When the number of “fluorine atoms capable of reacting with phenolic hydroxyl groups” in (Y-2) is one, (Y-2) works as a monofunctional compound, and in the case of two, it works as a bifunctional compound. In any case, a prepolymer having a crosslinkable functional group introduced in the side chain is obtained.
The number of crosslinkable functional groups in (Y-2) is preferably 1.

Specific examples of the compound (Y-2) include pentafluorostyrene, pentafluorobenzyl acrylate, pentafluorobenzyl methacrylate, pentafluorophenyl acrylate, pentafluorophenyl methacrylate, perfluorostyrene, pentafluorophenyl trifluorovinyl ether, 3- (penta Fluorinated aryls having a reactive double bond such as fluorophenyl) pentafluoro-1-propene and 2,3,4,5,6-pentafluorostilbene; Fluorinated aryl having a cyano group such as pentafluorobenzonitrile Fluorine-containing arylacetylenes such as pentafluorophenylacetylene and nonafluorobiphenylacetylene; phenylethynylpentafluorobenzene, phenylethynylnonafluorobi Eniru, fluorinated diaryl acetylene such as deca fluoro Tran and the like.
These may be used alone or in admixture of two or more. Since the crosslinking reaction proceeds at a relatively low temperature and the resulting prepolymer cured product has high heat resistance, the compound (Y-2) includes fluorine-containing arylacetylenes such as pentafluorophenylacetylene, pentafluorostyrene. Fluorine-containing aryls having a reactive double bond such as

[Dehydrofluorinating agent]
As the dehydrofluorinating agent (dehydrating agent) used for producing the precursor (P1) and the precursor (P2), a basic compound is preferable, and in particular, an alkali metal carbonate, hydrogencarbonate or hydroxide Things are preferred. Specific examples include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide and the like. As a dehydrofluorinating agent used when manufacturing a precursor (P1) and a precursor (P2), sodium carbonate, potassium hydroxide, or potassium carbonate is more preferable.

  The amount of the de-HF agent used is required to be 1 or more times in terms of molar ratio with respect to the number of moles of the phenolic hydroxyl group to be reacted, and preferably 1.1 to 3 times. In other words, the amount of the hydroxyl group of the compound (C) having a phenolic hydroxyl group or the total amount of the hydroxyl groups of the compound (C) and the compound (Y-1) must be 1 or more times in molar ratio. 1.1 to 3 times is preferable.

  The condensation reaction is preferably performed in a polar solvent. As the polar solvent, a solvent containing an aprotic polar solvent such as N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane and the like is preferable. The polar solvent may contain toluene, xylene, benzene, tetrahydrofuran, benzotrifluoride, xylene hexafluoride and the like as long as the solubility of the prepolymer to be produced is not lowered and the condensation reaction is not adversely affected. . By containing these, the polarity (dielectric constant) of the solvent changes, and the reaction rate can be controlled.

  The condensation reaction conditions are preferably 10 to 200 ° C. and 1 to 80 hours. More preferably, it is 2 to 60 hours at 20 to 180 ° C, and most preferably 3 to 48 hours at 50 to 160 ° C.

The number average molecular weight of the prepolymer is in the range of 1 × 10 ^{3 to} 5 × 10 ⁵ , preferably 1.5 × 10 ³ to 1 × 10 ⁵ . Within this range, the coating properties of the coating composition containing the prepolymer of the present invention will be good, and the resulting cured film will have good heat resistance, mechanical properties, solvent resistance, and the like.
In the use of an insulating film for an electronic device, a characteristic (so-called embedded flatness) that sufficiently penetrates between minute spaces of a base and smoothes the surface is required, and the number average molecular weight of the prepolymer is 1.5 × 10 range of ³ to 5 × 10 ⁴ being most preferred.

In the production method using the compound (Y-1), the number average molecular weight of the prepolymer is the sum of the compound (C), the compound (Y-1) and the compound (Q ′), and the fluorine-containing aromatic compound (B). It can be controlled by changing the charging ratio.
In the condensation reaction, the fluorine-containing aromatic compound (B) usually functions as a bifunctional compound. Therefore, the molecular weight is controlled in such a range that the total number of moles of hydroxyl groups of the compound (C), the compound (Y-1) and the compound (Q ′) does not exceed twice the number of moles of the fluorinated aromatic compound (B). It is preferable to adjust within.

  The number average molecular weight of the prepolymer in the production method using the compound (Y-2) is the sum of the fluorine-containing aromatic compound (B) and the compound (Y-2) and the sum of the compound (C) and the compound (Q ′). It can be controlled by changing the charging ratio. Here, similarly to the above, when the compound (Y-2) works as a monofunctional compound, the total number of moles of the hydroxyl group is twice the number of moles of the fluorine-containing aromatic compound (B) and the compound ( It is preferable to adjust within a range not exceeding the total number of moles of Y-2). When the compound (Y-2) functions as a bifunctional compound, the total number of moles of hydroxyl groups does not exceed twice the total number of moles of the fluorine-containing aromatic compound (B) and the compound (Y-2). It is preferable to adjust within.

  Moreover, in the manufacturing method using a compound (Y-2), when the reaction rates of a fluorine-containing aromatic compound (B) and a compound (Y-2) differ, the molecular weight and composition of the precursor or prepolymer obtained by an addition order are different. May be different. For example, when the reaction rate for the phenoxy group derived from the phenolic hydroxyl group of the compound (C) is (B)> (Y-2), the fluorine-containing aromatic compound (B) and the compound (Y-2) When charged at the same time, before all the compound (Y-2) is consumed, all the phenoxy groups may be consumed by the fluorine-containing aromatic compound (B), and the unreacted compound (Y-2) may remain. . In such a case, in order to increase the reaction rate of the compound (Y-2), it is preferable to charge the fluorine-containing aromatic compound (B) after first charging the compound (Y-2). However, in this method, the variation of the composition between the molecular chains of the obtained precursor tends to be large. When it is necessary to reduce the variation in the composition between the molecular chains of the obtained precursor, it is preferable to manufacture by batch preparation.

In the production method using the compound (Y-1), the amount of the compound (C) used is preferably 0.1 to 1 times, more preferably 0.3 to 0.00, in terms of the molar ratio to the fluorine-containing aromatic compound (B). It is 6 times, and the amount of the compound (Y-1) used is preferably 0.1 to 2 times, more preferably 0.2 to 1.5 times in terms of a molar ratio to the fluorine-containing aromatic compound (B).
In the production method using the compound (Y-2), the amount of the compound (C) used is preferably 0.5 to 2 times, more preferably 0.6 to 1 in terms of molar ratio to the fluorine-containing aromatic compound (B). It is 5 times, and the usage-amount of a compound (Y-2) is 0.1-2 times by molar ratio with respect to a fluorine-containing aromatic compound (B), More preferably, it is 0.2-1.5 times. When each value is in this range, the obtained prepolymer of the present invention has high heat resistance, which is preferable.

  The prepolymer of the present invention has the desired physical properties by appropriately selecting the compounds (Y-1) and (Y-2) according to the physical properties such as heat resistance and flexibility of the cured product obtained by curing the prepolymer. It is possible to produce a prepolymer from which a cured product can be obtained.

  The prepolymer of the present invention is subjected to neutralization, reprecipitation, after a condensation reaction in the intermediate step (for example, after synthesizing a precursor or after introducing a side chain represented by R′—O—), It is preferable to perform purification appropriately by a method such as extraction or filtration.

[Other co-condensation components]
In a cured product produced using a prepolymer, if the heat resistance is insufficient or the film or film made of the cured product is brittle, the heat resistance of the cured product is improved and the flexibility is improved. Therefore, other cocondensation components other than the above (B) (C) (Y-1) (Y-2) (Q ') can be added during the production of the prepolymer.
Examples of the other cocondensation component include a compound (Z) having two phenolic hydroxyl groups other than (Y-1) and (Q ′) for improving the flexibility of the cured film.

  Examples of the compound (Z) having two phenolic hydroxyl groups include bifunctional phenols such as dihydroxybenzene. These may be used alone or in combination of two or more.

[Compound (Q ′)]
The compound (Q ′) is represented by R′OH (where R ′ represents an organic group having 11 or more carbon atoms which does not have a fluorine atom). R ′ in the compound (Q ′) is the same as R ′ in the side chain represented by R′—O—.
The compound (Q ′) is preferably a monofunctional or bifunctional alcohol because it is easy to handle in the side chain introduction reaction. That is, if there are many functional groups (hydroxyl groups), the crosslinking reaction may proceed and gelation may occur easily. The number of functional groups of the compound (Q ′) is preferably 1 to 3. When the compound (Q ′) is a diol, the hydroxyl group on one side may be converted to an alkyl group or the like and used as a monool. 140-15000 are preferable and, as for the molecular weight of a compound (Q '), 200-8000 are more preferable.
Examples of the compound (Q ′) include alcohols (Q) and R—Ph—OH (where Ph represents a phenylene group) represented by the above formula (II), and alcohols represented by the above formula (II) (Q) is preferred.
Examples of alcohols represented by R-Ph-OH include both terminal phenolic silicone, both terminal phenolic polyethylene glycol, both terminal phenolic polytetramethylene glycol, both terminal phenolic polybutadiene, both terminal phenolic polyisoprene, The both terminal phenol type acrylonitrile polybutadiene copolymer etc. are mentioned.

Specific examples of the alcohol (Q) represented by the above formula (II) include the following.
Examples of the alcohol (Q1) in which R has a polyoxyalkylene chain include polyoxyethylene polyol, polyoxypropylene polyol, polyoxyethyleneoxypropylene polyol, polyoxybutylene polyol, and polyoxytetramethylene polyol. As the polyoxytetramethylene polyol, polyoxytetramethylene glycol is preferable.
Examples of the alcohol (Q2) in which R has a polyolefin chain include polyethylene polyol, polypropylene polyol, polybutadiene polyol, and polyisoprene polyol.
Examples of the alcohol (Q3) in which R has a polysiloxane chain (—Si—O—) include polydimethylsiloxane polyol, polymethylphenylsiloxane polyol, polydiphenylsiloxane polyol, and both-end carbinol type silicone.
When these alcohols (Q) are diols, a hydroxyl group at one end may be converted to an alkyl group or the like and used as a monool.

As the dehydrofluorinating agent used when reacting the compound (Q ′), the same deHF agent used for the condensation reaction of the compound (B), the compound (C) and the compound (Y) can be used. . That is, the deHF agent is preferably a basic compound, and particularly preferably an alkali metal hydride, carbonate, bicarbonate or hydroxide. Specific examples include sodium hydride, potassium hydride, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide, cesium hydroxide and the like. As the dehydrofluorinating agent used when the compound (Q ′) is reacted, sodium hydride, cesium carbonate, sodium hydroxide, potassium hydroxide or cesium hydroxide is more preferable.
The amount of the de-HF agent to be used is required to be 1 or more times in terms of the molar ratio with respect to the number of moles of the hydroxyl group of the compound (Q ′) to be used, and preferably 1.1 to 3 times.
The compound (Q ′) is preferably reacted in a polar solvent. Examples of polar solvents include ethereal solvents such as tetrahydrofuran and 1,4-dioxane, aprotic polar solvents such as N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane. The solvent to contain is preferable.
The reaction conditions are preferably 0 to 200 ° C. and 1 to 80 hours. More preferably, it is 2 to 60 hours at 20 to 180 ° C, and most preferably 3 to 48 hours at 30 to 100 ° C.

<Hardened product>
When external energy is applied to the prepolymer of the present invention, the crosslinkable functional group reacts to cause crosslinkage or chain extension between the crosslinkable prepolymer molecules, resulting in a cured product. The shape of the cured product is not particularly limited. For example, it is a film, a film, a molded body, or the like.
In particular, when a liquid coating composition containing the prepolymer of the present invention and a solvent is prepared, the coating composition is coated on a substrate, cured and formed into a film shape, the reaction of the crosslinkable functional group occurs. A uniform cured product (cured film) can be obtained which is easy to proceed uniformly. Therefore, the prepolymer of the present invention is suitable for producing a cured film.
<Coating composition>
The coating composition of the present invention contains the prepolymer of the present invention and a solvent. The coating composition containing the prepolymer of the present invention is obtained by dissolving or dispersing the prepolymer in a solvent. The coating composition of this invention is used suitably for manufacture of a cured film or a cured film. The coating composition of the present invention may contain other components as necessary.
<Photosensitive composition>
The negative photosensitive composition of this invention contains a photosensitive agent among the said coating compositions. That is, the negative photosensitive composition of the present invention contains the prepolymer, a photosensitive agent, and a solvent.

<Photosensitive agent>
The photosensitive agent used in the present invention has an action of causing or causing a reaction in the crosslinkable functional group of the prepolymer by irradiation with actinic radiation. The reaction in the crosslinkable functional group is a cross-linking reaction between prepolymer molecules or a chain extension reaction of prepolymer molecules, and the prepolymer becomes high molecular weight by the reaction.
Examples of the actinic radiation include X-rays, electron beams, ultraviolet rays, and visible rays.

It is preferable to use at least a photoinitiator (photoradical generator) or a photocrosslinking agent as the photosensitizer. You may use both together. Depending on the type of the crosslinkable functional group, an acid generator or a base generator can be used as the photosensitizer.
A photoinitiator is a substance that generates radicals by light irradiation and causes a reaction of a crosslinkable functional group.
Photoinitiators include benzoin alkyl ether derivatives, benzophenone derivatives, α-aminoalkylphenone series, oxime ester derivatives, thioxanthone derivatives, anthraquinone derivatives, acylphosphine oxide derivatives, glyoxyester derivatives, organic peroxides, trihalomethyltriazines Derivatives, titanocene derivatives and the like.
Specifically, IRGACURE 651, IRGACURE 184, DAROCURE 1173, IRGACURE 500, IRGACURE 2959, IRGACURE 754, IRGACURE 907, IRGACURE 369, IRGACURE 1300, IRGACURE 819, IRGACURE 819, IRGACURE 819, IRGACURE 819, IRGACURE 819, IRGACURE 819 IRGACURE 784, IRGACURE OXE01, IRGACURE OXE02, IRGACURE 250 (manufactured by Ciba Specialty Chemicals), KAYACURE DETX-S, KAYACURE CTX, KAYACURE BMS, KAYACURE 2-EAQ (Nippon Kayaku) TAZ-101, TAZ-102, TAZ-103, TAZ-104, TAZ-106, TAZ-107, TAZ-108, TAZ-110, TAZ-113, TAZ-114, TAZ-118, TAZ-122, TAZ- 123, TAZ-140, TAZ-204 (manufactured by Midori Chemical Co., Ltd.) and the like.
These photoinitiators can be used alone or in combination of two or more. In particular, a highly sensitive initiator is preferable in that it can be cured with low irradiation energy. IRGACURE 907 (α-aminoalkylphenone type), IRGACURE 369 (α-aminoalkylphenone type), IRGACURE OXE01 (oxime ester derivative), IRGACURE OXE02 (oxime ester derivative) are preferable as the high-sensitivity initiator, IRGACURE OXE01, IRGACURE OXE02 is particularly preferred.

  Examples of the photoacid generator include diazodisulfone, triphenylsulfonium, iodonium salt, disulfone, and sulfone. Specifically, TPS-105, DPI-102, DPI-105, DPI-106, DPI-109, DPI-201, BI-105, MPI-103, MPI-105, MPI-106, MPI-109, BBI -102, BBI-103, BBI-105, BBI-106, BBI-109, BBI-110, BBI-201, BBI-301, TPS-102, TPS-103, TPS-105, TPS-106, TPS-109 , TPS-1000, MDS-103, MDS-105, MDS-109, MDS-205, BDS-109, DTS-102, DTS-103, DTS-105, NDS-103, NDS-105, NDS-155, NDS159 , NDS-165, DS-100, DS-101, SI-101, SI- 05, SI-106, SI-106, SI-109, PI-105, PI-105, PI-109, NDI-101, NDI-105, NDI-106, NDI-109, PAI-101, PAI-106, PAI-1001, NAI-100, NAI-1002, NAI-1003, NAI-1004, NAI-101, NAI-105, NAI-106, NAI-109, DAM-101, DAM-102, DAM-103, DAM- 105, DAM-201, Benzoin tosylate, MBZ-101, MBZ-201, MBZ-301, PYR-100, DNB-101, NB-101, NB-201, TAZ-100, TAZ-101, TAZ-102, TAZ -103, TAZ-104, TAZ-106, TAZ-1 07, TAZ-108, TAZ-109, TAZ-110, TAZ-113, TAZ-114, TAZ-118, TAZ-122, TAZ-123, TAZ-140, TAZ-201, TAZ-203, TAZ-204, NI-101, NI-1002, NI-1003, NI-1004, NI-101, NI-105, NI-106, NI-109 (manufactured by Midori Chemical), WPAG-145, WPAG-170, WPAG-199, WPAG-281, WPAG-336, WPAG-367 (made by Wako Pure Chemical Industries, Ltd.), etc. are mentioned.

  Examples of the photobase generator include a Co amine complex system, an oxime carboxylic acid ester system, a carbamic acid ester system, and a quaternary ammonium salt system. Specific examples include TPS-OH, NBC-101, ANC-101 (manufactured by Midori Chemical Co., Ltd.) and the like.

  Examples of the photocrosslinking agent include bisazide series. The bisazido photocrosslinking agent decomposes the azide group by irradiation with actinic radiation to generate active nitrene, causing the addition of a crosslinkable functional group to a double bond or an insertion reaction into a C—H bond, thereby causing a crosslinking reaction. Wake up. Bisazide photocrosslinking agents are preferred because of their high sensitivity. Specific examples include 2,6-bis [3- (4-azidophenyl) -2-propenylidene] cyclohexanone and 2,6-bis [3- (4-azidophenyl) -2-propenylidene] -4-methylcyclohexanone. 2,6-bis [3- (4-azidophenyl) -2-propenylidene] -4-ethylcyclohexanone, 2,6-bis [3- (4-azidophenyl) -2-propenylidene] -4-propylcyclohexanone P-azidophenylsulfone, m-azidophenylsulfone, 4,4′-diazidostilbene, 4,4′-diazidobenzalacetophenone, 2,3′-diazido-1,4-naphthoquinone, 4,4 ′ -Diazidodiphenylmethane and the like. Of these, 2,6-bis [3- (4-azidophenyl) -2-propenylidene] -4-methylcyclohexanone is particularly preferred.

At least a part of the photosensitive agent needs to be sensitive to the wavelength of the actinic radiation (exposure wavelength) irradiated in the exposure process described later. As a result, the reaction of the cross-linking line functional group is caused by irradiation with actinic radiation in the exposure step, the prepolymer is increased in molecular weight, and the solubility in the developer is lowered.
For example, when the photoinitiator is not sensitive to the exposure wavelength or has low sensitivity, in addition to the photoinitiator, in addition to the photoinitiator, a photoinitiator aid and / or an increase in sensitivity. It is preferable to use a sensitizer together.

The photoinitiator aid is one that promotes the initiation reaction by using it together with the photoinitiator as compared to when the photoinitiator is used alone. Specific examples include amines, sulfones and phosphines. More specifically, triethanolamine, methyldiethanolamine, triisopropanolamine, Michler's ketone, 4,4′-diethylaminophenone, ethyl 4-dimethylaminobenzoate and the like can be mentioned.
A sensitizer absorbs and excites a radiation spectrum that is not absorbed by the photoinitiator, and transfers the absorption energy to the photoinitiator to cause an initiation reaction from the photoinitiator. Examples of sensitizers include benzophenone derivatives, anthraquinone derivatives, acetophenone derivatives, and the like.

The content of the photosensitive agent in the photosensitive composition of the present invention is not particularly limited as long as it is at least an amount that can reduce the solubility of the prepolymer in the developer by exposure. Desirably, the content of the photosensitizer is 0.1 to 30 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the prepolymer contained in the photosensitive composition.
When the content of the photosensitizer is not less than the lower limit of the above range, the irradiation energy of actinic radiation required in the exposure process does not increase too much, and when it is not more than the upper limit of the above range, the electrical properties and machine of the cured product The adverse effect on the characteristics can be prevented.

<Solvent>
The solvent for the coating composition of the present invention, particularly the photosensitive composition, may be any solvent that can dissolve or disperse the prepolymer, the photosensitive agent, and additives added as necessary. In addition, the coating composition of the present invention is formed by a desired method to form a coating film having a desired film thickness, good film thickness uniformity, and embedded flatness as required. It is preferable to use a solvent suitable for achieving the properties.
Examples of the solvent include aromatic hydrocarbons, dipolar aprotic solvents, ketones, esters, ethers, and halogenated hydrocarbons. The solvent may be the same as or different from the reaction solvent used in the production of the prepolymer described above. When using a different solvent, the prepolymer is once recovered from the reaction solution by a reprecipitation method or the like and dissolved or dispersed in a different solvent, or a known method such as an evaporation method or an ultrafiltration method is used. Thus, solvent replacement can be performed.

Aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene, cumene, mesitylene, tetralin, methylnaphthalene and the like. Examples of the dipole aprotic solvents include N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, γ-butyrolactone, dimethyl sulfoxide and the like.
Examples of ketones include cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methyl amyl ketone, and the like. Examples of ethers include tetrahydrofuran, pyran, dioxane, dimethoxyethane, diethoxyethane, diphenyl ether, anisole, phenetole, diglyme, and triglyme.
Esters include ethyl lactate, methyl benzoate, ethyl benzoate, butyl benzoate, benzyl benzoate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether Propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate and the like.
Examples of halogenated hydrocarbons include carbon tetrachloride, chloroform, methylene chloride, tetrachloroethylene, chlorobenzene, dichlorobenzene and the like.

  The amount of the solvent used is preferably adjusted so that the solid content concentration of the prepolymer in the coating composition of the present invention is 1 to 50% by mass, more preferably 5 to 40% by mass.

<Other ingredients>
It is preferable to add various catalysts or additives to the photosensitive composition of the present invention for the purpose of increasing the reaction rate when curing the prepolymer or reducing reaction defects.
For example, when the prepolymer contains an ethynyl group as a crosslinkable functional group, the catalyst contains amines such as aniline, triethylamine, aminophenyltrialkoxysilane, aminopropyltrialkoxysilane, molybdenum, nickel, etc. Organometallic compounds are preferred.
As the additive, a biscyclopentadienone derivative is preferable. An ethynyl group and a cyclopentadienone group (1-oxocyclopenta-2,5-dien-3-yl group) form an adduct by Diels-Alder reaction with heat, and then decarbonize to form an aromatic ring. Form. Therefore, when a biscyclopentadienone derivative is used, a bridge or chain extension in which an aromatic ring is a binding site is formed.

Specific examples of the biscyclopentadienone derivative include 1,4-bis (1-oxo-2,4,5-triphenyl-cyclopenta-2,5-dien-3-yl) benzene, 4,4′- Bis (1-oxo-2,4,5-triphenyl-cyclopenta-2,5-dien-3-yl) biphenyl, 4,4′-bis (1-oxo-2,4,5-triphenyl-cyclopenta -2,5-dien-3-yl) 1,1'-oxybisbenzene, 4,4'-bis (1-oxo-2,4,5-triphenyl-cyclopenta-2,5-diene-3- Yl) 1,1′-thiobisbenzene, 1,4-bis (1-oxo-2,5-di- [4-fluorophenyl] -4-phenyl-cyclopenta-2,5-dien-3-yl) Benzene, 4,4′-bis (1-oxo-2,4,5-tri Enyl-cyclopenta-2,5-dien-3-yl) 1,1 ′-(1,2-ethanediyl) bisbenzene, 4,4′-bis (1-oxo-2,4,5-triphenyl-cyclopenta -2,5-dien-3-yl) 1,1 '-(1,3-propanediyl) bisbenzene and the like.
Among these biscyclopentadienone derivatives, biscyclopentadienone derivatives having a wholly aromatic skeleton are preferable from the viewpoint of heat resistance. These may be used alone or in combination of two or more.

  In the coating composition of the present invention, in addition to a catalyst and / or an additive, stabilizers such as an ultraviolet absorber, an antioxidant, and a thermal polymerization inhibitor; a leveling agent, an antifoaming agent, a suspending agent, and a dispersing agent At least one additive selected from various additives well known in the coating field such as a surfactant, a crosslinking agent, a plasticizer, and a thickener may be blended. Moreover, when forming the film | membrane or film which has a void | hole, the substance etc. which can be removed after hollow body mentioned later and thin film formation can be mix | blended suitably.

  The prepolymer, the photosensitizer, and the solvent are mainly blended in the photosensitive composition so that the prepolymer is 1 to 60% by mass, preferably 2 to 50% by mass, and the photosensitizer is 0.1 to 20% by mass. The solvent is preferably 20 to 99% by mass, and more preferably 30 to 98% by mass.

<Curing film>
About the manufacturing method of hardened | cured material, a cured film is mentioned as a suitable example of hardened | cured material.
The coating composition of the present invention is applied to a suitable substrate surface to form a wet film, and then the solvent is removed by volatilization or the like, or after the removal, a curing treatment is performed to form a crosslinkable functional group in the prepolymer. A cured film can be formed by causing a crosslinking reaction.
As a method for forming the wet film, it is preferable to employ a coating method or a printing method. Examples of the coating method include known coating methods such as spin coating, dip coating, spray coating, die coating, bar coating, doctor coating, extrusion coating, scan coating, brush coating, and potting. Is mentioned. Examples of the printing method include nanoimprinting, screen printing, gravure printing, and ink jet printing.

  In addition, when the prepolymer contains a low molecular weight substance having a substantial vapor pressure at room temperature, in order to prevent volatilization at the time of baking, before applying the coating composition, the crosslinkable functional group in solution. A part of the group can be allowed to react. The method is preferably heating. As heating conditions, 1 to 50 hours are preferable at 50 ° C to 250 ° C, and more preferably 1 to 20 hours at 70 to 200 ° C. The reaction rate of the crosslinkable functional group in the solution is preferably less than 50 mol%, more preferably less than 30 mol% from the viewpoint of preventing the prepolymer from gelling in the solution.

  The thickness of the wet film formed by the coating composition can be appropriately set according to the shape of the cured film to be produced. For example, for the purpose of producing a film, it is preferable to form a wet film of about 0.01 to 500 μm on the substrate, more preferably 0.1 to 300 μm.

In the curing process, the crosslinkable functional group provides external energy that causes a reaction. Such external energy is selected according to the kind of the crosslinkable functional group present in the prepolymer.
Preferably, a crosslinkable functional group that reacts by heat is used and the curing treatment is performed by baking (heating). The heating condition is preferably about 150 to 450 ° C. for about 1 to 120 minutes, and more preferably about 160 to 350 ° C. for about 2 to 60 minutes. As the heating device, a hot plate, an oven, and a furnace (furnace) are preferable, and examples of the heating atmosphere include an inert gas atmosphere such as nitrogen or argon, air, oxygen, and reduced pressure. An inert gas atmosphere and / or reduced pressure is preferred. In order to secure the surface smoothness of the thin film or improve the fine space embedding property of the thin film, a pre-baking process of about 50 to 250 ° C. is added or the heating process is performed in several stages. Is preferred.
The reaction rate of the crosslinkable functional group in the cured film obtained after the curing treatment is preferably 30 to 100 mol%. By setting the reaction rate to 30 mol% or more, the heat resistance and chemical resistance of the cured film are improved. In this respect, the reaction rate is more preferably 50 mol% or more, and most preferably 70 mol% or more.

  The cured film obtained from the coating composition of the present invention can be peeled off from the base material and used as a single film, or used as a coating such as a water- and oil-repellent film while adhered to the base material. You can also. In the latter case, an adhesion promoter (adhesion improver) can be used to improve the adhesion between the cured film and the substrate.

Examples of the adhesion promoter include silane coupling agents, titanate coupling agents, aluminum coupling agents and the like. Silane coupling agents such as vinyl silanes, acrylic silanes, styryl silanes, epoxy silanes, and amino silanes are more preferable.
Examples of vinyl silanes include vinyl trichlorosilane, vinyl trimethoxy silane, and vinyl triethoxy silane. Examples of styrylsilanes include p-styryltrimethoxysilane and p-styryltriethoxysilane.
Examples of the acrylic silanes include 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropylmethyldiethoxy. Examples include silane.
Epoxysilanes include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane. Is exemplified.
Examples of aminosilanes include aliphatic aminosilanes such as 3-aminopropylmethyldiethoxysilane and 3-aminopropyltriethoxysilane, aminophenyltrimethoxysilane, aminophenyltriethoxysilane, and N-phenyl-3-aminopropyltrimethoxy. Aromatic group aminosilanes such as silane can be mentioned.
As a method for applying the adhesion promoter, a method of treating the substrate with the adhesion promoter before application of the coating composition or a method of adding the adhesion promoter to the coating composition is preferable. As a method for treating the substrate with an adhesion promoter, in the case of aminosilanes, a method of spin-coating the substrate as a 0.01 to 3 mass% alcohol-based solution can be mentioned. As the alcohol, methanol, ethanol, and isopropyl alcohol are preferable. In the method of adding the adhesion promoter to the prepolymer solution, the addition amount of the adhesion promoter is preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass with respect to the prepolymer contained. If the addition amount of the adhesion promoter is small, the effect of improving the adhesiveness is not sufficient, and if it is too much, the heat resistance is lowered.

<Method for producing cured film pattern by photolithography method>
By using the photosensitive composition of the present invention, a cured film pattern in which a negative concavo-convex shape is formed by a photolithographic method can be produced.
That is, an uneven shape in which the exposed portion corresponds to a convex portion through a step of forming a coating film from the photosensitive composition of the present invention on a substrate, a step of exposing the coating layer, and a step of developing after the exposure. Can be produced.

[Coating formation]
First, a photosensitive composition is applied on a substrate to form a wet film. The wet film is dried to form a coating film. As the method for forming this wet film, it is preferable to employ the coating method described above. When the finally obtained cured film is used as an insulating film for an electronic device, the spin coat method or the scan coat method is preferable from the viewpoint of film thickness uniformity.
The thickness of the wet film can be appropriately set according to the shape of the cured film to be obtained. For example, it is preferable to form a wet film having a thickness of about 0.01 to 500 μm on the substrate, and more preferably 0.1 to 300 μm.
The heating condition for drying the wet film is preferably a temperature at which the solvent is volatilized and the prepolymer crosslinkable functional group, the photosensitizer, the photoinitiator, and the sensitizer are not substantially reacted. Specifically, it is preferably about 30 seconds to 10 minutes at 50 to 250 ° C.

[Exposure process]
Next, the coating film formed on the substrate is exposed. In the exposure step, a prepolymer produced by a reaction of a crosslinkable functional group in an exposed portion irradiated with actinic radiation by irradiating actinic radiation (also referred to as exposure light in this specification) onto a desired pattern shape. Cross-linking between molecules and / or chain extension occurs. As a result, there is a difference in solubility in the developer between the exposed portion and the unexposed portion that has not been irradiated with actinic radiation.
As actinic radiation, the photosensitive agent contained in the photosensitive composition has sensitivity. Specific examples include X-rays, electron beams, ultraviolet rays, and visible rays. Among these, ultraviolet rays or visible rays are preferable, and those having a wavelength of 200 to 500 nm are more preferable. The most preferred light source is an ultra high pressure mercury arc.
Depending on the film thickness of the coating film and the type of the photosensitive agent contained in the photosensitive composition, the irradiation dose is such that the difference in solubility in the developer between the exposed part and the unexposed part is within a preferred range. Can be appropriately changed. For example, when the film thickness of the coating film is 10 μm, an appropriate dose is 100 to 2,000 mJ / cm ² .
Specifically, by using an exposure apparatus such as an aligner or a stepper and performing exposure through a mask in a pressure mode, a vacuum contact mode, a proximity mode, etc., a pattern of an exposed portion and an unexposed portion is formed on the coating film.

After the exposure light irradiation, a post-exposure baking process may be performed subsequently. When this post-exposure baking step is performed, the reaction rate of the reactive intermediate having a long lifetime generated photochemically in the coating film by irradiation with exposure light can be increased. That is, in the post-exposure baking process, the movement of the reactive intermediate present in the coating film is promoted, so that the probability of contact between the reactive intermediate and the reactive site is increased, and the reaction rate is improved. The heating temperature in the post-exposure bake varies depending on the type of the reactive intermediate, but is preferably 50 to 250 ° C. The heating time is preferably about 30 seconds to 10 minutes.
The movement of the reactive intermediate can also be promoted by heating during exposure. When heating is performed during exposure, the sensitivity of the photosensitizer and the like is increased by the heating. The heating temperature for baking during exposure varies depending on the type of the reactive intermediate, but is preferably 50 to 250 ° C.

[developing]
Next, the coating film after exposure is developed with a developer. Examples of the developing method include a spray method, a paddle method, an immersion method, and an ultrasonic method.
In the developing solution, the coating film in the exposed area is insoluble or only slightly soluble, and the coating film in the unexposed area uses a soluble solvent. Specific examples of the developer include aromatic hydrocarbons, dipolar aprotic solvents, ketones, esters, ethers, and halogenated hydrocarbons similar to the solvents mentioned as the solvent in the photosensitive composition. Is mentioned.
Conditions such as the concentration of the developer and the development time in the development step are appropriately set to such an extent that a desired uneven shape can be obtained according to the dissolution rate of the coating film in the exposed portion and the unexposed portion with respect to the developer.
By developing, the unexposed portion of the coating film is dissolved to a desired degree, and then rinsed as necessary. The rinsing solution is not particularly limited as long as it is the same as the developing solution, or is not as soluble in the coating film as the developing solution, and is compatible with the developing solution. For example, alcohols, the aforementioned ketones, the aforementioned esters and the like can be mentioned.
Specific examples of alcohols as the rinsing liquid include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, and tert-amyl. Alcohol, cyclohexanol, etc. are mentioned.

  The developed film is rinsed as necessary and then dried. Drying can be performed, for example, by high-speed spin. Furthermore, it is preferable to perform a post-development baking step to remove the solvent. The post-development baking step can be performed on a hot plate or in an oven. The heating conditions are preferably 80 to 200 ° C. and 0.5 to 60 minutes.

[Curing]
In this way, a film (pattern) having a concavo-convex shape formed on the surface is obtained. If this film is cured to a desired degree, it can be used as it is as a cured film pattern.
If the degree of curing is insufficient, the external energy can be further applied to cause the unreacted crosslinkable functional groups present in the film to react with each other, so that the curing can further proceed. By additionally reacting the crosslinkable functional group in this way, the prepolymer further crosslinks or chain extends, so that the heat resistance and solvent resistance of the film are improved.
Examples of the external energy include heat or actinic radiation. When actinic radiation is used, irradiation is performed in a state where a photosensitive agent having sensitivity to the actinic radiation exists in the photosensitive composition. The actinic radiation may have the same wavelength as the exposure light used in the exposure step or may be different. Heat is most preferable as the external energy.
The heating conditions for curing by heating are preferably 200 to 450 ° C. for about 1 to 120 minutes, more preferably 250 to 400 ° C. for about 2 to 60 minutes.
As a heating device, a hot plate, an oven, and a furnace (furnace) are preferable. Examples of the heating atmosphere include an inert gas atmosphere such as nitrogen and argon, air, oxygen, and reduced pressure. An inert gas atmosphere and reduced pressure are particularly preferable.
It is also preferable to carry out the heating process in several stages.
The reaction rate of the crosslinkable functional group in the cured film thus obtained is preferably 30 to 100 mol%. By setting the reaction rate to 30 mol% or more, the heat resistance and chemical resistance of the cured film are improved. In this respect, the reaction rate is more preferably 50 mol% or more, and most preferably 70 mol% or more.

[Descam]
In the cured film pattern thus obtained, an unnecessary film may remain in the unexposed area depending on the exposure and development conditions. In this case, you may perform the descum process which etches an unexposed part as needed. Examples of the etching gas in the descum process include oxygen gas, argon gas, and fluorocarbon-based gas. Etching conditions are preferably conditions that can remove unnecessary films and minimize the influence of the exposed portion on the film. The gas flow rate is preferably 10 to 200 sccm (unit: volume (cm ³ ) flow rate per minute at a specified temperature), processing pressure 1 to 50 Pa, output 10 to 1,000 W, processing time 1 to 600 seconds, and the like.

<Use of cured product>
According to the present invention, a prepolymer having a fluorine-containing polyaryl ether structure in the main chain and having a crosslinkable functional group and a specific side chain represented by R′—O— is obtained. Since the prepolymer has a fluorine-containing polyarylether structure and a crosslinkable functional group, the cured product has a low dielectric constant and high heat resistance. Moreover, since it has the specific side chain represented by said R'-O-, the outstanding elongation characteristic is obtained. That is, a low dielectric constant material having high heat resistance and improved toughness can be obtained. Since the toughness is improved, a cured product having good elongation characteristics and excellent flexibility can be obtained. Thereby, for example, the reliability of electronic components using a low dielectric constant material can be improved, and the yield can be improved.

Further, since the low dielectric constant material according to the present invention can be cured at a low temperature, it can be applied to electronic parts, electrical parts, optical parts and the like that are difficult to cure at a high temperature. Moreover, since low temperature curing can raise and lower the temperature in a short time, the productivity of these parts can be improved.
Furthermore, the obtained cured product simultaneously satisfies a low dielectric constant, a low water absorption rate and a high heat resistance. For this reason, in the element comprised using this hardened | cured material, the improvement of an electrical property is aimed at. Furthermore, since the cured product is hardly affected by moisture and heat, the electrical characteristics are improved and the reliability is improved.
Furthermore, since the photosensitive composition to which a photosensitive agent is added is photosensitive, the resist itself is not required when forming a cured film pattern having a concavo-convex shape by a photolithographic method.

The cured product or cured film produced using the prepolymer of the present invention is suitable for applications requiring low dielectric constant, heat-resistant toughness, water repellency and oil repellency.
In particular, the cured film pattern produced using the photosensitive composition of the present invention has an uneven shape on the surface, and is suitable for applications requiring water repellency and oil repellency. In the cured film pattern having a concavo-convex shape on the surface, in the concavo-convex shape of the surface, the film derived from the photosensitive composition of the present invention may remain in the concave portion, and the base material is exposed in part or all of the bottom surface of the concave portion You may do it. When it is preferable that the bottom surface of the recess also has water repellency and oil repellency, it is preferable that the bottom surface of the recess is covered with a film derived from the photosensitive composition of the present invention.
Specific examples of applications include molds, mold release materials (especially for forming fine patterns such as hot embossing and nanoimprint lithography), and surfaces for MEMS (microelectronic mechanical system) devices such as inkjet printer heads and sensors. Protective film; Copier fixing roll coating; Liquid lens member coating; Oil sealant; Bonding member or sealant coating; Automotive injector coating; Oil repellent waterproof breathable filter; Sealant; Bank material; Additives; Water and oil repellent films for household appliances and cooking utensils; Weather-resistant coatings; Moisture-proof coatings; -Oil repellent film);

Further, the prepolymer of the present invention is a cured product satisfying toughness, heat resistance, water repellency, oil repellency, non-adhesiveness, low friction, friction resistance, low dielectric constant, and low birefringence represented by stretch physical properties. Alternatively, since a cured film can be formed, it is suitable for the above-described applications and can be widely applied to other applications.
Specific examples of uses of the cured product or cured film of the prepolymer of the present invention include various battery membrane materials such as fuel cells; automotive engine pistons, copier fixing unit bearings, air conditioner compressor bearings, automotive engine bearings, cars Coating of compressor swash plate, automotive slide bearing, etc .; heat sink insulation coating for power semiconductor; insulation film for electronic device or multilayer wiring board; electronic component; LCD alignment film; optical waveguide; nonlinear optical material; It is done.

<Article>
The article having the cured film or cured film pattern of the present invention is not particularly limited, but preferred examples include molds, molds (particularly for forming fine patterns such as hot embossing and nanoimprint lithography), and ink jet printer heads. MEMS (microelectronic mechanical system) devices such as printers, photocopier fixing rolls, liquid lens members, oil seal materials, joint members or seal materials, automobile injectors, oil repellent waterproof breathable filters, sealants, bank materials Water and oil repellent materials for household appliances and cooking utensils; weather-resistant coatings; moisture-proof coatings; various protective films (heat and water repellent films, heat and oil repellent films); various films (heat and water repellent films, heat and water repellent films) Oil film); membrane materials for various batteries such as fuel cells; automotive engine pistons; Air bearing compressor bearings; Car engine bearings; Car compressor swash plates; Automotive sliding bearings; Power semiconductor heat sink insulation coatings; Insulating films for electronic devices or multilayer wiring boards; Electronic components; LCDs Alignment film; optical waveguide; nonlinear optical material; and the like.

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. Measurement items were measured by the following methods.
[Molecular weight]
The number average molecular weight in terms of polystyrene was determined from the vacuum-dried prepolymer powder by gel permeation chromatography (GPC method). Tetrahydrofuran was used as the carrier solvent.
[Confirmation of ether bond]
The vacuum-dried prepolymer powder was measured by IR and confirmed by absorption near 1300 cm ⁻¹ .
[Confirmation of crosslinkable functional groups]
The vacuum-dried prepolymer powder was dissolved in heavy acetone, NMR was measured, and the presence of a signal in a predetermined region was confirmed. When the crosslinkable functional group is a vinyl group, a signal appears near δ = 5.0 to 7.0 ppm.
[19F NMR spectrum]
A 19F NMR spectrum (1H 300.4 MHz, 19F 282.7 MHz, internal standard: CCl ₃ F) was measured with an NMR apparatus (manufactured by JEOL, JNM-AL300).

[Measurement of mechanical strength]
The elastic modulus, stress at break and elongation of the cured film were measured according to ASTM-D882 using a tensile tester (manufactured by Toyo Baldwin, Tensilon (registered trademark)). However, the distance between chucks was 10 mm, and the pulling speed was 0.5 mm / min. Moreover, the sample (film) to be used for measurement had a shape according to ASTM-D1822 (a dumbbell shape with a detail width of 3.18 mm and a length of 9.53 mm) and a thickness of 20 μm.

[Heat-resistant]
Thermogravimetric measurement (TG) was performed using a thermogravimetric / differential thermal analyzer (manufactured by Mac Science, TG-DTA2000). A nitrogen atmosphere was used, the temperature rising rate was 10 ° C. per minute, and the measurement was performed in the range from room temperature to 450 ° C. A 1% weight loss temperature was measured as an index of heat resistance.

[Synthesis Example 1] Synthesis of base polymer A To a 2000 mL glass four-necked flask equipped with a Dimroth condenser, thermocouple thermometer, and mechanical stirrer, (Y-2) pentafluorostyrene (36.6 g), (C) 1,1,1-tris (4-hydroxyphenyl) ethane (55.7 g) and dimethylacetamide (hereinafter referred to as DMAc) (830.2 g) were charged. While heating on an oil bath with stirring, when the liquid temperature reached 60 ° C., sodium carbonate (86.8 g) was quickly added as a deHF agent. The mixture was heated at 60 ° C. for 24 hours with continuous stirring. Next, a solution of perfluorobiphenyl (67.5 g) in DMAc (608 g) was added as (B), and the mixture was further heated at 60 ° C. for 17 hours. Thereafter, the reaction solution was cooled to room temperature and gradually added dropwise to about 5400 mL of 0.5N aqueous hydrochloric acid which was vigorously stirred to perform reprecipitation. After filtration and further washing with pure water twice, vacuum drying was performed at 60 ° C. for 12 hours to obtain a white powdery polymer. The obtained polymer was dissolved again in DMAc (558 g), and gradually dropped into 2232 mL of a vigorously stirred 0.5N hydrochloric acid methanol solution to perform reprecipitation. After filtration, and further washed twice with water / methanol = 2/1 (mass ratio), vacuum drying was performed at 70 ° C. for 12 hours to obtain a white powdery polymer (118 g).
The obtained polymer had an ether bond and a vinyl group, and the molecular weight was 5100. Hereinafter, this polymer is referred to as base polymer A.

[Synthesis Example 2] (Synthesis of 2, 3, 4, 5, 6-pentafluorostilbene)
In a nitrogen atmosphere, a 4-mL flask made of 50 ml glass equipped with a Dimroth condenser, thermocouple thermometer, and mechanical stirrer, iodobenzene (63.3 g), palladium acetate (1.4 g), tetrabutylammonium bromide (100.0 g) ), Potassium carbonate (57.9 g), and DMAc (20 ml). After stirring for 60 minutes at room temperature, pentafluorostyrene (74.0 g) was charged, heated on an oil bath, and heated at 100 ° C. for 3 hours. Thereafter, the reaction solution was cooled to room temperature and diluted with methylene chloride (200 ml). After filtration through celite, the organic layer was washed sequentially with ion-exchanged water and 0.5N hydrochloric acid. The solvent was distilled off under reduced pressure, and a dark brown solid was recovered. The target product was extracted from this solid with hexane and purified by silica gel column chromatography to obtain the title compound (10.1 g, purity 99.1% by mass).

[Synthesis Example 3] Synthesis of Base Polymer B Synthesized in Synthesis Example 5 as (Y-2) into a 100 mL glass four-necked flask equipped with a Dimroth condenser, thermocouple thermometer, and mechanical stirrer 2, 3, 4 5,1,6-Pentafluorostilbene (1.0 g) and (C) were charged with 1,1,1-tris (4-hydroxyphenyl) ethane (1.1 g) and DMAc (19.4 g). The mixture was heated on an oil bath with stirring, and when the liquid temperature reached 60 ° C., sodium carbonate (1.7 g) was quickly added as a deHF agent. The mixture was heated at 60 ° C. for 16 hours with continuous stirring. Next, a solution of perfluorobiphenyl (1.4 g) in DMAc (12.2 g) was added as (B), and the mixture was further heated at 60 ° C. for 26 hours. Thereafter, the reaction solution was cooled to room temperature, and gradually added dropwise to about 200 mL of 0.5N aqueous hydrochloric acid which was vigorously stirred to perform reprecipitation. After filtration, and further washed twice with pure water, vacuum drying was performed at 60 ° C. for 12 hours to obtain a white powdery polymer (2.4 g).
The obtained polymer had an olefin part which is an ether bond and a crosslinkable functional group, and the molecular weight was 5,000. Hereinafter, this polymer is referred to as base polymer B.

[Synthesis Example 4]
A 5-L glass four-necked flask equipped with a Dimroth condenser, thermocouple thermometer, and mechanical stirrer, (B) as perfluorobiphenyl (225 g), (C) as 1,3,5-trihydroxybenzene (40 g), DMAc (2388 g) was charged. The mixture was heated on an oil bath with stirring, and when the liquid temperature reached 60 ° C., sodium carbonate (153 g) was quickly added as a deHF agent. The mixture was heated at 60 ° C. for 37 hours while stirring was continued. Thereafter, the reaction solution was cooled to room temperature and gradually added dropwise to about 14 L of vigorously stirred 0.5N hydrochloric acid water for reprecipitation. After filtration, and further washed twice with pure water, vacuum drying was performed at 70 ° C. for 12 hours to obtain a white powdery polymer (242 g). The molecular weight was 7,824. Hereinafter, this polymer is referred to as precursor polymer C ′.

Synthesis Example 5 Synthesis of Base Polymer C Precursor polymer C ′ (3.1 g) obtained in Synthesis Example 4 was added to a 100 mL glass four-necked flask equipped with a Dimroth condenser, thermocouple thermometer, and mechanical stirrer. 2-allylphenol (0.6 g) and DMAc (33.0 g) were charged as Y-1). Stir at room temperature and quickly add sodium carbonate (0.7 g). Stir at room temperature for 65 hours. Thereafter, the mixture was gradually added dropwise to about 300 mL of vigorously stirred 0.2N hydrochloric acid to perform reprecipitation. After filtration, and further washed twice with pure water, vacuum drying was performed at 60 ° C. for 12 hours to obtain a white powdery polymer (3.5 g).
The obtained polymer had an ether bond and an allyl group, and the molecular weight was 11,500. Hereinafter, this polymer is referred to as base polymer C.

[Synthesis Example 6] Synthesis of Base Polymer D The precursor polymer C ′ (3.1 g) obtained in Synthesis Example 4 was added to a 100 mL glass four-necked flask equipped with a Dimroth condenser, thermocouple thermometer, and mechanical stirrer. 4-hydroxychalcone (1.0 g) and DMAc (33.0 g) were charged as Y-1). The mixture was stirred at room temperature, and sodium carbonate (0.7 g) was quickly added as a deHF agent. Stir at room temperature for 65 hours. Thereafter, the mixture was gradually added dropwise to about 300 mL of vigorously stirred 0.2N hydrochloric acid to perform reprecipitation. After filtration, and further washed twice with pure water, vacuum drying was performed at 60 ° C. for 12 hours to obtain a white powdery polymer (3.9 g).
The obtained polymer had an ether bond and a cinnamyl group, and the molecular weight was 8,700. Hereinafter, this polymer is referred to as a base polymer D.

[Synthesis Example 7] Introduction of side chain represented by R—CH ₂ — The inside of a 500 ml four-necked flask equipped with a stirring bar and a Dimroth reflux tube was replaced with nitrogen, and 14.98 g of base polymer A (Q ), 3.01 g of polyethylene glycol monomethyl ether (Mn2000) and 180 ml of tetrahydrofuran were sequentially added. After stirring the flask to make a homogeneous solution, 0.10 g of sodium hydride (purity 55% by mass) was added, and the temperature was raised to 50 ° C. The progress of the reaction was followed by 19F NMR, and the flask was cooled to room temperature after 24 hours. After filtering the reaction crude liquid, 160 g of the filtrate was slowly added dropwise to 800 ml of vigorously stirred methanol. The obtained solid was washed with 500 ml of methanol and then dried under reduced pressure at 70 ° C. for 12 hours to obtain 12 g of a light yellow prepolymer.
The molecular weight of this prepolymer was 13000, and it was confirmed by NMR analysis that 17 parts by mass of polyethylene glycol was introduced with respect to 100 parts by mass of the base polymer A by CH ₂ CH ₂ O.

[Synthesis Example 8] Introduction of a side chain represented by R—CH ₂ — The inside of a 100 ml four-necked flask equipped with a stirrer and a Dimroth reflux tube was replaced with nitrogen, and 4.98 g of the base polymer A (Q ) 0.98 g of polyisoprene (Mn 2500) containing both terminal hydroxyl groups and 60 ml of tetrahydrofuran were added in this order. The flask was stirred to obtain a homogeneous solution, 0.077 g of potassium hydroxide (purity 86% by mass) was added, and then the flask was heated until tetrahydrofuran was refluxed. The progress of the reaction was followed by 19F NMR, and the flask was cooled to room temperature after 18 hours. After filtering the reaction crude liquid, 45 g of the filtrate was slowly added dropwise to 230 ml of 0.5 N hydrogen chloride methanol solution with vigorous stirring. The obtained solid was washed with 300 ml of methanol and then dried under reduced pressure at 70 ° C. for 12 hours to obtain 4.2 g of a light yellow prepolymer.
The molecular weight of this prepolymer was 13000, and it was confirmed by NMR analysis that 13 parts by mass of polyisoprene was introduced with respect to 100 parts by mass of the base polymer A by repeating the isoprene skeleton. The 1% weight loss temperature was 421 ° C.

[Synthesis Example 9] Introduction of a side chain represented by R-Ph- The inside of a 50 ml three-necked flask equipped with a stirrer and a Dimroth reflux tube was replaced with nitrogen, and both terminal phenolic silicones (Q ') ( Mn3500) 0.50 g, tetrahydrofuran 30 ml, and sodium hydride (purity 55% by mass) 0.025 g were sequentially added. Further, 2.49 g of base polymer C was added to the flask, and the mixture was stirred at room temperature. The progress of the reaction was followed by 19F NMR, and after 69 hours, the reaction crude liquid was filtered. 36 g of the filtrate was slowly added dropwise to 180 ml of vigorously stirred methanol. The obtained solid was washed with 180 ml of methanol and then dried under reduced pressure at 70 ° C. for 12 hours to obtain 2.3 g of a white prepolymer.
The molecular weight of this prepolymer was 10,000, and it was confirmed by NMR analysis that the silicone had a repeating structure of a silicone skeleton and that 6 parts by mass of silicone was introduced with respect to 100 parts by mass of the base polymer C. The terminal of the silicone skeleton was -Ph-OH. The 1% weight loss temperature was 308 ° C.
In addition, the both terminal phenol type silicone used in this example is a compound having a repeating unit consisting of — [Si (CH ₃ ) ₂ O] — and having —CH ₂ CH ₂ PhOH at both ends.

[Synthesis Example 10] R-CH 2 _- Introduction of the side chain stirrer represented by the three-necked flask of 50ml with a Dimroth reflux condenser was purged with nitrogen, both end carbinol type silicone as (Q) (Mn5000) 0.25g, tetrahydrofuran 30ml, sodium hydride (purity 55 mass%) 0.050g was added in order. Further, 2.5 g of the base polymer C was added to the flask, and stirred at room temperature. The progress of the reaction was followed by 19F NMR, and the reaction crude liquid was filtered after 66 hours. 26 g of the filtrate was slowly added dropwise to 180 ml of vigorously stirred methanol. The obtained solid was washed with 180 ml of methanol and then dried under reduced pressure at 70 ° C. for 12 hours to obtain 1.9 g of a white prepolymer.
The molecular weight of this prepolymer was 10,000, and it was confirmed by NMR analysis that the silicone had a repeating structure of a silicone skeleton and 10 parts by mass of silicone was introduced with respect to 100 parts by mass of the base polymer C. The terminal of the silicone skeleton was —Si—C ₃ H ₆ —OH.
In addition, the both-end carbinol type silicone used in this example is a compound having a repeating unit consisting of — [Si (CH ₃ ) ₂ O] — and having —CH ₂ CH ₂ CH ₂ OH at both ends. .

[Synthesis Example 11] Introduction of a side chain represented by R—CH ₂ — A 100 mL glass four-necked flask equipped with a Dimroth condenser, a thermocouple thermometer, and a mechanical stirrer was charged with NaH (0.09 g) at a concentration of 55% by mass. ), Tetrahydrofuran (hereinafter referred to as THF) (60 ml). Next, polytetramethylene glycol (molecular weight 2,000) (1.0 g) was quickly charged as (Q) and stirred at room temperature for 30 minutes. Further, base polymer A (5.0 g) was quickly added and stirred at room temperature for 16 hours. Thereafter, the solution was gradually added dropwise to about 500 mL of a vigorously stirred 0.5N hydrochloric acid methanol solution to perform reprecipitation. After filtration, it was further washed once with methanol and then twice with pure water. Vacuum drying was performed at 60 ° C. for 12 hours to obtain a white powdery prepolymer (5.1 g).
The obtained prepolymer had an ether bond and a repeating structure of a tetramethyleneoxy group, and the molecular weight was 9,400. It was confirmed that 9.6 parts by weight of polytetramethylene glycol was introduced with respect to 100 parts by weight of the base polymer A. The 1% weight loss temperature was 256 ° C.

[Synthesis Example 12] Introduction of a side chain represented by R—CH ₂ — In Synthesis Example 11, NaH was changed to 0.17 g, and polytetramethylene glycol as (Q) was changed to a molecular weight of 1,000. The same operation as described above was performed to obtain 5.1 g of a prepolymer. The molecular weight of the obtained prepolymer was 10100, and the amount of polytetramethylene glycol introduced was 10.3 parts by mass with respect to 100 parts by mass of the base polymer A.

[Synthesis Example 13] R-CH ₂ - in the introduction Synthesis Example 11 of the side chain represented by, the same except that the 0.5g a molecular weight polytetramethylene glycol 1,000 as (Q) Operation was performed to obtain 5.1 g of a prepolymer.
The molecular weight of the obtained prepolymer was 11100, and the amount of polytetramethylene glycol introduced was 9.3 parts by mass with respect to 100 parts by mass of the base polymer A.

[Synthesis Example 14] R-CH ₂ - in the introduction Synthesis Example 11 of the side chain represented by the change of NaH to 0.05 g, similar except for using 0.5g of polytetramethylene glycol as (Q) As a result, 4.5 g of a prepolymer was obtained.
The molecular weight of the obtained prepolymer was 7900, and the amount of polytetramethylene glycol introduced was 2.5 parts by mass with respect to 100 parts by mass of the base polymer A.

[Synthesis Example 15] Synthesis of Prepolymer Into a 200 mL glass four-necked flask equipped with a Dimroth condenser, thermocouple thermometer, and mechanical stirrer, (Y-2) as pentafluorostyrene (2.93 g) and (C) 1,1,1-tris (4-hydroxyphenyl) ethane (4.46 g) and dimethylacetamide (hereinafter referred to as DMAc) (41.8 g) were charged. While heating on an oil bath with stirring, when the liquid temperature reached 60 ° C., sodium carbonate (6.94 g) was quickly added as a deHF agent. The mixture was heated at 60 ° C. for 20 hours with continuous stirring. Next, a solution prepared by dissolving 0.60 g of both-end phenolic silicone (Mn2060) in DMAc (30.60 g) as (B) and perfluorobiphenyl (5.40 g) as (Q ′) was added at 28 ° C. Heated for hours. Thereafter, the reaction solution was cooled to room temperature and gradually added dropwise to about 400 mL of vigorously stirred 0.5N aqueous hydrochloric acid for reprecipitation. After filtration, and further washed twice with pure water, vacuum drying was performed at 70 ° C. for 12 hours to obtain a white powdered prepolymer (11.0 g).

[Synthesis Example 16] Synthesis of prepolymer Into a 200 mL glass four-necked flask equipped with a Dimroth condenser, a thermocouple thermometer, and a mechanical stirrer, 1,1,1-tris (4-hydroxyphenyl) ethane (C) 4.46 g), (Q ′) as both-end phenol type silicone (Mn2060) 0.60 g, (B) as perfluorobiphenyl (5.40 g), and dimethylacetamide (hereinafter referred to as DMAc) (59.27 g) . While stirring on an oil bath, when the liquid temperature reaches 60 ° C., sodium carbonate (6.94 g) is quickly added as a deHF agent. Heat at 60 ° C. for 20 hours with continued stirring. Next, a solution prepared by dissolving 4-acetoxystyrene (2.45 g) in DMAc (13.86 g) as (Y-2) is added and further heated at 60 ° C. for 28 hours. Thereafter, the reaction solution is cooled to room temperature, and gradually added dropwise to about 400 mL of vigorously stirred 0.5N hydrochloric acid to perform reprecipitation. After filtration and further washing with pure water twice, a prepolymer is obtained by vacuum drying at 70 ° C. for 12 hours.

(Example 1)
The prepolymer obtained in Synthesis Example 7 is dissolved in cyclohexanone to give a 35% by mass solution, and 1 part by mass of Parkmill D (Nippon Oil) as a polymerization initiator is added to 100 parts by mass of the prepolymer and dissolved. And then filtered through a polytetrafluoroethylene (PTFE) filter having a pore diameter of 0.5 μm to obtain a coating composition. The obtained coating composition was spin-coated at 1000 rpm for 30 seconds on the copper layer of the silicon wafer (base material) on which the copper layer was laminated. Subsequently, curing was performed in an inert oven (DN43HI, manufactured by Yamato Scientific Co., Ltd.) at 160 ° C. for 1 hour in a nitrogen atmosphere. Thereafter, the substrate was immersed in a 0.5N ammonium persulfate aqueous solution and heated to 50 ° C. to dissolve the copper layer, and further washed with water and dried to obtain a self-supporting film of a cured film. When the mechanical strength of the obtained film was measured, the elastic modulus was 1.0 GPa, the stress at break was 53 MPa, and the elongation was 14%.

(Example 2)
The prepolymer obtained in Synthesis Example 8 was dissolved in cyclohexanone to give a 40% by mass solution. To this, 10 parts by weight of Park Mill D (Nippon Oil) was added to 100 parts by mass of the prepolymer, and the pore diameter was dissolved. The composition for application | coating was obtained by filtering with a 0.5 micrometer polytetrafluoroethylene (PTFE) filter.
Using the obtained coating composition, a self-supporting film of a cured film was obtained in the same manner as in Example 1. When the mechanical strength of the obtained film was measured, the elastic modulus was 1.0 GPa, the stress at break was 63 MPa, and the elongation was 13%.

(Example 3)
The prepolymer obtained in Synthesis Example 9 was dissolved in mesitylene to obtain a 40% by mass solution. To this, 10 parts by weight of Park Mill D (Japanese oil) was added to 100 parts by mass of the prepolymer, and the pore diameter was dissolved. The composition for application | coating was obtained by filtering with a 0.5 micrometer polytetrafluoroethylene (PTFE) filter.
Using the obtained coating composition, a self-supporting film of a cured film was obtained in the same manner as in Example 1. When the mechanical strength of the obtained film was measured, the elastic modulus was 1.3 GPa, the stress at break was 64 MPa, and the elongation was 7%.

Example 4
When the film mechanical strength was measured in the same manner as in Example 2 using the prepolymer obtained in Synthesis Example 11, the modulus of elasticity was 1.5 GPa, the stress at break was 65 MPa, and the elongation was 10%.

(Comparative Example 1)
In Example 1, the film mechanical strength was measured in the same manner as in Example 1 except that the base polymer A before introduction of the side chain was used instead of the prepolymer. The elastic modulus was 1.5 GPa, the stress at break was 64 MPa, The elongation was 5% and the elongation was inferior.

(Example 5) Formation of cured film pattern The prepolymer obtained in Synthesis Example 7 was placed in a sample bottle and dissolved in cyclohexanone to obtain a 40 mass% solution. 3 parts by mass of IRGACURE OXE01 as a photoinitiator was added to 100 parts by mass of the prepolymer, dissolved, and then filtered through a polytetrafluoroethylene (PTFE) filter having a pore diameter of 5 μm to obtain a negative photosensitive composition. The obtained negative photosensitive composition was spin-coated on a Si wafer at 1,000 rpm for 30 seconds and heated on a hot plate at 100 ° C. for 90 seconds to form a coating film. Next, the coating film was exposed with an exposure energy of 1,530 mJ / cm ² in a state where a light shielding portion was formed using a mask. The exposure was performed by using UL-7000 (manufactured by Quintel) and irradiating light of an ultra high pressure mercury lamp.
After exposure, it was baked at 100 ° C. for 1 minute, developed by being immersed in propylene glycol monomethyl acetate as a developer for 100 seconds, and rinsed with 2-propanol for 30 seconds. Nitrogen was blown, and heating was performed on a hot plate at 100 ° C. for 90 seconds and then at 200 ° C. for 90 seconds. The film thickness of the exposed portion was 14.23 μm, which was equivalent to the reference film thickness that was not developed. The film thickness of the unexposed part was 0.1 μm or less.

(Example 6) Formation of cured film pattern Except for using the prepolymer obtained in Synthesis Example 11 in Example 5, the process was performed up to the exposure step. After exposure, it was baked at 140 ° C. for 1 minute, developed by immersing in propylene glycol monomethyl acetate for 90 seconds, and rinsed with 2-propanol for 30 seconds. Nitrogen was blown, and heating was performed on a hot plate at 100 ° C. for 90 seconds and then at 200 ° C. for 90 seconds. The film thickness of the exposed portion was 6.58 μm, which was 90% of the reference film thickness that was not developed. The film thickness of the unexposed part was 0.1 μm or less.

Claims (24)

  A polymer having a fluorine-containing polyaryl ether structure in the main chain, having a crosslinkable functional group, and R′—O— (where R ′ does not have a fluorine atom and has 11 or more carbon atoms) A crosslinkable prepolymer characterized by having a side chain represented by: The side chain is represented by the following general formula (I)

[Wherein, R represents an organic group having 10 or more carbon atoms which does not have a fluorine atom. ]
The crosslinkable prepolymer according to claim 1, represented by:   The main chain has a halogen-substituted aromatic ring in which some or all of the hydrogen atoms bonded to the aromatic ring are substituted with halogen atoms, and the side chain is bonded to the halogen-substituted aromatic ring The crosslinkable prepolymer according to claim 1 or 2. A compound (Y-1) having a crosslinkable functional group and a phenolic hydroxyl group; and a compound (Y-2) having a crosslinkable functional group and an “aromatic ring substituted with a fluorine atom capable of reacting with a phenolic hydroxyl group” One or both of;
The following general formula (1)

[Wherein, n represents an integer of 0 to 2; a and b each independently represents an integer of 0 to 3; Rf ¹ and Rf ² each independently represents a fluorine-containing alkyl group having 8 or less carbon atoms; When a plurality of Rf ¹ or Rf ² are present, they may be the same or different from each other; F in the aromatic ring indicates that all the hydrogen atoms bonded to the aromatic ring are substituted with fluorine atoms. To express. ]
A fluorine-containing aromatic compound (B) represented by:
A precursor (P21) obtained by subjecting a compound (C) having no crosslinkable functional group and three or more phenolic hydroxyl groups to a condensation reaction in the presence of a dehydrofluorinating agent is combined with the side chain. The crosslinkable prepolymer according to claim 3, which is introduced. The following general formula (1)

[Wherein, n represents an integer of 0 to 2; a and b each independently represents an integer of 0 to 3; Rf ¹ and Rf ² each independently represents a fluorine-containing alkyl group having 8 or less carbon atoms; When a plurality of Rf ¹ or Rf ² are present, they may be the same or different from each other; F in the aromatic ring indicates that all the hydrogen atoms bonded to the aromatic ring are substituted with fluorine atoms. To express. ]
A fluorine-containing aromatic compound (B) represented by:
A precursor (P11) obtained by subjecting a compound (C) having no crosslinkable functional group and three or more phenolic hydroxyl groups to a condensation reaction in the presence of a dehydrofluorinating agent,
The crosslinkable prepolymer according to claim 3, wherein the side chain and a crosslinkable functional group are introduced.   Compound having crosslinkable functional group and crosslinkable functional group and phenolic hydroxyl group (Y-1); Compound having crosslinkable functional group and “aromatic ring substituted with fluorine atom capable of reacting with phenolic hydroxyl group” The crosslinkable prepolymer according to claim 5, which is a crosslinkable functional group derived from any one or both of (Y-2) and;   A polymer having a fluorine-containing polyaryl ether structure in the main chain, having a crosslinkable functional group, and having a “aromatic ring substituted with a halogen atom capable of reacting with a phenolic hydroxyl group” in the main chain (P2) and the compound (Q ′) represented by R′OH (wherein R ′ represents an organic group having 11 or more carbon atoms not having a fluorine atom), the presence of a dehydrofluorinating agent The manufacturing method of the crosslinkable prepolymer characterized by making it react below. The compound (Q ′) is represented by the following general formula (II)

[Wherein, R represents an organic group having 10 or more carbon atoms which does not have a fluorine atom. ]
The manufacturing method of the crosslinkable prepolymer of Claim 7 which is alcohol (Q) represented by these. The precursor (P2) has a crosslinkable functional group and a phenolic hydroxyl group-containing compound (Y-1); a crosslinkable functional group and “an aromatic ring substituted with a fluorine atom capable of reacting with a phenolic hydroxyl group” Any one or both of compound (Y-2);
The following general formula (1)

[Wherein, n represents an integer of 0 to 2; a and b each independently represents an integer of 0 to 3; Rf ¹ and Rf ² each independently represents a fluorine-containing alkyl group having 8 or less carbon atoms; When a plurality of Rf ¹ or Rf ² are present, they may be the same or different from each other; F in the aromatic ring indicates that all the hydrogen atoms bonded to the aromatic ring are substituted with fluorine atoms. To express. ]
A fluorine-containing aromatic compound (B) represented by:
A precursor (P21) obtained by subjecting a compound (C) having no crosslinkable functional group and three or more phenolic hydroxyl groups to a condensation reaction in the presence of a dehydrofluorinating agent is used. Or a method for producing a crosslinkable prepolymer according to 8. A precursor (P1) having a fluorine-containing polyarylether structure in the main chain and having “an aromatic ring substituted with a halogen atom capable of reacting with a phenolic hydroxyl group” in the main chain; and R′OH (Wherein R ′ represents an organic group having 11 or more carbon atoms having no fluorine atom), and the compound (Q ′) is reacted in the presence of a dehydrofluorinating agent,
A method for producing a crosslinkable prepolymer, further comprising introducing a crosslinkable functional group. The compound (Q ′) is represented by the following general formula (II)

[Wherein, R represents an organic group having 10 or more carbon atoms which does not have a fluorine atom. ]
The manufacturing method of the crosslinkable prepolymer of Claim 10 which is alcohol (Q) represented by these. As the precursor (P1), the following general formula (1)

[Wherein, n represents an integer of 0 to 2; a and b each independently represents an integer of 0 to 3; Rf ¹ and Rf ² each independently represents a fluorine-containing alkyl group having 8 or less carbon atoms; When a plurality of Rf ¹ or Rf ² are present, they may be the same or different from each other; F in the aromatic ring indicates that all the hydrogen atoms bonded to the aromatic ring are substituted with fluorine atoms. To express. ]
A fluorine-containing aromatic compound (B) represented by:
The precursor (P11) obtained by subjecting the compound (C) having no crosslinkable functional group and three or more phenolic hydroxyl groups to a condensation reaction in the presence of a dehydrofluorinating agent is used. Or a method for producing a crosslinkable prepolymer according to 11.   Compound (Y-1) having a crosslinkable functional group and a phenolic hydroxyl group is introduced as a method for introducing a crosslinkable functional group; a crosslinkable functional group and “an aromatic ring substituted with a fluorine atom capable of reacting with a phenolic hydroxyl group” The crosslinkable prepolymer according to any one of claims 10 to 12, which is a method of subjecting one or both of the compound (Y-2) having a benzene compound to a condensation reaction in the presence of a dehydrofluorinating agent. Manufacturing method. The following general formula (1)

[Wherein, n represents an integer of 0 to 2; a and b each independently represents an integer of 0 to 3; Rf ¹ and Rf ² each independently represents a fluorine-containing alkyl group having 8 or less carbon atoms; When a plurality of Rf ¹ or Rf ² are present, they may be the same or different from each other; F in the aromatic ring indicates that all the hydrogen atoms bonded to the aromatic ring are substituted with fluorine atoms. To express. ]
A fluorine-containing aromatic compound (B) represented by:
A step (S1) of allowing a compound (C) having no crosslinkable functional group and having 3 or more phenolic hydroxyl groups to undergo a condensation reaction in the presence of a dehydrofluorinating agent;
A compound (Y-1) having a crosslinkable functional group and a phenolic hydroxyl group; and a compound (Y-2) having a crosslinkable functional group and an “aromatic ring substituted with a fluorine atom capable of reacting with a phenolic hydroxyl group” Any one or both of which is subjected to a condensation reaction in the presence of a dehydrofluorinating agent to introduce a crosslinkable functional group (S2);
A compound (Q ′) represented by R′OH (where R ′ represents an organic group having 11 or more carbon atoms having no fluorine atom) is reacted in the presence of a dehydrofluorinating agent, Introducing a chain (S3);
A process for producing a crosslinkable prepolymer, comprising: The compound (Q ′) is represented by the following general formula (II)

[Wherein, R represents an organic group having 10 or more carbon atoms which does not have a fluorine atom. ]
The manufacturing method of the crosslinkable prepolymer of Claim 14 which is alcohol (Q) represented by these.   Hardened | cured material formed by hardening the crosslinkable prepolymer as described in any one of Claims 1-6.   The coating composition containing the crosslinkable prepolymer as described in any one of Claims 1-6, and a solvent.   A coating composition according to claim 17 is applied to a substrate to form a wet film, the solvent in the wet film is removed, and the crosslinking in the wet film is performed after the removal of the solvent or simultaneously with the removal of the solvent. Cured film obtained by curing an adhesive prepolymer.   An article having the cured film according to claim 18.   The negative photosensitive composition containing the crosslinkable prepolymer as described in any one of Claims 1-6, a photosensitive agent, and a solvent.   The negative photosensitive composition of Claim 20 in which the said photosensitive agent contains a photoinitiator or a photocrosslinking agent.   A step of forming a coating film from the negative photosensitive composition according to claim 20 or 21 on a substrate, and selectively exposing a part of the coating film, wherein the crosslinkable functional group A method of forming a cured film pattern, comprising: an exposure step that causes a reaction; and a step of developing after the exposure step.   A cured film pattern obtained by the forming method according to claim 22.   An article having the cured film pattern according to claim 23.