JP2008152239A - Negative photosensitive composition, cured film using same, and method for producing cured film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a negative photosensitive composition which enables easy formation of a water- and oil-repellent article having recessed and projected shape on the surface without using any photoresist. <P>SOLUTION: The negative photosensitive composition includes a crosslinkable prepolymer having a polyaryl ether structure in the backbone and also having a crosslinkable functional group and a side chain represented by general formula (I), a photosensitizing agent and a solvent, wherein R<SP>f</SP>represents a 3-50C fluorinated alkyl group (which may contain an oxygen atom forming an ether bond). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a negative photosensitive composition, a method for producing a cured film using the composition, a cured film obtained by the method, and an article having the cured film.

Materials having water repellency and oil repellency are widely used for applications such as nanoimprint, bank material, gas barrier film, and photoresist (see, for example, Patent Document 1 below). In general, examples of the patterning method (pattern (uneven shape) forming method) include dry etching, wet etching, screen printing, ink jet printing, and photolithography using the photosensitivity of the material itself.
If the material itself is photosensitive, the photoresist required for patterning the non-photosensitive material is no longer required, reducing the number of manufacturing steps and improving the yield. Can be expected. In addition, it has attracted attention because it is a process with a low environmental load, such as reducing the amount of solvent used.

Regarding a polymer having a polyaryl ether structure in the main chain, for example, in Patent Document 2 below, a compound having a phenolic hydroxyl group or a fluorine-substituted aromatic ring and a crosslinkable functional group, a fluorine-substituted aromatic compound, and a phenolic hydroxyl group are described. A method for producing a crosslinkable prepolymer having a polyaryl ether structure in the main chain and having a crosslinkable functional group introduced therein by condensing three or more compounds has been proposed.
JP 2005-60515 A JP 2005-105115 A

  The present invention has been made in view of the above circumstances, and has a novel structure that has an uneven shape on the surface, has excellent heat resistance, and can easily form an article having water repellency and oil repellency without using a photoresist. It is an object to provide a negative photosensitive composition, a method for producing a cured film using the composition, a cured film obtained by the method, and an article having the cured film.

In order to solve the above problems, the present invention is a negative photosensitive composition containing a crosslinkable prepolymer, a photosensitizer, and a solvent,
The negative photosensitivity, wherein the crosslinkable prepolymer has a polyaryl ether structure in the main chain, a crosslinkable functional group, and a side chain represented by the following general formula (I) A sex composition is provided.

［式中、Ｒ^ｆは炭素数３〜５０の含フッ素アルキル基（ただし、エーテル結合性の酸素原子を含んでいてもよい）を表す。］

[Wherein, R ^f represents a fluorine-containing alkyl group having 3 to 50 carbon atoms (however, it may contain an etheric oxygen atom). ]

  The present invention also includes a step of forming a coating film comprising the negative photosensitive composition of the present invention on a substrate, and selectively exposing a part of the coating film, wherein the crosslinkable functional group is exposed at the exposed portion. There is provided a method for producing a cured film, characterized by comprising an exposure step that causes the above reaction and a step of developing after the exposure step.

Moreover, this invention provides the cured film obtained by the manufacturing method of this invention.
The present invention also provides an article having the cured film of the present invention.

Since the negative photosensitive composition of the present invention itself has photosensitivity, it can form a cured film in which a negative concavo-convex shape is formed using a photolithographic method. Further, since it contains the specific crosslinkable prepolymer, a cured film having water repellency and oil repellency can be obtained.
According to the method for producing a cured film of the present invention, a cured film having an uneven shape in which an exposed portion exposed in the exposure step corresponds to a convex portion and an unexposed portion that has not been exposed corresponds to a concave portion is obtained. The cured film thus obtained has an uneven shape and water and oil repellency.
According to the present invention, an article provided with a concavo-convex shape and a cured film having water repellency and oil repellency can be used without using a photoresist and without performing a separate step of imparting water repellency and oil repellency. Can be easily formed.
The obtained cured film simultaneously satisfies a low dielectric constant, a low water absorption rate and a high heat resistance. For this reason, for example, when used for storage elements such as various memories, theoretical circuit elements such as microprocessors, etc., the electrical characteristics of the elements can be improved. In addition, since it is less susceptible to moisture and heat, it can improve reliability as well as electrical characteristics.
Moreover, the obtained cured film is excellent in alkali resistance. That is, even when exposed to an alkaline atmosphere, excellent water repellency and oil repellency are maintained.

  The negative photosensitive composition of the present invention (hereinafter sometimes simply referred to as photosensitive composition) contains a crosslinkable 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 a crosslinkable functional group of a crosslinkable prepolymer (hereinafter sometimes simply referred to as 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 crosslinking group, an acid generator (photoacid generator) or a base generator (photobase generator) can also 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 OX01, IRGACURE OXE02, IRGACURE 250 (Ciba Specialty Chemicals), KAYACURE DETX-S, KAYACURE CTX, KAYACURE BMS, KAYACURE 2-EAQ (Nippon Kayaku) Z-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 (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 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.

  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 (all product names, manufactured by Midori Chemical Co., Ltd.), WPAG-145, WPAG-170 , WPAG-199, WPAG-281, WPAG-336, WPAG-367 (all are product names, manufactured by Wako Pure Chemical Industries, Ltd.).

  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 (all are product names, manufactured by Midori Chemical Co., Ltd.).

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 used in combination with a photoinitiator to promote the initiation reaction more than when the photoinitiator is used alone. Specific examples include amines, sulfones and phosphines. More specifically, triethanolamine, methyldiethanolamine, triisopropanolamine, Michler ketone, 4,4′-diethylaminophenone, ethyl 4-dimethylaminobenzoate and the like can be mentioned.
A sensitizer absorbs a radiation spectrum that is not absorbed by a photoinitiator and excites it, and energy transfer of the absorption energy to the photoinitiator causes 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.

<Crosslinkable prepolymer>
The prepolymer used in the present invention is a polymer having a polyaryl ether structure in the main chain, has a crosslinkable functional group, and has a side chain represented by the following general formula (I).

［式中、Ｒ^ｆは炭素数３〜５０の含フッ素アルキル基（ただし、エーテル結合性の酸素原子を含んでいてもよい）を表す。］

[Wherein, R ^f represents a fluorine-containing alkyl group having 3 to 50 carbon atoms (however, it may contain an etheric oxygen atom). ]

[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.
“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 aromatic rings is regarded as a part of the carbon chain constituting the main chain.
The same applies below. ) In the carbon atom.
In the crosslinkable prepolymer in 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 part containing a polyaryl ether structure, or a part 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”.

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. The other aromatic ring is preferably the halogen-substituted aromatic ring, and more preferably the perfluoroaromatic ring.

[Crosslinkable functional group]
At least some of the crosslinkable functional groups in the prepolymer do not substantially react at the time of producing the prepolymer, and are irradiated with actinic radiation in the presence of a photosensitizer to cause crosslinking or chain extension between prepolymer molecules. It is a reactive functional group.
Moreover, it is preferable that this crosslinkable functional group reacts also by giving external energy other than actinic radiation, and causes the bridge | crosslinking or chain extension between prepolymer molecules. As the external energy, heat is preferable.
As a result, the prepolymer in the exposed area 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.

  When heat is used as the external energy, the crosslinkable functional group is preferably a reactive functional group that reacts at a temperature of 40 to 500 ° C. If the reaction temperature is too lower than the above range, stability during storage of the prepolymer or the photosensitive composition containing the prepolymer cannot be ensured, and if it is too high, thermal decomposition of the prepolymer itself will occur during the reaction. It is preferable that it exists in the said range. More preferably, it is 60-400 degreeC, and 70-350 degreeC is the most preferable.

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 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. From these points, a vinyl group and an ethynyl group are most preferable.
The methacryloyl (oxy) group means a methacryloyl group or a methacryloyloxy group. The same applies to the acryloyl (oxy) group.
All 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 and 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) include 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 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 Chains Represented by General Formula (I)]
In the general formula (I), R ^f represents a fluorine-containing alkyl group having 3 to 50 carbon atoms, and may contain an etheric oxygen atom. The fluorine-containing alkyl group as R ^f 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. The fluorine-containing alkyl group may be a chain alkyl group or a cycloalkyl group. The ring of the cycloalkyl group may be monocyclic or polycyclic.
R ^f is preferably linear, branched or cyclic. R ^f is preferably a perfluoroalkyl group in which all of the hydrogen atoms bonded to the carbon atoms of the alkyl group are substituted with fluorine atoms.
Among the side chains represented by the above general formula (I), those in which R ^f is linear are preferably those represented by the following general formula (I-1) or the following general formula (I-2). In the following general formula (I-1), m represents an integer of 1 to 5, R ^fa represents a fluorine-containing alkyl group having 4 to 50 carbon atoms, and may contain an etheric oxygen atom. m is more preferably an integer of 1 to 3.
More preferable examples of the side chain represented by the following general formula (I-1) include a monovalent group represented by the following general formula (I-1-1) or the following general formula (I-1-2). The monovalent group represented is mentioned.

Of the side chains represented by the above general formula (I), those in which R ^f is branched are preferably monovalent groups represented by the following general formula (I-3) or (I-4).

Among the side chains represented by the general formula (I), those in which R ^f is cyclic include monovalent groups represented by the following formula (I-5), (I-6) or (I-7) Is preferred.

The position at which the side chain represented by the general formula (I) 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 exists in the main chain, and a side chain represented by the general formula (I) 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 the side chain represented by the general formula (I) is bonded to the latter, that is, the halogen-substituted aromatic ring not constituting the 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 the general formula (I)” present in one molecule of the prepolymer may be one type or two or more types.
The content of the “side chain represented by the general formula (I)” in the prepolymer is preferably 0.01 to 1 g, more preferably 0.05 to 0.5 g, relative to 1 g of the prepolymer. When this content is at least the lower limit of the above range, the effect of improving water repellency and oil repellency can be obtained satisfactorily, and when it is at most the upper limit, heat resistance is good.

<Prepolymer production method>
The prepolymer used in the present invention comprises a fluorine-containing aromatic compound (B) represented by the general formula (1) and a compound (C) having three or more phenolic hydroxyl groups in the presence of a dehydrofluorinating agent. A step (S1) of performing a condensation reaction below, a compound (Y-1) having a crosslinkable functional group and a phenolic hydroxyl group; a crosslinkable functional group and “aroma substituted with a fluorine atom capable of reacting with a phenolic hydroxyl group” A compound (Y-2) having a “ring” and either or both of them in the presence of a dehydrofluorinating agent to introduce a crosslinkable functional group (S2), and the following general formula (II) The alcohol (Q) represented by) is reacted in the presence of a dehydrofluorinating agent to introduce a side chain (S3). In the following description, compound (Y-1) and compound (Y-2) may be collectively referred to as compound (Y).

［式中、Ｒ^ｆは炭素数３〜５０の含フッ素アルキル基（ただし、エーテル結合性の酸素原子を含んでいてもよい）を表す。］

[Wherein, R ^f represents a fluorine-containing alkyl group having 3 to 50 carbon atoms (however, it may contain an etheric oxygen atom). ]

  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, when the step (S1) and the step (S2) are performed, the step (S2) may be performed after the step (S1) is performed, and the step (S1) and the step (S2) are performed simultaneously. May be. The same applies when the step (S1) and the step (S3) are performed.

  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 reacted subsequently. 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)]
The prepolymer used in the present invention includes a polymer having a polyaryl ether structure in the main chain and a “aromatic ring substituted with a halogen atom capable of reacting with a phenolic hydroxyl group” in the main chain. It is preferable to react the precursor (P1) having the formula (II) with the alcohol (Q) represented by the general formula (II) in the presence of a dehydrofluorinating agent, and further introduce a crosslinkable functional group. Specifically, the precursor (P1) is obtained by performing the step (S1), the precursor (P1) and the alcohol (Q) are subjected to a condensation reaction, and then the compound (Y) is subjected to a condensation reaction. The prepolymer used in the present invention is obtained.
In this production method, the molecular weight of the prepolymer can be easily controlled by producing the precursor (P1) first. Moreover, when the reactivity of alcohol (Q) is low compared with compound (Y), it is suitable for reacting a desired amount of alcohol (Q). That is, it is preferable in that the introduction of a desired amount of the side chain represented by the general formula (I) can be 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), a fluorine-containing aromatic compound (B) represented by the general formula (1) and a compound (C) having three or more phenolic hydroxyl groups are defluorinated. It is preferable to use a precursor (P11) obtained by a condensation reaction in the presence of a hydrogenation agent. Thereafter, the side chain represented by the general formula (I) and the crosslinkable functional group are introduced. Preferably, after carrying out step (S1), step (S3) is carried out to introduce a side chain represented by general formula (I), and then step (S2) is carried out to introduce a crosslinkable functional group. For introducing the crosslinkable functional group, it is preferable to use the compound (Y-1) or the compound (Y-2).

[Production method using precursor (P2)]
Another method for producing the prepolymer used in the present invention is a polymer having a polyaryl ether structure in the main chain, having a crosslinkable functional group, and capable of reacting with a phenolic hydroxyl group in the main chain. It is also preferable to react the precursor (P2) having an “aromatic ring substituted with a halogen atom” and the alcohol (Q) represented by the general formula (II) 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 alcohol (Q) are subjected to a condensation reaction to be used in the present invention. A prepolymer 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 general formula (1), and a compound having three or more phenolic hydroxyl groups (C It is preferable to use a precursor (P21) obtained by a condensation reaction in the presence of a dehydrofluorinating agent. That is, it is preferable that the step (S1) and the step (S2) are simultaneously performed to introduce a crosslinkable functional group, and then the step (S3) is performed to introduce a side chain.
The precursor (P2) can also be obtained by carrying out the step (S1) to obtain the precursor (P1) and then carrying out the step (S2) to react the compound (Y).

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 the case of producing the precursor (P21) with both (i) and (ii), the fluorine-containing aromatic compound (B), the compound (C), the compound (Y-1) and the compound (Y-2) are prepared. The condensation reaction is carried out in the presence of a deHF agent.
When the side chain represented by the above general formula (I) is introduced into the precursor (P21) thus obtained, “a part or all of the hydrogen atoms bonded to the aromatic ring are substituted with fluorine atoms in the main chain. A prepolymer in which the side chain represented by the general formula (I) is bonded to the fluorine-containing aromatic ring is obtained.

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.
Furthermore, 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 the general formula (I) is introduced into an aromatic ring derived from the fluorine-containing aromatic compound (B) or the compound (Y-2).

  As shown in the following formula (2), the condensation reaction in the prepolymer production method used in the present invention is such that the phenoxy group derived from the phenolic hydroxyl group is the fluorine atom of the fluorine-containing aromatic compound (B). The bonded carbon atom and / or the carbon atom to which the fluorine atom (or halogen atom) of (Y-2) bonds is attacked, and then an ether bond is generated by a reaction mechanism in which 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.

By using the compound (Y-1) or (Y-2) having a crosslinkable functional group as a monomer for producing the prepolymer used in the present invention, a prepolymer having a crosslinkable functional group introduced therein can be obtained. As a result, when the prepolymer used in 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.
Further, by using the compound (C) having three 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. Thereby, a crosslinking group or a side chain represented by the above formula (I) can be introduced into the prepolymer without lowering the molecular weight of the prepolymer.
Furthermore, the flexibility in the cured product can be improved by using the fluorine-containing aromatic compound (B) represented by the general 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 used in 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 general 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 the general formula (I) can be bonded in the condensation reaction with the alcohol (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. If Rf ¹ there are a plurality in one molecule of the fluorinated aromatic compound (B), they may be the same or may be 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 said General formula (1), n is an integer of 0-2, 0 or 1 is preferable and 1 is the most preferable.

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 preferable as the fluorine-containing aromatic compound (B) in that the obtained cured product is excellent in the 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 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 become 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 used in 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, 3-ethynylphenol, 4-phenylethynylphenol, 4- (4-fluorophenyl) ethynyl. Examples include ethynylphenols such as phenol. 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, and 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; fluorinated aryls having a cyano group such as pentafluorobenzonitrile; containing fluorinated aryls such as pentafluorophenylacetylene and nonafluorobiphenylacetylene Fluorinated arylacetylenes; fluorinated diaries such as phenylethynylpentafluorobenzene, phenylethynylnonafluorobiphenyl, decafluorotolane, etc. Le acetylenes 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 is 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 used in 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 embedding 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.
The number average molecular weight in this specification is a value in terms of polystyrene by gel permeation chromatography method (GPC method).

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 alcohol (Q), and the fluorine-containing aromatic compound (B). It can be controlled by changing the charging ratio. In addition, it is preferable that the hydroxyl group does not remain in the prepolymer because water repellency and oil repellency are improved.
In the condensation reaction, the fluorine-containing aromatic compound (B) usually serves as a bifunctional compound. Therefore, the molecular weight is controlled so that the total number of moles of the hydroxyl groups of the compound (C), the compound (Y-1) and the alcohol (Q) does not exceed twice the number of moles of the fluorinated aromatic compound (B). It is preferable to adjust with.

  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 alcohol (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 time, 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 the 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. It is preferable for each value to be in this range because the resulting prepolymer used in the present invention has high heat resistance.
The prepolymer used in the present invention is preferably selected by appropriately selecting the compounds (Y-1) and (Y-2) according to physical properties such as heat resistance and flexibility of a cured product obtained by curing the prepolymer. A prepolymer from which a cured product having the above physical properties can be obtained can be produced.

  The prepolymer used in the present invention is neutralized, regenerated after the condensation reaction in the intermediate step (for example, after synthesizing the precursor or after introducing the side chain represented by the general formula (I)). It is preferable to carry out purification appropriately by a method such as precipitation, 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) for improving the flexibility of the cured film.

  Examples of the compound (Z) having two phenolic hydroxyl groups include dihydroxybenzene, dihydroxybiphenyl, dihydroxyterphenyl, dihydroxynaphthalene, dihydroxyanthracene, dihydroxyphenanthracene, dihydroxy-9,9-diphenylfluorene, dihydroxydibenzofuran, dihydroxydiphenyl ether. And bifunctional phenols such as dihydroxydiphenyl thioether, dihydroxybenzophenone, dihydroxy-2,2-diphenylpropane, dihydroxy-2,2-diphenylhexafluoropropane, and dihydroxybinaphthyl. These may be used alone or in combination of two or more.

[Alcohol (Q)]
In the present invention, in order to introduce the side chain represented by the general formula (I), it is preferable to use the alcohol (Q) represented by the general formula (II). In particular, it is preferable to react the “aromatic ring substituted with a halogen atom capable of reacting with a phenolic hydroxyl group” and the alcohol (Q) in the presence of a dehydrofluorinating agent.
The reaction between the “aromatic ring substituted with a halogen atom capable of reacting with a phenolic hydroxyl group” and the alcohol (Q) is derived from the hydroxyl group of the alcohol (Q), similarly to the reaction represented by the formula (2). The alkoxy group is attacked by 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 ether bond is formed by a reaction mechanism etc. in which the halogen atom is eliminated. Generate.
By this reaction, a side chain obtained by removing hydrogen from the hydroxyl group of alcohol (Q), that is, a side chain represented by the general formula (I) is introduced into the prepolymer.

^{R f} in the general formula (II) is the same as ^{R f} in the general formula (I). Specific examples of the alcohol (Q) represented by the general formula (II) include the following.
When an alcohol represented by the following general formula (II-1) is used, a prepolymer having a side chain represented by the above general formula (I-1) can be obtained. A prepolymer having side chains is obtained. The alcohol (Q) may be used alone or in combination of two or more.
Of the alcohols (Q) represented by the general formula (II), the linear ones are preferably those represented by the following general formula (II-1) or the following general formula (II-2). In the following general formula (II-1), m represents an integer of 1 to 5, R ^fa represents a fluorine-containing alkyl group having 4 to 50 carbon atoms, and may contain an etheric oxygen atom. m is more preferably an integer of 1 to 3.
More preferable examples of the alcohol (Q) represented by the following general formula (II-1) include an alcohol represented by the following general formula (II-1-1) or the following general formula (II-1-2). The alcohol represented is mentioned.

  Moreover, as a branched thing among alcohol (Q) represented by the said general formula (II), the alcohol represented by the following general formula (II-3) or (II-4) is preferable.

  Moreover, as a cyclic thing among alcohol (Q) represented by the said general formula (II), the alcohol represented by the following formula (II-5), (II-6), or (II-7) is preferable.

  As the dehydrofluorinating agent used when reacting the alcohol (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 alcohol (Q) is reacted, sodium hydride, cesium carbonate, sodium hydroxide, potassium hydroxide or cesium hydroxide is more preferable.

The amount of the deHF agent to be used is required to be 1 or more times in terms of molar ratio with respect to the number of moles of the hydroxyl group of the alcohol (Q) to be used, and preferably 1.1 to 3 times.
When reacting alcohol (Q), it is preferable to carry out 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.

<Solvent>
The solvent in the photosensitive composition of this invention should just be what can melt | dissolve or disperse a prepolymer, a photosensitive agent, and the additives added as needed. In addition, the photosensitive 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 necessary. 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 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 photosensitive 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.

  The photosensitive composition of the present invention also includes stabilizers such as UV absorbers, antioxidants and thermal polymerization inhibitors; surfactants such as leveling agents, antifoaming agents, suspending agents and dispersants; You may mix | blend at least 1 sort (s) of additives selected from the various well-known agents in the coating field, such as an agent; a plasticizer; a thickener.

  The prepolymer, the photosensitizer, and the solvent are mainly blended in the photosensitive composition. 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.

<Method for producing cured film>
By using the photosensitive composition of the present invention, a cured film having a negative uneven shape can be produced by a photolithographic method.
When the prepolymer in the photosensitive composition of the present invention contains a low molecular weight substance having a substantial vapor pressure at normal pressure, in order to prevent volatilization during baking in the production process of the cured film Before applying the photosensitive composition to the substrate, a part of the crosslinkable functional group may be reacted in the solution. The method is preferably heating. Heating conditions are preferably 50 to 250 ° C. and 1 to 50 hours, more preferably 70 to 200 ° C. and 1 to 20 hours. 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.

[Adhesion improver]
The cured film obtained from the photosensitive composition of the present invention can be peeled off from the substrate and used as a single film, or used as a coating such as a water- and oil-repellent film while adhered to the substrate. 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. Among these, silane coupling agents such as epoxy silanes, amino silanes, acrylic silanes, vinyl silanes, and styryl silanes are more preferable.
Epoxy silanes include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane. Illustrated.
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 are exemplified.
As acrylic silanes, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxy Examples include silane.
Examples of vinyl silanes include vinyl trichlorosilane, vinyl trimethoxy silane, and vinyl triethoxy silane. Examples of styrylsilanes include p-styryltrimethoxysilane and p-styryltriethoxysilane.

  As a method for applying the adhesion promoter, a method of treating the substrate with the adhesion promoter before application of the photosensitive composition or a method of adding the adhesion promoter to the photosensitive 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 alcohol, methanol, ethanol, and 2-propanol 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 8% 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 decreases.

[Method for producing cured film by photolithography]
The method for producing a cured film of the present invention includes a step of forming a coating film comprising the photosensitive composition of the present invention on a substrate, a part of the coating film is selectively exposed, and the crosslinking is performed at the exposed portion. An exposure step for causing a reaction of the functional group and a development step after the exposure step. Thereby, the cured film in which the uneven | corrugated shape in which the exposure part respond | corresponded to the convex part was formed is obtained.

[Coating film forming process]
First, a photosensitive composition is applied on a substrate to form a wet film. The wet film is pre-baked and dried to form a coating film.
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.

When the finally obtained cured film is used as an insulating film for electronic devices, a spin coat method or a 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, a wet film having a thickness of about 0.01 to 500 μm is preferably formed on the substrate, and more preferably 0.1 to 300 μm.
The heating condition for pre-baking the wet film is preferably a temperature at which the solvent is volatilized and the prepolymer crosslinkable functional group, photosensitizer, photoinitiator, sensitizer and other additives do not substantially react. 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 molecule due to a reaction of a crosslinkable functional group is irradiated in an exposed portion irradiated with actinic radiation by irradiating the desired pattern shape with actinic radiation (also referred to as exposure light in this specification). Cross-linking and / or chain extension between them 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, or the like, 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 step, the movement of the reactive intermediate present in the coating film is promoted, so that the contact probability 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 developer, 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 developing solution and the developing time in the developing 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 developing solution in the exposed and unexposed portions.

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 highly soluble 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 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.
If the degree of curing is insufficient, the external energy can be further applied to react with the unreacted crosslinkable functional group present in the film, whereby the curing can be further advanced. By additionally reacting the crosslinkable functional group in this manner, 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 is present 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. 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 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.

<Curing film>
The cured film produced using the photosensitive composition of the present invention is suitable for applications having an uneven shape on the surface and requiring water repellency and oil repellency. In the cured film of the present invention, in the uneven shape of the surface, the film derived from the photosensitive composition of the present invention may remain in the recess, or the base material may be exposed at a part or all of the bottom surface of the recess. Good. 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 the cured film of the present invention include molds, mold surface layers (particularly, fine pattern forming layers such as hot embossing and nanoimprint lithography); MEMS (microelectronic mechanical systems) such as inkjet printer heads and sensors. Surface protective film for devices; Coating of liquid lens members; Sealant; Bank material; Additive to resin; Moisture-proof coating; Various protective films (heat / water repellent film, heat / oil repellent film); -Water repellent film, heat and oil repellent film); Photoresist material; Topcoat material; Optical waveguide; Insulating film for electronic devices or multilayer wiring boards.

<Article>
The article having the cured film of the present invention is not particularly limited, but preferred examples include molds, molds (particularly, fine pattern forming layers such as hot embossing and nanoimprint lithography); ink jet printer heads, sensors, etc. MEMS (microelectronic mechanical system) devices; liquid lens members; sealing materials; bank materials; moisture-proof coatings; various protective films (heat-resistant / water-repellent films, heat-resistant / oil-repellent films); various films (heat-resistant / water-repellent films, heat-resistant) -Oil repellent film); heat-sink insulation coating for power semiconductors; insulation films for electronic devices or multilayer wiring boards; electronic members; LCD alignment films; optical waveguides;

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Each measurement item was measured by the following method.

[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, and NMR was measured to confirm that there was a signal in a predetermined region. When the crosslinkable functional group is a vinyl group, a signal appears at δ = 5.0 to 7.0 ppm, and when the crosslinkable functional group is an ethynyl group, a signal appears near δ = 4.5 ppm.

[Synthesis Example 1]
A precursor (P2-1) was produced by the production method (ii) using the compounds (B), (C), and (Y-2).
Into a 100 mL glass four-necked flask equipped with a Dimroth condenser, thermocouple thermometer, and mechanical stirrer, 2.2 g (0.01 mol) of pentafluorostyrene as compound (Y-2), 1, as compound (C) 3.3 g (0.01 mol) of 1,1-tris (4-hydroxyphenyl) ethane and 49.2 g of DMAc (N, N-dimethylacetamide) were charged as a solvent.
While stirring, the mixture was heated on an oil bath, and when the liquid temperature reached 60 ° C., 5.1 g (0.05 mol) of sodium carbonate was quickly added as a deHF agent. The mixture was heated at 60 ° C. for 24 hours while stirring was continued.
Next, a solution of 4.0 g (0.01 mol) of perfluorobiphenyl as compound (B) in 36.0 g of DMAc was added, 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 300 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 60 ° C. for 12 hours to obtain 7.5 g of a white powder precursor (P2-1).

Next, a side chain was introduced into the obtained precursor (P2-1) to produce a prepolymer.
That is, in a 50 mL Pyrex (registered trademark) four-necked flask equipped with a Dimroth condenser, a thermocouple thermometer, and a mechanical stirrer, 3 g of the precursor (P1-1) and CF ₃ (OCF ₂ CF ₂ as alcohol (Q) were added. ) 0.45 g (0.0005 mol) of _n OCF ₂ CH ₂ OH (molecular weight 1000) (hereinafter referred to as alcohol (Q-1)) and 32.2 g of tetrahydrofuran as a solvent were charged.
While stirring at room temperature, 0.06 g (0.001 mol) of sodium hydride (55% mineral oil dispersion) was added as a de-HXing agent. After the addition, the mixture was heated to 50 ° C. on an oil bath while stirring and stirred for 24 hours.
Thereafter, the reaction solution was cooled to room temperature and gradually added to 120 g of hydrochloric acid water-containing methanol (mixed solution of 6 g of hydrochloric acid and 114 g of methanol) to precipitate a fine brown powder. This fine brown powder was filtered, further washed with methanol three times, then with hexane three times, and vacuum-dried at 60 ° C. for 12 hours to obtain 2.8 g of a white gray powdery prepolymer A. It was.

The NMR spectrum data of the prepolymer A obtained in this example is shown below.
<NMR spectrum>
¹ H-NMR (300.4 MHz, solvent acetone-d6, standard: TMS) δ (ppm): 2.19 (C—CH ₃ ), 5.08 (CF ₂ —CH ₂ —O), 5.77 ( _{Ph-CH = CH 2),} 6.08 (Ph-CH = CH 2), 6.73 (Ph-CH = CH 2), 6.90~7.21 (Ph-H).
¹⁹ F-NMR (282.7 MHz, solvent acetone-d6, reference: CFCl ₃ ) δ (ppm): −55.2 (CF ₃ ), −77.9 (—CF ₂ —CH ₂ O), −88. _{2~-90.3 (CF 2 -O)} , - 138.3~-161.9 (Ph-F).

[Synthesis Example 2]
A precursor (P1-1) was produced using the compounds (B) and (C).
That is, in a 200 mL two-necked flask equipped with a Dimroth condenser and a stirrer chip, 1.79 g (0.014 mol) of 1,3,5-trihydroxybenzene as compound (C) and perfluorobiphenyl as compound (B) Was charged with 10.0 g (0.030 mol) and 106.14 g of DMAc as a solvent.
While stirring, the mixture was heated to 40 ° C. on an oil bath, 8.84 g (0.064 mol) of potassium carbonate was quickly added as a de-HF agent, and heated at 40 ° C. for 24 hours while continuing stirring.
Thereafter, the reaction liquid was cooled to room temperature and gradually poured into 300 mL of vigorously stirred 0.5N aqueous hydrochloric acid to precipitate a white powder. This white powder was filtered, further washed twice with pure water, and then vacuum dried at 80 ° C. for 12 hours to obtain 9.84 g of a white powder precursor (P1-1).

Next, a 50 mL Pyrex (registered trademark) four-necked flask equipped with a Dimroth condenser, thermocouple thermometer, and mechanical stirrer was charged with 3 g of precursor (P1-1) and 0.45 g of alcohol (Q-1) ( 0.0004 mol), and 31.1 g of DMAc was charged as a solvent.
While stirring, the mixture was heated to 60 ° C. on an oil bath, 0.56 g (0.002 mol) of cesium carbonate was quickly added as a deHF agent, and heated at 60 ° C. for 41 hours while stirring was continued.
Thereafter, the reaction solution was cooled to room temperature and gradually added to 120 g of vigorously stirred 0.5 mol / L hydrochloric acid to precipitate a white gray powder. The white gray powder was filtered and further washed with water three times, followed by vacuum drying at 60 ° C. for 12 hours to obtain 2.8 g of a white gray powdery polymer (p).

Subsequently, 2.5 g of the polymer (p) obtained by the above reaction, compound (Y-1-1) was added to a 50 mL Pyrex (registered trademark) four-necked flask equipped with a Dimroth condenser, a thermocouple thermometer, and a mechanical stirrer. ) Was charged with 0.50 g (0.003 mol) of 4-acetoxystyrene and 27.1 g of diethylene glycol dimethyl ether as a solvent. Acetoxystyrene undergoes hydrolysis in the reaction system and acts in the same way as hydroxystyrene.
While stirring, 1.1 g (0.009 mol) of potassium hydroxide (48% aqueous solution) was quickly added and stirred for 25 hours.
Thereafter, when gradually added to 120 g of 0.5 mol / L hydrochloric acid vigorously stirred, a white gray powder was precipitated. This white gray powder was filtered and further washed with water three times, followed by vacuum drying at 60 ° C. for 12 hours to obtain 2.5 g of a white gray powdery prepolymer B.
The obtained prepolymer B had an ether bond, a vinyl group as a crosslinkable functional group, and a fluorine-containing side chain.

[Synthesis Example 3]
In the same manner as in Synthesis Example 2, 2.8 g of a white gray powdery polymer (p) was obtained.
Subsequently, 2.5 g of the polymer (p) obtained by the above reaction, compound (Y-1-1) was added to a 50 mL Pyrex (registered trademark) four-necked flask equipped with a Dimroth condenser, a thermocouple thermometer, and a mechanical stirrer. ) Was charged with 0.25 g (0.002 mol) of 4-acetoxystyrene and 24.8 g of diethylene glycol dimethyl ether as a solvent. While stirring, 0.55 g (0.005 mol) of potassium hydroxide (48% aqueous solution) was quickly added and stirred for 44 hours. Thereafter, the same operation as in Synthesis Example 2 was performed to obtain 2.4 g of a white gray powdery prepolymer C.
The obtained prepolymer C had an ether bond, a vinyl group as a crosslinkable functional group, and a fluorine-containing side chain.

[Synthesis Example 4]
Synthesis Example 2 except that the amount of precursor (P1-1) was changed to 4 g, the amount of solvent was changed to 40.1 g, and the heating time at 60 ° C. was changed to 46 hours. In the same manner as above, 3.9 g of a white gray powdery polymer (p ′) was obtained.
Subsequently, 3 g of the polymer (p ′) obtained by the above reaction and the compound (Y-1-1) were added to a 50 mL Pyrex (registered trademark) four-necked flask equipped with a Dimroth condenser, a thermocouple thermometer, and a mechanical stirrer. As a solvent, 0.38 g (0.002 mol) of 4-acetoxystyrene and 30.4 g of diethylene glycol dimethyl ether as a solvent were charged. While stirring, 0.82 g (0.007 mol) of potassium hydroxide (48% aqueous solution) was quickly added and stirred for 24 hours. Thereafter, the same operation as in Synthesis Example 2 was performed to obtain 2.8 g of a prepolymer D in the form of white gray powder.
The obtained prepolymer D had an ether bond, a vinyl group as a crosslinkable functional group, and a fluorine-containing side chain.

[exposure]
In the following example, the exposure was performed by using UL-7000 (manufactured by Quintel) and irradiating light of an ultrahigh pressure mercury lamp. In addition, about the unexposed part, the light-shielding part was formed using metal foil or a mask.

[Example 1]
Prepolymer A obtained in Synthesis Example 1 was dissolved in propylene glycol monomethyl ether acetate (hereinafter PGMEA) to prepare a solution having a prepolymer concentration of 25% by mass (referred to as prepolymer solution A1). 10 g of the prepolymer solution A1 was placed in a sample bottle, and 0.05 g of IRGACURE 369 (manufactured by Ciba Specialty Chemicals) was added and dissolved as a photosensitizer to obtain a photosensitive composition.
This photosensitive composition was spin-coated on a silicon wafer at 1000 rpm for 30 seconds, and then pre-baked on a hot plate at 100 ° C. for 90 seconds to form a coating film.
This coating film was exposed to an irradiation energy of 1530 mJ / cm ² . After exposure, after baking at 140 ° C. for 1 minute, paddle development was performed for 40 seconds using PGMEA, and further rinse was performed for 30 seconds using PGMEA.
Then, after spin-drying at 2,000 rpm for 30 seconds, post-development baking was performed on a hot plate. The heating conditions were two stages of 100 ° C. and 90 seconds followed by 200 ° C. and 90 seconds.
In this way, a film was formed in which the exposed portion corresponds to the convex portion and the unexposed portion corresponds to the concave portion. When the film thickness of this film was measured, the film thickness of the exposed part was 0.82 μm, and the film thickness of the unexposed part was less than 0.10 μm. The reference film thickness after exposure and before the development process was 2.0 μm.

[Examples 2 to 5]
In Example 1, except that the irradiation energy or the post-exposure baking conditions were changed as shown in Table 1, a film having an uneven shape was obtained in the same manner as in Example 1. Table 1 shows the measurement results of the film thickness of the exposed part and the film thickness of the unexposed part in the obtained film.

As shown in the results of Table 1, irregularities were formed in Examples 1-5. Further, when Examples 1, 4 and 5 are compared, the exposure energy is the same, but it can be seen that the longer the heating time in post-exposure baking, the larger the film thickness of the exposed portion.
In Example 2, since the exposure energy was small, the difference in film thickness was small between the exposed area and the unexposed area. In Example 3, the film thickness of the exposed area was non-uniform. This is presumably because the exposure energy was insufficient.
From these results, it can be seen that the solubility of the exposed portion in the developer can be adjusted by the exposure energy and post-exposure baking conditions.

[Example 6]
Prepolymer B obtained in Synthesis Example 2 was dissolved in PGMEA to prepare a solution having a prepolymer concentration of 15% by mass (referred to as prepolymer solution B1). 10 g of the prepolymer solution B1 was put in a sample bottle, and 0.075 g of IRGACURE OXE01 (manufactured by Ciba Specialty Chemicals) was added and dissolved as a photosensitizer to obtain a photosensitive composition.
This photosensitive composition was spin-coated on a silicon wafer at 1000 rpm for 30 seconds, and then pre-baked on a hot plate at 60 ° C. for 90 seconds to form a coating film.
This coating film was exposed to an irradiation energy of 1530 mJ / cm ² . After the exposure, paddle development was performed for 40 seconds using PGMEA, and further rinse was performed for 30 seconds using PGMEA.
Then, after spin-drying at 2,000 rpm for 30 seconds, post-development baking was performed on a hot plate. The heating conditions were 100 ° C. and 90 seconds.
In this way, a film was formed in which the exposed portion corresponds to the convex portion and the unexposed portion corresponds to the concave portion. When the film thickness of this film was measured, the film thickness of the exposed part was 0.68 μm, and the film thickness of the unexposed part was less than 0.10 μm. In addition, the reference film thickness before performing the image development process after exposure was 1.0 micrometer.

[Examples 7 and 8]
In Example 6, except that the type of the prepolymer was changed as shown in Table 2, a film having an uneven shape was obtained in the same manner as in Example 6. Table 2 shows the measurement results of the film thickness of the exposed part and the film thickness of the unexposed part in the obtained film.

[Example 9]
The film having the irregular shape formed in Example 1 was further cured by heating in a vertical furnace at 300 ° C. for 30 minutes in a nitrogen atmosphere to obtain a final cured film. . About the obtained cured film, the exposed part and the contact angle for an unexposed part were measured, respectively. The results are shown in Table 3.

  The contact angle was measured by a droplet method under the condition of 25 ° C. using CA-A (product name) manufactured by Kyowa Interface Science Co., Ltd. For water repellency evaluation, about 1 μL of water was dropped to measure the contact angle, and for oil repellency evaluation, normal decane was dropped to measure the contact angle.

  From the results shown in Table 3, the exposed part made of the film formed using the photosensitive composition of the present invention is superior in water repellency and oil repellency compared to the unexposed part where the film hardly remains. Is recognized.

[Example 10]
[Alkali resistance evaluation]
Using the exposed portion of the cured film obtained in Example 9, an alkali resistance test was conducted.
About 1 μL of water was dropped on the exposed portion of the obtained cured film, and the contact angle (water contact angle after film formation) was measured (water repellency evaluation). Moreover, normal decane was dripped at the obtained cured film, and the contact angle (normal decane contact angle after film formation) was measured (oil repellency evaluation). The contact angle was measured by a droplet method using DM700 (product name) manufactured by Kyowa Interface Science Co., Ltd. at 25 ° C.
The cured film was immersed in a 0.1 mol / L sodium hydroxide aqueous solution and heated at 60 ° C. for 3 days. Then, after cooling and washing | cleaning with pure water, it was made to dry at room temperature, and the contact angle after an alkali test was measured by the method similar to the contact angle after the said film forming. The results are shown in Table 4.

  From this result, it is understood that the exposed portion made of the cured film formed using the photosensitive composition of the present invention has good oil repellency and water repellency even after the alkali test and has alkali resistance. It was.

[Examples 11 to 13]
The films formed in Examples 6 to 8 and having a concavo-convex shape were additionally cured by heating in a vertical furnace at 200 ° C. for 60 minutes in a nitrogen atmosphere to obtain a final cured film. Obtained. About the exposed part of the obtained cured film, the contact angle (contact angle after film forming) was measured by the following method, respectively.
That is, about 1 μL of water was dropped onto the exposed portion of the obtained cured film, and the contact angle was measured. Further, normal decane and xylene were added dropwise to measure the contact angle. The contact angle was measured by a droplet method using DM700 (product name) manufactured by Kyowa Interface Science Co., Ltd. at 25 ° C.
The cured film was immersed in a 0.1 mol / L sodium hydroxide aqueous solution and heated at 60 ° C. for 3 days. Then, after cooling and washing with pure water, it was dried at room temperature, and the contact angle after an alkali test was measured by the same method as the contact angle after film formation. The results are shown in Table 5.

  As shown in the results of Table 5, prepolymers B (Example 6), C (Example 7), and D (Example 8) have good oil repellency and water repellency before and after the alkali test, and have alkali resistance. I found out.

[Example 14]
The cured film obtained in Example 9 in powder form was used as a sample, and thermogravimetric analysis was performed using MTC1000S (product name) manufactured by Mac Science. As analysis conditions, the temperature was increased from room temperature to 600 ° C. at a rate of 10 ° C. per minute. The results are shown below.
1% weight loss temperature: 418 ° C.
3% weight loss temperature: 447 ° C.
5% weight loss temperature: 457 ° C.
From this result, it is recognized that the cured film obtained in Example 9 has good heat resistance.

Claims (9)

A negative photosensitive composition containing a crosslinkable prepolymer, a photosensitive agent, and a solvent,
The crosslinkable prepolymer has a polyaryl ether structure in the main chain, a crosslinkable functional group, and the following general formula (I)

[Wherein, R ^f represents a fluorine-containing alkyl group having 3 to 50 carbon atoms (however, it may contain an etheric oxygen atom). ]
A negative photosensitive composition having a side chain represented by the formula:   The main chain has a halogen-substituted aromatic ring in which part or all of the hydrogen atoms bonded to the aromatic ring are substituted with a halogen atom, and the side chain represented by the general formula (I) is The negative photosensitive composition according to claim 1, which is bonded to a halogen-substituted aromatic ring. The crosslinkable prepolymer is
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 three or more phenolic hydroxyl groups to a condensation reaction in the presence of a dehydrofluorinating agent,
The following general formula (I)

[Wherein, R ^f represents a fluorine-containing alkyl group having 3 to 50 carbon atoms (however, it may contain an etheric oxygen atom). ]
A side chain represented by
The negative photosensitive composition of Claim 2. The crosslinkable prepolymer is
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 three or more phenolic hydroxyl groups to a condensation reaction in the presence of a dehydrofluorinating agent,
The following general formula (I)

[Wherein, R ^f represents a fluorine-containing alkyl group having 3 to 50 carbon atoms (however, it may contain an etheric oxygen atom). ]
A side chain represented by
Further, a crosslinkable functional group is introduced,
The negative photosensitive composition of Claim 2.   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 negative photosensitive composition according to claim 4, which is a method of performing a condensation reaction in the presence of a dehydrofluorinating agent using any one or both of the compound (Y-2) having the formula:   The negative photosensitive composition as described in any one of Claims 1-5 in which the said photosensitive agent contains a photoinitiator or a photocrosslinking agent.   A step of forming a coating film comprising the negative photosensitive composition according to any one of claims 1 to 6 on a substrate, and selectively exposing a part of the coating film, The manufacturing method of the cured film characterized by having the exposure process which produces the reaction of the said crosslinkable functional group, and the process developed after this exposure process.   A cured film obtained by the production method according to claim 7.   An article having the cured film according to claim 8.