JP2005043876A - Photosensitive fluorine-containing resin composition, hardened film obtained from the composition, and method for forming pattern - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hardened product having excellent deposition preventing property and wiping property (antifouling property) against a water-repellent oil component or fingerprints and excellent characteristics such as thermal shock resistance and adhesion property, and also to provide a photosensitive fluorine-containing resin composition to easily obtain the above hardened product. <P>SOLUTION: The photosensitive fluorine-containing composition contains: (A) a fluorine-containing copolymer; (B) a compound having at least two alkyl etherified amino groups in the molecule; (C) a photosensitive acid generating agent; and (D) a solvent. The fluorine-containing copolymer (A) of the photosensitive fluorine-containing resin composition is a copolymer containing a structural unit (A1) derived from at least one kind of monomer selected from fluorine-containing methacrylates, fluoroolefin and fluoroolefin derivatives, and a structural unit (A2) derived from at least one kind of monomer selected from hydroxyl group-containing monomers, epoxy group-containing monomers and carboxyl group-containing monomers. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a photosensitive fluorine-containing resin composition and a cured film thereof. More specifically, the present invention relates to a photosensitive fluorine-containing resin composition used for a surface protective film (overcoat film) such as a display or a semiconductor element, and a cured film thereof.

  Conventionally, silicon-based sol-gel materials and ultraviolet curable resins having excellent scratch resistance have been widely used as hard coat materials used in displays such as LCDs. In addition, polyimide resins having excellent heat resistance and mechanical characteristics have been widely used for surface protective films used for semiconductor elements of electronic devices. However, these materials do not have sufficient functions to prevent the adhesion of dirt such as oil and fingerprints, and there is a problem that there is a concern that the visibility will be lowered on the display, and that malfunctions due to the adhesion of water and dirt components will occur on the semiconductor element. It was. For this reason, development of the resin composition which can form easily the protective film excellent in antifouling property, abrasion resistance, etc. was desired.

On the other hand, as a fluorine-based photosensitive resin, a curable resin composition containing a fluorine-containing copolymer obtained by polymerizing a monomer containing a fluorine atom and a monomer containing a hydroxyl group or an epoxy group (patent Document 1) and a radiation sensitive resin composition (Patent Document 2) containing a fluorine-containing copolymer of hexafluoropropylene and unsaturated carboxylic acid are known. However, Patent Documents 1 and 2 do not describe that a protective film excellent in antifouling property and scratch resistance can be formed from these resin compositions.
Japanese Patent Laid-Open No. 10-25388 JP 10-319593 A

  The present invention is intended to solve the problems associated with the prior art as described above, and is excellent in adhesion prevention and wiping properties (antifouling properties) of water-repellent oil components and fingerprints, and has thermal shock resistance and adhesion. It is an object of the present invention to provide a cured product excellent in properties such as properties and a photosensitive fluorine-containing resin composition for easily obtaining such a cured product. Furthermore, it is also an object to provide a photosensitive fluorine-containing resin composition that has excellent patternability (resolution) and is suitable for a surface protective film when mounting a semiconductor element.

  Another object of the present invention is to provide a cured film obtained by curing such a photosensitive fluorine-containing resin composition.

  The inventor has intensively studied to solve the above problems, and that the photosensitive fluorine-containing resin composition containing a copolymer having a fluorine atom in the molecule can form a cured product excellent in antifouling property and the like. The headline and the invention were completed.

That is, the photosensitive fluorine-containing resin composition according to the present invention is
(A) a copolymer having a fluorine atom in the molecule, (B) a compound having at least two amino groups alkylated in the molecule, (C) a photosensitive acid generator, and (D) a solvent It is characterized by containing.

The copolymer (A) having a fluorine atom in the molecule is
(A1) a structural unit derived from at least one monomer selected from fluorine-containing (meth) acrylic acid esters, fluoroolefins and fluoroolefin derivatives;
(A2) A copolymer containing a structural unit derived from at least one monomer selected from a hydroxyl group-containing monomer, an epoxy group-containing monomer, and a carboxyl group-containing monomer is preferable. .

The copolymer (A) having a fluorine atom in the molecule is
(A3) A copolymer further containing a structural unit derived from at least one monomer selected from vinyl compounds, (meth) acrylic acid esters, unsaturated carboxylic acid esters, (meth) acrylamides and unsaturated nitriles It is preferable that

  The structural unit (A1) is preferably a structural unit represented by the following formula (1).

(In formula (1), R ¹ represents hydrogen or a methyl group, and R ² represents a C 2-20 fluoroalkyl group).
The structural unit (A1) may be a structural unit represented by the following formula (2).

(In formula (2), R ³ represents a fluorine atom, a perfluoroalkyl group having 1 to 10 carbon atoms, perfluoroalkoxy group or a chlorine atom having 1 to 10 carbon atoms).
The structural unit (A2) is preferably a structural unit derived from a monomer containing a phenolic hydroxyl group.

  The copolymer (A) having a fluorine atom in the molecule preferably further contains a silicon atom, and more preferably contains a siloxane structural unit represented by the following formula (3).

(Wherein R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group or an aryl group having 6 to 20 carbon atoms).
The cured film according to the present invention can be obtained by curing the photosensitive fluorine-containing resin composition, and may have a pattern.

  In the pattern forming method according to the present invention, the photosensitive fluorine-containing resin composition is applied to a support, dried to form a coating film, exposed through a photomask, and then developed with an alkaline developer. It has the process to perform. Here, it is preferable to perform exposure using an exposure light source having an irradiation light wavelength of 300 nm to 500 nm.

The cured film having the pattern according to the present invention can be formed by the pattern forming method.
The antifouling film according to the present invention is characterized by comprising the cured film.

  The article and the antifouling article according to the present invention are articles on which the cured film or the antifouling film is formed.

  According to the present invention, it is possible to obtain a photosensitive fluorine-containing resin composition excellent in patterning properties by alkali development, and further excellent in prevention of wiping or wiping off water-repellent oil components and fingerprints as well as in thermal shock, A cured product having excellent properties such as adhesion can be obtained.

<Photosensitive fluorine-containing resin composition>
The photosensitive fluororesin composition according to the present invention comprises (A) a copolymer having a fluorine atom in the molecule, (B) a compound having at least two amino groups alkylated in the molecule, (C ) A photosensitive acid generator, and (D) a solvent. Further, in the present invention, if necessary, other additives such as oxirane ring-containing compounds such as alkali-soluble phenol resins and epoxy resins, metal oxide particles, cross-linked fine particles, adhesion aids, sensitizers and leveling agents are contained. May be.

Hereinafter, the components used in the present invention will be described.
(A) Copolymer having fluorine atom in molecule:
A copolymer having a fluorine atom in the molecule used in the present invention (hereinafter simply referred to as “fluorinated copolymer (A)”)
(A1) a structural unit derived from at least one monomer (a1) selected from fluorine-containing (meth) acrylic acid esters, fluoroolefins and fluoroolefin derivatives; (A2) a hydroxyl group-containing monomer and an epoxy group A structural unit derived from at least one monomer (a2) selected from a monomer containing and a carboxyl group-containing monomer;
A structure derived from at least one monomer (a3) selected from (A3) vinyl compounds, (meth) acrylic acid esters, unsaturated carboxylic acid esters, (meth) acrylamides and unsaturated nitriles as necessary. A copolymer containing units is preferred.

  Among such fluorine-containing copolymers (A), a copolymer in which the structural unit (A1) contains a structural unit represented by the following formula (1) or (2) is preferable.

(In formula (1), R ¹ represents hydrogen or a methyl group, and R ² represents a C 2-20 fluoroalkyl group).

(In formula (2), R ³ represents a fluorine atom, a perfluoroalkyl group having 1 to 10 carbon atoms, perfluoroalkoxy group or a chlorine atom having 1 to 10 carbon atoms).
Moreover, it is preferable that the said fluorine-containing copolymer (A) contains the structural unit induced | guided | derived from the monomer containing a phenolic hydroxyl group as said structural unit (A2).

  Furthermore, the fluorine-containing copolymer (A) preferably contains a silicon atom, particularly a siloxane structure represented by the following formula (3).

(Wherein R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group or an aryl group having 6 to 20 carbon atoms).
The copolymer (A) having a fluorine atom in the molecule used in the present invention is, for example,
At least one monomer (a1) selected from fluorine-containing (meth) acrylic acid esters, fluoroolefins and fluoroolefin derivatives;
At least one monomer (a2) selected from a hydroxyl group-containing monomer, an epoxy group-containing monomer and a carboxyl group-containing monomer;
If necessary, by copolymerizing with at least one monomer (a3) selected from vinyl compounds, (meth) acrylic acid esters, unsaturated carboxylic acid esters, (meth) acrylamides and unsaturated nitriles. Can be manufactured. Moreover, you may use a reactive emulsifier in the case of copolymerization.

  The fluorine-containing copolymer (A) is produced by further reacting a monomer (a4) containing a silicon atom, particularly a siloxane structure, to produce a silicon-containing fluorine-containing copolymer (A). Can do.

(A1) Monomer:
The monomer (a1) used in the present invention is a compound having a polymerizable unsaturated double bond and at least one fluorine atom, and includes, for example, a fluorine-containing (meth) acrylic acid ester, a fluoroolefin, and a fluoro Examples include olefin derivatives.

Examples of the fluorine-containing (meth) acrylic acid ester include trifluoroethyl (meth) acrylate and hexafluoroisopropyl (meth) acrylate.
Examples of the fluoroolefin include tetrafluoroethylene, hexafluoropropylene, 3,3,3-trifluoropropylene, and chlorotrifluoroethylene.

  Examples of fluoroolefin derivatives include alkyl perfluorovinyl ethers such as methyl trifluorovinyl ether and ethyl trifluorovinyl ether; alkoxyalkyl perfluorovinyl ethers such as methoxyethyl trifluorovinyl ether and ethoxyethyl trifluorovinyl ether; perfluoro (methyl vinyl ether) Perfluoro (alkyl vinyl ethers) such as perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether); and perfluoro (alkoxyalkyl vinyl ether) such as perfluoro (propoxypropyl vinyl ether). It is done.

These compounds can be used alone or in admixture of two or more.
The structural unit (A1) derived from such a monomer (a1) is usually 1 to 90% by weight, preferably 5 to 85% by weight, more preferably 10 to 10% in the fluorinated copolymer (A). It is desirable to be included in an amount of 70% by weight. When the proportion of the structural unit (A1) is less than the above lower limit, the fluorine content in the resulting fluorine-containing copolymer (A) tends to be excessive, and the cured product obtained by curing the photosensitive fluorine-containing resin composition Antifouling properties may not be sufficient. When the proportion of the structural unit (A1) exceeds the above upper limit, the solubility of the resulting fluorine-containing copolymer (A) in an organic solvent is remarkably lowered, and the photosensitive fluorine-containing resin composition is cured. The cured product obtained may have low transparency and adhesion to the substrate.

(A2) Monomer:
The monomer (a2) used in the present invention is a monomer copolymerizable with the monomer (a1) and contains at least one substituent selected from a hydroxyl group, an epoxy group, and a carboxyl group Monomer.

Examples of the hydroxyl group-containing monomer include hydroxyl group-containing vinyl ethers such as hydroxyethyl vinyl ether and hydroxybutyl vinyl ether; hydroxyl group-containing (meth) acrylic acid esters such as hydroxyethyl (meth) acrylate; p-hydroxystyrene, m-hydroxy Examples thereof include phenolic hydroxyl group-containing monomers such as styrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, and o-isopropenylphenol.

  Moreover, in this invention, a fluorine-containing copolymer (A) can also be manufactured using the monomer which protected the hydroxyl group of the said hydroxy styrenes, for example with t-butyl group or an acetoxy group. Specifically, after copolymerizing the monomer (a1) and a hydroxystyrene having a hydroxyl group protected, the obtained copolymer is deprotected by a known method such as deprotection under an acid catalyst. Thus, a fluorine-containing copolymer (A) containing a structural unit derived from hydroxystyrene is obtained.

Examples of the epoxy group-containing monomer include epoxy group-containing vinyl ethers such as glycidyl vinyl ether; and epoxy group-containing (meth) acrylic esters such as glycidyl (meth) acrylate.
Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid.

These compounds can be used alone or in admixture of two or more.
The structural unit (A2) derived from such a monomer (a2) is usually 2 to 80% by weight, preferably 5 to 75% by weight, more preferably 10 to 10% in the fluorine-containing copolymer (A). It is desirable to be included in an amount of 60% by weight. When the proportion of the structural unit (A2) is less than the lower limit, the patterning property of the photosensitive fluororesin composition is not sufficient, and when the ratio exceeds the upper limit, the cured product obtained by curing the photosensitive fluororesin composition is used. There is concern about a decrease in water resistance.

(A3) Monomer:
The monomer (a3) used in the present invention is not particularly limited as long as it is a monomer copolymerizable with the monomer (a1) and / or (a2). For example, a vinyl compound, (meth) Acrylic esters, unsaturated carboxylic esters, (meth) acrylamides and unsaturated nitriles.

As a vinyl compound, for example,
Methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl vinyl ether, lauryl vinyl ether, Alkyl vinyl ethers or cycloalkyl vinyl ethers such as cetyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether;
Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl versatic acid, vinyl stearate, benzoic acid;
Α-olefins such as ethylene, propylene and isobutene;
Styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-tert-butylstyrene, diisopropenylbenzene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 1 , 1-diphenylethylene, p-methoxystyrene, N, N-dimethyl-p-aminostyrene, N, N-diethyl-p-aminostyrene, vinylpyridine, vinylimidazole and the like.

As (meth) acrylic acid ester, for example,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, Amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, Decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl ) Acrylates, alkyl such isostearyl (meth) acrylate (meth) acrylates;
Phenoxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate;
Alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methoxybutyl (meth) acrylate;
Polyethylene glycol (meth) acrylates such as polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate;
Polypropylene glycol (meth) acrylates such as polypropylene glycol mono (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, nonylphenoxy polypropylene glycol (meth) acrylate;
Cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, bornyl (meth) acrylate, isobornyl ( Cycloalkyl (meth) acrylates such as (meth) acrylate and tricyclodecanyl (meth) acrylate;
Benzyl (meth) acrylate;
Tetrahydrofurfuryl (meth) acrylate is mentioned.

  Examples of (meth) acrylamide include acryloylmorpholine, diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, and tert. -Octyl (meth) acrylamide, 7-amino-3,7-dimethyloctyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide are mentioned.

  Examples of the unsaturated carboxylic acid ester include methyl crotonate, ethyl crotonate, propyl crotonate, butyl crotonate, methyl cinnamate, ethyl cinnamate, propyl cinnamate, butyl cinnamate, dimethyl itaconate, Examples include diethyl itaconate, dimethyl maleate, diethyl maleate, dimethyl fumarate and diethyl fumarate.

  Examples of unsaturated nitriles include (meth) acrylonitrile, α-chloroacrylonitrile, α-chloromethylacrylonitrile, α-methoxyacrylonitrile, α-ethoxyacrylonitrile, crotonic acid nitrile, cinnamic nitrile, itaconic acid dinitrile, maleic acid dinitrile. And fumarate dinitrile.

These compounds can be used alone or in admixture of two or more.
The structural unit (A3) derived from such a monomer (a3) is a fluorine-containing copolymer (A).
It is desirable that it is contained in an amount of usually 1 to 90% by weight, preferably 5 to 80% by weight, more preferably 10 to 70% by weight. If the proportion of the structural unit (A3) is less than the above lower limit, the type of solvent that can be used may be limited, and if it exceeds the above upper limit, the patterning property of the photosensitive fluorine-containing resin composition is not sufficient and is cured. There is concern about a decrease in water resistance of the cured product obtained in this manner.

(A4) Monomer:
The monomer (a4) used in the present invention is a monomer that contains a silicon atom and is copolymerizable with at least one monomer of the monomers (a1) to (a3). Although it does not restrict | limit, the compound which can introduce | transduce a siloxane structure into a fluorine-containing copolymer (A) is preferable, for example, an azo group containing polysiloxane compound is mentioned. This azo group-containing polysiloxane compound is an azo group-containing compound that can be easily thermally cleaved represented by -N = N-, and is produced by, for example, the method described in JP-A-6-93100. It can be done. Specific examples include compounds having the following structure.

(In the formula, m is 0 or an integer of 1 to 200, and n is an integer of 1 to 50).
Moreover, "VPS-0501", "VPS-1001" (above, Wako Pure Chemical Industries Ltd.) etc. can be used as a commercial item.

  This azo group-containing polysiloxane compound is also a thermal radical generator and acts as a polymerization initiator in the copolymerization reaction for obtaining the fluorine-containing copolymer (A). In this case, this azo group-containing polysiloxane compound and other radical polymerization initiator may be used in combination.

  The siloxane structure is usually contained in the fluorine-containing copolymer (A) in an amount of 0 to 20% by weight, preferably 0.1 to 15% by weight, more preferably 0.1 to 10% by weight. desirable. If the ratio of the siloxane structure is less than the above lower limit, the antifouling property of the cured product obtained by curing the photosensitive fluorine-containing resin composition may not be sufficient, and if it exceeds the above upper limit, the photosensitive fluorine-containing resin composition is cured. As a result, the adhesion of the cured product obtained to the base material is reduced, and repellency and the like are likely to occur when the coating material is applied.

Reactive emulsifier:
The fluorine-containing copolymer (A) used in the present invention may contain a structural unit (A5) derived from a reactive emulsifier. It is preferable to use a nonionic reactive emulsifier as the reactive emulsifier. As a nonionic reactive emulsifier, the compound represented by following formula (4) is mentioned, for example.

(In the formula, k = 1 to 20, m = 0 to 4, and n = 3 to 50).
In the present invention, as this nonionic reactive emulsifier, for example, “Adekalia Soap NE-5”, “Adekalia Soap NE-10”, “Adekalia Soap NE-20”, “Adekalia Soap NE-30”, Commercial products such as “ADEKA rear soap NE-40” (manufactured by Asahi Denka Kogyo Co., Ltd.) can be used.

  The structural unit (A5) is usually contained in the fluorinated copolymer (A) in an amount of 0 to 10% by weight, preferably 0.01 to 5% by weight, more preferably 0.05 to 2% by weight. It is desirable that When the proportion of the structural unit (A5) is within the above range, good coating properties and leveling properties can be obtained when the photosensitive fluorine-containing resin composition is used as a coating agent. When the proportion of the structural unit (A5) is less than the above lower limit, repelling or the like may occur when the coating agent is applied. When the proportion exceeds the above upper limit, the resulting photosensitive fluorine-containing resin composition is tacky. Since it becomes a thing, handling becomes difficult and when using it as a coating agent, moisture resistance falls.

(Polymerization of fluorinated copolymer (A))
The fluorine-containing copolymer (A) used in the present invention can be synthesized using the monomers (a1) and (a2) and, if necessary, the monomers (a3) and / or (a4). it can. Moreover, you may use a reactive emulsifier as needed. Preferred combinations of the monomers (a1) to (a4) include the following combinations.

(1) Combination of monomers (a1) and (a2):
For example,
Fluoroolefin / hydroxyl group-containing vinyl ether,
Fluoroolefin / epoxy group-containing vinyl ether,
Fluoroolefin / unsaturated carboxylic acid,
Fluoroolefin and perfluoro (alkyl vinyl ether) / hydroxyl-containing vinyl ether,
Fluorine-containing (meth) acrylic acid ester / hydroxyl group-containing (meth) acrylic acid ester,
Fluorine-containing (meth) acrylic acid ester / phenolic hydroxyl group-containing monomer,
Fluorine-containing (meth) acrylate / epoxy group-containing (meth) acrylate,
Fluorine-containing (meth) acrylic acid ester / unsaturated carboxylic acid,
Fluorine-containing (meth) acrylic acid ester / hydroxyl group-containing (meth) acrylic acid ester and unsaturated carboxylic acid,
Examples thereof include fluorine-containing (meth) acrylic acid ester / phenolic hydroxyl group-containing monomer and unsaturated carboxylic acid.

(2) Combination of monomers (a1), (a2) and (a3):
For example,
Fluoroolefin / hydroxyl group-containing vinyl ether / alkyl vinyl ether,
Fluoroolefin / epoxy group-containing vinyl ether / alkyl vinyl ether,
Fluoroolefin / unsaturated carboxylic acid / alkyl vinyl ether,
Fluoroolefin and perfluoro (alkyl vinyl ether) / hydroxyl-containing vinyl ether / alkyl vinyl ether,
Fluorine-containing (meth) acrylic acid ester / hydroxyl group-containing (meth) acrylic acid ester / (meth) acrylic acid ester,
Fluorine-containing (meth) acrylic acid ester / phenolic hydroxyl group-containing monomer / (meth) acrylic acid ester,
Fluorine-containing (meth) acrylic acid ester / epoxy group-containing (meth) acrylic acid ester / (meth) acrylic acid ester,
Fluorine-containing (meth) acrylic acid ester / unsaturated carboxylic acid / (meth) acrylic acid ester,
Fluorine-containing (meth) acrylic acid ester / hydroxyl group-containing (meth) acrylic acid ester and unsaturated carboxylic acid / (meth) acrylic acid ester,
Examples thereof include fluorine-containing (meth) acrylic acid ester / phenolic hydroxyl group-containing monomer and unsaturated carboxylic acid / (meth) acrylic acid ester.

(3) Combination of monomers (a1), (a2) and (a4):
For example,
Fluoroolefin / hydroxyl group-containing vinyl ether / azo group-containing polydimethylsiloxane,
Fluoroolefin / epoxy group-containing vinyl ether / azo group-containing polydimethylsiloxane,
Fluoroolefin / unsaturated carboxylic acid / azo group-containing polydimethylsiloxane,
Fluoroolefin and perfluoro (alkyl vinyl ether) / hydroxyl group-containing vinyl ether / azo group-containing polydimethylsiloxane,
Fluorine-containing (meth) acrylic acid ester / hydroxyl group-containing (meth) acrylic acid ester / azo group-containing polydimethylsiloxane,
Fluorine-containing (meth) acrylic acid ester / phenolic hydroxyl group-containing monomer / azo group-containing polydimethylsiloxane,
Fluorine-containing (meth) acrylic acid ester / epoxy group-containing (meth) acrylic acid ester / azo group-containing polydimethylsiloxane,
Fluorine-containing (meth) acrylic acid ester / unsaturated carboxylic acid / azo group-containing polydimethylsiloxane,
Fluorine-containing (meth) acrylic acid ester / hydroxyl group-containing (meth) acrylic acid ester and unsaturated carboxylic acid / azo group-containing polydimethylsiloxane,
Examples thereof include fluorine-containing (meth) acrylic acid ester / phenolic hydroxyl group-containing monomer and unsaturated carboxylic acid / azo group-containing polydimethylsiloxane.

(4) Combination of monomers (a1), (a2), (a3) and (a4):
For example,
Fluoroolefin / hydroxyl group-containing vinyl ether / alkyl vinyl ether / azo group-containing polydimethylsiloxane,
Fluoroolefin / epoxy group-containing vinyl ether / alkyl vinyl ether / azo group-containing polydimethylsiloxane,
Fluoroolefin / unsaturated carboxylic acid / alkyl vinyl ether / azo group-containing polydimethylsiloxane,
Fluoroolefin and perfluoro (alkyl vinyl ether) / hydroxyl group-containing vinyl ether / alkyl vinyl ether / azo group-containing polydimethylsiloxane,
Fluorine-containing (meth) acrylic acid ester / hydroxyl group-containing (meth) acrylic acid ester / (meth) acrylic acid ester / azo group-containing polydimethylsiloxane,
Fluorine-containing (meth) acrylic acid ester / phenolic hydroxyl group-containing monomer / (meth) acrylic acid ester / azo group-containing polydimethylsiloxane Fluorine-containing (meth) acrylic acid ester / epoxy group-containing (meth) acrylic acid ester / ( (Meth) acrylic acid ester / azo group-containing polydimethylsiloxane,
Fluorine-containing (meth) acrylic acid ester / unsaturated carboxylic acid / (meth) acrylic acid ester / azo group-containing polydimethylsiloxane,
Fluorine-containing (meth) acrylic acid ester / hydroxyl group-containing (meth) acrylic acid ester and unsaturated carboxylic acid / (meth) acrylic acid ester / azo group-containing polydimethylsiloxane,
And fluorine-containing (meth) acrylic acid ester / phenolic hydroxyl group-containing monomer and unsaturated carboxylic acid / (meth) acrylic acid ester / azo group-containing polydimethylsiloxane.

  The fluorine-containing copolymer (A) used in the present invention is polymerized by any polymerization method such as an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method or a solution polymerization method as long as it is a polymerization method using a radical polymerization initiator. can do. The polymerization operation mode can be appropriately selected from batch, semi-continuous or continuous operation modes. The polymerization conditions are not particularly limited, but for example, it is preferable to perform polymerization at a temperature in the range of 50 to 200 ° C. for a polymerization time of 1 to 100 hours.

Examples of the radical polymerization initiator include:
Diacyl peroxides such as acetyl peroxide and benzoyl peroxide;
Ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide;
Hydroperoxides such as hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide;
Dialkyl peroxides such as di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide;
peroxy esters such as tert-butyl peroxyacetate and tert-butyl peroxypivalate;
Azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile;
Examples thereof include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate.

The fluorine-containing copolymer (A) is preferably polymerized using a solvent. As a solvent that can be used at this time, for example,
Aliphatic carbonization such as n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane, methylcyclohexane A hydrogen-based solvent;
Benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propyl benzene, i-propyl benzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propyl benzene, n-amylnaphthalene, trimethylbenzene, etc. Aromatic hydrocarbon solvents;
Methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t- Pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-
Ethyl hexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, Monoalcohol solvents such as cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, cresol;
Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4, 2- Polyhydric alcohol solvents such as ethyl hexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin;
Acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-i- Ketone solvents such as butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, and fenchon;
Ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol Monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol diethyl ether , Diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono Ether solvents such as propyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran;
Diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec -Pentyl, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl acetate Ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl acetate Chill ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglycol acetate, ethyl propionate, N-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, phthalic acid Ester solvents such as diethyl;
Nitrogen-containing solvents such as N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone;
Examples thereof include sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propane sultone. These can be used alone or in combination of two or more.

  The reaction solution containing the fluorine-containing copolymer (A) obtained by the polymerization method can be used as a raw material for the photosensitive fluorine-containing resin composition as it is, but after appropriately post-treating the reaction solution, May be used. As this post-treatment, for example, a reprecipitation treatment can be carried out, and then a treatment of dissolving the purified fluorine-containing copolymer (A) in a solvent can be carried out. Examples of the reprecipitation treatment include a purification treatment in which the reaction solution is dropped into an insolubilizing solvent for the fluorinated copolymer (A) such as alcohol to solidify the fluorinated copolymer (A). Moreover, you may implement residual monomer removal from the obtained reaction solution as said post-process.

  Although the molecular weight of the fluorine-containing copolymer (A) used for this invention is not specifically limited, The weight average molecular weight (Mw) of polystyrene conversion measured by the gel permeation chromatography (GPC) method is 200,000 or less normally. , Preferably it is 5,000-100,000. If the weight average molecular weight is too small, physical properties such as heat resistance and elongation of the cured product obtained by curing the photosensitive fluorine-containing resin composition will decrease, and if too large, other components in the photosensitive fluorine-containing resin composition And the patterning characteristics of the photosensitive fluorine-containing resin composition may deteriorate. In the present invention, the fluorinated copolymer (A) is used in an amount of 5 to 70% by weight, preferably 10 to 60% by weight, based on the total amount of the photosensitive fluorinated resin composition.

(B) Compound having at least two amino groups alkylated in the molecule:
The compound having at least two or more alkyl etherified amino groups in the molecule (hereinafter referred to as “crosslinking agent (B)”) used in the present invention is a fluorine-containing copolymer (A) and / or described later. It is a compound that can react with the phenol resin (E) to form a cured product.

  Examples of such a crosslinking agent (B) include all or one of active methylol groups such as (poly) methylolated melamine, (poly) methylolated glycoluril, (poly) methylolated benzoguanamine, and (poly) methylolated urea. And nitrogen-containing compounds obtained by alkyl etherification of the part. Here, examples of the alkyl group include a methyl group, an ethyl group, a butyl group, and combinations thereof.

The crosslinking agent (B) may contain an oligomer component in which a part of the compound having at least two amino groups alkylated in the molecule is self-condensed.
Specific examples of the crosslinking agent (B) include hexamethoxymethylated melamine, hexabutoxymethylated melamine, tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril, and the like. , Or a mixture of two or more.

  The crosslinking agent (B) is used in an amount of 1 to 200 parts by weight, preferably 5 to 100 parts by weight, with respect to 100 parts by weight of the total amount of the fluorine-containing copolymer (A) and the phenol resin (E). Used. When the blending amount of the crosslinking agent (B) is less than the above lower limit, the photosensitive fluorine-containing resin composition is not sufficiently cured by exposure, the patterning characteristics of the photosensitive fluorine-containing resin composition are deteriorated, or the photosensitive In some cases, the scratch resistance of a cured product obtained by curing the fluororesin composition may be reduced. If the upper limit is exceeded, the resolution of the photosensitive fluororesin composition may be reduced.

(C) Photosensitive acid generator:
The photosensitive acid generator (C) used in the present invention is a compound that generates an acid upon irradiation with radiation or the like, and the alkyl ether group in the crosslinking agent (B) and the fluorine-containing copolymer are generated by the catalytic action of this acid. A negative pattern can be formed by cross-linking the polymer (A) and / or the phenol ring in the phenol resin (E) with a dealcoholization reaction.

  The photosensitive acid generator (C) is not particularly limited as long as it is a compound that generates an acid upon irradiation with radiation or the like. For example, an onium salt compound, a halogen-containing compound, a diazoketone compound, a sulfone compound, a sulfonic acid compound, a sulfone Examples include imide compounds and diazomethane compounds.

  Examples of the onium salt compounds include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like. Among such onium salts, specifically, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, triphenylsulfonium trifrio L-methanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, 4-t-butylphenyl diphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyl diphenylsulfonium p-toluenesulfonate, 4,7- Di-n-butoxynaphthyltetrahydrothiophenium triflate Etc. b methanesulfonate is preferred.

  Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds. Among such halogen-containing compounds, specifically, 1,10-dibromo-n-can, 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, phenyl-bis (trichloromethyl) ) -S-triazine, 4-methoxyphenyl-bis (trichloromethyl) -s-triazine, styryl-bis (trichloromethyl) -s-triazine, naphthyl-bis (trichloromethyl) -s-triazine, etc. Is preferred.

  Examples of the diazoketone compound include 1,3-diketo-2-diazo compounds, diazobenzoquinone compounds, diazonaphthoquinone compounds, and the like. Among such diazoketone compounds, specifically, 1,2-naphthoquinonediazide-4-sulfonic acid ester compounds of phenols are preferable.

  Examples of the sulfone compounds include β-ketosulfone compounds, β-sulfonylsulfone compounds, and α-diazo compounds of these compounds. Among such sulfone compounds, specifically, 4-trisphenacylsulfone, mesitylphenacylsulfone, bis (phenacylsulfonyl) methane, and the like are preferable.

  Examples of the sulfonic acid compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates. Among such sulfonic acid compounds, specifically, benzoin tosylate, pyrogallol tris trifluoromethane sulfonate, o-nitrobenzyl trifluoromethane sulfonate, o-nitrobenzyl p-toluene sulfonate and the like are preferable.

Specific examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoro Methylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide and the like.

  Specific examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, and bis (phenylsulfonyl) diazomethane.

  Such an acid generator (C) can be used individually by 1 type or in mixture of 2 or more types. Moreover, the compounding amount of the acid generator (C) is such that the fluorine-containing copolymer (A), the crosslinking agent (B) and the phenol are used from the viewpoint of ensuring the sensitivity, resolution, pattern shape, etc. of the photosensitive fluorine-containing resin composition. The amount is usually 0.1 to 10 parts by weight, preferably 0.3 to 5 parts by weight, based on 100 parts by weight of the total amount with the resin (E). In this case, if the blending amount of the acid generator (C) is less than the above lower limit, the photosensitive fluorine-containing resin composition may be insufficiently cured and heat resistance may be reduced. The transparency of the fluororesin composition to radiation may be reduced, and the pattern shape may be deteriorated.

(D) Solvent:
The solvent (D) used in the present invention is added in an appropriate amount in order to improve the handleability of the photosensitive fluorine-containing resin composition and to adjust the viscosity and storage stability. Such a solvent (D) is not particularly limited as long as it is an organic solvent that does not impair the object of the present invention.
Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate;
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether;
Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate;
Cellosolves such as ethyl cellosolve and butyl cellosolve;
Carbitols such as butyl carbitol;
Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate and isopropyl lactate;
Aliphatic carboxylic acid esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, isobutyl propionate;
Esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate;
Aromatic hydrocarbons such as toluene and xylene;
Ketones such as 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone;
Amides such as N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone;
Examples include lactones such as γ-butyrolacun.

These solvent (D) can be used individually by 1 type or in mixture of 2 or more types.
(E) Phenolic resin:
In the present invention, when the alkali solubility of the fluorine-containing copolymer (A) is insufficient, the phenol resin (E) can be used in combination. As such a phenol resin (E),
Examples thereof include novolak resins, polyhydroxystyrene and copolymers thereof, and low molecular phenol compounds. The compounding quantity of such a phenol resin (E) can be suitably determined so that the photosensitive fluorine-containing resin composition exhibits sufficient alkali solubility. Specifically, the phenol resin (E) can be used in the range of 0 to 200 parts by weight with respect to 100 parts by weight of the fluorine-containing copolymer (A). As a result, the patternability of the photosensitive fluorine-containing resin composition is improved.

(F) Epoxy compound:
In the present invention, an oxirane ring-containing compound (hereinafter referred to as “epoxy compound (F)”) can also be used. The epoxy compound (F) is not particularly limited as long as it contains an oxirane ring in the molecule. Specifically, the phenol novolac epoxy resin, the cresol novolac epoxy resin, the alicyclic epoxy resin, the aliphatic An epoxy resin etc. are mentioned. These epoxy compounds (F) are preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight with respect to 100 parts by weight of the total amount of the fluorine-containing copolymer (A) and the phenol resin (E). Can be used. As a result, the hardness and durability of the coating film are improved.

(G) Other additives:
The photosensitive fluorine-containing resin composition according to the present invention may contain other additives such as metal oxide fine particles, crosslinked fine particles, adhesion aids, sensitizers, leveling agents, and colorants.

  In the present invention, metal oxide fine particles and crosslinked fine particles having a diameter of usually 5 to 500 nm, preferably 10 to 100 nm are used. The blending amount of these fine particles is preferably 0 to 50 parts by weight with respect to 100 parts by weight of the total amount of the fluorinated copolymer (A) and the crosslinking agent (B). When the blending amount of the fine particles exceeds 50 parts by weight, the strength and heat resistance of the coating film are lowered, and the compatibility with other components in the photosensitive fluorine-containing resin composition is lowered.

Examples of the metal oxide particles include SrTiO ₃ , FeTiO ₃ , WO ₃ , SnO ₂ , Bi ₂ O ₃ , In ₂ O ₃ , ZnO, Fe ₂ O ₃ , RuO ₂ , CdO, CdS, CdSe, GaP,
GaAs, CdFeO ₃ , MoS ₂ , LaRhO ₃ , GaN, CdP, ZnS, ZnSe,
ZnTe, Nb ₂ O ₅ , ZrO ₂ , InP, GaAsP, InGaAlP, AlGaAs,
PbS, InAs, PbSe, InSb, SiO 2, Al 2 0 3, AlGaAs, Al (O
H) ₃ , Sb ₂ O ₅ , Si ₃ N ₄ , Sn—In ₂ O ₃ , Sb—In ₂ O ₃ , MgF, CeF ₃ , CeO ₂ , 3Al ₂ O ₃ .2SiO ₂ , BeO, SiC, AlN, Fe, Co, Co—FeO _x ,
_{CrO 2, Fe 4 N, BaTiO} 3, BaO-Al 2 O 3 -SiO 2, Ba _{ferrite, SmCO 5, YCO 5, CeCO} 5, PrCO 5, Sm 2 CO 17, Nd 2 Fe 14 B, Al 4 O 3 , Α-Si, SiN ₄ , CoO, Sb—SnO ₂ , Sb ₂ O ₅ , MnO ₂ , MnB, Co ₃ O ₄ , Co ₃ B, LiTaO ₃ , MgO, MgAl ₂ O ₄ , BeAl ₂ O ₄ , ZrSiO _{4, ZnSb, PbTe, GeSi,} FeSi 2, CrSi 2, CoSi 2, MnSi 1.73, Mg 2 Si, β-B, BaC, BP, TiB 2, ZrB 2, HfB 2, Ru 2 Si 3, TiO 2 ( rutile type, _{anatase), TiO 3, PbTiO 3,} Al 2 TiO 5, Zn 2 SiO 4, Zr 2 SiO 4, 2MgO 2 -Al 2 O 3 -5SiO 2, Nb 2 O 5, Li 2 O-Al 2 O ₃ 4SiO _2, Mg ferrite, Ni ferrite, Ni-Zn ferrite, Li ferrite, etc. Sr ferrite. By using such metal oxide particles, optical properties such as refractive index of a cured film obtained by curing a photosensitive fluorine-containing resin composition, electrical properties such as dielectric constant, insulation, and conductivity can be controlled. Can be controlled.

  The crosslinked fine particles can be obtained, for example, by emulsion polymerization of a radical polymerizable monomer. Specifically, for example, styrene / divinylbenzene copolymer, (meth) acrylic acid ester / polyfunctional (meth) acrylic acid ester copolymer and the like can be mentioned.

Examples of the adhesion assistant used in the present invention include tetramethoxysilane, tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 2-hydroxy. Ethyltrimethoxysilane, 2-hydroxyethyltritriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxy Propyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane How the various silane coupling agents and the like. By using these adhesion assistants, the tackiness of the cured film obtained by curing the photosensitive fluorine-containing resin composition and the adhesion to the substrate are improved.
(Photosensitive fluorine-containing resin composition)
The photosensitive fluorine-containing resin composition according to the present invention comprises the fluorine-containing copolymer (A), the crosslinking agent (B), the photosensitive acid generator (C) and the solvent (D), and optionally phenol. Resin (E), epoxy compound (F), reactive emulsifier and other additives are contained. A cured product obtained by curing such a photosensitive fluorine-containing resin composition is excellent in preventing water repellency oil components and fingerprints from being adhered or wiped off, and also excellent in properties such as thermal shock and adhesion. Yes. Furthermore, the said photosensitive fluorine-containing resin composition is excellent in the patternability by alkali image development.

Since the photosensitive fluorine-containing resin composition according to the present invention has the above characteristics, it can be suitably used as a surface protective film for displays, semiconductor elements and the like.
<Photosensitive fluorinated resin cured film>
(Method for producing cured film)
The cured film according to the present invention can be produced, for example, by the following method using the photosensitive fluorine-containing resin composition.

  The photosensitive fluorine-containing resin composition according to the present invention is applied to a support (a copper foil with resin, a copper-clad laminate, a silicon wafer with a metal sputtered film, an alumina substrate, a glass plate, a plastic plate, etc.) Dry to evaporate the solvent and form a coating film. Then, it exposes through a desired mask pattern and heat-processes (this heat processing is hereafter called "PEB"), and promotes reaction with a fluorine-containing copolymer (A) and a crosslinking agent (B). . Subsequently, it develops with an alkaline developing solution, and a desired pattern is obtained by dissolving and removing an unexposed part. Furthermore, heat treatment is performed to develop antifouling properties and the like to obtain a cured film such as an antifouling film. If patterning is not necessary, the entire surface may be exposed and heat-treated without a mask.

  As a method for applying the photosensitive fluorine-containing resin composition to the support, for example, a coating method such as a dipping method, a spray method, a bar coating method, a roll coating method, or a spin coating method can be used. The coating thickness can be appropriately controlled by adjusting the coating means and the solid content concentration and viscosity of the composition solution.

Examples of the radiation used for the exposure include an exposure light source having an irradiation light wavelength of 300 nm to 500 nm, for example, ultraviolet rays such as a low pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a g-line stepper, and an i-line stepper, an electron beam, and a laser beam. The exposure amount is appropriately determined depending on the light source used, the resin film thickness, and the like. For example, in the case of ultraviolet irradiation from a high-pressure mercury lamp, a resin film thickness of 1 to 50 μm is preferably about 1,000 to 50,000 J / m ² .

After the exposure, a post-exposure heating (PEB) treatment is performed to accelerate the curing reaction between the fluorine-containing copolymer (A) and the crosslinking agent (B) by the acid generated from the photosensitive acid generator (C). I do. The conditions are appropriately determined depending on the blending amount of the photosensitive fluorine-containing resin composition and the resin film thickness.
Usually, it is 70-150 degreeC, Preferably it is 80-120 degreeC, and about 1 to 60 minutes are preferable.

  Then, it develops with an alkaline developing solution, a desired pattern is formed by melt | dissolving and removing an unexposed part. Examples of the developing method include a shower developing method, a spray developing method, an immersion developing method, a paddle developing method, and the like. The developing conditions are preferably 20 to 40 ° C. and about 1 to 10 minutes. In addition, after developing with an alkaline developer, it is washed with water and dried.

  Examples of the alkaline developer include an alkaline aqueous solution in which an alkaline compound such as sodium hydroxide, potassium hydroxide, ammonia water, tetramethylammonium hydroxide, and choline is dissolved in water so as to have a concentration of about 1 to 10% by weight. Is mentioned. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution.

  Furthermore, in order to sufficiently develop the characteristics as an insulating film after development, it is preferable to sufficiently cure the photosensitive fluorine-containing resin composition by performing a heat treatment. Curing conditions are not particularly limited, but the photosensitive fluorine-containing resin composition is cured by heating at a temperature in the range of 50 to 200 ° C. for about 30 minutes to 10 hours depending on the use of the cured film. Is preferred.

  Moreover, you may heat in two steps in order to fully advance hardening of the photosensitive fluorine-containing resin composition, or to prevent the deformation | transformation of the obtained pattern shape. For example, in the first stage, heating is performed at a temperature in the range of 50 to 120 ° C. for about 5 minutes to 2 hours, and in the second stage, heating is performed at a temperature in the range of 80 to 200 ° C. for about 10 minutes to 10 hours. To cure.

In the heat treatment, a hot plate, an oven, an infrared furnace, or the like can be used as heating equipment.
(Curing film and article having the same)
The cured film according to the present invention is obtained by, for example, the above production method using the photosensitive fluorine-containing resin composition, and is excellent in preventing or wiping off water-repellent oil components and fingerprints. Excellent properties such as thermal shock and adhesion. Therefore, it is suitably used as a water repellent film or an antifouling film.

  Moreover, the cured film which has a fine pattern excellent in the resolution as shown in FIG. 1 can be obtained by forming the cured film which has a pattern using the said photosensitive fluorine-containing resin composition.

  The article according to the present invention is an article having the cured film on its surface. In particular, when the cured film is an antifouling film, the article is effective as an antifouling article. Examples of such articles include displays such as CRT, PDP, and LCD, touch panels, semiconductor elements, fingerprint reading sensors, and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by this Example. In the following examples and comparative examples, “parts” means parts by weight unless otherwise specified.

First, the evaluation method of each characteristic of the hardened | cured material implemented in the Example and the comparative example is demonstrated.
<Evaluation method>
Antifouling property:
A photosensitive resin composition was spin-coated on a 6-inch silicon wafer, and then heated on a hot plate at 110 ° C. for 3 minutes to produce a uniform coating film having a thickness of 2 μm. Thereafter, using the aligner, the coating film was irradiated with ultraviolet rays from a high-pressure mercury lamp through a pattern mask so that the exposure amount at a wavelength of 350 nm was 5,000 J / m ² . Then 11 on the hot plate
The film was heated at 0 ° C. for 3 minutes (post-exposure heating: PEB), and heated at 180 ° C. for 1 hour in a convection oven to obtain a cured film.

The contact angle of pure water with the obtained cured film was measured. Further, the wiping property of magic ink and fingerprint was evaluated according to the following criteria.
(Wiping property test)
Magic ink or fingerprints were attached to the surface of the obtained cured film, and the surface of the cured film was rubbed with Kimwipe (manufactured by Tokuma Kimberley). The wipeability was evaluated by the number of times the magic ink or fingerprint was wiped off.

AA: Wiped off once A: Wiped off 2-5 times B: Wiped off 5-10 times C: Wiped off more than 10 times or completely wiped off Abrasion resistance:
A photosensitive resin composition was spin-coated on a 6-inch silicon wafer, and a cured film was produced in the same manner as the antifouling property evaluation sample. The surface of the obtained cured film was subjected to 10 cycles of # 0000 steel wool under a load of 500 g / cm ² , and then the presence or absence of scratches on the surface of the cured film was observed.

AA: The cured film was not peeled off or scratched. A: The cured film surface had slight streak wounds. B: The cured film surface had many streak wounds. C : Cured film peeled off Adhesion:
A photosensitive resin composition was spin-coated on a 6-inch silicon wafer, and a cured film was produced in the same manner as the antifouling property evaluation sample. A wafer (hereinafter referred to as “test substrate”) coated with the obtained cured film was put into a PCT tester (manufactured by Tabay Espec Co., Ltd.) and treated for 168 hours under the condition of 121 ° C./100% RH. After that, the test substrate was placed on the grid tape method (JIS
K5400; 10 × 10 squares, 1 square is 1 mm × 1 mm), and a cross-cut test was performed, and adhesion was confirmed by the proportion of squares in which the cured film did not peel after the test for all squares.

Thermal shock resistance:
A photosensitive resin composition was spin-coated on a 6-inch silicon wafer, and a cured film was produced in the same manner as the antifouling property evaluation sample. The wafers coated with the obtained cured film were subjected to a resistance test using a thermal shock tester (manufactured by Tabai Espec Co., Ltd.) at -55 ° C / 30 minutes to 150 ° C / 30 minutes as one cycle. The number of cycles until a defect such as a crack occurred in the cured film was confirmed.

Resolution:
A photosensitive resin composition was spin-coated on a 6-inch silicon wafer and heated on a hot plate at 110 ° C. for 3 minutes to prepare a uniform coating film having a thickness of 2 μm. Thereafter, an aligner (MAS-150 manufactured by Suss Mitotec) was used to apply ultraviolet rays from a high-pressure mercury lamp through a pattern mask so that the exposure amount at a wavelength of 350 nm was 3,000 to 6,000 J / m ^2. Irradiated. Next, after heating (PEB) at 110 ° C. for 3 minutes on a hot plate, the wafer having the coating film after PEB was developed by immersing in an aqueous 2.38 wt% tetramethylammonium hydroxide solution at 23 ° C. for 90 seconds. The minimum dimension of the obtained pattern was taken as the resolution.

Next, each raw material used in Examples and Comparative Examples will be described.
<Fluorine-containing copolymer (A)>
(Synthesis Example 1)
After sufficiently replacing the inside of a stainless steel autoclave with an internal volume of 1.5 liters with a magnetic stirrer with nitrogen gas, 375 g of methyl isobutyl ketone, 39.2 g of ethyl vinyl ether (EVE), 47.9 g of 2-hydroxyethyl vinyl ether (HEVE), Furthermore, 50.0 g of Adekari Soap NE-30 (Asahi Denka Kogyo Co., Ltd.) as a nonionic reactive emulsifier, 5.0 g of 4-isopropylidene-1-methylcyclohexene-1 as a chain transfer agent, azo group-containing polysiloxane As a polymerization initiator, 2.5 g of VPS-0501 (manufactured by Wako Pure Chemical Industries, Ltd.) and 12.5 g of dilauroyl peroxide (LPO) were charged. Next, 196.64 g of hexafluoropropylene (HFP) was charged and the temperature increase was started. The pressure when the temperature in the autoclave reached 75 ° C. was 9.0 × 10 ⁵ Pa. The reaction was continued for 13 hours at 75 ° C. with stirring. Thereafter, when the pressure dropped to 6.1 × 10 ⁵ Pa, the autoclave was cooled with water to stop the reaction. After leaving it to stand at room temperature, the unreacted monomer was released and the autoclave was opened to obtain a polymer solution. The nonvolatile content concentration (active ingredient concentration) in this polymer solution was 33.1% as a result of measuring the polymer solution after drying it at 150 ° C. for 5 minutes on an aluminum dish.

  The obtained polymer solution was put into a methanol / water mixed solvent to precipitate a polymer, washed with a methanol / water mixed solvent, and vacuum dried at 50 ° C. to obtain 157 g of a fluorinated copolymer.

  Next, 120 g of this fluorinated copolymer, 180 g of methyl butyl ketone, 43.5 g of trimellitic anhydride, and 1.0 g of triethylbenzylammonium chloride were charged into a glass reactor equipped with a stirrer having an internal volume of 0.5 liter. The temperature started. The reaction was continued at 110 ° C. for 2 hours while stirring as it was to synthesize a fluorine-containing copolymer having a carboxyl group (hereinafter referred to as fluorine-containing copolymer (A-1)). This fluorine-containing copolymer (A-1) is dissolved in tetrahydrofuran (THF) to prepare a 0.5% solution. Using this solution, the number average molecular weight (Mn) in terms of polystyrene is determined by gel permeation chromatography. When calculated, it was 7,600.

(Synthesis Example 2)
The inside of a 1.5 liter stainless steel autoclave with a magnetic stirrer was sufficiently replaced with nitrogen gas, and then charged with 810 g of ethyl acetate, 102.6 g of ethyl vinyl ether (EVE), and 81.6 g of crotonic acid (CA), and further azo 2.5 g of VPS-0501 (manufactured by Wako Pure Chemical Industries, Ltd.) as the group-containing polysiloxane and 16.2 g of dilauroyl peroxide (LPO) as the polymerization initiator were charged. Next, 351.064 g of hexafluoropropylene (HFP) was charged and the temperature increase was started. The pressure when the temperature in the autoclave reached 70 ° C. was 7.6 × 10 ⁵ Pa. The reaction was continued for 12 hours at 70 ° C. with stirring. Then, when the pressure dropped to 6.3 × 10 ⁵ Pa, the autoclave was cooled with water,
The reaction was stopped. After leaving it to stand at room temperature, the unreacted monomer was released and the autoclave was opened to obtain a polymer solution. The non-volatile content concentration (active ingredient concentration) in this polymer solution was 21.1% as a result of measuring the polymer solution after drying it at 150 ° C. for 5 minutes on an aluminum dish.

The obtained polymer solution was poured into water to precipitate a polymer, washed with water, and vacuum dried at 50 ° C. to give 240 g of a fluorine-containing copolymer (hereinafter referred to as “fluorine-containing copolymer (A- 2) "). The number average molecular weight (Mn) of the fluorinated copolymer (A-2) was determined in the same manner as in Synthesis Example 1 and was 1,800.

(Synthesis Example 3)
The inside of a glass reactor equipped with a stirrer with an internal volume of 0.5 liter was sufficiently replaced with nitrogen gas, and then 150 g of butyl acetate and 2- (perfluorooctyl) ethyl acrylate (FA-108: manufactured by Osaka Organic Chemical Industry Co., Ltd.) 18 g, ethyl acrylate (EA) 28 g, isobornyl acrylate (IBOA) 9 g, 2-acryloyloxyethyl hexahydrophthalic acid (HOA-HH: manufactured by Kyoeisha Chemical Co., Ltd.) 45 g were charged as a polymerization initiator. 5.0 g of isobutyronitrile (AIBN) was charged and the temperature was raised. The reaction was continued for 6 hours at 75 ° C. with stirring, and further continued for 1 hour by raising the temperature to 100 ° C. Then, the reaction was stopped by cooling the reactor with water. The non-volatile content concentration (active ingredient concentration) in this polymer solution was 40.8% as a result of measurement by drying the polymer solution on an aluminum dish at 175 ° C. for 10 minutes.

  Further, the solvent was distilled off under reduced pressure to obtain 97.5 g of a fluorinated copolymer (hereinafter referred to as “fluorinated copolymer (A-3)”). The number average molecular weight (Mn) of this fluorinated copolymer (A-3) was determined in the same manner as in Synthesis Example 1 and was 8,000.

(Synthesis Example 4)
18 g of 2- (perfluorooctyl) ethyl acrylate (FA-108: manufactured by Osaka Organic Chemical Industry Co., Ltd.), 28 g of ethyl acrylate (EA), 9 g of isobornyl acrylate (IBOA), 2-acryloyloxyethyl hexahydrophthal Instead of 45 g of acid (HOA-HH: manufactured by Kyoeisha Chemical Co., Ltd.), 18 g of 2- (perfluorooctyl) ethyl acrylate (FA-108: manufactured by Osaka Organic Chemical Industry Co., Ltd.), 28 g of ethyl acrylate (EA), 9 g of isobornyl acrylate (IBOA), 45 g of 2-acryloyloxyethyl hexahydrophthalic acid (HOA-HH: manufactured by Kyoeisha Chemical Co., Ltd.), VPS-0501 (manufactured by Wako Pure Chemical Industries, Ltd.) as an azo group-containing polysiloxane A polymer solution was obtained in the same manner as in Synthesis Example 3 except that 1.0 g was used. The non-volatile content concentration (active ingredient concentration) in this polymer solution was 41.0% as a result of measuring the polymer solution after drying it at 175 ° C. for 10 minutes on an aluminum dish.

  Further, the solvent was distilled off under reduced pressure to obtain 98 g of a fluorinated copolymer (hereinafter referred to as “fluorinated copolymer (A-4)”). The number average molecular weight (Mn) of the fluorinated copolymer (A-4) was determined in the same manner as in Synthesis Example 1, and was 9,000.

(Synthesis Example 5)
18 g of 2- (perfluorooctyl) ethyl acrylate (FA-108: manufactured by Osaka Organic Chemical Industry Co., Ltd.), 28 g of ethyl acrylate (EA), 9 g of isobornyl acrylate (IBOA), 2-acryloyloxyethyl hexahydrophthal Instead of 45 g of acid (HOA-HH: manufactured by Kyoeisha Chemical Co., Ltd.), 18 g of 2- (perfluorooctyl) ethyl acrylate (FA-108: manufactured by Osaka Organic Chemical Industry Co., Ltd.), 18 g of ethyl acrylate (EA), Example of synthesis except that 9 g of isobornyl acrylate (IBOA), 45 g of 2-acryloyloxyethylhexahydrophthalic acid (HOA-HH: manufactured by Kyoeisha Chemical Co., Ltd.) and 10 g of 2-isopropenylphenol (PIPE) were used. 99 g of a fluorine-containing copolymer (hereinafter referred to as “fluorine-containing copolymer”). A-5) "hereinafter) was obtained. With respect to this fluorine-containing copolymer (A-5), the number average molecular weight (Mn) was determined in the same manner as in Synthesis Example 1, and it was 8,000.

(Synthesis Example 6)
150 g of ethyl lactate was used in place of butyl acetate, 18 g of 2- (perfluorooctyl) ethyl acrylate (FA-108: manufactured by Osaka Organic Chemical Industry Co., Ltd.), 28 g of ethyl acrylate (EA), isobornyl acrylate (IBOA) 9 g, instead of 45 g of 2-acryloyloxyethyl hexahydrophthalic acid (HOA-HH: manufactured by Kyoeisha Chemical Co., Ltd.), 2- (perfluorooctyl) ethyl acrylate (FA-108: Osaka Organic Chemical Industry Co., Ltd.) 18 g, ethyl acrylate (EA) 32 g, 2-acryloyloxyethyl hexahydrophthalic acid (HOA-HH: manufactured by Kyoeisha Chemical Co., Ltd.) 30 g, 2-isopropenylphenol (PIPE) 20 g, In the same manner as in Synthesis Example 4, 99 g of a fluorine-containing copolymer (hereinafter referred to as “fluorine-containing copolymer”). To give the body (A-6) "hereinafter). With respect to this fluorine-containing copolymer (A-6), the number average molecular weight (Mn) was determined in the same manner as in Synthesis Example 1, and was 9,000.

(Synthesis Example 7)
18 g of 2- (perfluorooctyl) ethyl acrylate (FA-108: manufactured by Osaka Organic Chemical Industry Co., Ltd.), 28 g of ethyl acrylate (EA), 9 g of isobornyl acrylate (IBOA), 2-acryloyloxyethyl hexahydrophthal Instead of 45 g of acid (HOA-HH: manufactured by Kyoeisha Chemical Co., Ltd.), 46 g of ethyl acrylate (EA), 9 g of isobornyl acrylate (IBOA), 2-acryloyloxyethyl hexahydrophthalic acid (HOA-HH: Kyoeisha) 99 g of a copolymer (hereinafter referred to as “copolymer (A-7)”) was obtained in the same manner as in Synthesis Example 3 except that 45 g of Chemical Co., Ltd. was used. The number average molecular weight (Mn) of this fluorinated copolymer (A-7) was determined in the same manner as in Synthesis Example 1, and was 10,500.

<Crosslinking agent (B)>
B1: Hexamethoxymethylmelamine (Mitsui Cytec Co., Ltd.,
(Product name: Cymel 300)
B2: Tetramethoxymethylglycoluril (Mitsui Cytec Co., Ltd.,
Product name: Cymel 1174)
<Acid generator (C)>
C1: 4,7-di-n-butoxynaphthyltetrahydrothiophenonium trifluoromethanesulfonate C2: styryl-bis (trichloromethyl) -s-triazine <Solvent (D)>
D1: Ethyl lactate <phenol resin (E)>
E1: Poly (p-hydroxystyrene) (manufactured by Maruzen Petrochemical Co., Ltd.)
Product name: Marca Linker S-2P)
<Epoxy resin (F)>
F1: Bisphenol A type epoxy resin (Japan Epoxy Resin Co., Ltd.,
Product name: EP-828)
F2: Bisphenol A type epoxy resin (Japan Epoxy Resin Co., Ltd.,
Product name: EP-152)
<Other additives (G)>
G1: Titanium oxide particles <Preparation and evaluation of photosensitive fluorine-containing resin composition>
<Examples 1 to 12>
In the proportions shown in Table 1, the fluorine-containing copolymer (A), the crosslinking agent (B), the acid generator (C), and if necessary, the phenol resin (E), the epoxy resin (F), and other additives ( G) was dissolved in the solvent (D) to prepare a photosensitive fluorine-containing resin composition. In addition, all the usage-amounts of component (A)-(C) and (E)-(G) are the values of solid content conversion.

The properties of this composition were measured according to the above evaluation methods. The obtained results are shown in Table 2.
<Comparative Example 1>
In the ratio shown in Table 1, the copolymer (A), the crosslinking agent (B), the acid generator (C), and the phenol resin (E) were dissolved in the solvent (D) to prepare a photosensitive resin composition.

  The properties of this composition were measured according to the above evaluation methods. The obtained results are shown in Table 2.

  By forming a protective film on the surface of an electronic device or the like using the photosensitive fluorine-containing resin composition according to the present invention, not only the surface of the electronic device or the like is protected from mechanical damage but also the surface of the electronic device or the like. Water-repellent oil components and fingerprints can be prevented from adhering to the surface, and when water-repellent oil components and fingerprints are attached, it can be easily wiped off. In the semiconductor element, malfunction due to attached components can be prevented.

FIG. 1 is a photomicrograph of a pattern obtained by patterning a cured film formed using the photosensitive fluorine-containing resin composition according to the present invention.

Claims (16)

  (A) a copolymer having a fluorine atom in the molecule, (B) a compound having at least two amino groups alkylated in the molecule, (C) a photosensitive acid generator, and (D) a solvent A photosensitive fluorine-containing resin composition comprising: The copolymer (A) having a fluorine atom in the molecule,
(A1) a structural unit derived from at least one monomer selected from fluorine-containing (meth) acrylic acid esters, fluoroolefins and fluoroolefin derivatives;
(A2) A copolymer containing a structural unit derived from at least one monomer selected from a hydroxyl group-containing monomer, an epoxy group-containing monomer, and a carboxyl group-containing monomer The photosensitive fluorine-containing resin composition according to claim 1. The copolymer (A) having a fluorine atom in the molecule,
(A3) A copolymer further containing a structural unit derived from at least one monomer selected from vinyl compounds, (meth) acrylic acid esters, unsaturated carboxylic acid esters, (meth) acrylamides and unsaturated nitriles The photosensitive fluorine-containing resin composition according to claim 2, wherein The photosensitive fluorine-containing resin composition according to claim 2 or 3, wherein the structural unit (A1) is a structural unit represented by the following formula (1):
(In formula (1), R ¹ represents hydrogen or a methyl group, and R ² represents a C 2-20 fluoroalkyl group). The photosensitive fluorine-containing resin composition according to claim 2 or 3, wherein the structural unit (A1) is a structural unit represented by the following formula (2):
(In formula (2), R ³ represents a fluorine atom, a perfluoroalkyl group having 1 to 10 carbon atoms, perfluoroalkoxy group or a chlorine atom having 1 to 10 carbon atoms).   The photosensitive fluorine-containing resin composition according to claim 2, wherein the structural unit (A2) is a structural unit derived from a monomer containing a phenolic hydroxyl group.   The photosensitive fluorine-containing resin composition according to any one of claims 1 to 6, wherein the copolymer (A) having a fluorine atom in the molecule further contains a silicon atom. The photosensitive fluorine-containing resin composition according to claim 7, wherein the copolymer (A) having a fluorine atom in the molecule contains a siloxane structural unit represented by the following formula (3):
(Wherein R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group or an aryl group having 6 to 20 carbon atoms).   The cured film obtained by hardening | curing the photosensitive fluorine-containing resin composition in any one of Claims 1-8.   The cured film which has a pattern obtained by hardening | curing the photosensitive fluorine-containing resin composition in any one of Claims 1-8.   The photosensitive fluorine-containing resin composition according to any one of claims 1 to 8 is applied to a support, dried to form a coating film, then exposed through a photomask, and then with an alkaline developer. A pattern forming method comprising a developing step.   The pattern forming method according to claim 11, wherein exposure is performed using an exposure light source having an irradiation light wavelength of 300 nm to 500 nm.   The cured film which has the pattern formed by the pattern formation method of Claim 11 or 12.   An antifouling film comprising the cured film according to claim 9, 10 or 13.   An article having the cured film according to claim 9, 10 or 13 formed on a surface thereof. An antifouling article having the antifouling film according to claim 14 formed on a surface thereof.