WO2016021501A1 - Photosensitive resin solution, method for forming patterning film, and method for finely working fluorine-containing resin film - Google Patents

Abstract

Provided is a photosensitive resin solution capable of easily forming a photosensitive resin film on a fluorine-containing resin film without creating film defects such as pinholes, without pretreating the fluorine-containing resin film surface. A photosensitive resin solution for forming a photosensitive resin film on a fluorine-containing resin film containing a fluorine-containing resin, the photosensitive resin solution containing a fluorine-containing polymer having a monomer (a1) having a fluoroalkyl group, and also having a monomer (a2) having an oxyalkylene group, wherein the proportion of the fluorine-containing polymer in the solid content in the solution is 0.001-20 mass%.

Description

Photosensitive resin solution, patterning film formation method, and fluorine-containing resin film fine processing method

The present invention relates to a photosensitive resin solution, a method for forming a patterning film, and a fine processing method for a fluorine-containing resin film.

A fluorine-containing resin film formed of an amorphous fluorine-containing resin (CYTOP (trademark, manufactured by Asahi Glass Co., Ltd.), Teflon (trademark) AF (manufactured by DuPont), etc.) that can be coated with a solution as a gate insulating film of an organic transistor, etc. It is used. In the insulating film made of the fluorine-containing resin film, a photosensitive resin film (photoresist) formed by applying a photosensitive resin solution (photoresist solution) on the insulating film is patterned, and the patterning film is used as a mask. It is necessary to etch the fluorine-containing resin film to form holes having a diameter of several μm to several tens of μm in the insulating film.

However, since a fluorine-containing resin film formed from a fluorine-containing resin having a high fluorine content such as an amorphous fluorine-containing resin is highly liquid repellent, a commercially available photosensitive resin solution cannot be directly applied. Conventionally, the surface of the fluorine-containing resin film has been made lyophilic by performing pretreatment using a reducing agent on the fluorine-containing resin film before the application of the photosensitive resin solution. There's a problem.

As a method for making the surface of the fluororesin film lyophilic, it is known to perform a plasma treatment with oxygen or argon (Non-Patent Document 1). However, in recent years, since all organic semiconductor elements are required to be so-called dry-drying processes in which devices are constructed by a solution coating process, plasma processing is not suitable as processing for lyophilicity.

In addition, it has been proposed to improve wettability by applying a silane coupling agent to the surface of the fluororesin film (Patent Document 1).
In addition, DuPont's Zonyl FSN (nonionic fluorosurfactant with a polyoxyethylene chain added to the perfluoroalkyl group) is blended into the photosensitive resin solution, and photosensitive on the fluororesin film without pretreatment. It has been proposed to apply a resin solution and pattern the formed photosensitive resin film, and then etch the fluorine-containing resin film to remove the photosensitive resin film (Patent Document 2).

Japanese Patent No. 5013167 Japanese Unexamined Patent Publication No. 7-3212291

However, when the method of Patent Document 1 is adopted, a photosensitive resin solution is applied after the treatment with the coupling agent to form a photosensitive resin film, and the fluorine-containing resin film is formed through the patterning film obtained by patterning. It is necessary to etch and remove the patterning film. Therefore, the number of processes increases and the operation is complicated.
Further, in the method of Patent Document 2, the wettability is insufficiently improved, and a photosensitive resin solution is applied at a time so as not to cause film defects such as unpainted or pinholes on the fluorine-containing resin film. It is difficult to form a uniform photosensitive resin film.

In the present invention, a photosensitive resin film free from film defects such as pinholes can be easily formed on the fluorine-containing resin film without pretreatment of the surface of the fluorine-containing resin film and without causing unpainted or uneven coating. It is an object of the present invention to provide a photosensitive resin solution, a patterning film forming method using the photosensitive resin solution, and a fluororesin film microfabrication method.

The present invention provides a photosensitive resin solution having the following configurations [1] to [12], a patterning film forming method, and a fluorine-containing resin film microfabrication method.
[1] A photosensitive resin solution for forming a photosensitive resin film on a fluorine-containing resin film,
The solution contains a fluoropolymer having a unit derived from a monomer represented by the following formula (a1) and a unit derived from a monomer represented by the following formula (a2):
A photosensitive resin solution, wherein a ratio of the fluoropolymer in a solid content of the solution is 0.001 to 20% by mass.

(Wherein R ¹ is a hydrogen atom, a methyl group, a cyano group, a phenyl group, a benzyl group, a fluorine atom, a chlorine atom or a trifluoromethyl group, and L is a group represented by the following formulas (L-1) to (L -8), and R ^f is a fluoroalkyl group having 1 to 20 carbon atoms or a fluoroalkyl group having 1 to 20 carbon atoms having an etheric oxygen atom.
R ² is a hydrogen atom, a methyl group or a chlorine atom, and R ³ is — (C _p H _2p O) _q —R ⁶ (where R ⁶ is a hydrogen atom or — (CH ₂ ) _r —R ⁷ ( R ⁷ is an alkoxy group having 1 to 8 carbon atoms, a hydrogen atom, a fluorine atom, a trifluoromethyl group, a hydroxy group or a cyano group, and r is an integer of 1 to 25), and p is 1 And an integer of 1 to 100, and q is an integer of 1 to 100.)

(Wherein, a to k are each independently an integer of 1 to 8, and m, n, s and t are each independently 0 or 1)

[2] R ¹ and R ² are both a hydrogen atom or a methyl group, R ^f is a perfluoroalkyl group, p is an integer of 1 to 6, q is an integer of 1 to 50, and r The photosensitive resin solution according to [1], wherein is an integer of 1 to 4, and R ⁷ is a hydroxy group or an alkoxy group.
[3] The photosensitive resin solution according to [1] or [2], wherein L is a group represented by the formula (L-1).

[4] the can _{(C p H 2p O) q} , (C 2 H 4 O) q, _{or, (C 2 H 4 O)} q2 - (C p 'H 2p' O) q3 ( although, p 'is Any one of 3 or 4, q2 and q3 each independently represents an integer of 1 to 50, and q2 + q3 = q and q2 ≧ q3)) solution.

[5] The photosensitive resin solution according to any one of [1] to [4], wherein the fluoropolymer is a polymer further having units derived from a monomer represented by the following formula (a3).

(In the above formula, R ⁴ is a hydrogen atom, a methyl group or a chlorine atom, R ⁵ is —R ⁸ —R ⁹ (where R ⁸ is a single bond or an alkylene group having 1 to 20 carbon atoms, R ⁹ is an alkoxy group having 1 to 8 carbon atoms, a hydrogen atom, a hydroxy group or a cyano group.)
[6] The photosensitive resin solution according to [5], wherein R ⁴ is a hydrogen atom or a methyl group, and R ⁵ is an alkyl group having 1 to 12 carbon atoms.

[7] The photosensitive resin solution according to any one of [1] to [6], comprising a positive photosensitive resin and a photosensitive compound.
[8] The photosensitive resin solution according to any one of [1] to [6], comprising a negative photosensitive resin and a photosensitive compound.

[9] The photosensitive resin solution according to any one of [1] to [9], wherein the fluorine-containing resin film is a film formed from a fluorine-containing cyclic ether resin.
[10] The photosensitive resin solution according to [9], wherein the fluorine-containing cyclic ether resin is a fluorine-containing cyclic ether resin made of a perfluorodiene cyclized polymer.

[11] On the fluororesin film, the photosensitive resin solution according to any one of [1] to [10] is applied to form a photosensitive resin film, and after exposing the photosensitive resin film through a mask, A patterning film forming method, wherein a patterning film is formed by patterning by development.
[12] A microfabrication method for a fluorine-containing resin film, in which the patterning film formed by the method of [11] is used as a mask and the fluorine-containing resin film is etched and patterned.

The photosensitive resin solution of the present invention has no pretreatment on the surface of the fluorine-containing resin film, and does not cause unpainted or uneven coating, and has no film defects such as pinholes on the fluorine-containing resin film. A resin film can be formed.
According to the patterning film forming method of the present invention, film pre-treatment on the surface of the fluorine-containing resin film is not performed, and undetained or uneven coating is not caused. A non-photosensitive resin film can be formed and a patterning film can be formed.
According to the fine processing method of a fluororesin film of the present invention, a fluororesin film having a desired pattern can be easily obtained.

It is a figure which shows an example of the formation method of the patterning film | membrane using positive photosensitive resin solution.

The following definitions of terms apply throughout this specification and the claims.
The “fluorinated polymer” means a polymer compound having a fluorine atom in the molecule.
The “unit” means a part derived from a monomer that exists in the polymer and constitutes the polymer. The unit derived from the monomer resulting from addition polymerization of a monomer having a carbon-carbon unsaturated double bond is a divalent unit generated by cleavage of the unsaturated double bond. Moreover, what unitally converted the structure of a unit after polymer formation is also called a unit. Hereinafter, in some cases, a unit derived from an individual monomer is referred to as a name obtained by adding “unit” to the monomer name.
The “solid content in the photosensitive resin solution” means a non-volatile component (a fluorine-containing polymer, a photosensitive resin, a photosensitive compound, a crosslinking agent, etc.) other than the solvent contained in the photosensitive resin solution.
In this specification, the monomer represented by the formula (a1) is referred to as a monomer (a1). The same applies to monomers represented by other formulas.
A group represented by the formula (L-1) is referred to as a group (L-1). Groups represented by other formulas are also described in the same manner.

[Photosensitive resin solution]
The photosensitive resin solution of the present invention is classified into two types: a positive photosensitive photosensitive resin solution and a negative photosensitive photosensitive resin solution. All contain a fluoropolymer.

(Fluoropolymer)
The fluoropolymer in the present invention (hereinafter also referred to as “fluoropolymer (A)”) is a unit derived from the monomer (a1) (hereinafter also referred to as unit (a1)) and the monomer. It is a fluoropolymer having units derived from (a2) (hereinafter also referred to as units (a2)).

<Unit (a1)>
In the formula (a1), R ¹ is preferably a hydrogen atom or a methyl group from the viewpoint of easy availability.
When L is a group (L-1) to (L-5) or (L-7), the carbon atom bonded to these groups in R ^f is a carbon atom bonded to a fluorine atom or a perfluoroalkyl group, Specifically, a carbon atom to which two fluorine atoms are bonded, a carbon atom to which a fluorine atom and a hydrogen atom are bonded, a carbon atom to which a fluorine atom and a trifluoromethyl group are bonded, and a carbon to which two trifluoromethyl groups are bonded. Atoms, etc. When L is a group (L-6) or (L-8), the carbon atom bonded to these groups of R ^f is not limited to the above, and specifically, a carbon atom bonded with two hydrogen atoms, It may be a carbon atom in which a hydrogen atom and a methyl group are bonded, or the like.
When R ^f is a fluoroalkyl group having an etheric oxygen atom, the etheric oxygen atom is present between carbon atoms, and two or more such etheric oxygen atoms may be present.
R ^f is preferably a perfluoroalkyl group having 1 to 20 carbon atoms from the viewpoint of excellent affinity for the fluorine-containing resin. A perfluoroalkyl group having 6 or less carbon atoms is preferred from the viewpoint of being less susceptible to environmental pollution. A perfluoroalkyl group having 4 to 6 carbon atoms is more preferable, and a linear perfluoroalkyl group having 4 to 6 carbon atoms is particularly preferable.
When R ^f is a fluoroalkyl group having 1 to 20 carbon atoms containing one or more hydrogen atoms, the end of the fluoroalkyl group is preferably —CF ₃ from the viewpoint of excellent affinity for the fluororesin.

In the formula (L-1), a is preferably an integer of 1 to 4 and particularly preferably 1 or 2 from the viewpoint of excellent affinity for the fluorine-containing resin.
In the formula (L-3), b is preferably an integer of 1 to 4, particularly preferably 1 or 2, from the viewpoint of affinity for the fluorine-containing resin.
c is preferably an integer of 1 to 4 and particularly preferably an integer of 1 or 2 from the viewpoint of affinity for the fluorine-containing resin.
m is preferably 1 from the viewpoint of affinity for the fluorine-containing resin.
In the formula (L-4), d is preferably an integer of 1 to 4 and particularly preferably 1 or 2 from the viewpoint of excellent affinity for the fluorine-containing resin.
In the formula (L-5), e is preferably an integer of 1 to 4, particularly preferably 1 or 2, from the viewpoint of excellent affinity for the fluorine-containing resin.
In the formula (L-6), f is preferably an integer of 1 to 4, particularly preferably 1 or 2, from the viewpoint of excellent affinity for the fluorine-containing resin.
g is preferably an integer of 1 to 3, particularly preferably 1, from the viewpoint of excellent affinity for a fluorine-containing resin.
n is preferably 1 from the viewpoint of affinity for the fluorine-containing resin.
In the formula (L-7), h is preferably an integer of 1 to 4 and more preferably 1 or 2 from the viewpoint of excellent affinity for the fluorine-containing resin.
i is preferably an integer of 1 to 3, particularly preferably 1, from the viewpoint of excellent affinity for the fluorine-containing resin.
s is preferably 1 from the viewpoint of affinity for the fluorine-containing resin.
In the formula (L-8), j is preferably an integer of 1 to 4, particularly preferably 1 or 2, from the viewpoint of excellent affinity for the fluorine-containing resin.
k is preferably an integer of 1 to 3, particularly preferably 1, from the viewpoint of excellent affinity for the fluorine-containing resin.
t is preferably 1 from the viewpoint of affinity for the fluorine-containing resin.

L is preferably a group (L-1) from the viewpoint of affinity for the fluorine-containing resin.
Specific examples of the monomer (a1) include the following monomers (a1-1) to (a1-18).

As the monomer (a1), (a1-1), (a1-6), (a1-11), and (a1-15) are preferable from the viewpoint of excellent affinity for the fluorine-containing resin, and (a1-11) ) And (a1-15) are particularly preferred.
The unit (a1) may be one type or two or more types.

<Unit (a2)>
In formula (a2), R ² is preferably a hydrogen atom or a methyl group from the viewpoint of easy polymerization.
When q is 2 or more, the types of (C _p H _2p O) present in plural may be the same or different. If they are different, the arrangement may be random, block, or alternating. When p is 3 or more, it may be a linear structure or a branched structure. The _{(C p H 2p O) (} CH 2 O), (CH 2 CH 2 O), (CH 2 CH 2 CH 2 O), include _{(CH (CH 3) CH 2} O) or the like.
p is preferably 1 to 6, and is preferably an integer of 3 to 6 and particularly preferably 3 or 4, from the viewpoint of excellent lipophilicity of the fluoropolymer (A). Moreover, from the point which is excellent in hydrophilicity, 1 or 2 is preferable and 2 is especially preferable.
q is preferably an integer of 1 to 50, more preferably an integer of 1 to 30, and particularly preferably an integer of 1 to 20 from the viewpoint of easy availability of raw materials.
r is preferably an integer of 1 to 4, particularly preferably 1 or 2, from the viewpoint of easy availability of raw materials.
R ⁷ is preferably a hydroxy group or an alkoxy group, particularly preferably a hydroxy group, from the viewpoint of easy availability of raw materials.

If the fluoropolymer (A) has a unit _{(a3), (C p H} 2p O) q _are either _{(C 2 H 4 O) q1} , (C 2 H 4 O) q2 - (C p _' H _2p' O) _q3 (wherein p 'represents an integer of 3 or 4, q1 represents an integer of 2 or more, q2 and q3 each independently represents an integer of 1 to 50, q2 + q3 = q and q2 It is preferable that ≧ q3. q1 is more preferably 2 to 20, q2 and q3 are more preferably q2 + q3 ≦ 50, and p ′ is more preferably 3.

Specific examples of the monomer (a2) include the following compounds.
CH ₂ ═CH—COO— (C ₂ H ₄ O) ₉ —H,
CH ₂ ═CH—COO— (C ₂ H ₄ O) ₄ —H,
CH ₂ ═CH—COO— (C ₂ H ₄ O) ₅ —H,
CH ₂ ═CH—COO— (C ₂ H ₄ O) ₉ —CH ₃ ,
CH ₂ ═C (CH ₃ ) —COO— (C ₂ H ₄ O) ₉ —H,
CH ₂ ═C (CH ₃ ) —COO— (C ₂ H ₄ O) ₄ —H,
CH ₂ ═C (CH ₃ ) —COO— (C ₂ H ₄ O) ₅ —H,
CH ₂ ═C (CH ₃ ) —COO— (C ₂ H ₄ O) ₉ —CH ₃ ,
CH ₂ ═CH—COO— (C ₂ H ₄ O) _q2 — (C ₃ H ₆ O) _q3 —H,
CH ₂ ═C (CH ₃ ) —COO— (C ₂ H ₄ O) _q2 — (C ₃ H ₆ O) _q3 —H,
CH ₂ ═CH—COO— (C ₂ H ₄ O) _q2 — (C ₃ H ₆ O) _q3 —CH _{3
CH 2 = C (CH 3)} -COO- (C 2 H 4 O) q2 - (C 3 H 6 O) q3 -CH 3,
CH ₂ ═CH—COO— (C ₂ H ₄ O) _q2 — (C ₄ H ₈ O) _q3 —H,
CH ₂ ═C (CH ₃ ) —COO— (C ₂ H ₄ O) _q2 — (C ₄ H ₈ O) _q3 —H,
_{CH 2 = CH-COO- (CH} 2 O) q4 - (C 2 H 4 O) q5 -CH 2 -OH and the like.
In the above formula, q2 and q3 are as described above, q4 is an integer of 1 to 20, and q5 is an integer of 1 to 50.
The unit (a2) may be one type or two or more types.

<Unit (a3)>
In addition to the units (a1) and (a2), the fluoropolymer (A) may have units derived from the monomer (a3) (hereinafter also referred to as units (a3)). For example, when the unit (a2) has only one or both of (CH ₂ O) and (CH ₂ CH ₂ O) as (C _p H _2p O), the fluoropolymer (A) has the unit (a3 ).

In formula (a3), R ⁴ is preferably a hydrogen atom or a methyl group from the viewpoint of easy polymerization.
When R ⁸ is an alkylene group having 1 to 20 carbon atoms, it may be linear or branched. An alkylene group having 1 to 12 carbon atoms is preferred, and an alkylene group having 1 to 8 carbon atoms is particularly preferred from the viewpoint of excellent affinity for other components in the photosensitive resin solution (ie, lipophilicity). The alkylene group may be a cycloalkylene group.
R ⁹ is preferably a hydrogen atom from the viewpoint of availability. Accordingly, R ⁵ is preferably an alkyl group having 1 to 12 carbon atoms, and particularly preferably an alkyl group having 1 to 8 carbon atoms.

Specific examples of the monomer (a3) include the following compounds.
CH ₂ ═CH—COO— (CH ₂ ) ₄ —H,
CH ₂ = CH-COO- (CH ₂ ) ₆ -H,
CH ₂ ═CH—COO— (CH ₂ ) ₈ —H,
CH ₂ ═CH—COO— (CH ₂ ) ₁₆ —H,
CH ₂ = CH-COO-CH ₂ CH (C ₂ H ₅ ) CH ₂ CH ₂ CH ₂ CH ₃ etc.
The unit (a3) may be one type or two or more types.

<Unit (a4)>
The fluoropolymer (A) has units (a4) derived from monomers other than the monomers (a1) to (a3) in addition to the units (a1) to (a3). Also good.
Specific examples of the monomer (a4) include the following compounds.
CH ₂ ═CH—COO—CH ₂ —C ₆ H ₅ ,
CH ₂ = CH-COO- (C ₂ H ₄ O) ₂ -C ₆ H ₅ ,
_{CH 2 = CH-COO- (C} 2 H 4 O) 4 -C 6 H 4 -C 9 H 19.
The unit (a4) may be one type or two or more types.

<Ratio of each unit>
The proportion of the unit (a1) with respect to the total units of the fluoropolymer (A) is preferably 5 to 95 mol%, particularly preferably 10 to 90 mol%. When the proportion of the unit (a1) is at least the lower limit, the affinity for the fluororesin is excellent, and the photosensitive resin solution can be easily applied onto the fluororesin film. When the proportion of the unit (a1) is not more than the above upper limit value, the affinity for other components of the photosensitive resin solution is excellent, and the storage stability of the photosensitive resin solution is excellent.

The ratio of the unit (a2) to the total units of the fluoropolymer (A) is preferably 95 to 5 mol%, particularly preferably 90 to 10 mol%. When the proportion of the unit (a2) is not less than the lower limit, the affinity for the other components of the photosensitive resin solution is excellent, and the storage stability of the photosensitive resin solution is excellent. When the proportion of the unit (a2) is not more than the above upper limit value, the affinity for the fluorine-containing resin is excellent, and the photosensitive resin solution can be easily applied onto the fluorine-containing resin film.
The total ratio of the unit (a1) and the unit (a2) in all units of the fluoropolymer (A) is preferably 30 to 100% by mass.

When the fluoropolymer (A) has the unit (a3), the ratio of the unit (a3) to the total of the unit (a1) and the unit (a2) is preferably 20 to 200 mol%, preferably 20 to 180 mol%. Is particularly preferred. If the ratio of the unit (a3) is not less than the lower limit, the affinity for the other components of the photosensitive resin solution is excellent, and the storage stability of the photosensitive resin solution is excellent. When the proportion of the unit (a3) is not more than the above upper limit value, the affinity for the fluorine-containing resin is excellent, and the photosensitive resin solution can be easily applied onto the fluorine-containing resin film.

When the fluoropolymer (A) has the unit (a4), the ratio of the unit (a4) to the total of the units (a1) and (a2) of the fluoropolymer (A) is 1 to 10 mol% 1 to 5 mol% is particularly preferable.

The number average molecular weight (Mn) of the fluoropolymer (A) is preferably from 1,000 to 100,000, particularly preferably from 1,000 to 50,000. When the number average molecular weight of the fluoropolymer (A) is at least the lower limit, the affinity for the fluororesin is excellent. If the number average molecular weight of the fluoropolymer (A) is not more than the above upper limit, the fluoropolymer (A) is easily dissolved in the solvent (D1).

The mass average molecular weight (Mw) of the fluoropolymer (A) is preferably from 1,000 to 200,000, particularly preferably from 1,000 to 100,000. If the mass average molecular weight of a fluoropolymer (A) is more than the said lower limit, it will be excellent in affinity with a fluororesin. When the mass average molecular weight of the fluoropolymer (A) is not more than the above upper limit, the fluoropolymer (A) is easily dissolved in the solvent (D1).

The molecular weight distribution (Mw / Mn) of the fluoropolymer (A) is preferably from 1 to 10, particularly preferably from 1.1 to 5. When the molecular weight distribution of the fluoropolymer (A) is within the above range, the affinity for the fluororesin forming the fluororesin film is excellent.

<Manufacturing method>
The fluorine-containing polymer (A) can be obtained by performing a polymerization reaction of monomers in a polymerization solvent using a known method.
The polymerization solvent is not particularly limited. For example, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), alcohols (methanol, 2-propyl alcohol, etc.), esters (ethyl acetate, butyl acetate, etc.), ethers (Diisopropyl ether, tetrahydrofuran, dioxane, etc.), glycol ethers (ethylene glycol, propylene glycol, ethyl ether or methyl ether of dipropylene glycol, etc.) and derivatives thereof, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated Hydrocarbons (perchloroethylene, 1,1,1-trichloroethane, trichlorotrifluoroethane, dichloropentafluoropropane, etc.), dimethylformamide, N-methyl-2-pyrrolidone, butyroacetone, Methyl sulfoxide (DMSO) and the like.

The total concentration of all the monomers in the reaction solution in the polymerization reaction for obtaining the fluoropolymer (A) is preferably 5 to 60% by mass, particularly preferably 10 to 40% by mass.

In the polymerization reaction for obtaining the fluoropolymer (A), it is preferable to use a polymerization initiator. Examples of the polymerization initiator include peroxides (benzyl peroxide, lauryl peroxide, succinyl peroxide, tert-butyl perpivalate, etc.), azo compounds, and the like.
Examples of the azo compound include 2,2′-azoisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, dimethyl-2,2′-azobisisobutyrate, 2,2′-azobis [ 2- (2-imidazolin-2-yl) propane], 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1′-azobis (2cyclohexane-1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 1,1′-azobis (1-acetoxy-1-phenylethane), dimethylazobisisobutyrate, 4,4′-azobis (4-cyano Herbic acid) is preferred, and 2,2′-azoisobutyronitrile, 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 4,4′-azobis (4-cyanovaleric acid) Particularly preferred.
The amount of the polymerization initiator used is preferably 0.1 to 1.5 parts by mass with respect to 100 parts by mass of the total amount of monomers.

In order to adjust the degree of polymerization (molecular weight) of the fluoropolymer (A), a chain transfer agent may be used in the polymerization reaction. By using a chain transfer agent, there is also an effect that the total concentration of monomers in the polymerization solvent can be increased.
Examples of chain transfer agents include alkyl mercaptans (tert-dodecyl mercaptan, n-dodecyl mercaptan, stearyl mercaptan, etc.), aminoethanethiol, mercaptoethanol, 3-mercaptopropionic acid, 2-mercaptopropionic acid, thiomalic acid, thioglycolic acid, 3,3′-dithio-dipropionic acid, 2-ethylhexyl thioglycolate, n-butyl thioglycolate, methoxybutyl thioglycolate, ethyl thioglycolate, 2,4-diphenyl-4-methyl-1-pentene, And carbon tetrachloride.
The amount of chain transfer agent used is preferably 0 to 2 parts by mass with respect to 100 parts by mass of the total amount of monomers.

The reaction temperature in the polymerization reaction is preferably in the range from room temperature to the boiling point of the reaction solution. From the viewpoint of efficiently using the polymerization initiator, it is preferably at least the half-life temperature of the polymerization initiator, more preferably from 30 to 90 ° C.

As a fluoropolymer (A), what was synthesize | combined may be used and a commercial item may be used.
Commercially available products of the fluoropolymer (A) include, for example, trade names: Surflon S-611, S-651, S-386 (all manufactured by AGC Seimi Chemical Co., Ltd.), trade names: Megafac F-556, F -557, F-559, F-560, F-563, F-567, R-40, R-41, R-43 (all manufactured by DIC) and the like.
A fluoropolymer (A) may be used individually by 1 type, and may use 2 or more types together.

(Positive photosensitive photosensitive resin solution)
The positive photosensitive photosensitive resin solution of the present invention comprises a fluoropolymer (A), a positive photosensitive resin (hereinafter also referred to as “positive photosensitive resin (B1)”), and a photosensitive compound. (Hereinafter also referred to as “photosensitive compound (C1)”) and a solvent (hereinafter also referred to as “solvent (D1)”). Further, if necessary, a phenolic hydroxyl group-containing compound (hereinafter also referred to as “phenolic hydroxyl group-containing compound (E1)”) and a component other than the above (hereinafter also referred to as “other component (F1)”). You may contain.

<Positive photosensitive resin (B1)>
The positive photosensitive resin (B1) is an alkali-insoluble resin that becomes alkali-soluble when irradiated with light. In the case of a photoresist film made of a positive photosensitive resin (B1) film, the exposed portion of the photoresist film becomes alkali-soluble, and the exposed portion is removed with an alkaline developer.
Examples of the positive photosensitive resin (B1) include a positive photosensitive novolac resin. As the positive photosensitive novolac resin, a known novolac resin that is usually used in a positive photosensitive photosensitive resin solution can be employed.

Specific examples of the positive photosensitive novolak resin include novolak resins obtained by reacting phenols and aldehydes in the presence of an acidic catalyst.
Examples of the phenols include the following compounds.
Phenol;
Cresols such as m-cresol, p-cresol, o-cresol;
Xylenols such as 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol;
m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 4-tert-butylphenol, 3-tert-butylphenol, 2-tert-butylphenol Alkylphenols such as 2-tert-butyl-4-methylphenol and 2-tert-butyl-5-methylphenol;
alkoxyphenols such as p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol, p-propoxyphenol, m-propoxyphenol;
isopropenylphenols such as o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol, 2-ethyl-4-isopropenylphenol;
Arylphenols such as phenylphenol;
Polyhydroxyphenols such as 4,4′-dihydroxybiphenyl, bisphenol A, resorcinol, hydroquinone, pyrogallol and the like.

Of these, m-cresol and p-cresol are particularly preferable as the phenols.
Phenols may be used alone or in combination of two or more. Among these, it is preferable to use two or more kinds in combination, and it is particularly preferable to use m-cresol and p-cresol in combination.

Examples of aldehydes include the following compounds.
Formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, butyraldehyde, trimethylacetaldehyde, acrolein, crotonaldehyde, cyclohexanealdehyde, furfural, furylacrolein, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde O-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, cinnamic aldehyde, etc. .

Of these, formaldehyde is preferable as the aldehydes from the viewpoint of easy availability.
Aldehydes may be used alone or in combination of two or more.

Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, formic acid, oxalic acid, paratoluenesulfonic acid, and the like, and oxalic acid is preferred.

The mass average molecular weight (Mw) of the positive photosensitive resin (B1) is preferably 2,000 to 50,000, particularly preferably 4,000 to 30,000. If the mass average molecular weight of the positive photosensitive resin (B1) is within the above range, the developability is excellent.

The positive photosensitive resin (B1) may be used alone or in combination of two or more. When two or more positive photosensitive resins (B1) are used in combination, it is easy to adjust the sensitivity of the photosensitive resin film to light.

<Photosensitive compound (C1)>
As the photosensitive compound (C1), a known photosensitive compound usually used in combination with a positive photosensitive resin can be employed, and examples thereof include naphthoquinonediazide group-containing compounds.
As a naphthoquinone diazide group-containing compound, a phenolic hydroxyl group-containing compound represented by the following formula (1), which is inexpensive and can prepare a highly sensitive positive photosensitive photosensitive resin solution, -A compound obtained by esterifying a naphthoquinonediazidesulfonic acid compound (hereinafter referred to as compound (C11)) is preferred.

Examples of the 1,2-naphthoquinonediazide sulfonic acid compound include 1,2-naphthoquinonediazide-5-sulfonyl compounds, 1,2-naphthoquinonediazide-4-sulfonyl compounds, and the like. Of these, 1,2-naphthoquinonediazide-5-sulfonyl compounds are preferred.

Examples of the naphthoquinonediazide group-containing compound other than the compound (C11) include a compound represented by the following formula (2) (hereinafter referred to as compound (2)) and a compound represented by the following formula (3) (hereinafter referred to as “compound”). And a compound obtained by esterifying one or both of the compound (3) and a 1,2-naphthoquinonediazidesulfonic acid compound.

The photosensitive compound (C1) may be used alone or in combination of two or more.

<Solvent (D1)>
When the solvent (D1) is contained, the viscosity of the positive-type photosensitive photosensitive resin solution is lowered, so that the application of the photosensitive resin solution is simplified. Therefore, it becomes easy to form a uniform positive photosensitive photosensitive resin film.
As a solvent (D1), the well-known solvent normally used for positive photosensitive resin solution can be employ | adopted.

Specific examples of the solvent (D1) include ethylene glycol alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol diethylene Diethylene glycol dialkyl ethers such as propyl ether and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate (PGMEA) and Propylene glycol alkyl ether acetates such as propylene glycol monopropyl ether acetate; ketones such as acetone, methyl ethyl ketone, cyclohexanone and methyl amyl ketone; aromatic hydrocarbons such as toluene and xylene; cyclic ethers such as dioxane; and 2 -Methyl hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxy acetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3- Examples thereof include esters such as methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate and ethyl acetoacetate. Of these, butyl acetate and PGMEA are particularly preferable from the viewpoint of easily forming a photosensitive resin film having a uniform film thickness.
A solvent (D1) may be used individually by 1 type, and may use 2 or more types together.

<Phenolic hydroxyl group-containing compound (E1)>
The positive photosensitive photosensitive resin solution preferably contains a phenolic hydroxyl group-containing compound (E1) having a molecular weight of 1,000 or less (hereinafter referred to as compound (E1)) for the purpose of improving sensitivity. By using the compound (E1), high sensitivity can be achieved at a relatively low cost. In addition, since a layer that is difficult to dissolve in the developer is formed on the surface layer of the photosensitive resin film, the amount of film reduction in the unexposed portion during development is reduced. As a result, development unevenness caused by the difference in development time can be suppressed.
The molecular weight of the compound (E1) is 1,000 or less, preferably 200 to 1,000.

As the compound (E1), a known phenolic hydroxyl group-containing compound having a molecular weight of 1,000 or less, which is usually used in a positive photosensitive photosensitive resin solution, can be employed. Especially, as a compound (E1), the above-mentioned compound (2) and compound (3) are preferable from the point which a sensitivity is especially excellent.
As the compound (E1), one type may be used alone, or two or more types may be used in combination.

<Other components (F1)>
Examples of the other component (F1) include surfactants other than the fluoropolymer (A), storage stabilizers, ultraviolet absorbers, and adhesion improvers.

<Ratio of each component>
The solid concentration in the positive photosensitive photosensitive resin solution is preferably 5 to 50% by mass, particularly preferably 10 to 40% by mass. If solid content concentration is more than the said lower limit, the photosensitive resin film will be hard to peel at the time of development. If the solid content concentration is less than or equal to the above upper limit value, exposure failure is unlikely to occur, and the thickness of the photosensitive resin film tends to be uniform.

The ratio of the fluoropolymer (A) in the positive photosensitive photosensitive resin solution is 0.001 to 20% by mass in the solid content (100% by mass) in the photosensitive resin solution, and 0.01 Is preferably 10 to 10% by mass, particularly preferably 0.1 to 5% by mass. If the ratio of a fluoropolymer (A) is more than the said lower limit, the applicability | paintability to a fluororesin film | membrane will be ensured. If the ratio of a fluoropolymer (A) is below the said upper limit, it can suppress that film defects, such as a pinhole, arise.
The proportion of the fluoropolymer (A) is appropriately adjusted depending on the type of the positive photosensitive resin, the coating method, the target film thickness of the photosensitive resin film, and the like.

The proportion of the positive photosensitive resin (B1) in the positive photosensitive photosensitive resin solution is preferably 5 to 40% by mass, and particularly preferably 10 to 35% by mass. If the ratio of positive photosensitive resin (B1) is more than the said lower limit, the photosensitive resin film will be hard to peel at the time of development. When the ratio of the positive photosensitive resin (B1) is equal to or less than the upper limit, exposure failure is unlikely to occur and the thickness of the photosensitive resin film is likely to be uniform.

The proportion of the photosensitive compound (C1) in the positive photosensitive resin solution is preferably 1 to 20% by mass with respect to 100 parts by mass in total of the positive photosensitive resin (B1) and the compound (E1). 5 to 15% by mass is particularly preferable. If the ratio of the photosensitive compound (C1) is not less than the lower limit, patterning of the photosensitive resin film becomes simple. If the ratio of the photosensitive compound (C1) is not more than the above upper limit value, it is easy to suppress the generation of a residue after development.

When the positive photosensitive photosensitive resin solution contains the compound (E1), the ratio of the compound (E1) in the positive photosensitive photosensitive resin solution is 1 with respect to the solid content excluding the compound (E1). -30% by mass is preferable, and 5-25% by mass is particularly preferable.

(Negative photosensitive photosensitive resin solution)
The negative photosensitive photosensitive resin solution of the present invention includes a fluoropolymer (A), a negative photosensitive resin (hereinafter also referred to as “negative photosensitive resin (B2)”), and photosensitive. It is preferable to contain a compound (hereinafter also referred to as “photosensitive compound (C2)”) and a solvent (hereinafter also referred to as “solvent (D2)”). Moreover, you may contain a crosslinking agent (henceforth "crosslinking agent (E2)") and components other than the above (henceforth "other component (F2)") as needed.

<Negative photosensitive resin (B2)>
The negative photosensitive resin (B2) is a solvent-soluble resin that becomes solvent-insoluble when irradiated with light. In the case of a photoresist film made of a negative photosensitive resin (B2) film, the exposed portion of the photoresist film becomes solvent-insoluble, and the unexposed solvent-soluble portion is removed by the solvent.
Examples of the negative photosensitive resin (B2) contained in the negative photosensitive photosensitive resin solution include a photosensitive resin having an acidic group and an ethylenic double bond in one molecule. Since the negative photosensitive resin (B2) has an ethylenic double bond, the exposed portion of the photosensitive resin film formed with the negative photosensitive photosensitive resin solution is a photopolymerization that is a photosensitive compound (C2). The initiator is polymerized and cured by the generated radicals, and becomes insoluble in the solvent. Since the unexposed portion is not cured, it is removed by dissolving in a developing solution such as a solvent. Moreover, when a negative photosensitive resin (B2) is alkali-soluble resin which has an acidic group etc., an unexposed part can be removed with an alkaline developing solution.

Examples of the group having an ethylenic double bond include a group having a polymerizable double bond such as a (meth) acryloyl group, an allyl group, a vinyl group, and a vinyloxy group, and a part or all of hydrogen atoms in the group. , A hydrocarbon group, preferably a group substituted with a methyl group. These groups may be one kind or two or more kinds.
Examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a phosphoric acid group. 1 type may be sufficient as an acidic group, and 2 or more types may be sufficient as it.

The negative photosensitive resin (B2) is not particularly limited, but is a resin (B2-1) having a side chain having an acidic group and a side chain having an ethylenic double bond, and an epoxy resin having an acidic group and an ethylenic group. And a resin (B2-2) having a double bond introduced therein. These may be used alone or in combination of two or more.

Resin (B2-1) is a side chain having a reactive group obtained by copolymerizing a monomer having a reactive group such as a hydroxyl group, a carboxy group, or an epoxy group and a monomer having an acidic group; It can be synthesized by dissolving a copolymer having a side chain having an acidic group, a compound having a functional group capable of bonding to the reactive group and an ethylenic double bond in a solvent and reacting them.

Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl ( (Meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate neopentyl glycol mono (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, 2-hydroxyethyl allyl ether, N-hydroxymethyl (meth) acrylic Bromide, N, N-bis (hydroxymethyl) (meth) acrylamide.

Examples of the monomer having a carboxy group include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof. These monomers are also used as monomers having an acidic group.

Examples of the monomer having an epoxy group include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl acrylate.

Examples of the monomer having a reactive group include an acid anhydride having an ethylenic double bond, a compound having an isocyanate group and an ethylenic double bond, and a compound having an acyl chloride group and an ethylenic double bond. .
Examples of the acid anhydride having an ethylenic double bond include maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, 3,4,5,6-tetrahydrophthal And acid anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, 2-buten-1-ylsuccinic anhydride, and the like.
Examples of the compound having an isocyanate group and an ethylenic double bond include 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate.
Examples of the compound having an acyl chloride group and an ethylenic double bond include (meth) acryloyl chloride.

Examples of the monomer having an acidic group include a monomer having a phosphoric acid group (such as 2- (meth) acryloyloxyethanephosphoric acid) in addition to the above-mentioned monomer having a carboxy group.
The copolymerization of the monomer having a reactive group and the monomer having an acidic group can be performed by a conventionally known method.

Resin (B2-2) can be synthesized by reacting an epoxy resin with a compound having a carboxy group and an ethylenic double bond and then reacting with a polybasic carboxylic acid or an anhydride thereof.
Specifically, an ethylenic double bond is introduced into the epoxy resin by reacting an epoxy resin with a compound having a carboxyl group and an ethylenic double bond. Next, a carboxyl group can be introduce | transduced by making polybasic carboxylic acid or its anhydride react with the epoxy resin in which the ethylenic double bond was introduce | transduced.

Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, trisphenol methane type epoxy resin, epoxy resin having a naphthalene skeleton, and the like.

A commercially available product may be used as the resin (B2-2).
Commercially available products include, for example, trade names: KAYARAD PCR-1069, K-48C, CCR-1105, CCR-1115, CCR-1159H, CCR-1235, TCR-1025, TCR-1064H, TCR-1286H, ZAR-1535H ZAR-2002H, ZFR-1491H, ZFR-1492H, ZCR-1571H, ZCR-1569H, ZCR-1580H, ZCR-1581H, ZCR-1588H, ZCR-1642H, ZCR-1664H, ZCR-1761H (above, Nippon Kayaku) And product name: EX1010 (manufactured by Nagase ChemteX Corporation).

As the negative photosensitive resin (B2), the photosensitive resin film is prevented from being peeled off during development, a high-resolution pattern is easily formed, the line linearity is excellent, and the surface is smooth. Resin (B2-2) is preferable from the viewpoint of easily obtaining.
Resin (B2-2) includes a resin in which an acidic group and an ethylenic double bond are introduced into a bisphenol A type epoxy resin, a resin in which an acidic group and an ethylenic double bond are introduced into a bisphenol F type epoxy resin, phenol Resin with acidic group and ethylenic double bond introduced into novolac epoxy resin, resin with acidic group and ethylenic double bond introduced into cresol novolac epoxy resin, or acidic group into trisphenolmethane epoxy resin A resin into which an ethylenic double bond is introduced is preferred.

The number of ethylenic double bonds that the negative photosensitive resin (B2) has in one molecule is preferably 3 or more on average, and particularly preferably 6 or more. If the number of ethylenic double bonds is equal to or more than the lower limit value, the alkali solubility between the exposed part and the unexposed part is likely to be different, and a fine pattern can be formed with a smaller exposure amount.

The acid value of the negative photosensitive resin (B2) is preferably 10 to 200 mgKOH / g, more preferably 30 to 150 mgKOH / g, and particularly preferably 50 to 100 mgKOH / g. When the acid value is in the above range, the storage stability and developability of the negative photosensitive resin solution are improved.

The mass average molecular weight (Mw) of the negative photosensitive resin (B2) is preferably 1.5 × 10 ³ to 50 × 10 ³ , particularly preferably 1.5 × 10 ³ to 30 × 10 ³ . If the mass average molecular weight of the negative photosensitive resin (B2) is within the above range, the developability is excellent.
The number average molecular weight (Mn) of the negative photosensitive resin (B2) is preferably 500 to 20 × 10 ³ , particularly preferably 1.0 × 10 ³ to 10 × 10 ³ . If the number average molecular weight of the negative photosensitive resin (B2) is within the above range, the developability is excellent.
A negative photosensitive resin (B2) may be used individually by 1 type, and may use 2 or more types together.

<Photosensitive compound (C2)>
Examples of the photosensitive compound (C2) used in combination with the negative photosensitive resin include a photopolymerization initiator.
As the photopolymerization initiator, a known photopolymerization initiator that is usually used in combination with a negative photosensitive resin can be adopted, and a compound that generates a radical by light is preferable.

Examples of the photopolymerization initiator include the following compounds.
Α-diketones such as benzyl, diacetyl, methylphenylglyoxylate, and 9,10-phenanthrenequinone;
Acyloins such as benzoin;
Acyloin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether;
Thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isofuropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diisopropylthioxanthone, thioxanthone-4-sulfone Thioxanthones such as acids;
Benzophenones such as benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone;
Acetophenone, 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2′-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl- [4- (methylthio) Acetophenones such as phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one;
Quinones such as anthraquinone, 2-ethylanthraquinone, camphorquinone and 1,4-naphthoquinone;
Aminobenzoic acids such as ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate ;
Halogen compounds such as phenacyl chloride and trihalomethylphenyl sulfone;
Acylphosphine oxides;
Peroxides such as di-t-butyl peroxide;
1,2-octanedione-1- [4- (phenylthio) -2- (o-benzoyloxime), ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] Oxime esters such as -1- (o-acetyloxime),
Aliphatic amines such as triethanolamine, methyldiethanolamine, triisoflopanolamine, n-butylamine, N-methyldiethanolamine, diethylaminoethyl methacrylate;
2-mercaptopentimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 1,4-butanol bis (3-mercaptobutyrate), tris (2-mercaptopropanoyloxyethyl) isocyanurate, pentaerythritol tetrakis (3 -Thiol compounds such as mercaptobutyrate).

Of these, benzophenones, aminobenzoic acids, aliphatic amines, and thiol compounds are preferred when used together with other radical initiators because they may exhibit a sensitizing effect.
As photopolymerization initiators, 2-methyl- [4- (methylthio) phenyl-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1- ON, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (o-benzoyloxime), ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3 -Il] -1- (o-acetyloxime), 4,4′-bis (diethylamino) benzophenone, or 2,4-diethylthioxanthone is more preferred. Furthermore, the combination of these and the said benzophenones is especially preferable.

A commercially available product may be used as the photopolymerization initiator.
Examples of commercially available products include IRGACURE OXE01 (trade name, manufactured by BASF, 1,2-octanedione-1- [4- (phenylthio) -2- (o-benzoyloxime)]), IRGACURE OXE02 (trade name, BASF, ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyloxime)), IRGACURE907 (trade name, manufactured by BASF, 2 -Methyl-1- [4- (methylthio) phenyl-2-morpholinopropan-1-one), IRGACURE369 (trade name, manufactured by BASF, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Butan-1-one) and the like.
A photosensitive compound (C2) may be used individually by 1 type, and may use 2 or more types together.

<Solvent (D2)>
When the solvent (D2) is contained, the viscosity of the negative photosensitive photosensitive resin solution is lowered, and thus the application of the photosensitive resin solution is simplified. Therefore, it becomes easy to form a uniform negative photosensitive photosensitive resin film.
As a solvent (D2), the well-known solvent normally used for a negative photosensitive photosensitive resin solution is employable. As a solvent (D2), what is necessary is just the thing which does not have reactivity with the other component in a negative photosensitive photosensitive resin solution, For example, the same thing as what was mentioned by the solvent (D1) is mentioned.
A solvent (D2) may be used individually by 1 type, and may use 2 or more types together.

<Crosslinking agent (E2)>
The negative photosensitive photosensitive resin solution may contain a crosslinking agent (E2) as an optional component that promotes radical curing. By using the crosslinking agent (E2), the curability of the negative photosensitive resin (B2) at the time of exposure is improved, and the exposure amount when forming a pattern can be reduced.
As a crosslinking agent (E2), the compound which has two or more ethylenic double bonds in 1 molecule, and does not have an acidic group is preferable.

Examples of the crosslinking agent (E2) include the following compounds.
Diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, trimethylol furopan Tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethoxy Isocyanuric acid triacrylate, ε-cafrolactone modified tris- (2-hydroxyethyl) isocyanurate triacrylate, bis {4 To (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane, N, N′-m-xylylene-bis (allylbicyclo [2.2.1] Pt-5-ene-2,3-dicarboximide), urethane acrylate and the like.
A crosslinking agent (E2) may be used individually by 1 type, and may use 2 or more types together.

<Other components (F2)>
Examples of the other component (F2) include surfactants other than the fluoropolymer (A), sensitizers, thermal crosslinkers, black colorants, polymer dispersants, dispersion aids, silane coupling agents, Examples thereof include fine particles, phosphoric acid compounds, curing accelerators, thickeners, sanitizers, antifoaming agents, leveling agents, repellency inhibitors, and ultraviolet absorbers.

<Ratio of each component>
The solid concentration in the negative photosensitive photosensitive resin solution is preferably 10 to 50% by mass, particularly preferably 15 to 40% by mass. If solid content concentration is more than the said lower limit, the photosensitive resin film will be hard to peel at the time of development. If the solid content concentration is less than or equal to the above upper limit value, exposure failure is unlikely to occur, and the thickness of the photosensitive resin film tends to be uniform.

The ratio of the fluoropolymer (A) in the negative photosensitive photosensitive resin solution is 0.001 to 20% by mass in the solid content (100% by mass) in the photosensitive resin solution. Is preferably 10 to 10% by mass, particularly preferably 0.1 to 5% by mass. If the ratio of a fluoropolymer (A) is more than the said lower limit, the applicability | paintability to a fluororesin film | membrane will be ensured. If the ratio of a fluoropolymer (A) is below the said upper limit, it can suppress that film defects, such as a pinhole, arise.
The ratio of the fluoropolymer (A) is appropriately adjusted according to the type of the negative photosensitive resin, the coating method, the target film thickness of the photosensitive resin film, and the like.

The proportion of the negative photosensitive resin (B2) in the negative photosensitive photosensitive resin solution is preferably 5 to 40% by mass, and particularly preferably 10 to 30% by mass. If the ratio of alkali-soluble resin (B2) is more than the said lower limit, the photosensitive resin film will be hard to peel at the time of development. If the ratio of the negative photosensitive resin (B2) is less than or equal to the above upper limit, poor exposure is unlikely to occur and the film thickness of the photosensitive resin film tends to be uniform.

The proportion of the photosensitive compound (C2) in the negative photosensitive resin solution is preferably 1 to 20% by mass, particularly preferably 1 to 15% by mass, based on the solid content in the photosensitive resin solution. If the ratio of the photosensitive compound (C1) is not less than the lower limit, patterning of the photosensitive resin film becomes simple. If the ratio of the photosensitive compound (C1) is not more than the above upper limit value, it is easy to suppress the generation of a residue after development.

In the negative photosensitive resin solution, the total amount of the negative photosensitive resin (B2) and the crosslinking agent (E2) is 50 to 95% by mass in the total solid content, and the crosslinking agent (E2) The ratio of the content of the negative photosensitive resin (B2) to the content of is preferably 15 to 85% by mass. Further, the total amount of the negative photosensitive resin (B2) and the crosslinking agent (E2) is 60 to 92% by mass in the total solid content, and the negative photosensitive resin with respect to the content of the crosslinking agent (E2). The content ratio of (B2) is more preferably 20 to 70% by mass. Further, the total amount of the negative photosensitive resin (B2) and the crosslinking agent (E2) is 65 to 90% by mass in the total solid content, and the negative photosensitive resin with respect to the content of the crosslinking agent (E2). The content ratio of (B2) is particularly preferably 20 to 55% by mass.
Within the above range, the storage stability of the negative photosensitive photosensitive resin solution is improved, and the wettability of the negative photosensitive photosensitive resin solution to the fluorine-containing resin film is improved.

Since the photosensitive resin solution of the present invention described above contains the fluoropolymer (A) at a specific ratio, it can be contained even without performing a pretreatment for making the surface of the fluororesin film lyophilic. A photosensitive resin film free from film defects such as pinholes can be easily formed on the fluororesin film. This is considered to be caused by the following.
When the photosensitive resin solution is applied onto the fluorine-containing resin film, the fluorine-containing polymer (A) in the photosensitive resin solution has the side chain having the fluorine atom of the unit (a1) directed toward the fluorine-containing resin film surface, And, the side chain having the lyophilic property of unit (a2) (considered to have lyophilic property by having (C _p H _2p O) _q ) is arranged in the opposite direction. This is considered to be because the portion of the fluororesin film surface to which the photosensitive resin solution is applied is surface-modified and made lyophilic.
Further, by using the photosensitive resin solution of the present invention, it is not necessary to go through a dry process such as plasma treatment when applying the photosensitive resin solution on the fluorine-containing resin film. In addition, the photosensitive resin film formed using the photosensitive resin solution is excellent in adhesion with the fluorine-containing resin film, and troubles such as peeling hardly occur even when the fluorine-containing resin film is wet-etched after patterning. Therefore, a dedrying process can be realized in microfabrication of a fluorine-containing resin film used for a gate insulating film of an organic transistor.
Moreover, the photosensitive resin film formed using the photosensitive resin solution of this invention is excellent also in photolithography patterning property.
Note that the positive photosensitive resin solution and the negative photosensitive resin solution are not limited to those described above.

[Fluorine-containing resin]
The fluororesin film targeted by the photosensitive resin solution of the present invention is formed from a fluororesin. The fluorine-containing resin is not particularly limited, and examples thereof include condensed fluorine-containing resins such as fluorine-containing acrylic resins and fluorine-containing polyimides, fluorine-containing ether resins, and fluorine-containing cyclic ether resins. These resins may be perfluoro products in which all hydrogen atoms are substituted with fluorine atoms, or may be those in which at least a part of fluorine atoms is substituted with chlorine atoms or the like. Further, these resins may have a trifluoromethane substituent.
The photosensitive resin solution of the present invention is also suitable for fluorine-containing cyclic ether resins (CYTOP (trademark, manufactured by Asahi Glass Co., Ltd.), Teflon (trademark) AF (manufactured by DuPont), etc.) having high liquid repellency. Without pretreatment of the film surface, a photosensitive resin film free from film defects such as pinholes can be easily formed on the fluorine-containing resin film. Therefore, it is particularly effective when forming a photosensitive resin film on a fluorine-containing resin film containing a fluorine-containing cyclic ether resin.

The fluorine-containing cyclic ether resin refers to a resin made of a polymer having a fluorine-containing cyclic ether structure. The fluorine-containing cyclic ether structure has an aliphatic ring composed of carbon atoms and oxygen atoms, and a fluorine atom or a fluorine atom-containing group (such as a fluoroalkyl group or a fluoroalkoxy group) is bonded to the carbon atom. Refers to the structure. The aliphatic ring is preferably a 5-membered or 6-membered ring having 1 or 2 oxygen atoms.
Further, the fluorinated cyclic ether resin tends to be an amorphous fluorinated resin by having a fluorinated cyclic ether structure in the main chain of the polymer. Having a fluorine-containing cyclic ether structure in the main chain of the polymer means that at least one carbon atom constituting the aliphatic ring is a carbon atom constituting the main chain of the polymer.
Examples of the fluorine-containing cyclic ether resin include polymers obtained by cyclopolymerization of perfluorodiene, two carbon atoms constituting the ring, or two carbon atoms constituting the ring and those outside the ring. A fluorine-containing resin comprising a copolymer of a perfluoroaliphatic cyclic monomer having a heavy bond and a perfluoroolefin is preferred. Examples of perfluorodienes include perfluoro (3-butenyl vinyl ether) and perfluoro (allyl vinyl ether). Examples of the perfluoroaliphatic cyclic monomer include 2,2-bis (trifluoromethyl) -4,5-difluoro-1,3-dioxole and 2-difluoromethylene-4,4,5,5-tetrafluoro-1 1,3-dioxolane and the like, and the perfluoroolefin includes tetrafluoroethylene.
The fluorine-containing cyclic ether resin is particularly preferably a fluorine-containing cyclic ether resin made of a polymer obtained by cyclopolymerizing perfluorodiene, which is easily an amorphous fluorine-containing resin. A fluorine-containing cyclic ether resin comprising a polymer obtained by cyclopolymerizing perfluorodiene is commercially available under the trade name CYTOP (trademark, manufactured by Asahi Glass Co., Ltd.).

[Method for forming patterning film and method for fine processing of fluorine-containing resin film]
The patterning film forming method of the present invention is a method of forming a patterning film using the photosensitive resin solution of the present invention. Hereinafter, a case where a positive photosensitive photosensitive resin solution is used will be described with reference to FIG. 1 as an example of a fine processing method of a fluorine-containing resin film using the patterning film forming method of the present invention.

For example, as shown in FIG. 1A, a positive photosensitive photosensitive resin solution is applied on a fluorine-containing resin film 12 containing a fluorine-containing cyclic ether resin formed on a substrate 10 and heated. As shown in FIG. 1B, a positive photosensitive photosensitive resin film 14 is formed on the fluorine-containing resin film 12.
A known method can be adopted as a method for applying the photosensitive resin solution, and examples thereof include a spin coating method.

Next, as shown in FIG. 1C, the photosensitive resin film 14 is exposed through a mask 16 on which a predetermined pattern is formed, and then the exposed portion is dissolved and removed by development to be patterned. ), A patterning film 18 is formed on the fluorine-containing resin film 12.
As a light source used for exposure, a light source usually used for patterning a positive photosensitive resin film can be employed.
A known method can be adopted as the exposure method.
As the developer used for the development, those usually used when patterning a positive photosensitive photosensitive resin film can be employed.
A known method can be adopted as the developing method.

Next, as shown in FIG. 1D, using the patterning film 18 as a mask, a portion of the fluororesin film 12 corresponding to the portion 18a where the patterning film 18 is not present is etched, as shown in FIG. Then, a hole 12 a having a diameter of several μm to several tens of μm is formed in the fluorine-containing resin film 12.
As an etching method, wet etching using a fluorine-containing solvent is preferable.

Next, by removing the patterning film 18, as shown in FIG. 1 (f), the fluorine-containing resin film 12 in which the holes 12 a are formed on the substrate 10 is obtained.

According to the method for forming a patterning film of the present invention described above, the photosensitive film can be easily photosensitized on the fluorine-containing resin film without pretreatment and without causing film defects such as unpainted areas, uneven coating, and pinholes. A resin film can be formed. As a result, a patterning film can be easily formed.
In addition, also when using a negative photosensitive photosensitive resin solution, a patterning film can be formed like the above-mentioned method.
Moreover, according to the fine processing method of the fluororesin film | membrane using the patterning film obtained with the formation method of this patterning film, the fluororesin film | membrane which has a desired pattern is obtained easily.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by the following description. Examples 1 to 8 and 13 to 16 are examples, and examples 9 to 12 are comparative examples.
[Evaluation methods]
(With or without unpainted)
The photosensitive resin film formed in each example was visually observed and judged according to the following criteria.
<Criteria>
○ (good): Applied to the entire surface of the fluorine-containing resin film.
Δ (possible): There is a portion that is not applied to the surface of the fluororesin film due to liquid repelling or the like.
X (defect): The photosensitive resin solution is repelled on the surface of the fluorine-containing resin film and is not applied at all.

(Existence of film defects)
The photosensitive resin film formed in each example was observed with a differential interference microscope, and the presence or absence of defects such as minute foreign matters was evaluated according to the following criteria. The microscope used BLY2-UMA manufactured by OLYMPUS, and the lens used Neo SPlan 5 NIC.
<Criteria>
○ (good): No film defects are observed.
X (defect): Film defects such as foreign matter and pinholes are observed.

(Photolithographic patterning)
The shape of the photosensitive resin film patterned by photolithography was observed at a magnification of 450 times with a microscope, and the patternability was evaluated according to the following criteria. The microscope used VHX DIGITAL MICROSCOPE manufactured by KEYENCE, and the lens used KEYENCE VH-Z450. The evaluation was performed for a cylindrical isolated hole pattern with a diameter of 30 μm and a line and space pattern with a line width of 30 μm and a space width of 30 μm.
<Criteria>
○ (Good): The pattern is open and there is no defect such as residue.
X (defect): The pattern is not open or there is a defect such as a residue.

[material]
The abbreviations of the raw materials used for the production of the fluoropolymer etc. are shown below.
(Monomer)
_{C6FMA: CH 2 = C (CH} 3) COO (CH 2) 2 (CF 2) 5 CF 3,
_{C6FA: CH 2 = CHCOO (CH} 2) 2 (CF 2) 5 CF 3,
2-EHA: 2-ethylhexyl acrylate _{(CH 2 = CHCOOCH 2 CH (} C 2 H 5) CH 2 CH 2 CH 2 CH 3).
PEG9A: Polyethylene glycol monoacrylate (EO number average 9) (CH ₂ ═CHCOO (C ₂ H ₄ O) ₉ H).
OMA: octyl methacrylate _{(CH 2 = C (CH 3} ) COO (CH 2) 8 H).
PEG4.5A: Polyethylene glycol monoacrylate (EO average number _{4.5) (CH 2 = CHCOO (} C 2 H 4 O) 4.5 H).
_{PEPEGA: CH 2 = CHCOO (C} 2 H 4 O) 10 (C 3 H 6 O) 20 (C 2 H 4 O) 10 H.
CTL-809M: Cyclopolymer of perfluoro (3-butenyl vinyl ether) (trade name “CYTOP CTL-809M”, manufactured by Asahi Glass Co., Ltd.)
MOI-BM: Methyl ethyl ketone oxime blocked product of 2-isocyanatoethyl methacrylate (CH ₂ ═C (CH ₃ ) COOC ₂ H ₄ NHCO—ON═C (CH ₃ ) C ₂ H ₅ ) (trade name “Karenz MOI-BM” , Made by Showa Denko)

[Production Example 1]
In a 100 mL pressure-resistant glass bottle, 15 g of OMA, 35 g of PEG4.5A, 0.41 g of V-601 (oil-soluble azo polymerization initiator, manufactured by Wako Pure Chemical Industries, Ltd.), m-xylene hexafluoride (manufactured by Central Glass Co., Ltd., the following) And 31.3 g of “m-XHF”) were sealed, sealed, and heated at 70 ° C. for 16 hours. To this reaction solution, 50 g of C6FMA, 100 g of m-XHF, and 1.2 g of V-601 were charged, sealed, and heated at 70 ° C. for 16 hours to obtain a fluoropolymer (A-1). As a result of measuring the copolymer composition of the fluoropolymer (A-1), C6FMA units (corresponding to the unit (a1)), PEG4.5A units (corresponding to the unit (a2)), and OMA units (corresponding to the unit (a3)). It was confirmed that the fluorine-containing polymer had a molar ratio of 36:40:24 (mass ratio of 50:35:15).

[Production Example 2]
A 100 mL pressure glass bottle was charged with 40 g of 2-EHA, 40 g of PEG9A, 0.66 g of V-601, and 49.8 g of m-XHF, sealed, and then heated at 70 ° C. for 16 hours. To this reaction liquid, 20 g of C6FA, 40 g of m-XHF, and 0.48 g of V-601 were charged, sealed, and then heated at 70 ° C. for 16 hours to obtain a fluoropolymer (A-2). As a result of measuring the copolymer composition of the fluoropolymer (A-2), C6FA units (corresponding to the unit (a1)), PEG9A units (corresponding to the unit (a2)), and 2-EHA units (corresponding to the unit (a3)). And a fluorine-containing polymer having a molar ratio of 14:24:62 (mass ratio of 20:40:40). As a result of measuring the molecular weight, the number average molecular weight (Mn) of the fluoropolymer (A-2) was 17,000, the mass average molecular weight (Mw) was 40,000, and the molecular weight distribution (mass average molecular weight (Mw) / The number average molecular weight (Mn) was 2.3.

[Production Example 3]
A 100 mL pressure-resistant glass bottle was charged with 80 g of PEPEGA, 0.66 g of V-601, and 49.8 g of m-XHF, sealed, and then heated at 70 ° C. for 16 hours. To this reaction solution, 20 g of C6FA, 40 g of m-XHF, and 0.48 g of V-601 were charged, sealed, and then heated at 70 ° C. for 16 hours to obtain a fluoropolymer (A-3). As a result of measuring the copolymer composition of the fluoropolymer (A-3), the molar ratio of C6FA unit (corresponding to unit (a1)) and PEPEGA unit (corresponding to unit (a2)) was 56:44 (mass ratio 20: 80).

[Production Example 4]
In a 50 mL pressure-resistant glass bottle, 3.10 g of C6FMA, 0.32 g of 2-hydroxyethyl methacrylate, 0.57 g of MOI-BM, 46 mg of thermal polymerization initiator V65 (manufactured by Wako Pure Chemical Industries, Ltd.) were added to AK-225G. It was dissolved in 36 g (manufactured by Asahi Glass Co., Ltd.) and reacted at 50 ° C. for 24 hours after nitrogen substitution. The obtained reaction solution was reprecipitated in 600 mL of hexa and dried under reduced pressure overnight at room temperature to obtain 3.1 g of a fluoropolymer (X).

[Example 1]
25% by mass of EP4020G (phenol resin, manufactured by Asahi Organic Materials Co., Ltd.) as the positive photosensitive resin (B1) and 4NT-300 (manufactured by Toyo Gosei Co., Ltd.) as the photosensitive compound (C1) with respect to the entire solution. 2.5% by mass, 0.03% by mass of the fluoropolymer (A-1) obtained in Production Example 1 as the fluoropolymer (A) (0.5% by mass in the solid content of the photosensitive resin solution) ), 72.48% by mass of propylene glycol monoethyl ether acetate (PGMEA) as a solvent (D1), and a positive photosensitive photosensitive resin solution (solid content concentration 27.53% by mass, solid content concentration). Was calculated from the charged amount).
A fluorine-containing resin CTL-809M was spin-coated on a Si substrate at 2,000 revolutions per minute and heated in an oven at 160 ° C. for 1 hour to form a fluorine-containing resin film having a thickness of 1 μm.
The photosensitive resin solution is spin-coated at 1,000 rpm for 30 seconds on the fluororesin film, and heated for 90 seconds on a hot plate heated to 60 ° C. A photosensitive resin film was formed.
Table 1 shows the results of evaluating the presence or absence of unpainted areas and the presence or absence of film defects.

[Examples 2 to 17]
The positive photosensitive photosensitivity was the same as in Example 1 except that the type of fluoropolymer (A) used and the fluoropolymer ratio in the solid content of the photosensitive resin solution were changed as shown in Table 1. A functional resin film was formed. As a comparative example, instead of the fluoropolymer (A), a nonionic fluorosurfactant having a structure in which a polyoxyethylene chain is added to a perfluoroalkyl group (“Surflon” (trademark) S-420, S-242 and S-243, manufactured by AGC Seimi Chemical Co., Ltd.) were used.
Table 1 shows the results of evaluating the presence or absence of unpainted areas and the presence or absence of film defects.

[Example 18]
A positive photosensitive photosensitive resin film was formed in the same manner as in Example 1 except that a PTFE sheet (Naflon tape, TOMBO9001, manufactured by Nichias) attached to a Si substrate was used as the fluorine-containing resin film.

[Examples 19 to 31]
The positive photosensitive photosensitivity was the same as in Example 18 except that the type of fluoropolymer (A) used and the fluoropolymer ratio in the solid content of the photosensitive resin solution were changed as shown in Table 2. A functional resin film was formed.
Table 2 shows the results of evaluating the presence or absence of unpainted areas and the presence or absence of film defects.

[Example 32]
10 parts of the fluoropolymer (X) obtained in Production Example 4 was mixed with 90 parts of 1H, 1H, 5H-octafluoropentanol, and a thermosetting fluororesin solution (solid content concentration 10 mass). %) Was prepared.
The fluorine-containing resin solution was spin-coated on a Si substrate at 1,450 revolutions per minute and heated in an oven at 200 ° C. for 30 minutes to form a fluorine-containing resin film (G) having a thickness of 0.8 μm.
A positive-type photosensitive resin film was formed in the same manner as in Example 2 except that the fluorine-containing resin film (G) was used as the fluorine-containing resin film.

[Examples 33 to 43]
The positive photosensitive photosensitivity was the same as in Example 32 except that the type of fluoropolymer (A) used and the fluoropolymer ratio in the solid content of the photosensitive resin solution were changed as shown in Table 3. A functional resin film was formed.
Table 3 shows the results of evaluating the presence or absence of unpainted areas and the presence or absence of film defects.

[Example 44]
21.13% by mass of KAYARAD ZCR-1761H (manufactured by Nippon Kayaku Co., Ltd., solid content: 60% by mass, remaining 40% by mass of PGMEA) as a negative photosensitive resin (B2) solution with respect to the whole solution, 12.68% by mass of A-9550 (manufactured by Shin-Nakamura Kogyo Co., Ltd.) as the agent (E2), IRGACURE907 (manufactured by BASF, 2-methyl-1- [4- ( 1.27% by mass of methylthio) phenyl] -2-morpholinopropan-1-one), 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) as the sensitizer as the other component (F2) 0.38% by mass of the fluoropolymer (A-1) obtained in Production Example 1 as the fluoropolymer (A) (0.25% by mass in the solid content of the photosensitive resin solution) %), Dissolved (D2) is blended in a proportion of 54.3% by mass of propylene glycol methyl ether (PGME), 5% by mass of isopropyl alcohol (IPA), and 5% by mass of water to prepare a negative photosensitive photosensitive resin solution. did.
A fluorine-containing resin CTL-809M was spin-coated on a Si substrate at 2,000 revolutions per minute and heated in an oven at 160 ° C. for 1 hour to form a fluorine-containing resin film having a thickness of 1 μm.
The photosensitive resin solution is spin-coated at 900 rpm for 10 seconds on the fluorine-containing resin film, and then heated for 90 seconds on a hot plate heated to 60 ° C., thereby obtaining a negative photosensitive film having a film thickness of 2.5 μm. A photosensitive resin film was formed.
Table 4 shows the results of evaluating the presence or absence of unpainted areas and the presence or absence of film defects.

[Example 45]
A negative photosensitive resin film was formed in the same manner as in Example 44 except that the fluoropolymer (A) used was changed as shown in Table 4.
Table 4 shows the results of evaluating the presence or absence of unpainted areas and the presence or absence of film defects.

As shown in Tables 1 to 4, in Examples 1 to 13, 18 to 27, and 32 to 39 using the photosensitive resin solution containing the fluorine-containing polymer (A) in a specific ratio, there is no unpainted and fluorine-containing polymer. A photosensitive resin film could be formed on the entire surface of the resin film, and there was no defect in the photosensitive resin film.
On the other hand, in Examples 14 to 17, 28 to 31, and 40 to 43, in which a fluorosurfactant was used instead of the fluoropolymer (A), the photosensitive resin solution could not be applied on the fluororesin film at all. A photosensitive resin film could not be formed.

[Example 46]
A positive photosensitive photosensitive resin solution obtained in the same manner as in Example 2 was spin-coated at 1,000 rpm for 30 seconds on the fluorine-containing resin film formed in the same manner as in Example 1, and heated to 60 ° C. The film was heated on the hot plate for 90 seconds to form a positive photosensitive photosensitive resin film having a thickness of 3 μm.
Next, using a high-pressure mercury lamp as a light source, the photosensitive resin film is exposed to an exposure energy of 200 mJ / cm ² through a mask (a cylindrical isolated hole pattern with a diameter of 30 μm), and the photosensitive resin film A part of (exposed part) was solubilized with alkali. The photosensitive resin film was subjected to paddle development for 60 seconds using a developer (NMD-W, concentration 2.38 mass%), and then rinsed with pure water for 30 seconds to obtain a patterning film. Thereafter, in order to remove the developer and pure water, spin drying was performed at 2,000 rpm for 30 seconds, and heating was performed at 100 ° C. for 90 seconds with a hot plate. The film thickness of the portion not removed by development was 2.5 μm.
Further, a patterning film was formed by the same method using a mask capable of cutting a line and space pattern having a line width of 30 μm and a space width of 30 μm.
Table 5 shows the evaluation results of photolithography patterning properties.

[Example 47]
A negative photosensitive photosensitive resin solution obtained in the same manner as in Example 44 was spin-coated on a fluorine-containing resin film formed in the same manner as in Example 1 at 900 rpm for 10 seconds and heated to 60 ° C. The plate was heated for 90 seconds to form a negative photosensitive photosensitive resin film having a thickness of 2.5 μm.
Next, using a high-pressure mercury lamp as a light source, the photosensitive resin film is exposed through a mask (a cylindrical isolated hole pattern with a diameter of 30 μm) so that the exposure energy is 400 mJ / cm ^2. A part of (exposed part) was cured. The photosensitive resin film was subjected to paddle development for 60 seconds using a developer (NMD-W, concentration 2.38 mass%), and then rinsed with pure water for 30 seconds to obtain a patterning film. Thereafter, in order to remove the developer and pure water, spin drying was performed at 2,000 rpm for 30 seconds, and heating was performed at 100 ° C. for 90 seconds with a hot plate. The film thickness of the part not removed by development was 2 μm.
Table 5 shows the evaluation results of photolithography patterning properties.

As shown in Table 5, in Examples 46 and 47 using the photosensitive resin solution containing the fluorine-containing polymer (A) at a specific ratio, in both the cylindrical isolated hole pattern and the line and space pattern, the photo Excellent lithography patterning property.

Applications of the fluorine-containing resin film obtained by using the photosensitive resin solution of the present invention include electrical insulating films, chemical or physical protective films, non-adhesive films in various electronic devices (semiconductor devices, etc.), etc. Etc. Specifically, interlayer insulating films for flexible devices, protective films for flexible devices, gate insulating films for organic thin film transistors, gate insulating films for oxide thin film transistors, capacitor insulating films, gate insulating films for memory transistors, semiconductor passivation, semiconductor elements Protective film, interlayer insulating film for multilayer wiring for high-density mounting, insulating layer for organic electroluminescence device, insulating film for rewiring, cover coat of flexible copper-clad plate, solder resist film, liquid crystal alignment film, protective film for color filter And resin posts such as semiconductor elements, and partition walls such as color filters.
In addition, the entire content of the specification, claims, abstract, and drawings of Japanese Patent Application No. 2014-159484 filed on August 5, 2014 is cited here as disclosure of the specification of the present invention. Incorporated.

DESCRIPTION OF SYMBOLS 10 Board | substrate 12 Fluorine-containing resin film 12a Hole 14 Photosensitive resin film 16 Mask 18 Patterning film 18a The part without the film | membrane of a patterning film

Claims (12)

1. A photosensitive resin solution for forming a photosensitive resin film on a fluorine-containing resin film,
   The solution contains a fluoropolymer having a unit derived from a monomer represented by the following formula (a1) and a unit derived from a monomer represented by the following formula (a2):
   A photosensitive resin solution, wherein a ratio of the fluoropolymer in a solid content of the solution is 0.001 to 20% by mass.
   

   

   (Wherein R ¹ is a hydrogen atom, a methyl group, a cyano group, a phenyl group, a benzyl group, a fluorine atom, a chlorine atom or a trifluoromethyl group, and L is a group represented by the following formulas (L-1) to (L -8), and R ^f is a fluoroalkyl group having 1 to 20 carbon atoms or a fluoroalkyl group having 1 to 20 carbon atoms having an etheric oxygen atom.
   R ² is a hydrogen atom, a methyl group or a chlorine atom, and R ³ is — (C _p H _2p O) _q —R ⁶ (where R ⁶ is a hydrogen atom or — (CH ₂ ) _r —R ⁷ ( R ⁷ is an alkoxy group having 1 to 8 carbon atoms, a hydrogen atom, a fluorine atom, a trifluoromethyl group, a hydroxy group or a cyano group, and r is an integer of 1 to 25), and p is 1 And an integer of 1 to 100, and q is an integer of 1 to 100.)
   

   

   (Wherein, a to k are each independently an integer of 1 to 8, and m, n, s and t are each independently 0 or 1)
2. R ¹ and R ² are both hydrogen atoms or methyl groups, R ^f is a perfluoroalkyl group, p is an integer of 1 to 6, q is an integer of 1 to 50, and r is 1 to The photosensitive resin solution according to claim 1, which is an integer of 4, and R ⁷ is a hydroxy group or an alkoxy group.
3. 3. The photosensitive resin solution according to claim 1, wherein L is a group represented by the formula (L-1).
4. Wherein _{(C p} H 2p _{O) q is, (C 2 H 4 O)} q, _{or, (C 2 H 4 O)} q2 - (C p 'H 2p' O) q3 ( although, p 'is 3 or 4 The photosensitive resin solution according to any one of claims 1 to 3, wherein q2 and q3 each independently represents an integer of 1 to 50, and q2 + q3 = q and q2≥q3. .
5. The photosensitive resin solution according to any one of Claims 1 to 4, wherein the fluoropolymer is a polymer further having units derived from a monomer represented by the following formula (a3).
   

   

   (In the above formula, R ⁴ is a hydrogen atom, a methyl group or a chlorine atom, R ⁵ is —R ⁸ —R ⁹ (where R ⁸ is a single bond or an alkylene group having 1 to 20 carbon atoms, R ⁹ is an alkoxy group having 1 to 8 carbon atoms, a hydrogen atom, a hydroxy group or a cyano group.)
6. The photosensitive resin solution according to claim 5, wherein R ⁴ is a hydrogen atom or a methyl group, and R ⁵ is an alkyl group having 1 to 12 carbon atoms.
7. 7. The photosensitive resin solution according to claim 1, comprising a positive photosensitive resin and a photosensitive compound.
8. The photosensitive resin solution according to any one of claims 1 to 6, comprising a negative photosensitive resin and a photosensitive compound.
9. The photosensitive resin solution according to any one of claims 1 to 8, wherein the fluorine-containing resin film is a film formed from a fluorine-containing cyclic ether resin.
10. The photosensitive resin solution according to claim 9, wherein the fluorine-containing cyclic ether resin is a fluorine-containing cyclic ether resin made of a perfluorodiene cyclized polymer.
11. The photosensitive resin solution according to any one of claims 1 to 10 is applied onto the fluorine-containing resin film to form a photosensitive resin film, and after exposing the photosensitive resin film through a mask, A patterning film forming method, wherein a patterning film is formed by patterning by development.
12. A fine processing method for a fluororesin film, wherein the patterning film formed by the method according to claim 11 is used as a mask to etch and pattern the fluororesin film.

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