JP2019143033A - Resin, photosensitive composition, substrate with liquid-repellent film, and method for producing the same - Google Patents

Abstract

To provide a resin providing a photosensitive composition capable of forming a liquid-repellent film perforated with a hole or groove in a thickness direction at a high aspect ratio; to provide a photosensitive composition capable of forming a liquid-repellent film perforated with a hole or groove in a thickness direction at a high aspect ratio; to provide a substrate with a liquid-repellent film using the photosensitive composition; and to provide a producing method therefor.SOLUTION: The resin includes a unit u1 having a fluorine-containing organic group, a unit u2 having an alkali-soluble group protected by an acid-dissociable group, and a unit u3 having an oxyalkylene group. The photosensitive composition includes the resin, a photo-acid generator, and a solvent.SELECTED DRAWING: None

Description

  The present invention relates to a resin, a photosensitive composition, a substrate with a liquid repellent film, and a method for producing the same.

  A biochip is a device that can detect biomolecules such as DNA, proteins, sugar chains, target compounds, etc. in large quantities simultaneously. As a highly sensitive detection method using a biochip, the beads are labeled with another antibody that specifically interacts with the target molecule, etc., and the target molecule interacts with the bead. There is a method of enclosing in an inner microwell and detecting by fluorescence analysis or the like.

  As a method for producing a biochip, there is a method using a photosensitive composition capable of forming a liquid repellent film having a predetermined pattern by photolithography. By forming a water-repellent film on a hydrophilic substrate using such a photosensitive composition, exposing in a predetermined pattern, and developing to expose a part of the hydrophilic substrate, the hydrophilic portion and the water-repellent portion are formed. Can be made separately. By making the bottom surface of the microwell hydrophilic and the water repellency of the side wall, beads can be efficiently accommodated in the microwell.

Photosensitive composition comprising a polymer having a fluoroalkyl group and a crosslinkable group or a polymer having a fluoroalkyl group and a polymer having a polymerizable crosslinkable group, as a photosensitive composition for a biochip, and containing a photoinitiator A composition has been proposed (Patent Document 1).
When the photosensitive film formed by applying the photosensitive composition of Patent Document 1 and removing the solvent as necessary is exposed, the polymerizable crosslinking group is crosslinked by the action of the acid generated from the photoinitiator in the exposed portion. To do. Therefore, when the exposed photosensitive film is developed, a non-exposed portion is removed, and a liquid repellent cured film having holes penetrating in the thickness direction is obtained.

International Publication No. 2017/082307

Increasing the aspect ratio, which is the ratio of the depth to the diameter of the microwell, makes it difficult for the beads contained in the microwell to jump out of the microwell.
However, in the photosensitive composition of Patent Document 1, it is difficult to sufficiently increase the aspect ratio of a fine hole such as a microwell. For example, when the film thickness is increased to increase the aspect ratio, the holes do not penetrate the film.

  An object of the present invention is to provide a resin from which a photosensitive composition capable of forming a liquid-repellent film in which holes or grooves penetrating in the thickness direction are formed with a high aspect ratio, and having high holes or grooves penetrating in the thickness direction. The present invention provides a photosensitive composition capable of forming a liquid repellent film formed at an aspect ratio, a substrate with a liquid repellent film using the photosensitive composition, and a method for manufacturing the same.

The present invention provides a resin, a photosensitive composition, a substrate with a liquid repellent film, and a method for producing the same, having the following configurations [1] to [10].
[1] A resin comprising a unit u1 having a fluorine-containing organic group, a unit u2 having an alkali-soluble group protected with an acid dissociable group, and a unit u3 having an oxyalkylene group.
[2] The resin according to [1], including a copolymer A including the unit u1, the unit u2, and the unit u3.
[3] The resin according to [1] or [2], including a copolymer B including the unit u1 and the unit u2, and a copolymer C including the unit u1 and the unit u3.
[4] The resin according to any one of [1] to [3], further including a unit u4 having a cyclic ether group.
[5] The resin according to any one of the above [1] to [4], comprising a terminal group represented by any one of the following formula 1, the following formula 2 and the following formula 3.
^{-X 1 -C (R 1) (} R 2) (R 3) Equation 1
-X ² -R ⁴ Equation 2
^{-X 3 -N (R 5) (} R 6) Equation 3
However, R ^{1 to} R ³ are each independently a hydroxyl group, an oxo group or a chain hydrocarbon group having 40 or less carbon atoms which may have an etheric oxygen atom, a cyclic group having 40 or less carbon atoms, a hydroxyl group, A halogen atom, an amino group, or a hydrogen atom, and at least two of R ^{1 to} R ³ are atoms or groups other than a hydrogen atom;
R ⁴ is a cyclic group having 40 or less carbon atoms,
R ⁵ and R ⁶ are each independently a hydroxyl group, an oxo group or a chain hydrocarbon group having 40 or less carbon atoms which may have an etheric oxygen atom, or a cyclic group having 40 or less carbon atoms,
X ^{1 to} X ³ each independently represent a single bond, —S—, —S—R ⁷ —, —R ⁸ —, —O—R ⁹ — or —O—, and R ⁷ , R ⁸ and R ⁹ Are each independently a linear alkylene group having 1 to 40 carbon atoms.
[6] A photosensitive composition comprising the resin according to any one of [1] to [5], a photoacid generator, and a solvent.
[7] The photosensitive composition of [6], wherein the photoacid generator has an extinction coefficient at a wavelength of 365 nm of 400 mL · g ⁻¹ · cm ⁻¹ or less.
[8] A substrate with a liquid repellent film having a liquid repellent film formed from the photosensitive composition of [6] or [7] on the surface of the substrate.
[9] The substrate with a liquid repellent film according to [8], which is used for a biochip.
[10] The photosensitive composition of [6] or [7] is applied to the surface of the substrate and dried to form a photosensitive film,
Exposing the photosensitive film;
A method for producing a substrate with a liquid repellent film, wherein the exposed photosensitive film is developed using an alkaline aqueous solution.

According to the resin of the present invention, a photosensitive composition capable of forming a liquid repellent film in which holes or grooves penetrating in the thickness direction are formed with a high aspect ratio is obtained.
According to the photosensitive composition of the present invention, a liquid repellent film in which holes or grooves penetrating in the thickness direction are formed with a high aspect ratio can be formed.
In the substrate with a liquid-repellent film of the present invention, the liquid-repellent film can be formed such that holes or grooves penetrating in the thickness direction are formed with a high aspect ratio.
According to the method for producing a substrate with a liquid repellent film of the present invention, a substrate with a liquid repellent film having a liquid repellent film in which holes or grooves penetrating in the thickness direction are formed with a high aspect ratio can be produced.

It is sectional drawing which shows each process in one Embodiment of the manufacturing method of the board | substrate with a liquid repellent film of this invention.

In this specification, the monomer represented by the formula m11 is referred to as a monomer m11. The same applies to monomers represented by other formulas.
The meanings of the following terms in this specification are as follows.
“Liquid-repellent film” refers to a film that exhibits liquid repellency compared to parts other than the liquid-repellent film (such as the substrate surface). Specifically, the contact angle of a given liquid is compared to parts other than liquid-repellent films It means a film that grows.
“Hydrophilic substrate” means a substrate exhibiting lyophilicity compared to a liquid repellent film, specifically, a substrate having a contact angle of a predetermined liquid smaller than that of the liquid repellent film.
The “end group” means a group present at the end of the main chain of the polymer.
“Cyclic ether” means a ring structure having an etheric oxygen atom between some carbon atoms of a saturated hydrocarbon ring.
An “etheric oxygen atom” means an oxygen atom that exists once between two carbon atoms.
“Unit based on monomer” is a general term for an atomic group directly formed by polymerizing one monomer molecule and an atomic group obtained by chemically converting a part of the atomic group.
“Monomer” means a compound having a polymerizable carbon-carbon double bond.
The “(meth) acryloyl group” is a general term for an acryloyl group and a methacryloyl group.
“(Meth) acrylate” is a general term for acrylate and methacrylate.
The “photo acid generator” means a compound that generates an acid when irradiated with light.
“Light” is a general term for ultraviolet rays, visible rays, infrared rays, electron beams and radiation.
The “absorption coefficient at a wavelength of 365 nm” is a value calculated by the Lambert Beer equation from the relationship between the concentration and the absorbance of a 0.001 to 0.1% by mass methanol solution of a photoacid generator.
The “ratio of each unit” in the resin and the polymer is determined from the integral ratio of peaks peculiar to each unit in the ¹ H-nuclear magnetic resonance (NMR) spectrum of the polymer.
The “weight average molecular weight” of the resin and the polymer is a standard polymethyl methacrylate conversion value obtained by gel permeation chromatography.
The dimensional ratio in FIG. 1 is different from the actual one for convenience of explanation.

〔resin〕
The resin of the present invention (hereinafter also referred to as “the present resin”) includes a unit u1 having a fluorine-containing organic group, a unit u2 having an alkali-soluble group protected with an acid-dissociable group, and a unit having an oxyalkylene group. u3.
The resin preferably further includes a unit u4 having a cyclic ether group.
The resin may further include a unit u5 other than the unit u1, the unit u2, the unit u3, and the unit u4 as necessary.

  The unit u1 has a fluorine-containing organic group. When this resin has unit u1, the film formed from the photosensitive composition containing this resin can exhibit liquid repellency.

Examples of the fluorine-containing organic group include a fluoroalkyl group which may have an etheric oxygen atom between carbon atoms, an alicyclic group having at least one fluorine atom, and the like. From the viewpoint that can be sufficiently imparted, a fluoroalkyl group which may have an etheric oxygen atom between carbon atoms is preferred.
The fluoroalkyl group may be linear or branched. The ratio of the number of fluorine atoms to the total number of hydrogen atoms and fluorine atoms in the fluoroalkyl group is preferably 50% or more.

As the fluoroalkyl group, a fluoroalkyl group having a perfluoroalkyl moiety which may have an etheric oxygen atom between carbon atoms is preferable.
The fluoroalkyl group having a perfluoroalkyl moiety include fluoroalkyl group represented by -R ¹³ -R ^f. However, R ^f, is a good perfluoroalkyl moiety may have an etheric oxygen atom between carbon atoms, R ¹³ is an alkylene moiety having no fluorine atom.

In the case where R ^f is a perfluoroalkyl moiety having no etheric oxygen atom, its carbon number is preferably an integer of 4 or more from the viewpoint of sufficiently imparting liquid repellency to the liquid repellent film, and has little influence on the environment. From the viewpoint, an integer of 6 or less is preferable. Therefore, the carbon number is preferably 4, 5 or 6, and 6 is particularly preferable. R ^f may be linear or branched, but is preferably linear.
When ^Rf is a perfluoroalkyl moiety having an etheric oxygen atom between carbon atoms, the number of etheric oxygen atoms is preferably 1 to 3. The number of carbon atoms of the perfluoroalkyl moiety further on the terminal side (opposite to the R ¹³ side) than the ethereal oxygen atom on the most terminal side is preferably 1-6. The number of carbon atoms in the perfluoroalkylene portion between the inter-etheric oxygen atoms and ether oxygen atom and R ¹³ is 1-4 are preferable. The perfluoroalkyl moiety having an etheric oxygen atom may be linear or branched as a whole, and the total number of carbon atoms is preferably 3 to 12, more preferably 4 to 8.
The _{^{R f, - (CF 2)}} 3 CF 3, - (CF 2) 4 CF 3, - (CF 2) 5 CF 3, -CF (CF 3) OCF 2 CF 2 CF 3, -CF 2 OCF 2 _{CF 2 OCF 3, -CF 2 OCF} 2 CF 2 OCF 2 CF 3, etc. _{-CF 2 OCF 2 CF 2 OCF 2} CF 2 OCF 3 , and the like.
R ¹³ may be linear or branched, but is preferably linear. The number of carbon atoms of R ¹³ is 1 to 6 preferably 1 to 4 is more preferred. R ¹³ is particularly preferably —CH ₂ — or —CH ₂ CH ₂ —.

The unit u1 is preferably a unit based on the monomer m1 having a fluorine-containing organic group. The monomer m1 is typically a compound having a fluorine-containing organic group and a polymerizable carbon-carbon double bond. As the monomer m1, a monomer composed of an ester of a monool represented by HO—R ¹³ —R ^f and an unsaturated monocarboxylic acid is preferable. Examples of the unsaturated monocarboxylic acid include methacrylic acid, acrylic acid, α-haloacrylic acid and the like.
The monomer ^m1, having a fluoroalkyl group represented by ^-R 13 -R ^f (meth) acrylate are particularly preferred. As such a (meth) acrylate, the following monomer m11 is mentioned, for example.
^{_{CH 2 = C (R 12)}} COO-R 13 -R f formula m11
However, R ¹² is hydrogen atom, a methyl group or a halogen atom.
Examples of the halogen atom for R ¹² include a fluorine atom and a chlorine atom.

Specific monomer _{m1 (m11), CH 2 =} C (CH 3) COO-C 2 H 4 - (CF 2) 3 CF 3, CH 2 = CHCOO-C 2 H 4 - (CF 2) _{3 CF 3, CH 2 = C} (CH 3) COO-C 2 H 4 - (CF 2) 4 CF 3, CH 2 = CHCOO-C 2 H 4 - (CF 2) 4 CF 3, CH 2 = C ( _{CH 3) COO-C 2 H} 4 - (CF 2) 5 CF 3, CH 2 = CHCOO-C 2 H 4 - (CF 2) 5 CF 3, CH 2 = C (CH 3) COO-CH 2 CF ( _{CF 3) OCF 2 CF 2 CF} 3, CH 2 = CHCOO-CH 2 CF (CF 3) OCF 2 CF 2 CF 3, CH 2 = C (CH 3) COO-CH 2 CF 2 OCF 2 CF 2 OCF 3, CH ₂ = CHCOO-CH _{2 F 2 OCF 2 CF 2 OCF 3} , CH 2 = C (CH 3) COO-CH 2 CF 2 OCF 2 CF 2 OCF 2 CF 3, CH 2 = CHCOO-CH 2 CF 2 OCF 2 CF 2 OCF 2 CF 3, _{CH 2 = C (CH 3)} COO-CH 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 3, CH 2 = CHCOO-CH 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 3 , and the like. Of these, CH ₂ ═C (CH ₃ ) COO—C ₂ H ₄ — (CF ₂ ) ₅ CF ₃ , and CH ₂ ═C (CH ₃ ) COO—CH ₂ CF in that good liquid repellency can be obtained. ₂ OCF ₂ CF ₂ OCF ₃ are preferred.
Monomer m1 may be used individually by 1 type, and may use 2 or more types together.

The unit u2 has an alkali-soluble group protected with an acid-dissociable group. When this resin contains unit u2, the composition containing this resin and a photo-acid generator has photosensitivity. When the photosensitive film containing the resin and the photoacid generator is exposed, the acid-dissociable group is dissociated in the exposed portion to produce an alkali-soluble group, and the exposed portion can be dissolved and removed with an aqueous alkali solution.
Examples of the alkali-soluble group include a carboxy group and a sulfonic acid group, and a carboxy group is preferable from the viewpoint of availability of monomers and ease of synthesis.

Examples of the alkali-soluble group protected with an acid-dissociable group include a group represented by —C (O) OC (R ²¹ ) (R ²² ) OR ²³ , —C (O) OC (R ²⁴ ) (R ²⁵ ). And a group represented by (R ²⁶ ). However, R ²¹ is an alkyl group or a cycloalkyl group, R ²² is a hydrogen atom, an alkyl group or a cycloalkyl group, and R ²³ is an alkyl group in which a part of the hydrogen atoms may be substituted, A cycloalkyl group in which part of the hydrogen atom may be substituted, or an aralkyl group in which part of the hydrogen atom may be substituted, and R ²¹ and R ²³ are linked to form a cyclic ether group. May be. R ²⁴ to R ²⁶ are each independently an alkyl group.
These groups are hydrolyzed by the action of an acid generated from the photoacid generator to produce a carboxy group.

R ²¹ is preferably a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms, and a methyl group is particularly preferable from the viewpoint of easy availability of the raw material monomer.
R ²² is preferably a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms. From the viewpoint of easy availability of the raw material monomer, a hydrogen atom is particularly preferable. preferable.
R ²³ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.
When R ²¹ and R ²³ are linked to form a cyclic ether group, it is preferable that R ²¹ and R ²³ are linked to form an alkylene group having 2 to 5 carbon atoms.
When a part of hydrogen atoms in the alkyl group, cycloalkyl group or aralkyl group of R ²³ is substituted, examples of the substituent include an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms. Group, halogen atom and the like. In the case where R ²³ has a substituent, preferable range of the total number of carbon atoms are as defined above.
R ^{24 to} R ²⁶ are each preferably an alkyl group having 1 to 40 carbon atoms, particularly a methyl group.

-C ^(O) as the ^{OC (R 21) (R 22} ) of the group represented by ^{OR 23 C (R 21) (} R 22) OR 23, 1- ethoxyethyl group, a 1-methoxyethyl group, 1- n-butoxyethyl group, 1-isobutoxyethyl group, 1- (2-chloroethoxy) ethyl group, 1- (2-ethylhexyloxy) ethyl group, 1-n-propoxyethyl group, 1-cyclohexyloxyethyl group, Examples include 1- (2-cyclohexylethoxy) ethyl group, 1-benzyloxyethyl group, and the like.
Examples of the group represented by —C (O) OC (R ²⁴ ) (R ²⁵ ) (R ²⁶ ) include a tert-butoxycarbonyl group (—C (O) OC (CH ₃ ) ₃ ) and the like.

As the alkali-soluble group protected with an acid-dissociable group, a group represented by —C (O) OC (R ²¹ ) (R ²² ) OR ²³ is preferable. The group represented by —C (O) OC (R ²¹ ) (R ²² ) OR ²³ has a lower activation energy for acid decomposition than a tert-butoxycarbonyl group and the like, and is easily generated by an acid from a photoacid generator. Hydrolyzes. Therefore, development is possible without performing post-exposure baking (PEB) after exposure. Moreover, when this resin contains the unit u4, it can suppress that the cyclic ether group of the unit u4 reacts with PEB, and bridge | crosslinking advances before image development.

The unit u2 is preferably a unit based on the monomer m2 having an alkali-soluble group protected with an acid-dissociable group. The monomer m2 is typically a compound having an alkali-soluble group protected with an acid-dissociable group and a polymerizable carbon-carbon double bond.
As the monomer m2, (meth) acrylate having an alkali-soluble group protected with an acid-dissociable group is particularly preferable. As such (meth) acrylate, the following monomer m21, the following monomer m22, etc. are mentioned, and monomer m21 is preferable.
CH ₂ = CH (R ²⁰ ) C (O) OC (R ²¹ ) (R ²² ) OR ²³ formula m21
^{_{CH 2 = CH (R 20)}} C (O) OC (R 24) (R 25) (R 26) Formula m22
^{However, R 20} is hydrogen atom or a methyl group.

Specific monomers m21 include 1-ethoxyethyl (meth) acrylate, 1-methoxyethyl (meth) acrylate, 1-n-butoxyethyl (meth) acrylate, 1-isobutoxyethyl (meth) acrylate, 1 -(2-chloroethoxy) ethyl (meth) acrylate, 1- (2-ethylhexyloxy) ethyl (meth) acrylate, 1-n-propoxyethyl (meth) acrylate, 1-cyclohexyloxyethyl (meth) acrylate, 1- Examples include (2-cyclohexylethoxy) ethyl (meth) acrylate, 1-benzyloxyethyl (meth) acrylate, and the like.
Specific examples of the monomer m22 include tert-butoxycarbonyl (meth) acrylate.
As the unit u2, one type may be used alone, or two or more types may be used in combination.

  The unit u3 has an oxyalkylene group. When the resin contains the unit u3, a liquid repellent film in which holes or grooves penetrating in the thickness direction are formed with a high aspect ratio can be formed from the photosensitive composition containing the resin.

As for carbon number of an oxyalkylene group, 2-4 are preferable. Examples of the oxyalkylene group include CH ₂ CH ₂ O, CH ₂ CH ₂ CH ₂ O, CH (CH ₃ ) CH ₂ O, CH ₂ CH ₂ CH ₂ CH ₂ O, and the like. Of these, an oxyethylene group is particularly preferred.
In the unit u3, the number of repeating oxyalkylene groups is preferably an integer of 1 to 30, more preferably an integer of 3 to 25, and particularly preferably 3 to 20.

The unit u3 is preferably a unit based on the monomer m3 having an oxyalkylene group. The monomer m3 is typically a compound having an oxyalkylene group and a polymerizable carbon-carbon double bond.
The monomer m3 is preferably a (meth) acrylate having an oxyalkylene group. As such a (meth) acrylate, the following monomer m31 is mentioned, for example.
^{_{CH 2 = CH (R 30)}} C (O) O (R 31 O) n R 32 Formula m31
^{However, R 30} is a hydrogen atom or a methyl ^{group, R 31} is an alkylene group having 2 to 4 carbon atoms, n is an integer of 1 to ^{30, R 32} is a hydrogen atom or an alkyl group.
R ³¹ is preferably an ethylene group. n is preferably an integer of 2 to 25, particularly preferably 3 to 20. The number of carbon atoms in the alkyl group for R ³² is preferably 1 to 25, more preferably 1 to 4, 1 or 2 are particularly preferred.

Specific examples of the monomer m31 include the following compounds.
_{CH 2 = CHC (O) O} (C 2 H 4 O) 9 H, CH 2 = CHC (O) O (C 2 H 4 O) 5 H, CH 2 = CHC (O) O (C 2 H 4 O ) ₄ H, CH ₂ ═CHC (O) O (C ₂ H ₄ O) ₃ H, CH ₂ ═CHC (O) O (C ₂ H ₄ O) ₉ CH ₃ , CH ₂ ═CHC (O) O ( _{C 2 H 4 O) 5 CH} 3, CH 2 = CHC (O) O (C 2 H 4 O) 4 CH 3, CH 2 = CHC (O) O (C 2 H 4 O) 3 CH 3, CH 2 _{= CHC (O) O (C} 2 H 4 O) 3 C 2 H 5, CH 2 = C (CH 3) C (O) O (C 2 H 4 O) 9 H, CH 2 = C (CH 3) _{C (O) O (C 2} H 4 O) 5 H, CH 2 = C (CH 3) C (O) O (C 2 H 4 O) 4 H, CH 2 = C (CH 3) C (O) O _{(C 2 4 O) 3 H, CH 2} = C (CH 3) C (O) O (C 2 H 4 O) 9 CH 3, CH 2 = C (CH 3) C (O) O (C 2 H 4 O) _{5 CH 3, CH 2 = C} (CH 3) C (O) O (C 2 H 4 O) 4 CH 3, CH 2 = C (CH 3) C (O) O (C 2 H 4 O) 3 CH _{3, CH 2 = C (CH} 3) C (O) O (C 2 H 4 O) 3 C 2 H 5, CH 2 = CHC (O) O (C 2 H 4 O) g1 (C 4 H 8 O _{) g2 H, CH 2 = CHC} (O) O (C 2 H 4 O) g1 (C 4 H 8 O) g2 CH 3, CH 2 = C (CH 3) C (O) O (C 2 H 4 O _{) g1 (C 4 H 8 O} ) g2 H, CH 2 = C (CH 3) C (O) O (C 2 H 4 O) g1 (C 4 H 8 O) g2 CH 3 and the like. However, g1 and g2 are each independently an integer of 1 or more, and g1 + g2 is an integer of 2 to 30.
As the unit u3, one type may be used alone, or two or more types may be used in combination.

The unit u4 is a unit having a cyclic ether group (except for the unit u2).
When this resin contains the unit u4, the liquid repellent film is subjected to heat treatment after development, whereby the cyclic ether group in the unit u4 and the alkali-soluble group (carboxy group or the like) generated by the dissociation of the acid-dissociable group in the unit u2. ) React with each other to form a crosslinked structure, and a liquid repellent film having better liquid repellency is formed.

The cyclic ether group is preferably a 3-membered or 4-membered cyclic ether group, and examples thereof include an epoxy group, an oxetane group, and a 3,4-epoxycyclohexyl group.
The cyclic ether group may be substituted with an alkyl group as long as the reactivity is not impaired. As for carbon number of an alkyl group, 1-6 are preferable.
The epoxy group and the 3,4-epoxycyclohexyl group are preferably unsubstituted. The oxetane group may be unsubstituted or substituted with an alkyl group, and is preferably a (3-alkyloxetane-3-yl) group.

As the cyclic ether group, an oxetane group which may be substituted with an epoxy group or an alkyl group is preferable for the following reasons, and an epoxy group is particularly preferable.
Epoxy groups and oxetane groups hardly react with alkali-soluble groups such as carboxy groups at a relatively low temperature, and easily react with alkali-soluble groups at a relatively high temperature. That is, the epoxy group and the oxetane group are unlikely to react with the alkali-soluble group formed by dissociation of the acid-dissociable group in the unit u2 by the acid generated from the photoacid generator by exposure, and the unit u2 is subjected to heat treatment after development. In this case, it easily reacts with a carboxy group formed by dissociation of an acid dissociable group. Therefore, the unit u4 and the unit u2 hardly form a cross-linked structure from exposure to development and does not affect the developability of the photosensitive film. On the other hand, the unit u4 and the unit u2 form a crosslinked structure by heat treatment after development, and a liquid repellent film including the crosslinked structure (hereinafter also referred to as “liquid repellent cured film”) is formed.

As a method for obtaining a polymer having a unit u4, (1) a method of copolymerizing a monomer m4 having a cyclic ether group and another monomer, (2) a monomer m4 ′ having a specific reaction site, After copolymerization with other monomers to obtain a polymer, the polymer has a reactive functional group capable of binding to the specific reaction site and a cyclic ether group (hereinafter referred to as “reactive compound”). And a method of reacting.).
The unit u4 of the polymer obtained by the method (1) is a unit based on the monomer m4 having a cyclic ether group. The unit u4 of the polymer obtained by the method (2) is a unit in which a cyclic ether group is introduced into the specific reaction site of a unit based on the monomer m4 ′ having a specific reaction site.
In the polymerization reaction of the monomer m4 or the like, the cyclic ether group of the monomer having a cyclic ether group usually does not react. Therefore, the unit u4 may be a unit based on the monomer m4 or a unit in which a cyclic ether group is introduced into the specific reaction site of the unit based on the monomer m4 ′. In terms of easy production, the unit is preferably based on the monomer m4.

The monomer m4 is typically a compound having a cyclic ether group and a polymerizable carbon-carbon double bond. The monomer m4 is preferably a (meth) acrylate having a cyclic ether group. As such (meth) acrylate, the following monomer m41 is mentioned, for example.
_{^{CH 2 = C (R 40)}} COO-R 41 -R 42 Formula m41
However, R ⁴⁰ is a hydrogen atom or a methyl group, R ⁴¹ is an alkylene group, and R ⁴² is a group containing a 3-membered or 4-membered cyclic ether group. R ⁴¹ preferably has 1 to 20 carbon atoms.
Specific examples of the monomer m4 include glycidyl (meth) acrylate, 4-glycidyloxybutyl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (meth) acrylate, 3,4-epoxycyclohexylmethyl ( And (meth) acrylate.

Examples of the specific reaction site of the monomer m4 ′ include a hydroxyl group, a carboxy group, an isocyanate group, an epoxy group, and an amino group.
The monomer m4 ′ is typically a compound having the specific reaction site and a polymerizable carbon-carbon double bond, and examples thereof include a (meth) acrylate having a hydroxyl group or a carboxyl group.
Specific examples of the monomer having a hydroxyl group as a specific reaction site among the monomers m4 ′ include 2-hydroxyethyl methacrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxy Examples include butyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 4-hydroxycyclohexyl (meth) acrylate.
Specific examples of the monomer having a carboxyl group as the specific reaction site in the monomer m4 ′ include acrylic acid, methacrylic acid, and vinyl acetic acid.

The reactive functional group of the reactive compound is appropriately selected according to the specific reaction site. For example, when the specific reaction site is a hydroxyl group, an isocyanate group, a carboxy group, a haloacyl group (acyl chloride group, etc.), an epoxy group and the like can be mentioned. When the specific reaction site is a carboxy group, a hydroxyl group, an isocyanate group, an epoxy group Etc.
Examples of the compound having an isocyanate group and a polymerizable crosslinking group include 2- (meth) acryloyloxyethyl isocyanate. Examples of the compound having an acyl chloride group and a polymerizable crosslinking group include (meth) acryloyl chloride. Examples of the compound having an epoxy group and a polymerizable crosslinking group include glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 3,4-epoxycyclohexylmethyl (meth) acrylate, and the like.
As the unit u4, one type may be used alone, or two or more types may be used in combination.

The unit u5 is a unit other than the unit u1, the unit u2, the unit u3, and the unit u4.
As the unit u5, a unit based on the monomer m5 having no fluorine-containing organic group, an alkali-soluble group protected with the acid-dissociable group, the oxyalkylene group or the cyclic ether group may be mentioned.
The monomer m5 typically has a polymerizable carbon-carbon double group that does not have the fluorine-containing organic group, the alkali-soluble group protected with the acid-dissociable group, the oxyalkylene group, and the cyclic ether group. A compound having a bond. Specific examples of the monomer m5 include the following compounds.
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, octyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, Dimethylaminoethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 2-{(meth) acryloyloxy} ethyl-2 ′-(trimethylammonio) ethyl Phosphate, 3-{(meth) acryloyloxy} propyl-2 '-(trimethylammonio) ethyl phosphate, 4-{(meth) acryloyloxy} butyl-2'-(trimethylammonio) ethyl phosphate, 5-{( Meth) acryloyloxy} pentyl-2 ′-(trimethylammonio) ethyl phosphate, 6-{(meth) acryloyloxy} hexyl-2 ′-(trimethylammonio) ethyl phosphate, 2-{(meth) acryloyloxy} ethyl -2 '-(triethylammonio) ethyl phosphate, 2-{(meth) acryloyloxy} ethyl-2'-(tripropylammonio) ethyl phosphate, 2-{(meth) acryloyloxy} ethyl-2 '-( Tributylammonio) ethyl phosphate, 2-{(medium Ta) acryloyloxy} ethyl-2 ′-(tricyclohexylammonio) ethyl phosphate, 2-{(meth) acryloyloxy} ethyl-2 ′-(triphenylammonio) ethyl phosphate, 2-{(meth) acryloyloxy } Ethyl-2 ′-(trimethanolammonio) ethyl phosphate, 2-{(meth) acryloyloxy} propyl-2 ′-(trimethylammonio) ethyl phosphate, 2-{(meth) acryloyloxy} butyl-2 ′ -(Trimethylammonio) ethyl phosphate, 2-{(meth) acryloyloxy} pentyl-2 '-(trimethylammonio) ethyl phosphate, 2-{(meth) acryloyloxy} hexyl-2'-(trimethylammonio) Ethyl phosphate, 2- (vinyloxy) ester Tyl-2 '-(trimethylammonio) ethyl phosphate, 2- (allyloxy) ethyl-2'-(trimethylammonio) ethyl phosphate, 2- (p-vinylbenzyloxy) ethyl-2 '-(trimethylammonio) Ethyl phosphate, 2- (p-vinylbenzoyloxy) ethyl-2 '-(trimethylammonio) ethyl phosphate, 2- (styryloxy) ethyl-2'-(trimethylammonio) ethyl phosphate, 2- (p-vinyl Benzyl) ethyl-2 ′-(trimethylammonio) ethyl phosphate, 2- (vinyloxycarbonyl) ethyl-2 ′-(trimethylammonio) ethyl phosphate, 2- (allyloxycarbonyl) ethyl-2 ′-(trimethylammoni) E) Ethyl phosphate, 2- (acryloylua) C) ethyl-2 '-(trimethylammonio) ethyl phosphate, 2- (vinylcarbonylamino) ethyl-2'-(trimethylammonio) ethyl phosphate, ethyl- (2'-trimethylammonioethylphosphorylethyl) fumarate, Butyl- (2′-trimethylammonioethyl phosphorylethyl) fumarate, hydroxyethyl- (2′-trimethylammonioethyl phosphorylethyl) fumarate, ethyl- (2′-trimethylammonioethyl phosphorylethyl) malate, butyl- (2 '-Trimethylammonioethyl phosphorylethyl) malate, hydroxyethyl- (2'-trimethylammonioethyl phosphorylethyl) malate, or the like.
As the unit u5, one type may be used alone, or two or more types may be used in combination.

  The proportion of the unit u1 in the resin is preferably 3 to 40 mol%, particularly preferably 5 to 30 mol%, based on all units of the resin. When the ratio of the unit u1 is not less than the lower limit of the above range, the liquid repellency can be sufficiently imparted to the liquid repellency film. When the ratio of the unit u1 is less than or equal to the upper limit of the above range, the development failure of the photosensitive film is suppressed and the pattern resolution is increased.

  The proportion of the unit u2 in the resin is preferably 10 to 70 mol%, particularly preferably 15 to 60 mol%, based on all units of the resin. When the ratio of the unit u2 is equal to or higher than the lower limit of the above range, the development failure of the photosensitive film is further suppressed, and the resolution of the pattern is further increased. When the ratio of the unit u2 is less than or equal to the upper limit of the above range, it is difficult to impair the effects of other units.

The ratio of the unit u3 in the resin is preferably 2 to 25 mol%, particularly preferably 2 to 15 mol%, based on all units of the resin. When the ratio of the unit u3 is not less than the lower limit of the above range, the holes or grooves formed in the photosensitive film can have a high aspect. When the ratio of the unit u3 is less than or equal to the upper limit value of the above range, it is difficult to impair the effects of other units.
In some cases, the sum of the ratio of the unit u1, the ratio of the unit u2, and the ratio of the unit u3 may not be 100 mol%, but the remainder in this case is a unit other than the unit u1, the unit u2, and the unit u3.

  The proportion of the unit u4 in the resin is preferably 0 to 70 mol%, particularly preferably 10 to 60 mol%, based on all units of the resin. When the ratio of the unit u4 is not less than the lower limit of the above range, the strength of the liquid repellent cured film is increased. When the ratio of the unit u4 is less than or equal to the upper limit value of the above range, it is difficult to impair the effects of other units.

  The proportion of the unit u5 in the resin is preferably 0 to 50 mol% in all units of the resin. When the ratio of the unit u5 is less than or equal to the upper limit of the above range, it is difficult to impair the effects of other units.

  The resin preferably contains a terminal group represented by any one of the following formula 1, the following formula 2 and the following formula 3 (hereinafter also referred to as “terminal group J”). When the resin contains a terminal group J, a photosensitive composition containing the resin, a photoacid generator and a solvent is applied onto a substrate and dried to form a photosensitive film. Thickness unevenness (coating unevenness) is less likely to occur. In particular, when the weight average molecular weight of the resin is about 6,000 to 20,000, the effect of suppressing coating unevenness is remarkable.

^{-X 1 -C (R 1) (} R 2) (R 3) Equation 1
-X ² -R ⁴ Equation 2
^{-X 3 -N (R 5) (} R 6) Equation 3
However, R ^{1 to} R ³ are each independently a hydroxyl group, an oxo group or a chain hydrocarbon group having 40 or less carbon atoms which may have an etheric oxygen atom, a cyclic group having 40 or less carbon atoms, a hydroxyl group, A halogen atom, an amino group, or a hydrogen atom, and at least two of R ^{1 to} R ³ are atoms or groups other than a hydrogen atom;
R ⁴ is a cyclic group having 40 or less carbon atoms,
R ⁵ and R ⁶ are each independently a hydroxyl group, an oxo group or a chain hydrocarbon group having 40 or less carbon atoms which may have an etheric oxygen atom, or a cyclic group having 40 or less carbon atoms,
X ^{1 to} X ³ each independently represent a single bond, —S—, —S—R ⁷ —, —R ⁸ —, —O—R ⁹ — or —O—, and R ⁷ , R ⁸ and R ⁹ Are each independently a linear alkylene group having 1 to 40 carbon atoms.

In R ^{1 to} R ³ , the chain hydrocarbon group having 40 or less carbon atoms may be linear or branched. Further, it may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. The number of unsaturated bonds (double bonds, triple bonds, etc.) of the unsaturated hydrocarbon group may be 1 to 20, for example.
The chain hydrocarbon group may have a hydroxyl group, an oxo group (═O), or an etheric oxygen atom (—O—). That is, it may be a group in which at least one of the hydrogen atoms of the chain hydrocarbon group is substituted with a hydroxyl group, and at least one of the methylene groups of the chain hydrocarbon group is a group substituted with> C═O. Alternatively, it may be a group having an etheric oxygen atom at the end of the chain hydrocarbon group or / and between the carbon atoms, or a group in which two or more of these groups are combined.
When the chain hydrocarbon group has a hydroxyl group, the bonding position of the hydroxyl group in the chain hydrocarbon group is not particularly limited. The number of hydroxyl groups of the chain hydrocarbon group may be, for example, 1 to 4.
When the chain hydrocarbon group has an oxo group, the bonding position of the oxo group in the chain hydrocarbon group is not particularly limited. The number of oxo groups in the chain hydrocarbon group may be, for example, 1 to 10.
When the chain hydrocarbon group has an etheric oxygen atom, the position of the etheric oxygen atom in the chain hydrocarbon group is not particularly limited. For example, it may be the terminal of the chain hydrocarbon group (the terminal bonded to C in Formula 1), may be between the carbon atoms of the chain hydrocarbon group, or may be both of them. . The number of etheric oxygen atoms contained in the chain hydrocarbon group may be, for example, 1 to 10.
When the chain hydrocarbon group does not have an etheric oxygen atom between carbon atoms, it is 1 to 40, preferably 1 to 20. When it has an etheric oxygen atom between carbon atoms, it is 2-40, and 2-20 are preferable.
Specific examples of the chain hydrocarbon group in R ^{1 to} R ³ include alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, isopropyl group, isobutyl group, and 2-ethylhexyl group; allyl group , An alkenyl group such as —C ₃ H ₆ CH═CH ₂ ; an acyl group such as —C (═O) CH ₂ CH ₃ , an acetyl group, and the like.

In R ^{1 to} R ³ , the cyclic group having 40 or less carbon atoms may be monocyclic or polycyclic. Further, it may be an alicyclic group or an aromatic group. Further, it may be a hydrocarbon cyclic group or a heterocyclic group containing an atom (hetero atom) other than a carbon atom in the ring skeleton. Examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom.
When the cyclic group is a hydrocarbon cyclic group, the number of carbon atoms is 3 to 40, and 5 to 20 is preferable. When it is a heterocyclic group, it is 2-40, and 2-20 are preferable.
A substituent may be bonded to the ring skeleton of the cyclic group. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms and an aryl group.
Specific examples of the hydrocarbon cyclic group among the cyclic groups represented by R ^{1 to} R ³ include alicyclic hydrocarbon groups such as cyclohexyl group, adamantyl group and norbornyl group, and aromatic hydrocarbons such as phenyl group and naphthyl group. Groups and the like. Specific examples of the heterocyclic group include a furyl group, a thiophenyl group, a pyridinyl group, and the like.
In R ^{1 to} R ³ , examples of the halogen atom include a chlorine atom, an iodine atom, and a bromine atom.

R ^{1 to} R ³ may be the same or different. However, at least two of R ^{1 to} R ³ are atoms or groups other than hydrogen atoms, that is, the chain hydrocarbon group, the cyclic group, a hydroxyl group, a halogen atom, or an amino group. The group represented by Formula 1 is bulky because at least two atoms or groups having a size larger than the hydrogen atom are bonded to C (carbon atom to which R ^{1 to} R ³ are bonded) in Formula 1. It has a structure.

Examples of R ⁴ include those similar to the cyclic group having 40 or less carbon atoms in R ^{1 to} R ³ , and preferred embodiments thereof are also the same.
Examples of the chain hydrocarbon having 40 or less carbon atoms in R ⁵ and R ⁶ include those similar to the cyclic group having 40 or less carbon atoms in R ^{1 to} R ³ , and preferred embodiments are also the same. However, when the chain hydrocarbon group in R ⁵ and R ⁶ has an etheric oxygen atom, the position of the etheric oxygen atom is between the carbon atoms of the chain hydrocarbon group.
Examples of the cyclic group having 40 or less carbon atoms in R ⁵ and R ⁶ include those similar to the cyclic group having 40 or less carbon atoms in R ^{1 to} R ³ , and preferred embodiments thereof are also the same.

The linear alkylene group of R ⁷ and R ⁸ can be represented by — (CH ₂ ) _p —. The number of carbon atoms of straight-chain alkylene group (- _{(CH 2) p} - value of p) is 1 to 40, 1 to 20 are preferred.
X ^{1 to} X ³ are preferably —S—R ⁷ — and —O— in terms of ease of chain transfer when a polymer is produced using a corresponding chain transfer agent.

Specific examples of the terminal group J include —S—CH ₂ —CH (OH) —CH ₂ OH, —S—CH ₂ —CH (CH ₂ CH ₃ ) —CH ₂ CH ₂ CH ₂ CH ₃ , —S—. R ¹⁰ (R ¹⁰ is a cyclohexyl group), —S—CH ₂ —R ¹¹ (R ¹¹ is a furyl group or a phenyl group), —CCl ₃ , —O—CH ₂ CH (CH ₃ ) ₂ , —CH (CH _{3) ) -C (= O) CH 2} CH 3, -O-CH 2 CH 2 R 10, -O-CH 2 CH (CH 2 CH 2 CH 2 CH 2 CH 2 CH 3) CH 2 CH 2 CH 2 CH 2 etc. CH ₂ CH ₂ CH ₂ CH ₃ and the like. In terms of low _{odor, -S-CH 2 -CH (OH} ) -CH 2 OH is preferred.

The terminal group J is typically a group derived from a chain transfer agent represented by any one of the following formula 11, the following formula 12 and the following formula 13 (hereinafter also referred to as “chain transfer agent j”). .
^{Z 1 -X 1 -C (R 1} ) (R 2) (R 3) Equation 11
Z ² —X ² —R ⁴ Formula 12
Z ³ —X ³ —N (R ⁵ ) (R ⁶ ) Formula 13
However, Z < ¹ > -Z < ³ > is a hydrogen atom or a halogen atom each independently.
Examples of the halogen atom in Z ^{1 to} Z ³ include a chlorine atom, an iodine atom, and a bromine atom.
Specific examples of the chain transfer agent j include thioglycerol, 2-ethylhexanethiol, cyclohexanethiol, furfuryl mercaptan, benzylthiol, carbon tetrachloride, isobutyl alcohol, 3-pentanone, cyclohexylethanol, 2-hexyl-1-decanol, and the like. Is mentioned.
As the chain transfer agent j, X ¹ in the formula 11 is preferably —S—R ⁷ — because the boiling point is high, the molecular weight can be easily adjusted and the handling is easy. From the viewpoint of low odor, thioglycerol is preferable.

The weight average molecular weight (Mw) of the resin is preferably 4,000 to 500,000, more preferably 5,000 to 200,000, still more preferably 6,000 to 20,000, and 6,000 to 19,000. Is particularly preferred. When Mw is within the above range, processing by lithography can be stably performed. In particular, when Mw is 15,000 or less, when the photosensitive film is exposed, the exposed portion is excellent in solubility in an alkaline aqueous solution, and a high aspect ratio hole or groove is easily formed.
The degree of dispersion (Mw / Mn), which is the ratio of Mw to the number average molecular weight (Mn) of the resin, is, for example, 1.2 to 2.8.
In addition, when Mw of this resin is 6,000-20,000, it is preferable that the terminal group J is included. Thereby, the coating nonuniformity at the time of apply | coating the photosensitive composition to the surface of a base material and forming a photosensitive film | membrane can be suppressed.

In the present resin, the unit u1, the unit u2 and the unit u3 may or may not be contained in one polymer, but are preferably contained in one polymer. When the unit u1, the unit u2, and the unit u3 are not included in one polymer, the resin includes two or more types of polymers including one or two of the unit u1, the unit u2, and the unit u3.
When this resin contains the unit u4, the unit u1, the unit u2, the unit u3 and the unit u4 may or may not be included in one polymer, but are included in one polymer. Is preferred. When the unit u1, the unit u2, the unit u3, and the unit u4 are not included in one polymer, the resin contains one, two, or three of the units u1, u2, unit u3, and unit u4. Two or more kinds of polymers are contained.
When this resin contains the terminal group J, the terminal group J may be contained in a part of polymer which comprises this resin, and may be contained in all.

A preferred embodiment of the present resin is a resin (hereinafter, also referred to as “resin P1”) including a copolymer A including units u1, u2, and u3. Since copolymer A contains unit u1, unit u2, and unit u3 in one molecule, the distribution of units u2 and unit u3 is not easily biased in the photosensitive film, and the patterning property and water resistance of the photosensitive film are excellent. .
The copolymer A constituting the resin P1 may be one type or two or more types. The copolymer A will be described in detail later.
Resin P1 may consist only of copolymer A, or may be a mixture of copolymer A and another polymer.
When the resin P1 includes the unit u4, the copolymer A may include the unit u4, and may further include another polymer including the unit u4. It is preferable that the copolymer A contains the unit u4 in that the uniformity of the distribution of the unit u4 is excellent. The same applies when the resin P1 contains the unit u5.

Another preferable embodiment of the present resin is a resin (hereinafter, also referred to as “resin P2”) including a copolymer B including the units u1 and u2 and a copolymer C including the units u1 and u3. ). Since both the copolymer B and the copolymer C contain the unit u1, they are excellent in miscibility. Therefore, the distribution of the unit u2 and the unit u3 in the photosensitive film is less likely to occur, and the patterning property and water resistance of the photosensitive film are excellent.
The copolymer B and the copolymer C constituting the resin P2 may each be one type or two or more types. The copolymer B and copolymer C will be described in detail later.
The resin P2 may be composed only of the copolymer B and the copolymer C, or may be a mixture of the copolymer B, the copolymer C, and another polymer.
When the resin P2 includes the unit u4, the copolymer B may include the unit u4, the copolymer C may include the unit u4, and both the copolymer B and the copolymer C may include the unit u4. Of course, another polymer containing the unit u4 may be further included. It is preferable that at least one of the copolymer B and the copolymer C contains the unit u4 in that the uniformity of the distribution of the unit u4 is excellent, and both the copolymer B and the copolymer C contain the unit u4. Is preferred. The same applies when the resin P2 contains the unit u5.

Preferred proportions (mol%) of units u1, u2, units u3, units u4 and units u5 in all units of resin P1 and resin P2 are the same as the preferred proportions of each unit in all units of the resin. is there.
The preferable Mw of each of the resin P1 and the resin P2 is the same as the preferable Mw of the resin.
The ratio of the copolymer A to the total mass of the resin P1 and the total ratio of the copolymer B and the copolymer C to the total mass of the resin P2 are each preferably 1 to 100 mass%, more preferably 5 to 100 mass%. 10 to 100% by mass is preferable.
The ratio of the copolymer B to the total mass of the copolymer B and the copolymer C is preferably 50 to 95% by mass in terms of easily setting the ratio of each unit in the resin P2 to the above-described preferable ratio. 95 mass% is more preferable, and 65-95 mass% is especially preferable.

(Copolymer A)
The polymer A includes a unit u1, a unit u2, and a unit u3. Copolymer A may further contain unit u4. The copolymer A may further contain a unit u5. The copolymer A may have a terminal group J.

The preferred ratio (mol%) of each of the units u1, u2, unit u3, unit u4 and unit u5 in all units of the copolymer A is the same as the preferred ratio of each unit in all units of the resin.
The preferable Mw of the copolymer A is the same as the preferable Mw of the present resin.

As a manufacturing method of the copolymer A, the following manufacturing method 1 is mentioned, for example.
Production method 1: A method of polymerizing a monomer mixture containing the monomer m1, the monomer m2, and the monomer m3.
The monomer mixture may further include at least one selected from the group consisting of the monomer m4 and the monomer m5.

The monomer mixture can be polymerized by a known polymerization method such as a solution polymerization method, a bulk polymerization method, or an emulsion polymerization method. Among these, the solution polymerization method is preferable.
In the solution polymerization, the ratio of the total mass of the monomer mixture to the total mass of the polymerization solvent (polymerization concentration) is preferably 5 to 70% by mass, and more preferably 10 to 40% by mass. The higher the polymerization concentration, the better the production efficiency of the copolymer A. The polymerization solvent is preferably the same as the solvent for the photosensitive composition.
Examples of the polymerization conditions include conditions at 40 to 60 ° C. for 5 to 30 hours.
In the polymerization, a polymerization initiator may be used, or a chain transfer agent may be used.
After the polymerization, a purification treatment such as filtration and reprecipitation, a solvent distillation, a solvent substitution and the like may be performed as necessary.

When the polymerization is carried out in the presence of the chain transfer agent j, a copolymer A having a terminal group J is obtained.
The amount of chain transfer agent j used can be appropriately selected according to the molecular weight of the copolymer to be produced, and varies depending on the amount of polymerization initiator used and the concentration of the polymerization solution, but typically constitutes a monomer mixture. It is 0.1-20 mol% with respect to the whole quantity (100 mol%) of a monomer, and 1-10 mol% is preferable.
In addition, when the usage-amount of a polymerization initiator increases, there exists a tendency for the usage-amount of the chain transfer agent required in order to set it as the desired molecular weight to decrease. When the solution concentration is low, the amount of the chain transfer agent used for obtaining a desired molecular weight tends to decrease.

When the copolymer A contains the unit u4, the copolymer A can also be produced by the following production method 2.
Production Method 2: A monomer mixture containing the monomer m1, the monomer m2, the monomer m3, and the monomer m4 ′ is polymerized to obtain a copolymer A ′. A method of reacting the reactive compound with the polymer A ′.
The monomer mixture may further include a monomer m5.

In Production Method 2, the monomer mixture can be polymerized in the same manner as Production Method 1.
The amount of the reactive compound used is preferably 10 to 100 mol%, more preferably 80 to 100 mol%, when the total number of specific reaction sites of the monomer m4 ′ is 100 mol%. The total number of specific reaction sites of monomer m4 ′ is (total number of moles of monomer m4 ′) × (number of specific reaction sites of monomer m4 ′) when monomer m4 ′ is one kind. ). When the monomer m4 ′ is a plurality of types, the same for each monomer as described above (total number of moles of monomer m4 ′) × (number of specific reaction sites of monomer m4 ′) The values are obtained, and the sum thereof is taken as the total number of specific reaction sites of the monomer m4 ′.
As a reaction condition at the time of making a reactive compound react, the conditions for 5 to 48 hours are mentioned at 0-60 degreeC, for example.
After the polymerization or after reacting the reactive compound, purification treatment such as filtration and reprecipitation, solvent distillation, solvent substitution and the like may be performed as necessary.

(Copolymer B)
Copolymer B includes unit u1 and unit u2. Copolymer B does not contain unit u3. Copolymer B may further contain unit u4. The copolymer B may further contain a unit u5.

The ratio of the unit u1 in all the units of the copolymer B is, for example, 3 to 70 mol%.
The ratio of the unit u2 in all the units of the copolymer B is, for example, 30 to 97 mol%.
The ratio of the unit u4 in all the units of the copolymer B is, for example, 0 to 60 mol%.
The ratio of the unit u5 in all the units of the copolymer B is, for example, 0 to 60 mol%.

The preferable Mw of the copolymer B is the same as the preferable Mw of the present resin.
The method for producing the copolymer B is the same as the method for producing the copolymer A. However, the monomer mixture used for the production of the copolymer B does not contain the monomer m3.

(Copolymer C)
Copolymer C includes unit u1 and unit u3. Copolymer C does not contain unit u2. The copolymer C may further contain a unit u4. Copolymer C may further contain unit u5.

The ratio of the unit u1 in all the units of the copolymer C is, for example, 3 to 80 mol%.
The ratio of the unit u3 in all the units of the copolymer C is, for example, 5 to 50 mol%.
The ratio of the unit u4 in all the units of the copolymer C is, for example, 0 to 60 mol%.
The ratio of the unit u5 in all the units of the copolymer C is, for example, 0 to 60 mol%.

The preferable Mw of the copolymer C is the same as the preferable Mw of the present resin.
The method for producing the copolymer C is the same as the method for producing the copolymer A. However, the monomer mixture used for the production of the copolymer C does not contain the monomer m2.

Since this resin contains the unit u1, the unit u2, and the unit u3, it can be combined with a photoacid generator to form a photosensitive composition.
According to the photosensitive composition containing the present resin and the photoacid generator, a lyophobic film having holes or grooves penetrating in the thickness direction can be formed by photolithography as described below.
The photosensitive composition containing the present resin and a photoacid generator is formed by applying the photosensitive composition onto a substrate and drying it as necessary. When this photosensitive film is selectively exposed with a pattern corresponding to the hole or groove to be formed, an acid is generated from the photoacid generator at the exposed portion of the photosensitive film, and the action causes acid dissociation of unit u2. The functional group is dissociated to produce an alkali-soluble group. Thereby, the solubility with respect to the aqueous alkali solution (developer) of an exposure part improves. On the other hand, in the unexposed area, the solubility in the alkaline aqueous solution does not substantially change. Therefore, when the exposed photosensitive film is developed with an alkaline aqueous solution, the exposed portion is dissolved and removed in the alkaline aqueous solution, while the unexposed portion remains without being removed. As a result, a film in which a hole or groove penetrating in the thickness direction is formed at the position of the exposed portion is formed. Since the film includes a fluorine-containing organic group derived from the unit u1, it exhibits liquid repellency.
By including the unit u3 in the resin, the hole or groove can have a high aspect ratio as compared with the case where the unit u3 is not included. For example, when an attempt is made to form holes having the same diameter, the film thickness at which the exposed portion can be completely removed after development can be increased. The reason why the hole or groove can have a high aspect ratio is that the oxyalkylene group of the unit u3 increases the affinity with the alkaline aqueous solution, and the alkaline aqueous solution easily penetrates into the exposed portion of the photosensitive film after exposure. .
The photosensitive composition is a positive photosensitive composition in which an exposed portion is dissolved and removed. On the other hand, the photosensitive composition of Patent Document 1 is a negative photosensitive composition in which an exposed part is cured and an unexposed part is dissolved and removed. In photolithography, in general, a positive type can form holes or grooves with higher resolution than a negative type.
Therefore, according to the photosensitive composition using the present resin, fine holes or grooves can be formed with a high aspect ratio. Such a hole or groove is useful as a microwell for accommodating beads or the like in a biochip.

[Photosensitive composition]
The photosensitive composition of the present invention (hereinafter also referred to as “the present composition”) contains the present resin, a photoacid generator, and a solvent. This composition may further contain other components other than this resin, a photo-acid generator, and a solvent. Note that volatile components such as a solvent are removed before exposure when forming the photosensitive film.

  The present resin contained in the present composition is preferably at least one selected from the group consisting of the resin P1 and the resin P2. Only one of the resin P1 and the resin P2 may be used, or both may be used in combination.

Extinction coefficient at wavelength 365nm of the photoacid generator is preferably 400mL ^· g ^{-1 · cm} -1 or less, 200mL ^· g ^{-1 · cm} -1 or less is more preferable. When the extinction coefficient is less than or equal to the above upper limit value, light that becomes noise generated from the liquid repellent film is suppressed when a biochip having a liquid repellent film formed from the present composition is subjected to fluorescence analysis. Specifically, the light that becomes noise is light that is observed as fluorescence when measured by a laser beam excitation type fluorescence analyzer.
The absorption coefficient at a wavelength of 365 nm of the photoacid generator is preferably as low as possible. For example, it may be 1 mL · g ⁻¹ · cm ⁻¹ or more, or 10 mL · g ⁻¹ · cm ⁻¹ or more. .

Examples of the photoacid generator include triarylsulfonium salts, diaryliodonium salts, sulfonyldiazomethane, and the like.
Specific examples of the cation moiety of the triarylsulfonium salt and diaryliodonium salt include triphenylsulfonium, diphenyl-4-methylphenylsulfonium, tris (4-methylphenyl) sulfonium, diphenyl-2,4,6-trimethylphenylsulfonium, 4- (phenylthio) phenyldiphenylsulfonium, diphenyliodonium, 4-isopropyl-4′-methyldiphenyliodonium, 4-methyl-4′-methylpropyldiphenyliodonium, bis (4-tert-butylphenyl) iodonium, 4-methoxyphenyl Phenyl iodonium is mentioned.
Specific examples of the anion moiety of the triarylsulfonium salt and diaryliodonium salt include trifluoromethanesulfonate, nonafluorobutanesulfonate, hexafluorophosphate, tetrafluoroborate, tris (pentafluoroethyl) trifluorophosphate, and tris (heptafluoropropyl). Examples thereof include trifluorophosphate, tris (nonafluoroisobutyl) trifluorophosphate, and bis (nonafluoroisobutyl) tetrafluorophosphate.
Specific examples of the sulfonyldiazomethane include bis (phenylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, and bis (p-toluenesulfonyl) diazomethane.
These photoacid generators may be used alone or in combination of two or more.

  As the photoacid generator, 4- (phenylthio) phenyldiphenylsulfonium tris (heptafluoropropyl) trifluorophosphate, 4- (phenylthio) has a small fluorescence generated from the liquid repellent film and is excellent in photoacid generation performance. Phenyldiphenylsulfonium tris (nonafluoroisobutyl) trifluorophosphate, 4- (phenylthio) phenyldiphenylsulfonium bis (nonafluoroisobutyl) tetrafluorophosphate, 4- (phenylthio) phenyldiphenylsulfonium (pentafluoroethyl) trifluorophosphate, diphenyl- 2,4,6-trimethylphenylsulfonium trifluoromethanesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium nonafluorobutans Honeto, bis (phenylsulfonyl) diazomethane, bis (p- toluenesulfonyl) diazomethane is preferred.

The solvent only needs to dissolve or disperse the resin and the photoacid generator, and preferably dissolves the solvent.
Examples of the solvent include fluorine-containing compounds (1H-tridecafluorohexane (Asahi Glass Co., Ltd., Asahi Clin (registered trademark) AC2000), 1,1,1,2,2,3,3,4,4,5,5,5. 6,6-tridecafluorooctane (Asahi Glass Co., Ltd., Asahiclin (registered trademark) AC6000), 1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane (Asahi Glass Co., Ltd.) Manufactured by Asahi Culin (registered trademark) AE3000), dichloropentafluoropropane (Asahi Glass Co., Ltd., Asahi Culin (registered trademark) AK-225) 1, 1, 1, 2, 3, 4, 4, 5, 5, 5 -Decafluoro-3-methoxy-2- (trifluoromethyl) pentane (Asahi Glass Co., Ltd., Cytop (registered trademark) CT-solv 100E), 1-methoxynonafluorobutane (Three M) Manufactured by Napan, Novec (registered trademark) 7100), 1-ethoxynonafluorobutane (manufactured by 3M Japan, Novec (registered trademark) 7200), 1,1,1,2,3,3-hexafluoro-4- ( 1,1,2,3,3,3-hexafluoropropoxy) pentane (manufactured by 3M Japan, Novec (registered trademark) 7600), 2H, 3H-perfluoropentane (manufactured by Mitsui DuPont Fluorochemical Co., Ltd., Vertrel (registered trademark) ) XF), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-octanol, 4,4,5,5,6,6 7,7,8,8,9,9,9-tridecafluoro-1-nonanol, hexafluorobenzene, hexafluoro-2-propanol, 2,2,3,3,4,4,5,5 Octafluoro-1-pentanol, 1H, 1H, 7H-dodecafluoro-1-heptanol, etc.), non-fluorine ketones (cyclopentanone, cyclohexanone, methyl amyl ketone, 2-butanone, etc.), non-fluorine esters (ethyl lactate, Methyl benzoate, ethyl benzoate, benzyl benzoate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol methyl ethyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene carbonate, etc.), non-fluorine ether ( Diethylene glycol methyl ethyl ether, tetrahydrofuran, dioxane, dimethoxyethane, diethoxyethane, anisole, diglyme, triglyme, etc.) It is. A solvent may be used individually by 1 type and may use 2 or more types together.

  As a solvent, from the point of high solubility, high boiling point, and excellent film forming properties, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol methyl ethyl ether, hexafluoro-2-propanol, 2,2, 3,3,4,4,5,5-octafluoro-1-pentanol, 1H, 1H, 7H-dodecafluoro-1-heptanol is preferred.

Other components that may be contained in the composition include copolymers other than the copolymers (A), (B), and (C), photosensitizers, antioxidants, thermal polymerization initiators, heat Examples thereof include a polymerization inhibitor, an adhesion promoter, a leveling agent, an antifoaming agent, a suspending agent, a dispersant, a plasticizer, and a thickener, and other additives.
As the adhesion promoter, a coupling agent such as a silane coupling agent can be used. Preferred examples of the silane coupling agent include 3-glycidoxypropyltriacoxysilane, 3-glycidoxypropylalkyldialkoxysilane, 3-methacryloxypropyltrialkoxysilane, and 3-methacryloxypropylalkyldialkoxysilane. , 3-chloropropyltrialkoxysilane, 3-mercaptopropyltrialkoxysilane, 3-aminopropyltrialkoxysilane, 3-aminopropylalkyldialkoxysilane, heptadecafluorooctyltrimethoxysilane, β- (3,4-epoxy (Cyclohexyl) ethyltrialkoxysilane, vinyltrichlorosilane, vinyltrialkoxysilane.
Of these, 3-glycidoxypropyltrialkoxysilane and 3-methacryloxypropyltrialkoxysilane are more preferable, and 3-glycidoxypropyltrialkoxysilane is more preferable.

  The ratio of the present resin in the present composition is preferably 10 to 70% by mass, more preferably 10 to 60% by mass, further preferably 10 to 50% by mass, and particularly preferably 10 to 40% by mass. If the ratio of this resin is more than the lower limit of the said range, film thickness control will become easy, and if it is below the said upper limit, applicability | paintability will be more excellent.

The ratio of the photoacid generator in the composition is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, further preferably 0.5 to 10% by mass, and 1 to 10% by mass. Is particularly preferred.
0-80 mass% is preferable, as for the ratio of the other component in this composition, 0-60 mass% is more preferable, 0-59 mass% is further more preferable, and 0-10 mass% is especially preferable.
The content of the solvent in the composition is the balance obtained by removing the resin, photoacid generator and other components from the composition.

  The present composition is a composition comprising 10 to 70% by mass of the present resin, 1 to 10% by mass of the photoacid generator, 20 to 89% by mass of the solvent, and 0 to 59% by mass of the other components. It is particularly preferable that the composition is composed of 10 to 40% by mass of the present resin, 1 to 4% by mass of the photoacid generator, 46 to 89% by mass of the solvent, and 0 to 10% by mass of the other components. preferable.

  This composition can be manufactured by mixing this resin, a photo-acid generator, a solvent, and another component as needed. The mixing order of each component is not particularly limited.

[Substrate with liquid repellent film]
The substrate with a liquid repellent film of the present invention has a liquid repellent film formed from the present composition on the surface of the substrate. The method for forming the liquid repellent film will be described in detail later.

Base materials include various glass plates, thermoplastic sheets (polypropylene, polyethylene, polycarbonate, polymethyl methacrylate, polystyrene, etc.), silicon wafers, metal substrates (stainless steel (SUS), aluminum, etc.); metals such as copper foil Examples thereof include a resin substrate having a foil attached to the surface.
As a base material, a thing with small fluorescence intensity is preferable.
As a base material, a glass plate is preferable from a heat resistant point, and a quartz glass plate is particularly preferable.
When the substrate with a liquid repellent film is for biochips, the substrate is preferably a hydrophilic substrate. Examples of the lyophilic substrate include the glass plate and thermoplastic plastic sheet described above. As the lyophilic substrate, those having a water contact angle of less than 50 degrees are preferred. The contact angle of water is measured by the method described in Examples described later.

Since the liquid repellent film contains a fluorine-containing organic group, it exhibits liquid repellency.
The fluorine content of the liquid repellent film (ratio of fluorine atoms in the liquid repellent film) is preferably 3 to 75% by mass, and more preferably 5 to 60% by mass. When the fluorine content is at least the lower limit of the above range, the liquid repellency is more excellent. When the fluorine content is not more than the upper limit of the above range, the solubility of the exposed portion of the exposed photosensitive film in the alkaline aqueous solution is good when the liquid repellent film is formed.

The fluorine content of the liquid repellent film is calculated from the ratio of the resin in the liquid repellent film, the fluorine content of the polymer constituting the resin, and the like.
The fluorine content of the polymer is obtained by the following formula.
Q _F = [19 × N _F / M _A ] × 100
However, Q _F is the fluorine content, and N _F is the sum of the values obtained by multiplying the number of fluorine atoms of the unit and the molar ratio of the unit to the total unit for each type of unit constituting the polymer. M _A is the sum of values obtained by multiplying the total of the atomic weights of all atoms constituting the unit and the molar ratio of the unit with respect to all units for each type of unit constituting the polymer.

  The water contact angle of the liquid repellent film is preferably 90 ° or more, and particularly preferably 95 ° or more. When the contact angle of water is not less than the lower limit, the liquid repellency is sufficiently excellent. A contact angle is measured by the method as described in the Example mentioned later. The contact angle can be adjusted by the fluorine content of the liquid repellent film.

The liquid repellent film preferably has a hole or groove penetrating in the thickness direction. In this case, a substrate with a liquid repellent film can be applied to the biochip.
The pores formed in the liquid repellent film can be used as a microwell that accommodates beads labeled with another antibody that specifically interacts with the target molecule in the biochip.

Examples of the shape of the hole viewed from the normal direction of the surface of the substrate with the liquid repellent film include a circle, an ellipse, a semicircle, a triangle, a quadrangle, a hexagon, and other polygons.
Examples of the shape of the groove viewed from the normal direction of the surface of the substrate with a liquid repellent film include a line shape, a wavy line shape, and a circle shape.

What is necessary is just to set suitably the magnitude | size of the hole or groove | channel seen from the normal line direction of the surface of a board | substrate with a liquid-repellent film according to the use etc. of a board | substrate with a liquid-repellent film.
When the shape of the hole in plan view is a circle, the diameter of the hole is preferably 0.1 to 1,000 μm, and more preferably 1 to 500 μm. When a plurality of holes are formed, the distance between adjacent holes is preferably 0.1 to 1,000 μm, and more preferably 1 to 500 μm.
When the shape of the groove in plan view is a line shape, the width of the groove is preferably 0.1 to 2,000 μm, and more preferably 1 to 1,000 μm. When a plurality of grooves are formed in parallel, the distance between adjacent grooves is preferably 0.1 to 2,000 μm, and more preferably 1 to 1,000 μm.

The aspect ratio of the hole or groove is preferably 1 or more, more preferably more than 1, and particularly preferably 1.2 or more. The upper limit of the aspect ratio is not particularly limited, but is 100, for example. When the aspect ratio is not less than the lower limit of the above range, beads or the like accommodated in the holes or grooves are unlikely to jump out of the holes or grooves.
The aspect ratio of the hole is the ratio of the groove depth (the thickness of the liquid repellent film) to the hole diameter. The hole diameter is a diameter when the hole is circular in plan view, and a short axis when the hole has a shape other than circular.
The aspect ratio of the groove is the ratio of the groove depth (the thickness of the liquid repellent film) to the width of the groove as viewed from the normal direction of the surface of the substrate with the liquid repellent film.

  When a plurality of holes or grooves are formed in the liquid repellent film, a pattern formed by arranging a plurality of holes or grooves includes a dot pattern in which the holes are arranged in the vertical direction and the horizontal direction, and a line-shaped groove. Are line-and-space patterns that are aligned in a predetermined direction with a predetermined interval, and lattice patterns in which line-shaped grooves are aligned in a vertical direction and a horizontal direction with a predetermined interval.

The thickness of the liquid repellent film can be set to 0.1 to 10 μm, for example.
A preferable value of the hole diameter or the groove width is determined depending on the application. Therefore, it is preferable that the thickness of the liquid repellent film is such that the aspect ratio of the hole or groove is within the above-described preferable range when a hole having a predetermined hole diameter or a groove having a predetermined width is formed.

When the substrate with a liquid repellent film is for a fluorescence analysis biochip, the fluorescence intensity of the liquid repellent film is preferably 15,000 or less, more preferably 10,000 or less, further preferably 5,000 or less, 000 or less is particularly preferable. If the fluorescence intensity is less than or equal to the upper limit, it is useful for fluorescence analysis.
The fluorescence intensity of the liquid repellent film is measured using a microarray scanner (Molecular Devices, GenePix 4000B) under the conditions of an excitation wavelength of 532 nm, a resolution of 5 μm, a laser output of 100%, and a photomultiplier voltage of 1,000 V.
The fluorescence intensity of the liquid repellent film can be adjusted by the type and content of the photoacid generator.

  In fluorescence analysis using a fluorescence analysis biochip, the fluorescence analysis biochip is irradiated with light and the emitted fluorescence is measured. The fluorescence analysis is preferably performed using a fluorescence microscope and a microarray scanner. Laser light is preferably used as the excitation light source. The excitation wavelength is preferably between 450 nm and 800 nm in order to excite commonly used fluorescent dyes, and wavelengths of 488 nm, 532 nm, 594 nm, 635 nm, and 650 nm are preferable. In particular, wavelengths of 532 nm and 635 nm are preferable. A photomultiplier tube is preferably used for measuring the emitted fluorescence.

[Method for producing substrate with liquid repellent film]
In the method for producing a substrate with a liquid repellent film of the present invention (hereinafter also referred to as “the present production method”), the composition is applied to the surface of the substrate and dried to form a photosensitive film. The photosensitive film is exposed, and the exposed photosensitive film is developed using an alkaline aqueous solution.

Hereinafter, an embodiment of the present manufacturing method will be described. In addition, this manufacturing method is not limited to the following one embodiment.
FIG. 1 is a cross-sectional view showing steps (a) to (c) in an embodiment of the present manufacturing method.
The manufacturing method of this embodiment has the following processes.
Process (a): The process of forming the photosensitive film | membrane 12 on the surface of the board | substrate 10 using this composition.
Step (b): A step of exposing the photosensitive film 12 in a predetermined pattern.
Step (c): A step of developing the exposed photosensitive film 12 with an alkaline aqueous solution to form a liquid repellent film 18 having a predetermined pattern.

When this resin contains the unit u4, the manufacturing method of this embodiment can have the following process in addition to the said process (a)-(c) as needed.
Step (d): A step of exposing the liquid repellent film 18.
Step (e): A step of applying heat treatment to the liquid repellent film 18 to form a crosslinked structure.

(Process (a))
As shown in FIG. 1, the composition is applied to the surface of a substrate 10 to form a wet photosensitive film (not shown), and dried to form a dry photosensitive film 12.

Examples of the coating method include a spray method, a roll coating method, a spin coating method, and a bar coating method.
The wet photosensitive film obtained by applying the present composition is preferably baked (hereinafter also referred to as pre-baking). By pre-baking, the solvent is quickly volatilized, and a dry photosensitive film 12 having no fluidity is obtained. Prebaking conditions are preferably 50 to 120 ° C. and 10 to 2,000 seconds.
The thickness of the photosensitive film 12 in the dry state is the thickness of the liquid repellent film 18 to be formed.

(Process (b))
After the step (a), as shown in FIG. 1, the photosensitive film 12 is irradiated with light from the light source 22 through a mask 20 having a predetermined pattern, and the photosensitive film 12 is exposed with a predetermined pattern.
In the exposed portion 14 of the exposed photosensitive film 12, an acid is generated from the photoacid generator, and the acid-dissociable group of the unit u2 in the resin is dissociated by the acid to generate an alkali-soluble group. Increases solubility in aqueous solutions. On the other hand, the solubility of the unexposed portion 16 of the photosensitive film 12 in the alkaline aqueous solution does not change. Therefore, when the photosensitive film 12 is developed in the next step (c), the exposed portion 14 is dissolved and removed, and a liquid repellent film 18 having a predetermined pattern is formed.

The pattern of the mask 20 is a pattern corresponding to the holes or grooves of the liquid repellent film 18 to be formed. When exposed through the mask 20, portions corresponding to the holes or grooves of the photosensitive film 12 are exposed.
The light is preferably a light beam having a wavelength of 100 to 500 nm, more preferably a light beam having a wavelength of 200 to 450 nm, and particularly preferably i-line (365 nm).
Examples of the light source 22 include a high-pressure mercury lamp, an (ultraviolet) LED, and a laser.
The exposure amount is preferably in the range of 5 to 10,000 mJ / cm ² .

After the exposure, a post-exposure bake (PEB) treatment can be performed on the coated film after the exposure, if necessary, in order to promote the dissociation reaction of the acid dissociable group.
The PEB treatment conditions are, for example, in the range of 50 to 150 ° C. and 10 to 2,000 seconds.

When this resin contains the unit u4, the PEB treatment is not performed or the PEB treatment is performed at a lower temperature in order to suppress formation of a crosslinked structure by reacting with the generated alkali-soluble group and the cyclic ether group. Preferably it is done. When this resin contains the unit u4, the PEB treatment temperature is preferably 50 to 130 ° C, more preferably 50 to 110 ° C, and particularly preferably 50 to 80 ° C.
Moreover, when this resin contains the unit u4, the acid-dissociable group can be satisfactorily dissociated without performing PEB treatment, so that the alkali-soluble group protected with the acid-dissociable group is —C (O) OC. A group represented by (R ²¹ ) (R ²² ) OR ²³ is preferred.

(Process (c))
After the step (b), as shown in FIG. 1, the exposed photosensitive film 12 is developed with an alkaline aqueous solution, and the exposed portion 14 is removed to form a liquid repellent film 18 having a predetermined pattern.
Examples of the alkali in the alkaline developer (alkaline aqueous solution) include alkali metal hydroxides (lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.), alkali metal carbonates (sodium carbonate, potassium carbonate, etc.), alkali metal bicarbonates. (Sodium bicarbonate, potassium bicarbonate, etc.), ammonium hydroxide (tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline hydroxide, etc.), sodium silicate, sodium metasilicate and the like. The pH of the alkaline aqueous solution is preferably 10-14. The alkaline aqueous solution may contain a water-soluble organic solvent (methanol, ethanol, etc.), a surfactant and the like. Examples of the surfactant include nonionic surfactants.

Examples of the developing method include a liquid piling method, a dipping method, and a shower method. The development time is, for example, 30 to 180 seconds.
After the development, the liquid repellent film 18 may be washed (rinsed) using a solvent, water, or the like that does not dissolve the liquid repellent film 18. The rinse time is, for example, 30 to 180 seconds.
After rinsing, the liquid repellent film 18 is preferably dried.

(Process (d))
After the step (c), the liquid repellent film 18 may be exposed (post-exposure) in order to dissociate the acid dissociable group of the unit u2 in the present resin, if necessary.
The exposure in the step (d) may be full exposure. The light and light source used for exposure may be the same as in step (b). The exposure amount is preferably in the range of 100 to 3,000 mJ / cm ² .

(Process (e))
After the step (d), the liquid repellent film 18 may be subjected to heat treatment (curing) in order to promote cross-linking of the resin contained in the liquid repellent film 18 as necessary.
When the resin has the unit u4, the liquid-repellent film 18 is heated to react the cyclic ether group of the unit u4 with the alkali-soluble group generated by dissociation of the acid-dissociable group of the unit u2 in the resin. Thus, a crosslinked structure is formed, and a liquid repellent cured film is formed. The liquid repellent cured film also corresponds to the liquid repellent film in the present invention.
Examples of the heat treatment method include a method using a heating device such as a hot plate or an oven. The conditions for the heat treatment are preferably 120 to 250 ° C. and 5 to 90 minutes.

  The liquid repellent film 18 has sufficient water resistance even in an uncrosslinked state. Therefore, even when the unit u4 is included, the step (d) and the step (e) may not be performed.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not construed as being limited thereto.
Examples 1 to 16 are examples, and examples 17 to 18 are comparative examples.

(Mw, Mw / Mn)
Mw and Mn of the polymer are calibration curves prepared using standard polymethyl methacrylate samples with known molecular weights from chromatograms obtained by a high-speed gel permeation chromatography (GPC) apparatus (HLC-8220, manufactured by Tosoh Corporation). Obtained using.

(Resolution and aspect ratio)
A photosensitive composition is spin-coated on the surface of a 4-inch silicon wafer (Mitsubishi Materials Trading Co., Ltd.) for 30 seconds at 1,000 rpm to 2,000 rpm, and 5 minutes at 100 ° C. using a hot plate. A photosensitive film in a dry state was formed by heating. A high pressure mercury lamp was used as a light source, and the photosensitive film was exposed through a mask (a mask capable of forming a circular hole pattern having a diameter of 4 μm and 6 μm) so that the exposure amount of i-line was 300 mJ / cm ² . The photosensitive film is developed for 40 seconds using NMD-W (manufactured by Tokyo Ohka Kogyo Co., Ltd.) as a developer (2.38 mass% tetramethylammonium hydroxide aqueous solution), and rinsed with pure water for 30 seconds. And a liquid repellent film having a hole pattern was formed. In order to remove the developer and the rinse solution, spin drying was performed at 2,000 rpm for 30 seconds. The entire surface of the developed substrate was post-exposed so that the i-line exposure amount was 1,000 mJ / cm ^2, and then post-baked at 150 ° C. for 30 minutes.
The cross-sectional shape of the liquid-repellent film after post-baking is observed with a scanning electron microscope microscope (JSM-IT100 manufactured by JEOL Ltd.), and the minimum hole pattern diameter X (μm) with holes opened and the film of the liquid-repellent film The aspect ratio (Y / X) was calculated from the thickness Y (μm).

(Protein adhesion)
The protein adsorption rate Q (%) was determined by the following procedures (1) to (6).
(1) Well preparation:
Dispense 4 mL of the photosensitive composition into each of three 35 mmφ glass petri dishes (manufactured by AGC Techno Glass Co., Ltd.), leave it for one day to evaporate the solvent, and form a dry coating film. When not crosslinked, the coating was exposed as it was, and when crosslinked, the exposure energy was 800 mJ / cm ² and heated at 150 ° C. for 30 minutes to form a coating layer on the well surface.
(2) Preparation of coloring solution and protein solution:
The coloring solution was 50 mL of peroxidase coloring solution (3,3 ′, 5,5′-tetramethylbenzidine (TMBZ), manufactured by KPL) and 3,3 ′, 5,5′-tetramethylbenzidine peroxidase substrate (TMB). A mixture of 50 mL of Peroxidase Substrate (manufactured by KPL) was used. As the protein solution, a protein (POD-goat anti mouse IgG, Biorad) diluted 16,000 times with a phosphate buffer solution (D-PBS, Sigma) was used.
(3) Protein adsorption:
3 mL of the protein solution was dispensed to each of the three glass petri dishes on which the coating layer obtained in (1) was formed, and left at room temperature for 1 hour. As a blank, in a 96-well microplate without any coating, 2 μL of the protein solution was dispensed into 3 wells (2 μL was dispensed per well).
(4) Cleaning of glass petri dish:
A phosphate buffer solution (D-PBS (Dulbecco) containing 0.05% by mass of a surfactant (Tween 20, manufactured by Wako Pure Chemical Industries, Ltd.), each of the three glass petri dishes subjected to protein adsorption in (3) above. Washed 4 times with 6 mL of phosphate buffered saline (manufactured by Sigma) (use 6 mL for each glass petri dish).
(5) Dispensing of coloring solution:
Dispense 3 mL of the coloring solution into each of the three glass dishes that have been washed in (4) above, and perform a coloring reaction for 7 minutes. Then, add 1.5 mL of 2N sulfuric acid to perform the coloring reaction. Stopped. In the blank, 100 μL of the coloring solution was dispensed into each well of a 96-well microplate (use 100 μL for each well), color development reaction was performed for 7 minutes, and 50 μL of 2N sulfuric acid was added (per well). The color reaction was stopped.
(6) Absorbance measurement and calculation of protein adsorption rate Q:
150 μL of each of the three glass petri dishes to which the color developing solution was dispensed in (5) above was taken and transferred to each of the 3 wells of a 96-well microplate. Absorbance was measured. Here, the average absorbance of the blank (N = 3) was A _0. The absorbance of the liquid is moved from the glass petri dish to a 96-well microplate and A _1, the protein adsorption rate Q ₁ was determined by the following equation. Three average protein adsorption rate Q ₁ obtained was protein adsorption rate Q. The protein adsorption rate Q is preferably 2% or less, particularly preferably 1% or less.
Q ₁ = A ₁ / {A ₀ × (100 / amount of dispensed blank protein solution (μL))} × 100
= A ₁ / {A ₀ × (100/2 μL)} × 100 [%]

(water resistant)
A photosensitive composition is spin-coated on the surface of a glass substrate (25 mm × 50 mm) and heated at 100 ° C. for 300 seconds using a hot plate. If uncrosslinked, it is left as it is, and then crosslinked at 150 ° C. for 30 minutes. Then, a dry photosensitive film having a thickness of 3 μm was formed. The glass substrate on which the photosensitive film was formed was immersed in water at 23 ° C. for 30 minutes. The film thickness of the photosensitive film before being immersed in water was T ₁ , the film thickness after being immersed in water for 30 minutes was T ₂ , and the water resistance D was determined from the following equation. The film thickness was measured using a stylus type film thickness meter (OM-DEKTAK-XT manufactured by Bruker).
D (%) = (T ₂ / T ₁ ) × 100

(Water contact angle)
The photosensitive composition is spin-coated on the surface of a glass substrate (25 mm × 50 mm), heated at 100 ° C. for 300 seconds using a hot plate, and then heated at 150 ° C. for 30 minutes to dry the photosensitive property in a thickness of 3 μm. A film was formed. The contact angle of about 2 μL of distilled water placed on the surface of the photosensitive film was measured at 23 ° C. using a contact angle meter (DM-701, manufactured by Kyowa Interface Science Co., Ltd.).

(Martens hardness)
A photosensitive composition is spin-coated on the surface of a glass substrate (25 mm × 50 mm) and heated at 100 ° C. for 300 seconds using a hot plate. If uncrosslinked, it is left as it is, and then crosslinked at 150 ° C. for 30 minutes. Then, a dry photosensitive film having a thickness of 3 μm was formed. The Martens hardness on the surface of the photosensitive film was measured using a picodenter (Fisher Instruments, HM500).

(Monomer, polymerization solvent and polymerization initiator)
Monomers, chain transfer agents, polymerization solvents and polymerization initiators used for the production of the following copolymers are as follows.
<Monomer m1>
C6FMA: 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl methacrylate. C6FMA was obtained by the method described in Example 1 of JP-A No. 2004-359616.
<Monomer m2>
EEMA: 1-ethoxyethyl methacrylate. EEMA was obtained by the method described in [0092] of WO 2017/126570.
<Monomer m3>
PEG9MA: methoxypolyethylene glycol methacrylate (PEG9MA) (manufactured by NOF Corporation, Blemmer (registered trademark) PME400).
PEG3MA: Ethoxypolyethylene glycol methacrylate (PEG3MA) (manufactured by Polymer Science).
<Monomer m4>
GMA: glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.).
<Chain transfer agent>
Thioglycerol (manufactured by Tokyo Chemical Industry Co., Ltd.).
<Solvent for polymerization>
PGMEA: Propylene glycol 1-monomethyl ether 2-acetate.
<Polymerization initiator>
V65: 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, V-65).

(resin)
<Copolymer A-1>
Dissolve 1.0 g of C6FMA, 3.95 g of GMA, 2.20 g of EEMA, 1.09 g of PEG9MA, 0.38 g of V65, and 0.10 g of thioglycerol in 9.54 g of PGMEA, and under nitrogen atmosphere The mixture was stirred at 50 ° C. for 24 hours, and further stirred at 70 ° C. for 2 hours to obtain a PGMEA solution of copolymer A-1.
The ratio (mol%) of each unit in the copolymer is 4.4 ppm (monomer m1 unit) of ¹ H-NMR (d-acetone, TMS), 3.3 ppm (monomer m2 unit), and 5. It calculated from the signal of 7 ppm (monomer m3 unit) and 4.1 ppm (monomer m4 unit).
Moreover, it has confirmed that the copolymer A-1 had the terminal group J from the signal of 2.5 ppm corresponding to the peak of the terminal group derived from thioglycerol.

<Copolymers A-2 to A-16, Copolymers X-1 to X-2 for Comparative Examples>
The copolymer A-2 to A-16, and the copolymer weight for the comparative example were the same as the procedure for producing the copolymer A-1, except that the type and amount of each monomer were changed. Combined X-1 to X-2 were produced. The ratio (mol%) of each unit in the copolymers A-2 to A-9, A-14 to A-16, and X-1 to X-2 was determined by ¹ H-NMR (d -Acetone, TMS). For copolymers A-10 to A-13 using PEG3MA, the charging ratio (mol%) of each monomer was defined as the ratio of each unit.
In Table 1, the ratio of each unit of each copolymer, Mw, and Mw / Mn are shown.

(Photoacid generator)
CPI210S: 4- (phenylthio) phenyldiphenylsulfonium tris (heptafluoropropyl) trifluorophosphate (manufactured by San Apro, CPI (trade name) -210S, extinction coefficient at wavelength 365 nm: 98 mL · g ⁻¹ · cm ⁻¹ ).

(Example 1)
5.0 g of the PGMEA solution of copolymer A-1 and 0.2 g of CPI210S were placed in a glass vial (20 mL) and stirred thoroughly to obtain a uniform solution. The obtained solution was filtered with a PTFE filter having a pore size of 0.20 μm to obtain a photosensitive composition.

(Examples 2 to 18)
Photosensitization was performed in the same manner as in Example 1 except that the PGMEA solutions of copolymers A-2 to A-16 and copolymers X-1 to X-2 were used instead of the PGMEA solution of copolymer A-1. Sex composition was obtained.

  Using the photosensitive composition of each example, the resolution and aspect ratio, water contact angle, water resistance, protein adhesion, and Martens hardness were evaluated. The results are shown in Table 2. In Example 14, since the copolymer A-14 did not have the unit u4, the Martens hardness was not evaluated.

  According to the photosensitive compositions of Examples 1 to 16, holes having an aspect ratio of 1.2 or more could be formed.

  The photosensitive composition of the present invention is a member or device having a patterned liquid repellent film, for example, a biochip having a patterned liquid repellent film, a pixel forming substrate having a patterned liquid repellent bank material It is useful for manufacturing an electrowetting device or the like having a patterned liquid repellent insulating film.

  DESCRIPTION OF SYMBOLS 10 Substrate, 12 Photosensitive film, 14 Exposed part, 16 Unexposed part, 18 Liquid repellent film, 20 Mask, 22 Light source

Claims (10)

  A resin comprising a unit u1 having a fluorine-containing organic group, a unit u2 having an alkali-soluble group protected with an acid-dissociable group, and a unit u3 having an oxyalkylene group.   The resin of Claim 1 containing the copolymer A containing the said unit u1, the said unit u2, and the said unit u3.   The resin according to claim 1 or 2, comprising a copolymer B containing the unit u1 and the unit u2, and a copolymer C containing the unit u1 and the unit u3.   The resin according to any one of claims 1 to 3, further comprising a unit u4 having a cyclic ether group. The resin as described in any one of Claims 1-4 containing the terminal group represented by either the following formula 1, the following formula 2, or the following formula 3.
^{-X 1 -C (R 1) (} R 2) (R 3) Equation 1
-X ² -R ⁴ Equation 2
^{-X 3 -N (R 5) (} R 6) Equation 3
However, R ^{1 to} R ³ are each independently a hydroxyl group, an oxo group or a chain hydrocarbon group having 40 or less carbon atoms which may have an etheric oxygen atom, a cyclic group having 40 or less carbon atoms, a hydroxyl group, A halogen atom, an amino group, or a hydrogen atom, and at least two of R ^{1 to} R ³ are atoms or groups other than a hydrogen atom;
R ⁴ is a cyclic group having 40 or less carbon atoms,
R ⁵ and R ⁶ are each independently a hydroxyl group, an oxo group or a chain hydrocarbon group having 40 or less carbon atoms which may have an etheric oxygen atom, or a cyclic group having 40 or less carbon atoms,
X ^{1 to} X ³ each independently represent a single bond, —S—, —S—R ⁷ —, —R ⁸ —, —O—R ⁹ — or —O—, and R ⁷ , R ⁸ and R ⁹ Are each independently a linear alkylene group having 1 to 40 carbon atoms.   The photosensitive composition containing resin as described in any one of Claims 1-5, a photo-acid generator, and a solvent. The photosensitive composition according to claim 6, wherein the photoacid generator has an extinction coefficient at a wavelength of 365 nm of 400 mL · g ⁻¹ · cm ⁻¹ or less.   A substrate with a liquid repellent film having a liquid repellent film formed from the photosensitive composition according to claim 6 on the surface of the substrate.   The substrate with a liquid repellent film according to claim 8, which is used for a biochip. A photosensitive composition according to claim 6 or 7 is applied to the surface of a substrate and dried to form a photosensitive film,
Exposing the photosensitive film;
The manufacturing method of the board | substrate with a liquid repellent film which develops the exposed photosensitive film | membrane using aqueous alkali solution, and forms a liquid repellent film.

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