WO2018008610A1 - 感光性組成物、重合体の製造方法、感光性組成物の製造方法、積層体の製造方法 - Google Patents
感光性組成物、重合体の製造方法、感光性組成物の製造方法、積層体の製造方法 Download PDFInfo
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- WO2018008610A1 WO2018008610A1 PCT/JP2017/024403 JP2017024403W WO2018008610A1 WO 2018008610 A1 WO2018008610 A1 WO 2018008610A1 JP 2017024403 W JP2017024403 W JP 2017024403W WO 2018008610 A1 WO2018008610 A1 WO 2018008610A1
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- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- QJAOYSPHSNGHNC-UHFFFAOYSA-N octadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCCCS QJAOYSPHSNGHNC-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- ZDYVRSLAEXCVBX-UHFFFAOYSA-N pyridinium p-toluenesulfonate Chemical compound C1=CC=[NH+]C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 ZDYVRSLAEXCVBX-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 229940032158 sodium silicate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical compound C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 1
- 239000012953 triphenylsulfonium Substances 0.000 description 1
- QKFJVDSYTSWPII-UHFFFAOYSA-N tris(4-methylphenyl)sulfanium Chemical compound C1=CC(C)=CC=C1[S+](C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 QKFJVDSYTSWPII-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
- C08F220/24—Esters containing halogen containing perhaloalkyl radicals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
Definitions
- the present invention relates to a photosensitive composition, a method for producing a polymer, a method for producing a photosensitive composition, and a method for producing a laminate.
- Patent Document 1 a method using a photosensitive composition capable of forming a liquid repellent film having a predetermined pattern by photolithography has been proposed (for example, Patent Document 1).
- a photosensitive composition capable of forming a liquid repellent film having a predetermined pattern by photolithography.
- a photosensitive composition capable of forming a liquid repellent film having a predetermined pattern by photolithography
- a water-repellent film is formed on a hydrophilic substrate, exposed in a predetermined pattern, developed, and a portion of the hydrophilic substrate is exposed, whereby a hydrophilic portion and a water-repellent portion are formed.
- Patent Document 1 A positive-type liquid repellent resist composition containing a fluorine-based polymer having a specific fluorine concentration and a weight average molecular weight has been proposed (Patent Document 1).
- Patent Document 1 A positive-type liquid repellent resist composition containing a fluorine-based polymer having a specific fluorine concentration and a weight average molecular weight has been proposed (Patent Document 1).
- Patent Document 1 As a method for adjusting the molecular weight, a method using a chain transfer agent is generally known. In the example of Patent Document 1, polymerization is performed using lauryl mercaptan as a chain transfer agent, and a fluorine-based polymer having a mass average molecular weight of 4600 to 6800 is synthesized.
- An object of the present invention is to provide a photosensitive composition capable of forming a liquid-repellent coating film with no coating unevenness, a method for producing the same, and a liquid-repellent coating film with no coating unevenness when used in the photosensitive composition. It is providing the manufacturing method of a polymer, and the manufacturing method of the laminated body using this photosensitive composition.
- the present invention provides a photosensitive composition, a method for producing a polymer, a method for producing a photosensitive composition, and a method for producing a laminate having the following constitutions [1] to [14].
- a photosensitive composition comprising at least one of the following resin P1 and the following resin P2 and a photoinitiator.
- Resin P1 A unit u1 that is a unit having an organic group having one or more fluorine atoms, a unit u2 that is a unit having a crosslinking group, and any one of the following formula 1, the following formula 2, and the following formula 3 Resin which consists of polymer A which is a polymer which has a terminal group.
- Resin P2 a polymer B having the unit u1 and not having the unit u2, and a polymer C having the unit u2 and not having the unit u1, A resin in which at least one of the polymer B and the polymer C is a polymer having a terminal group represented by any one of the formula 1, the formula 2, and the formula 3. -X 1 -C (R 1 ) (R 2 ) (R 3 ) ... 1 -X 2 -R 4 ...
- each of R 1 to R 3 independently represents 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 represents a cyclic group having 40 or less carbon atoms
- R 5 and R 6 each independently represent 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 represents a single bond, —S—, —S—R 7 —, —R 8 —, —O—R
- the photoinitiator is a photoacid generator, and the polymer A further includes a unit u3 which is a unit having an alkali-soluble group protected with an acid-dissociable group.
- Photosensitive composition [4] The photoinitiator is a photoacid generator, and at least one of the polymer B and the polymer C further includes a unit u3 which is a unit having an alkali-soluble group protected with an acid-dissociable group. , [1] or [2].
- a unit u3 in which any one or more of the polymer A, the polymer B, and the polymer C is a unit having an alkali-soluble group protected by the unit u1, the unit u2, and an acid dissociable group The photosensitive composition according to any one of [1] to [4], further comprising a unit u4 which is a unit other than [6]
- R 1 to R 3 are each independently a chain hydrocarbon group having 40 or less carbon atoms which may have a hydroxyl group, an oxo group or an etheric oxygen atom.
- R 4 represents a cyclic group having 40 or less carbon atoms
- R 5 and R 6 are each independently a chain hydrocarbon group having 40 or less carbon atoms, which may have a hydroxyl group, may have an oxo group, and may have an etheric oxygen atom, or
- X 1 to X 3 each independently represents a single bond, —S—, —S—R 7 —, —R 8 —, —O—R 9 — or —O—
- a monomer component comprising a monomer a1 which is a monomer having an organic group having one or more fluorine atoms and a monomer a2 ′ which is a monomer having a reaction site is represented by the following formula: 11, a polymer obtained by polymerizing in the presence of the chain transfer agent represented by any one of the following formula 12 and the following formula 13 and then having a reactive functional group capable of binding to the reaction site;
- a method for producing a polymer wherein a compound having a crosslinking group is reacted to obtain a polymer having a unit u2 which is a unit having a crosslinking group.
- R 1 to R 3 are each independently a chain hydrocarbon group having 40 or less carbon atoms which may have a hydroxyl group, an oxo group or an etheric oxygen atom.
- a monomer component containing monomer a2 which is a monomer having a crosslinking group (excluding a group containing an ethylenic double bond) is polymerized in the presence of the chain transfer agent to give polymer C.
- a method for producing a photosensitive composition wherein at least the polymer B, the polymer C, and a photoinitiator are mixed to obtain a photosensitive composition.
- R 1 to R 6 and X 1 to X 3 are as defined above, Z 1 to Z 3 each independently represents a hydrogen atom or a halogen atom.
- R 1 to R 6 and X 1 to X 3 are as defined above, Z 1 to Z 3 each independently represents a hydrogen atom or a halogen atom.
- R 1 to R 6 and X 1 to X 3 are as defined above, Z 1 to Z 3 each independently represents a hydrogen atom or a halogen atom.
- a method for producing a laminate having a substrate and a coating film laminated on the substrate comprising: applying a photosensitive composition of any one of [1] to [6] on a substrate to form a photosensitive film; exposing the photosensitive film to form a coating film; .
- the coating film has holes or grooves penetrating in the thickness direction, [13] The method for producing a laminate according to [13], wherein the photosensitive film is exposed with a pattern corresponding to the holes or grooves, and the photosensitive film is developed after the exposure.
- a liquid repellent coating film having no coating unevenness can be formed.
- a polymer capable of forming a liquid repellent coating film having no coating unevenness when used in a photosensitive composition is obtained.
- a photosensitive composition capable of forming a liquid-repellent coating film with no coating unevenness is obtained.
- a laminate having a liquid repellent coating film with no coating unevenness can be obtained.
- An object of the present invention is to provide a photosensitive composition capable of forming a liquid-repellent coating film with no coating unevenness, a method for producing the same, and a liquid-repellent coating film with no coating unevenness when used in the photosensitive composition. It is providing the manufacturing method of a polymer, and the manufacturing method of the laminated body using this photosensitive composition.
- Photoinitiator means a compound that generates at least one of a radical and an acid when irradiated with light.
- photo radical generator means a compound that generates radicals when irradiated with light.
- photo acid generator means a compound that generates an acid when irradiated with light.
- Liquid-repellent film means a film that exhibits liquid repellency compared to a portion other than the film, specifically, a film having a contact angle of a predetermined liquid larger than that of a part other than the film.
- lyophilic substrate means a substrate that exhibits lyophilicity compared to a liquid repellent film, specifically, a substrate that has a contact angle of a predetermined liquid smaller than that of a liquid repellent film.
- the “(meth) acryloyloxy group” is a general term for an acryloyloxy group and a methacryloyloxy group.
- (Meth) acrylate” is a general term for acrylate and methacrylate.
- (Meth) acrylic acid” is a general term for acrylic acid and methacrylic acid.
- the photosensitive composition of the present invention includes at least one of resin P1 and resin P2 and a photoinitiator.
- the composition may further contain a solvent.
- This composition may further contain other components other than the polymer A, the polymer B, the polymer C, the photoinitiator, and the solvent.
- Terminal group J The polymer A constituting the resin P1 and the polymer constituting the resin P2 (at least one of the polymer B and the polymer C) have the following specific terminal group (hereinafter also referred to as “terminal group J”).
- the terminal group J is a terminal group represented by any one of the following formula 1, the following formula 2, and the following formula 3.
- the said polymer when forming a coating film from this composition, it can suppress that an application
- each of R 1 to R 3 independently represents 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 represents a cyclic group having 40 or less carbon atoms,
- R 5 and R 6 are each independently a hydroxyl group, an oxo group, a chain hydrocarbon group having 40 or less carbon atoms which may have an etheric oxygen atom between carbon atoms, or a cyclic group having 40 or less carbon atoms.
- Indicate X 1 to X 3 each independently represents a single bond, —S—, —S—R 7 —, —R 8 —, —O—R 9 — or —O—, and each of R 7 , R 8 and R 9 Each independently represents a linear alkylene group having 1 to 40 carbon atoms.
- 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, for example, 1 to 20.
- 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.
- 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.
- the bonding position of the hydroxyl group in the chain hydrocarbon group is not particularly limited.
- the number of hydroxyl groups contained in the chain hydrocarbon group may be, for example, 1 to 4.
- the bonding position of the oxo group in the chain hydrocarbon group is not particularly limited.
- the number of oxo groups that the chain hydrocarbon group has may be, for example, 1 to 10.
- the position of the etheric oxygen atom in the chain hydrocarbon group is not particularly limited.
- 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.
- the chain hydrocarbon group has 1 to 40 carbon atoms and preferably 1 to 20 carbon atoms when it does not have an etheric oxygen atom between carbon atoms. When it has an etheric oxygen atom between carbon atoms, it is 2 to 40, preferably 2 to 20.
- chain hydrocarbon group in R 1 to R 3 examples include an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isopropyl group, an isobutyl group, and a 2-ethylhexyl group, and an 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.
- 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.
- the cyclic group is a hydrocarbon cyclic group, the number of carbon atoms is 3 to 40, preferably 5 to 20. In the case of a heterocyclic group, it is 2 to 40, preferably 2 to 20.
- a substituent may be bonded to the ring skeleton of the cyclic group.
- 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.
- 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. It is represented by the formula (1) when 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 the formula (1).
- the base has a bulky structure.
- R 4 examples 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 thereof are also the same.
- 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.
- the cyclic group having 40 or less carbon atoms in R 5 and R 6 examples 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 ) n —.
- the linear alkylene group has 1 to 40 carbon atoms (the value of n in — (CH 2 ) n —), preferably 1 to 20.
- X 1 to X 3 are preferably —S—R 7 — and —O— from the viewpoint of ease of chain transfer when a polymer is produced using a corresponding chain transfer agent.
- terminal group J examples 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 3 ) CH 2 CH 2 CH 2 etc. CH 2 CH 2 CH 2 CH 2 CH 3 and the like. From the viewpoint 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”).
- chain transfer agent j any one of the following formula 11, the following formula 12 and the following formula 13
- R 1 to R 6 and X 1 to X 3 are as defined above
- Z 1 to Z 3 each independently represents a hydrogen atom or a halogen atom. Examples of the halogen atom in Z 1 to Z 3 include a chlorine atom, an iodine atom, and a bromine atom.
- chain transfer agent j examples include thioglycerol, 2-ethylhexanethiol, cyclohexanethiol, furfuryl mercaptan, benzylthiol, carbon tetrachloride, isobutyl alcohol, 3-pentanone, cyclohexylethanol, 2-hexyl-1-decanol, and the like. Is mentioned.
- 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 unit u1 is a unit having an organic group having one or more fluorine atoms (hereinafter also referred to as “fluorinated organic group”).
- the coating film formed from this composition can exhibit liquid repellency because the polymer A and the polymer B have the unit u1.
- fluorine-containing organic group examples include a fluoroalkyl group optionally having an etheric oxygen atom between carbon atoms, an alicyclic group having one or more fluorine atoms, and the like.
- a fluoroalkyl group which may have an atom is preferred.
- the fluoroalkyl group may be linear or branched.
- the number of fluorine atoms relative to the total number of hydrogen atoms and fluorine atoms in the fluoroalkyl group is preferably 50% or more.
- fluoroalkyl group a fluoroalkyl group having a perfluoroalkyl moiety which may have an etheric oxygen atom between carbon atoms is preferable.
- fluoroalkyl group having a perfluoroalkyl moiety include a fluoroalkyl group represented by -R 13 -R f .
- R f represents an optionally perfluoroalkyl moiety may have an etheric oxygen atom between carbon atoms
- R 13 represents an alkylene moiety having no fluorine atom.
- R f is a perfluoroalkyl moiety having no etheric oxygen atom
- the carbon number thereof is preferably 4, 5 or 6, and 6 is particularly preferred.
- R f may be linear or branched, but is preferably linear.
- the number of etheric oxygen atoms is preferably 1 to 3.
- the number of carbon atoms of the perfluoroalkyl moiety at the terminal side (opposite side to the R 13 side) from the etheric oxygen atom is preferably 1-6.
- the number of carbon atoms in the perfluoroalkylene moiety between the etheric oxygen atoms and between the etheric oxygen atom and R 13 is preferably 1 to 4.
- the perfluoroalkyl moiety having an etheric oxygen atom may be linear or branched as a whole, and the total number of carbon atoms thereof is preferably 3 to 12, and more preferably 4 to 8.
- R f specifically, — (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 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.
- R 13 preferably has 1 to 6 carbon atoms, more preferably 2 to 4 carbon atoms.
- R 13 is particularly preferably —CH 2 CH 2 —.
- the unit u1 is preferably a unit based on the monomer a1, which is a monomer having a fluorine-containing organic group.
- the monomer a1 is typically a compound having a fluorine-containing organic group and an ethylenic double bond.
- the monomer a1 is preferably a monomer comprising an ester of a monool represented by HO—R 13 —R f and an unsaturated monocarboxylic acid. Examples of the unsaturated monocarboxylic acid include methacrylic acid, acrylic acid, ⁇ -haloacrylic acid and the like.
- (meth) acrylate and ⁇ -haloacrylate having a fluoroalkyl group represented by —R 13 —R f are particularly preferable.
- examples of such a monomer include a monomer represented by CH 2 ⁇ C (R 12 ) COO—R 13 —R f .
- R 12 represents a 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 monomers a1 include 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 ⁇ CHCOO—CH 2 CF (CF 3 ) COO—CH 2
- 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 are obtained in that good liquid repellency can be obtained.
- 2 OCF 2 CF 2 OCF 3 are preferred.
- Monomer a1 may be used individually by 1 type, and may use 2 or more types together.
- the unit u2 is a unit having a crosslinking group (except for the unit u1).
- the crosslinking group is a group that can be crosslinked by a radical or an acid.
- radicals or acids are generated from the photoinitiator at the exposed portion, and the crosslinkable group is crosslinked (cured) by the action.
- Examples of the group that can be cross-linked by a radical include a group containing an ethylenic double bond.
- Examples of the group containing an ethylenic double bond include a (meth) acryloyl group, an allyl group, and a vinyl group.
- Examples of the group that can be cross-linked by an acid include a group containing a 3-membered cyclic ether structure, a group containing a 4-membered cyclic ether structure, and a vinyloxy group.
- Examples of the group containing a 3-membered cyclic ether structure include an epoxy group and a 3,4-epoxycyclohexyl group.
- Examples of the group containing a 4-membered cyclic ether structure include an oxetane group.
- the group containing a 3-membered cyclic ether structure and the group containing a 4-membered cyclic ether structure may be substituted with an alkyl group as long as the reactivity is not impaired.
- the alkyl group preferably has 1 to 6 carbon atoms.
- the epoxy group and 3,4-epoxycyclohexyl group are preferably unsubstituted.
- the oxetane group may be unsubstituted or may be substituted with an alkyl group, and is preferably a (3-alkyloxetane-3-yl) group.
- a group containing an ethylenic double bond, a group containing a 3-membered cyclic ether structure, or a group containing a 4-membered cyclic ether structure is preferable, and a (meth) acryloyl group, a vinyloxy group, an epoxy group, an oxetane group,
- the (3-alkyloxetane-3-yl) group is more preferable because of high crosslinking reactivity.
- monomer a2 which is a monomer having a crosslinking group (excluding a group containing an ethylenic double bond) and another monomer are used together.
- Monomer a2 ′ which is a monomer having a reactive site, is copolymerized with another monomer to obtain a polymer, and then the polymer is bonded to the reactive site.
- compound b a compound having a reactive functional group and a crosslinking group
- the unit u2 of the polymer obtained by the method (2) is a unit formed by introducing a crosslinking group into the reaction site of the unit based on the monomer a2 ′.
- the unit u2 of the polymer A and the polymer C may be any.
- the crosslinkable group is a group containing an ethylenic double bond
- the monomer having the crosslinkable group also reacts in the polymerization reaction during the production of the polymer. Therefore, when the crosslinking group is a group containing an ethylenic double bond
- the unit u2 is preferably a unit formed by introducing a crosslinking group into the reaction site of the unit based on the monomer a2 ′.
- the unit u2 may be a unit based on the monomer a2 having a bridging group, or a unit based on the monomer a2 ′. It may be a unit formed by introducing a crosslinking group into the reaction site. In terms of easy production, the unit is preferably based on the monomer a2 having a crosslinking group.
- the monomer a2 is typically a compound having the crosslinking group and an ethylenic double bond.
- (meth) acrylate having a crosslinking group is preferable.
- the crosslinking group in the monomer a2 is preferably a group containing a 3-membered or 4-membered cyclic ether structure, particularly preferably an epoxy group, an oxetane group, or a (3-alkyloxetane-3-yl) group.
- Examples of the (meth) acrylate having a group containing a 3-membered or 4-membered cyclic ether structure as a crosslinking group include monomers represented by CH 2 ⁇ C (R 21 ) COO—R 22 —R 23.
- R 21 represents a hydrogen atom or a methyl group
- R 22 represents an alkylene group
- R 23 represents a group containing a 3-membered or 4-membered cyclic ether structure.
- R 22 preferably has 1 to 20 carbon atoms.
- Specific monomers a2 include glycidyl (meth) acrylate, 4-glycidyloxybutyl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (meth) acrylate, 3,4-epoxycyclohexylmethyl ( And (meth) acrylate.
- Monomer a2 may be used individually by 1 type, and may use 2 or more types together.
- Examples of the reactive site in the monomer a2 ′ include a hydroxyl group, a carboxy group, an isocyanate group, an epoxy group, and an amino group.
- a monomer having the reaction site and an ethylenic double bond is preferable.
- Examples of such a monomer include (meth) acrylates having a hydroxyl group or a carboxyl group.
- Specific examples of monomers having a hydroxyl group as a reactive site among the monomers a2 ′ include 2-hydroxyethyl methacrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl.
- (Meth) acrylate 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate and the like.
- Specific examples of the monomer having a carboxyl group as a reaction site in the monomer a2 ′ include acrylic acid, methacrylic acid, vinyl acetic acid and the like.
- Monomer a2 ' may be used individually by 1 type, and may use 2 or more types together.
- the reactive functional group of compound b is appropriately selected according to the reaction site.
- the reaction site is a hydroxyl group, an isocyanate group, a carboxy group, a haloacyl group (acyl chloride group, etc.), an epoxy group, etc.
- the reaction site is a carboxy group, a hydroxyl group, an isocyanate group, an epoxy group and the like can be mentioned.
- the compound having an isocyanate group and a crosslinking group include 2- (meth) acryloyloxyethyl isocyanate.
- the compound having an acyl chloride group and a crosslinking group include (meth) acryloyl chloride.
- Examples of the compound having an epoxy group and a crosslinking group include glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 3,4-epoxycyclohexylmethyl (meth) acrylate, and the like.
- the unit u3 is a unit having an alkali-soluble group protected with an acid-dissociable group.
- the photoinitiator preferably contains a photoacid generator.
- the photosensitive film can be developed with an alkaline developer.
- alkali-soluble group protected with an acid-dissociable group examples include a group represented by —C (O) OC (R 31 ) (R 32 ) OR 33 , —C (O) OC (R 34 ) (R 35 ) (R 36 ) and the like.
- R 31 represents an alkyl group or a cycloalkyl group
- R 32 represents a hydrogen atom, an alkyl group or a cycloalkyl group
- R 33 represents an alkyl group part of hydrogen atoms may be substituted
- R 34 to R 36 each independently represents an alkyl group having 1 to 40 carbon atoms.
- R 31 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.
- the R 32 a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, preferably a cycloalkyl group having 3 to 6 carbon atoms, from easily available in terms of monomer of raw materials, a hydrogen atom is particularly preferable.
- R 33 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.
- R 31 and R 33 are linked to form a cyclic ether, it is preferable that R 31 and R 33 are linked to form an alkylene group having 2 to 5 carbon atoms.
- 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.
- Examples of the group represented by —C (O) OC (R 31 ) (R 32 ) OR 33 include 1-ethoxyethyl group, 1-methoxyethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group.
- Examples of the group represented by —C (O) OC (R 34 ) (R 35 ) (R 36 ) include a tert-butoxycarbonyl group (—C (O) OC (CH 3 ) 3 ).
- the unit u3 is preferably a unit having a group represented by —C (O) OC (R 31 ) (R 32 ) OR 33 .
- the group represented by —C (O) OC (R 31 ) (R 32 ) OR 33 is more acidic than the group represented by —C (O) OC (R 34 ) (R 35 ) (R 36 ).
- PEB post-exposure baking
- the preferred unit is typically a unit based on a monomer represented by CH 2 ⁇ CH (R 30 ) C (O) OC (R 31 ) (R 32 ) OR 33 .
- R 30 is a hydrogen atom or a methyl group
- R 31 to R 33 are as defined above.
- Specific monomers 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 and 1-benzyloxyethyl (meth) acrylate.
- the unit u4 is a unit other than the unit u1, the unit u2, and the unit u3.
- Examples of the unit u4 include a unit based on the monomer a4 which is a unit having no alkali-soluble group protected by the fluorine-containing organic group, the crosslinking group, and the acid dissociable group.
- the monomer a4 is typically a compound having an ethylenic double bond that does not have an alkali-soluble group protected by the fluorine-containing organic group, the crosslinking group, and the acid-dissociable group.
- Specific monomers a4 include 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-methoxyethyl (meth) acrylate, methoxybut
- Polymer A has units u1 and units u2.
- the polymer A may further have a unit u3.
- the polymer A may further have a unit u4.
- the ratio of the unit u1 to the total of all units is preferably 10 to 90 mol%, more preferably 20 to 90 mol%.
- the ratio of unit u2 to the total of all units is preferably 10 to 90 mol%, more preferably 10 to 80 mol%.
- the ratio of the unit u3 to the total of all units is preferably 0 to 80 mol%, more preferably 0 to 70 mol%.
- the ratio of the unit u4 to the total of all units is preferably 0 to 80 mol%, and more preferably 0 to 60 mol%.
- the proportion of each structural unit in the polymer can be determined, for example, from the integral ratio of peaks specific to each unit in 1 H-NMR (nuclear magnetic resonance analysis).
- Preferred embodiments of the polymer A include the following polymer A1 and polymer A2.
- Polymer A1 A polymer having unit u1 and unit u2, having no unit u3, and having a terminal group J.
- Polymer A2 a polymer having unit u1, unit u2, and unit u3, the crosslinking group of unit u2 being a group that can be crosslinked by an acid, and having terminal group J.
- Each of the polymers A1 and A2 may further have a unit u4.
- Polymer A1 preferably has 10 to 29 mol% of unit u1 and 10 to 90 mol% of unit u2 with respect to the total of all units.
- the ratio of the sum of unit u1 and unit u2 to the total of all units is preferably 30 mol% or more, and may be 100 mol%.
- the polymer A2 preferably has 10 to 29 mol% of unit u1, 10 to 60 mol% of unit u2, and 20 to 80 mol% of unit u3 with respect to the total of all units.
- the total ratio of the unit u1, the unit u2 and the unit u3 to the total of all units is preferably 40 mol% or more, and may be 100 mol%.
- the mass average molecular weight (Mw) of the polymer A is not particularly limited, but is preferably 4,000 to 500,000, more preferably 5,000 to 200,000, still more preferably 6,000 to 20,000, 000 to 19,000 is particularly preferred. If the mass average molecular weight is within this range, processing by lithography can be stably performed. In particular, when the mass average molecular weight is 6,000 to 20,000, uneven coating of the coating film without the terminal group J is remarkable, and the utility of the present invention is high.
- the mass average molecular weight of the polymer A is a standard polymethyl methacrylate conversion value measured by gel permeation chromatography (GPC). The same applies to the mass average molecular weights of the polymers B and C.
- the following two manufacturing methods are mentioned, for example.
- a polymer having a terminal group J at the end of the main chain is obtained.
- -A monomer component containing the monomer a1 and the monomer a2 ' is polymerized in the presence of the chain transfer agent j to obtain a polymer, and the polymer b is reacted with the polymer.
- the monomer component may further include at least one selected from the group consisting of monomer a3 and monomer a4.
- the polymerization of the monomer component can be performed 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.
- a polymerization initiator may be used during the polymerization.
- the ratio of the total amount of monomers to the polymerization solvent is preferably 5 to 70% by mass, more preferably 10 to 40% by mass. The higher this ratio, the better the production efficiency of the present composition.
- the polymerization solvent is preferably the same as the solvent for the photosensitive composition.
- the amount of the chain transfer agent j used can be appropriately selected according to the molecular weight of the polymer to be produced, and varies depending on the amount of the polymerization initiator used and the monomer concentration. 0.1 to 20 mol%, preferably 1 to 10 mol%.
- 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.
- the monomer concentration is low, the amount of chain transfer agent used to obtain a desired molecular weight tends to be small. Examples of the polymerization conditions include conditions of 40 to 60 ° C. and 5 to 30 hours.
- the amount of the compound b used is preferably 10 to 100 mol% when the total number of reaction sites of units based on the monomer a2 ′ in the polymer is 100 mol%, 80 to 100 mol% is more preferable.
- the total number of reaction sites of the unit based on the monomer a2 ′ is (total number of moles of units based on the monomer a2 ′) ⁇ (monomer when the unit based on the monomer a2 ′ is one kind.
- the number of reaction sites of the unit based on a2 ′ is preferably 10 to 100 mol% when the total number of reaction sites of units based on the monomer a2 ′ in the polymer is 100 mol%, 80 to 100 mol% is more preferable.
- the total number of reaction sites of the unit based on the monomer a2 ′ is (total number of moles of units based on the monomer a2 ′) ⁇ (monomer when the unit based on the monomer
- reaction conditions for reacting compound (b) include, for example, the conditions of 0 to 60 ° C. for 5 to 48 hours. After polymerization or after reacting compound b, if necessary, purification treatment such as filtration and reprecipitation, treatment such as solvent distillation and solvent substitution may be performed.
- Polymer B is a polymer having unit u1 and not having unit u2.
- the polymer B may further have a unit u3.
- the polymer B may further have a unit u4.
- the ratio of the unit u1 to the total of all units is preferably 10 to 100 mol%, and more preferably 10 to 29 mol%.
- the ratio of the unit u3 to the total of all units is preferably 0 to 80 mol%, more preferably 0 to 70 mol%.
- the ratio of unit u4 to the total of all units is preferably 0 to 80 mol%, more preferably 0 to 70 mol%.
- Polymer B1 A polymer having a unit u1, no units u2 and u3, and having a terminal group J.
- Polymer B2 a polymer having unit u1 and unit u3, no unit u2, and having a terminal group J.
- Each of the polymers B1 and B2 may further have a unit u4.
- the polymer B1 preferably has 10 to 100 mol% of the unit u1 with respect to the total of all units.
- the polymer B2 preferably has 10 to 90 mol% of unit u1 and 20 to 80 mol% of unit u3 with respect to the total of all units.
- the ratio of the sum of unit u1 and unit u3 to the total of all units is preferably 30 mol% or more, and may be 100 mol%.
- the preferred range of the mass average molecular weight (Mw) of the polymer B is the same as that of the polymer A.
- the following manufacturing methods are mentioned, for example.
- the monomer component usually does not contain the monomer a2.
- the monomer component may further include at least one selected from the group consisting of monomer a3 and monomer a4. Polymerization of the monomer component can be carried out in the same manner as in the method for producing the polymer A described above.
- a monomer component is the same as that of the said manufacturing method.
- the polymerization of the monomer component can be carried out in the same manner as in the method for producing the polymer A described above except that the chain transfer agent j is not used.
- a chain transfer agent other than the chain transfer agent j may be used.
- Polymer C is a polymer having unit u2 and not having unit u1.
- the polymer C may further have a unit u3.
- the polymer C may further have a unit u4.
- the ratio of the unit u2 to the total of all units is preferably 10 to 100 mol%, and more preferably 10 to 90 mol%.
- the ratio of the unit u3 to the total of all units is preferably 0 to 90 mol%, more preferably 0 to 70 mol%.
- the ratio of the unit u4 to the total of all units is preferably 0 to 90 mol%, more preferably 0 to 80 mol%.
- Polymer C1 A polymer having a unit u2, no units u1 and u3, and having a terminal group J.
- Polymer C2 a polymer having unit u2 and unit u3, no unit u1, and having a terminal group J.
- Each of the polymers C1 and C2 may further have a unit u4.
- the polymer C1 preferably has 10 to 100 mol% of the unit u2 with respect to the total of all units.
- the polymer C2 preferably has 10 to 80 mol% of unit u2 and 20 to 90 mol% of unit u3 with respect to the total of all units.
- the total ratio of the unit u2 and the unit u3 to the total of all units is preferably 30 mol% or more, and may be 100 mol%.
- the preferred range of the mass average molecular weight (Mw) of the polymer C is the same as that of the polymer A.
- the following two manufacturing methods are mentioned, for example.
- the monomer component usually does not contain the monomer a1.
- the monomer component may further include at least one selected from the group consisting of monomer a3 and monomer a4.
- the polymerization of the monomer component and the reaction with the compound b in the above two production methods can be performed in the same manner as the two production methods in the production method of the polymer A described above.
- the following two manufacturing methods are mentioned, for example.
- the monomer component usually does not contain the monomer a1.
- the monomer component may further include at least one selected from the group consisting of monomer a3 and monomer a4.
- the polymerization of the monomer component can be carried out in the same manner as in the method for producing the polymer A described above except that the chain transfer agent j is not used.
- a chain transfer agent other than the chain transfer agent j may be used.
- the reaction with the compound b can be carried out in the same manner as the reaction with the compound b in the production method of the polymer A described above.
- the polymer A constituting the resin P1 may be one type or two or more types.
- Each of the polymer B and the polymer C constituting the resin P2 may be one type or two or more types.
- the ratio of the polymer B to the total amount of the polymer B and the polymer C is preferably 1% by mass or more, more preferably 5% by mass or more, and more preferably 10% by mass or more in terms of liquid repellency. More preferred is 20% by mass or more. In terms of curability and patterning property, 90% by mass or less is preferable, 80% by mass or less is more preferable, and 70% by mass or less is particularly preferable. Therefore, the ratio of the polymer B to the total amount of the polymer B and the polymer C is preferably 1 to 90% by mass.
- the polymer B When the polymer B does not have the unit 3, it is more preferably 1 to 50% by mass, and further preferably 1 to 40% by mass. When the polymer B has the unit 3, it is more preferably 1 to 90% by mass, further preferably 1 to 80% by mass, and particularly preferably 5 to 70% by mass. Only one of the resin P1 and the resin P2 may be used, or both may be used in combination.
- the photoinitiator examples include a photoradical generator and a photoacid generator. Each of these can be appropriately selected from known photoradical generators and photoacid generators.
- a photoradical generator is used as the photoinitiator
- a photoacid generator is used as the agent.
- the photoinitiator preferably has an extinction coefficient of 400 [mL ⁇ g ⁇ 1 ⁇ cm ⁇ 1 ] or less at a wavelength of 365 nm.
- the extinction coefficient is 400 [mL ⁇ g ⁇ 1 ⁇ cm ⁇ 1 ] or less, processing by lithography is possible.
- the light used as a noise is suppressed.
- the light that becomes noise is light that is observed as fluorescence when measured by a laser beam excitation type fluorescence analyzer.
- the extinction coefficient at a wavelength of 365 nm of the photoinitiator is more preferably 200 [mL ⁇ g ⁇ 1 ⁇ cm ⁇ 1 ] or less.
- the extinction coefficient is preferably 1 [mL ⁇ g ⁇ 1 ⁇ cm ⁇ 1 ] or more, more preferably 10 [mL ⁇ g ⁇ 1 ⁇ cm ⁇ 1 ] or more.
- the photo radical generator examples include 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-1-phenylacetophenone, methylphenylketone, dibenzoyl, benzophenone, benzoin isopropyl ether, 2- Hydroxy-2-methyl-1-phenyl-1-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1-hydroxy Examples include cyclohexyl-phenyl-ketone, 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl ⁇ -2-methyl-propan-1-one, and the like.
- 2,2-dimethoxy-1,2-diphenylethane-1-one 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxycyclohexyl-phenyl-ketone, 2-hydroxy -1- ⁇ 4- [4- (2-Hydroxy-2-methyl-propionyl) -benzyl] phenyl ⁇ -2-methyl-propan-1-one has low fluorescence of the resulting coating film, and is effective in photocuring performance. It is preferable because of its superiority.
- These photo radical generators may be used alone or in combination of two or more.
- photoradical generator examples include IRGACURE (trademark) 651 (manufactured by BASF), IRGACURE 184 (manufactured by BASF), IRGACURE 127 (manufactured by BASF), IRGACURE 500 (manufactured by BASF), IRGACURE 2959 (manufactured by BASF) BASF), 1173 (BASF) and the like.
- 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.
- Anion moieties include trifluoromethanesulfonate, nonafluorobutanesulfonate, hexafluorophosphate, tetrafluoroborate, tris (pentafluoroethyl) trifluorophosphate, tris (heptafluoropropyl) trifluorophosphate, tris (nonafluoroisobutyl) trifluoro Examples include phosphate and bis (nonafluoroisobutyl) tetrafluorophosphate.
- sulfonyldiazomethane examples include bis (phenylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, and the like.
- photoacid generators may be used alone or in combination of two or more.
- Specific product names of the photoacid generator include IRGACURE 250 (manufactured by BASF), CPI (trademark) -100P (manufactured by Sun Apro), CPI-210S (manufactured by Sun Apro), WPAG 199 (manufactured by Wako Pure Chemical Industries, Ltd.) Etc.
- Preferred combinations of the resin P1 and the photoinitiator in the present composition include the following combinations (1) to (3).
- the combination (1) or (2) is preferable, and the combination (2) is particularly preferable.
- Combination (1) A combination in which the resin P1 is the polymer A1, the crosslinking group of the unit u2 of the polymer A1 is a group that can be crosslinked by an acid, and the photoinitiator is a photoacid generator.
- Combination (2) A combination in which the resin P1 is the polymer A2 and the photoinitiator is a photoacid generator.
- Combination (3) Combination in which the resin P1 is the polymer A1, the crosslinking group of the unit u2 of the polymer A1 is a group that can be crosslinked by radicals, and the photoinitiator is a photoradical generator.
- the resin P2 and the photoinitiator in the present composition in the above combination (1) or (3), the combination in which the polymer A1 is changed to the following resin P21, or the above combination (2)
- the combination which changed the polymer A2 into the following resin P22, P23, or P24 is mentioned.
- the resin P21 or P24 is preferable from the viewpoint of easy patterning of the photosensitive film.
- the preferable ratio of the polymers B1 and B2 to the total amount of the polymers of the respective resins is the same as the preferable ratio of the polymer B to the total amount of the polymers of the resin P2.
- Resin P21 a resin composed of a polymer B1 and a polymer C1, and at least one of them has a terminal group J.
- Resin P22 a resin comprising polymer B1 and polymer C2, at least one of which has a terminal group J.
- Resin P23 Resin which consists of polymer B2 and polymer C1, and at least one of them has terminal group J.
- Resin P24 A resin comprising polymer B2 and polymer C2, at least one of which has a terminal group J.
- the solvent only needs to dissolve or disperse the resins P1 and P2 and the photoinitiator, and more preferably dissolves them.
- volatile components such as a solvent
- the solvent include fluorinated solvents and non-fluorinated solvents.
- fluorine-based solvent examples include Asahiklin (trademark) manufactured by Asahi Glass Co., Ltd., 1H-tridecafluorohexane (AC2000), 1,1,1,2,2,3,3,4,4,5, 5,6,6-tridecafluorooctane (AC6000), 1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane (AE3000), dichloropentafluoropropane (AK-) 225).
- Asahiklin trademark manufactured by Asahi Glass Co., Ltd.
- 1H-tridecafluorohexane AC2000
- 1,1,1,2,2,3,3,4,4,5 5,6,6-tridecafluorooctane
- AE3000 1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethanethane
- AK- dichloropentafluoropropane
- Cytop (trademark) CT-solv 100E (Asahi Glass Co., Ltd.), 1-methoxynonafluorobutane (manufactured by 3M Japan, Novec (trademark) 7100), 1-ethoxynonafluorobutane (manufactured by 3M Japan, Novec).
- non-fluorinated solvents include ketones such as cyclopentanone, cyclohexanone, methyl amyl ketone, 2-butanone, ethyl lactate, methyl benzoate, ethyl benzoate, benzyl benzoate, methyl cellosolve acetate, ethyl cell
- ketones such as cyclopentanone, cyclohexanone, methyl amyl ketone, 2-butanone, ethyl lactate, methyl benzoate, ethyl benzoate, benzyl benzoate, methyl cellosolve acetate, ethyl cell
- ketones such as cyclopentanone, cyclohexanone, methyl amyl ketone, 2-butanone, ethyl lactate, methyl benzoate, ethyl benzoate, benzyl benzoate, methyl cellosolve acetate, ethyl cell
- solvents may be used alone or in combination of two or more.
- solvents propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, hexafluoro-2-propanol, 2,2,3,3, in terms of high solubility, high boiling point and excellent film formability.
- 4,4,5,5-octafluoro-1-pentanol, 1H, 1H, 7H-dodecafluoro-1-heptanol is preferred.
- Examples of other components include radical crosslinking agents, acid crosslinking agents, adhesion promoters, and other additives.
- radical crosslinking agent examples include compounds having two or more ethylenic double bonds. In particular, a compound having 2 to 6 acryloyloxy groups is preferable.
- Specific radical crosslinking agents include diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and trimethylolpropane tri (meth).
- the acid crosslinking agent examples include compounds having a group that is crosslinked by the action of an acid.
- Specific examples of the acid crosslinking agent include hexamethylol methoxymethyl melamine, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 4,5-dimethoxy-1,3-bis (methoxymethyl) imidazolidine-1 -One, 1,3-bis (methoxymethyl) urea, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (2,3-epoxycyclopentyl) ether, ethylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl [(3-ethyloxetane-3-yl) methoxy] methyloxetane, diethylene glycol monovinyl ether, tri
- a coupling agent such as a silane coupling agent
- silane coupling agents include tetraethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, heptadecafluorooctyltrimethoxysilane, 3-chloropropyltrimethoxysilane, vinyltrimethylsilane. Examples include chlorosilane and vinyltrimethoxysilane.
- the total content of the resin P1 and the resin P2 in the composition is preferably 10 to 70% by mass, more preferably 10 to 60% by mass, and further more preferably 10 to 50% by mass with respect to the total mass of the composition. Preferably, 10 to 40% by mass is particularly preferable. If the total content of the resin P1 and the resin P2 in the composition is equal to or higher than the lower limit of the above range, the film thickness can be easily controlled, and if it is equal to or lower than the upper limit, the spin coatability is more excellent.
- the content of the photoinitiator in the composition is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and more preferably 0.5 to 10% by mass with respect to the total mass of the composition. % Is particularly preferred.
- the content of other components in the composition is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, based on the total mass of the composition.
- the content of the solvent in the composition is the remainder obtained by removing the resin P1, the resin P2, the photoinitiator and other components from the composition.
- the present composition comprises 10 to 70% by mass of at least one of the resin P1 and the resin P2, 1 to 10% by mass of the photoinitiator, 20 to 89% by mass of the solvent, and the like based on the total mass of the present composition Is preferably a composition containing 0 to 59% by mass of the following components: at least one of the resin P1 and the resin P2 is 10 to 40% by mass, the photoinitiator is 1 to 4% by mass, the solvent is 46 to 89% by mass, And a composition containing 0 to 10% by mass of other components.
- the present composition can be produced by mixing at least one of resin P1 and resin P2 and a photoinitiator. At this time, a solvent and other components may be mixed as necessary.
- the mixing order of each component is not particularly limited.
- this composition contains resin P2, the polymer B and the polymer C may be mixed previously before mixing photoinitiators etc., and may be mixed when mixing photoinitiators etc. You may perform the process of manufacturing the polymer A, the polymer B, or the polymer C before mixing each component.
- Each polymer can be produced by the procedure described above. Therefore, the production method of the present composition may be any of the following production methods 1 to 4.
- Production method 1 Polymer A is produced by polymerizing a monomer component containing monomer a1 and monomer a2 in the presence of chain transfer agent j, A method for producing a photosensitive composition, wherein at least the polymer A and a photoinitiator are mixed to obtain a photosensitive composition.
- Production method 2 A monomer component containing monomer a1 is polymerized in the presence of chain transfer agent j to obtain polymer B, A monomer component containing monomer a2 is polymerized in the presence of chain transfer agent j to obtain polymer C, A method for producing a photosensitive composition, wherein at least the polymer B, the polymer C, and a photoinitiator are mixed to obtain a photosensitive composition.
- Production Method 3 A monomer component containing monomer a1 is polymerized in the presence of chain transfer agent j to obtain polymer B, A method for producing a photosensitive composition, wherein at least the polymer B, the polymer C, and a photoinitiator are mixed to obtain a photosensitive composition.
- Production Method 4 A monomer component containing monomer a2 is polymerized in the presence of chain transfer agent j to obtain polymer C, A method for producing a photosensitive composition, wherein at least the polymer C, the polymer B, and a photoinitiator are mixed to obtain a photosensitive composition.
- the polymer C in the production method 3 and the polymer B in the production method 4 usually do not have the terminal group J, but may have it.
- polymerization is performed by a solution polymerization method during production of polymer A to obtain a polymer solution containing polymer A and a solvent, and a photoinitiator or the like is added to this polymer solution.
- a photoinitiator or the like is added to this polymer solution. The method of obtaining this composition is mentioned.
- the coating film formed from the present composition may have a hole or a groove penetrating in the thickness direction by photolithography as described below.
- the photosensitive composition containing at least one of resin P1 and resin P2 and a photoinitiator is formed by applying this composition on a base material and drying it as necessary.
- this photosensitive film is selectively exposed with a pattern corresponding to the hole or groove to be formed, radicals or acids are generated from the photoinitiator at the exposed portion of the photosensitive film, and the crosslinking group is crosslinked by the action. (Curing).
- the polymer constituting the resin P1 and the resin P2 does not have the unit u3, or when the photoinitiator is not a photoacid generator even though it has the unit u3, crosslinking of the exposed part causes Solubility in the developer is reduced.
- the solubility in the developer is not substantially changed. Therefore, when the exposed photosensitive film is developed with a developer, the unexposed portion is dissolved and removed in the developer, while the exposed portion remains without being removed. Thereby, a coating film (cured film) in which a hole or a groove penetrating in the thickness direction is formed at the position of the unexposed portion is formed, and the base material and the coating film provided on the surface of the base material are The laminated body which has is obtained.
- the photoacid generator was generated in the exposed portion during the exposure.
- the acid-dissociable group is dissociated by the action of an acid to generate an alkali-soluble group such as a carboxy group.
- an alkali-soluble group such as a carboxy group.
- the solubility with respect to the alkaline developing solution of an exposure part increases.
- the solubility in an alkaline developer is not substantially changed in the unexposed area. Therefore, when the exposed photosensitive film is developed with an alkali developer, the exposed portion is dissolved and removed in the alkali developer, while the unexposed portion remains without being removed.
- the composition is coated on a substrate to form a photosensitive film, and the photosensitive film is exposed to form a coating film.
- the laminated body which has a base material and the coating film laminated
- the material of the substrate is not particularly limited, and examples thereof include various glass plates, thermoplastic plastic sheets such as polypropylene, polyethylene, polycarbonate, polymethyl methacrylate, and polystyrene. From the viewpoint of heat resistance, a glass plate, particularly a quartz glass plate is preferred.
- the coating method of the present composition is not particularly limited, and examples thereof include a spray method, a roll coating method, a spin coating method, and a bar coating method.
- the wet coating film obtained by applying the present composition is preferably baked (hereinafter also referred to as pre-baking).
- pre-baking the solvent quickly evaporates and a dry coating film (photosensitive film) having no fluidity is obtained.
- the pre-baking conditions vary depending on the type of each component, the blending ratio, etc., but are preferably about 50 to 120 ° C. and about 10 to 2000 seconds.
- the film thickness of the dried coating film is not particularly limited, but is preferably 0.1 to 20 ⁇ m, more preferably 0.5 to 10.0 ⁇ m.
- the exposure may be an overall exposure for exposing the entire surface of the dry coating film, or a selective exposure for selectively exposing a part of the dry coating film.
- selective exposure is performed with a pattern corresponding to the holes or grooves to be formed.
- the dried coating film may be exposed through a mask having a predetermined pattern. If the polymer constituting the resin P1 and the resin P2 does not have the unit u3, or if the photoinitiator is not a photoacid generator even if it has the unit u3, the portion where the hole or groove is formed is exposed. Without exposure, the other parts are exposed.
- the photoinitiator is a photoacid generator, the part that forms the hole or groove is exposed, and the other part is exposed. Does not expose.
- the light used for exposure is light having a wavelength of 100 to 500 nm, preferably 200 to 450 nm, and particularly preferably i-line (365 nm).
- a high-pressure mercury lamp, (ultraviolet) LED, laser or the like as a light source.
- the exposure dose is preferably in the range of 5 to 2000 mJ / cm 2 .
- a post-exposure bake (PEB) treatment for accelerating the crosslinking reaction can be performed on the exposed coating film as necessary.
- the PEB treatment conditions are preferably in the range of 50 to 150 ° C. and 10 to 2000 seconds.
- the exposed dry coating film is developed as necessary. Development can be carried out using a developer.
- the developer is a solvent-based developer containing a solvent
- the unexposed portion is dissolved and removed by development.
- the developer is an alkaline developer
- at least one of the polymers constituting the resin P1 and the resin P2 has a unit u3
- the photoinitiator is a photoacid generator
- the solvent used in the solvent-based developer it is sufficient that the unexposed part can be selectively dissolved.
- the solvents mentioned above can be used.
- the alkali of the alkaline developer include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, sodium bicarbonate, and bicarbonate.
- alkali metal bicarbonates such as potassium, ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide, sodium silicate, and sodium metasilicate.
- the pH of the aqueous alkaline solution is preferably 10-14.
- the alkaline aqueous solution may contain a water-soluble organic solvent (methanol, ethanol, etc.), a surfactant and the like.
- 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 preferably 5 to 180 seconds. After development, the coating film on the substrate may be washed (rinsed) with a solvent that does not dissolve the coating film, water, or the like. After the development or rinsing, the coating film is preferably dried.
- the exposure can be performed in the same manner as described above.
- the heat treatment can be performed 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 coating film (cured film) obtained as described above contains a fluorine-containing organic group, it can function as a liquid repellent film.
- this coating film is one in which application unevenness is suppressed.
- a stylus type step gauge for thin film measurement can be used. According to the present invention, it is possible to obtain a coating film in which the surface of the film other than the holes and grooves is flat with no steps.
- the fluorine content of the coating film is preferably 15 to 75% by mass, more preferably 15 to 60% by mass.
- the fluorine content is not less than the lower limit of the above range, the liquid repellency is more excellent.
- the fluorine content is less than or equal to the upper limit of the above range, the solubility in the developer of the portion to be dissolved and removed by the developer is good when the coating film is formed.
- the fluorine content of the coating film can be adjusted by the fluorine content of the polymers A and B, the ratio of the polymers A and B in the photosensitive composition, and the like.
- the fluorine content of the coating film is calculated from the fluorine content of the polymers A and B, the ratio of the polymers A and B in the coating film, and the like.
- the fluorine content of the polymers A and B can be adjusted by the content ratio of the unit u1.
- the fluorine content of each of the polymers A and B is the ratio (mass%) of fluorine atoms in the polymer, and is determined by the following equation.
- Q F [19 ⁇ N F / M A ] ⁇ 100
- Q F is the fluorine content
- 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 film finally obtained preferably has a water contact angle of 90 ° or more, and particularly preferably has a water contact angle of 95 ° or more. If 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 coating film.
- the obtained laminate can be used as a biochip, for example.
- a lyophilic substrate is preferable as the substrate.
- the lyophilic substrate include the above-described various glass plates and thermoplastic plastic sheets.
- the lyophilic substrate those having a water contact angle of less than 50 degrees are preferred.
- the coating film has a plurality of holes or grooves.
- the coating film preferably has a fluorescence intensity of 15,000 or less, more preferably 10,000 or less, measured by the measurement method described in the Examples described later. 5,000 or less is more preferable, and 4,000 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 can be adjusted by the type and content of the photoinitiator.
- 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.
- 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.
- EEMA 1-ethoxyethyl methacrylate.
- EEMA was synthesized by the following procedure. 55.8 g of ethyl vinyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2.5 g of p-toluenesulfonic acid pyridinium salt (manufactured by ACROS) were mixed and purged with nitrogen in an ice bath for 30 minutes with stirring. To the mixture, 50.1 g of methacrylic acid (manufactured by Junsei Co., Ltd.) was added dropwise and stirred overnight at room temperature.
- j-1 Thioglycerol (manufactured by Tokyo Chemical Industry Co., Ltd.).
- j-2 Dodecanethiol (manufactured by Kanto Chemical Co., Inc.).
- j-3 Octadecanethiol (manufactured by Tokyo Chemical Industry Co., Ltd.).
- j-4 Mercaptoethanol (manufactured by Tokyo Chemical Industry Co., Ltd.).
- j-5 2-ethylhexanethiol (manufactured by Tokyo Chemical Industry Co., Ltd.).
- j-6 Cyclohexanethiol (manufactured by Tokyo Chemical Industry Co., Ltd.).
- j-7 Furfuryl mercaptan (Tokyo Chemical Industry Co., Ltd.).
- j-8 Benzylthiol (manufactured by Tokyo Chemical Industry Co., Ltd.).
- CPI210S 4- (phenylthio) phenyldiphenylsulfonium tris (heptafluoropropyl) trifluorophosphate (manufactured by San Apro, CPI (trade name) -210S, extinction coefficient at a wavelength of 365 nm: 98 mL ⁇ g ⁇ 1 ⁇ cm ⁇ 1 ).
- IRPAG103 2- [2- (propylsulfonyloxyimino) thiophene-3 (2H) -ylidene] -2- (2-methylphenyl) acetonitrile (manufactured by BASF, IRGACURE (trade name) PAG103, extinction coefficient at a wavelength of 365 nm: 11,000 mL ⁇ g ⁇ 1 ⁇ cm ⁇ 1 ).
- Mass average molecular weight Mw
- Mw mass average molecular weight of the polymer was determined by using a standard polymethyl methacrylate sample with a known molecular weight from a chromatogram obtained by a high-speed gel permeation chromatography (GPC) apparatus (manufactured by Tosoh Corporation, HLC-8220). Obtained using.
- GPC gel permeation chromatography
- a photosensitive composition was spin-coated on the surface of a 6-inch silicon wafer (manufactured by Mitsubishi Materials Trading Co., Ltd.) at 1,000 rpm for 30 seconds to form a wet photosensitive film. Immediately after spin coating, the formed photosensitive film was visually checked for coating unevenness due to repelling. A sample having no coating unevenness was rated as ⁇ (good), and a sample having coating unevenness on at least one side was rated as x (defective). Separately, 200 ⁇ L of the photosensitive composition was applied to the surface of a 6-inch silicon wafer. Bar 1 was used to form a wet photosensitive film. Immediately after the bar coating, the formed photosensitive film was visually checked for application unevenness due to repelling. In the same manner as described above, a sample having no coating unevenness was evaluated as ⁇ (good), and a sample having coating unevenness in at least one was rated as x (defective).
- a photosensitive composition is spin-coated on the surface of a silicon substrate with a SiO 2 film (30 mm square) for 30 seconds under the following conditions, and heated at 100 ° C. for 300 seconds using a hot plate, and dried in a thickness of 3 ⁇ m. A characteristic film was formed.
- Spin coating conditions 1,000 rpm / min when the solution concentration of the polymer PGMEA solution used in the photosensitive composition is 30%, and 2,000 rpm when the solution concentration is 40%.
- i-line is exposed through a photomask (a mask capable of forming a circular hole pattern whose diameter is changed by 1 ⁇ m from 2 ⁇ m to 10 ⁇ m) so that the exposure dose is as follows.
- the film was irradiated (exposed). Exposure amount: 300 mJ / cm 2 when the PAG is CPI210S, 100 mJ / cm 2 when the PAG is IRPAG103.
- the exposed photosensitive film is developed for 5 to 60 seconds using the following developer, or showered for 40 seconds using the following developer, and then rinsed for 30 seconds using pure water. It was. In order to remove the developer and the rinse solution, spin drying was performed at 2,000 rpm for 30 seconds. Then, in order to accelerate
- the obtained liquid repellent film was observed with a microscope (manufactured by KEYENCE, VHX DIGITAL MICROSCOPE), and the minimum hole pattern diameter ( ⁇ m) at which holes were opened was measured, and the value was taken as the resolution.
- the photosensitive composition is spin-coated on the surface of a quartz glass substrate (25 mm ⁇ 50 mm) at 1,000 rpm for 30 seconds, heated at 100 ° C. for 120 seconds using a hot plate, and then heated at 150 ° C. for 30 minutes. Thus, a dry photosensitive film having a thickness of 3 ⁇ m was formed.
- the contact angle of about 2 ⁇ L of distilled water placed on the surface of the photosensitive film was measured using a contact angle measuring device (DM-701, manufactured by Kyowa Interface Science Co., Ltd.).
- a photosensitive composition is spin-coated on the surface of a quartz glass substrate (25 mm ⁇ 50 mm) at 1,000 rpm for 30 seconds, and heated at 100 ° C. for 120 seconds using a hot plate, and dried at a thickness of 2 ⁇ m.
- a photosensitive film was formed.
- a high pressure mercury lamp was used as the light source, and the photosensitive film was exposed so that the exposure amount was 500 mJ / cm 2 .
- post-baking was performed at 150 ° C. for 30 minutes using a hot plate.
- the fluorescence intensity of the photosensitive film after post-baking was measured with a microarray scanner (Molecular Devices, GenePix 4000B) (excitation wavelength: 532 nm, resolution: 5 ⁇ m, laser output: 100%, photomultiplier voltage: 1,000 V).
- Table 1 shows the molar ratio (copolymerization ratio) of each unit in the polymer (A-7), the type and amount of chain transfer agent used in the polymerization, the mass average molecular weight (Mw), and the solution concentration.
- the copolymerization ratio was determined from the integral ratios of 2.5 ppm, 3.2 ppm, 4.3 ppm, and 5.7 ppm.
- a sample for NMR measurement was measured by adding 20% amount of hexane to the polymer PGMEA solution, filtering the precipitated solid with a PTFE filter having a pore size of 3 ⁇ m, and drying under reduced pressure.
- the amount of the chain transfer agent used represents a ratio (mol%) to the total number of moles of monomers used for the polymerization.
- the solution concentration is the concentration (% by mass) of the polymer in the PGMEA solution.
- 1 H-NMR (300.4 MHz, solvent: d-acetone, standard: TMS) ⁇ (ppm) of polymer (A-7): 1.4 to 1.9 (m, 14H), 2.5 (br 0.02H), 2.7 (br, 1.1H), 2.8 ppm (br, 1.9H), 3.2 (br, 0.5H), 3.6 (br, 1.0H), 3.8 (br, 1.7H), 4.3 (br, 1.4H), 5.7 (br, 1H).
- 2.5 (br, 0.02H) corresponds to the peak of the end group derived from thioglycerol. From this measurement result, it was confirmed that the polymer had a terminal group J.
- Example 1 After filtering 3.0 g of the polymer (A-1) PGMEA solution in a polymer equivalent amount with a PTFE filter having a pore size of 0.50 ⁇ m, it was placed in a glass vial (20 mL) together with 0.3 g of CPI210S and stirred thoroughly. A photosensitive composition was prepared. About the obtained photosensitive composition, applicability
- Photosensitive compositions of Examples 2 to 29, 31, and 32 were prepared in the same manner as in Example 1 except that the type of polymer or the type of PAG was changed as shown in Table 2.
- a photosensitive composition was prepared in the same manner as in Example 1 except that 3.0 g and 7.0 g of the polymer (A-28) reaction solution and the polymer (A-29) reaction solution were mixed, respectively.
- a photosensitive composition was prepared in the same manner as in Example 1 except that 1.0 g and 9.0 g of the reaction solution of the polymer (A-30) and the reaction solution of the polymer (A-32) were mixed, respectively.
- paintability, the resolution, the water contact angle, and the fluorescence intensity were evaluated. The results are shown in Table 2.
- Examples 1, 8 to 16, 19, 21, 23 to 31, 33 including a polymer obtained using a chain transfer agent (j-1, j-5 to j-8) corresponding to the chain transfer agent j A coating film excellent in liquid repellency with no coating unevenness could be formed. Also, patterning by photolithography was possible. Moreover, it was confirmed that the fluorescence intensity is sufficiently low and can be used for fluorescence analysis. Examples 2 to 7, 17, 18, 20 containing a polymer having a mass average molecular weight of 6,000 to 20,000 obtained by using a chain transfer agent (j-2 to j-4) other than the chain transfer agent j 22 and 32, the coating film had uneven coating. In Examples 24 to 27 where the polymer did not have the unit u1, there was no coating unevenness but the liquid repellency of the coating film was inferior.
- 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.
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Abstract
Description
分子量を調整する方法として連鎖移動剤を使用する方法が一般的に知られている。特許文献1の実施例では、連鎖移動剤としてラウリルメルカプタンを使用して重合が行われ、質量平均分子量4600~6800のフッ素系ポリマーが合成されている。
[1]下記樹脂P1及び下記樹脂P2の少なくとも一方と光開始剤とを含む感光性組成物。
樹脂P1:フッ素原子を1つ以上有する有機基を有する単位である単位u1と、架橋基を有する単位である単位u2と、下式1、下式2及び下式3のいずれかで表される末端基とを有する重合体である重合体Aからなる樹脂。
樹脂P2:前記単位u1を有し、前記単位u2を有しない重合体である重合体Bと、前記単位u2を有し、前記単位u1を有しない重合体である重合体Cとからなり、前記重合体B及び前記重合体Cの少なくとも一方が、前記式1、前記式2及び前記式3のいずれかで表される末端基を有する重合体である、樹脂。
-X1-C(R1)(R2)(R3) ・・・1
-X2-R4 ・・・2
-X3-N(R5)(R6) ・・・3
ただし、R1~R3はそれぞれ独立に、水酸基、オキソ基もしくはエーテル性酸素原子を有していてもよい炭素数40以下の鎖式炭化水素基、炭素数40以下の環式基、水酸基、ハロゲン原子、アミノ基、又は水素原子を示し、R1~R3のうち少なくとも2つは水素原子以外の原子又は基であり、
R4は炭素数40以下の環式基を示し、
R5及びR6はそれぞれ独立に、水酸基、オキソ基もしくはエーテル性酸素原子を有していてもよい炭素数40以下の鎖式炭化水素基、又は炭素数40以下の環式基を示し、
X1~X3はそれぞれ独立に、単結合、-S-、-S-R7-、-R8-、-O-R9-又は-O-を示し、R7、R8及びR9はそれぞれ独立に、炭素数1~40の直鎖アルキレン基を示す。
[3]前記光開始剤が光酸発生剤であり、前記重合体Aが、酸解離性基で保護されたアルカリ可溶性基を有する単位である単位u3をさらに有する、[1]又は[2]の感光性組成物。
[4]前記光開始剤が光酸発生剤であり、前記重合体B及び前記重合体Cの少なくとも一方が、酸解離性基で保護されたアルカリ可溶性基を有する単位である単位u3をさらに有する、[1]又は[2]の感光性組成物。
[5]前記重合体A、前記重合体B及び前記重合体Cのいずれか1以上が、前記単位u1、前記単位u2及び酸解離性基で保護されたアルカリ可溶性基を有する単位である単位u3以外の単位である単位u4をさらに有する、[1]~[4]のいずれかの感光性組成物。
[6]前記樹脂P1及び前記樹脂P2の合計の含有量が、前記感光性組成物の総質量に対し、10~70質量%である、[1]~[5]のいずれかの感光性組成物。
Z1-X1-C(R1)(R2)(R3) ・・・11
Z2-X2-R4 ・・・12
Z3-X3-N(R5)(R6) ・・・13
ただし、R1~R3はそれぞれ独立に、水酸基を有していてもよくオキソ基を有していてもよくエーテル性酸素原子を有していてもよい炭素数40以下の鎖式炭化水素基、炭素数40以下の環式基、水酸基、ハロゲン原子、アミノ基、又は水素原子を示し、R1~R3のうち少なくとも2つは水素原子以外の原子又は基であり、
R4は炭素数40以下の環式基を示し、
R5及びR6はそれぞれ独立に、水酸基を有していてもよくオキソ基を有していてもよくエーテル性酸素原子を有していてもよい炭素数40以下の鎖式炭化水素基、又は炭素数40以下の環式基を示し、
X1~X3はそれぞれ独立に、単結合、-S-、-S-R7-、-R8-、-O-R9-又は-O-を示し、R7、R8及びR9はそれぞれ独立に、炭素数1~40の直鎖アルキレン基を示し、
Z1~Z3はそれぞれ独立に、水素原子又はハロゲン原子を示す。
[8]フッ素原子を1つ以上有する有機基を有する単量体である単量体a1と、反応部位を有する単量体である単量体a2’とを含む単量体成分を、下式11、下式12及び下式13のいずれかで表される連鎖移動剤の存在下に重合させて重合体を得た後、該重合体に、前記反応部位と結合しうる反応性官能基と架橋基とを有する化合物を反応させて、架橋基を有する単位である単位u2を有する重合体とする、重合体の製造方法。
Z1-X1-C(R1)(R2)(R3) ・・・11
Z2-X2-R4 ・・・12
Z3-X3-N(R5)(R6) ・・・13
ただし、R1~R3はそれぞれ独立に、水酸基を有していてもよくオキソ基を有していてもよくエーテル性酸素原子を有していてもよい炭素数40以下の鎖式炭化水素基、炭素数40以下の環式基、水酸基、ハロゲン原子、アミノ基、又は水素原子を示し、R1~R3のうち少なくとも2つは水素原子以外の原子又は基であり、
R4は炭素数40以下の環式基を示し、
R5及びR6はそれぞれ独立に、水酸基を有していてもよくオキソ基を有していてもよくエーテル性酸素原子を有していてもよい炭素数40以下の鎖式炭化水素基、又は炭素数40以下の環式基を示し、
X1~X3はそれぞれ独立に、単結合、-S-、-S-R7-、-R8-、-O-R9-又は-O-を示し、R7、R8及びR9はそれぞれ独立に、炭素数1~40の直鎖アルキレン基を示し、
Z1~Z3はそれぞれ独立に、水素原子又はハロゲン原子を示す。
フッ素原子を1つ以上有する有機基を有する単量体である単量体a1と、架橋基(ただし、エチレン性二重結合を含む基を除く)を有する単量体である単量体a2とを含む単量体成分を、下式11、下式12及び下式13のいずれかで表される連鎖移動剤の存在下に重合させて重合体Aを製造し、
少なくとも前記重合体Aと光開始剤とを混合して感光性組成物を得る、感光性組成物の製造方法。
Z1-X1-C(R1)(R2)(R3) ・・・11
Z2-X2-R4 ・・・12
Z3-X3-N(R5)(R6) ・・・13
ただし、R1~R6、X1~X3はそれぞれ前記と同義であり、
Z1~Z3はそれぞれ独立に、水素原子又はハロゲン原子を示す。
[10]前記[1]~[6]のいずれかの感光性組成物の製造方法であって、
フッ素原子を1つ以上有する有機基を有する単量体である単量体a1を含む単量体成分を、下式11、下式12及び下式13のいずれかで表される連鎖移動剤の存在下に重合させて重合体Bを得て、
架橋基(ただし、エチレン性二重結合を含む基を除く)を有する単量体である単量体a2を含む単量体成分を、前記連鎖移動剤の存在下に重合させて重合体Cを得て、
少なくとも前記重合体Bと前記重合体Cと光開始剤とを混合して感光性組成物を得る、感光性組成物の製造方法。
Z1-X1-C(R1)(R2)(R3) ・・・11
Z2-X2-R4 ・・・12
Z3-X3-N(R5)(R6) ・・・13
ただし、R1~R6、X1~X3はそれぞれ前記と同義であり、
Z1~Z3はそれぞれ独立に、水素原子又はハロゲン原子を示す。
[11]前記[1]~[6]のいずれかの感光性組成物の製造方法であって、
フッ素原子を1つ以上有する有機基を有する単量体である単量体a1を含む単量体成分を、下式11、下式12及び下式13のいずれかで表される連鎖移動剤の存在下に重合させて重合体Bを得て、
少なくとも前記重合体Bと前記重合体Cと光開始剤とを混合して感光性組成物を得る、感光性組成物の製造方法。
Z1-X1-C(R1)(R2)(R3) ・・・11
Z2-X2-R4 ・・・12
Z3-X3-N(R5)(R6) ・・・13
ただし、R1~R6、X1~X3はそれぞれ前記と同義であり、
Z1~Z3はそれぞれ独立に、水素原子又はハロゲン原子を示す。
[12]前記[1]~[6]のいずれかの感光性組成物の製造方法であって、
架橋基(ただし、エチレン性二重結合を含む基を除く)を有する単量体である単量体a2を含む単量体成分を、下式11、下式12及び下式13のいずれかで表される連鎖移動剤の存在下に重合させて重合体Cを得て、
少なくとも前記重合体Cと前記重合体Bと光開始剤とを混合して感光性組成物を得る、感光性組成物の製造方法。
Z1-X1-C(R1)(R2)(R3) ・・・11
Z2-X2-R4 ・・・12
Z3-X3-N(R5)(R6) ・・・13
ただし、R1~R6、X1~X3はそれぞれ前記と同義であり、
Z1~Z3はそれぞれ独立に、水素原子又はハロゲン原子を示す。
基材上に、[1]~[6]のいずれかの感光性組成物を塗布して感光性膜を形成し、前記感光性膜を露光し、塗膜を形成する、積層体の製造方法。
[14]前記塗膜が、厚さ方向に貫通した孔又は溝を有し、
前記感光性膜の露光を、前記孔又は溝に対応したパターンで行い、露光後に前記感光性膜を現像する、[13]の積層体の製造方法。
本発明の重合体の製造方法によれば、感光性組成物に用いたときに塗布ムラのない撥液性の塗膜を形成できる重合体が得られる。
本発明の感光性組成物の製造方法によれば、塗布ムラのない撥液性の塗膜を形成できる感光性組成物が得られる。
本発明の積層体の製造方法によれば、塗布ムラのない撥液性の塗膜を有する積層体が得られる。
本発明の目的は、塗布ムラのない撥液性の塗膜を形成できる感光性組成物及びその製造方法、感光性組成物に用いたときに塗布ムラのない撥液性の塗膜を形成できる重合体の製造方法、並びに該感光性組成物を用いた積層体の製造方法を提供することにある。
「光開始剤」とは、光を照射することによってラジカル及び酸の少なくとも一方を発生する化合物を意味する。
「光ラジカル発生剤」とは、光を照射することによってラジカルを発生する化合物を意味する。
「光酸発生剤」とは、光を照射することによって酸を発生する化合物を意味する。
「撥液性膜」とは、該膜以外の部分に比べて撥液性を示す膜、具体的には所定の液の接触角が該膜以外の部分に比べて大きい膜を意味する。
「親液性基材」とは、撥液性膜に比べて親液性を示す基材、具体的には所定の液の接触角が撥液性膜に比べて小さい基材を意味する。
「(メタ)アクリロイルオキシ基」とは、アクリロイルオキシ基及びメタクリロイルオキシ基の総称である。
「(メタ)アクリレート」とは、アクリレート及びメタクリレートの総称である。
「(メタ)アクリル酸」とは、アクリル酸及びメタクリル酸の総称である。
本発明の感光性組成物(以下、「本組成物」とも記す。)は、樹脂P1及び樹脂P2の少なくとも一方と、光開始剤とを含む。
本組成物は、溶剤をさらに含んでいてもよい。
本組成物は、重合体A、重合体B、重合体C、光開始剤及び溶剤以外の他の成分をさらに含んでいてもよい。
樹脂P1を構成する重合体A、及び、樹脂P2を構成する重合体(重合体B、重合体Cの少なくとも一方)は下記特定の末端基(以下、「末端基J」とも記す。)を有する。
末端基Jは、下式1、下式2及び下式3のいずれかで表される末端基である。上記重合体が末端基Jを有することで、本組成物から塗膜を形成する際に塗布ムラが発生することを抑制できる。
-X1-C(R1)(R2)(R3) ・・・1
-X2-R4 ・・・2
-X3-N(R5)(R6) ・・・3
R4は炭素数40以下の環式基を示し、
R5及びR6はそれぞれ独立に、水酸基、オキソ基もしくは炭素原子間にエーテル性酸素原子を有していてもよい炭素数40以下の鎖式炭化水素基、又は炭素数40以下の環式基を示し、
X1~X3はそれぞれ独立に、単結合、-S-、-S-R7-、-R8-、-O-R9-又は-O-を示し、R7、R8及びR9はそれぞれ独立に、炭素数1~40の直鎖アルキレン基を示す。
鎖式炭化水素基は、水酸基を有していてもよく、オキソ基(=O)を有していてもよく、エーテル性酸素原子(-O-)を有していてもよい。すなわち、鎖式炭化水素基の水素原子の少なくとも1つが水酸基で置換された基であってもよく、鎖式炭化水素基のメチレン基の少なくとも1つが>C=Oで置換された基であってもよく、鎖式炭化水素基の末端又は/及び炭素原子間にエーテル性酸素原子を有する基であってもよく、これらの基の2種以上を組み合わせた基であってもよい。
鎖式炭化水素基が水酸基を有する場合、該鎖式炭化水素基における水酸基の結合位置は特に限定されない。該鎖式炭化水素基が有する水酸基の数は、例えば1~4個であってよい。
鎖式炭化水素基がオキソ基を有する場合、該鎖式炭化水素基におけるオキソ基の結合位置は特に限定されない。該鎖式炭化水素基が有するオキソ基の数は、例えば1~10個であってよい。
鎖式炭化水素基がエーテル性酸素原子を有する場合、該鎖式炭化水素基におけるエーテル性酸素原子の位置は特に限定されない。例えば鎖式炭化水素基の末端(式1中のCに結合する側の末端)であってもよく、鎖式炭化水素基の炭素原子間であってもよく、それらの両方であってもよい。鎖式炭化水素基が有するエーテル性酸素原子の数は、例えば1~10個であってよい。
鎖式炭化水素基の炭素数は、炭素原子間にエーテル性酸素原子を有しない場合には、1~40であり、1~20が好ましい。炭素原子間にエーテル性酸素原子を有する場合には、2~40であり、2~20が好ましい。
R1~R3における鎖式炭化水素基の具体例としては、メチル基、エチル基、n-プロピル基、n-ブチル基、イソプロピル基、イソブチル基、2-エチルヘキシル基等のアルキル基、アリル基、-C3H6CH=CH2等のアルケニル基、-C(=O)CH2CH3、アセチル基等のアシル基等が挙げられる。
環式基の炭素数は、炭化水素環式基である場合には、3~40であり、5~20が好ましい。複素環式基である場合には、2~40であり、2~20が好ましい。
環式基の環骨格に置換基が結合していてもよい。置換基としては、例えば炭素数1~20のアルキル基、アリール基等が挙げられる。
R1~R3における環式基のうち炭化水素環式基の具体例としては、シクロヘキシル基、アダマンチル基、ノルボルニル基等の脂環式炭化水素基、フェニル基、ナフチル基等の芳香族炭化水素基等が挙げられる。複素環式基の具体例としては、フリル基、チオフェニル基、ピリジニル基等が挙げられる。
R1~R3において、ハロゲン原子としては、塩素原子、ヨウ素原子、臭素原子等が挙げられる。
R5及びR6における炭素数40以下の鎖式炭化水素としては、R1~R3における炭素数40以下の環式基と同様のものが挙げられ、好ましい態様も同様である。ただし、R5及びR6における鎖式炭化水素基がエーテル性酸素原子を有する場合、エーテル性酸素原子の位置は、鎖式炭化水素基の炭素原子間である。
R5及びR6における炭素数40以下の環式基としては、R1~R3における炭素数40以下の環式基と同様のものが挙げられ、好ましい態様も同様である。
X1~X3としては、対応する連鎖移動剤を用いて重合体を製造する際の連鎖移動のしやすさの点で、-S-R7-、-O-が好ましい。
Z1-X1-C(R1)(R2)(R3) ・・・11
Z2-X2-R4 ・・・12
Z3-X3-N(R5)(R6) ・・・13
ただし、R1~R6、X1~X3はそれぞれ前記と同義であり、
Z1~Z3はそれぞれ独立に、水素原子又はハロゲン原子を示す。
Z1~Z3におけるハロゲン原子としては、塩素原子、ヨウ素原子、臭素原子等が挙げられる。
連鎖移動剤jとしては、沸点が高く分子量調整が容易で、取り扱いやすい点から、式11中のX1が-S-R7-であるものが好ましい。低臭気性の点では、チオグリセロールが好ましい。
フルオロアルキル基は、直鎖状、分岐状のいずれであってもよい。フルオロアルキル基における水素原子とフッ素原子の合計数に対するフッ素原子の数は50%以上が好ましい。
ペルフルオロアルキル部分を有するフルオロアルキル基としては、-R13-Rfで表されるフルオロアルキル基が挙げられる。ただし、Rfは炭素原子間にエーテル性酸素原子を有していてもよいペルフルオロアルキル部分を示し、R13はフッ素原子を有しないアルキレン部分を示す。
Rfがエーテル性酸素原子を有するペルフルオロアルキル部分の場合、エーテル性酸素原子の数は、1~3が好ましい。エーテル性酸素原子より末端側(R13側とは反対側)のペルフルオロアルキル部分の炭素数は1~6が好ましい。エーテル性酸素原子間及びエーテル性酸素原子とR13との間のペルフルオロアルキレン部分の炭素数は、1~4が好ましい。エーテル性酸素原子を有するペルフルオロアルキル部分は全体としては直鎖でも分岐鎖でもよく、その全炭素数は3~12が好ましく、4~8がより好ましい。
Rfとしては、具体的には、-(CF2)3CF3、-(CF2)4CF3、-(CF2)5CF3、-CF(CF3)OCF2CF2CF3、-CF2OCF2CF2OCF3、-CF2OCF2CF2OCF2CF3、-CF2OCF2CF2OCF2CF2OCF3等が挙げられる。
R13は、直鎖状でも分岐状でもよいが直鎖状が好ましい。R13の炭素数は1~6が好ましく、2~4がより好ましい。R13としては、-CH2CH2-が特に好ましい。
単量体a1としては、HO-R13-Rfで表されるモノオールと不飽和モノカルボン酸とのエステルからなる単量体が好ましい。不飽和モノカルボン酸としては、例えばメタクリル酸、アクリル酸、α-ハロアクリル酸等が挙げられる。
単量体a1としては、-R13-Rfで表されるフルオロアルキル基を有する、(メタ)アクリレート及びα-ハロアクリレートが特に好ましい。このような単量体としては、例えばCH2=C(R12)COO-R13-Rfで表される単量体が挙げられる。ただし、R12は水素原子、メチル基又はハロゲン原子を示す。R12のハロゲン原子としては、フッ素原子、塩素原子等が挙げられる。
単量体a1は、1種を単独で用いてもよく、2種以上を併用してもよい。
3員環状エーテル構造を含む基、4員環状エーテル構造を含む基は、反応性を損なわない限り、アルキル基が置換していてもよい。アルキル基の炭素数は1~6が好ましい。
エポキシ基、3,4-エポキシシクロヘキシル基は、無置換であることが好ましい。オキセタン基は、無置換であってもよくアルキル基が置換していてもよく、(3-アルキルオキセタン-3-イル)基であることが好ましい。
前記(1)の方法で得られる重合体が有する単位u2は、単量体a2に基づく単位である。前記(2)の方法で得られる重合体が有する単位u2は、単量体a2’に基づく単位の前記反応部位に架橋基を導入することにより形成された単位である。重合体A及び重合体Cが有する単位u2は、いずれであってもよい。
架橋基がエチレン性二重結合を含む基の場合、重合体製造時の重合反応において該架橋基を有する単量体も反応する。そのため、架橋基がエチレン性二重結合を含む基の場合、単位u2は、単量体a2’に基づく単位の前記反応部位に架橋基を導入することにより形成された単位であることが好ましい。
架橋基が3員又は4員の環状エーテル構造を含む基の場合、重合反応において該架橋基を有する単量体は通常反応しない。そのため、架橋基が3員又は4員の環状エーテル構造を含む基の場合、単位u2は、架橋基を有する単量体a2に基づく単位であってもよく、単量体a2’に基づく単位の前記反応部位に架橋基を導入することにより形成された単位であってもよい。製造が容易な点では、架橋基を有する単量体a2に基づく単位であることが好ましい。
単量体a2としては、架橋基を有する(メタ)アクリレートが好ましい。
単量体a2における架橋基としては、3員又は4員の環状エーテル構造を含む基が好ましく、エポキシ基、オキセタン基、(3-アルキルオキセタン-3-イル)基が特に好ましい。
架橋基として3員又は4員の環状エーテル構造を含む基を有する(メタ)アクリレートとしては、例えばCH2=C(R21)COO-R22-R23で表される単量体が挙げられる。ただし、R21は水素原子又はメチル基を示し、R22はアルキレン基を示し、R23は3員又は4員の環状エーテル構造を含む基を示す。R22の炭素数は1~20が好ましい。
具体的な単量体a2としては、グリシジル(メタ)アクリレート、4-グリシジルオキシブチル(メタ)アクリレート、(3-エチルオキセタン-3-イル)メチル(メタ)アクリレート、3,4-エポキシシクロヘキシルメチル(メタ)アクリレート等が挙げられる。単量体a2は、1種を単独で用いてもよく、2種以上を併用してもよい。
単量体a2’としては、該反応部位とエチレン性二重結合とを有する単量体が好ましい。このような単量体としては、水酸基又はカルボキシル基を有する(メタ)アクリレートが挙げられる。
単量体a2’のうち反応部位として水酸基を有する単量体の具体例としては、2-ヒドロキシエチルメタクリレート、2-ヒドロキシプロピル(メタ)アクリレート、3-ヒドロキシプロピル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート、5-ヒドロキシペンチル(メタ)アクリレート、6-ヒドロキシヘキシル(メタ)アクリレート、4-ヒドロキシシクロヘキシル(メタ)アクリレート等が挙げられる。
単量体a2’のうち反応部位としてカルボキシル基を有する単量体の具体例としては、アクリル酸、メタクリル酸、ビニル酢酸等が挙げられる。
単量体a2’は、1種を単独で用いてもよく、2種以上を併用してもよい。
イソシアネート基及び架橋基を有する化合物としては、2-(メタ)アクリロイルオキシエチルイソシアネート等が挙げられる。塩化アシル基及び架橋基を有する化合物としては、(メタ)アクリロイルクロライド等が挙げられる。エポキシ基及び架橋基を有する化合物としては、グリシジル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレートグリシジルエーテル、3,4-エポキシシクロヘキシルメチル(メタ)アクリレート等が挙げられる。
R32としては、水素原子、炭素数1~6の直鎖又は分岐のアルキル基、炭素数3~6のシクロアルキル基が好ましく、原料の単量体の入手容易な点から、水素原子が特に好ましい。
R33としては、炭素数1~10の直鎖又は分岐のアルキル基、炭素数3~10のシクロアルキル基、炭素数7~10のアラルキル基が好ましい。
R31とR33が連結して環状エーテルを形成する場合、R31とR33が連結して炭素数2~5のアルキレン基を形成することが好ましい。
R33のアルキル基、シクロアルキル基又はアラルキル基中の水素原子の一部が置換されている場合、その置換基としては、たとえば、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基、ハロゲン原子等が挙げられる。
-C(O)OC(R31)(R32)OR33で表される基としては、例えば1-エトキシエチル基、1-メトキシエチル基、1-n-ブトキシエチル基、1-イソブトキシエチル基、1-(2-クロルエトキシ)エチル基、1-(2-エチルヘキシルオキシ)エチル基、1-n-プロポキシエチル基、1-シクロヘキシルオキシエチル基、1-(2-シクロヘキシルエトキシ)エチル基、1-ベンジルオキシエチル基等が挙げられる。
-C(O)OC(R34)(R35)(R36)で表される基としては、例えばtert-ブトキシカルボニル基(-C(O)OC(CH3)3)が挙げられる。
単位u3としては、-C(O)OC(R31)(R32)OR33で表される基を有する単位が好ましい。-C(O)OC(R31)(R32)OR33で表される基は、-C(O)OC(R34)(R35)(R36)で表される基に比べ酸分解の活性化エネルギーが低く、光酸発生剤からの酸によって容易に加水分解する。そのため、露光後にポストエクスポージャーベーク(PEB)を行わなくても現像が可能となる。
上記好ましい単位は、典型的には、CH2=CH(R30)C(O)OC(R31)(R32)OR33で表される単量体に基づく単位である。ただし、R30は、水素原子又はメチル基であり、R31~R33は前記と同義である。
具体的な単量体としては、1-エトキシエチル(メタ)アクリレート、1-メトキシエチル(メタ)アクリレート、1-n-ブトキシエチル(メタ)アクリレート、1-イソブトキシエチル(メタ)アクリレート、1-(2-クロルエトキシ)エチル(メタ)アクリレート、1-(2-エチルヘキシルオキシ)エチル(メタ)アクリレート、1-n-プロポキシエチル(メタ)アクリレート、1-シクロヘキシルオキシエチル(メタ)アクリレート、1-(2-シクロヘキシルエトキシ)エチル(メタ)アクリレート、1-ベンジルオキシエチル(メタ)アクリレート等が挙げられる。
単位u4としては、前記含フッ素有機基、前記架橋基及び前記酸解離性基で保護されたアルカリ可溶性基を有しない単位である単量体a4に基づく単位が挙げられる。
単量体a4は、典型的には、前記含フッ素有機基、前記架橋基及び前記酸解離性基で保護されたアルカリ可溶性基を有しない、エチレン性二重結合を有する化合物である。
具体的な単量体a4としては、メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、n-ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、ヘキシル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、オクチル(メタ)アクリレート、デシル(メタ)アクリレート、イソデシル(メタ)アクリレート、ラウリル(メタ)アクリレート、ステアリル(メタ)アクリレート、ベンジル(メタ)アクリレート、イソボルニル(メタ)アクリレート、アダマンチル(メタ)アクリレート、ジメチルアミノエチル(メタ)アクリレート、2-メトキシエチル(メタ)アクリレート、メトキシブチル(メタ)アクリレート、2-エトキシエチル(メタ)アクリレート、2-ブトキシエチル(メタ)アクリレート、2-フェノキシエチル(メタ)アクリレート、メトキシポリエチレングリコール(メタ)アクリレート、エトキシポリエチレングリコール(メタ)アクリレート、プロポキシポリエチレングリコール(メタ)アクリレート、ブトキシポリエチレングリコール(メタ)アクリレート(ただし、前記ポリエチレングリコール鎖のオキシエチレン基の数は2から300の範囲である)、2-{(メタ)アクリロイルオキシ}エチル-2’-(トリメチルアンモニオ)エチルホスフェート、3-{(メタ)アクリロイルオキシ}プロピル-2’-(トリメチルアンモニオ)エチルホスフェート、4-{(メタ)アクリロイルオキシ}ブチル-2’-(トリメチルアンモニオ)エチルホスフェート、5-{(メタ)アクリロイルオキシ}ペンチル-2’-(トリメチルアンモニオ)エチルホスフェート、6-{(メタ)アクリロイルオキシ}ヘキシル-2’-(トリメチルアンモニオ)エチルホスフェート、2-{(メタ)アクリロイルオキシ}エチル-2’-(トリエチルアンモニオ)エチルホスフェート、2-{(メタ)アクリロイルオキシ}エチル-2’-(トリプロピルアンモニオ)エチルホスフェート、2-{(メタ)アクリロイルオキシ}エチル-2’-(トリブチルアンモニオ)エチルホスフェート、2-{(メタ)アクリロイルオキシ}エチル-2’-(トリシクロヘキシルアンモニオ)エチルホスフェート、2-{(メタ)アクリロイルオキシ}エチル-2’-(トリフェニルアンモニオ)エチルホスフェート、2-{(メタ)アクリロイルオキシ}エチル-2’-(トリメタノールアンモニオ)エチルホスフェート、2-{(メタ)アクリロイルオキシ}プロピル-2’-(トリメチルアンモニオ)エチルホスフェート、2-{(メタ)アクリロイルオキシ}ブチル-2’-(トリメチルアンモニオ)エチルホスフェート、2-{(メタ)アクリロイルオキシ}ペンチル-2’-(トリメチルアンモニオ)エチルホスフェート、2-{(メタ)アクリロイルオキシ}ヘキシル-2’-(トリメチルアンモニオ)エチルホスフェート、2-(ビニルオキシ)エチル-2’-(トリメチルアンモニオ)エチルホスフェート、2-(アリルオキシ)エチル-2’-(トリメチルアンモニオ)エチルホスフェート、2-(p-ビニルベンジルオキシ)エチル-2’-(トリメチルアンモニオ)エチルホスフェート、2-(p-ビニルベンゾイルオキシ)エチル-2’-(トリメチルアンモニオ)エチルホスフェート、2-(スチリルオキシ)エチル-2’-(トリメチルアンモニオ)エチルホスフェート、2-(p-ビニルベンジル)エチル-2’-(トリメチルアンモニオ)エチルホスフェート、2-(ビニルオキシカルボニル)エチル-2’-(トリメチルアンモニオ)エチルホスフェート、2-(アリルオキシカルボニル)エチル-2’-(トリメチルアンモニオ)エチルホスフェート、2-(アクリロイルアミノ)エチル-2’-(トリメチルアンモニオ)エチルホスフェート、2-(ビニルカルボニルアミノ)エチル-2’-(トリメチルアンモニオ)エチルホスフェート、エチル-(2’-トリメチルアンモニオエチルホスホリルエチル)フマレート、ブチル-(2’-トリメチルアンモニオエチルホスホリルエチル)フマレート、ヒドロキシエチル-(2’-トリメチルアンモニオエチルホスホリルエチル)フマレート、エチル-(2’-トリメチルアンモニオエチルホスホリルエチル)マレート、ブチル-(2’-トリメチルアンモニオエチルホスホリルエチル)マレート、又はヒドロキシエチル-(2’-トリメチルアンモニオエチルホスホリルエチル)マレート等が挙げられる。
単量体a4は、1種を単独で用いてもよく、2種以上を併用してもよい。
全単位の合計に対する単位u2の割合は、10~90モル%が好ましく、10~80モル%がより好ましい。
全単位の合計に対する単位u3の割合は、0~80モル%が好ましく、0~70モル%がより好ましい。
全単位の合計に対する単位u4の割合は、0~80モル%が好ましく、0~60モル%がより好ましい。
重合体における各構成単位の割合は、例えば、1H-NMR(核磁気共鳴分析)における各単位に特有のピークの積分比から求めることができる。
重合体A1:単位u1と単位u2とを有し、単位u3を有さず、末端基Jを有する重合体。
重合体A2:単位u1と単位u2と単位u3とを有し、単位u2の架橋基が酸により架橋し得る基であり、末端基Jを有する重合体。
重合体A1、A2は各々、単位u4をさらに有していてもよい。
重合体Aの質量平均分子量は、ゲルパーミエーションクロマトグラフィ(GPC)より測定される標準ポリメチルメタクリレート換算の値である。重合体B、Cの質量平均分子量も同様である。
・前記単量体a1と前記単量体a2とを含む単量体成分を、前記連鎖移動剤jの存在下に重合させる方法。
・前記単量体a1と前記単量体a2’とを含む単量体成分を、前記連鎖移動剤jの存在下に重合させて重合体を得て、該重合体に前記化合物bを反応させる方法。
単量体成分の重合は、溶液重合法、バルク重合法、乳化重合法等の公知の重合法によって実施できる。このうち溶液重合法が好ましい。重合の際、重合開始剤を用いてもよい。
溶液重合において、重合溶媒に対する単量体全量の割合は、5~70質量%が好ましく、10~40質量%がより好ましい。この割合が高いほど、本組成物の製造効率が優れる。感光性組成物が溶剤を含む場合、重合溶媒としては、感光性組成物の溶剤と同じものが好ましい。
連鎖移動剤jの使用量は、製造する重合体の分子量に応じて適宜選定でき、重合開始剤の使用量や単量体濃度によっても異なるが、典型的には、単量体の全量に対して0.1~20モル%であり、1~10モル%が好ましい。なお、重合開始剤の使用量が増えると、所望の分子量とするために必要な連鎖移動剤の使用量は少なくなる傾向がある。また、単量体濃度が低いと、所望の分子量とするために必要な連鎖移動剤の使用量は少なくなる傾向がある。
重合条件としては、例えば40~60℃で5~30時間の条件が挙げられる。
化合物(b)を反応させる際の反応条件としては、例えば0~60℃で5~48時間の条件が挙げられる。
重合後、又は化合物bを反応させた後、必要に応じて、ろ過、再沈等の精製処理、溶媒留去、溶媒置換等の処理を行ってもよい。
全単位の合計に対する単位u3の割合は、0~80モル%が好ましく、0~70モル%がより好ましい。
全単位の合計に対する単位u4の割合は、0~80モル%が好ましく、0~70モル%がより好ましい。
重合体B1:単位u1を有し、単位u2及び単位u3を有さず、末端基Jを有する重合体。
重合体B2:単位u1及び単位u3を有し、単位u2を有さず、末端基Jを有する重合体。
重合体B1、B2は各々、単位u4をさらに有していてもよい。
重合体B2は、全単位の合計に対して単位u1を10~90モル%、単位u3を20~80モル%有することが好ましい。全単位の合計に対する単位u1と単位u3との合計の割合は、30モル%以上が好ましく、100モル%であってもよい。
・前記単量体a1を含む単量体成分を、前記連鎖移動剤jの存在下に重合させる方法。
上記製造方法において、単量体成分は、通常、単量体a2を含まない。該単量体成分は、単量体a3及び単量体a4からなる群から選ばれる少なくとも1種をさらに含んでもよい。
単量体成分の重合は、前述の重合体Aの製造方法と同様に実施できる。
・前記単量体a1を含む単量体成分を、前記連鎖移動剤jの不在下に重合させる方法。
単量体成分は前記製造方法と同様である。
単量体成分の重合は、連鎖移動剤jを用いない以外は、前述の重合体Aの製造方法と同様に実施できる。重合の際、連鎖移動剤j以外の連鎖移動剤を用いてもよい。
全単位の合計に対する単位u3の割合は、0~90モル%が好ましく、0~70モル%がより好ましい。
全単位の合計に対する単位u4の割合は、0~90モル%が好ましく、0~80モル%がより好ましい。
重合体C1:単位u2を有し、単位u1及び単位u3を有さず、末端基Jを有する重合体。
重合体C2:単位u2及び単位u3を有し、単位u1を有さず、末端基Jを有する重合体。
重合体C1、C2は各々、単位u4をさらに有していてもよい。
重合体C2は、全単位の合計に対して単位u2を10~80モル%、単位u3を20~90モル%有することが好ましい。全単位の合計に対する単位u2と単位u3との合計の割合は、30モル%以上が好ましく、100モル%であってもよい。
・前記単量体a2を含む単量体成分を、前記連鎖移動剤jの存在下に重合させる方法。
・前記単量体a2’を含む単量体成分を、前記連鎖移動剤jの存在下に重合させて重合体を得て、該重合体に前記化合物bを反応させる方法。
上記2つの製造方法それぞれにおいてにおいて、単量体成分は、通常、単量体a1を含まない。該単量体成分は、単量体a3及び単量体a4からなる群から選ばれる少なくとも1種をさらに含んでもよい。
上記2つの製造方法における単量体成分の重合や化合物bとの反応は、前述の重合体Aの製造方法における2つの製造方法と同様に実施できる。
・前記単量体a2を含む単量体成分を、前記連鎖移動剤jの不在下に重合させる方法。
・前記単量体a2’を含む単量体成分を、前記連鎖移動剤jの不在下に重合させて重合体を得て、該重合体に前記化合物bを反応させる方法。
上記2つの製造方法製造方法それぞれにおいてにおいて、単量体成分は、通常、単量体a1を含まない。該単量体成分は、単量体a3及び単量体a4からなる群から選ばれる少なくとも1種をさらに含んでもよい。
単量体成分の重合は、連鎖移動剤jを用いない以外は、前述の重合体Aの製造方法と同様に実施できる。重合の際、連鎖移動剤j以外の連鎖移動剤を用いてもよい。
化合物bとの反応は、前述の重合体Aの製造方法における化合物bとの反応と同様に実施できる。
樹脂P2を構成する重合体B及び重合体Cはそれぞれ1種でも2種以上でもよい。
樹脂P2において、重合体Bと重合体Cとの合計量に対する重合体Bの割合は、撥液性の点では、1質量%以上が好ましく、5質量%以上がより好ましく、10質量%以上がさらに好ましく、20質量%以上が特に好ましい。硬化性、パターニング性の点では、90質量%以下が好ましく、80質量%以下がより好ましく、70質量%以下が特に好ましい。
したがって、重合体Bと重合体Cとの合計量に対する重合体Bの割合は、1~90質量%が好ましい。重合体Bが単位3を有しない場合には、1~50質量%がより好ましく、1~40質量%がさらに好ましい。重合体Bが単位3を有する場合には、1~90質量%がより好ましく、1~80質量%がさらに好ましく、5~70質量%が特に好ましい。
樹脂P1及び樹脂P2は、いずれか一方のみを用いてもよく、両方を併用してもよい。
重合体A及び重合体Cにおける架橋基がラジカルにより架橋し得る基である場合は、光開始剤として光ラジカル発生剤が用いられ、架橋基が酸により架橋し得る基である場合は、光開始剤として光酸発生剤が用いられる。
光開始剤の波長365nmでの吸光係数は、200[mL・g-1・cm-1]以下がより好ましい。また、該吸光係数は1[mL・g-1・cm-1]以上が好ましく、10[mL・g-1・cm-1]以上がより好ましい。
光ラジカル発生剤の具体的な商品名としてはIRGACURE(商標) 651(BASF社製)、IRGACURE 184(BASF社製)、IRGACURE 127(BASF社製)、IRGACURE 500(BASF社製)、IRGACURE 2959(BASF社製)、1173(BASF社製)等が挙げられる。
トリアリールスルホニウム塩、ジアリールヨードニウム塩のカチオン部分の具体例としては、トリフェニルスルホニウム、ジフェニル-4-メチルフェニルスルホニウム、トリス(4-メチルフェニル)スルホニウム、ジフェニル-2,4,6-トリメチルフェニルスルホニウム、4-(フェニルチオ)フェニルジフェニルスルホニウム、ジフェニルヨードニウム、4-イソプロピル-4’-メチルジフェニルヨードニウム、4-メチル-4’-メチルプロピルジフェニルヨードニウム、ビス(4-tert-ブチルフェニル)ヨードニウム、4-メトキシフェニルフェニルヨードニウムが挙げられる。アニオン部分としては、トリフルオロメタンスルホネート、ノナフルオロブタンスルホネート、ヘキサフルオロホスフェート、テトラフルオロボレート、トリス(ペンタフルオロエチル)トリフルオロホスフェート、トリス(ヘプタフルオロプロピル)トリフルオロホスフェート、トリス(ノナフルオロイソブチル)トリフルオロホスフェート、ビス(ノナフルオロイソブチル)テトラフルオロホスフェート等が挙げられる。
スルホニルジアゾメタンの具体例としては、ビス(フェニルスルホニル)ジアゾメタン、ビス(tert-ブチルスルホニル)ジアゾメタン、ビス(シクロヘキシルスルホニル)ジアゾメタン、ビス(p-トルエンスルホニル)ジアゾメタンなどが挙げられる。
これらのうち、4-(フェニルチオ)フェニルジフェニルスルホニウムトリス(ヘプタフルオロプロピル)トリフルオロホスフェート、4-(フェニルチオ)フェニルジフェニルスルホニウムトリス(ノナフルオロイソブチル)トリフルオロホスフェート、4-(フェニルチオ)フェニルジフェニルスルホニウムビス(ノナフルオロイソブチル)テトラフルオロホスフェート、4-(フェニルチオ)フェニルジフェニルスルホニウム(ペンタフルオロエチル)トリフルオロホスフェート、ジフェニル-2,4,6-トリメチルフェニルスルホニウムトリフルオロメタンスルホネート、ジフェニル-2,4,6-トリメチルフェニルスルホニウムノナフルオロブタンスルホネート、ビス(フェニルスルホニル)ジアゾメタン、ビス(p-トルエンスルホニル)ジアゾメタンが、得られる塗膜の蛍光が小さく、光硬化性能に優れるために好ましい。これらの光酸発生剤は単独で用いても、2種類以上混合して用いてもよい。
光酸発生剤の具体的な商品名としてはIRGACURE 250(BASF社製)、CPI(商標)-100P(サンアプロ社製)、CPI-210S(サンアプロ社製)、WPAG199(和光純薬工業社製)等が挙げられる。
組み合わせ(1):樹脂P1が重合体A1であり、重合体A1の単位u2の架橋基が酸により架橋し得る基であり、光開始剤が光酸発生剤である組み合わせ。
組み合わせ(2):樹脂P1が重合体A2であり、光開始剤が光酸発生剤である組み合わせ。
組み合わせ(3):樹脂P1が重合体A1であり、重合体A1の単位u2の架橋基がラジカルにより架橋し得る基であり、光開始剤が光ラジカル発生剤である組み合わせ。
樹脂P21:重合体B1と重合体C1とからなり、それらの少なくとも一方が末端基Jを有する樹脂。
樹脂P22:重合体B1と重合体C2とからなり、それらの少なくとも一方が末端基Jを有する樹脂。
樹脂P23:重合体B2と重合体C1とからなり、それらの少なくとも一方が末端基Jを有する樹脂。
樹脂P24:重合体B2と重合体C2とからなり、それらの少なくとも一方が末端基Jを有する樹脂。
溶剤としては、フッ素系溶剤、非フッ素系溶剤等が挙げられる。
これらの溶剤のうち、溶解性が高く、沸点が高く成膜性に優れる点で、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、ヘキサフルオロ-2-プロパノール、2,2,3,3,4,4,5,5-オクタフルオロ-1-ペンタノール、1H,1H,7H-ドデカフルオロ-1-ヘプタノールが好ましい。
具体的なラジカル架橋剤としては、ジエチレングリコールジ(メタ)アクリレート、テトラエチレングリコールジ(メタ)アクリレート、トリプロピレングリコールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、1,10-デカンジオールジ(メタ)アクリレート、2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-ヘキサデカフルオロ-1,10-デカンジオールジ(メタ)アクリレート、2,2,3,3,4,4,5,5,6,6,7,7-ドデカフルオロ-1,8-オクタンジオールジ(メタ)アクリレート、2,2,3,3,4,4,5,5-デカフルオロ-1,6-ヘキサンジオールジ(メタ)アクリレート、(CH2=CHCOO-CH2)2C(CH3)NHCOO-CH2-(CF2)4-CH2-OCONHC(CH3)(CH2OCOCH=CH2)2、(CH2=CHCOO-CH2)2C(CH3)NHCOO-CH2-(CF2)6-CH2-OCONHC(CH3)(CH2OCOCH=CH2)2、(CH2=CHCOO-CH2)2C(CH3)NHCOO-CH2-(CF2)8-CH2-OCONHC(CH3)(CH2OCOCH=CH2)2等が挙げられる。
これらのうち、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、(CH2=CHCOO-CH2)2C(CH3)NHCOO-CH2-(CF2)4-CH2-OCONHC(CH3)(CH2OCOCH=CH2)2、(CH2=CHCOO-CH2)2C(CH3)NHCOO-CH2-(CF2)6-CH2-OCONHC(CH3)(CH2OCOCH=CH2)2、(CH2=CHCOO-CH2)2C(CH3)NHCOO-CH2-(CF2)8-CH2-OCONHC(CH3)(CH2OCOCH=CH2)2が樹脂との相溶性が高く、かつ硬化性も高いため望ましい。
本組成物中の他の成分の含有割合は、本組成物の総質量に対し、0~20質量%が好ましく、0~10質量%がより好ましい。
本組成物中の溶剤の含有量は、本組成物から樹脂P1、樹脂P2、光開始剤及び他の成分を除いた残部である。
各成分の混合順序は特に限定されない。
本組成物が樹脂P2を含む場合、重合体B及び重合体Cは、光開始剤等の混合前に予め混合されていてもよく、光開始剤等を混合する際に混合されてもよい。
各成分を混合する前に、重合体A、重合体B又は重合体Cを製造する工程を行ってもよい。各重合体の製造は、前記の手順で製造できる。
したがって、本組成物の製造方法は、以下の製造方法1~4のいずれかであってよい。
製造方法1:単量体a1と単量体a2とを含む単量体成分を、連鎖移動剤jの存在下に重合させて重合体Aを製造し、
少なくとも前記重合体Aと光開始剤とを混合して感光性組成物を得る、感光性組成物の製造方法。
製造方法2:単量体a1を含む単量体成分を、連鎖移動剤jの存在下に重合させて重合体Bを得て、
単量体a2を含む単量体成分を、連鎖移動剤jの存在下に重合させて重合体Cを得て、
少なくとも前記重合体Bと前記重合体Cと光開始剤とを混合して感光性組成物を得る、感光性組成物の製造方法。
製造方法3:単量体a1を含む単量体成分を、連鎖移動剤jの存在下に重合させて重合体Bを得て、
少なくともこの重合体Bと重合体Cと光開始剤とを混合して感光性組成物を得る、感光性組成物の製造方法。
製造方法4:単量体a2を含む単量体成分を、連鎖移動剤jの存在下に重合させて重合体Cを得て、
少なくともこの重合体Cと重合体Bと光開始剤とを混合して感光性組成物を得る、感光性組成物の製造方法。
製造方法3における重合体C、製造方法4における重合体Bは通常、末端基Jを有していないが、有していても差し支えない。これらの重合体として、市販の重合体を用いてもよい。
製造方法1の一態様として、重合体Aの製造時に重合を溶液重合法により行って、重合体Aと溶剤とを含む重合体溶液を得て、この重合体溶液に光開始剤等を添加して本組成物を得る方法が挙げられる。
本組成物は感光性を有するため、下記のようにフォトリソグラフィによって、本組成物から形成される塗膜を、厚さ方向に貫通した孔又は溝を有するものとすることもできる。
樹脂P1及び樹脂P2を構成する重合体が単位u3を有しない場合、又は単位u3を有していても光開始剤が光酸発生剤ではない場合には、架橋基の架橋によって、露光部の現像液に対する溶解性が低下する。一方、未露光部では、現像液に対する溶解性は実質的に変化しない。そのため、露光後の感光性膜を現像液により現像すると、未露光部は現像液に溶解し除去され、一方、露光部は除去されずに残る。これにより、未露光部の位置に厚さ方向に貫通した孔又は溝が形成された塗膜(硬化膜)が形成されて、基材と、該基材の表面に設けられた塗膜とを有する積層体が得られる。
樹脂P1及び樹脂P2を構成する重合体の少なくとも一種が単位u3を有し、光開始剤が光酸発生剤である場合には、前記の露光の際、露光部において光酸発生剤から発生した酸の作用によって酸解離性基が解離し、カルボキシ基等のアルカリ可溶性基が生成する。これにより、露光部のアルカリ現像液に対する溶解性が高まる。一方、未露光部では、アルカリ現像液に対する溶解性は実質的に変化しない。そのため、露光後の感光性膜をアルカリ現像液により現像すると、露光部はアルカリ現像液に溶解し除去され、一方、未露光部は除去されずに残る。これにより、露光部の位置に厚さ方向に貫通した孔又は溝が形成された塗膜(硬化膜)が形成されて、基材と、該基材の表面に設けられた塗膜とを有する積層体が得られる。
本組成物の塗布方法としては、特に限定されず、例えばスプレー法、ロールコート法、スピンコート法、バー塗布法等が挙げられる。
プリベーク条件は、各成分の種類、配合割合などによっても異なるが、好ましくは50~120℃、10~2000秒間程度である。
乾燥塗膜の膜厚は特に制限されないが、0.1~20μmが好ましく、0.5~10.0μmがより好ましい。
樹脂P1及び樹脂P2を構成する重合体が単位u3を有しない場合、又は単位u3を有していても光開始剤が光酸発生剤ではない場合には、孔又は溝を形成する部分は露光せず、それ以外の部分を露光する。樹脂P1及び樹脂P2を構成する重合体の少なくとも一種が単位u3を有し、光開始剤が光酸発生剤である場合には、孔又は溝を形成する部分を露光し、それ以外の部分には露光しない。
露光後、必要に応じて、露光後の塗膜に対し、架橋反応を促進するための露光後ベーク(PEB)処理を行うことができる。PEB処理条件は好ましくは50~150℃、10~2000秒間の範囲である。
現像液が溶剤を含む溶剤系現像液である場合、現像により未露光部が溶解除去される。
現像液がアルカリ現像液であり、樹脂P1及び樹脂P2を構成する重合体の少なくとも一種が単位u3を有し、光開始剤が光酸発生剤である場合には、現像により露光部が溶解除去される。
アルカリ現像液(アルカリ水溶液)のアルカリとしては、例えば水酸化リチウム、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物、炭酸ナトリウム、炭酸カリウム等のアルカリ金属炭酸塩、重炭酸ナトリウム、重炭酸カリウム等のアルカリ金属重炭酸塩、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、コリンヒドロキシド等のアンモニウムヒドロキシド、ケイ酸ナトリウム、メタケイ酸ナトリウム等が挙げられる。アルカリ水溶液のpHは、10~14が好ましい。アルカリ水溶液は、水溶性有機溶媒(メタノール、エタノール等)、界面活性剤等を含んでもよい。界面活性剤としては非イオン性界面活性剤が挙げられる。
現像方法としては、液盛り法、ディッピング法、シャワー法等が挙げられる。現像時間は5~180秒間が好ましい。
現像後、基材上の塗膜に対し、該塗膜を溶解しない溶剤、水等を用いて洗浄(リンス)を行ってもよい。
現像後又はリンス後は、塗膜を乾燥することが好ましい。
その後、架橋を促進するために、塗膜に対して露光(ポスト露光)及び加熱処理(キュア)を行ってもよい。露光は前記と同様にして実施できる。加熱処理は、ホットプレート、オーブン等の加熱装置を用いて実施できる。加熱処理の条件は、120~250℃、5~90分間が好ましい。
塗布ムラの指標として、薄膜計測用の触針式段差計を用いることができる。本発明によれば、孔や溝以外の部分の膜表面が段差がなく平坦である塗膜を得ることができる。
塗膜のフッ素含量は、重合体A、Bのフッ素含量、感光性組成物中の重合体A、Bの割合等により調整できる。
塗膜のフッ素含量は、重合体A、Bのフッ素含量、塗膜中の重合体A、Bの割合等から算出される。重合体A、Bのフッ素含量は、単位u1の含有割合等により調整できる。
QF=[19×NF/MA]×100
ただし、QFは、フッ素含量であり、NFは、重合体を構成する単位の種類毎に、単位のフッ素原子数と、全単位に対する当該単位のモル比率とを乗じた値の総和であり、MAは、重合体を構成する単位の種類毎に、単位を構成する全ての原子の原子量の合計と、全単位に対する当該単位のモル比率とを乗じた値の総和である。
塗膜が有する孔又は溝は、典型的には複数である。
蛍光強度は、光開始剤の種類及び含有量により調整できる。
例1、8~16、19、21、23~25は実施例であり、他の例は比較例である。
以下の化合物を原料等として用いた。
C6FMA:3,3,4,4,5,5,6,6,7,7,8,8,8-トリデカフルオロオクチルメタクリレート。C6FMAは、特開2004-359616号公報の例1に記載の方法によって得た。
GMA:グリシジルメタクリレート(東京化成工業社製)。
EEMA:1-エトキシエチルメタクリレート。
EEMAは、下記の手順で合成した。
エチルビニルエーテル(東京化成社製)の55.8g及びp-トルエンスルホン酸ピリジニウム塩(ACROS社製)の2.5gを混合し、撹拌しながら氷浴中で30分間窒素置換した。混合物にメタクリル酸(純正化学社製)の50.1gを滴下し、一晩室温で撹拌した。反応液に炭酸水素ナトリウム(関東化学社製)の0.8g、硫酸ナトリウム(関東化学社製)の1.4gを加え、固形分を3μm径のポリテトラフルオロエチレン(以下、PTFEとも記す。)フィルタでろ過し、ろ液を減圧留去した。残った液体を10mmHgで減圧蒸留し、40℃で得られた液体を分取し、1-エトキシエチルメタクリレート(EEMA)を得た。
EEMAの1H-NMR(300.4MHz、溶媒:d-アセトン、基準:テトラメチルシラン(TMS))δ(ppm):1.1(t、3H)、1.4(d、3H)、1.9(s、3H)、3.5~3.7(m、2H)、5.6(s、1H)、5.9(q、1H)、6.1(s、1H)。
PGMEA:プロピレングリコールモノメチルエーテルアセテート。
V65:2,2’-アゾビス(2,4-ジメチルバレロニトリル)(和光純薬工業社製)。
j-1:チオグリセロール(東京化成工業社製)。
j-2:ドデカンチオール(関東化学社製)。
j-3:オクタデカンチオール(東京化成工業社製)。
j-4:メルカプトエタノール(東京化成工業社製)。
j-5:2-エチルヘキサンチオール(東京化成工業社製)。
j-6:シクロヘキサンチオール(東京化成工業社製)。
j-7:フルフリルメルカプタン(東京化成工業社製)。
j-8:ベンジルチオール(東京化成工業社製)。
CPI210S:4-(フェニルチオ)フェニルジフェニルスルホニウムトリス(ヘプタフルオロプロピル)トリフルオロホスフェート(サンアプロ社製、CPI(商品名)-210S、波長365nmにおける吸光係数:98mL・g-1・cm-1)。
IRPAG103:2-[2-(プロピルスルホニルオキシイミノ)チオフェン-3(2H)-イリデン]-2-(2-メチルフェニル)アセトニトリル(BASF社製、IRGACURE(商品名)PAG103、波長365nmにおける吸光係数:11,000mL・g-1・cm-1)。
(1H-NMR)
化合物の1H-NMRスペクトルは、FT-NMR装置(日本電子社製、JNM-AL300)を用いて測定した。
重合体の質量平均分子量は、高速ゲルパーミエーションクロマトグラフィ(GPC)装置(東ソー社製、HLC-8220)によって得られたクロマトグラムから、分子量既知の標準ポリメチルメタクリレート試料を用いて作成した検量線を用いて求めた。
6インチシリコンウェハ(三菱マテリアルトレーディング社製)の表面に感光性組成物を、1,000回転/分で30秒間スピンコートして、湿潤状態の感光性膜を形成した。スピンコートした直後、形成された感光性膜について、目視にてハジキによる塗布ムラがあるかを確認した。塗布ムラがないものを○(良好)、少なくとも一方に塗布ムラがあるものを×(不良)とした。
別途、6インチシリコンウェハの表面に感光性組成物の液量200μLを、No.1のバーを用いてバーコートして、湿潤状態の感光性膜を形成した。バーコートした直後、形成された感光性膜について目視にてハジキによる塗布ムラがあるかを確認した。前記と同様、塗布ムラがないものを○(良好)、少なくとも一方に塗布ムラがあるものを×(不良)とした。
SiO2膜付シリコン基板(30mm角)の表面に感光性組成物を、以下の条件で30秒間スピンコートし、ホットプレートを用いて100℃で300秒間加熱して厚さ3μmの乾燥状態の感光性膜を形成した。
スピンコート条件:感光性組成物に用いた重合体PGMEA溶液の溶液濃度が30%の場合は1,000回転/分、該溶液濃度が40%の場合は2,000回転/分。
露光量:PAGがCPI210Sの場合は300mJ/cm2、PAGがIRPAG103の場合は100mJ/cm2。
ただし、重合体A-1、30、31を用いた場合には、現像前に120℃で120秒間加熱処理(Post Exposure Bake)を行った。
現像液:重合体がEEMA単位(単位u3)を有する場合は、NMD-W(東京応化工業社製、2.38質量%のテトラメチルアンモニウムヒドロキシド水溶液、界面活性剤入り)を用い、重合体がEEMA単位を有しない場合はPGMEAを用いた。
石英ガラス基板(25mm×50mm)の表面に感光性組成物を、1,000回転/分で30秒間スピンコートし、ホットプレートを用いて100℃で120秒間加熱し、次いで150℃で30分間加熱して厚さ3μmの乾燥状態の感光性膜を形成した。感光性膜の表面に置いた、約2μLの蒸留水の接触角を、接触角測定装置(協和界面科学社製、DM-701)を用いて測定した。
石英ガラス基板(25mm×50mm)の表面に感光性組成物を、1,000回転/分で30秒間スピンコートし、ホットプレートを用いて100℃で120秒間加熱して厚さ2μmの乾燥状態の感光性膜を形成した。光源として高圧水銀ランプを用い、露光量が500mJ/cm2となるように感光性膜を露光した。次いで、ホットプレートを用いて150℃で30分間ポストベークを行った。
ポストベーク後の感光性膜の蛍光強度をマイクロアレイスキャナー(Molecular Devices社製、GenePix4000B)で測定した(励起波長532nm、解像度5μm、レーザ出力100%、フォトマルチプライヤーの電圧1,000V)。
C6FMAの4.00g、GMAの1.97g、EEMAの3.66g、連鎖移動剤であるj-1(チオグリセロール)の0.10g、及びV65の0.40gをPGMEAの22.4gに溶解し、窒素置換した後、50℃で24時間振とうした。その後、70℃に昇温し2時間振とうした。得られた反応液を孔径0.45μmのナイロンフィルタでろ過し、重合体(A-7)のPGMEA溶液を得た。
重合体(A-7)中の各単位のモル比(共重合比)、重合に使用した連鎖移動剤の種類と使用量、質量平均分子量(Mw)及び溶液濃度を表1に示す。共重合比は、2.5ppm、3.2ppm、4.3ppm、及び5.7ppmの積分比から求めた。NMRの測定用サンプルは、重合体のPGMEA溶液の20倍量のヘキサンに加え、析出した固体を孔径3μmのPTFEフィルタでろ過し減圧乾燥したものを測定した。連鎖移動剤の使用量は、重合に用いた単量体の総モル数に対する割合(モル%)を示した。溶液濃度はPGMEA溶液中の重合体の濃度(質量%)である。
重合体(A-7)の1H-NMR (300.4MHz、溶媒:d-アセトン、基準:TMS)δ(ppm):1.4~1.9(m、14H)、2.5(br、0.02H)、2.7(br、1.1H)、2.8ppm(br、1.9H)、3.2(br、0.5H)、3.6(br、1.0H)、3.8(br、1.7H)、4.3(br、1.4H)、5.7(br、1H)。
2.5(br、0.02H)が、チオグリセロール由来の末端基のピークに相当する。この測定結果から、重合体が末端基Jを有することが確認できた。
連鎖移動剤の種類及び使用量、共重合する単量体の種類及び共重合比を表1に示すようにした以外は製造例A-7と同様にして、重合体(A-1)~(A-6)、(A-8)~(A-32)各々のPGMEA溶液を得た。
重合体(A-1)のPGMEA溶液の重合体換算量で3.0gを孔径0.50μmのPTFEフィルタでろ過した後、CPI210Sの0.3gとともにガラスバイアル(20mL)に入れ、充分に撹拌し、感光性組成物を調製した。
得られた感光性組成物について、塗布性、解像度、水接触角、蛍光強度の評価を行った。結果を表2に示す。
重合体の種類又はPAGの種類を表2に示すように変更した以外は、例1と同様にして例2~29、31、32の感光性組成物を調製した。
〔例30〕
重合体(A-28)の反応液と重合体(A-29)の反応液を、それぞれ3.0g、7.0g混合した以外は実施例1と同様に感光性組成物を調製した。
〔例33〕
重合体(A-30)の反応液と重合体(A-32)の反応液を、それぞれ1.0g、9.0g混合した以外は実施例1と同様に感光性組成物を調製した。
得られた感光性組成物について、塗布性、解像度、水接触角、蛍光強度の評価を行った。結果を表2に示す。
連鎖移動剤j以外の連鎖移動剤(j-2~j-4)を用いて得た、質量平均分子量が6,000~20,000の重合体を含む例2~7、17、18、20、22、32では、塗膜に塗布ムラがあった。
重合体が単位u1を有しない例24~27では、塗布ムラはなかったものの、塗膜の撥液性が劣っていた。
なお、2016年07月08日に出願された日本特許出願2016-136414号、2016年07月08日に出願された日本特許出願2016-136415号及び2017年04月28日に出願された日本特許出願2017-090779号の明細書、特許請求の範囲および要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
Claims (14)
- 下記樹脂P1及び下記樹脂P2の少なくとも一方と光開始剤とを含む感光性組成物。
樹脂P1:フッ素原子を1つ以上有する有機基を有する単位である単位u1と、架橋基を有する単位である単位u2と、下式1、下式2及び下式3のいずれかで表される末端基とを有する重合体である重合体Aからなる樹脂。
樹脂P2:前記単位u1を有し、前記単位u2を有しない重合体である重合体Bと、前記単位u2を有し、前記単位u1を有しない重合体である重合体Cとからなり、前記重合体B及び前記重合体Cの少なくとも一方が、前記式1、前記式2及び前記式3のいずれかで表される末端基を有する重合体である、樹脂。
-X1-C(R1)(R2)(R3) ・・・1
-X2-R4 ・・・2
-X3-N(R5)(R6) ・・・3
ただし、R1~R3はそれぞれ独立に、水酸基、オキソ基もしくはエーテル性酸素原子を有していてもよい炭素数40以下の鎖式炭化水素基、炭素数40以下の環式基、水酸基、ハロゲン原子、アミノ基、又は水素原子を示し、R1~R3のうち少なくとも2つは水素原子以外の原子又は基であり、
R4は炭素数40以下の環式基を示し、
R5及びR6はそれぞれ独立に、水酸基、オキソ基もしくはエーテル性酸素原子を有していてもよい炭素数40以下の鎖式炭化水素基、又は炭素数40以下の環式基を示し、
X1~X3はそれぞれ独立に、単結合、-S-、-S-R7-、-R8-、-O-R9-又は-O-を示し、R7、R8及びR9はそれぞれ独立に、炭素数1~40の直鎖アルキレン基を示す。 - 前記重合体A、前記重合体B及び前記重合体Cが、それぞれ、質量平均分子量が6,000~20,000である、請求項1に記載の感光性組成物。
- 前記光開始剤が光酸発生剤であり、
前記重合体Aが、酸解離性基で保護されたアルカリ可溶性基を有する単位である単位u3をさらに有する、請求項1又は2に記載の感光性組成物。 - 前記光開始剤が光酸発生剤であり、
前記重合体B及び前記重合体Cの少なくとも一方が、酸解離性基で保護されたアルカリ可溶性基を有する単位である単位u3をさらに有する、請求項1又は2に記載の感光性組成物。 - 前記重合体A、前記重合体B及び前記重合体Cのいずれか1以上が、前記単位u1、前記単位u2及び酸解離性基で保護されたアルカリ可溶性基を有する単位である単位u3以外の単位である単位u4をさらに有する、請求項1~4のいずれか一項に記載の感光性組成物。
- 前記樹脂P1及び前記樹脂P2の合計の含有量が、前記感光性組成物の総質量に対し、10~70質量%である、請求項1~5のいずれか一項に記載の感光性組成物。
- フッ素原子を1つ以上有する有機基を有する単量体である単量体a1と、架橋基(ただし、エチレン性二重結合を含む基を除く)を有する単量体である単量体a2とを含む単量体成分を、下式11、下式12及び下式13のいずれかで表される連鎖移動剤の存在下に重合させて重合体を得る、重合体の製造方法。
Z1-X1-C(R1)(R2)(R3) ・・・11
Z2-X2-R4 ・・・12
Z3-X3-N(R5)(R6) ・・・13
ただし、R1~R3はそれぞれ独立に、水酸基を有していてもよくオキソ基を有していてもよくエーテル性酸素原子を有していてもよい炭素数40以下の鎖式炭化水素基、炭素数40以下の環式基、水酸基、ハロゲン原子、アミノ基、又は水素原子を示し、R1~R3のうち少なくとも2つは水素原子以外の原子又は基であり、
R4は炭素数40以下の環式基を示し、
R5及びR6はそれぞれ独立に、水酸基を有していてもよくオキソ基を有していてもよくエーテル性酸素原子を有していてもよい炭素数40以下の鎖式炭化水素基、又は炭素数40以下の環式基を示し、
X1~X3はそれぞれ独立に、単結合、-S-、-S-R7-、-R8-、-O-R9-又は-O-を示し、R7、R8及びR9はそれぞれ独立に、炭素数1~40の直鎖アルキレン基を示し、
Z1~Z3はそれぞれ独立に、水素原子又はハロゲン原子を示す。 - フッ素原子を1つ以上有する有機基を有する単量体である単量体a1と、反応部位を有する単量体である単量体a2’とを含む単量体成分を、下式11、下式12及び下式13のいずれかで表される連鎖移動剤の存在下に重合させて重合体を得た後、該重合体に、前記反応部位と結合しうる反応性官能基と架橋基とを有する化合物を反応させて、架橋基を有する単位である単位u2を有する重合体とする、重合体の製造方法。
Z1-X1-C(R1)(R2)(R3) ・・・11
Z2-X2-R4 ・・・12
Z3-X3-N(R5)(R6) ・・・13
ただし、R1~R3はそれぞれ独立に、水酸基を有していてもよくオキソ基を有していてもよくエーテル性酸素原子を有していてもよい炭素数40以下の鎖式炭化水素基、炭素数40以下の環式基、水酸基、ハロゲン原子、アミノ基、又は水素原子を示し、R1~R3のうち少なくとも2つは水素原子以外の原子又は基であり、
R4は炭素数40以下の環式基を示し、
R5及びR6はそれぞれ独立に、水酸基を有していてもよくオキソ基を有していてもよくエーテル性酸素原子を有していてもよい炭素数40以下の鎖式炭化水素基、又は炭素数40以下の環式基を示し、
X1~X3はそれぞれ独立に、単結合、-S-、-S-R7-、-R8-、-O-R9-又は-O-を示し、R7、R8及びR9はそれぞれ独立に、炭素数1~40の直鎖アルキレン基を示し、
Z1~Z3はそれぞれ独立に、水素原子又はハロゲン原子を示す。 - 請求項1~6のいずれか一項に記載の感光性組成物の製造方法であって、
フッ素原子を1つ以上有する有機基を有する単量体である単量体a1と、架橋基(ただし、エチレン性二重結合を含む基を除く)を有する単量体である単量体a2とを含む単量体成分を、下式11、下式12及び下式13のいずれかで表される連鎖移動剤の存在下に重合させて重合体Aを製造し、
少なくとも前記重合体Aと光開始剤とを混合して感光性組成物を得る、感光性組成物の製造方法。
Z1-X1-C(R1)(R2)(R3) ・・・11
Z2-X2-R4 ・・・12
Z3-X3-N(R5)(R6) ・・・13
ただし、R1~R6、X1~X3はそれぞれ前記と同義であり、
Z1~Z3はそれぞれ独立に、水素原子又はハロゲン原子を示す。 - 請求項1~6のいずれか一項に記載の感光性組成物の製造方法であって、
フッ素原子を1つ以上有する有機基を有する単量体である単量体a1を含む単量体成分を、下式11、下式12及び下式13のいずれかで表される連鎖移動剤の存在下に重合させて重合体Bを得て、
架橋基(ただし、エチレン性二重結合を含む基を除く)を有する単量体である単量体a2を含む単量体成分を、前記連鎖移動剤の存在下に重合させて重合体Cを得て、
少なくとも前記重合体Bと前記重合体Cと光開始剤とを混合して感光性組成物を得る、感光性組成物の製造方法。
Z1-X1-C(R1)(R2)(R3) ・・・11
Z2-X2-R4 ・・・12
Z3-X3-N(R5)(R6) ・・・13
ただし、R1~R6、X1~X3はそれぞれ前記と同義であり、
Z1~Z3はそれぞれ独立に、水素原子又はハロゲン原子を示す。 - 請求項1~6のいずれか一項に記載の感光性組成物の製造方法であって、
フッ素原子を1つ以上有する有機基を有する単量体である単量体a1を含む単量体成分を、下式11、下式12及び下式13のいずれかで表される連鎖移動剤の存在下に重合させて重合体Bを得て、
少なくとも前記重合体Bと前記重合体Cと光開始剤とを混合して感光性組成物を得る、感光性組成物の製造方法。
Z1-X1-C(R1)(R2)(R3) ・・・11
Z2-X2-R4 ・・・12
Z3-X3-N(R5)(R6) ・・・13
ただし、R1~R6、X1~X3はそれぞれ前記と同義であり、
Z1~Z3はそれぞれ独立に、水素原子又はハロゲン原子を示す。 - 請求項1~6のいずれか一項に記載の感光性組成物の製造方法であって、
架橋基(ただし、エチレン性二重結合を含む基を除く)を有する単量体である単量体a2を含む単量体成分を、下式11、下式12及び下式13のいずれかで表される連鎖移動剤の存在下に重合させて重合体Cを得て、
少なくとも前記重合体Cと前記重合体Bと光開始剤とを混合して感光性組成物を得る、感光性組成物の製造方法。
Z1-X1-C(R1)(R2)(R3) ・・・11
Z2-X2-R4 ・・・12
Z3-X3-N(R5)(R6) ・・・13
ただし、R1~R6、X1~X3はそれぞれ前記と同義であり、
Z1~Z3はそれぞれ独立に、水素原子又はハロゲン原子を示す。 - 基材と、前記基材上に積層された塗膜とを有する積層体の製造方法であって、
基材上に、請求項1~6のいずれか一項に記載の感光性組成物を塗布して感光性膜を形成し、前記感光性膜を露光し、塗膜を形成する、積層体の製造方法。 - 前記塗膜が、厚さ方向に貫通した孔又は溝を有し、
前記感光性膜の露光を、前記孔又は溝に対応したパターンで行い、露光後に前記感光性膜を現像する、請求項13に記載の積層体の製造方法。
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6366211A (ja) * | 1986-09-05 | 1988-03-24 | Sunstar Giken Kk | ジヒドロキシル基含有縮合性マクロモノマ− |
JPH06157983A (ja) * | 1992-11-19 | 1994-06-07 | Nissan Motor Co Ltd | 塗料用樹脂組成物 |
JP2013080203A (ja) * | 2011-09-22 | 2013-05-02 | Fujifilm Corp | ポジ型感光性アクリル樹脂およびポジ型感光性樹脂組成物 |
JP2015161894A (ja) * | 2014-02-28 | 2015-09-07 | 住友化学株式会社 | 感光性樹脂組成物 |
JP2015179257A (ja) * | 2014-02-28 | 2015-10-08 | 住友化学株式会社 | 感光性樹脂組成物 |
JP2016018691A (ja) * | 2014-07-09 | 2016-02-01 | Jsr株式会社 | 表示又は照明装置 |
JP2016172835A (ja) * | 2015-03-18 | 2016-09-29 | 東洋インキScホールディングス株式会社 | シリカ分散体、および、活性エネルギー線硬化性樹脂組成物 |
WO2017082307A1 (ja) * | 2015-11-10 | 2017-05-18 | 旭硝子株式会社 | 蛍光分析バイオチップ用感光性組成物、蛍光分析バイオチップの製造方法および蛍光分析バイオチップ |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5516484A (en) | 1978-07-24 | 1980-02-05 | Tokyo Inst Of Technol | Band semiconductor laser |
KR101118074B1 (ko) * | 2003-11-21 | 2012-04-13 | 디아이씨 가부시끼가이샤 | 플루오르 함유 광경화성 조성물 |
CN103019034B (zh) * | 2011-09-22 | 2017-05-24 | 富士胶片株式会社 | 正型感光性树脂组成物、硬化膜及其制造方法、图案、mems结构体制造方法、干及湿蚀刻方法 |
EP3406640A1 (en) * | 2016-01-19 | 2018-11-28 | Agc Inc. | Photosensitive resin composition for biochip and method for forming liquid-repellent film |
-
2017
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- 2017-07-03 WO PCT/JP2017/024403 patent/WO2018008610A1/ja active Application Filing
- 2017-07-03 CN CN201780042319.2A patent/CN109415467A/zh active Pending
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Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6366211A (ja) * | 1986-09-05 | 1988-03-24 | Sunstar Giken Kk | ジヒドロキシル基含有縮合性マクロモノマ− |
JPH06157983A (ja) * | 1992-11-19 | 1994-06-07 | Nissan Motor Co Ltd | 塗料用樹脂組成物 |
JP2013080203A (ja) * | 2011-09-22 | 2013-05-02 | Fujifilm Corp | ポジ型感光性アクリル樹脂およびポジ型感光性樹脂組成物 |
JP2015161894A (ja) * | 2014-02-28 | 2015-09-07 | 住友化学株式会社 | 感光性樹脂組成物 |
JP2015179257A (ja) * | 2014-02-28 | 2015-10-08 | 住友化学株式会社 | 感光性樹脂組成物 |
JP2016018691A (ja) * | 2014-07-09 | 2016-02-01 | Jsr株式会社 | 表示又は照明装置 |
JP2016172835A (ja) * | 2015-03-18 | 2016-09-29 | 東洋インキScホールディングス株式会社 | シリカ分散体、および、活性エネルギー線硬化性樹脂組成物 |
WO2017082307A1 (ja) * | 2015-11-10 | 2017-05-18 | 旭硝子株式会社 | 蛍光分析バイオチップ用感光性組成物、蛍光分析バイオチップの製造方法および蛍光分析バイオチップ |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020188681A1 (ja) * | 2019-03-18 | 2020-09-24 | 株式会社ニコン | 露光システム、露光装置、及び露光方法 |
WO2020189729A1 (ja) * | 2019-03-18 | 2020-09-24 | 株式会社ニコン | 露光システム、露光装置、及び露光方法 |
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TW201821456A (zh) | 2018-06-16 |
KR20190028646A (ko) | 2019-03-19 |
CN109415467A (zh) | 2019-03-01 |
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