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WO2020095774A1 - Copolymère, et composition de résine contenant ce copolymère - Google Patents

Copolymère, et composition de résine contenant ce copolymère Download PDF

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Publication number
WO2020095774A1
WO2020095774A1 PCT/JP2019/042472 JP2019042472W WO2020095774A1 WO 2020095774 A1 WO2020095774 A1 WO 2020095774A1 JP 2019042472 W JP2019042472 W JP 2019042472W WO 2020095774 A1 WO2020095774 A1 WO 2020095774A1
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WO
WIPO (PCT)
Prior art keywords
group
copolymer
meth
acrylate
resin composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2019/042472
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English (en)
Japanese (ja)
Inventor
優介 青木
恭章 川口
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Holdings Corp
Original Assignee
Showa Denko KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Showa Denko KK filed Critical Showa Denko KK
Priority to KR1020217011625A priority Critical patent/KR102611643B1/ko
Priority to CN201980073052.2A priority patent/CN113039216B/zh
Priority to JP2020555992A priority patent/JP7347442B2/ja
Publication of WO2020095774A1 publication Critical patent/WO2020095774A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • 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
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/14—Esterification
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • 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
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings

Definitions

  • the present invention relates to a copolymer, a resin composition containing the copolymer, and a resist.
  • the present application claims priority based on Japanese Patent Application No. 2018-210789 filed in Japan on November 8, 2018, and the content thereof is incorporated herein.
  • photosensitive resin compositions curable by active energy rays such as ultraviolet rays and electron rays have been widely used in the fields of various coatings, printing, paints, adhesives and the like.
  • photosensitive resin compositions curable by active energy rays can be used as solder resists, color filters, black matrices, black column spacers, photo spacers, protective film resists, etc. It is used.
  • the required properties for curable photosensitive resin compositions are becoming more diverse and sophisticated. These required properties include, for example, short-time curability in consideration of productivity, low-temperature curability that suppresses thermal damage to applied members, and the like.
  • the low reflectivity of electronic material members is emphasized in order to enhance the functionality of various devices. Therefore, in recent years, the development of members with the theme of low reflectivity has been earnestly studied. For example, in microlenses used in digital cameras, smartphones, etc., there is an increasing demand for coating a low reflectance layer along the surface of the microlens. By coating the low-reflectance layer, the reflected light from the concave portions between the lenses can be significantly suppressed, the S / N ratio can be improved, and a high-quality image with little noise can be realized.
  • an image display device such as a liquid crystal display or an organic EL display
  • external light such as sunlight or a fluorescent lamp
  • the external light diffuses after reaching the inside of the substrate of the image display device.
  • the visibility of the screen is reduced. Therefore, for the purpose of improving visibility, there is an increasing demand for a low-reflection display in which various members constituting the image display device substrate are made to have a low reflectance to minimize the reflection of external light. Examples of these members include a transparent substrate, a color filter, a black matrix, a column spacer, and a protective film.
  • Patent Documents 1 and 2 by introducing a fluorine atom introducing another monomer group and a fluorine-containing (meth) acrylate, the solubility is improved and smooth coatability of the cured film is realized.
  • a resin can be provided.
  • the photolithography method includes exposure with active energy rays such as ultraviolet rays and electron beams, and a developing step with an alkali developing solution.
  • the photosensitive resin composition used in this method is required to have sensitivity to active energy rays and alkali developability.
  • an alkali-soluble resin is used as the binder of the coating film forming the member.
  • a reactive diluent, a photopolymerization initiator, and if necessary, an additive such as a colorant are included.
  • the alkali-soluble resin To improve the sensitivity of the alkali-soluble resin, it is necessary to introduce a functional group that causes a reaction during exposure to active energy rays.
  • a functional group an ethylenically unsaturated group is generally mentioned.
  • the method of introducing an acid group is the most general.
  • the acid group include a carboxy group, a phosphoric acid group and a sulfonic acid group.
  • a black matrix, a color filter (a colored pattern of each pixel of R / G / B), a protective film, and the like are repeatedly formed like an image display device substrate, an alkali-soluble resin as a binder of a coating film is used. , High degradability, high heat yellowing, high solvent resistance, etc. are required.
  • the conventional resin has a low degree of fluorine substitution in the fluorine-containing (meth) acrylate and a low composition ratio of the fluorine-containing (meth) acrylate in all the monomers, so that it is possible to provide a satisfactory low refractive index acrylic resin. Is insufficient.
  • the conventional resin is not a photosensitive resin that can be cured by active energy rays such as ultraviolet rays and electron beams, but exhibits photocurability by blending with other photosensitive resins and additives. For the purpose of improving productivity, a photosensitive resin composition that exhibits photocurability with a single liquid is in high demand, but a photosensitive acrylic resin having a satisfactory low refractive index has not been provided yet.
  • fluorine-containing acrylic resins including conventional resins, generally have poor affinity with alkali developers, and further improvement in alkali developability is necessary to satisfy the strict dimensional accuracy of the members. is there.
  • the present invention has been made in order to solve the above problems, and provides an acrylic resin having an excellent low refractive index in one liquid while exhibiting both photocurability and alkali developability, and the resin Accordingly, it is an object of the present invention to provide a photosensitive resin composition used for a resist that contributes to low reflection and high definition of all electronic material members such as microlenses and image display devices.
  • the unsaturated carboxylic acid (a-4) is ring-opened and added to the epoxy group of the epoxy group-containing copolymer (P1), and the hydroxy group formed by ring opening of the epoxy group is polybasic acid.
  • a copolymer (A1) obtained by adding an anhydride (a-5) The epoxy group-containing copolymer (P1) is Consisting of a structural unit derived from a polymerizable monomer (a-1A) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and a structural unit derived from a polymerizable monomer (a-1B) represented by the following chemical formula (1) At least one selected from the group; A structural unit derived from a fluorine-containing (meth) acrylate (a-2) represented by the following chemical formula (2), A copolymer containing a structural unit derived from an epoxy group-containing (meth) acrylate (a-3), A copolymer having an acid value of 20 KOHmg / g or more.
  • X and X ′ in the formula (1) each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R 1 and R 2 each independently.
  • R3 represents a hydrogen atom or a methyl group
  • L represents —O—, —O—CH 2 —CH (OH) —CH 2 —, —O—NH—C ( ⁇ O) —CH. 2 --CH 2-
  • each Z independently represents a hydrogen atom, a fluorine atom, a CF 3 group, a C 2 F 5 group, a C 3 F 7 group or a hydroxy group
  • n is 0 to It is an integer of 12.
  • at least three fluorine atoms are included in the formula (2).
  • the carboxy group-containing copolymer (P2) is Consisting of a structural unit derived from a polymerizable monomer (a-1A) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and a structural unit derived from a polymerizable monomer (a-1B) represented by the following chemical formula (1) At least one selected from the group; A structural unit derived from a fluorine-containing (meth) acrylate (a-2) represented by the following chemical formula (2), A copolymer containing a structural unit derived from an unsaturated carboxylic acid (a-4), A copolymer having an acid value of 20 KOHmg / g or more.
  • X and X ′ in the formula (1) each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R 1 and R 2 each independently.
  • R3 represents a hydrogen atom or a methyl group
  • L represents —O—, —O—CH 2 —CH (OH) —CH 2 —, —O—NH—C ( ⁇ O) —CH. 2 --CH 2-
  • each Z independently represents a hydrogen atom, a fluorine atom, a CF 3 group, a C 2 F 5 group, a C 3 F 7 group or a hydroxy group
  • n is 0 to It is an integer of 12.
  • at least three fluorine atoms are included in the formula (2).
  • the polymerizable monomer (a-1A) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms is dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate.
  • [10] contains a colorant (E), The resin composition according to any one of [7] to [9], wherein the colorant (E) is at least one selected from the group consisting of dyes and pigments.
  • a resist comprising a cured product of the resin composition according to [9] or [10].
  • the present invention it is possible to provide an acrylate-based copolymer having an excellent low refractive index while exhibiting photocurability.
  • the resin composition of the present invention can be suitably used for a resist that contributes to low reflection and high definition of all electronic material members such as microlenses and image display devices.
  • the first embodiment of the copolymer (A) of the present invention is such that the unsaturated carboxylic acid (a-4) is ring-opened and added to the epoxy group of the epoxy group-containing copolymer (P1).
  • the epoxy group-containing copolymer (P1) is a structural unit derived from a polymerizable monomer (a-1A) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and a polymerizable unit represented by the above chemical formula (1). At least one selected from the group consisting of structural units derived from the monomer (a-1B), a structural unit derived from the fluorine-containing (meth) acrylate (a-2) represented by the chemical formula (2), and an epoxy group-containing It is a copolymer containing a structural unit derived from (meth) acrylate (a-3).
  • the epoxy group-containing copolymer (P1) preferably further contains a constituent unit derived from a hydroxy group-containing (meth) acrylate (a-6).
  • the (meth) acrylate means one or more selected from methacrylate and acrylate.
  • Epoxy group-containing copolymer (P1) The epoxy group-containing copolymer (P1) relating to the copolymer (A1) of the present embodiment (hereinafter sometimes simply referred to as “copolymer (P1)”) is a crosslinker having 10 to 20 carbon atoms. At least one selected from the group consisting of a polymerizable monomer (a-1A) having a cyclic hydrocarbon group and a polymerizable monomer (a-1B) represented by the following chemical formula (1) and the following chemical formula (2) It is a copolymer of the monomer (M1) containing the indicated fluorine-containing (meth) acrylate (a-2) and the epoxy group-containing (meth) acrylate (a-3).
  • the fluorine equivalent of the epoxy group-containing copolymer (P1) is preferably 100 g / mol or less, more preferably 30 to 100 g / mol, and further preferably 40 to 100 g / mol.
  • the monomer (M1) of the copolymer (P1) of the present embodiment preferably further contains a hydroxy group-containing (meth) acrylate (a-6). When the hydroxy group-containing (meth) acrylate (a-6) is copolymerized, alkali developability can be further enhanced.
  • the above-mentioned monomer (M1) of the copolymer (P1) of the present embodiment is other than the above-mentioned monomers (a-1A), (a-1B), (a-2), (a-3) and (a-6).
  • Other polymerizable monomer (a-7) may be included.
  • the polymerizable monomer (a-1A) (hereinafter sometimes simply referred to as “monomer (a-1A)”) has a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms.
  • the bridged cyclic hydrocarbon means one having a structure represented by the following formula (3) or (4) represented by adamantane and norbornane, and the bridged cyclic hydrocarbon group is , Refers to a group corresponding to the rest of the structure except for some hydrogen.
  • the polymerizable monomer (a-1A) does not include the later-described polymerizable monomer (a-1B).
  • a and B each represent a linear or branched alkylene group (including cyclic group), R4 represents a hydrogen atom or a methyl group.
  • a and B may be the same or different. , Or the branches of A and B may be connected to form a ring.
  • a ', B', and D each represent a linear or branched alkylene group (including cyclic group), and R5 represents a hydrogen atom or a methyl group.
  • a ', B', and D. May be the same or different, and the branches of A ′, B ′, and D may be connected to form a ring.
  • the monomer (a-1A) is preferably a (meth) acrylate having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms, and has an adamantyl (meth) acrylate or a structure represented by the following formula (5) ( More preferred is (meth) acrylate. ..
  • R6 to R8 each represent a hydrogen atom or a methyl group.
  • R9 and R10 may be a hydrogen atom or a methyl group, or may be bonded to each other to form a saturated or unsaturated ring.
  • the ring is preferably a 5-membered ring or a 6-membered ring. * Represents a bond linked to the (meth) acrylate group.
  • Examples of the monomer (a-1A) include dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate and adamantyl (meth) acrylate. These may be used alone or in combination of two or more.
  • polymerizable Monomer (a-1B) The polymerizable monomer (a-1B) (hereinafter sometimes simply referred to as “monomer (a-1B)”) is a monomer represented by the following general formula (1).
  • X and X ′ in the formula (1) each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R 1 and R 2 each independently.
  • the monomer (a-1B) is not particularly limited as long as it has the chemical structure represented by the general formula (1).
  • examples of X and X'representing a linear or branched hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Group, isobutyl group, t-butyl group and the like.
  • examples of the substituent of the hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, which is represented by R1 and R2 include an alkoxy group and an aryl group.
  • R1 and R2 are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, t-amyl group, stearyl group, lauryl group, 2-ethylhexyl group.
  • a linear or branched alkyl group such as; cyclohexyl group, t-butylcyclohexyl group, dicyclopentadienyl group, tricyclodecanyl group, isobornyl group, adamantyl group, 2-methyl-2-adamantyl group, etc.
  • Examples thereof include a cyclic group; an alkyl group substituted with an alkoxy group such as a 1-methoxyethyl group and a 1-ethoxyethyl group; an alkyl group substituted with an aryl group such as a phenylaralkyl group.
  • Examples of the monomer (a-1B) having the chemical structure represented by the general formula (1) include norbornene, norbornene (bicyclo [2.2.1] hept-2-ene), and 5-methylbicyclo [2.2]. .1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene, 8-methyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene, 8-ethyltetracyclo [4.4.0.1 2,5 .
  • the monomer (a-1A) and / or the monomer (a-1B) contributes to smooth coatability of the cured film, high thermal decomposition resistance, and high heat yellowing. Further, it is possible to suppress the decrease in the solubility of the copolymer in the solvent due to the presence of fluorine.
  • One of the monomer (a-1A) and the monomer (a-1B) may be used, or both of them may be used. Among them, it is preferable to use one or more selected from adamantyl (meth) acrylate, a (meth) acrylate having a structure represented by the above formula (5), and norbornene.
  • Dicyclopentenyl (meth) acrylate, dicyclopenta It is more preferable to use one or more selected from nyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate and norbornene.
  • fluorine-containing (meth) acrylate (a-2) The fluorine-containing (meth) acrylate (a-2) (hereinafter sometimes simply referred to as “monomer (a-2)”) is a fluorine-containing (meth) acrylate represented by the following chemical formula (2).
  • R3 represents a hydrogen atom or a methyl group
  • L represents —O—, —O—CH 2 —CH (OH) —CH 2 —, —O—NH—C ( ⁇ O) —CH. 2 --CH 2-
  • each Z independently represents a hydrogen atom, a fluorine atom, a CF 3 group, a C 2 F 5 group, a C 3 F 7 group or a hydroxy group
  • n is 0 to It is an integer of 12.
  • at least three fluorine atoms are included in the formula (2).
  • the fluorine-containing (meth) acrylate (a-2) is not particularly limited as long as it is represented by the above formula (2).
  • the use of the fluorine-containing (meth) acrylate (a-2) makes it possible to lower the refractive index of the resin, but the effect becomes remarkable when the monomer contains three or more fluorine atoms.
  • n 13
  • further lowering of the refractive index can be expected, but there is a risk that the hardness of the cured film may not be sufficiently exhibited, so that n is in the range of 0 to 12.
  • fluorine-containing (meth) acrylate (a-2) a commercially available product may be used, or a reactive (meth) acrylic acid such as (meth) acrylic acid, glycidyl (meth) acrylate, or 2-isocyanatoethyl (meth) acrylate may be used.
  • a reactive (meth) acrylic acid such as (meth) acrylic acid, glycidyl (meth) acrylate, or 2-isocyanatoethyl (meth) acrylate may be used.
  • Acrylic acid derivative and fluoroalcohol may be self-condensed and prepared.
  • Epoxy group-containing (meth) acrylate (a-3) The epoxy group-containing (meth) acrylate (a-3) (hereinafter sometimes simply referred to as “monomer (a-3)”) is not particularly limited as long as it is a monomer having an epoxy group and an ethylenically unsaturated group. Not done. Specific examples include glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and 3,4-epoxycyclohexylmethyl (meth) acrylate. In particular, glycidyl (meth) acrylate is preferable from the viewpoint of easy availability and good reactivity.
  • the (meth) acrylate having a hydroxy group, a carboxy group, and an epoxy group is a monomer (a-3).
  • hydroxy group-containing (meth) acrylate (a-6) is not particularly limited as long as it is a (meth) acrylate containing one or more hydroxy groups.
  • Specific examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxypentyl (meth) acrylate, 4-hydroxypentyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 4-hydroxyhexyl (meth) acrylate, 5-hydroxyhexyl (meth) acrylate, 6-hydroxyhexyl ( (Meth) acrylate, 5-hydroxy-3-methyl-pentyl (meth) acrylate, cyclohexane-1,4-dimethanol-mono (meth) acrylate, 2- (2-hydroxyethyloxy) ethyl (meth) a Relate, 2,3-dihydroxy (meth) acrylate, butane triol mono (meth) acrylate, pentane trio
  • the epoxy group-containing copolymer (P1) relating to the copolymer (A) according to one aspect of the present invention includes the monomer (a-1A), the monomer (a-1B), the monomer (a-2), and Copolymerization of the monomer (a-3) and other polymerizable monomer (a-7) other than the above-mentioned monomer (a-6) (hereinafter sometimes simply referred to as “monomer (a-7)”). It may be done.
  • the other polymerizable monomer (a-7) is a copolymerizable monomer other than the above-mentioned monomers (a-1A), (a-1B), (a-2) and (a-3).
  • This monomer (a-7) is generally a radically polymerizable compound having an ethylenically unsaturated group, and specific examples thereof include dienes such as butadiene; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl.
  • (Meth) acrylate iso-propyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) ) Acrylate, neopentyl (meth) acrylate, benzyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl (Meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, ethylcyclohexyl (meth) acrylate, rosin (me
  • the ratio of the structure derived from each monomer is the value of the molar ratio of each polymerizable monomer added for the copolymerization reaction.
  • the mixing ratio (molar ratio) of each monomer is not particularly limited, but when the total amount of the monomers (M1) constituting the epoxy group-containing copolymer (P1) is 100 mol%, the monomer (a-1A) and The total blending ratio of the monomer (a-1B) is preferably 1 to 40 mol%, more preferably 2 to 20 mol%.
  • the mixing ratio of the monomer (a-1A) and the monomer (a-1B) is 1 mol% or more, desired thermal decomposition resistance, thermal yellowing resistance, and good solubility in a solvent can be obtained.
  • the blending ratio is 40 mol% or less, the blending ratio of the monomer (a-2) and the monomer (a-3) becomes sufficiently large, and the copolymer (A) having a desired refractive index and curability. Is obtained.
  • the mixing ratio of the monomer (a-2) is preferably 20 to 90 mol%, more preferably 30 to 85 mol%.
  • the copolymer (A) having a sufficiently low refractive index can be obtained. If the blending ratio of the monomer (a-2) is 90 mol% or less, the blending ratio of the monomer (a-1A) and / or the monomer (a-1B) and the monomer (a-3) will be sufficiently high, and the desired amount will be obtained. A copolymer (A) having thermal decomposition resistance, curability, and good solubility in a solvent can be obtained.
  • the mixing ratio of the monomer (a-3) is preferably 9 to 70 mol%, more preferably 13 to 65 mol%.
  • the blending ratio of the monomer (a-3) is 9 mol% or more, sufficient curability can be exhibited when the photosensitive resin composition is formed, and the fluororesin and other photocurable resin having no photocurability can be used. It is possible to provide a photosensitive resin composition having good affinity as compared with a photosensitive resin composition in which a photocurable component is mixed. If the blending ratio of the monomer (a-3) is 70 mol% or less, the blending ratio of the monomer (a-1A) and / or the monomer (a-1B) and the monomer (a-2) will be sufficiently high, and the desired amount will be obtained. A copolymer (A) having thermal decomposition resistance and refractive index can be obtained.
  • the blending ratio of the monomer (a-6) is preferably 0 to 50%, more preferably 0 to 20%.
  • the epoxy group-containing copolymer (P) according to the present invention can be produced by using a copolymerization reaction.
  • the copolymerization reaction carried out in the present invention can be carried out according to a radical polymerization method known in the art.
  • a monomer used for copolymerization may be dissolved in a solvent, a polymerization initiator may be added to the solution, and the reaction may be performed at 50 to 130 ° C. for 1 to 20 hours.
  • the monomer used for the copolymerization and the polymerization initiator may be added dropwise to the solvent adjusted to 50 to 130 ° C. for the reaction.
  • the solvent that can be used in this copolymerization reaction is not particularly limited as long as it is inert to radical polymerization, and a commonly used organic solvent can be used.
  • a commonly used organic solvent can be used.
  • Specific examples include glycol ether solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; aromatic solvents such as toluene and xylene; ester solvents such as ethyl acetate, isopropyl acetate and ethyl lactate. These may be used alone or in combination of two or more. Of these, glycol ether solvents are preferred.
  • the amount of the solvent used in the copolymerization reaction is not particularly limited, but is generally 30 to 1000 parts by mass, preferably 50 to 800 parts by mass, when the total amount of the monomers used in the copolymerization is 100 parts by mass.
  • the amount of the solvent used is 1000 parts by mass or less, the decrease in the molecular weight of the copolymer (P) due to the chain transfer action is suppressed, and the viscosity of the copolymer (P) is controlled within an appropriate range. be able to.
  • an abnormal polymerization reaction can be prevented, the polymerization reaction can be stably performed, and coloring and gelation of the copolymer (P) can be prevented. You can also
  • the polymerization initiator that can be used in this copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and a commonly used organic peroxide catalyst or azo compound can be used.
  • the amount of the polymerization initiator used in this copolymerization reaction is not particularly limited, but is generally 0.5 to 20 parts by mass, preferably 1.0 to 10 parts by mass when the total amount of the monomers used in the copolymerization is 100 parts by mass. 10 parts by mass.
  • the fluorine equivalent of the epoxy group-containing copolymer (P1) is the mass of the polymer per the number of moles of fluorine atom, and is a calculated value calculated based on the amount of the monomer used. If this value is 100 g / mol or less, the refractive index of the acrylic resin as an acrylic resin that exhibits photocurability by adding an unsaturated carboxylic acid (a-4) or an ethylenically unsaturated group-containing reactive monomer (b-2) It is possible to obtain the copolymer (A) of the present invention having a sufficiently low value.
  • the fluorine equivalent is preferably 30 to 100 g / mol, more preferably 40 to 100 g / mol.
  • the unsaturated group-containing copolymer (A1) is obtained by ring-opening addition of the unsaturated carboxylic acid (a-4) to the epoxy group of the epoxy group-containing copolymer (P1), and further by opening the epoxy group.
  • the polybasic acid anhydride (a-5) is added to the resulting hydroxy group and the hydroxy group of the monomer (a-6).
  • the copolymer (A1) of the present embodiment is excellent in photosensitivity because it contains the structural unit derived from the addition reaction in which the unsaturated carboxylic acid (a-4) and the polybasic acid anhydride (a-5) participate. At the same time when the double bond is introduced, a hydroxy group having excellent alkali developability can be obtained by ring opening of the epoxy group. Further, by adding a polybasic acid anhydride to the obtained hydroxy group, a carboxy group can be introduced to enhance the alkali developability. With this structural unit, sufficient hardness of the cured product is exhibited, and high solvent resistance is exhibited.
  • the affinity of the copolymer with an alkali developing solution is increased, and a highly precise curing pattern can be formed, and strict dimensional accuracy is realized. To do. Further, the curability due to heat can be simultaneously exhibited by leaving the whole amount of the epoxy group without reacting with the unsaturated carboxylic acid (a-4).
  • the unsaturated carboxylic acid (a-4) includes, among acid groups, a carboxy group which has a high reactivity with an epoxy group and an ethylenic unsaturated group. There is no particular limitation as long as it is a monomer having a group.
  • the monomer examples include (meth) acrylic acid, itaconic acid, crotonic acid, cinnamic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyl Examples thereof include oxyethylhexahydrophthalic acid.
  • (meth) acrylic acid is preferable from the viewpoints of easy availability and good reactivity.
  • polybasic acid anhydride (a-5) The polybasic acid anhydride is not particularly limited as long as it has an acid anhydride structure having good reactivity with a hydroxy group, but a polybasic acid anhydride having a ring structure that does not generate a by-product after the reaction is preferable.
  • 1,2,3,6-tetrahydrophthalic anhydride hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, bicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride , Methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, succinic anhydride, octenylsuccinic anhydride and the like.
  • the reaction ratio of the unsaturated carboxylic acid (a-4) is preferably 10 to 70 mol%, more preferably 10 to 70 mol% when the total amount of the monomers (M1) constituting the epoxy group-containing copolymer (P1) is 100 mol%. It is preferably 15 to 65 mol%.
  • the blending ratio of the unsaturated carboxylic acid (a-4) is 10 mol% or more, sufficient curability can be exhibited in the photosensitive resin composition.
  • it is 70 mol% or less a sufficient mixing ratio of the monomer (a-1A) and / or the monomer (a-1B) and the monomer (a-2) is ensured to obtain desired thermal decomposition resistance and refractive index.
  • the copolymer (A) having is obtained.
  • the ratio of the unsaturated carboxylic acid (a-4) to be added to the number of moles of the epoxy group contained in the epoxy group-containing copolymer (P1) is preferably 90 to 100 mol%, and It is preferably 95 to 100 mol%.
  • the addition ratio of the unsaturated carboxylic acid (a-4) is 90% or more, sufficient curability can be exhibited when the photosensitive resin composition is prepared, and other fluororesins having no photocurability can be obtained. It is possible to provide a photosensitive resin composition having a good affinity as compared with the photosensitive resin composition in which the photocurable component of (1) is mixed.
  • the reaction ratio of the polybasic acid anhydride (a-5) is not particularly limited as long as the reaction is performed so that the acid value of the copolymer (A1) is 20 KOHmg / g or more.
  • the total amount of the monomers (M1) constituting the epoxy group-containing copolymer (P1) is 100 mol%, it is preferably 5 to 30 mol%, more preferably 5 to 20 mol%.
  • the blending ratio of the polybasic acid anhydride (a-5) is 5 mol% or more, the copolymer (A1) having a desired alkali developability can be obtained.
  • the compounding ratio of the monomer (a-1A) and / or the monomer (a-1B), the monomer (a-2) and the monomer (a-4) is sufficiently secured to obtain a desired amount.
  • the copolymer (A1) having the above-mentioned thermal decomposition resistance, refractive index, and curability can be obtained.
  • the polybasic acid anhydride (a- The addition ratio of 5) is preferably 10 to 90 mol%, more preferably 10 to 70 mol%.
  • the addition ratio of the polybasic acid anhydride (a-5) is 10 mol% or more, the copolymer (A1) having a desired alkali developability can be obtained. Further, when the content is 90% mol% or less, the unreacted product of the polybasic acid anhydride (a-5) does not remain and the desired copolymer (A1) is obtained.
  • the unsaturated group-containing copolymer (A1) preferably has a structure represented by the following formula (6).
  • X and X ′ each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms
  • R 1 and R 2 are each independently It is a hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom, a carboxy group or a substituent, and may have a cyclic structure connecting R1 and R2.
  • R11 is a substituent having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms.
  • L is a chain of any one of —O—, —O—CH 2 —CH (OH) —CH 2 —, and —O—NH—C ( ⁇ O) —CH 2 —CH 2 —.
  • Each Z independently represents a hydrogen atom, a fluorine atom, a CF 3 group, a C 2 F 5 group, a C 3 F 7 group or a hydroxy group, and n is an integer of 0 to 12. However, in the formula (6), at least three fluorine atoms are included.
  • R12 to R14 each independently represent a hydrogen atom or a methyl group.
  • One of R15 is a hydroxy group and the other is a substituent represented by the following chemical formula (7).
  • one of R16 is a substituent represented by the following chemical formula (7), and the other is a substituent represented by the following chemical formula (8).
  • L ′ is a divalent hydrocarbon group having 1 to 6 carbon atoms which may have a substituent
  • L ′′ is a hydrogen atom or a hydrocarbon group which connects L ′′ and L ′ to form a cyclic structure
  • x1, x2, y, a, b, and c are molar ratios of the respective structural units, y, a, and b are larger than 0, and x1, x2, and c may be 0.
  • x1 and x2 are never 0 at the same time.
  • the bonding order of each structural unit is not limited to that shown in the formula, and a block polymer or a random polymer may be formed. * Represents a bond. )
  • R17 represents a hydrogen atom or a methyl group. * Represents a bond.
  • R18 and R19 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and has a cyclic structure connecting R18 and R19. May be. * Represents a bond.
  • R11 is a substituent having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms, and is preferably an adamantyl group or a group having a structure represented by the following formula (5). ..
  • R6 to R8 each represent a hydrogen atom or a methyl group.
  • R9 and R10 may be a hydrogen atom or a methyl group, or may be bonded to each other to form a saturated or unsaturated ring.
  • the ring is preferably a 5-membered ring or a 6-membered ring. * Represents a bond linked to the (meth) acrylate R11.)
  • the unsaturated group-containing copolymer (A1) is obtained by adding a polymerization inhibitor and a catalyst to a solution of the copolymer (P1) having an epoxy group and then adding the unsaturated carboxylic acid (a-4). After the addition, the epoxy group is subjected to a ring-opening addition reaction under the condition of 50 to 150 ° C., preferably 80 to 130 ° C., and then the polybasic acid anhydride (a-5) is added to perform the ring-opening addition reaction of the epoxy group. It can be produced by reacting under the same conditions as.
  • the reaction When reacting the unsaturated carboxylic acid (a-4) and then the polybasic acid anhydride (a-5), it is used for the copolymerization reaction when producing the above-mentioned copolymer (P1) having an epoxy group. Since there is no particular problem even if the solvent is contained, the reaction can be carried out without removing the solvent after the completion of the copolymerization reaction.
  • the polymerization inhibitor is added to prevent gelation due to polymerization of the introduced double bond.
  • the type is not particularly limited, and specific examples thereof include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, dibutylhydroxytoluene and the like.
  • the catalyst is also not particularly limited, but specifically, tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, and organic metals such as chromium and tin. A compound etc. are mentioned.
  • the second embodiment of the copolymer (A) of the present invention is a hydroxy obtained by ring-opening addition of the carboxyl group-containing copolymer (P2) to the epoxy group of the epoxy group-containing (meth) acrylate (a-3). It is an unsaturated group-containing copolymer (A2-I) having a group and is characterized by having an acid value of 20 KOHmg / g or more.
  • the epoxy group-containing copolymer (P2) is a structural unit derived from the polymerizable monomer (a-1A) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and the polymerizable monomer represented by the chemical formula (1).
  • the (meth) acrylate means one or more selected from methacrylate and acrylate.
  • the carboxy group-containing copolymer (P2) (hereinafter sometimes simply referred to as “copolymer (P2)”) related to the copolymer (A2-I) of the present embodiment has 10 to 20 carbon atoms. At least one selected from the group consisting of a polymerizable monomer having a bridged cyclic hydrocarbon group (a-1A) and a polymerizable monomer represented by the chemical formula (1) (a-1B); ) Is a copolymer of the monomer (M2) containing the fluorine-containing (meth) acrylate (a-2) and the unsaturated carboxylic acid (a-4).
  • the fluorine equivalent of the carboxy group-containing copolymer (P2) is preferably 100 g / mol or less, more preferably 30 to 100 g / mol, and further preferably 40 to 100 g / mol.
  • the monomer (M2) of the copolymer (P2) of this embodiment preferably further contains a hydroxy group-containing (meth) acrylate (a-6). When the hydroxy group-containing (meth) acrylate (a-6) is copolymerized, alkali developability can be further enhanced. Further, the above-mentioned monomer (M2) of the copolymer (P2) of the present embodiment may contain other polymerizable monomer (a-7).
  • a-1A polymerizable monomer
  • a-1B polymerizable monomer
  • a fluorine-containing (meth) acrylate a-2
  • an unsaturated carboxylic acid a-4
  • a hydroxy group a polymerizable monomer (a-6)
  • a-7 polymerizable monomer (a-7)
  • the ratio of each monomer-derived structure is the value of the molar ratio of each polymerizable monomer added for the copolymerization reaction.
  • the mixing ratio (molar ratio) of each monomer is not particularly limited, but when the total amount of the monomers (M2) constituting the carboxy group-containing copolymer (P2) is 100 mol%, the monomer (a-1A) and The total blending ratio of the monomer (a-1B) is preferably 1 to 40 mol%, more preferably 2 to 20 mol%.
  • the mixing ratio of the monomer (a-1A) and the monomer (a-1B) is 1 mol% or more, desired thermal decomposition resistance, thermal yellowing resistance, and good solubility in a solvent can be obtained.
  • the blending ratio is 40 mol% or less, the blending ratio of the monomer (a-2) or the monomer (a-4) becomes sufficiently large, and the copolymer (A) having a desired refractive index and curability. Is obtained.
  • the mixing ratio of the monomer (a-2) is preferably 20 to 90 mol%, more preferably 30 to 85 mol%.
  • the blending ratio of the monomer (a-2) is 20 mol% or more, the copolymer (A) having a sufficiently low refractive index can be obtained.
  • the blending ratio of the monomer (a-2) is 90 mol% or less, the blending ratio of the monomer (a-1A) and / or the monomer (a-1B) and the monomer (a-4) is sufficiently high, and the desired amount is obtained.
  • a copolymer (A) having thermal decomposition resistance, curability, and good solubility in a solvent can be obtained.
  • the mixing ratio of the monomer (a-4) is preferably 9 to 70 mol%, more preferably 13 to 65 mol%.
  • the blending ratio of the monomer (a-4) is 9 mol% or more, sufficient curability can be exhibited when the photosensitive resin composition is prepared, and the fluororesin and other photocurable resins which do not have photocurability can be obtained. It is possible to provide a photosensitive resin composition having good affinity as compared with a photosensitive resin composition in which a photocurable component is mixed. If the blending ratio of the monomer (a-4) is 70 mol% or less, the blending ratio of the monomer (a-1A) and / or the monomer (a-1B) and the monomer (a-2) will be sufficiently high, and the desired amount will be obtained. A copolymer (A2) having thermal decomposition resistance and refractive index is obtained.
  • the mixing ratio of the monomer (a-6) is preferably 0 to 50 mol%, more preferably 0 to 20 mol%.
  • the carboxy group-containing copolymer (P2) according to the present invention can be produced by using a copolymerization reaction, like the copolymer (P1) according to the first embodiment.
  • the fluorine equivalent of the carboxyl group-containing copolymer (P2) is the mass of the polymer per the number of moles of the fluorine atom, and is a calculated value calculated based on the amount of the monomer used. If this value is 100 g / mol or less, the refractive index of the acrylic resin that exhibits photocurability by adding an epoxy group-containing (meth) acrylate (a-3) or a polybasic acid anhydride (a-5) will be high. It is possible to obtain a sufficiently low copolymer (A2) of the present invention.
  • the fluorine equivalent is preferably 30 to 100 g / mol, more preferably 40 to 100 g / mol.
  • the unsaturated group-containing copolymer (A2-I) is obtained by ring-opening addition of the carboxy group-containing copolymer (P2) to the epoxy group of the epoxy group-containing (meth) acrylate (a-3).
  • the copolymer (A2-I) of the present embodiment contains a structural unit derived from an addition reaction in which the epoxy group-containing (meth) acrylate (a-3) participates, a double bond excellent in photosensitivity is introduced. At the same time, a hydroxy group can be obtained by ring opening of the epoxy group. Curability can be exhibited by light or heat, and alkali developability can be exhibited. With this structural unit, sufficient hardness of the cured product is exhibited, and high solvent resistance is exhibited. Furthermore, the carboxy group can be introduced at the same time by leaving the whole amount of the carboxy group contained in the carboxy group-containing copolymer (P2) without reacting with the epoxy group.
  • the affinity of the copolymer with the alkali developing solution is increased.
  • a highly precise cured pattern can be formed and strict dimensional accuracy is realized.
  • epoxy group-containing (meth) acrylate (a-3) and polybasic acid anhydride (a-5) according to the present embodiment are the same as those according to the first embodiment, and the description thereof will be omitted.
  • the reaction ratio of the epoxy group-containing (meth) acrylate (a-3) is not particularly limited as long as the reaction is performed so that the acid value of the copolymer (A2-I) is 20 KOHmg / g or more.
  • the total amount of the monomers (M2) constituting the carboxy group-containing copolymer (P2) is 100 mol%, it is preferably 5 to 40 mol%, more preferably 5 to 20 mol%.
  • the compounding ratio of the epoxy group-containing (meth) acrylate (a-3) is 5 mol% or more, sufficient curability can be exhibited in the photosensitive resin composition.
  • the compounding ratio of the monomer (a-1A) and / or the monomer (a-1B), the monomer (a-2) and the monomer (a-4) is sufficiently secured to obtain a desired amount.
  • a copolymer (A2-I) having thermal decomposition resistance, refractive index, and alkali developability can be obtained.
  • the ratio of the epoxy group-containing (meth) acrylate (a-3) to be added to the number of moles of the carboxy group contained in the carboxy group-containing copolymer (P2) is preferably 10 to 90 mol%. %, And more preferably 10 to 70 mol%.
  • the addition ratio of the epoxy group-containing (meth) acrylate (a-3) is 10 mol% or more, sufficient curability can be exhibited when the photosensitive resin composition is prepared and photocurability is not exerted. It is possible to provide a photosensitive resin composition having good affinity as compared with a photosensitive resin composition in which a fluororesin and another photocurable component are mixed. Further, when it is 90% mol% or less, the unreacted product of the epoxy group-containing (meth) acrylate (a-3) does not remain, and the desired copolymer (A2-I) is obtained.
  • the unsaturated group-containing copolymer (A2-I) preferably has a structure represented by the following formula (9-I).
  • X and X ′ each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms
  • R 1 and R 2 are each independently A hydrogen atom, a carboxy group or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent and may have a cyclic structure connecting R1 and R2.
  • R11 is a substituent having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms.
  • L is a chain of any one of —O—, —O—CH 2 —CH (OH) —CH 2 —, and —O—NH—C ( ⁇ O) —CH 2 —CH 2 —.
  • Each Z independently represents a hydrogen atom, a fluorine atom, a CF 3 group, a C 2 F 5 group, a C 3 F 7 group or a hydroxy group, and n is an integer of 0 to 12.
  • R12, R13, and R20 each independently represent a hydrogen atom or a methyl group, one of R21 is a hydrogen atom, and the other is a substituent represented by the following chemical formula (10).
  • x1, x2, y, d, and e are molar ratios of the respective constituent units, y, d, and e are larger than 0, and x1 and x2 may be 0. However, x1 and x2 are never 0 at the same time.
  • the bonding order of each structural unit is not limited to that shown in the formula, and a block polymer or a random polymer may be formed. )
  • R22 represents a hydrogen atom or a methyl group
  • L ′ ′′ represents a divalent hydrocarbon group having 1 to 6 carbon atoms, which may have a substituent, and is represented by the formula (9- One of R21s in I) (that is, R of the formula (10) where R is not linked may be connected to form a ring structure. * Represents a bond)
  • R11, X, X ', R1 and R2 in formula (9-I) are the same as in formula (6).
  • the unsaturated group-containing copolymer (A2-I) is obtained by adding a polymerization inhibitor and a catalyst to a solution of the copolymer (P2) having a carboxy group, and then adding an epoxy group-containing (meth) acrylate ( It can be produced by adding a-3) and reacting under the same conditions as in the ring-opening addition reaction of the epoxy group of the first embodiment.
  • the third embodiment of the copolymer (A) of the present invention is a hydroxy obtained by ring-opening addition of the carboxyl group-containing copolymer (P2) to the epoxy group of the epoxy group-containing (meth) acrylate (a-3).
  • An unsaturated group-containing copolymer (A2-II) obtained by adding a polybasic acid anhydride (a-5) to a hydroxy group of an unsaturated group-containing copolymer (A2-I) having a group, The acid value is 20 KOHmg / g or more. Since the unsaturated group-containing copolymer (A2-I) according to the third embodiment is the same as the unsaturated group-containing copolymer (A2-I) according to the second embodiment, the description thereof will be omitted.
  • the unsaturated group-containing copolymer (A2-II) is an unsaturated group obtained by adding a polybasic acid anhydride (a-5) to the hydroxy group of the unsaturated group-containing copolymer (A2-I). It is a containing copolymer.
  • the hydroxy group is a hydroxy group formed by ring-opening addition of the carboxyl group-containing copolymer (P2) to the epoxy group of the epoxy group-containing (meth) acrylate (a-3) and a monomer (a-6) which is an optional component. ) Is a hydroxy group.
  • the copolymer (A2-II) of the present embodiment contains the structural unit derived from the addition reaction in which the epoxy group-containing (meth) acrylate (a-3) and the polybasic acid anhydride (a-5) participate. At the same time as introducing a double bond having excellent photosensitivity, a hydroxy group having excellent alkali developability can be obtained by ring opening of the epoxy group. With this structural unit, sufficient hardness of the cured product is exhibited, and high solvent resistance is exhibited. Further, the carboxy group can be introduced at the same time by leaving the whole amount of the carboxy group contained in the carboxy group-containing copolymer (P2) with the epoxy group and leaving a part thereof.
  • a polybasic acid anhydride (a-5) to the hydroxy group to increase the amount of carboxylic acid introduced.
  • a polybasic acid anhydride a-5
  • carboxylic acid can be introduced at the same time by not reacting the whole amount of the unsaturated carboxylic acid with the epoxy group and leaving a part thereof.
  • the amount of carboxylic acid introduced can be increased by adding a polybasic acid anhydride to the obtained hydroxy group.
  • the reaction ratio of the epoxy group-containing (meth) acrylate (a-3) is the same as the reaction ratio of the epoxy group-containing (meth) acrylate (a-3) of the copolymer (A2-I) of the second embodiment. ..
  • the reaction ratio of the polybasic acid anhydride (a-5) is preferably 5 to 30 mol% when the total amount of the monomers (M2) constituting the carboxy group-containing copolymer (P2) is 100 mol%. It is more preferably 5 to 20 mol%.
  • the blending ratio of the polybasic acid anhydride (a-5) is 5 mol% or more, the alkali developability of the copolymer (A2-I) can be further enhanced.
  • the amount is 30 mol% or less, the compounding ratio of the monomer (a-1A) and / or the monomer (a-1B) and the monomer (a-2) is sufficiently secured to obtain desired thermal decomposition resistance and refractive index.
  • a copolymer (A2-II) having is obtained.
  • the polybasic acid anhydride (a) is added to the total number of moles of the epoxy group-containing (meth) acrylate (a-3) and the monomer (a-6) of the unsaturated group-containing copolymer (A2-I).
  • the ratio of -5) is preferably 10 to 90 mol%, more preferably 10 to 70 mol%.
  • the addition ratio of the polybasic acid anhydride (a-5) is 10 mol% or more, a copolymer (A2-II) having a desired alkali developability can be obtained.
  • the content is 90 mol% or less, the unreacted product of the polybasic acid anhydride (a-5) does not remain, and the desired copolymer (A2-II) is obtained.
  • the unsaturated group-containing copolymer (A2-II) of this embodiment preferably has a structure represented by the following formula (9-II).
  • X and X ′ each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms
  • R 1 and R 2 are each independently A hydrogen atom, a carboxy group or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent and may have a cyclic structure connecting R1 and R2.
  • R11 is a substituent having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms.
  • L is a chain of any one of —O—, —O—CH 2 —CH (OH) —CH 2 —, and —O—NH—C ( ⁇ O) —CH 2 —CH 2 —.
  • Each Z independently represents a hydrogen atom, a fluorine atom, a CF 3 group, a C 2 F 5 group, a C 3 F 7 group or a hydroxy group, and n is an integer of 0 to 12.
  • R12, R13, and R20 each independently represent a hydrogen atom or a methyl group
  • R23 is a substituent represented by the following chemical formula (8).
  • One of R21 is a hydrogen atom and the other is a substituent represented by the following chemical formula (10).
  • x1, x2, y, d, e, and f are molar ratios of the respective constituent units, y, d, e, and f are larger than 0, and x1 and x2 may be 0. However, x1 and x2 are never 0 at the same time.
  • the bonding order of each structural unit is not limited to that shown in the formula, and a block polymer or a random polymer may be formed.
  • R18 and R19 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and has a cyclic structure connecting R18 and R19. May be. * Represents a bond.
  • R 22 represents a hydrogen atom or a methyl group
  • L ′ ′′ represents a divalent hydrocarbon group having 1 to 6 carbon atoms, which may have a substituent, and is represented by the formula (9- One ring of R21 in II) (that is, R21 in which * in formula (10) is not linked) may be connected to form a ring structure. * Represents a bond.
  • the unsaturated group-containing copolymer (A2-II) is prepared by producing the unsaturated group-containing copolymer (A2-I) and then adding the polybasic acid anhydride (a-5) to the mixture at 50 to 150 ° C. Preferably, it can be produced by reacting a hydroxy group with a polybasic acid anhydride (a-5) at 80 to 130 ° C.
  • the polybasic acid anhydride (a-5) When the polybasic acid anhydride (a-5) is reacted, there is no particular problem even if the solvent used in the above-mentioned copolymerization reaction is contained. Therefore, the solvent is not removed after the completion of the copolymerization reaction.
  • the reaction can be carried out.
  • the polymerization inhibitor is added to prevent gelation due to polymerization of the introduced double bond.
  • the type is not particularly limited, and specific examples thereof include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, dibutylhydroxytoluene and the like.
  • the catalyst is also not particularly limited, but specifically, tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, and organic metals such as chromium and tin. A compound etc. are mentioned.
  • the fourth embodiment of the copolymer (A) of the present invention is a hydroxy obtained by ring-opening addition of the carboxy group-containing copolymer (P2) to the epoxy group of the epoxy group-containing (meth) acrylate (a-3).
  • the fourth embodiment of the copolymer of the present invention is preferably a mixture of the unsaturated group-containing copolymer (A2-I) and the unsaturated group-containing copolymer (A2-II).
  • the unsaturated group-containing copolymer (A2-I) and the unsaturated group-containing copolymer (A2-II) according to the fourth embodiment are respectively the unsaturated group-containing copolymer (A2) according to the second embodiment.
  • -I) and the unsaturated group-containing copolymer (A2-II) according to the third embodiment the description thereof will be omitted.
  • the polybasic acid anhydride (a-5) is added to the unsaturated group-containing copolymer (A2-II).
  • the addition amount of the polybasic acid anhydride (a-5) is adjusted to obtain an unsaturated group-containing copolymer (A2-I) and an unsaturated group-containing copolymer (A2-II). It may be a mixture of.
  • the molecular weight (polystyrene-equivalent weight average molecular weight) of the copolymer (A) of the present invention obtained in the above-mentioned first embodiment to fourth embodiment is preferably 1,000 to 50,000, more preferably 3,000 to 40,000. ..
  • this molecular weight is 1,000 or more, the solvent resistance and thermal decomposition resistance of the cured film can be sufficiently secured.
  • the molecular weight is 50,000 or less, the molecular weight and the viscosity can be controlled in an appropriate range, which is practical.
  • the acid value (JIS K6901 5.3) of the copolymer (A) of the present invention is 20 KOHmg / g or more, preferably 20 to 300 KOHmg / g, and more preferably 30 to 100 KOHmg / g. If the acid value is less than 20 KOHmg / g, developability may be deteriorated and unexposed portions (non-cured portions) may be generated as residues. On the other hand, when the acid value is 300 KOHmg / g or less, the exposed portion (cured portion) is not easily dissolved in the alkali developing solution.
  • the hydroxyl equivalent of the copolymer (A) of the present invention is preferably 200 to 4000 g / mol, more preferably 500 to 3000 g / mol.
  • the hydroxyl equivalent of the copolymer (A) of the present invention is preferably 200 to 4000 g / mol, more preferably 500 to 3000 g / mol.
  • the water repellency of the alkaline developer is increased, but by controlling the hydroxyl group equivalent to 4000 g / mol or less, more preferably 3000 g / mol or less, the water repellency of the alkaline developer is suppressed and good developing property is obtained.
  • the hydroxyl group equivalent is 200 g / mol or more, the introduction amount of other substituents necessary for the present invention can be sufficiently secured, and desired curability, heat decomposition resistance, heat yellowing and refractive index can be obtained.
  • the unsaturated group equivalent of the copolymer (A) is preferably 3000 g / mol or less, more preferably 100 to 3000 g / mol, and further preferably 500 to 2000 g / mol.
  • the unsaturated group equivalent is 100 g / mol or more, it is more effective to further enhance the thermal decomposition resistance and the thermal yellowing resistance.
  • the refractive index of the copolymer (A) is preferably less than 1.50 under the conditions of 589 nm and 20 ° C. When it is less than 1.50, the refractive index is sufficiently lower than the refractive index of the fluorine-free photocurable acrylic resin, and good low reflectance of the cured film can be obtained.
  • the resin composition of the present invention contains a copolymer (A) and a solvent (B).
  • the resin composition of the present invention may further contain a reactive diluent (C), a photopolymerization initiator (D) and a colorant (E).
  • a photosensitive resin composition By containing the photopolymerization initiator (D), a photosensitive resin composition can be obtained.
  • the solvent (B) is not particularly limited as long as it is a solvent that does not react with the copolymer (A).
  • the same solvent as used in the production of the copolymer (A) can be used, and the solvent contained after the reaction can be used as it is or further added.
  • the solvent contained after the reaction can be used as it is or further added.
  • other components when added, they may coexist there.
  • the solvent (B) examples include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, isopropyl acetate, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol.
  • examples thereof include monomethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monoethyl ether acetate and diethylene glycol ethyl ether acetate.
  • glycol ether solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate used in the production of the copolymer (A) are preferable.
  • the blending amount of the solvent (B) in the resin composition or the photosensitive resin composition of the present embodiment is generally 30 to 1000 parts by mass when the total amount of the components excluding the solvent (B) in the composition is 100 parts by mass. Parts, preferably 50 to 800 parts by weight, more preferably 100 to 700 parts by weight. If it is the compounding quantity of this range, it will become a resin composition or a photosensitive resin composition which has suitable viscosity.
  • the reactive diluent (C) is not particularly limited, but those containing an ethylenically unsaturated double bond, a vinyl group and a (meth) acryloyloxy group are preferable. Specific examples thereof include aromatic vinyl monomers such as styrene, ⁇ -methylstyrene, ⁇ -chloromethylstyrene, vinyltoluene, divinylbenzene, diallylphthalate and diallylbenzenephosphonate; polycarboxylic acids such as vinyl acetate and vinyl adipate.
  • Monomers methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, ⁇ -hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, ethylene glycol di (meth) acrylate , Diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylol (Meth) acrylic monomers such as propane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (meth) acrylate of tris (hydroxyethyl) isocyanurate; triallyl cyanurate Etc.
  • a polyfunctional (meth) acrylate having a plurality of (meth) acryloyloxy groups is preferable, and a polyfunctional (meth) acrylate having three or more (meth) acryloyloxy groups is more preferable.
  • the compounding amount of the reactive diluent (C) in the resin composition or photosensitive resin composition of the present embodiment is generally 10 when the total amount of the components excluding the solvent (B) in the composition is 100% by mass. ⁇ 90% by mass, preferably 20 to 80% by mass, more preferably 25 to 70% by mass. If it is the compounding quantity of this range, it will become a resin composition or photosensitive resin composition which has suitable viscosity, and a photosensitive resin composition has suitable photocurability.
  • the photopolymerization initiator (D) is not particularly limited, but specific examples thereof include benzoin such as benzoin, benzoin methyl ether, and benzoin ethyl ether, and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1 , 1-dichloroacetophenone, 4- (1-t-butyldioxy-1-methylethyl) acetophenone and other acetophenones; 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and other anthraquinones Thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ket
  • the blending amount of the photopolymerization initiator (D) in the photosensitive resin composition of the present embodiment is 100 parts by mass based on the total amount of the copolymer (A) and the reactive diluent (C) in the photosensitive resin composition. Then, it is generally 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass. A blending amount within this range results in a photosensitive resin composition having appropriate photocurability.
  • the colorant (E) is not particularly limited as long as it can be dissolved or dispersed in the solvent (B), and known dyes or pigments can be used.
  • a dye is used as the colorant (E)
  • a pigment is used as the colorant (E)
  • the heat resistance of the colored pattern is higher than when a dye is used.
  • Dyes and pigments may be used in combination depending on the required performance and the intended pixel color.
  • dye an acid dye having an acidic group such as a carboxy group, from the viewpoint of solubility in a solvent (B) or an alkali developing solution, interaction with other components in the resin composition for a color filter, heat resistance, and the like, It is preferable to use a salt of an acidic dye with a nitrogen compound, a sulfonamide body of an acidic dye, or the like. Specific examples of such dyes include acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90.
  • Pigment Specific examples of the pigment include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and other yellow pigments; C.I. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and the like; orange pigments; I.
  • the total amount of the components excluding the solvent (B) in the photosensitive resin composition is 100 parts by mass.
  • the amount is 5 to 80 parts by mass, more preferably 5 to 70 parts by mass, and further preferably 10 to 60 parts by mass.
  • a known dispersant may be added to the photosensitive resin composition from the viewpoint of improving the dispersibility of the pigment.
  • the dispersant it is preferable to use a polymer dispersant having excellent dispersion stability over time.
  • polymer dispersants include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified esters. Examples include a system dispersant.
  • EFKA manufactured by EFKA CHEMICALS BV (EFKA)
  • Disperbyk manufactured by Big Chemie
  • Disparon manufactured by Kusumoto Kasei Co., Ltd.
  • SOLSPERSE manufactured by Zeneca
  • the blending amount of the dispersant in the photosensitive resin composition of the present embodiment may be appropriately set according to the type of pigment used.
  • composition of resin composition In the resin composition of the present embodiment, the copolymer (A) and the solvent (B) are blended in such amounts that the total amount of the components excluding the solvent (B) in the resin composition is 100 parts by mass. (A) is 50 to 100 parts by mass, and the solvent (B) is 30 to 1000 parts by mass, preferably 50 to 800 parts by mass, more preferably 100 to 700 parts by mass.
  • the resin composition of the present embodiment contains the reactive diluent (C)
  • the blending amounts of the copolymer (A), the solvent (B) and the reactive diluent (C) are the same as those of the solvent in the resin composition.
  • the copolymer (A) is 10 to 90 parts by mass
  • the solvent (B) is 30 to 1000 parts by mass
  • the reactive diluent (C) is 10 to 10 parts by mass.
  • 90 parts by mass preferably 20 to 80 parts by mass of the copolymer (A), 50 to 800 parts by mass of the solvent (B), and 20 to 80 parts by mass of the reactive diluent (C)
  • the copolymer (A) is 30 to 75 parts by mass
  • the solvent (B) is 100 to 700 parts by mass
  • the reactive diluent (C) is 25 to 70 parts by mass.
  • the resin composition of the present embodiment in addition to the above components, in order to impart predetermined properties, known coupling agents, leveling agents, known additives such as thermal polymerization inhibitors, and known colorants. You may mix
  • the blending amount of these additives is not particularly limited as long as the effects of the present invention are not impaired.
  • the resin composition of the present embodiment is a photosensitive resin composition containing a photopolymerization initiator (D), a copolymer (A), a solvent (B), a reactive diluent (C), a photopolymerization initiator
  • the blending amount of (D) is preferably 5 to 80 parts by mass of the copolymer (A) and the solvent (B ) Is 30 to 1000 parts by mass
  • the reactive diluent (C) is 10 to 90 parts by mass
  • the photopolymerization initiator (D) is 0.1 to 30 parts by mass, and more preferably the copolymer (A).
  • the solvent (B) is 50 to 800 parts by mass
  • the reactive diluent (C) is 20 to 80 parts by mass
  • the photopolymerization initiator (D) is 0.5 to 20 parts by mass
  • the copolymer (A) is 10 to 60 parts by mass
  • the solvent (B) is 100 to 700 parts by mass
  • the reactive diluent (C) is 25 to 70 parts by mass.
  • the photopolymerization initiator (D) is 1 to 15 parts by weight.
  • the photosensitive resin composition of the present embodiment contains the colorant (E), the copolymer (A), the solvent (B), the reactive diluent (C), the photopolymerization initiator (D), the colorant
  • the amount of the (E) compounded is generally 5 to 80 parts by mass of the copolymer (A) and the solvent (B). 30 to 1000 parts by mass, reactive diluent (C) 10 to 89.9 parts by mass, photopolymerization initiator (D) 0.1 to 30 parts by mass, colorant (E) 5 to 80 parts by mass.
  • the copolymer (A) is 8 to 70 parts by mass
  • the solvent (B) is 50 to 800 parts by mass
  • the reactive diluent (C) is 20 to 80 parts by mass
  • the colorant (E) is 5 to 70 parts by mass
  • the copolymer (A) is 10 to 60 parts by mass
  • the solvent (B) is 10 parts by mass.
  • To 700 parts by weight reactive diluent (C) is 25 to 70 parts by weight
  • the photopolymerization initiator (D) 1 to 15 parts by mass
  • the colorant (E) is 10 to 60 parts by weight.
  • the resin composition of the present embodiment can be produced by mixing the above components using a known mixing device.
  • the resin composition of the present embodiment is prepared by first preparing the resin composition containing the copolymer (A) and the solvent (B), and then preparing the reactive diluent (C) and the photopolymerization initiator (D). It is also possible to mix and manufacture.
  • the resin composition can be used for preparing the photosensitive resin composition of the present embodiment, and can also be used for other purposes.
  • the photosensitive resin composition of the present embodiment obtained as described above has excellent sensitivity to light, and since it has alkali developability, it can be developed by using an alkaline aqueous solution, and thermal decomposition It is possible to provide a high-definition cured product (curing pattern) excellent in heat resistance, heat-resistant yellowing and low reflectance. Therefore, the photosensitive resin composition of the present embodiment, various resists, in particular, a microlens surface capable of suppressing reflected light, a substrate incorporated in an image display device capable of suppressing reflection of external light, a color filter, a black matrix. It is suitable for use as a resist used for manufacturing a column spacer, a protective film, and the like.
  • the photosensitive resin composition of the present embodiment gives a cured film excellent in various properties such as heat decomposition resistance, heat yellowing, high transparency, and low reflectivity, and therefore various coatings, adhesives, printing It is also suitable for use as a binder for inks and the like.
  • the resist of the present invention refers to a cured film obtained from the above photosensitive resin composition.
  • the resist of one embodiment of the present invention includes a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyamideimide substrate, a polyimide substrate, an aluminum substrate, a printed wiring board, an array substrate, and other substrates on which the present invention is applied.
  • the photosensitive resin composition is applied and the coating film is exposed to light to cure the exposed portion. Then, by baking, a predetermined cured film can be formed on the substrate.
  • the method for applying the photosensitive resin composition is not particularly limited, but a screen printing method, a roll coating method, a curtain coating method, a spray coating method, a spin coating method, a slit coating method or the like can be used.
  • the solvent (B) may be volatilized by heating using a heating means such as a circulation oven, an infrared heater, or a hot plate, if necessary.
  • the heating conditions are not particularly limited and may be appropriately set depending on the type of photosensitive resin composition used. Generally, heating may be performed at a temperature of 50 ° C. to 120 ° C. for 30 seconds to 30 minutes.
  • the light source used for the exposure is not particularly limited, but a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp and the like can be used.
  • the amount of exposure is also not particularly limited, and may be appropriately adjusted according to the type of photosensitive resin composition used.
  • the alkaline aqueous solution used for development is not particularly limited, but an aqueous solution of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide or the like; an aqueous solution of an amine compound such as ethylamine, diethylamine or dimethylethanolamine; 3 -Methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ - Methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methoxyethylaniline and their water-soluble p-phenylenediamine compounds such as sulfates, hydrochlorides or p-toluenesulfonates Etc.
  • an amine compound such as ethylamine
  • aqueous solution of a p-phenylenediamine compound can be used.
  • an antifoaming agent or a surfactant may be added to these aqueous solutions, if necessary. Further, it is preferable to wash with water and dry after the development with the above alkaline aqueous solution.
  • the baking conditions are not particularly limited, and heat treatment may be performed depending on the type of photosensitive resin composition used. Generally, heating may be performed at 130 to 250 ° C. for 10 to 60 minutes.
  • a desired colored pattern can be formed by sequentially repeating the above-mentioned coating, exposure, development and baking using the photosensitive resin composition for black matrix and the photosensitive resin composition for pixels. ..
  • the method for forming a colored pattern by photocuring has been described.
  • a photosensitive resin composition containing a curing accelerator and a known epoxy resin is used instead of the photopolymerization initiator (D)
  • an inkjet method can be used. It is also possible to form a desired colored pattern by applying the coating method and then heating.
  • the molecular weight (Mw) means a standard polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) under the following conditions.
  • GPC gel permeation chromatography
  • A Developing solvent: Tetrahydrofuran Detector: Differential refractometer (Showdex RI-71S) (Showa Denko KK) Flow rate: 1 mL / min
  • the refractive index means the refractive index of the copolymer (A) measured using a refractometer.
  • the refractive index of the resin composition (sample) containing the copolymer (A) and the solvent (B) of the present invention is measured under the following conditions, and then the refractive index of the solvent (B) is measured under the following conditions.
  • the content (solid content) of the copolymer (A) contained in the sample was measured according to JIS K6901 5.11, and the refractive index of the copolymer (A) alone contained in the sample was calculated using the following formula. calculate.
  • Example 1 A production example of a resin composition (sample) containing the copolymer (A) and the solvent (B) of the present invention is shown below.
  • Example 1 "Synthesis of Copolymer (A)" 302.4 g of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, and the mixture was stirred while substituting with nitrogen and heated to 80 ° C.
  • Example 7 "Synthesis of Copolymer (A)"
  • a-1A dicyclopentanyl methacrylate
  • a-2 2,2,2-trifluoroethyl methacrylate
  • a-4 methacrylic acid
  • a solution containing the copolymer (A) of Example 7 was obtained.
  • 118.8 g of propylene glycol monomethyl ether acetate was added as a solvent (B), and sample No. Got 7.
  • the total amount of the monomers (a-1A), (a-2) and (a-4) is calculated as 100 mol%, the mixing ratio of each monomer and the fluorine equivalent of the carboxy group-containing copolymer (P2)
  • Table 2 shows the molecular weight, acid value, hydroxyl group equivalent, unsaturated group equivalent, and refractive index of the polymer (A2).
  • Example 8 "Synthesis of Copolymer (A)"
  • a copolymer (A) of Example 8 was produced in the same manner as in Example 7 except that the mixing ratios of the monomers shown in Table 1 were used, and propylene glycol monomethyl ether acetate was added as a solvent (B) to obtain a sample. No. Got 8.
  • Table 2 shows the molecular weight, acid value, hydroxyl group equivalent, unsaturated group equivalent, and refractive index of the copolymer (A2) contained in the sample.
  • sample No. 1-8, No. 10 was used to prepare a transparent photosensitive resin composition.
  • ⁇ Preparation of transparent photosensitive resin composition Sample No. 1-8, No. 10 parts by mass of pentaerythritol tetraacrylate (reactive diluent (C)) and 10 parts by mass of 2,2-dimethoxy-2-phenylacetophenone (photopolymerization initiator (D)) per 100 parts by mass of the solid content of 10.
  • C pentaerythritol tetraacrylate
  • D photopolymerization initiator
  • propylene glycol monomethyl ether acetate was added so that the solvent (B) was 210 parts by mass to prepare a transparent photosensitive resin composition.
  • the residue of the sample excluding the solvent is defined as "solid content”.
  • ⁇ Pattern formation by transparent photosensitive resin composition The prepared transparent photosensitive resin composition was spin-coated on a 5 cm square glass substrate (alkali-free glass substrate) so that the average thickness of the final cured coating film would be 2.5 ⁇ m, and then 3 ° C. at 100 ° C. The solvent was volatilized by heating for a minute. Next, the entire surface of the coating film was exposed with an apparatus (exposure amount: 80 mJ / cm 2 ), photocured, and then baked at 230 ° C. for 30 minutes to obtain a transparent resist which was a cured coating film.
  • Tables 3 and 4 show the evaluation results of the thermal decomposition resistance and the yellowing resistance of the transparent resist.
  • sample No. 1 to 11 were used to prepare a black photosensitive resin composition.
  • ⁇ Preparation of black pigment dispersion> In a SUS container filled with 180 parts by mass of zirconia beads having a diameter of 0.5 mm, 10 parts by mass of carbon black, 34 parts by mass of propylene glycol monomethyl ether acetate, and 6 parts by mass of a dispersant (Disperbyk-manufactured by BYK Japan KK 161) was added and mixed by a paint shaker for 3 hours and dispersed to obtain a black pigment dispersion liquid.
  • ⁇ Pattern formation with black photosensitive resin composition (with development)>
  • the prepared black photosensitive resin composition was spin-coated on a 5 cm square glass substrate (alkali-free glass substrate) so that the average thickness of the final cured coating film would be 1.0 ⁇ m, and then 3 ° C. at 100 ° C.
  • the solvent was volatilized by heating for a minute.
  • a line-and-space or dot-pattern photomask was placed on the substrate to expose the coating film (exposure amount 300 mJ / cm 2 ), and after photocuring, a 0.2 mass% potassium hydroxide aqueous solution was used. It was developed and further baked at 230 ° C. for 30 minutes to obtain a black resist as a cured coating film.
  • the prepared black photosensitive resin composition was spin-coated on a 5 cm square glass substrate (alkali-free glass substrate) so that the average thickness of the final cured coating film would be 1.0 ⁇ m, and then 3 ° C. at 100 ° C. The solvent was volatilized by heating for a minute. Next, the entire surface of the coating film was exposed (exposure amount 300 mJ / cm 2 ), photocured, and then baked at 230 ° C. for 30 minutes to obtain a black resist as a cured coating film.
  • the black resist was evaluated for developability, solvent resistance, and reflectance.
  • Tables 5 and 6 show the evaluation results of the developability, solvent resistance, and reflectance of the black resist.
  • the photosensitive resin composition of the present invention can provide a resist that contributes to low reflection and high definition of all electronic material members such as microlenses and image display devices.

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Abstract

L'invention fournit une résine acrylique qui présente une photosensibilité exprimant un photodurcissement, et qui simultanément présente une excellente faiblesse d'indice de réfraction. Le copolymère de l'invention est tel qu'un acide carboxylique insaturé (a-4) est additionné par ouverture de cycle à un groupe époxy d'un copolymère (P1) comprenant un groupe époxy, un anhydride d'acide polybasique (a-5) est additionné à un groupe hydroxy produit par ouverture de cycle du groupe époxy, et son indice d'acide est supérieur ou égal à ２０ＫＯＨｍｇ／ｇ. Le copolymère (P1) comprenant un groupe époxy contient : au moins une sorte d'unité structurale choisie dans un groupe constitué d'une unité structurale dérivée d'un monomère polymérisable (a-1A) ayant un groupe hydrocarbure cyclique ponté en C10 à C20, et d'une unité structurale dérivée d'un monomère polymérisable (a-1B) représenté par la formule chimique (1) ; une unité structurale dérivée d'un (méth)acrylate (a-2) comprenant un fluor représenté par la formule chimique (2) ; et une unité structurale dérivée d'un (méth)acrylate (a-3) comprenant un groupe époxy.
PCT/JP2019/042472 2018-11-08 2019-10-30 Copolymère, et composition de résine contenant ce copolymère Ceased WO2020095774A1 (fr)

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US20220204671A1 (en) * 2020-12-24 2022-06-30 Rohm And Haas Electronic Materials Korea Ltd. Fluorinated acrylate-based copolymer and photosensitive resin composition comprising same
JPWO2022168974A1 (fr) * 2021-02-08 2022-08-11

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