CN105934713A - Active energy ray-curable resin composition, and spacer for display elements and/or color filter protective film using same - Google Patents

Active energy ray-curable resin composition, and spacer for display elements and/or color filter protective film using same Download PDF

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Publication number
CN105934713A
CN105934713A CN201580005712.5A CN201580005712A CN105934713A CN 105934713 A CN105934713 A CN 105934713A CN 201580005712 A CN201580005712 A CN 201580005712A CN 105934713 A CN105934713 A CN 105934713A
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Prior art keywords
methyl
compound
acid
epoxy
reactive
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CN201580005712.5A
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CN105934713B (en
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山本和义
小渊香津美
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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    • 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
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/064—Polymers containing more than one epoxy group per molecule
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/144—Polymers containing more than one epoxy group per molecule
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • 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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • 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
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • 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
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Epoxy Resins (AREA)
  • Liquid Crystal (AREA)
  • Electroluminescent Light Sources (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Optical Filters (AREA)

Abstract

The purpose of the present invention is to provide: an active energy ray-curable resin composition which has good developability, curability and high-speed coatability; and a spacer for display elements and a color filter protective film, each of which has excellent heat-resistant transparency, flatness, flexibility and toughness. An active energy ray-curable resin composition for spacers for display elements or color filter protective films, which contains a reactive polycarboxylic acid compound (A), a reactive compound (B) other than the reactive polycarboxylic acid compound (A), a photopolymerization initiator (C) and an organic solvent (D). The reactive polycarboxylic acid compound (A) is obtained by having a reaction product of at least an epoxy resin (a) having two or more epoxy groups in each molecule and a compound (b) having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in each molecule additionally react with a polybasic acid anhydride (d). The epoxy resin (a) having two or more epoxy groups in each molecule is a naphthalene skeleton-containing epoxy resin.

Description

Active energy ray-curable resin composition and Use display element sept and/or the light filter protecting film of said composition
Technical field
The present invention relates to active energy ray-curable resin composition, display element sept And/or light filter protecting film.
Background technology
In display device material, use always and comprise binder polymer, photopolymerizable monomer Resin combination with Photoepolymerizationinitiater initiater etc..In recent years, (it is used for as display device material LCD, EL, PDP, FED (SED), rear projection display, Electronic Paper or digital camera etc. Material, particularly display element, display element periphery material), such as color liquid crystal display arrangement (LCD) quickly popularize.It is said that in general, the structure of color liquid crystal display arrangement is: by light filter with The electrode base boards such as TFT substrate are opposed and arrange about 1 μm～the clearance portion of about 10 μm, in this gap Filling liquid crystal compound in portion, and will seal with encapsulant about.
The structure of light filter is: layer successively from the side near transparency carrier on the transparent substrate It is laminated with in order to the boundary portion shading between pixel is formed as the black-matrix layer of predetermined pattern, is Formation each pixel and generally with regulation order arrange red (R), green (G), the dyed layer of blue (B), Protecting film and ELD.It addition, in light filter and the electrode base board opposed with it Side, face is provided with alignment films.It addition, in clearance portion, in order to by light filter and electrode base board it Between cell gap keep fixing and uniformly, be dispersed with and there is the granule (パ Le) of fixing particle diameter make For sept, or formed there is and the column of height that cell gap is corresponding or striated interval Thing.And, liquid crystal layer saturating of each underlying pixel being colored as shades of colour it is positioned at by control Light rate, can obtain coloured image.Such light filter is not limited to color liquid crystal display arrangement, It is used also as the EL of other display device, rear projection display etc..
Above-mentioned dyed layer, protecting film and sept can use resin formation.Dyed layer needs Each of pixel for shades of colour is formed as the pattern of regulation.For protecting film, In view of adaptation, the seal of sealing, it is preferably able to only by being formed on transparency carrier The protecting film of the region overlay of dyed layer.It addition, sept needs to be accurately disposed at black square In the formation region of battle array layer, i.e. in non-display area.Therefore, use can be held by photomask Changing places to limit wants the curable resin in the region solidified to be formed between dyed layer, protecting film and column Parting.
It addition, in order to form dyed layer, protecting film or column spacer, by curable resin Coated face exposure after use organic solvent when developing, numerous in terms of operation and liquid waste processing Miscellaneous, economy, stability are not enough, therefore develop introduce in curable resin acidic-group, The curable resin that alkaline aqueous solution develops can be utilized after exposure.In these purposes, The formation of alignment films, transparency electrode formation time apply high temperature (200 DEG C～260 DEG C or its more than), Therefore it is required that thermostability is the highest, especially for also requirement for colored resist, sept The material that heat-resisting coloring is excellent.
In patent documentation 1, use by with in primary amine and cresol novolak epoxy The sour modified epoxy acrylic ester of resin and the photoresist that obtains as light spacer with and The component of polymer of light filter photosensitive polymer combination.But, containing such primary amine The salt of compound, the coating of compositions of water, flatness are poor, fill for slit type coater etc. The suitability put can not be said to be sufficient.
It addition, in patent documentation 2, use cresol novolak type epoxy resin or phenol phenol The sour modified epoxy acrylic ester of Novolac type epoxy resin is as light spacer photoresist The component of polymer of compositions.But, there is radiosensitivity, developability poor, not being can The problem of the level being entirely satisfactory.
In patent documentation 3, use acrylic acid, dihydromethyl propionic acid and cresol novolak Epoxy resin addition and the product that obtains carry out caprolactone modification, carry out tetrahydrochysene neighbour's benzene two again The active energy ray-curable resin that formic anhydride is modified and obtains as light filter protecting film or Person's flexible printing wiring board component of polymer of resist ink composite.Although as combination The developability of the component of polymer of the main component of thing, flexibility are excellent, but between existing as light The problem of the elastic recovery rate variance required by parting.
In patent documentation 4, disclose containing the Polycarboxylic acid resin containing unsaturated group Resin combination is used for solder resist, but for protecting for display element sept, light filter Cuticula is entirely without record.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2004-109752 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2007-010885 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2004-300266 publication
Patent documentation 4: Japanese Unexamined Patent Publication 4-165358 publication
Summary of the invention
Invent problem to be solved
It is an object of the invention to improve above-mentioned problem of the prior art, it is provided that developability, solidification Property, the active energy ray-curable resin composition that high speed coatability is good, and resistance to heat penetration Bright property, flatness, flexibility, the display element sept of good-toughness and light filter protection Film.
Means for solving the above
The present inventor has carried out research extensively and profoundly to solve the problems referred to above, it was found that The resin combination with specific compound and composition can solve the problem that the problems referred to above, and completes The present invention.
That is, the present invention relates to:
(1) a kind of for display element sept or the active energy beam of light filter protecting film Curable resin composition, it contains reactive polycarboxylic compounds (A), except reactive polynary Reactive compounds (B), Photoepolymerizationinitiater initiater (C) and organic solvent beyond carboxylic acid compound (A) (D), wherein,
Reactive polycarboxylic compounds (A) is for making to have at least two epoxy in a part The epoxy resin (a) of base and a part have more than one polymerisable ethylenically unsaturated group and The compound (b) of more than one carboxyl and a part as required have at least two The product (E) of the compound (c) of hydroxyl and more than one carboxyl further with multi-anhydride (d) The reactive polycarboxylic compounds (A) reacted and obtain,
The epoxy resin (a) in a part with at least two epoxy radicals is the ring containing naphthalene skeleton Epoxy resins.
(2) the invention still further relates to as described in above-mentioned (1) for display element sept or colour filter The active energy ray-curable resin composition of sheet protecting film, wherein, reactive polybasic carboxylic acid Compound (A) is the epoxy resin (a) and making to have at least two epoxy radicals in a part Molecule has the chemical combination of more than one polymerisable ethylenically unsaturated group and more than one carboxyl Thing (b) and a part have the compound (c) of at least two hydroxyl and more than one carboxyl Product (E) further with multi-anhydride (d) reaction and the reactive polycarboxylic acid that obtains Compound (A), has the epoxy resin (a) of at least two epoxy radicals for containing naphthalene skeleton in a part Epoxy resin, a part has the epoxy resin (a) of at least two epoxy radicals for containing naphthalene The epoxy resin of skeleton.
(3) the invention still further relates to as described in above-mentioned (1) or (2) for display element sept or The active energy ray-curable resin composition of light filter protecting film, wherein, reactive chemical combination Thing (B) is any in (methyl) acrylate more than simple function, difunctionality and trifunctional One or more.
(4) the invention still further relates to using for display element as according to any one of above-mentioned (1)～(3) Sept or the active energy ray-curable resin composition of light filter protecting film, wherein, make For the use ratio in resin combination, relative to reactive polycarboxylic compounds (A) 100 matter Amount part, reactive compounds (B) is 30 mass parts～250 mass parts.
(5) the invention still further relates to a kind of display element sept, it is appointed by above-mentioned (1)～(4) One described active energy ray-curable resin composition is formed.
(6) the invention still further relates to a kind of light filter protecting film, it is by any one of above-mentioned (1)～(4) Described active energy ray-curable resin composition is formed.
Invention effect
The active energy ray curable containing reactive polycarboxylic compounds (A) of the present invention The developability of resin combination is excellent, has high radiosensitivity, using the teaching of the invention it is possible to provide heat resistant transparent, Flatness, flexibility, the display element sept of good-toughness and light filter protecting film.
Detailed description of the invention
Hereinafter, the present invention is described in detail.
Reactive polycarboxylic compounds (A) in the present invention can have in a part by making The epoxy resin (a) of at least two epoxy radicals and a part has more than one polymerisable In the compound (b) of ethylenically unsaturated group and more than one carboxyl and a part as required The product of the compound (c) with at least two hydroxyl and more than one carboxyl is further React with multi-anhydride (d) and obtain.
That is, the reactive polycarboxylic compounds (A) in the present invention can be by making epoxy resin (a) React with multi-anhydride (d) with the product (E) of compound (b)；Or make epoxy resin (a) and change The product (E) of compound (b) and compound (c) is reacted with multi-anhydride (d) and is obtained.
As the epoxy resin in a part in the present invention with at least two epoxy radicals A (), can enumerate the epoxy resin containing naphthalene skeleton.
As this epoxy resin containing naphthalene skeleton, such as, such as Japanese Unexamined Patent Publication 4-165358 institute Record, can urge in acid with aphthols by making the dihydroxymethyl compounds such as double (methylol) paracresol Reaction under agent and the phenolic novolac that obtains reacts with epihalohydrins compound in the presence of a base and Obtain.
Additionally, the material that can obtain from market as the epoxy resin containing naphthalene skeleton can be enumerated Such as NC-7000, NC-7300, NC-7700 (Nippon Kayaku K. K's manufacture), EXA-4750 (Dainippon Ink. & Chemicals Inc's manufacture) etc..
In the present invention, it is characterised in that use the epoxy resin containing naphthalene skeleton as asphalt mixtures modified by epoxy resin Fat (a).But it is also possible to according to circumstances and with other in addition to the epoxy resin containing naphthalene skeleton A part has the epoxy resin of at least two epoxy radicals and for reacting.
As other epoxy resin, can enumerate such as: phenol novolak type epoxy resin, Cresol novolak type epoxy resin, three hydroxyphenyl methane type epoxy resin, dicyclopentadiene Phenol-type epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, connection phenolic epoxy Resin, bisphenol A novolac type epoxy resin, Biformyl type epoxy resin, ester ring type epoxy Resin, hetero ring type epoxy resin etc..
As phenol novolak type epoxy resin, can enumerate such as: EPICLON N-770 (Dainippon Ink. & Chemicals Inc's manufacture), D.E.N438 (Dow Chemical's system Make), EPIKOTE 154 (oiling Shell epoxy resin Co., Ltd. manufacture), EPPN-201, RE-306 (Nippon Kayaku K. K's manufacture) etc..As cresol novolak type epoxy resin, can To enumerate such as: EPICLON N-695 (Dainippon Ink. & Chemicals Inc's manufacture), EOCN-102S, EOCN-103S, EOCN-104S (Nippon Kayaku K. K's manufacture), UVR-6650 (Dow Chemical's manufacture), ESCN-195 (Sumitomo Chemical Company Ltd's manufacture) Deng.
As three hydroxyphenyl methane type epoxy resin, can enumerate such as: EPPN-503, EPPN-502H, EPPN-501H (Nippon Kayaku K. K's manufacture), TACTIX-742 (Tao Shi Chemical company manufactures), EPIKOTE E1032H60 (oiling Shell epoxy resin Co., Ltd. system Make) etc..As dicyclopentadiene phenol-type epoxy resin, can enumerate such as: XD-1000 (day This chemical medicine Co., Ltd. manufacture), EPICLON EXA-7200 (big Japanese ink chemical industry strain formula Commercial firm manufactures), TACTIX-556 (Dow Chemical's manufacture) etc..
As bisphenol-type epoxy resin, can enumerate such as: EPIKOTE 828, EPIKOTE 1001 (oilings Shell epoxy resin Co., Ltd. manufacture), UVR-6410 (Dow Chemical's system Make), D.E.R-331 (Dow Chemical's manufacture), YD-8125 (Dongdu chemical conversion company manufacture), The bisphenol A type epoxy resins such as NER-1202, NER-1302 (Nippon Kayaku K. K's manufacture), UVR-6490 (Dow Chemical's manufacture), YDF-8170 (Dongdu chemical conversion society manufactures), The bisphenol f type epoxy resins etc. such as NER-7403, NER-7604 (Nippon Kayaku K. K's manufacture).
As connection phenol-type epoxy resin, can enumerate such as: NC-3000, NC-3000-H (day This chemical medicine Co., Ltd. manufacture) etc. '-biphenyl diphenol type epoxy resin, YX-4000 (oiling Shell ring Epoxy resins Co., Ltd. manufacture) etc. di-toluene phenol-type epoxy resin, YL-6121 (oiling Shell Epoxy resin Co., Ltd. manufactures) etc..As bisphenol A novolac type epoxy resin, Ke Yilie Illustrate such as: EPICLON N-880 (Dainippon Ink. & Chemicals Inc's manufacture), EPIKOTE E157S75 (oiling Shell epoxy resin Co., Ltd. manufacture) etc..
The material that can obtain from market as Biformyl type epoxy resin can be enumerated such as GTR-1800 (Nippon Kayaku K. K's manufacture) etc..As alicyclic epoxy resin, Ke Yilie Illustrate such as EHPE-3150 (Co., Ltd.'s Daicel manufactures) etc..As hetero ring type epoxy resin, can To enumerate such as TEPIC (Nissan Chemical Ind Ltd's manufacture) etc..
A part in the present invention has more than one polymerisable ethylenically unsaturated group and one The reactivity of active energy beam is carried out instead by the compound (b) of individual above carboxyl for giving Should.As long as ethylenically unsaturated group and each comfortable molecular memory of carboxyl the most do not limit at more than one System.As these compounds, monocarboxylic acid compound, polycarboxylic compounds can be enumerated.
As a part has the monocarboxylic acid compound of a carboxyl, can enumerate such as: (methyl) acrylic compounds or .beta.-methylacrylic acid, alpha-cyano cinnamic acid, cinnamic acid or saturated or unsaturated two Unit's acid and the product of the single glycidyl compound containing unsaturated group.In above-mentioned, As (methyl) acrylic compounds, can enumerate such as: (methyl) acrylic acid, β-styryl propylene Acid, β-furfuryl acrylic acid, (methyl) acrylic acid dimer, as saturated or unsaturated dicarboxylic acid anhydride Reaction with same mole product with (methyl) acrylate derivative in a part with a hydroxyl Half esters, derive with (methyl) acrylic acid list ethylene oxidic ester as saturated or unsaturated dibasic acid Half esters etc. of the reaction with same mole product of species.
Additionally, as a part has the polycarboxylic compounds of two or more carboxyl, permissible Enumerate: as in a part, there is the equimolar of (methyl) acrylate derivative of multiple hydroxyl Half esters of product, as saturated or unsaturated dibasic acid and the (first with multiple epoxy radicals Base) half esters etc. of reaction with same mole product of glycidyl acrylate derivatives class.
Among these, the sensitivity in time making active energy ray-curable resin composition From the standpoint of, most preferably can enumerate: (methyl) acrylic acid, (methyl) acrylic acid and 6-caprolactone Product or cinnamic acid.As compound (b), preferred compound does not have hydroxyl.
A part in the present invention has the change of at least two hydroxyl and more than one carboxyl Compound (c) reacts for introducing hydroxyl in carboxylate compound.
As in a part used as required in the present invention, there is at least two hydroxyl With the concrete example of the compound (c) of more than one carboxyl, can enumerate such as: dihydromethyl propionic acid, Dimethylolpropionic acid, dihydroxymethyl acetic acid, dimethylolpropionic acid, dihydroxymethyl valeric acid, dihydroxy Methylhexanoic acids etc. are containing polyhydric monocarboxylic acid class etc..As particularly preferred compound (c), can To enumerate such as dihydromethyl propionic acid etc..
Among these, it is considered to above-mentioned epoxy resin (a) and compound (b) and the reaction of compound (c) Stability time, compound (b) and compound (c) be preferably monocarboxylic acid, though and use unitary In the case of carboxylic acid and polybasic carboxylic acid, with total mole of monocarboxylic integral molar quantity/polybasic carboxylic acid The value that amount represents is preferably also more than 15.
As this reaction epoxy resin (a) and compound (b) and the chemical combination used as required The total ingredient proportion of carboxylic acid of thing (c), it should suitably change according to purposes.That is, by whole epoxies In the case of yl carboxylic acid esterification, due to the epoxy radicals of not remained unreacted, therefore as reactive The storage stability of epoxy carboxylic acids's ester compounds is high.In this case, merely with by introducing The reactivity that double bond produces.
On the other hand, by reducing the inventory of carboxylic acid compound wittingly and remained unreacted Residual epoxy base, can comprehensively utilize the reactivity produced by the unsaturated bond introduced and by residual The reaction that the epoxy radicals stayed causes, the polyreaction such as caused by light cationic catalyst or heat Polyreaction.But, in this case, it should be noted that research reactive epoxy carboxylic acids esterification The preservation of compound (E) and manufacturing condition.
When manufacturing reactive epoxy carboxylic acids's ester compounds (E) of not residual epoxy base, compound (b) The total amount of the compound (c) used as required is preferred relative to above-mentioned epoxy resin (a) 1 equivalent It is 90～120 equivalent %.If this scope, then can manufacture under conditions of more stable. When compound (b) is more than this scope with total inventory of the compound (c) used as required, residual The compound (b) of excess and compound (c), the most preferred.
It addition, wittingly in the case of residual epoxy base, compound (b) and the total amount of compound (c) It is preferably 20～90 equivalent % relative to above-mentioned epoxy resin (a) 1 equivalent.Time beyond this scope, The reaction further caused by epoxy radicals will not be sufficiently carried out.In this case it is necessary to fill Divide the gelation in attention response, the ageing stability of reactive epoxy carboxylic acids's ester compounds (E).
About usage rate when use compound (b) and compound (c), with the mol ratio of carboxylic acid Meter, preferred compound (b): compound (c) be 95:5～5:95, more preferably 95:5～ The scope of 40:60.It is if within the range, then good to the sensitivity of active energy beam, And can introduce and enough make reactive epoxy carboxylic acids's ester compounds (E) react with multi-anhydride (d) Hydroxyl.
Carboxylic esterification reaction can be reacted under condition of no solvent or can also be with after solvent dilution Reaction.As at this solvent that can use, as long as be inert molten to carboxylic esterification reaction Agent is just not particularly limited.
The preferably usage amount of solvent suitably should be adjusted according to the viscosity of obtained resin, purposes Joint, preferably with relative to solid constituent 100 weight portion be 90～30 weight portions, more preferably 80～ The mode of 50 weight portions uses.
If particular instantiation, then can enumerate such as: toluene, dimethylbenzene, ethylbenzene, tetramethyl The aliphatic solvents such as the aromatic hydrocarbon solvents such as benzene, hexane, octane, decane and as they The petroleum ether of mixture, unleaded gas, solvent naphtha etc., esters solvent, ether solvent, Ketones solvent etc..
As esters solvent, can enumerate: the second such as ethyl acetate, propyl acetate, butyl acetate Ring-type esters, ethylene glycol monomethyl ether acetate, the diethylene glycol lists such as dialkylaminobenzoic acid esters, gamma-butyrolacton Methyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, Triethylene glycol ethyl ether monoacetate, Diethylene glycol monobutyl ether monoacetate, propylene glycol methyl ether acetate, butanediol monomethyl ether acetic acid Single alkylene glycol monoalkyl ethers monoacetate class such as ester or pol yalkylene glycol monoalkyl ether list second Esters of gallic acid, dialkyl glutarate, dialkyl succinate, hexanedioic acid dialkyl ester etc. are polynary Alkyl-carboxylic acid esters etc..
As ether solvent, can enumerate: alkyl ether, the second two such as ether, ethyl-butyl ether Diethylene glycol dimethyl ether, ethylene glycol diethyl ether, dimethyl ether, dipropylene glycol diethyl ether, three second The ring-type ethers such as glycol ethers, oxolane etc. such as glycol dimethyl ether, triethylene glycol diethyl ether.
As ketones solvent, can enumerate: acetone, butanone, methyl propyl ketone, methyl Isobutyl ketone, Ketohexamethylene, isophorone etc..
In addition, can other reactive compounds (B) described later etc. individually or be mixed with Machine solvent is carried out.In this case, when using as solidification compound, can be direct Use in the form of compositions, the most preferably.
During reaction, in order to promote reaction, catalyst is preferably used, about the use of this catalyst Amount, relative to reactant i.e. epoxy resin (a), carboxylic acid compound (b), the change that uses as required Compound (c) and be according to circumstances added with solvent etc. reactant total amount 100 weight portion usually 0.1～10 weight portions.Reaction temperature now is usually 60 DEG C～150 DEG C, it addition, during reaction Between be preferably 5～60 hours.As the concrete example of the catalyst that can use, example can be enumerated As: triethylamine, benzyl dimethylamine, triethyl ammonium chloride, benzyltrimethylammonium bromide, benzyl Trimethyl ammonium iodide, triphenylphosphine, antimony triphenyl, methyl triphenyl antimony, octanoic acid chromium, octanoic acid The known general base catalyst etc. such as zirconium.
It addition, as thermal polymerization inhibitor, hydroquinone monomethyl ether, 2-methyl pair are preferably used Benzodiazepines, hydroquinone, diphenylpicrylhydrazine, diphenylamines, 3,5-di-t-butyl-4-hydroxy-methylbenzene Deng.
This reaction reaches below 5mgKOH/g, excellent with the acid number of sample while suitably sampling Selecting the moment reaching below 3mgKOH/g is terminal.
As the preferred molecular weight range of so obtained reactive epoxy carboxylic acids's ester compounds (E), By GPC measure by the scope that the weight average molecular weight of polystyrene conversion is 500～50000, More preferably 1000～30000.
When this molecular weight is less than this scope, it is impossible to play the toughness of solidfied material fully, it addition, Time more excessive than this scope, viscosity raises, it is difficult to coating etc..
Then, acid addition operation is described in detail.Acid addition operation is in order to previous operation In reactive epoxy carboxylic acids's ester compounds (E) of obtaining introduces carboxyl, thus it is many to obtain reactivity Unit carboxylic acid compound (A) and carry out.That is, multi-anhydride (d) is made to produce with being reacted by carboxylic esterification Raw hydroxyl carries out additive reaction, introduces carboxyl from there through ester bond.
As the concrete example of multi-anhydride (d), as long as such as molecule has the change of acid anhydride structure Compound the most all can use, particularly preferred alkaline aqueous solution developability, thermostability, hydrolytic resistance Etc. excellent succinic anhydrides, phthalic anhydride, tetrabydrophthalic anhydride, hexahydro neighbour's benzene two Formic anhydride, itaconic anhydride, 3-methyl-tetrahydro phthalic anhydride, 4-methyl-hexahydro O-phthalic Anhydride, trimellitic anhydride or maleic anhydride.
The reaction making multi-anhydride (d) addition can be by adding in above-mentioned carboxylic esterification reactant liquor Multi-anhydride (d) is carried out.Addition suitably should change according to purposes.
About the addition of multi-anhydride (d), such as will be by the reactive polybasic carboxylic acid of the present invention When compound (A) uses as the resist of alkali developable, preferably put into make to finally give anti- The solid constituent acid number (according to JISK5601-2-1:1999) of answering property polycarboxylic compounds (A) reaches Value of calculation to 40～120mg KOH/g, more preferably up to 60～120mg KOH/g Multi-anhydride (d).Solid constituent acid number now within the range time, the photonasty tree of the present invention The alkaline aqueous solution developability of oil/fat composition demonstrates good developability.That is, for good The span of control of patternability and excessively development is big, and will not remain the anhydride of excess.
During reaction, in order to promote reaction, catalyst is preferably used, the usage amount phase of this catalyst For reactant, i.e. by epoxide (a), carboxylic acid compound (b) and the change used as required Reactive epoxy carboxylic acids's ester compounds (E) that compound (c) obtains and multi-anhydride (d), according to circumstances Total amount 100 weight portion of the reactant of the solvent etc. added is usually 0.1～10 weight portions.Now Reaction temperature be usually 60 DEG C～150 DEG C, it addition, the response time is preferably 5～60 hours. As the concrete example of the catalyst that can use, can enumerate such as: triethylamine, benzyl diformazan Amine, triethyl ammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenyl Phosphine, antimony triphenyl, methyl triphenyl antimony, octanoic acid chromium, zirconium caprylate etc..
This acid additive reaction can be reacted under condition of no solvent or can also be with after solvent dilution Reaction.As at this solvent that can use, as long as be inert solvent to acid additive reaction Just it is not particularly limited.It addition, use solvent in the carboxylic esterification as previous operation reacts In the case of manufacturing, under the conditions of being inert to this two reaction, solvent can not be removed And it is supplied directly to the sour additive reaction as subsequent processing.The solvent that can use can be with carboxylic The solvent phase that can use in Esterification reaction is same.
The preferably usage amount of solvent suitably should be adjusted according to the viscosity of obtained resin, purposes Joint, preferably with relative to solid constituent 100 weight portion be 90～30 weight portions, more preferably 80～ The mode of 50 weight portions uses.
In addition, can reactive compounds described later (B) etc. individually or mix organic molten Agent is carried out.In this case, when using as solidification compound, can be directly with group The form of compound uses, the most preferably.
It addition, thermal polymerization inhibitors etc. are preferably used in reacting the same of illustration with above-mentioned carboxylic esterification The material of sample.
This reaction is just reaching the acid number of setting with the acid number of product while suitably sampling Moment in the range of negative 10% is terminal.
As the preferred molecular weight ranges of reactive polycarboxylic compounds (A), pass through GPC Measure by the scope that the weight average molecular weight of polystyrene conversion is 500～50000, more preferably 1000～30000.
The reactive polycarboxylic compounds (A) use ratio in this resin combination be about 5～ About 69 weight %, preferably from about 8～about 59 weight %.
As the reactive compounds (B) that can use in the present invention, radical reaction can be enumerated The esters of acrylic acid of type, other epoxy compound species of cationoid reaction type, sensitive to this both sides The so-called reactive oligomers class such as vinyl compound class.
As the esters of acrylic acid of radical reaction type, can enumerate such as: simple function (methyl) More than acrylate, difunctionality (methyl) acrylate, trifunctional (methyl) acrylate, poly- Ester (methyl) acrylate, carbamate (methyl) acrylate oligomer, polyester (methyl) third Olefin(e) acid ester oligomer, epoxy (methyl) acrylate oligomer etc..
As simple function (methyl) acrylate, can enumerate such as: acryloyl morpholine；(methyl) Acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 4-hydroxyl fourth (methyl) acrylate of the hydroxyls such as ester；Hexamethylene-1,4-dimethanol list (methyl) acrylate, (methyl) tetrahydrofurfuryl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid tetrahydrochysene two Polycyclopentadithio.henes thiazolinyl ester, (methyl) acrylic acid dihydro dicyclopentadiene base ester, (methyl) acrylic acid Aliphatic (methyl) acrylate, (methyl) the acrylic acid benzene such as dihydro dicyclopentadiene epoxide ethyl ester Epoxide ethyl ester, phenyl (gathering) ethyoxyl (methyl) acrylate, (methyl) acrylic acid are to cumyl benzene oxygen Base ethyl ester, (methyl) acrylic acid tribromophenoxy ethyl ester, (methyl) acrylic acid thiophenyl ethyl ester, (first Base) acrylic acid 2-hydroxyl-3-phenoxy-propyl, phenylphenol (gathering) ethyoxyl (methyl) acrylate, Aromatic series (methyl) acrylate such as phenylphenol epoxy (methyl) acrylate.
As difunctionality (methyl) acrylate, can enumerate: BDO two (methyl) propylene Acid esters, 1,6-HD two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, three Cyclodecane dimethanol (methyl) acrylate, bisphenol-A (gathering) ethyoxyl two (methyl) acrylate, Bisphenol-A (gathering) propoxyl group two (methyl) acrylate, Bisphenol F (gathering) ethyoxyl two (methyl) acrylic acid Ester, ethylene glycol bisthioglycolate (methyl) acrylate, (gathering) ethylene glycol bisthioglycolate (methyl) acrylate, hydroxyl are special Two (methyl) acrylate (such as Japan's chemical medicine of the 6-caprolactone addition product of valeric acid DOPCP KAYARAD HX-220, HX-620 etc. that Co., Ltd. manufactures) etc..
As multifunctional (methyl) acrylate more than trifunctional, can enumerate: two (three hydroxyl first Base propane) four (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, trihydroxy methyl Octane three (methyl) acrylate, trimethylolpropane (gathering) ethyoxyl three (methyl) acrylate, Trimethylolpropane (gathering) propoxyl group three (methyl) acrylate, trimethylolpropane (gathering) ethyoxyl The methylol classes such as (gathering) propoxyl group three (methyl) acrylate；Tetramethylolmethane three (methyl) acrylate, Tetramethylolmethane (gathering) ethyoxyl four (methyl) acrylate, tetramethylolmethane (gathering) propoxyl group four (methyl) Acrylate, tetramethylolmethane four (methyl) acrylate, dipentaerythritol four (methyl) acrylate, The Ji Wusi such as dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate Alcohols；Three [(methyl) acrylyl oxy-ethyl] isocyanuric acid ester, caprolactone modification three [(methyl) propylene Acyloxyethyl] isocyanuric acid ester etc.；Succinate modified pentaerythritol triacrylate, succinic acid change Property Dipentaerythritol Pentaacrylate class.
As (gathering) ester (methyl) acrylate oligomer, can enumerate such as: as ethylene glycol, Diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, (gathering) The glycolss such as ethylene glycol, (gathering) propylene glycol, 1,4-butanediol, 1,6-HD, 1,8-ethohexadiol, 1,9-nonanediol, 2-methyl isophthalic acid, 8-ethohexadiol, 3-methyl isophthalic acid, 5-pentanediol, 2,4-diethyl-1,5- The straight or branched alkyl diol class such as pentanediol, 2-butyl-2-ethyl-1,3-propanediol, hexamethylene Ester ring type alkyl diol class, bisphenol-A (gathering) ethyoxyl glycol or the bisphenol-As (gathering) such as-1,4-dimethanol The diol compounds such as propoxyl group glycol and above-mentioned binary acid or (gathering) ester of the product of its anhydride Glycol and (methyl) acrylic acid product etc..
As carbamate (methyl) acrylate oligomer, can enumerate such as: make as two Alcoholic compound (such as, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, Tripropylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-HD, 1,8-ethohexadiol, 1,9-nonyl two Alcohol, 2-methyl isophthalic acid, 8-ethohexadiol, 3-methyl isophthalic acid, 5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, hexamethylene-1,4-dimethanol, Polyethylene Glycol, polypropylene glycol, Polymer with bis phenol A ethyoxyl glycol, polymer with bis phenol A propoxyl group glycol etc.) or these diol compounds with Binary acid or its anhydride (such as, succinic acid, adipic acid, Azelaic Acid, dimeric dibasic acid, isophthalic diformazan Acid, p-phthalic acid, phthalic acid or their anhydride) product polyester-diol with Organic multiple isocyanate (such as, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate etc. Chain saturated hydrocarbons isocyanates, isophorone diisocyanate, norbornene alkyl diisocyanate, Dicyclohexyl methyl hydride diisocyanate, di-2-ethylhexylphosphine oxide (4-cyclohexyl isocyanate), hydrogenated diphenyl The rings such as methane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated tolylene diisocyanate Shape saturated hydrocarbons isocyanates, 2,4 toluene diisocyanate, 1,3-XDI, PPDI, 3,3 '-dimethyl-4,4 '-biphenyl diisocyanate, 6-isopropyl-1,3-benzene Group diisocyanate, 1, the aromatic polyisocyanate such as 5-naphthalene diisocyanate) reaction, then add The product etc. becoming (methyl) acrylate of hydroxyl and obtain.
As epoxy (methyl) acrylate oligomer, for having compound and (methyl) of epoxy radicals Acrylic acid carboxylate compound.Can enumerate such as: phenol novolak-type epoxy (methyl) Acrylate, cresol novolak type epoxy (methyl) acrylate, three (hydroxyphenyl) methane type ring Oxygen (methyl) acrylate, dicyclopentadiene phenolic epoxy (methyl) acrylate, bisphenol A-type Epoxy (methyl) acrylate, bisphenol F type epoxy (methyl) acrylate, connection phenolic epoxy (methyl) Acrylate, bisphenol A novolac type epoxy (methyl) acrylate, epoxy (first containing naphthalene skeleton Base) acrylate, Biformyl type epoxy (methyl) acrylate, hetero ring type epoxy (methyl) acrylic acid Ester etc..
As vinyl compound class, can enumerate: vinyl ethers, phenylethylene, other Vinyl compound.As vinyl ethers, can enumerate: ethyl vinyl ether, propyl group second Alkene ether, hydroxyethyl vinylethers, ethylene glycol divinyl ether etc..As phenylethylene, can To enumerate: styrene, methyl styrene, ethyl styrene etc..As other vinyl chemical combination Thing, can enumerate Triallyl isocyanurate, trimethyl allyl isocyanuric acid ester etc..
It addition, as cationoid reaction type monomer, as long as typically there is the compound of epoxy radicals Just it is not particularly limited.Can enumerate such as: (methyl) glycidyl acrylate, methylglycidyl Glycerin ether, ethyl ether, butyl glycidyl ether, bisphenol A diglycidyl ether, (Union Carbide Corporation manufactures 3,4-7-oxa-bicyclo[4.1.0 formic acid 3,4-epoxycyclohexanecarboxylate " Cyracure UVR-6110 " etc.), 3,4-7-oxa-bicyclo[4.1.0 formic acid 3,4-epoxycyclohexyl ethyl ester, Vinyl cyclohexene dioxide (" ELR-4206 " that Union Carbide Corporation manufactures etc.), Fructus Citri Limoniae Alkene dioxide (" Celloxide 3000 " that Daicel chemical industrial company manufactures etc.), pi-allyl Cyclohexene dioxide, 3,4-epoxy-4-methylcyclohexyl-2-expoxy propane, 2-(3,4-epoxy hexamethylene Base)-5,5-spiral shell-3,4-7-oxa-bicyclo[4.1.0-trimethylene-formal, adipic acid two (3,4-epoxycyclohexyl) Ester (" Cyracure UVR-6128 " that Union Carbide Corporation manufactures etc.), adipic acid two (3,4- Epoxycyclohexyl-methyl) ester, double (3,4-epoxycyclohexyl) ether, double (3,4-epoxycyclohexyl-methyl) Ether, double (3,4-epoxycyclohexyl) di-ethyl siloxane etc..
Among these, as reactive compounds (B), good from polymerism, improve obtained by From the viewpoint of the intensity of sept etc., most preferably (first more than simple function, difunctionality, trifunctional Base) acrylate etc..
The reactive compounds (B) of the present invention can be used alone can also be by two or more mixing Use.As the use ratio of reactive compounds in said composition (B), many relative to reactivity Unit's carboxylic acid compound (A) 100 weight portion, preferably 30 weight portions～250 weight portions, more preferably It is 50 weight portions～200 weight portions.The usage amount of reactive compounds (B) be 30 weight portions～ During 250 weight portion, the sensitivity of said composition, obtained display element sept etc. resistance to Hot better with elastic characteristic.
As the Photoepolymerizationinitiater initiater (C) of the present invention, for active energy beam sensitivity is produced energy Reach initiation reaction polycarboxylic compounds (A) and in addition to reactive polycarboxylic compounds (A) The composition of spike of polymerization of reactive compounds (B).As such Photoepolymerizationinitiater initiater (C), can enumerate: O-acyl group oxime compound, acetophenone compound, united imidazole etc..
As O-acyl group oxime compound, can enumerate such as: ethyl ketone-1-[9-ethyl-6-(2-methyl Benzoyl)-9H-carbazole-3-base]-1-(O-acetyl group oxime), 1-[9-ethyl-6-benzoyl-9H- Carbazole-3-base]-octane-1-ketoxime-O-acetas, 1-[9-ethyl-6-(2-methyl benzoyl)-9H- Carbazole-3-base]-ethane-1-ketoxime-O-benzoate, 1-[9-normal-butyl-6-(2-ethylbenzoyl Base)-9H-carbazole-3-base]-ethane-1-ketoxime-O-benzoate, ethyl ketone-1-[9-ethyl-6-(2-methyl -4-tetrahydrofuran base benzoyl)-9H-carbazole-3-base]-1-(O-acetyl group oxime), ethyl ketone-1-[9-second Base-6-(2-methyl-4-THP trtrahydropyranyl benzoyl)-9H-carbazole-3-base]-1-(O-acetyl group oxime), Ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base benzoyl)-9H-carbazole-3-base]-1-(O- Acetyl group oxime), ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolyl) Anisoyl }-9H-carbazole-3-base]-1-(O-acetyl group oxime) etc..Wherein, preferred ethyl ketone -1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-1-(O-acetyl group oxime), ethyl ketone -1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base anisoyl)-9H-carbazole-3- Base]-1-(O-acetyl group oxime) or ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxy Heterocycle amyl group) anisoyl }-9H-carbazole-3-base]-1-(O-acetyl group oxime).These O-acyls Base oxime compound can be used alone can also be used in mixed way two or more.
As acetophenone compound, can enumerate such as: α-aminoketone compound, alpha-alcohol ketone Compound.
As α-aminoketone compound, can enumerate such as: 2-benzyl-2-dimethylamino-1-(4- Morphlinophenyl)-butane-1-ketone, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholine-4-base- Phenyl)-butane-1-ketone, 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholino propane-1-ketone etc..
As alpha-hydroxyacetone compounds, can enumerate such as: 1-phenyl-2-hydroxy-2-methyl propane -1-ketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 4-(2-hydroxyl-oxethyl) benzene Base-(2-hydroxyl-2-propyl group) ketone, 1-hydroxycyclohexyl phenyl ketone etc..
In these acetophenone compounds, preferably α-aminoketone compound, more preferably 2-benzyl-2-two Methylamino-1-(4-morphlinophenyl)-butane-1-ketone or 2-dimethylamino-2-(4-methyl benzyl Base)-1-(4-morpholine-4-base phenyl)-butane-1-ketone.
As united imidazole, can enumerate such as: 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '- Four (4-carboethoxyphenyl)-1,2 '-bisglyoxaline, 2,2 '-bis-(2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl -1,2 '-bisglyoxaline, 2,2 '-bis-(2,4 dichloro benzene bases)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '- Double (2,4,6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline etc..Among these, preferably 2,2 '-bis-(2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-bis-(2,4 dichloro benzenes Base)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline or 2,2 '-bis-(2,4,6-trichlorophenyl)-4,4 ', 5,5 '-four Phenyl-1,2 '-bisglyoxaline, more preferably 2,2 '-bis-(2,4-Dichlorobenzene base)-4,4 ', 5,5 '-tetraphenyl-1,2 '- Bisglyoxaline.
It addition, as Photoepolymerizationinitiater initiater (C), it is possible to use commercially available product, can enumerate such as: 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholino propane-1-ketone (Irgacure 907), 2-(4-methyl benzyl Base)-2-(dimethylamino)-1-(4-morphlinophenyl) butane-1-ketone (Irgacure 379), ethyl ketone -1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-1-(O-acetyl group oxime) (Irgacure OXE02) (it is Ciba Specialty Chemicals above to manufacture).
In the active energy ray-curable resin composition of the present invention, by the resin of the present invention When the solid constituent of compositions is set to 100 weight %, the usage amount of above-mentioned (C) composition is usually 1 More than weight % and below 10 weight %, more than preferably 1 weight % and below 7 weight %.
It addition, above-mentioned Photoepolymerizationinitiater initiater (C) can also be with curing accelerator (F) using.As energy Enough curing accelerators, can enumerate such as: triethanolamine, diethanolamine, N-methyl Diethanolamine, benzoic acid 2-methylamino ethyl ester, dimethylamino benzoylformaldoxime, to dimethylamino The hydrogen donors such as amine, 2-mercaptobenzothiazole such as yl benzoic acid isopentyl ester, EPA.By this When the solid constituent of bright resin combination is set to 100 weight %, the use of these curing accelerators More than amount usually 0 weight % and below 5 weight %.
As organic solvent (D), be preferably used each constituent is dissolved equably or disperses and The solvent not reacted with each constituent.As such organic solvent (D), can enumerate above-mentioned Aromatic hydrocarbon solvent, aliphatic solvent and as their petroleum ether of mixture, unleaded vapour Oil, solvent naphtha etc., esters solvent, ether solvent, ketones solvent etc., can arrange in addition Citing is such as alcohols, ethylene glycol monoalkyl ether class, propylene-glycol monoalky lether class, diethylene glycol list alkane Base ethers, diethylene glycol monoalkyl ether acetate class, dipropylene glycol monoalkylether class, dipropyl two Alcohol monoalkyl ether acetate class, lactic acid ester, aliphatic carboxylic acid esters, amide-type, ketone etc.. These organic solvents can be used alone can also be used in mixed way two or more.
As organic solvent (D), specifically, can enumerate such as: the alcohols such as benzylalcohol；Second two The ethylene glycol lists such as alcohol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether Alkyl ether；Propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol list The propylene-glycol monoalky lether classes such as butyl ether；The diethyl such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether Glycol monoalkyl ethers；Diethylene glycol monomethyl ether acetas, diethylene glycol monoethyl ether acetas, The diethylene glycol monoalky lethers such as Diethylene glycol monopropyl ether acetas, butyl carbitol acetate Acetate esters；Dipropylene glycol monomethyl ether, DPE, dipropylene glycol monopropyl ether, two The dipropylene glycol monoalkylether classes such as propylene glycol monobutyl ether；Dipropylene glycol monomethyl ether acetas, dipropyl 2-ethoxyethanol acetas, dipropylene glycol monopropyl ether acetas, Dipropylene glycol mono-n-butyl Ether acetas Deng dipropylene glycol monoalkylether acetate esters；Methyl lactate, ethyl lactate, lactic acid n-propyl ester, Isopropyl lactate, n-butyl lactate, isobutyl lactate, N_amyl lactate, isoamyl lactate etc. Lactic acid ester；Hydroxyl ethyl acetate, 2-hydroxy-2-methyl ethyl propionate, 2-hydroxy-3-methyl fourth Acetoacetic ester, ethoxy ethyl acetate, 3-methoxy methyl propionate, 3-methoxypropionate, 3- Ethoxypropanoate, 3-ethoxyl ethyl propionate, acetic acid 3-methoxybutyl, acetic acid 3-first Base-3-methoxybutyl, propanoic acid 3-methyl-3-methoxybutyl, butanoic acid 3-methyl-3-methoxyl group fourth The fat such as ester, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate Race's carboxylic acid esters；N-METHYLFORMAMIDE, N,N-dimethylformamide, N-methylacetamide, N, N- The amide-types such as dimethyl acetylamide；The ketone such as N-Methyl pyrrolidone, gamma-butyrolacton etc..These are molten Agent solvent can be used alone can also be used in mixed way two or more.
As the solid component concentration in said composition, usually more than 10 weight % and 40 weights Amount below %, more than preferably 15 weight % and below 35 weight %.By by said composition Solid component concentration is set as above-mentioned scope, it is possible to increase coating, improve film thickness uniformity, And can effectively suppress the generation of crawling.
As the viscosity at 25 DEG C of said composition, usually more than 1.0mPa s and Below 1000mPa s.It is preferably more than 2.0mPa s and 100mPa below s.By inciting somebody to action The viscosity of said composition is set as above-mentioned scope, it is possible to can keep film with good Balancing relization Even if thick uniformity and generation crawling also are able to the viscosity of spontaneously uniform degree.
As what the active energy ray-curable resin composition of the present invention used as required Alkali soluble resin (G), such as can be by having the monomer of hydroxyl, having olefinic double bond Anhydride, have the monomer of carboxyl, the monomer with epoxy radicals etc., have phenolic hydroxyl group monomer, Have sulfonic monomer, other monomer, above-mentioned simple function (methyl) acrylic ester copolymer manufacture.
As the concrete example of the monomer with hydroxyl, can enumerate: (methyl) acrylic acid 2-hydroxyl Ethyl ester, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 3-hydroxy propyl ester, (methyl) third Olefin(e) acid 4-hydroxybutyl, (methyl) acrylic acid 5-hydroxyl pentyl ester, (methyl) acrylic acid own ester of 6-hydroxyl, (methyl) acrylic acid 4-hydroxycyclohexyl, neopentyl glycol single (methyl) acrylate, (methyl) propylene Acid 3-chlorine-2-hydroxyl propyl ester, glycerol list (methyl) acrylate, 2-hydroxyethyl vinyl ether, 4- Hydroxybutyl vinyl ether, cyclohexanediol mono vinyl ether, 2-hydroxyethyl allyl ether, N- Methylol (methyl) acrylamide, double (methylol) (methyl) acrylamides of N, N-etc..
As the concrete example of the anhydride with olefinic double bond, can enumerate: maleic anhydride, clothing health Ice drops in anhydride, citraconic anhydride, phthalic anhydride, 3-methyl nadic anhydride, methyl-5- Sheet alkene-2,3-dicarboxylic acid anhydride, 3,4,5,6-tetrabydrophthalic anhydride, cis-1,2,3,6-tetrahydrochysene neighbour's benzene Dicarboxylic acid anhydride, 2-butylene-1-base-succinic anhydrides etc..
As the concrete example of the monomer with carboxyl, can enumerate: acrylic acid, methacrylic acid, Vinyl acetic acid .beta.-methylacrylic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid or their salt.
As the concrete example of the monomer with epoxy radicals, can enumerate: (methyl) acrylic acid shrinks sweet Grease, acrylic acid 3,4-epoxycyclohexanecarboxylate.
As having the monomer of phenolic hydroxyl group, can enumerate o-hydroxystyrene, a hydroxy styrenes, 4-Vinyl phenol etc..Furthermore it is possible to enumerate more than one hydrogen atom of the phenyl ring of these monomers By alkyl such as methyl, ethyl, normal-butyls；The alkoxyls such as methoxyl group, ethyoxyl, n-butoxy； Halogen atom；The haloalkyl that more than one hydrogen atom of alkyl is substituted with halogen atoms；Nitro； Cyano group；The substituted monomer such as amide groups.
As having sulfonic monomer, can enumerate: vinyl sulfonic acid, styrene sulfonic acid, (first Base) allyl sulphonic acid, 2-hydroxyl-3-(methyl) allyloxy propane sulfonic acid, (methyl) acrylic acid-2-sulfo group Ethyl ester, (methyl) acrylic acid-2-sulphopropyl, 2-hydroxyl-3-(methyl) acryloxy propane sulfonic acid, 2-(methyl) acrylamide-2-methylpro panesulfonic acid etc..
As other monomer, can enumerate: hydrocarbon belongs to olefines, vinyl ethers, isopropenyl Ethers, allyl ether series, vinyl ester, pi-allyl esters, (methyl) esters of acrylic acid, (first Base) acrylic amide, aromatic ethenyl compound, chloro-alkenes class, conjugated diene.These Compound can contain functional group, as functional group, such as carbonyl, alkoxyl can be enumerated Deng.In particular it is preferred that (methyl) esters of acrylic acid, (methyl) acrylic amide, because of by combining The excellent heat resistance of the sept that thing is formed.
During by alkali soluble resin (G) copolymerization, can be by existing at polymerization initiator in a solvent Lower by incompatible for unsaturated compound radical polymerization manufacture.Above-mentioned solvent can be used, can be independent Use can also be used in mixed way two or more.
As being used for manufacturing the polymerization initiator used in the polyreaction of alkali soluble resin (G), The commonly known material as radical polymerization initiator can be used.Draw as radical polymerization Send out agent, can enumerate such as: 2,2 '-azodiisobutyronitrile (AIBN), 2, double (2, the 4-diformazans of 2 '-azo Base valeronitrile), the azo-compound such as 2,2 '-azo double (4-methoxyl group-2,4-methyl pentane nitrile)；Peroxidating Benzoyl, lauroyl peroxide, the peroxidating pivalic acid tert-butyl ester, 1,1 '-bis(t-butylperoxy) The organic peroxides such as hexamethylene and hydrogen peroxide.Peroxide is used to draw as radical polymerization When sending out agent, peroxide and reducing agent can be used together thus obtain oxidation-reduction type and cause Agent.
In the polyreaction being used for manufacturing alkali soluble resin (G), for Molecular regulator amount, can To use molecular weight regulator.As molecular weight regulator, can enumerate such as: chloroform, four The halogenated hydrocarbons such as carbon tetrabromide；N-hexyl mercaptan, n octylmercaptan, n-dodecyl mercaptan, uncle The thio-alcohol such as lauryl mercaptan, TGA；Dimethyl disulfide xanthate, curing The xanthic acid esters such as diisopropyl xanthate；Terpinolene, α-methylstyrenedimer etc..
As the monomer that there is hydroxyl relative to above-mentioned, there is the anhydride of olefinic double bond, there is carboxylic The monomer of base, the monomer with epoxy radicals etc., have phenolic hydroxyl group monomer, have sulfonic Monomer etc. have the monomer (e) of reactive group, have and can be bonded with above-mentioned reactive group Functional group and the compound (f) of olefinic double bond, such as following combination can be enumerated.
(1) relative to having the monomer (e) of hydroxyl, there is the anhydride (f) of olefinic double bond；
(2) relative to having the monomer (e) of hydroxyl, there is the chemical combination of NCO and olefinic double bond Thing (f)；
(3) relative to having the monomer (e) of hydroxyl, there is the compound of chlorine acyl group and olefinic double bond (f)；
(4) relative to having the anhydride (e) of olefinic double bond, there is the compound of hydroxyl and olefinic double bond (f)；
(5) relative to having the monomer (e) of carboxyl, there is the compound of epoxy radicals and olefinic double bond (f)；
(6) relative to having the monomer (e) of epoxy radicals, there is the compound of carboxyl and olefinic double bond (f)。
As the concrete example of the anhydride with olefinic double bond, above-mentioned example can be enumerated.
As the concrete example of the compound with NCO and olefinic double bond, can enumerate 2-(methyl) acryloyloxyethyl isocyanate, 1,1-(double (methyl) acryloyloxymethyl) ethyl Isocyanates etc..
As the concrete example of the compound with chlorine acyl group and olefinic double bond, (methyl) can be enumerated Acryloyl chloride.
As the concrete example of the compound with hydroxyl and olefinic double bond, above-mentioned tool can be enumerated There is the example of the monomer of hydroxyl.
As the concrete example of the compound with epoxy radicals and olefinic double bond, can enumerate above-mentioned There is the example of the monomer of epoxy radicals.
As the concrete example of the compound with carboxyl and olefinic double bond, above-mentioned tool can be enumerated There is the example of the monomer of carboxyl.
Make copolymer and there is the functional group and the change of olefinic double bond can being bonded with reactive group During compound (f) reaction, as the solvent used in reaction, it is possible to use the synthesis of above-mentioned copolymer The solvent of middle illustration.
Additionally, it is preferred that cooperation polymerization inhibitor.As polymerization inhibitor, it is possible to use public inhibition Agent, specifically can enumerate 2,6 ditertiary butyl p cresol.
Furthermore it is possible to add catalyst, nertralizer.Such as, make to have the copolymer of hydroxyl with When there is the compound reaction of NCO and olefinic double bond, it is possible to use tin compound etc.. As tin compound, can enumerate: dibutyl tin laurate, double (maleic mono-ester) dibutyl Stannum, tin dilaurate dioctyl tin, double (maleic mono-ester) dioctyl tin, dibutyltin diacetate etc..
When making the monomer with hydroxyl and the compound with chlorine acyl group and olefinic double bond react, can To use base catalyst.As base catalyst, can enumerate: triethylamine, pyridine, two Monomethylaniline., tetramethylurea etc..
As the Mw of alkali soluble resin (G), preferably 2 × 103～1 × 105, more preferably 5×103～5 × 104.By the Mw of alkali soluble resin (G) is set as 2 × 103~ 1×105, radiosensitivity and the developability that can improve said composition (accurately form desired The characteristic of pattern form).
Additionally, can be as required in the active energy ray-curable resin composition of the present invention Add surfactant, levelling agent, defoamer, filler, UV absorbent, light stabilizer, Antioxidant, polymerization inhibitor, cross-linking agent, adhesion aid, pigment, dyestuff etc., give mesh respectively Mark functional.As levelling agent, defoamer, fluorochemical, silicone can be enumerated Compound, acrylic compounds etc., as UV absorbent, can enumerate benzotriazole Compound, benzophenone compound, compound in triazine class etc., as light stabilizer, permissible Enumerate hindered amine compound, benzoate compounds etc., as antioxidant, Ke Yilie Lift phenolic compound etc., as polymerization inhibitor, p methoxy phenol, methyl can be enumerated to benzene two Phenol, hydroquinone etc., as cross-linking agent, can enumerate above-mentioned polyisocyanates, melamine Amines etc..
In addition, (so-called lazy as the resinae that active energy beam is not shown reactivity Property polymer), it is possible to use such as other epoxy resin, phenolic resin, polyurethane resin, poly- Ester resin, ketone resin, cresol resin, xylene resin, diallyl phthalate tree Fat, styrene resin, guanamine resin, natural and synthetic rubber, acrylic resin, polyene Hydrocarbon resin and their modifier.These materials preferably in resin combination at 40 weight portions Use in following scope.
The active energy ray-curable resin composition of the present invention contains usually in the composition The reactive polycarboxylic compounds (A) of 5～69 weight %, preferably 8～59 weight %；Generally It is 3～64 weight %, other reactive compounds (B) being preferably 5～59 weight %；Generally It is 1～10 weight %, the Photoepolymerizationinitiater initiater (C) being preferably 1～7 weight %；Usually 60～ The organic solvent (D) of 90 weight %, preferably 65～85 weight %.Can contain as required 0～ Other composition of 80 weight %.
<display element sept and the forming method of light filter protecting film>
The display element sept formed by this active energy ray-curable resin composition is fitted When being included in the invention.The forming method of this display element sept is through following operation.
(1) be applied to said composition on substrate to be formed film operation,
(2) above-mentioned film at least some of is irradiated lonizing radiation operation,
(3) operation the film after above-mentioned irradiation lonizing radiation developed and
(4) operation that the film after above-mentioned development is heated.
The light filter protecting film formed by this active energy ray-curable resin composition is the most suitable It is included in the invention.As the forming method of this light filter protecting film, by this resin combination It is adjusted to proper viscosity and makes coating fluid, by this coating solution in the formation of such as light filter There is the surface of dyed layer side, formed therefrom.
The active energy ray-curable resin composition using the present invention is formed by photoetching process The method of light spacer and/or light filter protecting film illustrates.
By the known method such as roller coat, spin coating, spraying, slot coated by the activity of the present invention Energy ray curable resin composition is uniformly applied on substrate so that it is is dried and forms sense Photosensitive resin composition layer.As apparatus for coating, it is possible to use known apparatus for coating, permissible Enumerate such as: spin coater, Kohler coater, roll coater, metering bar coater, curtain coater, recessed Version coating machine and comma coater etc..
Heating makes it be dried (preliminary drying) as required.As baking temperature, preferably more than 50 DEG C, More preferably more than 70 DEG C, additionally, it is preferred that less than 150 DEG C, more preferably 120 Below DEG C.It is preferably more than 30 seconds drying time, more preferably more than 1 minute, it addition, Preferably less than 20 minutes, more preferably less than 10 minutes.
Then, active energy beam is utilized to carry out photosensitive resin composition by the photomask of regulation The exposure of nitride layer.If the active energy ray-curable resin composition of the present invention, it is then Make to be that diameter is about 5 μm～about 10 μm (area is about 20 μm2～about 100 μm2) mask open Portion, it is also possible to precision well, i.e. in diameter 6 μm～12 μm (area 30 μm2～120 μm2) In the range of formed.
As the active energy beam for exposure, as long as the resin combination of the present invention can be made Solidification is just not particularly limited.The active energy ray-curable resin composition of the present invention utilizes Active energy beam easily solidifies.Here, as the concrete example of active energy beam, Ke Yilie Lift electromagnetic wave, the α such as ultraviolet, visible ray, infrared ray, X-ray, gamma-rays, laser beam to penetrate The particle ray etc. such as line, β ray, electron ray.If it is considered that the applicable purposes of the present invention, Then among these active energy beams, preferably ultraviolet, laser rays, visible ray or electronics is penetrated Line.As light exposure, it is not particularly limited, preferably 20～1000mJ/cm2。
Then, utilize developer solution to remove unexposed portion, develop.Here, for development Developer solution can use organic solvent, but aqueous alkali is preferably used.Can be as developer solution The aqueous alkali used can be enumerated such as: sodium hydroxide, potassium hydroxide, sodium carbonate, carbonic acid The aqueous solution of the inorganic base such as potassium, sodium bicarbonate；Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide Aqueous solution Deng organic base.These aqueous alkalis may be used singly or in combin two kinds with On, alternatively, it is also possible to add use anion surfactant, cationic surfactant, The water such as the surfactant such as amphoteric surfactant, nonionic surfactant, methanol, ethanol Solubleness organic solvent.From the viewpoint of obtaining suitable developability, the alkali in aqueous alkali is dense Degree is preferably 0.1～5 weight %.As developing method, there are impregnation method, spray mode, liquid ExecuteMode, vibration impregnation method, preferably spray mode.The temperature of developer solution preferably exists 25 DEG C～40 DEG C uses.Developing time suitably determines according to the dissolubility of thickness, resist.
In order to solidify more reliably, can carry out as required heating (baking).Toast Time, as baking temperature, preferably 120 DEG C～250 DEG C.Baking time is according to firing equipment Kind and different, carry out the most on hot plate can be set as 5 minutes～30 during heating process Minute, carry out in an oven can be set as during heating process 30 minutes～90 minutes.Can also Use the substep baking etc. carrying out more than twice heating process.
As the thickness of sept formed, preferably 0.1 μm～8 μm, more preferably 0.1 μm～ 6 μm, particularly preferred 0.1 μm～4 μm.
The sept formed in this forming method be without crawling, have flatness highly, Soft and that plastic deformation is little sept.Can be suitable for liquid crystal display cells, organic EL shows Show the display elements such as element.
It addition, as light filter protecting film, preferably 0.5 μm～100 μm, more preferably 1 μm～ 10μm.When thickness is too small, it is difficult to obtain the performance required by the protecting film such as barrier, flatness, When thickness is excessive, sometimes the transparency etc. performance reduce.
Embodiment
Hereinafter, illustrate in greater detail the present invention by embodiment, but the present invention is not real by these Execute the restriction of example.It addition, in embodiment, except as otherwise noted, " part " represents weight portion, " % " represents weight %.
Softening point, epoxide equivalent, acid number measure under the following conditions.
1) epoxide equivalent: by being measured according to the method for JIS K7236:2001.
2) softening point: by being measured according to the method for JIS K7234:1986.
3) acid number: by being measured according to the method for JIS K0070:1992.
Synthesis example 1-1
With thermometer, reflux condenser, blender glass container in put into the double (hydroxyl of 2,6- Methyl) paracresol 168 weight portion (1.0 moles) and alpha-Naphthol 1008 weight portion (7.0 moles), add Enter hexone 1500mL as solvent, in a nitrogen atmosphere, at room temperature stir Mix.It is slowly added p-methyl benzenesulfonic acid 1.7 weight in the way of attention heating, liquid temperature are less than 50 DEG C Amount part (being 1.0 weight % relative to paracresol dihydroxymethyl compound).Add in oil bath after interpolation Heat, to 50 DEG C, is reacted 2 hours, is subsequently adding hexone 500mL, is transferred to point Liquid funnel, washes.After being washed to rinse water display neutrality, under reduced pressure concentration of organic layers, Thus obtain faint yellow goo 370 weight portion.Softening temperature (JIS K2425 ring and ball method) is 112 DEG C, hydroxyl equivalent (g/mol) is 138.
Then, with thermometer, agitating device, Dropping funnel and generation water separation device In 1L reactor, put into above-mentioned faint yellow goo (hydroxyl equivalent (g/mol) 138) 138 weight portions With chloropropylene oxide 460 weight portion, carry out nitrogen displacement.Then, by 5 hours dropping 48 weight % Sodium hydrate aqueous solution 85 weight portion.During dropping reaction temperature 60 DEG C, pressure 100～ By the azeotropic of the water of generation water and sodium hydrate aqueous solution with chloropropylene oxide under conditions of 150mmHg Being rejected to continuously outside reaction system, chloropropylene oxide is back in system.Then, decompression is lower reclaims The unreacted chloropropylene oxide of excess, is subsequently adding hexone 500mL, cleans extremely The water layer display neutrality of the water of 100mL.Under reduced pressure concentrate hexone layer, thus Obtain epoxy resin product (EP1) 170 weight portion of faint yellow solid.
The softening temperature (JIS K2425) of this product is 75 DEG C, and epoxide equivalent (g/mol) is 213. It addition, this product is carried out gpc analysis as a result, the composition amounts of epoxy resin of formula (1) is 57 Weight %.Epoxy resin product obtains M in mass spectrum (FAB-MS)+588, thereby confirm that and have The composition of following structure is main component.
Synthesis example 1-2
With thermometer, reflux condenser, blender glass container in put into the double (hydroxyl of 2,6- Methyl) paracresol 168 weight portion (1.0 moles) and betanaphthol 1008 weight portion (7.0 moles), add Enter hexone 1500mL as solvent, in a nitrogen atmosphere, at room temperature stir Mix.It is slowly added p-methyl benzenesulfonic acid 1.7 weight in the way of attention heating, liquid temperature are less than 50 DEG C Amount part (being 1.0 weight % relative to paracresol dihydroxymethyl compound).Add in oil bath after interpolation Heat, to 80 DEG C, is reacted 2 hours, is subsequently adding hexone 500mL, is transferred to point Liquid funnel, washes.After being washed to rinse water display neutrality, under reduced pressure concentration of organic layers, Thus obtain yellow solid 371 weight portion.Softening temperature (JIS K2425 ring and ball method) is 113 DEG C, Hydroxyl equivalent (g/mol) is 138.
Then, with thermometer, agitating device, Dropping funnel and generation water separation device In 1L reactor, put into above-mentioned yellow solid (hydroxyl equivalent (g/mol) 138) 138 weight portions and table Chloropharin 460 weight portion, carries out nitrogen displacement, then by 5 hours dropping 48 weight % hydroxides Sodium water solution 85 weight portion.At reaction temperature 60 DEG C, pressure 100～150mmHg during dropping Under conditions of arrange continuously with the azeotropic of chloropropylene oxide by generating water and the water of sodium hydrate aqueous solution Except, in addition to reaction system, chloropropylene oxide is back in system.Then, decompression is lower reclaims excess not The chloropropylene oxide of reaction, is subsequently adding hexone 500mL, cleans the water to 100mL Water layer display neutrality.Under reduced pressure concentrate methyl iso-butyl ketone (MIBK) layer, thus obtain pale yellow colored solid Epoxy resin product (EP2) 169 weight portion of body.The softening temperature of this product is 76 DEG C, epoxy Equivalent (g/mol) is 214.It addition, the composition amounts of the epoxy resin of formula (1) in product is 55 weights Amount %, is M in mass spectrum (FAB-MS)+588。
Synthesis example 1-3
With thermometer, reflux condenser, blender glass container in implement nitrogen purging While, addition naphthols-cresol novolac resin (when making naphthols and cresol and aldehyde reaction, During in naphthols and cresol, naphthol content is 70 mass %, whole naphthols, alpha-Naphthol is 5 mass % Under the conditions of reaction and the resin that obtains: softening point 110 DEG C) 160 weight portions, chloropropylene oxide 370 weight Part (being 4 molar equivalents relative to phenolic resin), dimethyl sulfoxide 37 weight portion, under agitation Dissolve, be warming up to 40 DEG C～45 DEG C.Then, the sodium hydroxide of lamellar was added by several times with 90 minutes 41 weight portions, react 2 hours, 70 DEG C of reactions 1 hour at 40 DEG C the most further.Reaction After end, wash with water 500 weight portion, use rotary evaporator under reduced pressure from oil reservoir In be distilled off excess chloropropylene oxide equal solvent class.Hexone is added in residue 500 weight portions, are warming up to 70 DEG C.Under agitation add the sodium hydrate aqueous solution of 30 weight % 10 weight portions, carry out reaction in 1 hour, and the rinse water then carrying out being washed to oil reservoir is neutrality, Rotary evaporator is used under reduced pressure hexone to be distilled off from the solution obtained Deng, thus obtain epoxy resin product (EP3) 196 weight portion.
The softening temperature of this product is 93 DEG C, and epoxide equivalent (g/mol) is melting at 233,150 DEG C Melt-viscosity (ICI melt viscosity 1 cone) is 1.3Pa s.It addition, in 13C-NMR, 74-76ppm The total amount of peak area be 64:36 with the ratio of the total amount of the peak area of 68～71ppm.
Embodiment 1-1～1-6
[preparation of reactive polycarboxylic compounds (A)]
Synthesis example 1-1 as epoxy resin (a) of amount described in addition table 1～1-3 obtain The acrylic acid as compound (b) (be called for short AA, Mw=72) of amount described in epoxy resin, table 1, The dihydromethyl propionic acid as compound (c) (being called for short DMPA, Mw=134) of amount described in table 1. Add the triphenylphosphine 3g as catalyst, the propylene glycol monomethyl ether monoacetate as solvent makes Solid constituent reaches 80 weight % of reactant liquor, reacts 24 hours at 100 DEG C, thus obtains anti- Answering property epoxy carboxylic acids's ester compounds (E) solution.With solid constituent acid number (AV:mgKOH/g) for 5 Following as reaction end, carry out next reaction.About acid value measuring, enter in reaction solution Row measures, and is converted into the acid number with solid component meter.
Then, reactive epoxy carboxylic acids's ester compounds (E) solution adds amount described in table 1 As the tetrabydrophthalic anhydride (being called for short THPA) of multi-anhydride (d) and as the third of solvent Glycol monomethyl ether monoacetate makes solid constituent reach 65 weight %, is heated to 100 DEG C, then Carry out acid additive reaction, thus obtain reactive polycarboxylic compounds (A) solution.Solid is become Acid number (AV:mgKOH/g) is divided to be recorded in table 1.
Comparative example 1-1,1-2: compare the preparation with reactive polycarboxylic compounds
Add connection phenol-type epoxy resin NC-3000H (Japan chemical medicine system, the ring of amount described in table 1 Oxygen equivalent 288g/eq), the cresol novolak type epoxy resin of amount described in table 1 EOCN-103S (Japan chemical medicine system, epoxide equivalent 200g/eq), the conduct of amount described in table 1 The acrylic acid of compound (b).Add the triphenylphosphine 3g as catalyst, the propylene glycol as solvent Monomethyl ether monoacetate makes solid constituent reach 80 weight % of reactant liquor, reacts 24 at 100 DEG C Hour, thus obtain carboxylate compound solution.With solid constituent acid number (AV:mgKOH/g) For below 5mgKOH/g as reaction end, carry out next reaction.
Then, reactive epoxy carboxylic acids's ester compounds solution adds the work of amount described in table 1 For the tetrabydrophthalic anhydride (being called for short THPA) of multi-anhydride and the propylene glycol list first as solvent Ether monoacetate makes solid constituent reach 65 weight %, is heated to 100 DEG C, then carries out acid and adds Become reaction, thus obtain comparing with reactive polycarboxylic compounds's solution.By solid constituent acid Value (AV:mgKOH/g) is recorded in table 1.
Comparative example 1-3: compare the preparation with reactive caprolactone modification polycarboxylic compounds
Add 200g cresol novolak type epoxy resin EOCN-103S (Japan's chemical medicine strain formula meeting Society's system, epoxide equivalent 200g/eq), 58g acrylic acid, 40g dihydromethyl propionic acid, 3g is as urging The triphenylphosphine of agent, adds the propylene glycol monomethyl ether monoacetate as solvent and makes solid constituent Reach 80 weight % of reactant liquor, react 24 hours at 100 DEG C.Then, add 68g ε-oneself Lactone, reacts 8 hours.Then, the 91g tetrahydrophthalic acid as multi-anhydride is added Acid anhydride (being called for short THPA) and the propylene glycol monomethyl ether monoacetate as solvent make solid constituent reach 65 weight %, are heated to 100 DEG C, then carry out acid additive reaction, thus obtain comparing with reaction
Property caprolactone modification polycarboxylic compounds's solution.Solid constituent acid number (AV:mgKOH/g) is
70mgKOH/g。
[table 1]
Table 1 embodiment 1 and the reactive polycarboxylic compounds of comparative example 1
It should be noted that the unit of the numerical value of each composition in table 1 is g (gram).
It addition, the details of each composition used in the compositions of embodiment and comparative example is as follows Shown in.
<reactive compounds (B)>
B-1: dipentaerythritol acrylate and the mixture of Dipentaerythritol Pentaacrylate (KAYARAD DPHA, Japan's chemical medicine manufacture)
<Photoepolymerizationinitiater initiater (C)>
C-1: ethyl ketone-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-1-(O-acetyl Base oxime) (Irgacure OXE02, BASF AG manufacture)
<organic solvent (D)>
PGMEA: propylene glycol methyl ether acetate
DEGDM: diethylene glycol dimethyl ether
<other optional member>
<surfactant (H)>
H-1: organosilicone surfactants (eastern beautiful DOW CORNING organosilicon company system, SH8400FLUID)
<preparation of said composition>
Embodiment 2-1
Obtain in embodiment 1-1 comprising the amount being equivalent to 100 weight portions (solid constituent) is anti- Answer in the product solution as reactive polycarboxylic compounds (A) and add as reactive compounds (B) (B-1) 100 weight portion, as Photoepolymerizationinitiater initiater (C) (C-1) 10 weight portion and PGMEA, DEGDM as organic solvent reach desired solid component concentration, mixed Cooperation is (H-1) 0.2 weight portion of surfactant (H), is entered by the membrane filter of aperture 0.2 μm Row filters, and thus prepares said composition (S-1).It should be noted that organic molten in table 2 The numerical value of agent is the weight ratio of PGMEA and DEGDM.
Embodiment 2-2～2-6 and comparative example 2-1～2-3
In addition to the kind of each composition and use level (weight portion) are become as described in table 2, with Embodiment 2-1 similarly operates, and prepares embodiment 2-2～2-6 and comparative example 2-1～2-3 Compositions.It should be noted that the numerical value of the organic solvent in table 2 be PGMEA with The weight ratio of DEGDM.
[table 2]
<evaluation>
For embodiment 2-1～2-6 and the compositions of comparative example 2-1～2-3 and by its film The sept formed carries out following evaluation.Evaluation result is collected and is shown in Table 3.
(viscosity)
Use E type viscometer (Toki Sangyo Co., Ltd.'s system, TV-200), at measuring 25 DEG C The viscosity (mPa s) of each compositions.
(solid component concentration)
Accurate weighing said composition 0.3g in aluminum dish, adds diethylene glycol dimethyl ether about 1g, so After 175 DEG C on hot plate be dried 60 minutes, by be dried before and after weight obtain in said composition Solid component concentration (weight %).
(outward appearance of film)
Use slotting die coaters (Co., Ltd.'s Techno Machine system, physics and chemistry die head), 100 × 100mm formed chromium film glass on be coated with said composition, drying under reduced pressure to 0.5 torr, Then 100 DEG C of preliminary dryings 2 minutes on hot plate, thus film is formed, then with 200mJ/cm2 Light exposure be exposed, be consequently formed from formed chromium film glass upper surface thickness be The film of 4 μm.Under sodium vapor lamp, observe by the naked eye the outward appearance of this film.Now, investigate whole Uneven (or many be upwardly formed in coating direction or the side that intersects with it of striated in film The linear inequality of bar), vaporific inequality (cloud form uneven), pin trace are uneven (supports at substrate and formed on pin Point-like is uneven) appearance situation.The situation almost not observing any one these inequalities is judged For " zero (well) ", it will be observed that the situation of any one inequality is judged as that " △ is (slightly on a small quantity Difference) ", situation about substantially observing is judged as " × (poor) ".
(flatness)
Pin contact measuring machine (Tokyo Precision Co., Ltd manufactures, SURFCOM) is used to measure logical The thickness of the film on the glass of the formation chromium film crossing aforesaid way making.Film thickness uniformity is passed through Measure the thickness of 9 measuring points and calculated by following formula.For 9 measuring points, if substrate is short When direction of principal axis is X, long axis direction is Y, (X [mm], Y [mm]) be (50,10), (50,20), (50,30)、(50,40)、(50,50)、(50,60)、(50,70)、(50,80)、(50,90).Film When thick uniformity is less than 2%, it is judged that thickness thickness has good uniformity.
Film thickness uniformity (%)=FT (X, Y) max-FT (X, Y) min} × 100/{2 × FT (X, Y)avg.}
In above formula, FT (X, Y) max is the maximum in the thickness of 9 measuring points, FT (X, Y) minima during min is the thickness of 9 measuring points, FT (X, Y) avg. is 9 measuring points Meansigma methods in thickness.
(high speed coatability)
The alkali-free glass substrate of 100mm × 100mm use slit coater be coated, As application conditions, substrate is 150 μm with the distance of nozzle, is 2.5 μm with the thickness after exposure Mode spray coating fluid from nozzle, the translational speed of nozzle is in 120mm/ second～200mm/ second In the range of change, and find out that not produce the striated that caused by crawling (liquid cuts れ) uneven Big speed.Now, even if when the most not producing striated inequality with speed more than the 180mm/ second, May determine that as coping with high-speed coating.
(radiosensitivity)
Sputtering at 100mm × 100mm has use spin-coating method coating on the glass substrate of ITO to be somebody's turn to do Compositions, then preliminary drying 3 minutes on the hot plate of 90 DEG C, are consequently formed the painting of thickness 3.5 μm Film.Then, across the circle being formed with diameter 12 μm as peristome on obtained film The photomask of shape pattern also uses ultraviolet exposure apparatus according (Co., Ltd. O ak makes institute, model HMW-680GW) it is exposed.Then, the potassium hydroxide aqueous solution utilizing 0.05 mass % exists 25 DEG C develop 60 seconds, then with pure water clean 1 minute, then in the baking oven of 230 DEG C after Toast 30 minutes, be consequently formed the sept comprising pattern-like overlay film.Now, toast after investigation After residual film ratio (thickness (before rear baking) after thickness × 100/ exposure of the overlay film after rear baking) be Minimum exposure amount when more than 90%, using this value as sensitivity.This value is 55mJ/cm2Below Time, it may be said that sensitivity is good.
(development residue)
It addition, by visualization upper surface of base plate, confirm there is noresidue.Evaluation criterion is such as Lower described.
Zero ... noresidue
△ ... have a small amount of residue
× ... residue is many
(compression performance)
Except light exposure being set as the sensitivity being equivalent to be determined by the evaluation of above-mentioned radiosensitivity Beyond the light exposure of degree, operate in the same manner as the evaluation of radiosensitivity, shape on substrate Become to comprise the sept of cylindrical pattern.Now, when changing exposure across the diameter of photomask A diameter of 20 μm of the bottom portion after toasting after making.About this sept, use minute-pressure contracting Testing machine (FISCHERSCOPE H100C, Fisher Instruments Co., Ltd. manufacture), makes With the plane pressure head that 50 μm are square, be compressed test with the load of 50mN, measure relative to The change of the compression displacement amount of load, and by the displacement during load of 50mN and removing Displacement calculation response rate (%) during the load of 50mN.Now, response rate is more than 70% also And the displacement during load of 50mN is when being more than 0.15 μm, it may be said that be possess high response rate and Both flexibilities, the sept with compression performance.
(thermostability)
Use TG/DTA (SII Co., Ltd. manufactures, TG/DTA6200) to measure above-mentioned solidification to be coated with Film.It is documented in 250 DEG C and keeps the mass change after 1 hour.Rate of change is the least, then thermostability The best.
(total light transmittance)
The alkali-free glass substrate of 50mm × 50mm uses spin coater be coated, and reduce pressure Be dried to 0.5 torr, then on hot plate, form film with 100 DEG C of preliminary dryings 2 minutes, then with 200mJ/cm2Light exposure be exposed, be consequently formed the film that thickness is 4 μm.For having The evaluation substrate of above-mentioned cured coating film use haze meter (electricity Se Industrial Co., Ltd of Japan manufactures, TC-H3DPK) it is measured.
(resistance to thermal transmittance)
The above-mentioned evaluation substrate with cured coating film is carried out 1 hour heat treatment at 250 DEG C, and Spectrophotometer (Hitachi Ltd. manufactures, U-3310) is used to measure 400nm, 540nm The absorbance of wavelength light.
[table 3]
According to the above results it will be apparent that, compared with the compositions of comparative example 2-1～2-3, implement The active-energy containing the reactive polycarboxylic compounds (A) in the present invention of example 2-1～2-6 is penetrated The developability of line curable resin composition, curable are better, thermostability, heat resistant transparent, Flatness, flexibility, toughness are more excellent.In addition, it is found that with embodiment 2-1, embodiment 2-3 Compare with embodiment 2-5, in the preparation of reactive polycarboxylic compounds (A), also use work Embodiment 2-2 of DMPA, embodiment 2-4 and embodiment 2-6 for compound (c) have more excellent Good compression performance.
With reference to specific mode, the present invention is illustrated in detail, but for art technology Personnel are it is readily apparent that can carry out without departing from the spirit and scope of the present invention Various changes and correction.
It should be noted that the Japan Patent Shen that the application proposed based on January 30th, 2014 Please (Japanese Patent Application 2014-015809), it is quoted by quoting overall.It addition, be hereby incorporated Be incorporated herein in an integrated manner all referring to content.
Industrial applicability
The developability of the active energy ray-curable resin composition of the present invention, curable, height Speed coating is good, it is possible to form thermostability, heat resistant transparent, flatness, flexibility, tough Display element sept that property is excellent and light filter protecting film.Therefore, said composition is suitable as For being used for forming the display element sept such as liquid crystal display cells, organic EL, light filter protection The material of film.

Claims (6)

1. one kind is used for display element sept or the active energy beam of light filter protecting film Curable resin composition, it contains reactive polycarboxylic compounds (A), except reactive polynary Reactive compounds (B), Photoepolymerizationinitiater initiater (C) and organic solvent beyond carboxylic acid compound (A) (D), wherein,
Reactive polycarboxylic compounds (A) is for making to have at least two epoxy in a part The epoxy resin (a) of base and a part have more than one polymerisable ethylenically unsaturated group and The compound (b) of more than one carboxyl and a part as required have at least two The product (E) of the compound (c) of hydroxyl and more than one carboxyl further with multi-anhydride (d) The reactive polycarboxylic compounds (A) reacted and obtain,
The epoxy resin (a) in a part with at least two epoxy radicals is the ring containing naphthalene skeleton Epoxy resins.
2. as claimed in claim 1 for display element sept or light filter protecting film Active energy ray-curable resin composition, wherein,
Reactive polycarboxylic compounds (A) is for making to have at least two epoxy in a part The epoxy resin (a) of base and a part have more than one polymerisable ethylenically unsaturated group and The compound (b) of more than one carboxyl and a part have at least two hydroxyl and one The product (E) of the compound (c) of above carboxyl is reacted with multi-anhydride (d) further and is obtained Reactive polycarboxylic compounds (A),
The epoxy resin (a) in a part with at least two epoxy radicals is the ring containing naphthalene skeleton Epoxy resins,
The epoxy resin (a) in a part with at least two epoxy radicals is the ring containing naphthalene skeleton Epoxy resins.
3. as claimed in claim 1 or 2 for display element sept or light filter protection The active energy ray-curable resin composition of film, wherein, reactive compounds (B) is for being selected from Any one or two kinds in (methyl) acrylate more than simple function, difunctionality and trifunctional with On.
4. as according to any one of claims 1 to 3 for display element sept or filter The active energy ray-curable resin composition of color chips protecting film, wherein, as resin combination Use ratio in thing, relative to reactive polycarboxylic compounds (A) 100 mass parts, reaction Property compound (B) is 30 mass parts～250 mass parts.
5. a display element sept, it is by according to any one of Claims 1 to 4 Active energy ray-curable resin composition is formed.
6. a light filter protecting film, it is by the activity according to any one of Claims 1 to 4 Energy ray curable resin composition is formed.
CN201580005712.5A 2014-01-30 2015-01-27 Active energy ray-curable resin composition and the display element spacer and/or colour filter protective film for using the composition Expired - Fee Related CN105934713B (en)

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