CN102459171B - Oxime ester compound, radical polymerization initiator, polymerizable composition, negative resist and image pattern - Google Patents

Oxime ester compound, radical polymerization initiator, polymerizable composition, negative resist and image pattern Download PDF

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Publication number
CN102459171B
CN102459171B CN201080026403.3A CN201080026403A CN102459171B CN 102459171 B CN102459171 B CN 102459171B CN 201080026403 A CN201080026403 A CN 201080026403A CN 102459171 B CN102459171 B CN 102459171B
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unsubstituted
replace
replacement
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alkyl
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CN102459171A (en
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和田宗大
菅野真树
岩田贯
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Artience Co Ltd
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Toyo Ink SC Holdings Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • G03F7/031—Organic compounds not covered by group G03F7/029

Abstract

Disclosed are a novel oxime ester compound, which is capable of functioning as a highly sensitive radical polymerization initiator, and a curable composition using the same. Also disclosed are a negative resist material, which is appropriately usable particularly as a photoresist material, and an image pattern-forming method using said negative resist. A radical polymerization initiator (A) is represented by general formula (1). In general formula (1), R1 and R2 are selected from an alkyl group, an aryl group, a heterocyclic group, etc.; R3 to R5 are selected from a hydrogen atom, an alkyl group, etc.; R6 to R9 are selected from a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, etc.; and R10 to R14 are selected from a hydrogen atom, a cyano group, a nitro group, a haloalkyl group, a sulfinyl group, a sulfonyl group, an acyl group, etc., provided that all of R10 to R14 are not hydrogen atoms at the same time.

Description

Oxime ester compound, radical polymerization initiator, Polymerizable composition, negative resist and picture pattern
Technical field
The present invention relates to oxime ester compound, contain radical polymerization initiator, the Polymerizable composition that has used it that it forms, used its negative resist and used its picture pattern formation method.And then, relate to moulding resin, cast resin, light chisel resin, sealing agent, dental polymer resin, printing-ink, coating, press plate photoresist, printing color proof, colour filter resist, black matrix resist, liquid crystal light sensitive spacer, rear projection screen material, optical fiber, plasma display timber, dry film photoresist, printed base plate resist, scolder resist, semi-conductor photo-resist, microelectronics resist, the parts manufacture resist of micromachine, etching resist, microlens array, insulation material, hologram material, optical converter, waveguide material, outer coating agent, powder coated dose, caking agent, tackiness agent, releasing agent, optical recording medium, sticky solid, release-coated agent, use the image recording material composition of microcapsule, various devices.
Background technology
To have the function of light trigger be known (with reference to non-patent literature 1, patent documentation 1,2) to certain oxime ester compound in the past.In addition, with the optical free radical polymerization starter of composition, alpha-ketoxime ester cpds (with reference to patent documentation 3) is disclosed as the photosensitive polyimide precursor of plus or minus type.In addition, certain α is disclosed, α '-diketone oxime ester compound (with reference to patent documentation 4～8).In addition, certain adjacent acyl group oxime ester compound (with reference to patent documentation 9～13) is disclosed.In order to tackle raising and the new various techniques that propose of productivity, pursue at large the high sensitive of polymerization starter in recent years.This has been carried out to active research, result has obtained obvious progress, nonetheless, also requires further to improve susceptibility and boosts productivity.
In addition, in various fields, adopted in recent years the photo-resist method that uses photoresist.Photo-resist method is adopted with the following method conventionally: for example at the substrate surface that required image will be set by coating or form photo-sensitive resin from other base material transfer printings, follow this photo-sensitive resin across former figure irradiation energy line, after exposure, utilize solvent or alkaline aqueous solution to remove unexposed portion by development treatment, thereby form the image corresponding with this former figure.About the example that utilizes this photo-resist method, for example, certain negative resist is disclosed as the material (with reference to patent documentation 14～16) that is used to form display panel spacer.In addition, certain negative resist is disclosed as electrical and electronic parts manufacture, printed base plate material (with reference to patent documentation 17～19) for manufacture.There is the anti-corrosion agent composition as radical polymerization initiator by certain adjacent acyl group oxime ester as more high sensitive anti-corrosion agent composition is known recently, and disclose certain negative resist as the material (with reference to patent documentation 20) that is used to form display panel spacer.In addition, certain negative resist is disclosed as electrical and electronic parts manufacture, printed base plate material (with reference to patent documentation 21) for manufacture.These resists are all as anti-corrosion agent composition performance function, but in recent years in order to tackle raising and the new various techniques that propose of productivity, anti-corrosion agent composition is more and more required to have high function and new function, particularly require more high sensitive anti-corrosion agent composition, and carrying out energetically the exploitation of various anti-corrosion agent compositions.
Prior art document
Patent documentation
Patent documentation 1: United States Patent (USP) the 3rd, 558, No. 309 specification sheetss
Patent documentation 2: United States Patent (USP) the 4th, 255, No. 513 specification sheetss
Patent documentation 3: Japanese kokai publication hei 7-140, No. 658 communiques
Patent documentation 4: United States Patent (USP) the 5th, 019, No. 482 specification sheets
Patent documentation 5: Japanese kokai publication sho 62-184, No. 056 communique
Patent documentation 6: Japanese kokai publication sho 62-273, No. 259 communiques
Patent documentation 7: Japanese kokai publication sho 62-286, No. 961 communiques
Patent documentation 8: Japanese kokai publication sho 62-201, No. 859 communiques
Patent documentation 9: TOHKEMY 2001-233, No. 842 communiques
Patent documentation 10: TOHKEMY 2000-80, No. 068 communique
Patent documentation 11: Japanese Unexamined Patent Application Publication 2004-534, No. 797 communiques
Patent documentation 12: No. 2007/062963 communique of international monopoly
Patent documentation 13: No. 2008/078678 communique of international monopoly
Patent documentation 14: Japanese kokai publication hei 11-174464 communique
Patent documentation 15: TOHKEMY 2001-226449 communique
Patent documentation 16: TOHKEMY 2002-341531 communique
Patent documentation 17: Japanese kokai publication hei 10-198033 communique
Patent documentation 18: TOHKEMY 2002-236362 communique
Patent documentation 19: TOHKEMY 2002-249644 communique
Patent documentation 20: TOHKEMY 2001-261761 communique
Patent documentation 21: TOHKEMY 2001-302871 communique
Non-patent literature
Non-patent literature 1:European polymer Journal, 1970,6,933-943
Summary of the invention
Invent problem to be solved
The object of this invention is to provide and can bring into play as the novel oxime ester cpds of the function of high sensitive radical polymerization initiator and use the solidification compound of this compound, described radical polymerization initiator can produce living radical effectively by irradiation energy line, particularly light, and makes at short notice free-radical polymerised compound generation polymerization.
Another object of the present invention is to provide negative resist material and has used the picture pattern formation method of this negative resist, the curing speed of described negative resist material is exceedingly fast, and utilize energy line can perform well in high-definition pattern exposure or directly paint, in addition very excellent with the adaptation of substrate, particularly there is the alkali-developable that can perform well in photo anti-corrosion agent material.
Solve the method for problem
The present inventor has considered above-mentioned variety of issue, and repeatedly furthers investigate in order to address these problems, and result has completed the present invention., a mode of the present invention relates to the compound being represented by following general formula (1).
General formula (1)
[changing 1]
(in formula, R 1represent to replace or unsubstituted alkenyl, replace or unsubstituted alkyl, replace or unsubstituted alkoxyl group, replace or unsubstituted aryl, replace or unsubstituted aryloxy, replace or unsubstituted heterocyclic radical, replace or unsubstituted heterocyclic oxy group, replace or unsubstituted alkyl alkylthio base, replace or unsubstituted sulfur alkyl aryl, replace or unsubstituted alkyl sulphinyl, replace or unsubstituted aryl sulfonyl kia, replace or unsubstituted alkyl sulphonyl, replace or unsubstituted aryl sulfonyl, replace or unsubstituted acyl group, replace or unsubstituted acyloxy, replace or unsubstituted amino, replace or unsubstituted phosphino-, replace or unsubstituted formamyl, or replacement or unsubstituted sulfamyl.
R 2represent to replace or unsubstituted alkenyl, replace or unsubstituted alkyl, replace or unsubstituted alkoxyl group, replace or unsubstituted aryl, replace or unsubstituted aryloxy, replace or unsubstituted heterocyclic radical, replace or unsubstituted heterocyclic oxy group, replace or unsubstituted alkyl alkylthio base, replace or unsubstituted sulfur alkyl aryl, replace or unsubstituted alkyl sulphinyl, replace or unsubstituted aryl sulfonyl kia, replace or unsubstituted alkyl sulphonyl, replace or unsubstituted aryl sulfonyl, replace or unsubstituted acyloxy, or replacement or unsubstituted amino.
R 3～R 5represent independently of one another hydrogen atom, halogen atom, cyano group, nitro, replacement or unsubstituted alkenyl, replacement or unsubstituted alkyl, replacement or unsubstituted alkoxyl group, replacement or unsubstituted aryl, replacement or unsubstituted aryloxy, replacement or unsubstituted heterocyclic radical, replacement or unsubstituted heterocyclic oxy group, replacement or unsubstituted alkyl alkylthio base, replacement or unsubstituted sulfur alkyl aryl, replacement or unsubstituted acyl group or replacement or unsubstituted amino.
R 6～R 9represent independently of one another hydrogen atom, halogen atom, cyano group, haloalkyl, replace or unsubstituted alkyl, replace or unsubstituted alkoxyl group, replace or unsubstituted aryl, replace or unsubstituted aryloxy, replace or unsubstituted heterocyclic radical, replace or unsubstituted heterocyclic oxy group, replace or unsubstituted alkenyl, replace or unsubstituted alkyl alkylthio base, replace or unsubstituted sulfur alkyl aryl, replace or unsubstituted alkyl sulphinyl, replace or unsubstituted aryl sulfonyl kia, replace or unsubstituted alkyl sulphonyl, replace or unsubstituted aryl sulfonyl, replace or unsubstituted amino, or the substituting group being represented by following general formula (2).
General formula (2)
[changing 2]
(in formula, R 1' and R 2' and R 1and R 2synonym.)
R 10～R 14represent independently of one another hydrogen atom, halogen atom, cyano group, nitro, haloalkyl, replacement or unsubstituted alkyl sulphinyl, replacement or unsubstituted aryl sulfonyl kia, replacement or unsubstituted alkyl sulphonyl, replacement or unsubstituted aryl sulfonyl or replacement or unsubstituted acyl group, R 10～R 14it is not all hydrogen atom simultaneously.)
In addition, a mode of the present invention relates to R 10～R 14in at least one be the above-claimed cpd of nitro or replacement or unsubstituted acyl group.
In addition, a mode of the present invention relates to R 10～R 14in at least one be the above-claimed cpd of nitro or following general formula (3).
General formula (3)
[changing 3]
(in formula, R 15～R 19represent independently of one another hydrogen atom, halogen atom, cyano group, nitro, haloalkyl, replace or unsubstituted alkyl, replace or unsubstituted alkoxyl group, replace or unsubstituted aryl, replace or unsubstituted aryloxy, replace or unsubstituted heterocyclic radical, replace or unsubstituted heterocyclic oxy group, replace or unsubstituted alkenyl, replace or unsubstituted alkyl alkylthio base, replace or unsubstituted sulfur alkyl aryl, replace or unsubstituted acyl group, or replacement or unsubstituted amino.)
In addition, a mode of the present invention relates to R 12for the above-claimed cpd of nitro or above-mentioned general formula (3).
In addition, a mode of the present invention relates to the radical polymerization initiator (A) that contains above-claimed cpd and form.
In addition, a mode of the present invention relates to and contains the Polymerizable composition that above-mentioned radical polymerization initiator (A) and free-radical polymerised compound (B) form.
In addition, a mode of the present invention relates to and also contains the above-mentioned Polymerizable composition that sensitizing agent (C) forms.
In addition, a mode of the present invention relates to and also contains the above-mentioned Polymerizable composition that coloring components (D) forms.
In addition, a mode of the present invention relates to and also contains the above-mentioned Polymerizable composition that alkali soluble resin (E) forms.
In addition, a mode of the present invention relates to and also contains the negative resist that above-mentioned Polymerizable composition forms.
In addition, a mode of the present invention relates to the manufacture method of further above-mentioned Polymerizable composition irradiation energy line being carried out the polymkeric substance of polymerization.
In addition, a mode of the present invention relates to a kind of formation method of picture pattern, it is characterized in that, further, at the folded above-mentioned negative resist of layers on substrates, irradiation energy line carries out polymerization partly, utilizes alkaline-based developer to remove non-irradiated part.
In addition, a mode of the present invention relates to the picture pattern that method forms that forms by above-mentioned picture pattern.
The theme that the disclosed content of the application relates to No. 2009-143790, Japan's patent application Patent of on June 17th, 2009 application, enrolls to globality this application specification sheets in order to reference here.
Invention effect
Compound of the present invention is to replace and to have the alpha-ketoxime ester cpds of electron-attracting substituent as feature on the phenyl at N-phenyl carbazole skeleton, effectively to produce living radical by the irradiation of energy line, particularly light.Therefore, can be provided as radical polymerization initiator and have the compound of remarkable and good effect.
In addition, by (A) uses using compound of the present invention as radical polymerization initiator, can provide the Polymerizable composition with superperformance.Can provide at for example moulding resin from industrial, cast resin, light chisel resin, sealing agent, dental polymer resin, printing-ink, jetted ink, coating, press plate photoresist, printing color proof, colour filter resist, black matrix resist, liquid crystal light sensitive spacer, rear projection screen material, optical fiber, plasma display timber, dry film photoresist, printed base plate resist, scolder resist, semi-conductor photo-resist, microelectronics resist, the parts manufacture resist of micromachine, etching resist, microlens array, insulation material, hologram material, optical converter, waveguide material, outer coating agent, powder coated dose, caking agent, tackiness agent, releasing agent, optical recording medium, sticky solid, the oligopolymer of practicality in the fields such as release-coated agent, polymkeric substance, the Polymerizable composition that can be provided for obtaining the radical polymerization initiator of the cured article with superperformance and use it.
Particularly Polymerizable composition of the present invention can perform well in high-definition pattern exposure or directly paint, in addition, very excellent with the adaptation of substrate.Therefore, can provide the high sensitive negative resist that can perform well in photo anti-corrosion agent material and the picture pattern formation method that has used this negative resist.
Embodiment
Below, describe embodiments of the present invention in detail.
First, compound of the present invention is described.The feature of compound of the present invention is to represent as general formula (1), on the phenyl of N-phenyl carbazole skeleton, replaces and has electron-attracting substituent.In addition, by thering is this structure, even if compound of the present invention is not to the rayed of this wavelength region may and can very effectively decompose with sensitizing agent yet.Its result, composition of the present invention can be used as and effectively produces the high sensitive material of a large amount of free radicals and bring into play function.
General formula (1)
[changing 4]
In general formula, R 1for replacing or unsubstituted alkenyl, replace or unsubstituted alkyl, replace or unsubstituted alkoxyl group, replace or unsubstituted aryl, replace or unsubstituted aryloxy, replace or unsubstituted heterocyclic radical, replace or unsubstituted heterocyclic oxy group, replace or unsubstituted alkyl alkylthio base, replace or unsubstituted sulfur alkyl aryl, replace or unsubstituted alkyl sulphinyl, replace or unsubstituted aryl sulfonyl kia, replace or unsubstituted alkyl sulphonyl, replace or unsubstituted aryl sulfonyl, replace or unsubstituted acyl group, replace or unsubstituted acyloxy, replace or unsubstituted amino, replace or unsubstituted phosphino-, replace or unsubstituted formamyl, or replacement or unsubstituted sulfamyl.Wherein, consider as the synthetic aspect of compound, aspect of performance while using as initiator etc., preferably replace or unsubstituted alkyl, replacement or unsubstituted alkoxyl group, replacement or unsubstituted aryl, replacement or unsubstituted aryloxy or replacement or unsubstituted heterocyclic radical, more preferably replace or unsubstituted alkyl, replacement or unsubstituted aryl or replacement or unsubstituted heterocyclic radical.
As R 1in replacement or unsubstituted alkenyl, can enumerate carbon number and be 1 to 18 straight chain shape, chain, monocycle shape or condensation polycyclic shape alkenyl.In their structure, also can there are multiple carbon-carbon double bonds.As concrete example, can enumerate vinyl, 1-propenyl, allyl group, crotyl, 3-butenyl, pseudoallyl, isobutenyl, 1-pentenyl, pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, cyclopentenyl, cyclohexenyl, 1,3-butadienyl, cyclohexadienyl, cyclopentadienyl etc., but be not limited to these groups.
As R 1in replacement or unsubstituted alkyl, can enumerate carbon number and be 1 to 18 straight chain shape, chain, monocycle shape or condensation polycyclic shape alkyl; Or carbon number is 2 to 18, and according to circumstances contain straight chain shape, chain, monocycle shape or the condensation polycyclic shape alkyl of 1 above ehter bond (O-).Be 1 to 18 straight chain shape, the concrete example of chain, monocycle shape or condensation polycyclic shape alkyl as carbon number, can enumerate methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, octadecyl, sec.-propyl, isobutyl-, isopentyl, sec-butyl, the tertiary butyl, sec.-amyl sec-pentyl secondary amyl, tert-pentyl, tertiary octyl group, neo-pentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norcamphyl, bornyl, 4-decyl cyclohexyl etc., but be not limited to these groups.In addition, be 2 to 18 as carbon number, and according to circumstances contain the straight chain shape of 1 above ehter bond, the concrete example of branched-chain alkyl, can enumerate-CH 2-O-CH 3,-CH 2-CH 2-O-CH 2-CH 3,-CH 2-CH 2-CH 2-O-CH 2-CH 3,-(CH 2-CH 2-O) n-CH 3(herein, n is 1 to 8) ,-(CH 2-CH 2-CH 2-O) m-CH 3(herein, m is 1 to 5) ,-CH 2-CH (CH 3)-O-CH 2-CH 3-,-CH 2-CH-(OCH 3) 2deng, but be not limited to these groups.
Be 2 to 18 as carbon number, and according to circumstances contain 1 the above monocycle shape of ehter bond or concrete example of condensation polycyclic shape alkyl, can enumerate following group, but be not limited to these groups.
[changing 5]
As R 1in replacement or unsubstituted alkoxyl group, can enumerate carbon number and be 1～18 straight chain shape, chain, monocycle shape or condensation polycyclic shape alkoxyl group; Or carbon number is 2 to 18, and according to circumstances contain straight chain shape, chain, monocycle shape or the condensation polycyclic shape alkoxyl group of 1 above ehter bond.The straight chain shape that is 1～18 as carbon number, prop up chain, the concrete example of monocycle shape or condensation polycyclic shape alkoxyl group, can enumerate methoxyl group, oxyethyl group, propoxy-, butoxy, pentyloxy, hexyloxy, heptan oxygen base, octyloxy, the ninth of the ten Heavenly Stems oxygen base, the last of the ten Heavenly stems oxygen base, dodecyloxy, octadecane oxygen base, isopropoxy, isobutoxy, isopentyloxy, sec-butoxy, tert.-butoxy, secondary pentyloxy, tertiary pentyloxy, tertiary octyloxy, neopentyl oxygen, ring propoxy-, cyclobutoxy group, cyclopentyloxy, cyclohexyloxy, Buddha's warrior attendant alkoxyl group, norborneol oxygen base, borneol oxygen base, 4-decyl cyclohexyloxy etc., but be not limited to these groups.In addition, be 2 to 18 as carbon number, and according to circumstances contain the straight chain shape of 1 above ehter bond, the concrete example of a chain alkoxyl group, can enumerate-O-CH 2-O-CH 3,-O-CH 2-CH 2-O-CH 2-CH 3,-O-CH 2-CH 2-CH 2-O-CH 2-CH 3,-O-(CH 2-CH 2-O) n-CH 3(herein, n is 1 to 8) ,-O-(CH 2-CH 2-CH 2-O) m-CH 3(herein, m is 1 to 5) ,-O-CH 2-CH (CH 3)-O-CH 2-CH 3-,-O-CH 2-CH-(OCH 3) 2deng, but be not limited to these groups.
Be 2 to 18 as carbon number, and according to circumstances contain 1 the above monocycle shape of ehter bond or concrete example of condensation polycyclic shape alkoxyl group, can enumerate following group, but be not limited to these groups.
[changing 6]
As R 1in replacement or unsubstituted aryl, can enumerate carbon number and be 6 to 24 monocycle or condensation polycyclic aryl, as concrete example, can enumerate phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 9-anthryl, 2-phenanthryl, 3-phenanthryl, 9-phenanthryl, 1-pyrenyl, 5-naphthacenyl (naphthacenyl), 1-indenyl, 2-camomile cyclic group, 1-acenaphthenyl, 2-fluorenyl, 9-fluorenyl, 3-perylene base, o-tolyl, between tolyl, p-methylphenyl, 2, 3-xylyl, 2, 5-xylyl, Lai Ji, to cumenyl, to dodecylphenyl, to cyclohexyl phenyl, 4-xenyl, adjacent fluorophenyl, between chloro-phenyl-, to bromophenyl, p-hydroxybenzene, between carboxyl phenyl, adjacent sulfydryl phenyl, to cyano-phenyl, m-nitro base, between azido-phenyl etc., but be not limited to these groups.
As R 1in replacement or unsubstituted aryloxy, can enumerate carbon number and be 6～18 monocycle or condensation polycyclic aryloxy.As concrete example, can enumerate phenoxy group, 1-naphthyloxy, 2-naphthyloxy, 9-anthracene oxygen base, the luxuriant and rich with fragrance oxygen base of 9-, 1-pyrene oxygen base, 5-tetracene oxygen base, 1-indenes oxygen base, 2-camomile epoxy group(ing), 1-acenaphthene oxygen base, 9-fluorenes oxygen base etc., but be not limited to these groups.
As R 1in replacement or unsubstituted heterocyclic radical, aromatic series or aliphatic heterocyclic radical that can to enumerate the carbon number that contains nitrogen-atoms, Sauerstoffatom, sulphur atom, phosphorus atom be 4～24.As concrete example, can enumerate 2-thienyl (thienyl), 2-benzothienyl, naphtho-[2,3-b] thienyl, 3-thianthrenyl (チ ア Application ト レ ニ Le), 2-thienyl (チ ア Application ス レ ニ Le), 2-furyl, 2-benzofuryl, pyranyl, isobenzofuran-base, benzopyranyl, oxa-anthryl, fen thiophene base, 2H-pyrryl, pyrryl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, indolizine base, pseudoindoyl, 3H-indyl, 2-indyl, 3-indyl, 1H-indazolyl, purine radicals (プ リ ニ Le), 4H-quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolyl, cinnolines base, pteridine radicals, 4aH-carbazyl, 2-carbazyl, 3-carbazyl, β-carboline base, phenanthridinyl, 2-acridyl, perimidinyl, diaza phenanthryl, phenazinyl, phenarsazine base, isothiazolyl, phenothiazinyl, different azoles quinoline base, furazan base, 3-fen piperazine base, isochroman base, chromanyl, pyrrolidyl, pyrrolinyl, imidazolidyl, imidazolinyl, pyrazolidyl, pyrazolinyl, piperidyl, piperazinyl, indoline base, isoindoline base, quinuclidinyl, morpholinyl, thioxanthene ketone group, 4-quinolyl, 4-isoquinolyl, 3-phenothiazinyl, 2-fen thiophene base, 3-tonka bean camphor base etc., but be not limited to these groups.
As R 1in replacement or unsubstituted heterocyclic oxy group, monocycle shape or condensation polycyclic shape heterocyclic oxy group that can to enumerate the carbon number that contains nitrogen-atoms, Sauerstoffatom, sulphur atom, phosphorus atom be 4～18.As concrete example, can enumerate 2-furans oxygen base, 2-thiophene oxy, 2-indoxyl, 3-indolol, 2-cumarone oxygen base, 2-thionaphthene oxygen base, 2-carbazole oxygen base, 3-carbazole oxygen base, 4-carbazole oxygen base, 9-acridine oxygen base etc., but be not limited to these groups.
As R 1in replacement or unsubstituted alkyl alkylthio base, can enumerate carbon number and be 1 to 18 straight chain shape, chain, monocycle shape or condensation polycyclic shape alkyl sulfenyl.As concrete example, can enumerate methylthio group, ethylmercapto group, rosickyite base, butylthio, penta sulfenyl, own sulfenyl, pungent sulfenyl, last of the ten Heavenly stems sulfenyl, dodecane sulfenyl, octadecane sulfenyl etc., but be not limited to these groups.
As R 1in replacement or unsubstituted sulfur alkyl aryl, can enumerate carbon number and be 6～18 monocycle shape or condensation polycyclic shape artyl sulfo.As concrete example, can enumerate thiophenyl, 1-naphthalene sulfenyl, 2-naphthalene sulfenyl, 9-anthracene sulfenyl, the luxuriant and rich with fragrance sulfenyl of 9-etc., but be not limited to these groups.
As R 1in replacement or unsubstituted alkyl sulphinyl, be preferably carbon number and be 1～20 alkyl sulphinyl.As concrete example; can enumerate methylsulfinyl, ethyl sulfinyl, propyl group sulfinyl, sec.-propyl sulfinyl, butyl sulfinyl, hexyl sulfinyl, cyclohexyl sulfinyl, octyl group sulfinyl, 2-ethylhexyl sulfinyl, decanoyl sulfinyl, lauroyl sulfinyl, octadecanoyl sulfinyl, cyano methyl sulfinyl, methoxymethyl sulfinyl etc., but be not limited to these groups.
As replacing or unsubstituted aryl sulfonyl kia, be preferably carbon number and be 6～30 aryl sulfonyl kia.As concrete example, can enumerate phenyl sulfinyl, 1-naphthyl sulfinyl, 2-naphthyl sulfinyl, 2-chloro-phenyl-sulfinyl, 2-aminomethyl phenyl sulfinyl, 2-p-methoxy-phenyl sulfinyl, 2-butoxy phenyl sulfinyl, 3-chloro-phenyl-sulfinyl, 3-trifluoromethyl sulfinyl, 3-cyano-phenyl sulfinyl, 3-nitrophenyl sulfinyl, 4-fluorophenyl sulfinyl, 4-cyano-phenyl sulfinyl, 4-p-methoxy-phenyl sulfinyl, 4-methyl sulfanyl phenyl sulfinyl, 4-phenyl sulfanyl phenyl sulfinyl, 4-dimethylaminophenyl sulfinyl etc., but be not limited to these groups.
As R 1in replacement or unsubstituted alkyl sulphonyl, be preferably carbon number and be 1～20 alkyl sulphonyl.As concrete example; can enumerate methyl sulphonyl, ethylsulfonyl, sulfonyl propyl base, sec.-propyl alkylsulfonyl, butyl alkylsulfonyl, hexyl alkylsulfonyl, cyclohexyl alkylsulfonyl, octyl group alkylsulfonyl, 2-ethylhexyl alkylsulfonyl, decanoyl alkylsulfonyl, lauroyl alkylsulfonyl, octadecanoyl alkylsulfonyl, cyano methyl alkylsulfonyl, methoxymethyl alkylsulfonyl etc., but be not limited to these groups.
As R 1in replacement or unsubstituted aryl sulfonyl, be preferably carbon number and be 6～30 aryl sulfonyl.As concrete example, can enumerate phenyl sulfonyl, 1-naphthyl alkylsulfonyl, 2-naphthyl alkylsulfonyl, 2-chloro-phenyl-alkylsulfonyl, 2-aminomethyl phenyl alkylsulfonyl, 2-p-methoxy-phenyl alkylsulfonyl, 2-butoxy phenyl alkylsulfonyl, 3-chloro-phenyl-alkylsulfonyl, 3-trifluoromethyl alkylsulfonyl, 3-cyano-phenyl alkylsulfonyl, 3-nitrophenyl alkylsulfonyl, 4-fluorophenyl alkylsulfonyl, 4-cyano-phenyl alkylsulfonyl, 4-p-methoxy-phenyl alkylsulfonyl, 4-methyl sulfanyl phenyl sulfonyl, 4-phenyl sulfanyl phenyl sulfonyl, 4-dimethylaminophenyl alkylsulfonyl etc., but be not limited to these groups.
As R 1in replacement or unsubstituted acyl group, can enumerate and combine hydrogen atom or carbon number is that aliphatic carbonyl, the carbon number of 1 to 18 straight chain shape, chain, monocycle shape or condensation polycyclic shape is the carbonyl that replaces of 2 to 20 alkoxyl group, to combine carbon number be that carbonyl, the carbon number of 6 to 18 monocycle shape or condensation polycyclic shape aryl is the carbonyl that replaces of 6 to 18 monocycle shape or condensation polycyclic shape aryloxy, combines monocycle shape that the carbon number that contains nitrogen-atoms, Sauerstoffatom, sulphur atom, phosphorus atom is 4～18 or the carbonyl of condensation polycyclic shape heterocyclic radical.As concrete example, can enumerate formyl radical, ethanoyl, propionyl, butyryl radicals, isobutyryl, pentanoyl, isovaleryl, valeryl, lauroyl, myristoyl, palmitoyl, stearyl-, cyclopentylcarbonyl, cyclohexyl-carbonyl, acryl, methacryloyl, crotonyl, isocrotonoyl, oleoyl, cinnamoyl, methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, butoxy carbonyl, hexyloxy carbonyl, carbonyl octyloxy, the last of the ten Heavenly stems oxygen base carbonyl, octadecane oxygen base carbonyl, trifluoromethoxy carbonyl, benzoyl, toluyl, 1-naphthoyl, 2-naphthoyl, 9-anthracene carbonyl, phenyloxycarbonyl, 4-methylphenoxy carbonyl, 3-nitro-phenoxy carbonyl, 4-dimethylamino phenyloxycarbonyl, 2-methyl sulfanyl phenyloxycarbonyl, 1-Naphthoyloxy carbonyl, 2-Naphthoyloxy carbonyl, 9-anthracene oxygen base carbonyl, 3-furoyl base, 2-Thenoyl, nicotinoyl, different nicotinoyl etc., but be not limited to these groups.
As R 1in replacement or unsubstituted acyloxy, can enumerate carbon number and be 2～20 acyloxy.As concrete example, can enumerate acetoxyl group, propionyloxy, butyryl acyloxy, penta acyloxy, trifluoromethyl carbon acyloxy, benzoyloxy group, 1-naphthalene carbon acyloxy, 2-naphthalene carbon acyloxy etc.
As R 1in replacement or unsubstituted amino, can enumerate amino, alkylamino, dialkyl amido, arylamino, ammonia diaryl base, alkyl aryl amino, benzylamino, dibenzyl amino etc.
Herein, as alkylamino, can enumerate methylamino, ethylamino, propyl group amino, butyl amino, amyl group amino, hexyl amino, heptyl amino, octyl group amino, nonyl amino, decyl amino, dodecyl amino, octadecyl amino, isopropylamino, isobutylamino, isopentyl amino, sec-butyl amino, tertiary butyl amino, sec.-amyl sec-pentyl secondary amyl amino, tert-pentyl amino, tertiary octyl group amino, neo-pentyl amino, cyclopropylamino, cyclobutyl amino, cyclopentyl amino, cyclohexyl amino, suberyl amino, ring octyl group amino, cyclo-dodecyl amino, 1-adamantine amino, 2-adamantine amino etc., but be not limited to these groups.
As dialkyl amido, can enumerate dimethylamino, diethylamino, dipropyl amino, dibutylamino, diamyl amino, dihexyl amino, diheptyl amino, dioctyl amino, dinonyl amino, didecyl amino, two (dodecyl) amino, two (octadecyl) amino, diisopropylaminoethyl, diisobutyl amino, diisoamyl amino, methylethyl amino, methyl-propyl amino, methyl butyl amino, methyl-isobutyl amino, cyclopropylamino, pyrrolidyl, piperidyl, piperazinyl etc., but be not limited to these groups.
As arylamino, can enumerate anilino, 1-naphthylamino, 2-naphthylamino, adjacent toluino, a toluino, p-totuidine base, 2-benzidino-, 3-benzidino-, 4-benzidino-, 1-fluorenes amino, 2-fluorenes amino, 2-thiazole amino, p-terphenyl amino etc., but be not limited to these groups.
As ammonia diaryl base, can enumerate diphenyl amino, xylyl amino, N-phenyl-1-naphthylamino, N-phenyl-2-naphthylamino etc., but be not limited to these groups.
As alkyl aryl amino, can enumerate methylphenylamine base, N-methyl-2-pyridyl, N-ethylaniline base, N propyl aniline base, N-butylbenzene amido, N-isopropyl benzene amido, N-amylbenzene amido, N-methyl isophthalic acid-naphthylamino etc., but be not limited to these groups.
As R 1in replacement or unsubstituted phosphino-, can enumerate carbon number and be 2 to 50 phosphino-.As concrete example; can enumerate dimethyl phosphino-, diethyl phosphino-, dipropyl phosphino-, diphenylphosphino, dimethoxy phosphino-, diethoxy phosphino-, dibenzoyl phosphino-, two (2; 4,6-trimethylphenyl) phosphino-etc., but be not limited to these groups.
As R 1in replacement or unsubstituted formamyl, can enumerate carbon number and be 1 to 30 formamyl.As concrete example, can enumerate N-methylamino formyl radical, N-ethylamino formyl radical, N-propyl group formamyl, N-butyl formamyl, N-hexyl formamyl, N-cyclohexyl carboxyamide base, N-octyl group formamyl, N-decyl formamyl, N-octadecyl formamyl, N-phenyl amino formyl radical, N-2-aminomethyl phenyl formamyl, N-2-chloro-phenyl-formamyl, N-2-isopropyl phenyl formamyl, N-2-(2-ethylhexyl) phenyl amino formyl radical, N-3-chloro-phenyl-formamyl, N-3-nitrophenyl formamyl, N-3-cyano-phenyl formamyl, N-4-p-methoxy-phenyl formamyl, N-4-cyano-phenyl formamyl, N-4-methyl sulfanyl phenyl amino formyl radical, N-4-phenyl sulfanyl phenyl amino formyl radical, N-methyl-N-phenyl amino formyl radical, N, N-formyl-dimethylamino, N, N-dibutylamino formyl radical, N, N-diphenyl amino formyl radical etc., but be not limited to these groups.
As R 1in replacement or unsubstituted sulfamyl, can enumerate carbon number and be 0 to 30 sulfamyl.As concrete example, can enumerate sulfamyl, N-alkylsulfamoyl group, N-ammonia aryl sulfonyl, N, N-dialkyl sulfamine, N, N-ammonia diaryl alkylsulfonyl, N-alkyl-N-ammonia aryl sulfonyl etc.More particularly, can enumerate N-methyl sulfamyl, N-ethyl sulfamyl, N-propyl group sulfamyl, N-butyl sulfamyl, N-hexyl sulfamyl, N-cyclohexyl sulfamyl, N-octyl group sulfamyl, N-2-ethylhexyl sulfamyl, N-decyl sulfamyl, N-octadecyl sulfamyl, N-phenyl sulfamoyl base, N-2-aminomethyl phenyl sulfamyl, N-2-chloro-phenyl-sulfamyl, N-2-p-methoxy-phenyl sulfamyl, N-2-isopropyl phenyl formamyl, N-3-chloro-phenyl-sulfamyl, N-3-nitrophenyl sulfamyl, N-3-cyano-phenyl sulfamyl, N-4-p-methoxy-phenyl sulfamyl, N-4-cyano-phenyl sulfamyl, N-4-dimethylaminophenyl sulfamyl, N-4-methyl sulfanyl phenyl sulfamoyl base, N-4-phenyl sulfanyl phenyl sulfamoyl base, N-methyl-N-phenyl sulfamoyl base, N, N-dimethylamino alkylsulfonyl, N, N-dibutylamine alkylsulfonyl, N, N-phenylbenzene sulfamyl etc., but be not limited to these groups.
R 2for replacing or unsubstituted alkenyl, replace or unsubstituted alkyl, replace or unsubstituted alkoxyl group, replace or unsubstituted aryl, replace or unsubstituted aryloxy, replace or unsubstituted heterocyclic radical, replace or unsubstituted heterocyclic oxy group, replace or unsubstituted alkyl alkylthio base, replace or unsubstituted sulfur alkyl aryl, replace or unsubstituted alkyl sulphinyl, replace or unsubstituted aryl sulfonyl kia, replace or unsubstituted alkyl sulphonyl, replace or unsubstituted aryl sulfonyl, replace or unsubstituted acyloxy, or replacement or unsubstituted amino.Wherein, the viewpoints such as the aspect of performance from the synthetic aspect as compound, while using as initiator are considered, be preferably and replace or unsubstituted alkenyl, replacement or unsubstituted alkyl, replacement or unsubstituted alkoxyl group, replacement or unsubstituted aryl, replacement or unsubstituted aryloxy, replacement or unsubstituted heterocyclic radical, replacement or unsubstituted heterocyclic oxy group or replacement or unsubstituted acyloxy, more preferably replace or unsubstituted alkenyl, replacement or unsubstituted alkyl, replacement or unsubstituted aryl or replacement or unsubstituted heterocyclic radical.
As R 2in replacement or unsubstituted alkenyl, replace or unsubstituted alkyl, replace or unsubstituted alkoxyl group, replace or unsubstituted aryl, replace or unsubstituted aryloxy, replace or unsubstituted heterocyclic radical, replace or unsubstituted heterocyclic oxy group, replace or unsubstituted alkyl alkylthio base, replace or unsubstituted sulfur alkyl aryl, replace or unsubstituted alkyl sulphinyl, replace or unsubstituted aryl sulfonyl kia, replace or unsubstituted alkyl sulphonyl, replace or unsubstituted aryl sulfonyl, replace or unsubstituted acyloxy, with replacement or unsubstituted amino, with aforementioned R 1in replacement or unsubstituted alkenyl, replace or unsubstituted alkyl, replace or unsubstituted alkoxyl group, replace or unsubstituted aryl, replace or unsubstituted aryloxy, replace or unsubstituted heterocyclic radical, replace or unsubstituted heterocyclic oxy group, replace or unsubstituted alkyl alkylthio base, replace or unsubstituted sulfur alkyl aryl, replace or unsubstituted alkyl sulphinyl, replace or unsubstituted aryl sulfonyl kia, replace or unsubstituted alkyl sulphonyl, replace or unsubstituted aryl sulfonyl, replace or unsubstituted acyloxy, with replacement or unsubstituted amino synonym.
R 3～R 5represent independently of one another hydrogen atom, halogen atom, cyano group, nitro, replacement or unsubstituted alkenyl, replacement or unsubstituted alkyl, replacement or unsubstituted alkoxyl group, replacement or unsubstituted aryl, replacement or unsubstituted aryloxy, replacement or unsubstituted heterocyclic radical, replacement or unsubstituted heterocyclic oxy group, replacement or unsubstituted alkyl alkylthio base, replacement or unsubstituted sulfur alkyl aryl, replacement or unsubstituted acyl group or replacement or unsubstituted amino.Wherein, the viewpoints such as the aspect of performance from the synthetic aspect as compound, while using as initiator are considered, be preferably hydrogen atom, halogen atom, nitro, replacement or unsubstituted alkyl, replacement or unsubstituted aryl, replacement or unsubstituted heterocyclic radical, more preferably hydrogen atom, nitro, replacement or unsubstituted alkyl, replacement or unsubstituted aryl.
As R 3～R 5in halogen atom, can enumerate fluorine atom, chlorine atom, bromine atoms, iodine atom.
As R 3～R 5in replacement or unsubstituted alkenyl, replacement or unsubstituted alkyl, replacement or unsubstituted alkoxyl group, replacement or unsubstituted aryl, replacement or unsubstituted aryloxy, replacement or unsubstituted heterocyclic radical, replacement or unsubstituted heterocyclic oxy group, replacement or unsubstituted alkyl alkylthio base, replacement or unsubstituted sulfur alkyl aryl, replacement or unsubstituted acyl group and replacement or unsubstituted amino, with aforementioned R 1in replacement or unsubstituted alkenyl, replacement or unsubstituted alkyl, replacement or unsubstituted alkoxyl group, replacement or unsubstituted aryl, replacement or unsubstituted aryloxy, replacement or unsubstituted heterocyclic radical, replacement or unsubstituted heterocyclic oxy group, replacement or unsubstituted alkyl alkylthio base, replacement or unsubstituted sulfur alkyl aryl, replacement or unsubstituted acyl group and replacement or unsubstituted amino synonym.
R 6～R 9represent independently of one another hydrogen atom, halogen atom, cyano group, haloalkyl, replace or unsubstituted alkyl, replace or unsubstituted alkoxyl group, replace or unsubstituted aryl, replace or unsubstituted aryloxy, replace or unsubstituted heterocyclic radical, replace or unsubstituted heterocyclic oxy group, replace or unsubstituted alkenyl, replace or unsubstituted alkyl alkylthio base, replace or unsubstituted sulfur alkyl aryl, replace or unsubstituted alkyl sulphinyl, replace or unsubstituted aryl sulfonyl kia, replace or unsubstituted alkyl sulphonyl, or replacement or unsubstituted aryl sulfonyl, replace or unsubstituted amino, or the substituting group being represented by following general formula (2).
Wherein, the viewpoints such as the aspect of performance from the synthetic aspect as compound, while using as initiator are considered, be preferably hydrogen atom, halogen atom, cyano group, haloalkyl, replacement or unsubstituted alkyl, replacement or unsubstituted aryl, replacement or unsubstituted heterocyclic radical or replacement or unsubstituted amino, more preferably hydrogen atom, cyano group, replacement or unsubstituted alkyl, replacement or unsubstituted aryl.
General formula (2)
[changing 7]
(in formula, R 1' and R 2' and R 1and R 2synonym.)
R 6～R 9in halogen atom and R 3～R 5in halogen atom synonym.
As R 6～R 9in haloalkyl, the alkyl that can to enumerate carbon number that all hydrogen atoms are replaced by above-mentioned halogen atom be 1～15, as concrete example, can enumerate trifluoromethyl, trichloromethyl, trisbromomethyl, three iodomethyls, pentafluoroethyl group, pentachloro-ethyl, pentabromo-ethyl, pentaiodo ethyl, trifluoro two bromotrifluoromethanes, tribromo diiodo-ethyl, seven fluoropropyls, heptachlor propyl group, seven bromopropyls, nine fluorine butyl, nine chlorobutyls, nine brombutyls, 11 fluorine amyl groups, 11 chlorine amyl groups, ten monobromo amyl groups, ten trifluoro hexyls, ten trichlorine hexyls, 15 fluorine heptyl, 17 fluorine octyl groups, 19 fluorine nonyls, 21 fluorine decyls, 20 trifluoro undecyl, 25 fluorine dodecyls etc., but be not limited to these groups.
As above-mentioned haloalkyl, the characteristic aspect from synthetic aspect, while using as radical polymerization initiator (A) is considered, preferred trifluoromethyl, pentafluoroethyl group.
R 6～R 9in replacement or unsubstituted alkyl, replacement or unsubstituted alkoxyl group, replacement or unsubstituted aryl, replacement or unsubstituted aryloxy, replacement or unsubstituted heterocyclic radical, replacement or unsubstituted heterocyclic oxy group, replacement or unsubstituted alkenyl, replacement or unsubstituted alkyl alkylthio base, replacement or unsubstituted sulfur alkyl aryl, replacement or unsubstituted alkyl sulphinyl, replacement or unsubstituted aryl sulfonyl kia, replacement or unsubstituted alkyl sulphonyl, replacement or unsubstituted aryl sulfonyl and replacement or unsubstituted amino, with aforementioned R 1in replacement or unsubstituted alkyl, replace or unsubstituted alkoxyl group, replace or unsubstituted aryl, replace or unsubstituted aryloxy, replace or unsubstituted heterocyclic radical, replace or unsubstituted heterocyclic oxy group, replace or unsubstituted alkenyl, replace or unsubstituted alkyl alkylthio base, replace or unsubstituted sulfur alkyl aryl, replace or unsubstituted alkyl sulphinyl, replace or unsubstituted aryl sulfonyl kia, replace or unsubstituted alkyl sulphonyl, replace or unsubstituted aryl sulfonyl, with replacement or unsubstituted amino synonym.
Here, R 6～R 9as long as above-mentioned group just has no particular limits, but the characteristic aspect consideration from synthetic aspect, while using as radical polymerization initiator (A), at R 6～R 9in while containing the group beyond hydrogen, preferably R 7for the group beyond hydrogen.
R 10～R 14represent independently of one another hydrogen atom, halogen atom, cyano group, nitro, haloalkyl, replacement or unsubstituted alkyl sulphinyl, replacement or unsubstituted aryl sulfonyl kia, replacement or unsubstituted alkyl sulphonyl, replacement or unsubstituted aryl sulfonyl or replacement or unsubstituted acyl group, R 10～R 14it is not all hydrogen atom simultaneously.
R 10～R 14in haloalkyl, with aforementioned R 6～R 9in haloalkyl synonym, replace or unsubstituted alkyl sulphinyl, replacement or unsubstituted aryl sulfonyl kia, replacement or unsubstituted alkyl sulphonyl, replacement or unsubstituted aryl sulfonyl and replacement or unsubstituted acyl group, with aforementioned R 1in replacement or unsubstituted alkyl sulphinyl, replacement or unsubstituted aryl sulfonyl kia, replacement or unsubstituted alkyl sulphonyl, replacement or unsubstituted aryl sulfonyl and replacement or unsubstituted acyl group synonym.
Characteristic aspect consideration from synthetic aspect, while using as radical polymerization initiator (A), R 10～R 14be preferably nitro or replacement or unsubstituted acyl group, more preferably nitro or following general formula (3).
General formula (3)
[changing 8]
(in formula, R 15～R 19represent independently of one another hydrogen atom, halogen atom, cyano group, nitro, haloalkyl, replace or unsubstituted alkyl, replace or unsubstituted alkoxyl group, replace or unsubstituted aryl, replace or unsubstituted aryloxy, replace or unsubstituted heterocyclic radical, replace or unsubstituted heterocyclic oxy group, replace or unsubstituted alkenyl, replace or unsubstituted alkyl alkylthio base, replace or unsubstituted sulfur alkyl aryl, replace or unsubstituted acyl group, or replacement or unsubstituted amino.)
Preferably replace or unsubstituted alkyl, replacement or unsubstituted alkoxyl group, replacement or unsubstituted aryl, replacement or unsubstituted aryloxy, replacement or unsubstituted heterocyclic oxy group, replacement or unsubstituted alkyl alkylthio base, replacement or unsubstituted sulfur alkyl aryl or replacement or unsubstituted amino, more preferably replace or unsubstituted alkoxyl group, replacement or unsubstituted alkyl alkylthio base or replacement or unsubstituted amino.
Wherein, consider as the synthetic aspect of compound, aspect of performance while using as initiator etc., at R 15～R 19in while containing the substituting group beyond hydrogen, the substituent location optimization beyond hydrogen is R 15, R 17, R 19, R more preferably 17.
R 15～R 19in haloalkyl and aforementioned R 6～R 9in haloalkyl synonym; replace or unsubstituted alkyl, replacement or unsubstituted alkoxyl group, replacement or unsubstituted aryl, replacement or unsubstituted aryloxy, replacement or unsubstituted heterocyclic radical, replacement or unsubstituted heterocyclic oxy group, replacement or unsubstituted alkenyl, replacement or unsubstituted alkyl alkylthio base, replacement or unsubstituted sulfur alkyl aryl, replacement or unsubstituted acyl group and replacement or unsubstituted amino, with R 1in replacement or unsubstituted alkyl, replacement or unsubstituted alkoxyl group, replacement or unsubstituted aryl, replacement or unsubstituted aryloxy, replacement or unsubstituted heterocyclic radical, replacement or unsubstituted heterocyclic oxy group, replacement or unsubstituted alkenyl, replacement or unsubstituted alkyl alkylthio base, replacement or unsubstituted sulfur alkyl aryl, replacement or unsubstituted acyl group and replacement or unsubstituted amino synonym.
And then, when (A) uses using compound of the present invention as radical polymerization initiator, consider particularly preferably R from the intermiscibility to solvent, resin 10～R 14for the situation of general formula (3).
Here, the characteristic aspect from synthetic aspect, while using as radical polymerization initiator (A) is considered, preferred R 12for the group beyond hydrogen.
Aforesaid R 1～R 19in substituent hydrogen atom can further be replaced by other substituting group.
As other substituting group, for example, can enumerate fluorine atom, chlorine atom, bromine atoms, the halogen groups such as iodine atom, methoxyl group, oxyethyl group, the alkoxyl groups such as tert.-butoxy, phenoxy group, to aryloxy such as tolyloxys, methoxycarbonyl, butoxy carbonyl, the alkoxy carbonyls such as phenyloxycarbonyl, acetoxyl group, propionyloxy, the acyloxy such as benzoyloxy group, ethanoyl, benzoyl, isobutyryl, acryl, methacryloyl, the acyl groups such as methoxalyl, methyl sulfanyl, the alkyl alkylthio bases such as tertiary butyl sulfanyl, phenyl sulfanyl, the sulfur alkyl aryls such as p-methylphenyl sulfanyl, methylamino, the amino alkylamino that waits of cyclohexyl, dimethylamino, diethylamino, morpholino base, the dialkyl amidos such as piperidyl, phenyl amino, the amino arylamino that waits of p-methylphenyl, methyl, ethyl, the tertiary butyl, the alkyl such as dodecyl, phenyl, p-methylphenyl, xylyl, cumyl, naphthyl, anthryl, the aryl such as phenanthryl, furyl, the heterocyclic radicals such as thienyl, in addition, can also enumerate hydroxyl, carboxyl, formyl radical, sulfydryl, sulfo group, methylsulfonyl, p-toluenesulfonyl, amino, nitro, cyano group, trifluoromethyl, trichloromethyl, trimethyl silyl, phosphinico-, phosphono, trimethylammonium ammonium, dimethyl sulfonium base, triphenyl phenacyl base etc.
The concrete example of above-described compound of the present invention is represented as follows, but the structure of compound of the present invention is not limited to these.
[changing 9]
[changing 10]
[changing 11]
[changing 12]
[changing 13]
[changing 14]
[changing 15]
[changing 16]
[changing 17]
[changing 18]
[changing 19]
[changing 20]
[changing 21]
[changing 22]
[changing 23]
[changing 24]
[changing 25]
[changing 26]
[changing 27]
[changing 28]
[changing 29]
[changing 30]
[changing 31]
The compound being represented by general formula (1) is to obtain by modulating intermediate and modulating precursor with it.Intermediate is the ketone compound being represented by general formula (4).Below, in the situation that there is no special reason, " intermediate " represents ketone compound.
General formula (4)
[changing 32]
(in formula, R 2～R 14with the R in general formula (1) 2～R 14synonym.)
Generally, ketone compound easily obtains as raw material.The whole bag of tricks that in addition, can utilize that known synthetic method in the past, for example Japanization association compile, record in the 4th edition, new experimental chemistry lecture, the 14th volume, 751 (ball is kind) and easily obtaining.All enroll in this specification sheets the literature as reference.For with Publication about Document too.
The ketoboidies of the various carbazole compounds that particularly represented by general formula (4) can easily obtain by Knut Fridell-Kerafyrm thatch acylation reaction, for example, can be obtained by the same method of the method for recording for No. 3992725 with Japanese Patent.
Precursor when the synthetic compound being represented by general formula (1) is the oxime being represented by following general formula (5).Below, in the situation that there is no special reason, " precursor " represents oxime compound.
General formula (5)
[changing 33]
(in formula, R 2～R 14with the R in general formula (1) 2～R 14synonym.)
The ketone compound that the oxime that general formula (5) represents can pass through general formula (4) to represent is as intermediate, for example Org.React., 7, <1953>, 327 or Japanization association compiles, the whole bag of tricks of recording in the 4th edition, experimental chemistry lecture, the 14th volume, 1316 pages (ball is kind) obtain.And then, also can for example, be obtained by the synthetic method of the oxime of recording in commercially available textbook (J.March, Advanced Organic Organic Chemistry, 4th Edition, Wiley Interscience, 1992).
One of optimum oxime synthetic method is to utilize the nitrosification of the active methylene group of nitrous acid or alkyl nitrite.For example, at Organic Syntheses Coll.Vol.VI, pp 840, Organic Syntheses Coll.Vol.III, pp 191 and 513, Organic Syntheses Coll.Vol.II, pp 202,204 and 363, J.Am.Chem.Soc., 47, <1925>, 2033, J.Chem.Soc., 117, <1920>, 590, J.Am.Chem.Soc., 51, <1929>, in 2264, record reaction conditions, be suitable for manufacturing oxime.Nitrous acid is generated by Sodium Nitrite conventionally.Alkyl nitrite is for example methyl nitrite, nitrous acid isopropyl ester, butyl nitrite, Isopentyl nitrite.
The oxime compound that the compound that general formula (1) represents represents take general formula (5) is as precursor, can manufacture as follows: the oxime that the method for for example above-mentioned record of the method for being recorded by document obtains and acyl chlorides or acid anhydrides are in the such non-active solvent of for example tetrahydrofuran (THF), benzene or dimethyl formamide, under the such tertiary amine of for example triethylamine of alkali exists, or react in the such basic solvent of pyridine.
Such reaction is known for those skilled in the art, generally-15 ℃～+ 50 ℃, preferably carry out at 0～30 ℃.
Whole oxime ester bases exists with two stereoscopic configurations (Z) or (E).Can separate its isomer by common method, but also can adopt the mixture of isomer as light-initiated kind.Thereby, the invention still further relates to the mixture of the stereoscopic configurations isomer of the compound of general formula (1).
The compound that general formula of the present invention (1) represents can utilize mass analysis value, ultimate analysis value and 1h-NMR etc. in the past known analytical method easily identify.
Then, the situation that (A) uses using compound of the present invention as radical polymerization initiator is described.
The most common not longer wavelength of specific absorption ultraviolet region of known alpha-ketoxime ester cpds in the past, thereby lack active near ultraviolet near infrared light.On the other hand, the radical polymerization initiator (A) being represented by general formula of the present invention (1) is by importing electron-attracting substituent on the phenyl at N-phenyl carbazole base, can there is absorption band near ultraviolet to visible region, and there is activity than these near ultraviolets to the longer wavelength region may of visible ray.
In addition, as mentioned above, radical polymerization initiator of the present invention (A) has the ketone type oxime ester structure that general formula (1) represents.Than in the past, more known radical polymerization initiator had more high sensitive to radical polymerization initiator of the present invention (A), and this may be due to following enumerated 3 reasons (possibility), but its detailed content is not yet clear and definite.
As the 1st reason, with regard to radical polymerization initiator of the present invention (A), the carbazole chromophoric group representing due to general formula (1) has good absorption, therefore can absorb extremely well the energy being brought by the energy line giving.And then, also can think, because the energy of gained is effective to the decomposition of oxime esteratic site, therefore irradiate by energy line and decompose rapidly, and moment just can generate a large amount of free radicals.
As the 2nd reason, can think that radical polymerization initiator of the present invention (A) is by having ketone type oxime ester structure, as shown in following, inactive imido free radical as spike decomposes rapidly, and further generation can be brought into play the resolvent (carbazyl free radical) as the function of spike.If ketone type oxime ester not necessarily generates free radical in a large number, if the imido free radical generating is quasi-steady, decompose slack-offly, the growing amount of free radical is fewer than theoretical amount.It is subject to had chromophoric very large impact.And can think, because radical polymerization initiator of the present invention (A) is by having the structure shown in general formula (1), according to certain reason, the decomposition of decomposing produced imido free radical by rayed is very fast, and result has generated a large amount of free radicals.
In addition, think and as mentioned above, because the decomposition of imido free radical is very fast, therefore suppressed combination again by radical polymerization initiator of the present invention (A).Again in conjunction with in more situation, just reduce by decomposing the spike producing, therefore as the function reduction of radical polymerization initiator.
As the 3rd reason, can enumerate the effect of carbazole that the above-mentioned electron-attracting substituent of bringing into play good chromophoric function replaces and the synergy of the effect of ketone type oxime ester.
[changing 34]
Radical polymerization initiator of the present invention (A) irradiates the function of bringing into play as very high sensitive radical polymerization initiator by energy line, therefore, can positively realize use polyreaction, the crosslinking reaction etc. of known radical polymerization initiator in the past in the shorter time.As its result, can realize the significantly high sensitive of the various uses of having applied these reactions, the raising of characteristic.Below, the method for utilizing of radical polymerization initiator of the present invention (A) is described.
The composition that contains radical polymerization initiator of the present invention (A) and free-radical polymerised compound (B) can be used as by energy line and irradiates and the Polymerizable composition that is cured rapidly and positively, can obtains the cured article with good characteristic uses.
Describe for free-radical polymerised compound of the present invention (B).Free-radical polymerised compound of the present invention (B) is the compound with the ethylenic unsaturated bond of free redical polymerization.What is called has the compound of ethylenic unsaturated bond of free redical polymerization as long as have the compound of ethylenic unsaturated bond of at least more than one free redical polymerization in molecule, can be any compound, can there is the chemical forms such as monomer, oligopolymer, polymkeric substance.
Example as the compound of this ethylenic unsaturated bond with free redical polymerization can be enumerated unsaturated carboxylic acid and salt, ester, carbamate, acid amides and the acid anhydrides such as vinylformic acid, methacrylic acid, methylene-succinic acid, β-crotonic acid, iso-crotonic acid, toxilic acid, vinyl cyanide, vinylbenzene, also have the free-radical polymerised compounds such as various unsaturated polyesters, unsaturated polyether, unsaturated polyester acid amides, unsaturated polyurethanes, the present invention is not limited to this.Below enumerate the concrete example of the free-radical polymerised compound (B) in the present invention.
The example of esters of acrylic acid:
The example of monofunctional alkyl esters of acrylic acid:
Methyl acrylate, ethyl propenoate, propyl acrylate, isopropyl acrylate, butyl acrylate, vinylformic acid isopentyl ester, Ethyl acrylate, ethyl acrylate, Octyl acrylate, decyl acrylate, vinylformic acid dodecane ester, vinylformic acid octadecane ester, isobornyl acrylate, cyclohexyl acrylate, vinylformic acid two cyclopentenes esters, vinylformic acid dicyclopentenyl 2-ethoxyethyl acetate, benzyl acrylate.
The example of simple function hydroxy acryl acid ester class:
2-Hydroxy ethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-chloropropyl acrylate, vinylformic acid-2-hydroxyl-3-phenoxy group propyl ester, vinylformic acid-2-hydroxyl-3-allyloxy propyl ester, 2-acryloxy ethyl-2-hydroxypropyl phthalic ester.
The example of simple function Halogen esters of acrylic acid:
Vinylformic acid-2,2,2-trifluoro ethyl ester, vinylformic acid-2,2,3,3-tetrafluoro propyl ester, vinylformic acid-1H-hexafluoro isopropyl ester, vinylformic acid-1H, 1H, 5H-octafluoro pentyl ester, vinylformic acid-1H, 1H, 2H, 2H-17 fluorine esters in the last of the ten Heavenly stems, vinylformic acid-2, the bromo-4-butyl of 6-bis-phenyl ester, vinylformic acid-2,4,6-tribromophenoxy ethyl ester, 2,4,6-tribromophenol 3EO addition acrylate.
Simple function contains the example of ether esters of acrylic acid:
Vinylformic acid-2-methoxyl group ethyl ester, 1, 3-butyleneglycol methyl ether acrylate, vinylformic acid butoxyethyl, methoxyl group triethylene glycol acrylate, methoxy poly (ethylene glycol) #400 acrylate, methoxyl group dipropylene glycol acrylate, methoxyl group tripropylene glycol acrylate, methoxyl group polypropylene glycol acrylate, oxyethyl group Diethylene Glycol acrylate, vinylformic acid ethyl carbitol ester, acrylic acid-2-ethyl hexyl carbitol ester, tetrahydrofurfuryl acrylate, vinylformic acid phenoxy ethyl, phenoxy group Diethylene Glycol acrylate, phenoxy group polyethylene glycol acrylate, tolyl polyethylene glycol acrylate, vinylformic acid is to Nonylphenoxy ethyl ester, to Nonylphenoxy polyethylene glycol acrylate, glycidyl acrylate.
Simple function contains the example of carboxy acrylic ester class:
Senecioate-carboxyl ethyl ester, mono succinate acryloxy ethyl ester, ω-carboxyl polycaprolactone single-acrylate, 2-acrylyl oxy-ethyl phthalandione hydrogen ester, 2-acryloyl-oxy propyl group phthalandione hydrogen ester, 2-acryloyl-oxy propyl group six hydrogen phthalandione hydrogen esters, 2-acryloyl-oxy propyl group tetrahydrochysene phthalandione hydrogen ester.
The example of other monofunctional acrylates:
N, N-dimethyl amino ethyl acrylate, N, N-dimethylaminopropyl acrylate, vinylformic acid morpholino ethyl ester, trimethylsiloxy ethyl propylene acid esters, phenylbenzene-2-acryloxy ethyl phosphonic acid ester, 2-acryloxy ethyl phosphate ester acid, caprolactone modification-2-acryloxy ethyl phosphate ester acid.
The example of two functional acrylate's classes:
1,4 butanediol diacrylate, 1,6 hexanediol diacrylate, glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyoxyethylene glycol #200 diacrylate, polyoxyethylene glycol #300 diacrylate, polyoxyethylene glycol #400 diacrylate, polyoxyethylene glycol #600 diacrylate, propylene glycol diacrylate, tripropylene glycol diacrylate, four propylene glycol diacrylates, polypropylene glycol #400 diacrylate, polypropylene glycol #700 diacrylate, neopentylglycol diacrylate, neopentyl glycol PO modification diacrylate, hydroxypivalic acid DOPCP diacrylate, the caprolactone affixture diacrylate of hydroxypivalic acid DOPCP, 1,6-hexylene glycol two (2-hydroxyl-3-acryloxy propyl group) ether, two (4-propenyloxy group polyethoxye phenyl) propane, 1,9-nonanediol diacrylate, pentaerythritol diacrylate, pentaerythritol diacrylate monostearate, pentaerythritol diacrylate mono benzoate, bisphenol a diacrylate, EO modified bisphenol A diacrylate, PO modified bisphenol A diacrylate, Hydrogenated Bisphenol A diacrylate, the modified hydrogenated bisphenol a diacrylate of EO, the modified hydrogenated bisphenol a diacrylate of PO, Bisphenol F diacrylate, EO modified bisphenol F diacrylate, PO modified bisphenol F diacrylate, EO modification tetrabromo-bisphenol diacrylate, tristane dihydroxymethyl diacrylate, tricarbimide EO modification diacrylate.
The example of trifunctional esters of acrylic acid:
Glycerine PO modification triacrylate, Viscoat 295, TriMethylolPropane(TMP) EO modification triacrylate, TriMethylolPropane(TMP) PO modification triacrylate, tricarbimide EO modification triacrylate, tricarbimide EO modification 6-caprolactone modification triacrylate, 1; 3,5-triacryl perhydro-s-triazine, pentaerythritol triacrylate, Dipentaerythritol triacrylate tripropionate.
The example of esters of acrylic acids more than four senses:
Tetramethylol methane tetraacrylate, Dipentaerythritol tetraacrylate, Dipentaerythritol five acrylate mono-propionates, dipentaerythritol acrylate, tetramethylol methane tetraacrylate, oligomer ester tetraacrylate, three (acryloxy) phosphoric acid ester.
The example of methyl acrylic ester:
The example of monofunctional alkyl methyl acrylic ester:
Methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, methacrylic isoamyl valerate, N-Hexyl methacrylate, the own ester of methacrylic acid-2-, methacrylic acid-2-ethylhexyl, Octyl methacrylate, decyl-octyl methacrylate, methacrylic acid dodecane ester, methacrylic acid octadecane ester, isobornyl methacrylate, cyclohexyl methacrylate, methacrylic acid two cyclopentenes esters, methacrylic acid dicyclopentenyl 2-ethoxyethyl acetate, benzyl methacrylate.
The example of simple function hydroxyl methyl acrylic ester:
Methacrylic acid-2-hydroxy methacrylate, methacrylic acid-2-hydroxy propyl ester, methacrylic acid-2-hydroxyl-3-chlorine propyl ester, methacrylic acid-2-hydroxyl-3-phenoxy group propyl ester, methacrylic acid-2-hydroxyl-3-allyloxy propyl ester, 2-methacryloxyethyl-2-hydroxypropyl phthalic ester.
The example of simple function Halogen methyl acrylic ester:
Methacrylic acid-2,2,2-trifluoro ethyl ester, methacrylic acid-2,2,3,3-tetrafluoro propyl ester, methacrylic acid-1H-hexafluoro isopropyl ester, methacrylic acid-1H, 1H, 5H-octafluoro pentyl ester, methacrylic acid-1H, 1H, 2H, 2H-17 fluorine esters in the last of the ten Heavenly stems, methacrylic acid-2, the bromo-4-butyl of 6-bis-phenyl ester, methacrylic acid-2,4,6-tribromophenoxy ethyl ester, 2,4,6-tribromophenol 3EO addition methacrylic ester.
Simple function contains the example of ether methyl acrylic ester:
Methacrylic acid-2-methoxyl group ethyl ester, 1, 3-butyleneglycol methyl ether methacrylate, methacrylic acid butoxyethyl, methoxyl group triethylene glycol methacrylic ester, methoxy poly (ethylene glycol) #400 methacrylic ester, methoxyl group dipropylene glycol methacrylic ester, methoxyl group tripropylene glycol methacrylic ester, methoxyl group polypropylene glycol methacrylic ester, oxyethyl group Diethylene Glycol methacrylic ester, methacrylic acid-2-ethylhexyl carbitol ester, tetrahydrofurfuryl methacrylate, methacrylic acid phenoxy ethyl, phenoxy group Diethylene Glycol methacrylic ester, phenoxy group polyethylene glycol methacrylate-styrene polymer, tolyl polyethylene glycol methacrylate-styrene polymer, methacrylic acid is to Nonylphenoxy ethyl ester, to Nonylphenoxy polyethylene glycol methacrylate-styrene polymer, glycidyl methacrylate.
Simple function contains the example of carboxyl methyl acrylic ester:
Methacrylic acid-β-carboxyl ethyl ester, mono succinate methacryloxy ethyl ester, ω-carboxyl polycaprolactone monomethacrylates, 2-methylacryoyloxyethyl phthalandione hydrogen ester, 2-methacryloxypropyl phthalandione hydrogen ester, 2-methacryloxypropyl six hydrogen phthalandione hydrogen esters, 2-methacryloxypropyl tetrahydrochysene phthalandione hydrogen ester.
The example of other simple function methacrylic esters:
Dimethylaminoethyl acrylate methyl base amino methyl, methacrylic acid-N, N-dimethylamino ethyl ester, methacrylic acid-N, N-dimethylamino propyl ester, methacrylic acid morpholino ethyl ester, methacrylic acid trimethylsiloxy ethyl ester, phenylbenzene-2-methacryloxyethyl phosphoric acid ester, 2-methacryloxyethyl phosphate ester acid, caprolactone modification-2-methacryloxyethyl phosphate ester acid.
The example of two sense methyl acrylic esters:
BDO dimethacrylate, HDDMA, ethylene glycol dimethacrylate, Diethylene Glycol dimethacrylate, TEGDMA, TEG dimethacrylate, polyoxyethylene glycol #200 dimethacrylate, polyoxyethylene glycol #300 dimethacrylate, polyoxyethylene glycol #400 dimethacrylate, polyoxyethylene glycol #600 dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, four propylene glycol dimethacrylates, polypropylene glycol #400 dimethacrylate, polypropylene glycol #700 dimethacrylate, neopentylglycol dimethacrylate, neopentyl glycol PO modification dimethacrylate, hydroxypivalic acid DOPCP dimethacrylate, the caprolactone affixture dimethacrylate of hydroxypivalic acid DOPCP, 1,6-hexylene glycol two (2-hydroxy-3-methyl acryloxy propyl group) ether, 1,9-nonanediol dimethacrylate, dimethyl pentaerythritol acrylate, dimethyl pentaerythritol acrylate monostearate, dimethyl pentaerythritol acrylate mono benzoate, 2,2-bis-(4-metacryloxy polyethoxye phenyl) propane, bisphenol a dimethacrylate, EO modified bisphenol A dimethacrylate, PO modified bisphenol A dimethacrylate, Hydrogenated Bisphenol A dimethacrylate, the modified hydrogenated bisphenol a dimethacrylate of EO, the modified hydrogenated bisphenol a dimethacrylate of PO, Bisphenol F dimethacrylate, EO modified bisphenol F dimethacrylate, PO modified bisphenol F dimethacrylate, EO modification tetrabromo-bisphenol dimethacrylate, tristane dihydroxymethyl dimethacrylate, tricarbimide EO modification dimethacrylate.
The example of trifunctional methyl acrylic ester:
Glycerine PO modification trimethacrylate, trimethylolethane trimethacrylate methacrylic ester, trimethylolpropane trimethacrylate, TriMethylolPropane(TMP) EO modification trimethacrylate, TriMethylolPropane(TMP) PO modification trimethacrylate, tricarbimide EO modification trimethacrylate, tricarbimide EO modification 6-caprolactone modification trimethacrylate, 1; 3,5-trimethylammonium acryl perhydro-s-triazine, pentaerythritol acrylate trimethyl, Dipentaerythritol trimethacrylate tripropionate.
The example of methyl acrylic esters more than four senses:
Pentaerythritol tetramethylacrylate, Dipentaerythritol pentamethyl-acrylate mono-propionate, Dipentaerythritol hexamethyl acrylate, tetramethylol methane tetramethyl-acrylate, oligomer ester tetramethyl-acrylate, three (methacryloxy) phosphoric acid ester.
The example of allyl ester class:
Glycidyl allyl ether, Phthalic acid, diallyl ester, trimellitic acid triallyl, triallyl isocyanurate.
The example of amides:
Acrylamide, N hydroxymethyl acrylamide, diacetone acrylamide, N; N-DMAA, N; N-diethyl acrylamide, NIPA, acryloyl morpholine, Methacrylamide, N-methylol methacrylamide, two acetone Methacrylamides, N; N-dimethylmethacryl amide, N, N-diethylmethyl acrylamide, N-isopropyl methyl acrylamide, methacryloyl morpholine.
The example of styrenic:
Vinylbenzene, 4-Vinyl phenol, to chloro-styrene, to bromstyrol, p-methylstyrene, to methoxy styrene, to tert.-butoxy vinylbenzene, to tertbutyloxycarbonyl vinylbenzene, to tertbutyloxycarbonyl oxygen vinylbenzene, 2,4-phenylbenzene-4-methyl-1-pentene.
The example of other vinyl compounds:
Vinyl acetate, monochloro vinyl acetate, vinyl benzoate, trimethylacetic acid vinyl acetate, vinyl butyrate, vinyl laurate, vinyl hexanediacetate, methacrylic vinyl acetate, Vinyl crotonate, 2 ethyl hexanoic acid vinyl acetate, N-vinylcarbazole, NVP etc.
Above-mentioned free-radical polymerised compound (B) can easily obtain as the commercially available product of manufacturers shown below.Can enumerate " light acrylate (ラ イ ト ア Network リ レ mono-ト) " that for example common prosperity society oil chemical industry (strain) society manufactures, " light ester (ラ イ ト エ ス テ Le) ", " epoxy ester ", " urethane acrylate " and " high functionality oligopolymer " series, " NK ester " and " NK oligopolymer " series that society of Xin Zhong village chemistry (strain) manufactures, Hitachi changes into " FANCRYL " series that industry (strain) society manufactures, " ARONIX M " series that East Asia synthetic chemistry (strain) society manufactures, " functional monomer " series that large eight chemical industry (strain) society manufactures, " special acrylic monomers " series that Osaka organic chemistry industry (strain) society manufactures, " ACRYESTER " and " DIABEAM oligopolymer (ダ イ ヤ PVC one system オ リ go マ mono-) " series that society of Mitsubishi's beautiful sun (strain) manufactures, " KAYARAD " and " KAYAMAR mono-" series that chemical drug (strain) society of Japan manufactures, " vinylformic acid/methacrylate monomer " series that (strain) Japanese catalyst society manufactures, " NICHIGO-UV purple light urethane acrylate oligomer " series that synthetic chemical industry (strain) society of Japan manufactures, " vinyl carboxylates monomer " series that SHIN-ETSU HANTOTAI's vinyl acetate (strain) society manufactures, " functional monomer " series that (strain) Xing Renshe manufactures etc.
And then free-radical polymerised compound (B) can be enumerated the compound of recording in document shown below.Can enumerate " linking agent handbook " (1981 that under mountain for example, the third-class people in Shanxi compiles, great achievement society), add " UVEB solidifies handbook (raw material volume) " (1985 that rattan looks clearly volume, polymer publication meeting), RadTech research association compiles, clear " actual techniques of new photoresist " compiled of Japanese red pine (1987, CMC), " the high molecular precise treatment of Thermocurable " that rattan far away has just been compiled (1986, CMC), " the vibrin handbook " of the flourish youth's work in Long mountain (1988, Nikkan Kogyo Shimbun), (2002, " application of UVEB curing technology and the market " that RadTech research association compiles, CMC).
Free-radical polymerised compound of the present invention (B) can only use one, also can mix two or more and use by arbitrary ratio in order to put forward high expected characteristic.
With respect to free-radical polymerised compound (B) 100 weight parts, the usage quantity of the radical polymerization initiator of the present invention (A) in Polymerizable composition is 0.1 to 100 weight part, be preferably 3 to 60 weight parts.
Polymerizable composition of the present invention can mix with tackiness agents such as organic high molecular polymers, is applied on the polymeric films such as sheet glass, aluminium sheet, other metal sheets, polyethylene terephthalate and uses.
Can enumerate polymkeric substance, the multipolymers such as polyacrylate(s), poly-alpha-alkyl esters of acrylic acid, polyamide-based, polyvinyl acetal class, polyoxymethylene class, polyurethanes, polycarbonate-based, polystyrene type, polyvinylesters class as mixing with Polymerizable composition of the present invention the tackiness agent using.More specifically can enumerate polymethacrylate, polymethylmethacrylate, polyethyl methacrylate, Polyvinyl carbazole, Polyvinylpyrolidone (PVP), polyvinyl butyral, polyvinyl acetate (PVA), novolac resin, resol, epoxy resin, Synolac, also have the known organic high molecular polymer of industry of " actual techniques of new photoresist " (, CMC in 1987) and " 10188 commodity chemical " 657～767 pages of the clear supervision of Japanese red pine (1988, chemical industry day newspaper office) records.
In addition, in order further to improve susceptibility, Polymerizable composition of the present invention can also and be used with other polymerization starters.
As mixing with Polymerizable composition of the present invention and other polymerization starters of use, can enumerate as follows: Japanese Patent Publication 59-1281 communique, the pyrrolotriazine derivatives that Japanese Patent Publication 61-9621 communique and Japanese kokai publication sho 60-60104 communique are recorded, the organo-peroxide that Japanese kokai publication sho 59-1504 communique and Japanese kokai publication sho 61-243807 communique are recorded, Japanese Patent Publication 43-23684 communique, Japanese Patent Publication 44-6413 communique, the diazonium compound that No. 3567453 specification sheets of Japanese Patent Publication 47-1604 communique and USP recorded, No. 2848328 specification sheets of USP, the organic azide that No. 2940853 specification sheets of No. 2852379 specification sheets of USP and USP recorded, Japanese Patent Publication 36-22062 communique, Japanese Patent Publication 37-13109 communique, the o-quinone two nitrine classes that Japanese Patent Publication 38-18015 communique and Japanese Patent Publication 45-9610 communique are recorded, with Japanese Patent Publication 55-39162 communique, the iodine of the 1307th page of (1977) record of Japanese kokai publication sho 59-140203 communique and " macromole (MACROMOLECULES) " the 10th volume compound is the various of representative compound, the azo-compound that Japanese kokai publication sho 59-142205 communique is recorded, Japanese kokai publication hei 1-54440 communique, No. 109851 specification sheets of European patent, No. 126712 specification sheets of European patent, the metal arene complex compound of the 174th page of (1986) record of " imaging Scientific Magazine (J.IMAG.SCI.) " the 30th volume, the two luxuriant titanium classes that Japanese kokai publication sho 61-151197 communique is recorded, the transition metal complex that contains the transition metal such as ruthenium that " COORDINATION CHEMISTRY REVIEW " the 84th volume 85th～277 pages (1988) and Japanese kokai publication hei 2-182701 communique are recorded, the aluminate complex compound that Japanese kokai publication hei 3-209477 communique is recorded, the borate compound that Japanese kokai publication hei 2-157760 communique is recorded, 2 of Japanese kokai publication sho 55-127550 communique and the record of Japanese kokai publication sho 60-202437 communique, 4, 5-triarylimidazoles dipolymer, the Organohalogen compounds that carbon tetrabromide and Japanese kokai publication sho 59-107344 communique are recorded, sulfonium complex compound or oxygen sulfonium complex compound that Japanese kokai publication hei 5-255347 communique is recorded, the keto-amine compound that Japanese kokai publication sho 54-99185 communique and Japanese kokai publication sho 63-264560 communique are recorded, TOHKEMY 2001-264530 communique, TOHKEMY 2001-261761 communique, TOHKEMY 2000-80068 communique, TOHKEMY 2001-233842 communique, Japanese Unexamined Patent Application Publication 2004-534797 communique, USP3558309 specification sheets (1971), the oxime ester compound that USP4202697 specification sheets (1980) and Japanese kokai publication sho 61-24558 communique are recorded etc.Usage quantity during about these polymerization starters of use, preferably contains with the scope of 0.01 to 10 weight part with respect to free-radical polymerised compound (B) 100 weight parts.
In addition, the polymerization when preventing from preserving, can add thermal polymerization inhibitor in Polymerizable composition of the present invention.
Can enumerate p methoxy phenol, quinhydrones, alkyl replacement quinhydrones, pyrocatechol, tert-butyl catechol, phenothiazine etc. as the concrete example that can add the thermal polymerization inhibitor in Polymerizable composition of the present invention to.Usage quantity while using these thermal polymerization inhibitors, preferably adds with the scope of 0.001 to 5 weight part with respect to free-radical polymerised compound (B) 100 weight parts.
In addition, in order further to promote polymerization, Polymerizable composition of the present invention can also add polymerization promotor, the chain transfer catalyst take amine and mercaptan, disulphide etc. as representative.
Can enumerate for example N-phenylglycine as adding polymerization promotor in Polymerizable composition of the present invention and the concrete example of chain transfer catalyst to, trolamine, N, the amines such as N-Diethyl Aniline, the thio-alcohol that No. 4414312 specification sheets of USP and Japanese kokai publication sho 64-13144 communique are recorded, the disulfides that Japanese kokai publication hei 2-291561 communique is recorded, the thiones that No. 3558322 specification sheets of USP and Japanese kokai publication sho 64-17048 communique are recorded, adjacent acyl group thiol oxime acid esters and N-alkoxy pyridines thiones that Japanese kokai publication hei 2-291560 communique is recorded.
Polymerizable composition of the present invention can also mix according to object oxygen scavenger and reductive agent, photographic fog preventing agent, the preventing agent of fading, halation preventing agent, white dyes, tensio-active agent, tinting material, extender, softening agent, fire retardant, antioxidant, UV light absorber, whipping agent, mould inhibitor, static inhibitor, magnetic substances such as using dyestuff, organic and mineral dye, phosphine, phosphonate, phosphite or give additive, the diluting solvent etc. of other various characteristicses.
In order to promote polymerization, Polymerizable composition of the present invention can also add sensitizing agent (C).Because sensitizing agent can improve the activity to the light of near infrared region to ultraviolet, preferably add sensitizing agent in the situation that need to promote polymerizability.
Concrete example as this sensitizing agent can be enumerated the unsaturated ketone take chalcone derivative and dibenzalacetone etc. as representative, take benzil and camphorquinone etc. as representative 1, 2-derovatives, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivative, xanthene derivative, thioxanthene derivative, xanthone derivative, thioxanthone derivates, coumarin derivatives, ketone group coumarin derivatives, cyanines derivative, portion spends cyanines derivative, the sheep polymethine pigments such as cyanines (Oxonol) derivative of mixing, acridine derivatives, azine derivatives, thiazine derivative, oxazine derivative, indoline derivative thing, azulene derivatives, azulene salt derivative, the sour cyanines derivative in side, derivatives of porphyrin, Tetraphenyl porphyrin derivative, triarylmethane derivatives, Tetrabenzoporphyrin derivative, four pyrazinyl tetraazatetradecane porphyrin derivatives, phthalocyanine derivates, four azepine tetraazatetradecane porphyrin derivatives, four quinoxalinyl tetraazatetradecane porphyrin derivatives, naphthalocyanine derivative, sub-phthalocyanine derivates, pyridine salt derivative, sulfo-pyridine salt derivative, Tetraphylline (Tetraphylline) derivative, A Nule (anulene) derivative, volution pyran derivate, volution oxazine derivative, sulfo-volution pyran derivate, carbazole derivative, metal arene complex compound, organic ruthenium complex compound, michaelis ketone derivative etc.In addition, concrete example also can be enumerated the sensitizing agent of the middle record of " specific function material " (, CMC in 1986) of the people such as " functional pigmented chemistry " (, CMC in 1981), gloomy loyal three youths in the pond volume of people's volume such as " pigment handbook " (, talk society in 1986), the former letter in great river of people's volumes such as the former letter in great river.In addition, also can enumerate the sensitizing agent that ultraviolet is shown to absorption to the light display of near infrared region.Sensitizing agent is not limited to above-mentioned example.With regard to sensitizing agent, these materials can use according to arbitrary proportion two or more as required.In above-mentioned sensitizing agent, can enumerate thioxanthone derivates, michaelis ketone derivative etc. as the sensitizing agent of sensitization Photoepolymerizationinitiater initiater of the present invention especially aptly.More specifically can enumerate 2,4-diethyl thioxanthone, CTX, 2,4-bis-clopenthixal ketones, ITX, ITX, the chloro-4-propoxy-of 1-thioxanthone, 4,4 '-bis-(dimethylamino) benzophenone, 4,4 '-bis-(diethylamino) benzophenone etc., but be not limited to these.
About using the usage quantity of sensitizing agent of the present invention when (C), be 0.01 to 60 weight part, be preferably 0.01 to 30 weight part, 0.1 to 10 weight part more preferably with respect to free-radical polymerised compound (B) 100 weight parts.
Polymeric composition of the present invention can add coloring components (D) according to carrying out painted object.As coloring components (D), can use known pigment in the past.In addition, in order to obtain required form and aspect, can contain dyestuff in the scope that does not reduce thermotolerance, weathering resistance.In order to obtain required depth of shade, form and aspect, these can use separately or two or more at random mixes use.
As pigment, can use such as pigment dyestuff, mineral dye or carbon black (such as Shawinigan black, thermally oxidized black, furnace treated black etc.), pigment can mix two or more to use.
As pigment dyestuff, can enumerate such as diketopyrrolopyrrolecocrystals series pigments, azo pigment (such as azo, tetrazo, polyazo etc.), phthualocyanine pigment (such as copper phthalocyanine, copper halide phthalocyanine, metal-free phthalocyanine etc.), anthraquione pigmentss (such as aminoanthraquinone, diamino DIANTHRAQUINONE, anthracene pyrimidine, yellow anthrone, anthanthrone, indanthrone, pyranthrone, violanthrone etc.), quinacridone pigment, two piperazine series pigments, purple cyclic ketones series pigments, perylene pigments, thioindigo series pigments, isoindoline series pigments, isoindolinone pigment, quinophthalone series pigments, reduction pigments or metal complex series pigments etc.
As mineral dye, such as can enumerate titanium oxide, the flowers of zinc, zinc sulphide, white lead, calcium carbonate, settleability barium sulfate, white carbon black, white lake, kaolin, talcum, wilkinite, iron oxide black, carbon black, cadmium red, red iron oxide, chrome vermillion, molybdic acid orange, chrome vermilion, lead and yellow-collation, cadmium yellow, iron oxide yellow, titan yellow, chromic oxide, chrome green (viridian) pigment, cobalt titanate green, cobalt green, turkey blue, victoria green, ultramarine, Prussian blue, cobalt blue, azure, cobalt silicon indigo plant, cobalt zinc silicon indigo plant, manganese violet or cobalt violet etc.
As carbon black, can enumerate for example Degussa company system " Special Black 350, 250, 100, 550, 5, 4, 4A, 6 " " Printex U, V, 140U, 140V, 95, 90, 85, 80, 75, 55, 45, 40, P, 60, L6, L, 300, 30, 3, 35, 25, A, G ", system " the REGAL 400R of Cabot company, 660R, 330R, 250R " " MOGUL E, L ", system " the MA7 of society of Mitsubishi Chemical, 8, 11, 77, 100, 100R, 100S, 220, 230 " " #2700, #2650, #2600, #200, #2350, #2300, #2200, #1000, #990, #980, #970, #960, #950, #900, #850, #750, #650, #52, #50, #47, #45, #45L, #44, #40, #33, #332, #30, #25, #20, #10, #5, CF9, #95, #260 " etc.
In addition, below, the color index for pigment (C.I.) number that can be used for polymeric composition of the present invention is represented.
As red pigment, such as can use C.I. Pigment red 7,9,14,41,48:1,48:2,48:3,48:4,81:1,81:2,81:3,97,122,123,146,149,168,177,178,180,184,185,187,192,200,202,208,210,215,216,217,220,223,224,226,227,228,240,246,254,255,264,272 etc., but be not limited to this.
As yellow ultramarine, can use for example C.I. Pigment Yellow 73 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199 etc., but be not limited to this.
As orange pigments, such as can use C.I. pigment orange 36,43,51,55,59,61 etc., but be not limited to this.
As veridian, such as can use C.I. pigment Green 7,10,36, the veridians such as 37 etc., but be not limited to this.
As blue pigments, such as can use C.I. pigment Blue 15,15:1,15:2,15:3,15:4,15:6,16,22,60,64 etc., but be not limited to this.
As violet pigment, such as can use C.I. pigment violet 1,19,23,27,29,30,32,37,40,42,50 etc., but be not limited to this.
As black pigment, can use such as C.I. Pigment black 1,6,7,12,20,31 etc., but be not limited to this.
These pigment can mix two or more and use with arbitrary proportion.
Usage quantity when adding as the pigment of these coloring components (D), is 0.01～100 weight part, is preferably 1～60 weight part with respect to free-radical polymerised compound (B) 100 weight parts.
From the viewpoint of the uptake factor (suitability of spectrum) of visible ray and transparent, the particle diameter of pigment is preferably fully little with respect to visible light wavelength.That is, pigment optimization average primary particle diameter is below the above 0.3 μ m of 0.01 μ m, particularly preferably below the above 0.1 μ m of 0.01 μ m.In addition, primary particle size refers to the diameter of the pigment particles of least unit, measures with electron microscope.
The primary particle size of pigment can be controlled in suitable scope with known diverting device such as sand mill, kneader, twin-roll machine etc.
In addition, while adding pigment to polymeric composition of the present invention, in order to improve the dispersiveness of pigment and the storage stability of polymeric composition, can use pigment derivative, pigment dispersing agent.
Here, pigment derivative refers to and in organic pigment, introduces substituent compound.In organic pigment, also comprise the flaxen aromatic series polynuclear compounds such as the phthalic imidine system that is not generally called as pigment, naphthalene system, naphthoquinones system, anthracene system, anthraquinone system.
As pigment derivative, can use the material of recording in Japanese kokai publication sho 63-305173 communique, Japanese Patent Publication 57-15620 communique, Japanese Patent Publication 59-40172 communique, Japanese Patent Publication 63-17102 communique, Japanese Patent Publication 5-9469 communique, Japanese kokai publication hei 06-306301 communique, TOHKEMY 2001-220520 communique, TOHKEMY 2003-238842 communique etc.These can use separately or two or more mixes use.
As pigment dispersing agent, can use salt, high molecular unsaturated acid ester, high-molecular copolymer, modified polyurethane, modified polyacrylate, the polyether ester type negatively charged ion of salt, long-chain polyaminoamide and the polar acid ester of salt, the high molecular poly carboxylic acid of hydroxyl carboxylicesters, long-chain polyaminoamide and high molecular acid esters is promoting agent, naphthalene sulfonic acidformaldehyde condensation product salt, aromatic sulphonic acid formaldehyde condensation products salt, polyethylene oxide alkyl phosphate, polyethylene oxide nonylplenyl ether, stearylamine acetic ester etc.
As the concrete example of pigment dispersing agent, can enumerate BYK Chemie company system " Anti-Terra-U (polyaminoamide phosphate) ", " Anti-Terra-203/204 (high molecular polycarboxylate) ", " Disperbyk-101 (polyaminoamide phosphate and acid esters), 107 (hydroxyl carboxylicesterss), 110, 111 (multipolymers that contain acidic group), 130 (polymeric amide), 161, 162, 163, 164, 165, 166, 170 (high-molecular copolymers) ", " 400 ", " Bykumen " (high molecular unsaturated acid ester), " BYK-P104, P105 (high molecular unsaturated acid poly carboxylic acid) ", " P104S, 240S (high molecular unsaturated acid poly carboxylic acid and silicon system) ", " Lactimon (long-chain amine, unsaturated acid poly carboxylic acid and silicon) ".
In addition, can enumerate the system " EFKA44 of Efka CHEMICALS company, 46, 47, 48, 49, 54, 63, 64, 65, 66, 71, 701, 764, 766 ", " EFKA polymkeric substance 100 (modified polyacrylate), 150 (fatty family is polymer-modified), 400, 401, 402, 403, 450, 451, 452, 453 (modified polyacrylates), 745 (copper phthalocyanine systems) ", common prosperity society chemistry society's system " FLOWLEN TG-710 (oligourethane) ", " FLOWNON SH-290, SP-1000 ", " Polyflow No.50E, No.300 (acrylic copolymer) ", nanmu originally changes into society's system " DISPARLON KS-860, 873SN, 874 (macromolecule dispersing agents), #2150 (aliphatics polycarboxylic acid), #7004 (polyether ester type) ".
And then, can enumerate Hua Wangshe system " DEMOL RN, N (naphthalene sulfonic acidformaldehyde condensation product sodium salt), MS, C, SN-B (aromatic sulphonic acid formaldehyde condensation products sodium salt), EP ", " HOMOGENOL L-18 (polyocarboxy acid type polymer) ", " Emulgen 920, 930, 931, 935, 950, 985 (polyethylene oxide nonylplenyl ethers) ", " ACETAMIN 24 (coconut amine acetic ester (コ コ Na Star Star ア ミ Application ア セ テ mono-ト)), 86 (stearylamine acetic ester) ", Avecia society system " Solsperse 5000 (phthalocyanine ammonium salt system), 13940 (polyesteramine systems), 17000 (fatty acid amine systems), 24000GR, 32000, 33000, 39000, 41000, 53000 ", day system " the Nikkol T106 (polyethylene oxide sorbitan monooleate) of photochemistry society, MYS-IEX (polyoxyethylene monostearate), Hexagline 4-0 (six glyceryl four oleic acid esters) ", system " the Adisper PB821 of aginomoto fine chemistry company, 822, 824 " etc.
There is no particular limitation for the addition of above-mentioned pigment derivative and pigment dispersing agent, but be preferably 0.1～40 weight part, 0.1～30 weight part more preferably with respect to pigment 100 weight parts.
As the dyestuff that can contain in order to obtain required form and aspect, can enumerate azo based dye, anthraquinone based dye, phthalocyanine based dye, quinonimine based dye, quinoline based dye, nitro based dye, phosphinylidyne based dye, methine based dye etc.
As azo based dye, can enumerate for example C.I. acid yellow 11, C.I. acid orange 7, C.I. Xylene Red 37, C.I. acid red 18 0, C.I. acid blue 29, C.I. directly red 28, C.I. directly red 83, C.I. direct Huang 12, C.I. direct orange 26, C.I. sun green 28, C.I. sun green 59, C.I. reactive yellow 2, C.I. reactive red 17, C.I. reactive red 120, C.I. reactive black 5, C.I. DISPERSE ORANGE 30 200 5, C.I. part loose red 58, C.I. part loose indigo plant 165, C.I. alkali blue 41, C.I. Basic Red 18, C.I. medium red 7, C.I. medium Huang 5, C.I. Mordant Black 7 etc., but be not limited to this.
As anthraquinone based dye, can enumerate such as C.I. Vat blue 4, C.I. Acid Blue 40, C.I. ACID GREEN 25, C.I. Reactive Blue 19 100, C.I. reactive blue 49, C.I. disperse red 60, C.I. Disperse Blue-56, C.I. Disperse Blue-60 etc., but be not limited to this.
In addition,, as phthalocyanine based dye, can enumerate such as C.I. vat blue 5 etc.; As quinonimine based dye, can enumerate such as C.I. Basic Blue 3, C.I. alkali blue 9 etc.; As quinoline based dye, can enumerate such as C.I. solvent yellow 33, C.I. quinoline yellow, C.I. dispersion yellow 64 etc.; As nitro based dye, can enumerate such as C.I. turmeric yellow 1, C.I. von Muller's indicator 3, C.I. Disperse Yellow 42 etc., but be not limited to this.
Usage quantity while adding these dyestuffs, be 0.01～100 weight part, be preferably 1～60 weight part with respect to free-radical polymerised compound (B) 100 weight parts, but as mentioned above, consider from the viewpoint of thermotolerance, weathering resistance, preferably usage quantity is not too much.
Form and use etc. for image for the photo anti-corrosion agent material as so-called alkali developable, Polymerizable composition of the present invention can mix and use with alkali soluble resin (E).Alkali soluble resin of the present invention (E) as long as the developing solution that plays the effect of tackiness agent and use in forming when picture pattern for this development treatment operation, just there is no particular limitation particularly preferably alkaline-based developer to be had to solubility.Wherein preferably as the alkali soluble resin of carboxy-containing copolymer, particularly preferably there is the multipolymer (hereinafter to be referred as " carboxy-containing copolymer ") of the ethylenically unsaturated monomer (hereinafter to be referred as " copolymerizable unsaturated monomer ") that the ethylenically unsaturated monomer (hereinafter to be referred as " containing carboxyl unsaturated monomer ") of more than 1 carboxyl and other can copolymerization.
Can enumerate the unsaturated monocarboxylic classes such as vinylformic acid, methacrylic acid, β-crotonic acid, α-chloroacrylic acid, TRANSCINNAMIC ACID as the example containing carboxyl unsaturated monomer; Unsaturated dicarboxylic acid or its anhydrides such as toxilic acid, maleic anhydride, fumaric acid, methylene-succinic acid, itaconic anhydride, citraconic acid, citraconic anhydride, methylfumaric acid; Unsaturated polycarboxylic acid more than ternary or its anhydrides; List [(methyl) acryloxyalkyl] the ester class of the polycarboxylic acids more than binary such as mono succinate (2-acryloxy ethyl), mono succinate (2-methacryloxyethyl), phthalic acid list (2-acryloxy ethyl), phthalic acid list (2-methacryloxyethyl); ω-carboxyl polycaprolactone single-acrylate, ω-carboxyl polycaprolactone monomethacrylates etc. have list (methyl) esters of acrylic acid of the polymkeric substance of carboxyl and hydroxyl etc. at two ends.These are containing in carboxyl unsaturated monomer, and mono succinate (2-acryloxy ethyl) and phthalic acid list (2-acryloxy ethyl) are sold with the trade(brand)name of M-5300 and M-5400 (East Asia synthetic (strain) manufactures) respectively.Above-mentionedly can use separately or mix two or more and use containing carboxyl unsaturated monomer.
In addition, as copolymerizable unsaturated monomer such as can enumerate vinylbenzene, alpha-methyl styrene, adjacent Vinyl toluene, a Vinyl toluene, to Vinyl toluene, to chloro-styrene, O-methoxy vinylbenzene, meta-methoxy vinylbenzene, to methoxy styrene, adjacent vinyl benzyl methyl ether, a vinyl benzyl methyl ether, to vinyl benzyl methyl ether, adjacent vinyl benzyl glycidyl ether, a vinyl benzyl glycidyl ether, to aromatic ethenyl compounds such as vinyl benzyl glycidyl ethers, the indenes classes such as indenes, 1-methyl indenes
Methyl acrylate, methyl methacrylate, ethyl propenoate, β-dimethyl-aminoethylmethacrylate, vinylformic acid n-propyl, n propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-BMA, isobutyl acrylate, Propenoic acid, 2-methyl, isobutyl ester, sec-butyl acrylate, the secondary butyl ester of methacrylic acid, tert-butyl acrylate, Tert-butyl Methacrylate, 2-Hydroxy ethyl acrylate, methacrylic acid-2-hydroxy methacrylate, 2-hydroxypropyl acrylate, methacrylic acid-2-hydroxy propyl ester, vinylformic acid-3-hydroxy propyl ester, methacrylic acid-3-hydroxy propyl ester, vinylformic acid-2-hydroxyl butyl ester, methacrylic acid-2-hydroxyl butyl ester, vinylformic acid-3-hydroxyl butyl ester, methacrylic acid-3-hydroxyl butyl ester, vinylformic acid-4-hydroxyl butyl ester, methacrylic acid-4-hydroxyl butyl ester, allyl acrylate, allyl methacrylate(AMA), benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, vinylformic acid-2-methoxyl group ethyl ester, methacrylic acid-2-methoxyl group ethyl ester, vinylformic acid-2-phenoxy ethyl, methacrylic acid-2-phenoxy ethyl, methoxyl group Diethylene Glycol acrylate, methoxyl group Diethylene Glycol methacrylic ester, methoxyl group triethylene glycol acrylate, methoxyl group triethylene glycol methacrylic ester, MPEG acrylate, MPEG methacrylic ester, methoxyl group dipropylene glycol acrylate, methoxyl group dipropylene glycol methacrylic ester, isobornyl acrylate, isobornyl methacrylate, vinylformic acid Dicyclopentadiene (DCPD) ester, methacrylic acid Dicyclopentadiene (DCPD) ester, vinylformic acid-2-hydroxyl-3-phenoxy group propyl ester, methacrylic acid-2-hydroxyl-3-phenoxy group propyl ester, glycerine mono acrylic ester, the unsaturated carboxylate types such as glycerin monomethyl acrylic ester,
The unsaturated carboxylic acid aminoalkyl ester classes such as vinylformic acid-2-amino ethyl ester, methacrylic acid-2-amino ethyl ester, vinylformic acid-2-dimethylamino ethyl ester, methacrylic acid-2-dimethylamino ethyl ester, the amino propyl ester of vinylformic acid-2-, the amino propyl ester of methacrylic acid-2-, vinylformic acid-2-dimethylamino propyl ester, methacrylic acid-2-dimethylamino propyl ester, the amino propyl ester of vinylformic acid-3-, the amino propyl ester of methacrylic acid-3-, vinylformic acid-3-dimethylamino propyl ester, methacrylic acid-3-dimethylamino propyl ester
Glycidyl acrylate, the unsaturated carboxylic acid glycidyl ester classes such as glycidyl methacrylate, vinyl acetate, propionate, vinyl butyrate, the vinyl carboxylates classes such as vinyl benzoate, methoxy ethylene, ethyl vinyl ether, the unsaturated ethers such as glycidyl allyl ether, vinyl cyanide, methacrylonitrile, α-chloro-acrylonitrile, the vinyl cyanide based compounds such as vinyl cyanide fork, acrylamide, Methacrylamide, α-propenyl chloride acid amides, N-2-hydroxyethyl acrylamide, the unsaturated acyl amines such as N-2-hydroxyethyl methacrylamide, maleimide, N-phenylmaleimide, the unsaturated acid imides such as N-N-cyclohexylmaleimide, 1,3-butadiene, isoprene, the aliphatics conjugated dienes such as chloroprene, polystyrene, polymethyl acrylate, polymethylmethacrylate, the positive butyl ester of polyacrylic acid, Vinalac 5920, the end of the polymer molecular chains such as polysiloxane has the macromonomer class of single acryl or monomethyl acryl etc.These copolymerizable unsaturated monomers can use separately or mix two or more and use.
In the present invention, preferred carboxy-containing copolymer (hereinafter referred to as " carboxy-containing copolymer (R) ") is by (P) and (Q) polymerization and obtaining; Described (P) is using vinylformic acid and/or methacrylic acid as neccessary composition, according to circumstances further contain at least a kind of compound being selected from mono succinate (2-acryloxy ethyl), mono succinate (2-methacryloxyethyl), ω-carboxyl polycaprolactone single-acrylate and ω-carboxyl polycaprolactone monomethacrylates containing carboxyl unsaturated monomer composition; Described (Q) is at least a kind that is selected from vinylbenzene, methyl acrylate, methyl methacrylate, 2-Hydroxy ethyl acrylate, methacrylic acid-2-hydroxy methacrylate, allyl acrylate, allyl methacrylate(AMA), benzyl acrylate, benzyl methacrylate, glycerine mono acrylic ester, glycerin monomethyl acrylic ester, N-phenylmaleimide, Group-capped Polystyrene Macromer and polymethylmethacrylate macromonomer.
Can enumerate (methyl) vinylformic acid/(methyl) methyl acrylate copolymer as the concrete example of carboxy-containing copolymer (R), (methyl) vinylformic acid/(methyl) benzyl acrylate multipolymer, (methyl) vinylformic acid/(methyl) 2-Hydroxy ethyl acrylate/(methyl) benzyl acrylate multipolymer, (methyl) vinylformic acid/(methyl) methyl acrylate/Group-capped Polystyrene Macromer multipolymer, (methyl) vinylformic acid/(methyl) methyl acrylate/polymethylmethacrylate macromonomer multipolymer, (methyl) vinylformic acid/(methyl) benzyl acrylate/Group-capped Polystyrene Macromer multipolymer, (methyl) vinylformic acid/(methyl) benzyl acrylate/polymethylmethacrylate macromonomer multipolymer, (methyl) vinylformic acid/(methyl) 2-Hydroxy ethyl acrylate/(methyl) benzyl acrylate/Group-capped Polystyrene Macromer multipolymer, (methyl) vinylformic acid/(methyl) 2-Hydroxy ethyl acrylate/(methyl) benzyl acrylate/polymethylmethacrylate macromonomer multipolymer, methacrylic acid/vinylbenzene/(methyl) benzyl acrylate/N-phenylmaleimide multipolymer, (methyl) vinylformic acid/mono succinate [2-(methyl) acryloxy ethyl]/vinylbenzene/(methyl) benzyl acrylate/N-phenylmaleimide multipolymer, (methyl) vinylformic acid/mono succinate [2-(methyl) acryloxy ethyl]/vinylbenzene/(methyl) allyl acrylate/N-phenylmaleimide multipolymer, (methyl) vinylformic acid/vinylbenzene/(methyl) benzyl acrylate/glycerine list (methyl) acrylate/N-phenylmaleimide multipolymer, (methyl) vinylformic acid/ω-carboxyl polycaprolactone list (methyl) acrylate/vinylbenzene/(methyl) benzyl acrylate/glycerine list (methyl) acrylate/N-phenylmaleimide multipolymer etc.
The substituting group existing in carboxy-containing copolymer molecule can also be modified by other materials.For example, by making a part for the carboxyl existing in this polymkeric substance and knownly thering is monomer that glycidyl etc. has reactive functional group of same carboxyl and react and modify, the cross-linking set relevant with radical polymerization can also be set in molecule.Glycidyl (methyl) alkyl acrylate can be used as such monomer, for example glycidyl (methyl) vinylformic acid, glycidyl (methyl) methyl acrylate, glycidyl (methyl) ethyl propenoate, glycidyl (methyl) butyl acrylate, glycidyl (methyl) ethyl acrylate can be enumerated.In addition; the hydroxyl existing in this polymkeric substance by with the condensation such as 2-acryloxy ethyl isocyanate, 2-methacryloyl ethyl isocyanate (clear and electrician's (strain) manufactures " Karenz MOI "), same polymerization crosslinking point also can be set.
The copolymerization ratio containing carboxyl unsaturated monomer in carboxy-containing copolymer is preferably 5～50 % by weight.For example fruit of above-mentioned copolymerization ratio is less than 5 % by weight, the anti-corrosion agent composition obtaining has the tendency of reduction to the solvability of alkaline-based developer, on the other hand, if exceed 50 % by weight, the solvability of alkaline-based developer is become to excessive, in the time developing by alkaline-based developer, there is easy generation resist film to come off and the tendency of the film be full of cracks of imaging surface from base material.The polystyrene conversion weight-average molecular weight (hereinafter referred to as Mw) that alkali soluble resin of the present invention is measured by gel permeation chromatography (GPC, eluent: tetrahydrofuran (THF)) is preferably 3,000～300,000, more preferably 5,000～100,000.In addition, the polystyrene conversion number-average molecular weight (hereinafter referred to as Mn) that alkali soluble resin of the present invention is measured by gel permeation chromatography (GPC, eluent: tetrahydrofuran (THF)) is preferably 3,000～60,000, more preferably 5,000～25,000.In the present invention, by using this alkali soluble resin with specific Mw and Mn, can obtain the radioactive rays responsive type composition of developability excellence.Can form thus and there is the picture pattern of pattern edge clearly, while development, on the substrate of irradiation portion not and on light shield layer, be difficult to produce that residue, ground pollute, film is residual etc. simultaneously.In addition, the ratio (Mw/Mn) of the Mw of alkali soluble resin of the present invention and Mn is preferably 1～5, and particularly preferably 1～4.
The resin that can enumerate phenolic varnish type resin or polycarboxylated styrene etc. and have phenol hydroxyl as the alkali soluble resin (E) beyond above-mentioned carboxy-containing copolymer, their modification body is also included within alkali soluble resin of the present invention (E).
In the present invention, alkali soluble resin (E) can use separately or mixes two or more and use.
Usage quantity while using alkali soluble resin (E) in the present invention is 10～600 weight parts with respect to free-radical polymerised compound (B) 100 weight parts.
In the time of polyreaction, by giving the energy of the generations such as ultraviolet ray, visible rays, near infrared ray etc., electron beam, polymerization can obtain the polymkeric substance as target to Polymerizable composition of the present invention.As the light source of giving energy, preferably there is the light source of predominant wavelength luminous in the wavelength region may of 250nm to 450nm.As the example of light source with predominant wavelength luminous in the wavelength region may of 250nm to 450nm, can enumerate ultrahigh pressure mercury lamp, high voltage mercury lamp, medium pressure mercury lamp, xenon-mercury lamp, metal halide lamp, high-power metallic halide lamp, xenon lamp, pulsed illumination xenon lamp, deuterium lamp, luminescent lamp, Nd-YAG3 times ripple laser, He-Cd laser, nitrogen laser, Xe-Cl excimer laser, Xe-F excimer laser, semi-conductor and excite the various light sources such as Solid State Laser.In addition " rock ripple Physicochemical dictionary the 4th edition " (, the rock ripple in 1987) that, in this specification sheets, the definition of said ultraviolet ray, visible ray, near infrared ray etc. is compiled based on people such as Kubos bright five.
Polymerizable composition of the present invention can be applied to various ink, jetted ink, outer dope, various brush plate material, photo-resist, electronic photo, directly brush the various recording mediums such as sensitive materials, microcapsule such as plate material, optical fiber, hologram material and then caking agent, tackiness agent, glue solid, release-coated agent, sealing agent and various coating.
[picture pattern formation method]
Containing the Polymerizable composition of the present invention that basic resin (E) forms can be used as: on base material after coating, expose with energy line partly and solidify, utilize alkaline-based developer to remove unexposed part, the negative resist using while forming picture pattern.
The picture pattern formation method that has used the negative resist of the present invention that contains basic resin (E) is described.First, on the surface of base material, be coated with after the fluid composition of negative resist, carry out prebake and make solvent evaporation and form film.Then film is become after pattern-like across photomask exposure, utilize alkaline-based developer to develop, dissolve the unexposed portion of removing film.Then, after carrying out as required, cure, thereby can form target image pattern.
Be coated with the fluid composition of negative resist on base material time, can adopt the known coating processes such as spraying, spin coating, slot coated, roller coat.Coating thickness can suitably change according to purposes, but as dried thickness, preferably 0.1～200 μ m, 0.2～100 μ m more preferably.
In addition; can also use as follows negative resist of the present invention;; on the basement membrane by mainly the polyester take polyethylene terephthalate as representative, polypropylene, polyethylene etc. form, negative resist layer of the present invention is set; clamp this negative resist layer, the so-called industry known mode that is called as dry film with protective membrane as required.This dry film is normally peeled off said protection film, and closely sealed will formation on the base material of resist pattern is layered on base material and uses with heating condition and then with pressurized conditions as required.Pattern exposure while using negative resist of the present invention in dry film mode also can be under the state of not peeling off above-mentioned basement membrane and is implemented, and now, removes above-mentioned basement membrane and implement alkaline development after exposure.
The energy that obtains the irradiation of polymkeric substance in order to make the negative resist polymerization of the present invention that contains basic resin (E) is identical with the situation that is obtained polymkeric substance by above-mentioned polymeric composition of the present invention.
Therefore, contain the negative resist of the present invention that basic resin (E) forms, by giving by low pressure mercury lamp, medium pressure mercury lamp, high voltage mercury lamp, ultrahigh pressure mercury lamp, xenon lamp, pulsed illumination xenon lamp, carbon arc lamp, metal halide lamp, luminescent lamp, tungsten lamp, argon laser, helium cadmium laser, He-Ne Lasers, krypton ion laser, various semiconductor lasers, YAG laser, photodiode, CRT light source, plasma light source, electron beam, gamma-rays, ArF excimer laser, KrF excimer laser, the energy that the various light sources such as F2 laser produce, can obtain subject polymer, cured article.
Therefore,, in picture pattern formation method of the present invention, can in the time of exposure, use the energy line by above-mentioned light source.Particularly preferably wavelength is at the energy line of the scope of 190～450nm.Exposure is due to also relevant with thickness, thus can not determine without exception, but be generally 0.5～100000J/m 2.
Can enumerate film or the substrate of for example glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamidoimide, polyimide, epoxy glass system as the base material using in picture pattern formation method of the present invention, but be not limited to this.In addition, as required also can be in advance these base materials be implemented to utilize the suitable pre-treatment such as chemical reagent processing, Cement Composite Treated by Plasma, ion plating, sputter, gas-phase reaction method, vacuum evaporation of silane coupling agent etc.
Can be for example to contain any one in liquid method, pickling process, shower method, spray method etc. as the developing method adopting in picture pattern formation method of the present invention.Development time at 20～30 ℃, preferably 5～300 seconds.In addition, can use for example sodium hydroxide as alkaline-based developer, potassium hydroxide, sodium carbonate, water glass, Starso, the inorganic bases such as ammonia, ethamine, the primary amine classes such as Tri N-Propyl Amine, diethylamide, the secondary amine classes such as di-n-propyl amine, Trimethylamine, methyl diethylamide, ethyl dimethyl amine, the tertiary amines such as triethylamine, dimethylethanolamine, methyldiethanolamine, the alkanol tertiary amines such as trolamine, pyrroles, piperidines, N-methyl piperidine, N-crassitude, 30-diazabicyclo [5.4.0]-7-undecylene, 1, 5-diazabicyclo [4.3.0]-tertiary amines such as 5-nonene, Tetramethylammonium hydroxide, the aqueous solution of the basic cpds such as quaternary ammonium salt such as tetraethyl ammonium hydroxide.In addition, in the aqueous solution of above-mentioned basic cpd, also can add in right amount the water-miscible organic solvent such as methyl alcohol, ethanol and/or tensio-active agent.
Compound of the present invention by irradiation energy line particularly light can effectively generate living radical, so can bring into play the function of high sensitive radical polymerization initiator.Therefore the radical-polymerizable composition that, contains radical polymerization initiator of the present invention (A) is the high sensitive Polymerizable composition that can carry out in the short period of time polymerization.Therefore, the Polymerizable composition of the application of the invention, can provide the suitable negative resist with alkali-developable as photo anti-corrosion agent material and use the picture pattern formation method of this negative resist.And then, by adopting this picture pattern formation method that suitable picture pattern can be provided.
Embodiment
Describe by the following examples the present invention in detail, but the present invention has more than and is limited to following embodiment.In addition, in the situation that being not particularly limited, in example, " part " expression " weight part ".
First, compound of the present invention is represented to synthesis example.
Embodiment 1
Radical polymerization initiator: compound (1) synthetic
First the compound (A) of the synthetic intermediate as compound (1), as follows.
[changing 35]
compound (A)
100.0g N-benzophenone base carbazole is dissolved in 1000ml chloroform, adds 85.0g aluminum chloride, 0 ℃ stir under, dripped 32.0g propionyl chloride through 2 hours and be dissolved in the solution of 500ml chloroform.After dropping finishes, stir 4 hours at 25 ℃.Reaction solution is poured in 2000g frozen water, extracted with 2000ml chloroform.Use dried over mgso organic layer, filtration drying agent, then carries out recrystallization by chloroform/methanol to residue, obtains thus 105.0g compound (A) (yield 90.5%).
Then, use compound (A) compound (B) of the synthetic precursor as compound (1) as follows obtaining.
[changing 36]
compound (B)
100.0g compound (A) is dissolved in the mixing solutions of 1000ml tetrahydrofuran (THF) and 500ml concentrated hydrochloric acid, under room temperature stirs, dripped 38.4g nitrite tert-butyl through 1 hour.After dropping finishes, stirring at room temperature 5 hours.Reaction solution is injected to 1600ml frozen water, extract with 1600ml chloroform.Organic layer is washed to (500ml × 3 time), and by dried over mgso, then filtration drying agent, heats up in a steamer desolventizing, with normal hexane wash residual thing, obtains thus 99.8g compound (B) (yield 93.0%).
Then, use the following synthetic compound (1) of the compound (B) obtaining.
In 300ml ethyl acetate, stir 30.0g compound (B), add 6.3g diacetyl oxide, 10.6g sodium acetate, and reflux 3 hours.Then, reaction solution is injected to 500ml frozen water, be extracted with ethyl acetate resultant, organic layer is washed to (300ml × 3 time), by dried over mgso, then filtration drying agent, heats up in a steamer desolventizing, residue is carried out to recrystallization with ethyl acetate-hexane, obtain thus 31.4g compound (1) (yield 95.4%).
Embodiment 2
Radical polymerization initiator: compound (2) synthetic
First the compound (C) of the synthetic intermediate as compound (2), as follows.
[changing 37]
compound (C)
100.0g N-benzophenone base carbazole is dissolved in 1000ml chloroform, adds 84.0g aluminum chloride, 0 ℃ stir under, dripped 36.8g butyryl chloride through 2 hours and be dissolved in the solution of 500ml chloroform.After dropping finishes, stir 4 hours at 25 ℃.Reaction solution is poured in 2000g frozen water, extracted with 2000ml chloroform.Use dried over mgso organic layer, filtration drying agent, then carries out recrystallization by chloroform/methanol to residue, obtains thus 105.3g compound (C) (yield 87.6%).
Then, use compound (C) compound (D) of the synthetic precursor as compound (2) as follows obtaining.
[changing 38]
compound (D)
100.0g compound (C) is dissolved in the mixing solutions of 1000ml tetrahydrofuran (THF) and 500ml concentrated hydrochloric acid, under room temperature stirs, dripped 37.0g nitrite tert-butyl through 1 hour.After dropping finishes, stirring at room temperature 5 hours.Reaction solution is injected to 1600ml frozen water, extract with 1600ml chloroform.Organic layer is washed to (500ml × 3 time), and by dried over mgso, then filtration drying agent, heats up in a steamer desolventizing, with normal hexane wash residual thing, obtains thus 89.3g compound (D) (yield 83.5%).
Then, use the following synthetic compound (2) of the compound (D) obtaining.
In 300ml ethyl acetate, stir 30.0g compound (D), add 6.1g diacetyl oxide, 10.3g sodium acetate, and reflux 3 hours.Then, reaction solution is injected to 500ml frozen water, be extracted with ethyl acetate resultant, organic layer is washed to (300ml × 3 time), and by dried over mgso, then filtration drying agent, heats up in a steamer desolventizing, residue is carried out to recrystallization with ethyl acetate-hexane, obtain thus 30.0g compound (2) (yield 91.4%).
Embodiment 3
Radical polymerization initiator: compound (7) synthetic
Use ice bath cooling while mix 30.0g compound (B), 10.5g triethylamine, 6.8g propionyl chloride and 300ml tetrahydrofuran (THF), then, after 1 hour, further stir 2 hours at 50 ℃ in stirring at room temperature.Then, reaction solution is injected to 600ml frozen water, with 300ml ethyl acetate extraction resultant, organic layer is washed to (200ml × 3 time), by dried over mgso, then filtration drying agent, heats up in a steamer desolventizing, make residue recrystallization with ethylene dichloride-hexane, obtained 33.0g compound (7) (yield 97.4%).
Embodiment 4
Radical polymerization initiator: compound (46) synthetic
First the compound (E) of the synthetic intermediate as compound (46), as follows.
[changing 39]
compound (E)
100.0g N-(p-nitrophenyl) carbazole is dissolved in 1000ml chloroform, adds 101.8g aluminum chloride, 0 ℃ stir under, dripped the solution that 56.0g caproyl chloride is dissolved in to 500ml chloroform through 2 hours.After dropping finishes, stir 4 hours at 25 ℃.Reaction solution is poured in 2000g frozen water, extracted with 2000ml chloroform.Use dried over mgso organic layer, filtration drying agent, then carries out recrystallization by chloroform/methanol to residue, obtains thus 122.5g compound (E) (yield 91.4%).
Then, use compound (E) compound (F) of the synthetic precursor as compound (46) as follows obtaining.
[changing 40]
compound (F)
100.0g compound (E) is dissolved in the mixing solutions of 1000ml tetrahydrofuran (THF) and 500ml concentrated hydrochloric acid, under room temperature stirs, dripped 40.0g nitrite tert-butyl through 1 hour.After dropping finishes, stirring at room temperature 5 hours.Reaction solution is injected to 1600ml frozen water, extract with 1500ml chloroform.Organic layer is washed to (500ml × 3 time), and by dried over mgso, then filtration drying agent, heats up in a steamer desolventizing, with normal hexane wash residual thing, obtain thus 102.8g compound (F) (yield 95.9%).
Then, use the following synthetic compound (46) of the compound (F) obtaining.
In 500ml ethyl acetate, stir 50.0g compound (F), add 18.5g diacetyl oxide, 10.9g sodium acetate, and reflux 3 hours.Then, reaction solution is injected to 500ml frozen water, be extracted with ethyl acetate resultant, organic layer is washed to (500ml × 3 time), and by dried over mgso, then filtration drying agent, heats up in a steamer desolventizing, residue is carried out to recrystallization with ethyl acetate-hexane, obtain thus 55.2g compound (46) (yield 88.7%).
Embodiment 5
Radical polymerization initiator: compound (244) synthetic
First the compound (G) of the synthetic intermediate as compound (244), as follows.
[changing 41]
compound (G)
100.0g N-benzophenone base carbazole is dissolved in 1000ml chloroform, adds 126.7g aluminum chloride, 0 ℃ stir under, dripped 58.6g propionyl chloride through 2 hours and be dissolved in the solution of 500ml chloroform.After dropping finishes, stir 4 hours at 25 ℃.Reaction solution is poured in 2000g frozen water, extracted with 2000ml chloroform.Use dried over mgso organic layer, filtration drying agent, then carries out recrystallization by chloroform/methanol to residue, obtains thus 109.3g compound (G) (yield 82.7%).
Then, use compound (G) compound (H) of the synthetic precursor as compound (244) as follows obtaining.
[changing 42]
compound (H)
100.0g compound (G) is dissolved in the mixing solutions of 1000ml tetrahydrofuran (THF) and 500ml concentrated hydrochloric acid, under room temperature stirs, dripped 67.3g nitrite tert-butyl through 1 hour.After dropping finishes, stirring at room temperature 5 hours.Reaction solution is injected to 1600ml frozen water, extract with 1600ml chloroform.Organic layer is washed to (500ml × 3 time), and by dried over mgso, then filtration drying agent, heats up in a steamer desolventizing, with normal hexane wash residual thing, obtains thus 103.6g compound (H) (yield 94.3%).
Then, use the following synthetic compound (244) of the compound (H) obtaining.
In 500ml ethyl acetate, stir 50.0g compound (H), add 30.4g diacetyl oxide, 17.7g sodium acetate, and reflux 3 hours.Then, reaction solution is injected to 500ml frozen water, be extracted with ethyl acetate resultant, organic layer is washed to (400ml × 3 time), by dried over mgso, then filtration drying agent, heats up in a steamer desolventizing, residue is carried out to recrystallization with ethyl acetate-hexane, obtain thus 58.3g compound (244) (yield 97.7%).
Embodiment 6
Radical polymerization initiator: compound (259) synthetic
First the compound (I) of the synthetic intermediate as compound (259), as follows.
[changing 43]
compound (I)
100.0g N-benzophenone base carbazole is dissolved in 800ml chloroform, adds 128.6g aluminum chloride, 0 ℃ stir under, dripped the solution that 49.0g phenyllacetyl chloride is dissolved in to 300ml chloroform through 2 hours.After dropping finishes, stir 4 hours at 25 ℃.Reaction solution is stirred at 0 ℃ again, dripped the solution that 33.8g propionyl chloride is dissolved in to chloroform 200ml through 2 hours.After dropping finishes, stir 3 hours at 25 ℃.Reaction solution is poured in 1800g frozen water, extracted with 2000ml chloroform.Use dried over mgso organic layer, filtration drying agent, then carries out recrystallization by chloroform/methanol to residue, obtains thus 128.6g compound (I) (yield 85.6%).
Then, by the compound obtaining (I) compound (J) of the synthetic precursor as compound (259) as follows.
[changing 44]
compound (J)
100.0g compound (I) is dissolved in the mixing solutions of 1000ml tetrahydrofuran (THF) and 500ml concentrated hydrochloric acid, under room temperature stirs, dripped 59.3g nitrite tert-butyl through 1 hour.After dropping finishes, stirring at room temperature 5 hours.Reaction solution is injected to 1600ml frozen water, extract with 1600ml chloroform.Organic layer is washed to (500ml × 3 time), and by dried over mgso, then filtration drying agent, heats up in a steamer desolventizing, with normal hexane wash residual thing, obtains thus 101.7g compound (J) (yield 91.5%).
Then, use the following synthetic compound (259) of the compound (J) obtaining.
In 500ml ethyl acetate, stir 50.0g compound (J), add 26.4g diacetyl oxide, 15.6g sodium acetate, and reflux 3 hours.Then, reaction solution is injected to 500ml frozen water, be extracted with ethyl acetate resultant, organic layer is washed to (400ml × 3 time), by dried over mgso, then filtration drying agent, heats up in a steamer desolventizing, residue is carried out to recrystallization with ethyl acetate-hexane, obtain thus 50.8g compound (259) (yield 88.8%).
Embodiment 7
Radical polymerization initiator: compound (263) synthetic
Synthesizing of compound (263)
Use ice bath cooling while mix 30.0g compound (H), 17.6g triethylamine, 9.8g Benzoyl chloride and 300ml tetrahydrofuran (THF), then, after 1 hour, further stir 2 hours at 50 ℃ in stirring at room temperature.After again using ice bath cooling reaction solution, add 5.5g Acetyl Chloride 98Min.,, after 1 hour, further stir 2 hours at 50 ℃ in stirring at room temperature.Then, reaction solution is injected to 600ml frozen water, with 300ml ethyl acetate extraction resultant, organic layer is washed to (200ml × 3 time), by dried over mgso, then filtration drying agent, heats up in a steamer desolventizing, with the refining residue of silica gel chromatography (hexane/chloroform), obtain 25.3g compound (7) (yield 65.7%).
Embodiment 8～108
Carry out respectively oximate and esterification according to the condition shown in table 1, can obtain compound of the present invention.
The condition of esterification
Condition (A): similarly to Example 1, utilize diacetyl oxide and sodium acetate to carry out synthetic method
Condition (B): similarly to Example 3, utilize acyl chlorides and triethylamine to carry out synthetic method
Condition (B) ': similarly to Example 7, utilize 2 kinds of acyl chlorides and triethylamine to carry out synthetic method
[table 1]
Table 1
In table, " compound " refers to the compound of the present invention by being synthesized into.
To the compound obtaining in embodiment 1～108, in conjunction with ultimate analysis (C, H, N) (2400CHN processed of Perkinelmer Inc.) result and utilize the mass analysis result of EI-MS (PolarisQ of Thermo company system) to carry out structural confirmation.Results of elemental analyses is shown in to table 2, mass analysis be the results are shown in to table 3.
[table 2]
The results of elemental analyses of the synthetic compound of table 2
[table 3]
The mass analysis result of the synthetic compound of table 3
Embodiment 109～254, comparative example 1～12
Then, the compound of the present invention that the general formula obtaining (1) is represented, as radical polymerization initiator (A), joins in Polymerizable composition as follows, detects the solidified nature of polymkeric substance.
[solidified nature test]
Coordinate 4 weight part radical polymerization initiators (A), 0 or 1 weight part sensitizing agent, 10 weight parts Dap Tohto DT170 (Dongdu changes into (strain) diallyl phthalate resin processed), 85 weight part two trimethylolpropane tetra-acrylate as free-radical polymerised compound (B), heating and melting and make coating liquid.For the structure of the compound for comparative example and sensitizing agent, be shown in table 4 (following comparative example is also with reference to table 4).The radical polymerization initiator (A) and the sensitizing agent (C) that use are shown in to table 5.Utilize metering bar coater (#3) on PET film, to apply this coating liquid.With the condition of transmission speed 40m/ minute, 45m/ minute or 50m/ minute, this painting application is carried out after uviolizing (high voltage mercury lamp 130W/cm1 lamp), carry out wiping with cotton, determine that tunicle has or not scuffing.The results are shown in table 5.Here can will after uviolizing, under higher transmission speed, not have the situation scratching to be judged as good.
[metewand]
5: confirm that tunicle does not scratch
4: confirm that tunicle has scuffing extremely slightly
3: confirm that tunicle has scuffing a little
2: confirm that tunicle has scuffing
1: confirm that tunicle has a lot of scuffings
[table 4]
Table 4
[table 5]
Table 5
The known optical polymerism composition (embodiment 109～216) that has used radical polymerization initiator of the present invention (A) has high solidified nature compared with having used in the past the optical polymerism composition of known radical polymerization initiator (comparative example 1～6).And then, also the known and optical polymerism composition (embodiment 217～254) of having used radical polymerization initiator of the present invention (A) and sensitizing agent with and used the situation (comparative example 7～12) of known radical polymerization initiator and sensitizing agent in the past to compare, there is high solidified nature.Compared with when particularly known ketone type oxime ester used as Photoepolymerizationinitiater initiater in the past with general, ketone type oxime ester compound of the present invention is evident as high sensitive.Although unclear detailed reason, but think that Photoepolymerizationinitiater initiater of the present invention (A) produces very effective free radical by the excellent chromophoric group shown in general formula (1) and mating of ketone type oxime ester structure and decomposes, result has been brought into play high sensitive.
In addition, the known optical polymerism composition that has used radical polymerization initiator of the present invention (A) itself also shows very high solidified nature (embodiment 109～216), but pass through and use sensitizing agent (C), can further improve solidified nature (embodiment 217～254).
And then, use R 10～R 14in at least one be the radical polymerization initiator of the present invention (A) of nitro or replacement or unsubstituted acyl group optical polymerism composition (embodiment 109～147,174～185,187,190～195,204～212,215,216) with used R 7～R 10in at least one while being the radical polymerization initiator substituent of the present invention (A) beyond above-mentioned substituting group (embodiment 148～173,186,188,189,196～203,213～214) compare and there is high solidified nature.Although unclear detailed reason; but known Photoepolymerizationinitiater initiater of the present invention is by replacing electron-attracting substituent on the N position phenyl at carbazyl; can bring into play function as excellent chromophoric group, further replace therein nitro or acyl group, can bring significant effect.
And then, R 10～R 14in at least one be general formula (3) represent acyl group time (embodiment 109～111,113～127,174～178,187,190～192,204,205,210); compared with (embodiment 142～147,179～181,216), show high solidified nature when being acyl group beyond above-mentioned; same with nitro, show in the present embodiment the highest solidified nature.
In addition, the known R that used 12for the optical polymerism composition (embodiment 112,128～141,193～195,206～209) of the radical polymerization initiator of the present invention (A) of nitro has excellent solidified nature than (embodiment 182～185,211,212) beyond it.Although unclear detailed reason, the position that nitro the most effectively plays a role is R 12possibility high, also shown identical tendency for other substituting group (acyl group etc.).,, in known same substituent situation, be preferably substituted in R 12situation.
Embodiment 255～281, comparative example 13～18
Be prepared as follows alkali soluble resin and join in Polymerizable composition, the test of being cured property and development.
[preparation of acrylic resin soln (1)]
In reaction soln, add 800 weight part pimelinketone, be on one side heated to 100 ℃ on one side to nitrogen injection in container, the mixture that dripped following monomer and thermal polymerization at this temperature through 1 hour carries out polyreaction.
After dropping, further after 3 hours, add the material that 2.0 weight part Diisopropyl azodicarboxylates is dissolved in to 50.0 weight part pimelinketone 100 ℃ of reactions, further continue reaction 1 hour at 100 ℃, obtain weight-average molecular weight and be the solution of approximately 40,000 acrylic resin.Be cooled to after room temperature, the about 2g resin solution of sampling, with 180 ℃ of heat dryings 20 minutes, measures nonvolatile component, in synthetic resin solution, adds pimelinketone above, and making nonvolatile component is 20%, has prepared acrylic resin soln (1).The acrylic resin soln (1) obtaining is the solution that contains alkali soluble resin of the present invention (E).
[solidified nature test]
Add 100 weight parts as Dipentaerythritol five acrylate (Sartomer company, SR399) of free-radical polymerised compound (B), 500 weight parts as the acrylic resin soln (1) of the solution that contains alkali soluble resin (E), 400 weight parts as the pimelinketone of solvent, 6 weight parts are shown in table 6 compound as radical polymerization initiator (A), mix, prepared the solution of uniform Polymerizable composition.
Above-mentioned Polymerizable composition solution is filtered with the disk filter in 0.2 μ m aperture, apply at the upper spin coater that uses of stainless steel plate (#600 grinding), in baking oven, within 3 minutes, remove desolventizing with 80 ℃ of heat dryings.After dry, the thickness of the Polymerizable composition forming on stainless steel plate is 2 μ m.This Polymerizable composition film is irradiated to the light (4.6mW/cm of high voltage mercury lamp across the bandpass filter of the light of transmission 350nm to 380nm optionally 2), the IR spectrum of mensuration Polymerizable composition film, by the characteristic absorption 810cm of acryl (ア Network リ Le base) -1the variation of absorption intensity calculate rate of consumption before rayed, the acryl (ア Network リ Le base) of rayed after 10 seconds.Show the result in table 6.
[table 6]
Table 6
Example numbering Radical polymerization initiator The rate of consumption (%) of acryl
Embodiment 255 Compound (1) 38.5
Embodiment 256 Compound (2) 38.3
Embodiment 257 Compound (13) 37.8
Embodiment 258 Compound (24) 37.2
Embodiment 259 Compound (174) 36.6
Embodiment 260 Compound (44) 37.4
Embodiment 261 Compound (53) 37.0
Embodiment 262 Compound (65) 37.1
Embodiment 263 Compound (195) 36.3
Embodiment 264 Compound (85) 35.3
Embodiment 265 Compound (187) 34.8
Embodiment 266 Compound (109) 33.2
Embodiment 267 Compound (119) 32.5
Embodiment 268 Compound (100) 33.5
Embodiment 269 Compound (234) 32.4
Embodiment 270 Compound (124) 34.4
Embodiment 271 Compound (134) 33.3
Embodiment 272 Compound (145) 33.5
Embodiment 273 Compound (150) 34.1
Embodiment 274 Compound (157) 32.9
Embodiment 275 Compound (244) 37.7
Embodiment 276 Compound (252) 37.8
Embodiment 277 Compound (268) 38.0
Embodiment 278 Compound (280) 37.4
Embodiment 279 Compound (291) 36.3
Embodiment 280 Compound (298) 35.9
Embodiment 281 Compound (300) 33.0
Comparative example 13 Compound (310) 2.1
Comparative example 14 Compound (311) 3.1
Comparative example 15 Compound (312) 5.2
Comparative example 16 Compound (313) 17.8
Comparative example 17 Compound (314) 16.5
Comparative example 18 Compound (315) 19.2
Used the Polymerizable composition (embodiment 255～281) of radical polymerization initiator of the present invention (A) with using known oxime ester when radical polymerization initiator uses compared with (comparative example 13～18), can more effectively produce free radical by rayed, make acrylic polymerization.Even if make slightly further polymerization of acryloyl (ア Network リ Le), the impact of the raising on the productivity of pursuing is in recent years also very large, the radical polymerization initiator (A) of the application of the invention, can tackle more high sensitive technique.
In addition, Polymerizable composition before the rayed forming on the stainless steel plate of embodiment 255～281 be impregnated at 20 ℃ in the tetramethylammonium hydroxide aqueous solution of 0.2 % by weight concentration to approximately 1 minute, result is dissolved with suitable speed, has confirmed that Polymerizable composition of the present invention can be developed by alkaline-based developer.
Embodiment 282～353, comparative example 19～33
Be prepared as follows alkali soluble resin and join in Polymerizable composition, the test of being cured property and development.
[preparation of acrylic resin soln (2)]
In reaction soln, add 370 weight part pimelinketone, be on one side heated to 80 ℃ on one side to nitrogen injection in container, the mixture that dripped following monomer and thermal polymerization at this temperature through 1 hour carries out polyreaction.
Be cooled to after room temperature, the about 2g acrylic resin soln of sampling, with 180 ℃ of heat dryings 20 minutes, measure nonvolatile component, in just now synthetic acrylic resin soln, add pimelinketone, making nonvolatile component is 20 % by weight, thereby has prepared acrylic resin soln (2).The weight-average molecular weight of the acrylic resin obtaining is 40000.The acrylic resin soln (2) obtaining is the solution that contains alkali soluble resin of the present invention (E).
[solidified nature test]
Add 100 weight parts as Dipentaerythritol five acrylate (Sartomer company, SR399) of free-radical polymerised compound (B), 500 weight parts as the acrylic resin soln (2) of the solution that contains alkali soluble resin (E), 200 weight parts as the propylene glycol methyl ether acetate of solvent, be respectively weight part that table 7 records as the compound shown in the table 7 of radical polymerization initiator (A) and sensitizing agent (C), mix, prepare the solution of uniform Polymerizable composition.
Above-mentioned Polymerizable composition solution is filtered with the disk filter in 0.2 μ m aperture, on the sheet glass that is 1mm at thickness, use spin coater to apply, in baking oven, within 3 minutes, remove desolventizing with 80 ℃ of heat dryings.After dry, the thickness of the Polymerizable composition film forming on sheet glass is 5 μ m.To this Polymerizable composition film, use Japanese light splitting (strain) SS-25CP type to divide light illuminator, by the irradiation energy of high voltage mercury lamp, irradiation time was varied to for 13 stages and exposes, then develop 1 minute with 1% aqueous sodium carbonate at 20 ℃, Polymerizable composition under the illumination wavelength of 365nm is not melted to required minimum energy and be defined as susceptibility, show the result in table 7.
[table 7]
Table 7
Use the Polymerizable composition (embodiment 282～353) of radical polymerization initiator of the present invention (A) compared with the Polymerizable composition that has used known oxime ester as radical polymerization initiator (comparative example 19～33), there is obviously high susceptibility.In addition, Polymerizable composition of the present invention is also high sensitive very not also with sensitizing agent in the situation that, but passes through and use sensitizing agent, can obtain more high sensitive.
Embodiment 354～425, comparative example 34～48
[pattern form test]
The exposure energy that Polymerizable composition film on the glass substrate of making in embodiment 282～353 and comparative example 19～33 is irradiated to 10 seconds 365nm with the pattern mask (20 μ m × 2 μ m resolving power) of regulation take exposing clearance approximately 100 μ m is as 4.5mW/cm 2the light of high voltage mercury lamp.Then, at room temperature developed for 60 seconds with the tetramethylammonium hydroxide aqueous solution of 0.2 % by weight, remove unexposed portion, after cleaning with pure water, by the cured article obtaining in baking oven with 230 ℃ of heating 30 minutes.The pattern form obtaining on glass substrate is evaluated by following method.Show the result in table 8.
(pattern form evaluation method)
The pattern form that utilizes observation by light microscope to obtain on glass substrate, carries out the linear evaluation of pattern.The grade of evaluating is as follows.
Zero: rectilinearity is good
×: rectilinearity is poor
-: insufficient owing to solidifying, do not observe pattern
[table 8]
Table 8
Use the Polymerizable composition (embodiment 354～425) of radical polymerization initiator of the present invention (A) to be, the rectilinearity of the pattern form obtaining on glass substrate is good, on the other hand, the Polymerizable composition (comparative example 34～48) using known oxime ester as radical polymerization initiator, the rectilinearity of the pattern form obtaining on glass substrate is poor or insufficiently cannot observe pattern form because solidifying.
Embodiment 426～498, comparative example 49～63
[pattern fitness test]
By the pattern forming substrate of making in embodiment 354～425 and comparative example 34～48 under 121 ℃, 100%RH, 2atm, the condition of 24 hours, implement after PCT (pressure cooker) test, at 20 μ m drafting department sticking glass paper self-adhesive tapes, carry out stripping test, thus evaluation pattern generating adaptation.Show the result in table 9.
The grade of evaluating is as follows.
Zero: do not find peeling off of 20 μ m patterns
×: find peeling off of 20 μ m patterns
-: because solidifying insufficient cannot evaluation
[table 9]
Table 9
Use the situation (embodiment 426～498) of Polymerizable composition of the present invention, the pattern obtaining on glass substrate is good to the adaptation of substrate, on the other hand, used the situation (comparative example 49～63) as the Polymerizable composition of radical polymerization initiator by known oxime ester, pattern is insufficient to the adaptation of substrate.
Embodiment 499～606, comparative example 64～91
According to below, prepare pigment dispersion, then, the tint permanence polymerizable compound that preparation contains it.
[preparation of red pigment dispersion]
After the mixture of following composition is uniformly mixed, utilize EIGER shredder (EIGER Japanese firm system " mini M-250 MKII ") to disperse 2 hours, then filter with the strainer of 5 μ m, make red pigment dispersion.
[changing 45]
[preparation of veridian dispersion]
Use the mixture of following composition, similarly make veridian dispersion with red pigment dispersion.
Copper halide phthualocyanine pigment (C.I. pigment green 36)
[changing 46]
[preparation of blue pigment dispersion]
The mixture of following composition and red pigment dispersion are similarly operated and made blue pigment dispersion.
[changing 47]
Cu-pc; Copper phthalocyanine residue
[preparation of black pigment dispersion]
The mixture of following composition and red pigment dispersion are similarly operated and made black pigment dispersion.
Carbon black (society of Mitsubishi Chemical manufactures " MA77 ") 12.0 weight parts
Acrylic resin soln 40.0 weight parts
Pimelinketone 48.0 weight parts
[red Polymerizable composition]
Compound (1) using 58 weight part red pigment dispersion, 20 parts by weight of acrylic acid resin solutions (2), 3 weight part Viscoat 295s (Xin Zhong village chemistry society's system " NK ester ATMPT "), 2 weight parts as radical polymerization initiator (A), the mixture of 17 weight part pimelinketone are uniformly mixed to after evenly, with the strainer filtration of 1 μ m, thereby obtain red Polymerizable composition of the present invention (embodiment 499).
[blue Polymerizable composition]
Compound (1) using 54 weight part blue pigment dispersion, 15 parts by weight of acrylic acid resin solutions (2), 4 weight part Viscoat 295s (Xin Zhong village chemistry society's system " NK ester ATMPT "), 4 weight parts as radical polymerization initiator (A), the mixture of 25 weight part pimelinketone are uniformly mixed to after evenly, with the strainer filtration of 1 μ m, thereby obtain blue Polymerizable composition of the present invention (embodiment 500).
[green Polymerizable composition]
Compound (1) using 67 weight part veridian dispersions, 11 parts by weight of acrylic acid resin solutions (2), 3 weight part Viscoat 295s (Xin Zhong village chemistry society's system " NK ester ATMPT "), 2 weight parts as radical polymerization initiator (A), the mixture of 18 weight part pimelinketone are uniformly mixed to after evenly, with the strainer filtration of 1 μ m, thereby obtain green Polymerizable composition of the present invention (embodiment 501).
[black Polymerizable composition]
Compound (1) using 75 weight part black pigment dispersions, 9 parts by weight of acrylic acid resin solutions (2), 3 weight part Viscoat 295s (Xin Zhong village chemistry society's system " NK ester ATMPT "), 3 weight parts as radical polymerization initiator (A), the mixture of 13 weight part pimelinketone are uniformly mixed to after evenly, with the strainer filtration of 1 μ m, thereby obtain black Polymerizable composition of the present invention (embodiment 502).
Coloured polymerized composition to embodiment 503～606, comparative example 64～91 is also made as follows.
[red Polymerizable composition]
Compound as radical polymerization initiator (A) (1) is replaced as to the compound shown in table 10, in addition, similarly carries out with embodiment 499, obtained respectively the red Polymerizable composition shown in table 10.
[blue Polymerizable composition]
Compound as radical polymerization initiator (A) (1) is replaced as to the compound shown in table 10, in addition, similarly carries out with embodiment 500, obtained respectively the blue Polymerizable composition shown in table 10.
[green Polymerizable composition]
Compound as radical polymerization initiator (A) (1) is replaced as to the compound shown in table 10, in addition, similarly carries out with embodiment 501, obtained respectively the green Polymerizable composition shown in table 10.
[black Polymerizable composition]
Compound as radical polymerization initiator (A) (1) is replaced as to the compound shown in table 10, in addition, similarly carries out with embodiment 502, obtained respectively the black Polymerizable composition shown in table 10.
[table 10]
Table 10
[pattern of filter section and black matrix forms]
The coloured polymerized composition obtaining is utilized to of all kinds being respectively after the thickness shown in table 11 of thickness after spin-coating method cures after the glass substrate of 10cm × 10cm is applied as, in cleaning oven with 70 ℃ of prebake 15 minutes.Then, this substrate is cooled to after room temperature, utilizes ultrahigh pressure mercury lamp, across photomask ultraviolet exposure.Then, utilize the aqueous sodium carbonate of 23 ℃ to carry out after spray development this substrate, with ion exchanged water cleaning, carry out air-dry.Then, in clean baking oven, with 230 ℃ carry out 30 minutes after cure, on substrate, form the filter section of strip.
[table 11]
Table 11
Red Blue Green Black
(μ m) for thickness 1.40 1.80 1.80 1.10
Thickness: the formation thickness of filter section of all kinds and black matrix
[evaluation]
With the susceptibility and the filter section that utilizes aforesaid method to form or the pattern form of black matrix of following method evaluation gained coloured polymerized composition.Show the result in table 12.
(susceptibility)
The irradiation exposure that the pattern of the filter section of formation or black matrix is completed according to the picture size of photomask is as the susceptibility of resist.The grade of evaluating is as follows.
◎: be less than 40mJ/cm 2
Zero: 40mJ/cm 2above and be less than 80mJ/cm 2
△: 80mJ/cm 2above and be less than 250mJ/cm 2
×: 250mJ/cm 2above
(pattern form)
The shape of the pattern of the filter section forming or black matrix is evaluated by the rectilinearity of (1) pattern, the cross-sectional shape of (2) pattern.
For (1), utilize opticmicroscope to observe and evaluate.The grade of evaluating is as follows.
Zero: rectilinearity is good
△: rectilinearity is poor locally
×: rectilinearity is poor
For (2), utilize scanning electronic microscope (SEM) to observe and evaluate.The grade of evaluating is as follows.
Zero: positive conical by its shape.
△: non-conical by its shape.
×: reverse tapered shapes.
(residual film ratio evaluation)
Will be through overexposure (100mJ/cm 2), develop, after cure the thickness measured after operation with form coated film and dry after each coloured polymerized composition of measuring thickness be compared to residual film ratio.The grade of evaluating is as follows.
More than zero: 70%
×: be less than 70%
[table 12]
Table 12
As shown in table 12, use the very high sensitive of coloured polymerized composition (embodiment 499～606) of the radical polymerization initiator (A) of general formula (1) expression, the rectilinearity of the pattern obtaining and cross-sectional shape are also good, on the other hand, the susceptibility of the coloured polymerized composition (comparative example 64～91) using known oxime ester compound as radical polymerization initiator is poor, and the rectilinearity of pattern and cross-sectional shape also can not get good result.
And then, use the coloured polymerized composition (embodiment 499～606) of the radical polymerization initiator (A) that general formula (1) represents by utilization, can obtain high residual film ratio and form the film of middle production stability excellence at film.On the other hand, the residual film ratio of the coloured polymerized composition (comparative example 64～91) using known oxime ester compound as radical polymerization initiator is poor, does not reach sufficient level in film forms.
Known, to use compound of the present invention as radical polymerization initiator optical polymerism composition, even with in the past known by the optical polymerism composition comparison of radical polymerization initiator and sensitizing agent use, its solidified nature is also excellent.Known, by the contribution of this high solidified nature, can tackle more high sensitive technique.In addition, think bring the compound of the present invention of high like this solidified nature be by absorb light well and can by the carbazole chromophoric group shown in tremendous free-radical generating efficiency the general formula (1) improving and can produce in a large number by utilizing light-struck decomposition free radical ketone type oxime ester structure synergetic property bring good effect.
In industry, utilize possibility
The present invention relates to novel oxime ester cpds, used it radical polymerization initiator (A), used it Polymerizable composition, used its negative resist and used its picture pattern formation method.Compound performance of the present invention is as the function to the very high sensitive free-radical generating agent of the irradiation of energy line.Therefore, use the radical polymerization initiator of the present invention (A) of compound of the present invention, can make the free radical that utilizes the irradiation of passing through energy line in the past using to produce carry out rapidly and positively as polymerization, the crosslinking reaction etc. of catalyzer, its result, can expect that the high sensitive of the energy line to various uses or sufficient reacting carry out characteristic raising of brought various uses etc.As expecting high sensitive by the present invention, the example of the purposes that characteristic improves, can enumerate the moulding resin that has utilized polymerization or crosslinking reaction, cast resin, light chisel resin, sealing agent, dental polymer resin, printing-ink, jetted ink, coating, press plate photoresist, printing color proof, colour filter resist, black matrix resist, liquid crystal light sensitive spacer, rear projection screen material, optical fiber, plasma display timber, dry film photoresist, printed base plate resist, scolder resist, semi-conductor photo-resist, microelectronics resist, the parts manufacture resist of micromachine, etching resist, microlens array, insulation material, hologram material, optical converter, waveguide material, outer coating agent, powder coated dose, caking agent, tackiness agent, releasing agent, optical recording medium, sticky solid, release-coated agent, use the image recording material composition of microcapsule, various devices etc.

Claims (13)

1. on the phenyl of N-phenyl carbazole skeleton, replace an alpha-ketoxime ester cpds that has electron-attracting substituent, it is represented by following general formula (1):
[changing 1]
In formula, R 1represent to replace or unsubstituted alkenyl, replace or unsubstituted alkyl, replace or unsubstituted alkoxyl group, replace or unsubstituted aryl, replace or unsubstituted aryloxy, replace or unsubstituted heterocyclic radical, replace or unsubstituted heterocyclic oxy group, replace or unsubstituted alkyl alkylthio base, replace or unsubstituted sulfur alkyl aryl, replace or unsubstituted alkyl sulphinyl, replace or unsubstituted aryl sulfonyl kia, replace or unsubstituted alkyl sulphonyl, replace or unsubstituted aryl sulfonyl, replace or unsubstituted acyl group, replace or unsubstituted acyloxy, replace or unsubstituted amino, replace or unsubstituted phosphino-, replace or unsubstituted formamyl, or replacement or unsubstituted sulfamyl,
R 2represent to replace or unsubstituted alkenyl, replace or unsubstituted alkyl, replace or unsubstituted alkoxyl group, replace or unsubstituted aryl, replace or unsubstituted aryloxy, replace or unsubstituted heterocyclic radical, replace or unsubstituted heterocyclic oxy group, replace or unsubstituted alkyl alkylthio base, replace or unsubstituted sulfur alkyl aryl, replace or unsubstituted alkyl sulphinyl, replace or unsubstituted aryl sulfonyl kia, replace or unsubstituted alkyl sulphonyl, replace or unsubstituted aryl sulfonyl, replace or unsubstituted acyloxy, or replacement or unsubstituted amino,
R 3～R 5represent independently of one another hydrogen atom, halogen atom, cyano group, nitro, replacement or unsubstituted alkenyl, replacement or unsubstituted alkyl, replacement or unsubstituted alkoxyl group, replacement or unsubstituted aryl, replacement or unsubstituted aryloxy, replacement or unsubstituted heterocyclic radical, replacement or unsubstituted heterocyclic oxy group, replacement or unsubstituted alkyl alkylthio base, replacement or unsubstituted sulfur alkyl aryl, replacement or unsubstituted acyl group or replacement or unsubstituted amino
R 6～R 9represent independently of one another hydrogen atom, halogen atom, cyano group, haloalkyl, replace or unsubstituted alkyl, replace or unsubstituted alkoxyl group, replace or unsubstituted aryl, replace or unsubstituted aryloxy, replace or unsubstituted heterocyclic radical, replace or unsubstituted heterocyclic oxy group, replace or unsubstituted alkenyl, replace or unsubstituted alkyl alkylthio base, replace or unsubstituted sulfur alkyl aryl, replace or unsubstituted alkyl sulphinyl, replace or unsubstituted aryl sulfonyl kia, replace or unsubstituted alkyl sulphonyl, replace or unsubstituted aryl sulfonyl, replace or unsubstituted amino, or the substituting group being represented by following general formula (2),
[changing 2]
In formula, R 1' and R 2' and R 1and R 2synonym,
R 10～R 14represent independently of one another hydrogen atom, halogen atom, cyano group, nitro, haloalkyl, replacement or unsubstituted alkyl sulphinyl, replacement or unsubstituted aryl sulfonyl kia, replacement or unsubstituted alkyl sulphonyl, replacement or unsubstituted aryl sulfonyl or replacement or unsubstituted acyl group, R 10～R 14be not all hydrogen atom simultaneously,
At R 1～R 14in,
Described replacement or unsubstituted alkenyl are that carbon number is 1 to 18 straight chain shape, chain, monocycle shape or condensation polycyclic shape alkenyl;
Described replacement or unsubstituted alkyl are that carbon number is 1 to 18 straight chain shape, chain, monocycle shape or condensation polycyclic shape alkyl; Or carbon number is 2 to 18 and contains or do not contain straight chain shape, chain, monocycle shape or the condensation polycyclic shape alkyl of more than 1 ehter bond (O-);
Described replacement or unsubstituted alkoxyl group are that carbon number is 1～18 straight chain shape, chain, monocycle shape or condensation polycyclic shape alkoxyl group; Or carbon number is 2 to 18 and contains or do not contain straight chain shape, chain, monocycle shape or the condensation polycyclic shape alkoxyl group of more than 1 ehter bond;
Described replacement or unsubstituted aryl are that carbon number is 6 to 24 monocycle or condensation polycyclic aryl;
Described replacement or unsubstituted aryloxy are that carbon number is 6～18 monocycle or condensation polycyclic aryloxy;
Described replacement or unsubstituted heterocyclic radical are aromatic series or the aliphatic heterocyclic radicals that the carbon number that contains nitrogen-atoms, Sauerstoffatom, sulphur atom, phosphorus atom is 4～24;
Described replacement or unsubstituted heterocyclic oxy group are monocycle shape or the condensation polycyclic shape heterocyclic oxy groups that the carbon number that contains nitrogen-atoms, Sauerstoffatom, sulphur atom, phosphorus atom is 4～18;
Described replacement or unsubstituted alkyl alkylthio base are that carbon number is 1 to 18 straight chain shape, chain, monocycle shape or condensation polycyclic shape alkyl sulfenyl;
Described replacement or unsubstituted sulfur alkyl aryl are that carbon number is 6～18 monocycle shape or condensation polycyclic shape artyl sulfo;
Described replacement or unsubstituted alkyl sulphinyl are that carbon number is 1～20 alkyl sulphinyl;
That carbon number is 6～30 aryl sulfonyl kia as replacement or unsubstituted aryl sulfonyl kia;
Described replacement or unsubstituted alkyl sulphonyl are that carbon number is 1～20 alkyl sulphonyl;
Described replacement or unsubstituted aryl sulfonyl are that carbon number is 6～30 aryl sulfonyl;
Described replacement or unsubstituted acyl group are that to combine hydrogen atom or carbon number be 1 to 18 straight chain shape, prop up chain, the aliphatic carbonyl of monocycle shape or condensation polycyclic shape, carbon number is the carbonyl that 2 to 20 alkoxyl group replaces, combine carbon number and be 6 to 18 monocycle shape or the carbonyl of condensation polycyclic shape aryl, carbon number is the carbonyl that 6 to 18 monocycle shape or condensation polycyclic shape aryloxy replace, combine and contain nitrogen-atoms, Sauerstoffatom, sulphur atom, the carbon number of phosphorus atom is 4～18 monocycle shape or the carbonyl of condensation polycyclic shape heterocyclic radical,
Described replacement or unsubstituted acyloxy are that carbon number is 2～20 acyloxy;
Described replacement or unsubstituted phosphino-are that carbon number is 2 to 50 phosphino-;
Described replacement or unsubstituted formamyl are that carbon number is 1 to 30 formamyl;
Described replacement or unsubstituted sulfamyl are that carbon number is 0 to 30 sulfamyl;
Described replacement or unsubstituted amino are amino, alkylamino, dialkyl amido, arylamino, ammonia diaryl base, alkyl aryl amino, benzylamino or dibenzyl amino.
2. compound according to claim 1, is characterized in that, described R 10～R 14in at least one be nitro or replacement or unsubstituted acyl group.
3. compound according to claim 1 and 2, is characterized in that, described R 10～R 14in at least one be nitro or following general formula (3):
[changing 3]
In formula, R 15～R 19represent independently of one another hydrogen atom, halogen atom, cyano group, nitro, haloalkyl, replace or unsubstituted alkyl, replace or unsubstituted alkoxyl group, replace or unsubstituted aryl, replace or unsubstituted aryloxy, replace or unsubstituted heterocyclic radical, replace or unsubstituted heterocyclic oxy group, replace or unsubstituted alkenyl, replace or unsubstituted alkyl alkylthio base, replace or unsubstituted sulfur alkyl aryl, replace or unsubstituted acyl group, or replacement or unsubstituted amino.
4. compound according to claim 3, is characterized in that, described R 12for nitro or described general formula (3).
5. a radical polymerization initiator (A), is characterized in that, contains the compound described in any one in claim 1～4.
6. a Polymerizable composition, is characterized in that, contains radical polymerization initiator claimed in claim 5 (A) and free-radical polymerised compound (B).
7. Polymerizable composition according to claim 6, is characterized in that, also contains sensitizing agent (C).
8. Polymerizable composition according to claim 6, is characterized in that, also contains coloring components (D).
9. according to the Polymerizable composition described in any one in claim 6～8, it is characterized in that, also contain alkali soluble resin (E).
10. a negative resist, is characterized in that, contains Polymerizable composition claimed in claim 9.
The manufacture method of 11. 1 kinds of polymkeric substance, is characterized in that, the Polymerizable composition irradiation energy line described in any one in claim 6～9 is carried out to polymerization.
The formation method of 12. 1 kinds of picture patterns, is characterized in that, at the folded negative resist claimed in claim 10 of layers on substrates, irradiation energy line and carry out polymerization partly, utilizes alkaline-based developer to remove non-irradiated part.
13. negative resists claimed in claim 10 are in the application forming in picture pattern.
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